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WO2008054560A2 - Certaines compositions de polyester qui comprennent du cyclobutanediol, du cyclohexanediméthanol, et de l'acide trans-cyclohexanedicarboxylique supérieur - Google Patents

Certaines compositions de polyester qui comprennent du cyclobutanediol, du cyclohexanediméthanol, et de l'acide trans-cyclohexanedicarboxylique supérieur Download PDF

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Publication number
WO2008054560A2
WO2008054560A2 PCT/US2007/015713 US2007015713W WO2008054560A2 WO 2008054560 A2 WO2008054560 A2 WO 2008054560A2 US 2007015713 W US2007015713 W US 2007015713W WO 2008054560 A2 WO2008054560 A2 WO 2008054560A2
Authority
WO
WIPO (PCT)
Prior art keywords
mole
polyester
acid residues
cyclohexanedimethanol
residues
Prior art date
Application number
PCT/US2007/015713
Other languages
English (en)
Other versions
WO2008054560A3 (fr
Inventor
Leslie Shane Moody
Emmett Dudley Crawford
Jeremy Richards Lizotte
Original Assignee
Eastman Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/588,906 external-priority patent/US8193302B2/en
Priority claimed from US11/588,883 external-priority patent/US20070105993A1/en
Priority claimed from PCT/US2006/042292 external-priority patent/WO2007053549A1/fr
Priority claimed from US11/588,524 external-priority patent/US20100096589A1/en
Priority claimed from US11/588,527 external-priority patent/US20100087574A1/en
Priority claimed from US11/588,907 external-priority patent/US20070106054A1/en
Priority claimed from US11/588,554 external-priority patent/US20070100125A1/en
Priority claimed from PCT/US2006/041917 external-priority patent/WO2007053434A1/fr
Priority claimed from US11/588,458 external-priority patent/US20070100122A1/en
Priority claimed from US11/635,434 external-priority patent/US7737246B2/en
Priority claimed from US11/635,433 external-priority patent/US20070142511A1/en
Priority claimed from US11/706,791 external-priority patent/US20070232779A1/en
Priority claimed from US11/706,476 external-priority patent/US20070232778A1/en
Priority claimed from PCT/US2007/007632 external-priority patent/WO2007126855A1/fr
Priority claimed from PCT/US2007/010551 external-priority patent/WO2007139653A1/fr
Priority claimed from US11/773,275 external-priority patent/US8586701B2/en
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Publication of WO2008054560A2 publication Critical patent/WO2008054560A2/fr
Publication of WO2008054560A3 publication Critical patent/WO2008054560A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • the present invention generally relates to polyester compositions made from made from cyclohexanedicarboxylic acid (CHDA) or an ester thereof, 2,2,4,4-tetramethyl-i ,3-cyclobutanediol (TMCD) or an ester thereof, and cyclohexanedimethanol (CHDM) or an ester thereof, and mixtures thereof, have certain combinations of two or more of high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviolet radiation, and chemical resistance.
  • CHDA cyclohexanedicarboxylic acid
  • TMCD 2,2,4,4-tetramethyl-i ,3-cyclobutanediol
  • CHDM cyclohexanedimethanol
  • Polyesters comprising significant amounts of aromatic monomers, such as terephthalic acid (TPA) or isophthalic acid (IPA) absorb significant amounts of ultraviolet (UV) radiation due to terephthalate and/or isophthalate moieties. Over time, this can lead to degradation of physical properties, discoloration, and haze. Addition of competitive UV absorbers (UVAs) helps to stabilize against these deleterious effects of UV radiation, however, significant amounts of the UVAs must be used to adequately protect the aromatic polyester. Typically, aliphatic polyesters do not absorb significant amounts of ultraviolet (UV) radiation but many exhibit low glass transition temperatures (T 9 ).
  • poly(1,4- cyclohexanedimethylene-1 ,4-cyclohexanedicarboxylate) Although somewhat higher than the T g s of many other aliphatic polyesters from straight- or branched-chain monomers, poly(1,4- cyclohexanedimethylene-1 ,4-cyclohexanedicarboxylate) also exhibits a relatively low (about 66 0 C) glass transition temperature. This has practical importance, since T 9 often sets an upper temperature limit for the use of an amorphous thermoplastic polymer. Additionally, poly(1,4-cyclohexanedimethylene-1 ,4- cyclohexanedicarboxylate) crystallizes relatively rapidly, making it difficult to form amorphous articles, especially in thick parts.
  • the Tg range of the polyesters of the present invention can be from greater than about 66°up to about 155°C.
  • Uses for these higher T 9 amorphous and essentially aliphatic copolyesters of the present invention include but are not limited to: protective cap-layers for higher T 9 resins, such as available aromatic copolyesters, whose T g s are in the range of about 70°-130°C, but are less easily or more expensively stabilized than the polyesters of the present invention.
  • a high concentration of UV absorber in a very thin cap-layer would be much less expensive than bulk- stabilization of the underlying substrate.
  • the polyesters of the present invention are also useful for weatherable injection molding applications, where it would be expensive to bulk-stabilize an aromatic resin. These copolyesters can also be used in many applications where a tough, weatherable polymer is required. [0005] Some of the copolyesters of this invention have also been shown to possess greatly improved chemical resistance when exposed to lipids and isopropanol compared to certain aromatic polyesters with similar T g s. Also, the invention includes a process where the compositions of the present invention can be produced in a timely fashion on standard equipment. Bulky, secondary diols, such as TMCD, are generally.
  • the total reaction time has been shortened such that the compositions of the present invention can be produced on a time scale more similar to that of other polyesters known in the art using typical production equipment known in the art.
  • polyester compositions containing cyclohexanedicarboxylic acid, 2,2,4 ,4-tetramethyM ,3-cyclobutanediol, cyclohexanedimethanol, or their chemical equivalents, and alternatively, other modifying diols and dicarboxylic acids or their chemical equivalents, with certain monomer compositions and inherent viscosities are believed to be unexpectedly superior to copolyesters known in the art with respect to their T 9 , notched Izod impact strength and low absorption of ultraviolet radiation.
  • the materials of the invention are particularly useful for weathering/weatherable end-use applications and/or outdoor end-use applications.
  • certain polyesters and/or polyester compositions of the invention are superior to certain commercial polymers with respect to a combination of two or more of high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain densities, flexural modulus, weatherabiliy, low absorption of ultraviolet radiation, and chemical resistance.
  • certain polyesters and/or polyester compositions of the invention are superior to certain commercial polymers with respect to three or more of high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviolet radiation, and chemical resistance.
  • certain polyesters and/or polyester compositions of the invention are superior to certain commercial polymers with respect to a combination of four or more of high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviofet radiation, and chemical resistance.
  • certain polyesters and/or polyester compositions of the invention are superior to certain commercial polymers with respect to a combination of all of the following properties: high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviolet radiation, and chemical resistance.
  • the processes of making the polyesters useful in the invention can comprise a batch or continuous process.
  • the processes of making the polyesters useful in the invention comprise a continuous process.
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • (B) a glycol component comprising: (i) 65 to 75 mole % 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol residues; and
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the inherent viscosity of the polyester is from 0.72 to 0.85 dl_/g as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.25 g/50 ml at 25 0 C; and wherein the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • the invention relates to a polyester composition
  • a polyester composition comprising at least one polyester which comprises:
  • the polyester has a glass transition temperature of from greater than
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; optionally, at least one antioxidant as described herein, and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; and at least one antioxidant as described herein; and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; and optionally, at least one antioxidant as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; and at least one antioxidant as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; optionally, at least one antioxidant as described herein, and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; and at least one antioxidant as described herein; and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; and optionally, at least one antioxidant as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; and at least one antioxidant as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; optionally, at least one hindered amine light stabilizer as described herein, and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; and at least one hindered amine light stabilizer as described herein; and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; and optionally, at least one hindered amine light stabilizer as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer comprising at least one of the polyesters of the invention; and at least one hindered amine light stabilizer as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; optionally, at least one hindered amine light stabilizer as described herein, and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; and at least one hindered amine light stabilizer as described herein; and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; and optionally, at least one hindered amine light stabilizer as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a protective layer comprising at least one of the polyesters of the invention; and at least one hindered amine light stabilizer as described herein, and at least one ultraviolet light absorbing compound.
  • the invention relates to a polyester composition
  • a polyester composition comprising any of the polyesters described herein comprising from about 0.01 to about 30 mole % of aliphatic dicarboxylic acid residues, other than cyclohexanedicarboxylic acid residues, having up to 20 carbon atoms.
  • the invention relates to a polyester composition
  • a polyester composition comprising any of the polyesters described herein comprising from about 0.01 to about 30 mole % of aliphatic dicarboxylic acid residues, other than cyclohexanedicarboxylic acid residues, chosen from malonic acid residues, succinic acid residues, glutaric acid residues, adipic acid residues, suberic acid residues, azelaic acid residues, sebacic acid residues, and the like.
  • the invention relates to a polyester composition
  • a polyester composition comprising any of the polyesters described herein comprising from about 0.01 to about 30 mole % of aliphatic dicarboxylic acid residues, other than cyclohexanedicarboxylic acid residues, chosen from at least one of succinic acid residues and adipic acid residues.
  • the polyester compositions of the invention can include at least one hindered amine light stabilizer compound.
  • the polyester compositions of the invention can include at least one ultraviolet light absorbing compound.
  • the polyester compositions of the invention can include at least one hindered amine light stabilizer compound and at least one ultraviolet light absorbing compound. [0093] In one embodiment, the polyester compositions of the invention comprises no hindered amine light stabilizer compounds.
  • the polyester compositions of the invention comprise no ultraviolet light absorbing compounds.
  • the invention includes thermoformed sheet(s) which can comprise any of the polyester compositions of the invention.
  • the polyesters useful in the invention can comprise at least one phosphate ester described herein which is present as a thermal stabilizer.
  • the polyesters useful in the invention can comprise at least one hindered phenol antioxidant described herein which is present as a thermal stabilizer.
  • the polyesters useful in the invention contain at least one branching agent.
  • certain polyesters useful in the invention may be amorphous or semicrystalline. In one aspect, certain polyesters useful in the invention can have a relatively low crystallinity. Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
  • any of the polyester(s), polyester compositions and/or processes of making the polyesters useful in the invention may comprise at least one tin compound.
  • any of the polyester(s), polyester compositions and/or processes of making the polyesters useful in the invention may comprise at least one phosphorus compound.
  • any of the polyester(s), polyester compositions and/or processes of making the polyesters useful in the invention may comprise at least one tin compound, and at least one phosphorus compound.
  • the amount of tin atoms in the polyesters useful in the invention can be from 0 to 600 ppm tin atoms based on the weight of the final polyester. [00104] In one aspect, the amount of tin atoms in the polyesters useful in the invention can be from 50 to 600 ppm tin atoms based on the weight of the final polyester.
  • the amount of tin atoms in the polyesters useful in the invention can be from 50 to 400 ppm tin atoms based on the weight of the final polyester.
  • the amount of titanium atoms in the polyesters useful in the invention can be from 0 to 100 ppm titanium atoms based on the weight of the final polyester.
  • the amount of titanium atoms in the polyesters useful in the invention can be from 1 to 100 ppm titanium atoms based on the weight of the final polyester.
  • the polyester compositions are useful in articles of manufacture including, but not limited to, extruded, calendered, and/or molded articles including, but not limited to, injection molded articles, extruded articles, cast extrusion articles, profile extrusion articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles and extrusion stretch blow molded articles.
  • extruded, calendered, and/or molded articles including, but not limited to, injection molded articles, extruded articles, cast extrusion articles, profile extrusion articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles and extrusion stretch blow molded articles.
  • These articles can include, but are not limited to, films, bottles, containers, sheet, multi-layer sheet, and/or fibers.
  • the polyester compositions useful in the invention may be used in various types of film and/or sheet, including but not limited to extruded film(s) and/or sheet(s), calendered film ⁇ s) and/or sheet(s), compression molded film(s) and/or sheet(s), solution casted film(s) and/or sheet(s).
  • Methods of making film and/or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.
  • the invention is related to thermoformed film(s) and/or sheet(s) comprising the polyester(s) and/or polyester compositions of the invention.
  • the invention is related to articles of manufacture which incorporate the thermoformed film and/or sheet of the invention.
  • the polyesters useful in the invention can be amorphous or semicrystalline.
  • certain polyesters useful in the invention can have a relatively low crystallinity.
  • Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
  • polyesters and/or polyester composition(s) of the invention formed from cyclohexanedicarboxylic acid or an ester thereof, cyclohexanedimethanol or an ester thereof, 2,2,4,4-tetramethyl-1,3- cydobutanediol or an ester thereof, can have a unique combination of two or more of chosen from: high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviolet radiation, and chemical resistance.
  • T 9 glass transition temperature
  • certain polyesters and/or polyester compositions of the invention can have a unique combination of three or more of high notched Izod impact strength, certain glass transition temperature (Tg), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviolet radiation, and chemical resistance.
  • certain polyesters and/or polyester compositions of the invention can have a unique combination of four or more of high notched Izod impact strength, certain glass transition temperature (Tg), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviolet radiation, and chemical resistance.
  • certain polyesters and/or polyester compositions of the invention can have a unique combination of all of the following properties: high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain densities, flexural modulus, weatherability, low absorption of ultraviolet radiation, and chemical resistance.
  • polyesters and/or polyester compositions containing some or all of the aforementioned properties are useful in many applications, these properties are particularly useful for building and construction materials, auto panels, and optical media applications.
  • the processes of making the polyesters useful in the invention can comprise a batch or continuous process.
  • the processes of making the polyesters useful in the invention comprise a continuous process.
  • tin When tin is added to to the polyesters and/or polyester compositions and/or process of making the polyesters of the invention, it is added to the process of making the polyester in the form of a tin compound.
  • the amount of the tin compound added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of tin atoms present in the final polyester, for example, by weight measured in ppm.
  • the amount of the phosphorus compound added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of phosphorus atoms present in the final polyester, for example, by weight measured in ppm.
  • titanium When titanium is added to to the polyesters and/or polyester compositions and/or process of making the polyesters of the invention, it is added to the process of making the polyester in the form of a titanium compound.
  • the amount of the titanium compound added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of titanium atoms present in the final polyester, for example, by weight measured in ppm.
  • polystyrene resin is intended to include “copolyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds, for example, branching agents.
  • the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol such as, for example, glycols and diols.
  • glycocol as used herein includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds, for example, branching agents.
  • the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybutyric acid
  • the difunctional hydroxyl compound may be an aliphatic nucleus bearing 2 hydroxyl substituents such as, for example, 1 ,3-cyclohexanediol or 1 ,4-cyclohexanediol.
  • the term "residue”, as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer.
  • the term “repeating unit”, as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group.
  • the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, and/or mixtures thereof.
  • the term "diacid” includes multifunctional acids, for example, branching agents.
  • the term “dicarboxylic acid” is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof, useful in a reaction process with a diol to make polyester.
  • cyclohexanedicarboxylic acid residues make up part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % cyclohexanedicarboxylic acid residues and/or esters thereof and/or mixtures thereof may be used.
  • 4-cyclohexanedicarboxylic acid esters make up part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % 1,4- cyclohexanedicarboxylic acid esters may be used.
  • dimethyl-1 ,4-cyclohexanedicarboxylate makes up part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % dimethyl-1 ⁇ -cyclohexanedicarboxylate may be used.
  • cyclohexanedicarboxylic acid is intended to include cyclohexanedicarboxylic acid itself and residues thereof as well as any derivative or isomer of cyclohexanedicarboxylic acid, including its associated esters, half-esters, salts, half-salts and/or mixtures thereof or equivalents thereof. Any of 1 ,1-, 1 ,2-, 1 ,3-, 1 ,4- isomers of cyclohexanedicarboxylic acids or esters thereof or mixtures thereof may be present in the aliphatic acid component of this invention. Cis and trans isomers do not exist for 1,1 -cyclohexanedicarboxylic acid.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 70 to 99 mole % in the trans form and 1 to 30 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 70 to 98 mole % in the trans form and 2 to 30 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 70 to 90 mole % in the trans form and 10 to 30 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 80 to 98 mole % in the trans form and 2 to 20 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 90 to 98 mole % in the trans form and 2 to 10 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 90 to 98 mole % in the trans form and 2 to 10 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 92 to 98 mole % in the trans form and 2 to 8 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 95 to 98 mole % in the trans form and 2 to 5 mole % in the cis form.
  • the cyclohexanedicarboxylic acid can be present in the polyesters of the invention in an amount of 78 to 87 mole % in the trans form and 13 to 22 mole % in the cis form.
  • the total mole percentages of cis- and trans- cyclohexanedicarboxylic acid residues for each isomer of cyclohexanedicarboxylic acid residues in the polyester is equal to 100 mole %.
  • the polyesters used in the present invention typically can be prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues.
  • the polyesters of the present invention therefore, can contain substantially equal molar proportions of acid residues (100 mole%) and diol (and/or multifunctional hydroxyl compound) residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%.
  • the mole percentages provided in the present disclosure may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
  • a polyester containing 10 mole% cyclohexanedicarboxylic acid means the polyester contains 10 mole% cyclohexanedicarboxylic acid residues out of a total of 100 mole% acid residues.
  • a polyester containing 30 mole% 2,2,4,4- tetramethyl-1,3-cyclobutanediol means the polyester contains 30 mole% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues out of a total of 100 mole% diol residues.
  • the T 9 of the polyesters useful in the polyester compositions of the invention can be at least one of the following ranges: 60 to 155°C; 60 to 150 0 C; 60 to 145°C; 60 to 140 0 C; 60 to 135°C; 60 to 130 0 C; 60 to 125°C; 60 to 120 0 C; 60 to 115°C; 60 to 110 0 C; 60 to 105 0 C; 60 to 100 0 C; 60 to 95 0 C; 60 to 90°C; 60 to 85°C; 60 to 80 0 C; 60 to 75°C; 60 to 70°C; 60 to 65°C; 65 to 155 0 C; 65 to 150 0 C; 65 to 145°C; 65 to 140°C; 65 to 135°C; 65 to 130°C; 65 to 125°C; 65 to 120 0 C; 65 to 115°C; 65 to 110 0 C; 65 to 105 0 C; 65 to 100°C; 65 to 95°C;
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 1 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 99 mole % cyclohexanedimethanol; 1 to 95 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 5 to 99 mole % cyclohexanedimethanol; 1 to 90 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 10 to 99 mole % cyclohexanedimethanol; 1 to 85 mole % 2,2,4,4- tetramethyM ,3-cyclobutanediol and 15 to 99 mole % cyclohexanedimethanol; 1 to 80 mole % 2,2,2,4,4-tetramethy
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 5 to 99 mole % 2,2,4,4-tetramethyM, 3- cyclobutanediol and 1 to 95 mole % cyclohexanedimethanol; 5 to 95 mole % 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol and 5 to 95 mole % cyclohexanedimethanol; 5 to 90 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 10 to 95 mole % cyclohexanedimethanol; 5 to 85 mole % 2,2,4,4-tetramethyl- 1,3-cyclobutanediol and 15 to 95 mole % cyclohexanedimethanol; 5 to 80 mole % 2,2,4,4-tetramethyl-1
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 5 to less than 50 mole % 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol and greater than 50 to 95 mole % cyclohexanedimethanol; 5 to 45 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 55 to 95 mole % cyclohexanedimethanol; 5 to 40 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 60 to 95 mole % cyclohexanedimethanol; 5 to 35 mole % 2,2,4,4- tetramethyl-1,3-cyclobutanediol and 65 to 95 mole % cyclohexanedimethanol; 5 to less than 35 mole % 2,2,4,4- tetramethyl-1,3
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 10 to 99 mole % 2,2,4,4-tetramethyl-i ,3- cyclobutanediol and 1 to 90 mole % cyclohexanedimethanol; 10 to 95 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 5 to 90 mole % cyclohexanedimethanol; 10 to 90 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 10 to 90 mole % cyclohexanedimethanol; 10 to 85 mole % 2,2,4,4- tetramethyM ,3-cyclobutanediol and 15 to 90 mole % cyclohexanedimethanol; 10 to 80 mole % 2,2,4,4-tetramethyl-i ,
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: greater than 10 to 99 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 1 to less than 90 mole % cyclohexanedimethanol; greater than 10 to 95 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 5 to less than 90 mole % cyclohexanedimethanol; greater than 10 to 90 mole % 2, 2,4,4-tetramethyM ,3-cyclobutanediol and 10 to less than 90 mole % cyclohexanedimethanol; greater than 10 to 85 mole % 2,2,4,4- tetramethyM ,3-cyclobutanediol and 15 to less than 90 mole % cyclohexanedimethanol;
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 11 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 89 mole % cyclohexanedimethanol; 11 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 89 mole % cyclohexanedimethanol; 11 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 89 mole % cyclohexanedimethanol; 11 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 15 to 89 mole % cyclohexanedimethanol; 11 to 80 mole % 2,2,4,4-tetramethyM ,3-
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 15 to 99 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol and 1 to 85 mole % cyclohexanedimethanol; 15 to 95 mole % 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol and 5 to 85 mole % cyclohexanedimethanol; 15 to 90 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 10 to 85 mole % cyclohexanedimethanol; 15 to 85 mole % 2,2,4,4- tetramethyM ,3-cyclobutanediol and 15 to 85 mole % cyclohexanedimethanol; 15 to 80 mole % 2,2,4,4-
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 20 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 80 mole % cyclohexanedimethanol; 20 to 95 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 5 to 80 mole % cyclohexanedimethanol; 20 to 90 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 10 to 80 mole % cyclohexanedimethanol; 20 to 85 mole % 2,2,4,4- tetramethyM ,3-cyclobutanediol and 15 to 80 mole % cyclohexanedimethanol; 20 to 80 mole % 2,2,4,4
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 25 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 75 mole % cyclohexanedimethanol; 25 to 95 mole % 2,2,4,4-tetramethyM, 3-cyclobutanediol and 5 to 75 mole % cyclohexanedimethanol; 25 to 90 mole % 2,2,4,4-tetramethyM, 3-cyclobutanediol and 10 to 75 mole % cyclohexanedimethanol; 25 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 15 to 75 mole % cyclohexanedimethanol; 25 to 80 mole % 2,2,4.4-tetramethyl
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 30 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 70 mole % cyclohexanedimethanol; 30 to 95 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 5 to 70 mole % cyclohexanedimethanol; 30 to 90 mole % 2,2,4 ,4-tetramethyM,3-cyclobutanediol and 10 to 70 mole % cyclohexanedimethanol; 30 to 85 mole % 2,2,4,4- tetramethyM ,3-cyclobutanediol and 15 to 70 mole % cyclohexanedimethanol; 30 to 80 mole % 2,
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 35 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 65 mole % cyclohexanedimethanol; 35 to 95 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 5 to 65 mole % cyclohexanedimethanol; 35 to 90 mole % 2,2,4,4-tetramethyM, 3-cyclobutanediol and 10 to 65 mole % cyclohexanedimethanol; 35 to 85 mole % 2,2,4,4- tetramethyM ,3-cyclobutanediol and 15 to 65 mole % cyclohexanedimethanol; 35 to 80 mole % 2,2,4,4
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 40 to 99 mole % 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol and 1 to 60 mole % cyclohexanedimethanol; 40 to 95 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 5 to 60 mole % cyclohexanedimethanol; 40 to 90 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 10 to 60 mole % cyclohexanedimethanol; 40 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 15 to 60 mole % cyclohexanedimethanol; 40 to 80 mole % 2,2,4,4-tetra
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 45 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 55 mole % cyclohexanedimethanol; 45 to 95 mole % 2,2,4,4-tetramethyM , 3-cyclobutanediol and 5 to 55 mole % cyclohexanedimethanol; 45 to 90 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 10 to 55 mole % cyclohexanedimethanol; 45 to 85 mole % 2,2,4,4- tetramethyM, 3-cyclobutanediol and 15 to 55 mole % cyclohexanedimethanol; 45 to 80 mole % 2,2,4,4-
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: greater than 50 to 99 mole % 2,2,4,4- tetramethyl-1,3-cyclobutanediol and 1 to less than 50 mole % cyclohexanedimethanol; greater than 50 to 95 mole % 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol and 5 to less than 50 mole % cyclohexanedimethanol; greater than 50 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to less than 50 mole % cyclohexanedimethanol; greater than 50 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 15 to less than 50 mole % cyclohexanedimethanol; greater than
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: greater than 51 to 99 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 1 to less than 49 mole % cyclohexanedimethanol; greater than 51 to 95 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 5 to less than 49 mole % cyclohexanedimethanol; greater than 51 to 90 mole % 2,2,4,4-tetramethyl-i ,3-cyclobutanediol and 10 to less than 49 mole % cyclohexanedimethanol; greater than 51 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 15 to less than 49 mole % cyclohexaned
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 55 to 99 mole % 2,2,4,4-tetramethyM,3- cyclobutanediol and 1 to 45 mole % cyclohexanedimethanol; 55 to 95 mole % 2,2,4,4-tetramethyl-i ,3-cyclobutanediol and 5 to 45 mole % cyclohexanedimethanol; 55 to 90 mole % 2,2,4 ,4-tetramethyl-1,3-cyclobutanediol and 10 to 45 mole % cyclohexanedimethanol; 55 to 85 mole % 2,2,4,4- tetramethyl-1,3-cyclobutanediol and 15 to 45 mole % cyclohexanedimethanol; 55 to 80 mole % 2,2,4,4-tetramethyM,3- cyclo
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 60 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 40 mole % cyclohexanedimethanol; 60 to 95 mole % 2,2,4,4-tetramethyM, 3-cyclobutanediol and 5 to 40 mole % cyclohexanedimethanol; 60 to 90 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 10 to 40 mole % cyclohexanedimethanol; 60 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 15 to 40 mole % cyclohexanedimethanol; 60 to 80 mole % 2,2,4 ,4
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 65 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 35 mole % cyclohexanedimethanol; 65 to 95 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 5 to 35 mole % cyclohexanedimethanol; 65 to 90 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 10 to 35 mole % cyclohexanedimethanol; 65 to 85 mole % 2,2,4,4- tetramethyl-1,3-cyclobutanediol and 15 to 35 mole % cyclohexanedimethanol; 65 to 80 mole % 2,2,4 ,
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 70 to 99 mole % 2,2,4,4-tetramethyM ,3- cyclobutanediol and 1 to 30 mole % cyclohexanedimethanol; 70 to 95 mole % 2,2,4,4-tetramethyM ,3-cyclobutanediol and 5 to 30 mole % cyclohexanedimethanol; 70 to 90 mole % 2,2,4 ,4-tetramethyM ,3-cyclobutanediol and 10 to 30 mole % cyclohexanedimethanol; 70 to 85 mole % 2,2,4,4- tetramethyl-1,3-cyclobutanediol and 15 to 30 mole % cyclohexanedimethanol; 70 to 80 mole % 2,2,4,4-tetramethyl-1,3-
  • the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 75 to 99 mole % 2,2,4,4-tetramethyl-1,3- cyclobutanediol and 1 to 25 mole % cyclohexanedimethanol; 75 to 95 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 5 to 25 mole % cyclohexanedimethanol; 75 to 90 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 10 to 25 mole % cyclohexanedimethanol; and 75 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 15 to 25 mole % cyclohexanedimethanol.
  • the polyesters useful in the invention may exhibit at least one of the following inherent viscositiy ranges as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.25 g/50 ml at 25°C: 0.35 to 1.2 dl_/g; 0.35 to 1.1 dl_/g; 0.35 to 1 dL/g; 0.35 to less than 1 dl_/g; 0.35 to 0.98 dL/g; 0.35 to 0.95 dL/g; 0.35 to 0.90 dl_/g; 0.35 to 0.85 dL/g; 0.35 to 0.80 dL/g; 0.35 to 0.75 dL/g; 0.35 to less than 0.75 dL/g; 0.35 to 0.72 dL/g; 0.35 to 0.70 dL/g; 0.35 to less than 0.70 dL/g; 0.35 to 0.68 dL/g; 0.35
  • compositions useful in the invention can possess at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that compositions useful in the invention can possess at least one of the T 9 ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that compositions useful in the invention can possess at least one of the inherent viscosity ranges described herein, at least one of the T 9 ranges described herein, and at least one of the monomer ranges for the compositions described herein unless otherwise stated.
  • the dicarboxylic acid component of the polyesters useful in the invention can comprise up to 10 mole %, up to 5 mole%, or up to 1 mole % of one or more modifying aromatic dicarboxylic acids.
  • Yet another embodiment contains 0 mole % modifying aromatic dicarboxylic acids.
  • the amount of one or more modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole %.
  • modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and which can be linear, para- oriented, or symmetrical.
  • Examples of modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7- naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and esters thereof.
  • the modifying aromatic dicarboxylic acid is isophthalic acid.
  • the modifying aromatic dicarboxylic acid is terephthalic acid.
  • terephthalic acid is intended to include terephthalic acid itself and residues thereof as well as any derivative of terephthalic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and/or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester.
  • terephthalic acid or an ester thereof such as, for example, dimethyl terephthalate or a mixture of terephthalic acid residues and an ester thereof can make up a portion or all of the aromatic dicarboxylic acid component, if any, used to form the polyesters useful in the invention.
  • terephthalic acid residues can make up a portion or all of the aromatic dicarboxylic acid component, if any, used to form the polyesters useful in the invention.
  • the terms "terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein.
  • dimethyl terephthalate is part or all of the aromatic dicarboxylic acid component, if any, used to make the polyesters useful in the present invention.
  • the carboxylic acid component of the polyesters useful in the invention can be further modified with up to 10 mole %, such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids. Certain embodiments can also comprise 0.01 to 10 mole %, such as 0.1 to 10 mole %, 1 or 10 mole %, 5 to 10 mole % of one or more modifying aliphatic dicarboxylic acids.
  • Yet another embodiment contains 0 mole % modifying aliphatic dicarboxylic acids.
  • the total mole % of the dicarboxylic acid component is equal to 100 mole %.
  • adipic acid and/or glutaric acid are provided in the modifying aliphatic dicarboxylic acid component of the invention.
  • esters of dicarboxylic acids or their corresponding esters and/or salts may be used instead of the dicarboxylic acids.
  • Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters.
  • the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.
  • the molar ratio of cis/trans 2,2,4,4- tetramethyl-1,3-cyclobutanediol can vary from the pure form of each and mixtures thereof.
  • the molar percentages for cis and/or trans 2,2,4,4,-tetramethyl-1,3-cyclobutanediol are greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30 mole % trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30 mole % cis; or 50 to 70 mole % cis and 50 to 30 mole % trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % cis
  • the molar ratio of cis/trans 2,2,4 ,4-tetramethyl-1,3-cyclobutanediol can vary within the range of 50/50 to 0/100, for example, between 40/60 to 20/80. In an additional embodiment, the molar ratio of trans/cis 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol can vary within the range of 50/50 to 0/100, for example, between 40/60 to 20/80.
  • the cyclohexanedimethanol may be cis, trans, or a mixture thereof, for example, a cis/trans ratio of 60:40 to 40:60 or a cis/trans ratio of 70:30 to 30:70.
  • the trans-cyclohexanedimethanol can be present in an amount of 60 to 80 mole % and the cis-cyclohexanedimethanol can be present in an amount of 20 to 40 mole % wherein the total percentages of cis- cyclohexanedimethanol and trans-cyclohexanedimethanol is equal to 100 mole %.
  • the trans-cyclohexanedimethanol can be present in an amount of 60 mole % and the cis-cyclohexanedimethanol can be present in an amount of 40 mole %. In particular embodiments, the trans- cyclohexanedimethanol can be present in an amount of 70 mole % and the cis- cyclohexanedimethanol can be present in an amount of 30 mole %. Any of 1 ,1-, 1 ,2-, 1 ,3-, 1 ,4- isomers of cyclohexanedimethanol or mixtures thereof may be present in the glycol component of this invention. Cis and trans isomers do not exist for 1,1-cyclohexanedimethanol.
  • the polyesters useful in the invention comprise 1 ,4-cyclohexanedimethanol. In another embodiment, the polyesters useful in the invention comprise 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol.
  • the molar ratio of cis/trans 1,4-cyclohexandimethanol can vary within the range of 50/50 to 0/100, for example, between 40/60 to 20/80.
  • the glycol component of the polyester portion of the polyester compositions useful in the invention can contain 98 mole % or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1,3- cyclobutanediol or cyclohexanedimethanol; in one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain 25 mole % or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol or cyclohexanedimethanol or ethylene glycol; in one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain 20 mole % or less of one or more modifying glycols which are not 2,2,4,4-tetramethyM ,3- cyclobutanediol or cyclohexanedimethanol or ethylene glycol; in one embodiment, the polyesters
  • the polyesters useful in the invention can contain 10 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 5 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 3 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 2 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 0 mole % modifying glycols.
  • Modifying glycols useful in the polyesters useful in the invention refer to diols other than 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, and cyclohexanedimethanol and can contain 2 to 16 carbon atoms.
  • suitable modifying glycols include, but are not limited to, ethylene glycol, diethyiene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1,4- butanediol, 1,5-pentanediol, 1 ,6-hexanediol, polytetramethylene glycol, polyethylene glycol, and/or mixtures thereof.
  • the modifying glycols include, but are not limited to, at least one of 1 ,3-propanediol and 1,4-butanediol.
  • at least one modifying glycol is diethyiene glycol.
  • the diethyiene glycol is not added as a separate monomer but is formed during polymerization.
  • the polyesters useful in the polyester compositions of the invention can comprise from 0 to 10 mole percent, for example, from 0.01 to 5 mole percent, from 0.01 to 1 mole percent, from 0.05 to 5 mole percent, from 0.05 to 1 mole percent, or from 0.1 to 0.7 mole percent, or from 0.1 to 0.5 mole percent, based on the total mole percentages of either the diol or diacid residues; respectively, of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof.
  • the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polyester.
  • the polyester(s) useful in the invention can thus be linear or branched.
  • branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
  • multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
  • the branching monomer residues can comprise 0.1 to 0.7 mole percent of one or more residues chosen from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1 ,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid.
  • the branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Patent Nos. 5,654,347 and 5,696,176, whose disclosure regarding branching monomers is incorporated herein by reference.
  • the polyesters of the invention can comprise at least one chain extender.
  • Suitable chain extenders include, but are not limited to, multifunctional (including, but not limited to, bifunctional) isocyanates, multifunctional epoxides, including for example .epoxylated novolacs, and phenoxy resins.
  • chain extenders may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, chain extenders can be incorporated by compounding or by addition during conversion processes such as injection molding or extrusion.
  • the amount of chain extender used can vary depending on the specific monomer composition used and the physical properties desired but is generally about 0.1 percent by weight to about 10 percent by weight, such as about 0.1 to about 5 percent by weight, based on the total weight of the polyester.
  • T 9 glass transition temperature of the polyesters useful in the invention was determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C/min.
  • thermoformable sheet is an example of an article of manufacture provided by this invention.
  • the polyesters of the invention can be amorphous or semicrystalline.
  • certain polyesters useful in the invention can have relatively low crystallinity.
  • Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
  • certain polyesters useful in this invention can be visually clear.
  • the term "visually clear” is defined herein as an appreciable absence of cloudiness, haziness, and/or muddiness, when inspected visually.
  • polycarbonate including but not limited to, bisphenol A polycarbonates
  • the blends can be visually clear.
  • the polyesters useful in the invention and/or the polyester compositions of the invention can have color values L*, a* and b* which can be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va.
  • the color determinations are averages of values measured on either pellets of the polyesters or plaques or other items injection molded or extruded from them. They are determined by the L*a*b* color system of the CIE (International Commission on Illumination) (translated), wherein L* represents the lightness coordinate, a* represents the red/green coordinate, and b* represents the yellow/blue coordinate.
  • CIE International Commission on Illumination
  • the b* values for the polyesters useful in the invention can be from - 12 to less than 12 and the L* values can be from 50 to 90.
  • the b* values for the polyesters useful in the invention can be present in one of the following ranges: from -10 to 10; -10 to less than 10; -10 to 9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; from -5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9;
  • the L* value for the polyesters useful in the invention can be present in one of the following ranges: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 79 to 90.
  • Notched Izod impact strength is a common method of measuring toughness. Notched Izod impact strength is measured herein at 23 0 C with a 10-mil notch in a 3.2mm (1 /8-inch) thick bar determined according to ASTM D256.
  • certain polyesters useful in the invention can exhibit a notched Izod impact strength of at least 250 J/m (5 ft-lb/in) at 23°C with a 10-mil notch in a 3.2mm (1/8-inch) thick bar determined according to ASTM D256.
  • certain polyesters useful in the invention can exhibit a notched Izod impact strength of at least 500 J/m (10 ft-lb/in) at 23°C with a 10-mil notch in a 3.2mm (1/8-inch) thick bar determined according to ASTM D256.
  • certain polyesters useful in the invention can exhibit any density, for example, a density of from 1.05 to 1.2 g/ml at 23°C as determined using a gradient density column at 23°C, and/or for example, a density of from 1.09 to 1.15 g/ml at 23°C as determined using a gradient density column at 23°C
  • Certain polyester(s) and/or polyester compositions of the invention have improved environmental stress cracking resistance. Generally, environmental stress cracking resistance testing according to the present invention is described in R. L. Bergen, Jr., SPE J. 667-670 (1962) entitled "Stress cracking of rigid thermoplastics". Certain polyester(s) and/or polyester compositions of the invention can have a lipid critical strain of at least 0.6 % or at least 0.7% or at least 0.8 % or at least 0.9 % or of greater than 0.9 %. Certain polyester(s) and/or polyester compositions of the invention can have an isopropanol critical strain of at least 0.9 % or at least 1.0 % or of greater than 1.0 %.
  • Certain polyester(s) and/or polyester compositions of the invention can have a lipid critical strain of at least 0.9 % and an isopropanol critical strain of greater than 1.0 %.
  • Lipid critical strain and/or isopropanol critical strain are measured as demonstrated by the Examples of the present invention and can be measured as described in in R. L. Bergen, Jr., SPE J. 667-670 (1962) entitled "Stress cracking of rigid thermoplastics”.
  • the phosphorus compound(s) useful in the invention can be an organic compound such as, for example, a phosphorus acid ester containing halogenated or non-halogenated organic substituents.
  • the phosphorus compound(s) useful in the invention can comprise a wide range of phosphorus compounds well-known in the art such as, for example, phosphines, phosphites, phosphinites, phosphonites, phosphinates, phosphonates, phosphine oxides, and phosphates.
  • Examples of phosphorus compounds useful in the invention can include tributyl phosphate, triethyl phosphate, tri-butoxyethyl phosphate, t- butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyl dimethyl phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, t-butylphenyl diphenylphosphate, resorcinol bis(diphenyl phosphate), tribenzyl phosphate, phenyl ethyl phosphate, trimethyl thionophosphate, phenyl ethyl thionophosphate, dimethyl methylphosphonate, diethyl methylphosphonate, diethyl pentylphosphonate, dilauryl
  • phosphorus compounds useful in the invention can be any of the previously described phosphorus-based acids wherein one or more of the hydrogen atoms of the acid compound (bonded to either oxygen or phosphorus atoms) are replaced with alkyl, branched alkyl, substituted alkyl, alkyl ethers, substituted alkyl ethers, alkyl-aryl, alkyl-substituted aryl, aryl, substituted aryl, and mixtures thereof.
  • phosphorus compounds useful in the invention include but are not limited to, the above described compounds wherein at least one of the hydrogen atoms bonded to an oxygen atom of the compound is replaced with a metallic ion or an ammonium ion.
  • the esters can contain alkyl, branched alkyl, substituted alkyl, alkyl ethers, aryl, and/or substituted aryl groups.
  • the esters can also have at least one alkyl group and at least one aryl group.
  • the number of ester groups present in the particular phosphorus compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present on the phosphorus compound used.
  • an alkyl phosphate ester can include one or more of the mono-, di-, and tri alkyl phosphate esters; an aryl phosphate ester includes one or more of the mono-, di-, and tri aryl phosphate esters; and an alkyl phosphate ester and/or an aryl phosphate ester also include, but are not limited to, mixed alkyi aryl phosphate esters having at least one alkyl and one aryl group.
  • the phosphorus compounds useful in the invention include but are not limited to alkyl, aryl or mixed alkyl aryl esters or partial esters of phosphoric acid, phosphorus acid, phosphinic acid, phosphonic acid, or phosphonous acid.
  • the alkyl or aryl groups can contain one or more substituents.
  • the phosphorus compounds useful in the invention comprise at least one phosphorus compound chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, diphosphites, salts of phosphoric acid, phosphine oxides, and mixed aryl alkyl phosphites, reaction products thereof, and mixtures thereof.
  • the phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.
  • the phosphorus compounds useful in the invention can include at least one phosphate ester.
  • the phosphorus compounds useful in the invention comprise at least one phosphorus compound chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof.
  • the phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.
  • the phosphorus compounds useful in the invention can include at least one phosphate ester.
  • the phosphate esters useful in the invention can include but are not limited to alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, and/or mixtures thereof.
  • the phosphate esters useful in the invention are those where the groups on the phosphate ester include are alkyl, alkoxy- alky ⁇ phenyl, or substituted phenyl groups. These phosphate esters are generally referred to herein as alkyl and/or aryl phosphate esters. Certain preferred embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates, and mixtures of such phosphates, wherein the alkyl groups are preferably those containing from 2 to 12 carbon atoms, and the aryl groups are preferably phenyl.
  • Representative alkyl and branched alkyl groups are preferably those containing from 1-12 carbon atoms, including, but not limited to, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl and dodecyl.
  • Substituted alkyl groups include, but are not limited to, those containing at least one of carboxylic acid groups and esters thereof, hydroxy! groups, amino groups, keto groups, and the like.
  • alkyl-aryl and substituted alkyl-aryl groups are those wherein the alkyl portion contains from 1-12 carbon atoms, and the aryl group is phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxyl, and the like are substituted for hydrogen at any carbon position on the phenyl ring.
  • Preferred aryl groups include phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxyl and the like are substituted for hydrogen at any position on the phenyl ring.
  • the phosphate esters useful in the invention include but are not limited to dibutylphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, and/or mixtures thereof, including particularly mixtures of tributyl phosphate and tricresyl phosphate, and mixtures of isocetyl diphe ⁇ yl phosphate and 2-ethylhexyl diphenyl phosphate.
  • At least one phosphorus compound useful in the invention comprises at least one aryl phosphate ester.
  • At least one phosphorus compound useful in the invention comprises at least one unsubstituted aryl phosphate ester.
  • At least one phosphorus compound useful in the invention comprises at least one aryl phosphate ester which is not substituted with benzyl groups.
  • any of the phosphorus compounds useful in the invention may comprise at least one alkyl phosphate ester.
  • the phosphate esters useful in the invention as thermal stabilizers and/or color stabilizers include but are not limited to, at least one of the following: trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.
  • the phosphate esters useful in the invention as thermal stabilizers and/or color stabilizers include but are not limited to, at least one of the following: triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.
  • the phosphate esters useful as thermal stabilizers and/or color stabilizers in the invention can include but are not limited to, at least one of the following: triaryl phosphates and mixed alkyl aryl phosphates.
  • At least one phosphorus compound useful in the invention can comprise, but is not limited to, triaryl phosphates, such as, for example, triphenyl phosphate.
  • at least one one thermal stabilizer comprises, but is not limited to Merpol A.
  • at least one thermal stabilizer useful in the invention comprises, but is not limited to, at least one of triphenyl phosphate and Merpol A.
  • Merpol A is a phosphate ester commercially available from Stepan Chemical Co and/or E.I. duPont de Nemours
  • any of the phosphorus compounds useful in the invention may comprise at least one triaryl phosphate ester which is not substituted with benzyl groups.
  • the polyester compositions and/or processes of the invention may comprise 2-ethylhexyl diphenyl phosphate.
  • any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one mixed alkyl aryl phosphite, such as, for example, bis(2,4- dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).
  • any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one one phosphine oxide.
  • any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one salt of phosphoric acid such as, for example, KH2PO4 and Zn3(PO 4 ) 2 .
  • phosphorus is added to the polyesters and/or polyester compositions and/or process of making the polyesters of the invention, it is added in the form of a phosphorus compound, for example, at least one phosphate ester(s).
  • the amount of phosphorus compound(s), (for example, at least one phosphate ester), is added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of phosphorus atoms present in the final polyester, for example, by weight measured in ppm.
  • Amounts.of phosphorus compound(s) added during polymerization and/or post manufacturing can include but are not limited to: 1 to 5000 ppm; 1 to 1000 ppm, 1 to 900 ppm, 1 to 800 ppm, 1 to 700 ppm. 1 to 600 ppm, 1 to 500 ppm, 1 to 400 ppm, 1 to 350 ppm, 1 to 300 ppm, 1 to 250 ppm, 1 to 200 ppm, 1 to 150 ppm, 1 to 100 ppm;10 to 5000 ppm; 10 to 1000 ppm, 10 to 900 ppm, 10 to 800 ppm, 10 to 700 ppm.
  • suitable catalysts for use in the processes of the invention to make the polyesters useful in the invention can include at least one titanium compound.
  • the polyester compositions of the invention may also comprise at least one of the titanium compounds useful in the processes of the invention.
  • Catalysts other than tin and titanium useful in making the polyesters useful in the invention may include, but are not limited to, those based on gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and an aluminum compound with lithium hydroxide or sodium hydroxide.
  • the catalyst can be a combination of at least one tin compound and at least one titanium compound.
  • Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to
  • the process can be carried out in either a batch or continuous process. In one embodiment, the process is carried out in a continuous process.
  • the polyesters of the invention can be prepared using at least one tin compound in addition to the titanium compound as catalyst(s).
  • Tin catalysts and titanium catalysts may be used singly or in combination.
  • M is an alkali metal, e.g. lithium, sodium, or potassium
  • M' is an alkaline earth metal such as Mg, Ca or Sr
  • each R represents an alkyl radical containing from 1 to 8 carbon atoms
  • each R' radical represents a substituent selected from those consisting of alkyl radicals containing from 1 to 8 carbon atoms (i. e. R radicals) and aryl radicals of the benzene series containing from 6 to 9 carbon atoms (e.g. phenyl, tolyl, benzyl, phenylethyl, etc., radicals)
  • Ac represents an acyl radical derived from an organic acid containing from 2 to 18 carbon atoms (e.g. acetyl, butyryl, lauroyl, benzoyl, stearoyl, etc. ).
  • novel bimetallic alkoxide catalysts can be made as described by Meerwein, Ann. 476, 113 (1929). As shown by Meerwein, these catalysts are not merely mixtures of the two metallic alkoxides. They are definite compounds having a salt-like structure. These are the compounds depicted above by the Formulas A through H. Those not specifically described by Meerwein can be prepared by procedures analogous to the working examples and methods set forth by Meerwein.
  • the other tin compounds can also be made by various methods such as those described in United States Patent 5,239,020, in addition to the following literature:
  • For the preparation of diaryl tin dihalides see Ber. 62, 996 (1929); J. Am. Chem. Soc. 49, 1369 (1927).
  • For the preparation of dialkyl tin dihalides see J. Am. Chem. Soc. 47, 2568 (1925) ; CA. 41, 90 (1947).
  • For the preparation of diaryl tin oxides see J. Am. Chem. Soc. 48, 1054 (1926).
  • the tin alkoxides (Formulas I and J) and the bimetallic alkoxides (Formulas A through H) contain R substituents which can represent both straight chain and branched chain alkyl radicals, e.g. diethoxide, tetramethoxide, tetrabutoxide, tetra-tert-butoxide, tetrahexoxide, etc.
  • the alkyl derivatives (Formulas K and L) contain one or more alkyl radicals attached to a tin atom through a direct C-Sn linkage, e.g. dibutyl tin, dihexyl tin, tetra-butyl tin, tetraethyl tin, tetramethyl tin, dioctyl tin, etc.
  • Two of the tetraalkyl radicals can be replaced with an oxygen atom to form compounds having Formula M, e.g. dimethyl tin oxide, diethyl tin oxide, dibutyl tin oxide, diheptyl tin oxide, etc.
  • the tin catalyst comprises dimethyl tin oxide.
  • Complexes can be formed by reacting dialkyl tin oxides with alkali metal alkoxides in an alcohol solution to form compounds having Formula N, which compounds are especially useful catalysts, e.g. react dibutyl tin oxide with sodium ethoxide, etc. This formula is intended to represent the reaction products described. Tin compounds containing alkyl and alkoxy radicals are also useful catalysts (see Formula O), e.g. diethyl tin diethoxide, dibutyl tin dibutoxide, dihexyl tin dimethoxide, etc.
  • Salts derived from dialkyl tin oxides reacted with carboxylic acids or hydrochloric acid are also of particular value as catalysts; see Formulas P and Q.
  • these catalytic condensing agents include dibutyl tin diacetate, diethyl tin dibutyrate, dibutyl tin dilauroate, dimethyl tin dibenzoate, dibutyl tin dichloride, diethyl tin dichloride, dioctyl tin dichloride, dihexyl tin distearate, etc.
  • the tin compounds having Formulas K, L and M can be prepared wherein one or more of the R 1 radicals represents an aryl radical of the benzene series, e.g. phenyl, tolyl, benzyl, etc.
  • R 1 radicals represents an aryl radical of the benzene series, e.g. phenyl, tolyl, benzyl, etc.
  • examples include diphenyl tin, tetraphenyl tin, diphenyl dibutyl tin, ditolyl diethyl tin, diphenyl tin oxide, dibenzyl tin, tetrabenzyl tin, di([B-phenylethyl) tin oxide, dibenzyl tin oxide, etc.
  • catalysts useful in the present invention include, but are not limited to, one of more of the following: butyltin tris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide, and dimethyl tin oxide.
  • catalysts useful in the present invention include, but are not limited to, one or more of the following: butyltin tris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide, and dimethyl tin oxide.
  • Processes for preparing polyesters using tin-based catalysts are well known and described in the aforementioned U.S. Pat. No.
  • the polyester portion of the polyester compositions useful in the invention can be made by processes known from the literature such as, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more glycols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Patent No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
  • the polyester in general may be prepared by condensing the dicarboxylic acid or dicarboxylic acid ester with the glycol in the presence of the tin catalysts and/or titanium catalysts described herein at elevated temperatures increased gradually during the course of the condensation up to a temperature of about 225°-310° C, in an inert atmosphere, and conducting the condensation at low pressure during the latter part of the condensation, as described in further detail in U.S. Pat. No. 2, 720, 507 incorporated herein by reference.
  • this invention relates to a process for preparing copolyesters of the invention.
  • the process relates to preparing copolyesters comprising cyclohexanedicarboxylic acid, 2,2,4,4- tetramethyl-1,3-cyclobutanediol, and cyclohexanedimethanol.
  • This process comprises the steps of:
  • Step (B) polycondensing the product of Step (A) by heating it at a temperature of 230 to 320 0 C for 1 to 12 hours;
  • Reaction times for the esterification Step (A) are dependent upon the selected temperatures, pressures, and feed mole ratios of glycol to dicarboxylic acid.
  • step (A) can be carried out until 50% by weight or more of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol has been reacted.
  • Step (A) may be carried out under pressure, ranging from 0 psig to 100 psig.
  • reaction product as used in connection with any of the catalysts useful in the invention refers to any product of a polycondensation or esterification reaction with the catalyst and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
  • Step (B) and Step (C) can be conducted at the same time. These steps can be carried out by methods known in the art such as by placing the reaction mixture under a pressure ranging, from 0.002 psig to below atmospheric pressure, or by blowing hot nitrogen gas over the mixture.
  • the polyesters of the present invention are prepared by procedures known to persons skilled in the art.
  • the reaction of the diol and dicarboxylic acid may be carried out using conventional polyester polymerization conditions or by melt phase processes, but those with sufficient crystallinity may be made by melt phase followed by solid phase polycondensation techniques. Stirring or appropriate conditions are used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture.
  • the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps:
  • Step (II) heating the product of Step (I) at a temperature of 230 0 C to 320 0 C for 1 to 12 hours, under at least one pressure chosen from the range of the final pressure of Step (I) to 0.02 torr absolute, to form a final polyester; the total mole % of said glycol component is equal to 100 mole %; wherein the inherent viscosity of said polyester is from 0.35 to 1.2 dl_/g as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/100 ml at 25 0 C; and wherein said polyester has a Tg of from 60 to 155°C.
  • the invention comprises a process for making any of the polyesters useful in the invention comprising the following steps: (I) heating a mixture at at least one temperature chosen from 150 0 C to 250 0 C, under at least one pressure chosen from the range of 0 psig to 50 psig wherein said mixture comprises:
  • (B) a glycol component comprising: i) 1 to 99 mole % of 2, 2, 4, 4-tetra methyl- 1 , 3- cyclobutanediol residues; and ii) 1 to 99 mole % of cyclohexanedimethanol residues; wherein the total mole % of said dicarboxylic acid component is equal to 100 mole %; and wherein the molar ratio of glycol component/dicarboxylic acid component added in Step (I) is 0.9-1.5/1; wherein the mixture in Step (I) is heated in the presence of: (i) at least one catalyst comprising at least one tin compound, and, optionally, at least one catalyst chosen from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds and an aluminum compound with lithium hydroxide or sodium hydroxide; and (ii) optionally, at least one thermal stabilizer chosen from at least one phosphate ester as described herein, reaction products thereof, and
  • Step (II) heating the product of Step (I) at a temperature of 230 0 C to 32O 0 C for 1 to 12 hours, under at least one pressure chosen from the range of the final pressure of Step (I) to 0.02 torr absolute, to form a final polyester; the total mole % of said glycol component is equal to 100 mole %; wherein the inherent viscosity of said polyester is from 0.35 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/100 ml at 25 0 C; and wherein said polyester has a Tg of from 60 to 155°C.
  • the pressure and times used in Step (II) can be staged as follows: 1 to 60 minutes at 300 to 100 torr; 1 to 60 minutes at 99 to 20 torr; 1 to 60 minutes at 19 to 3 torr; up to 12 hours at 0.02 to 3 torr.
  • the pressures in Step (II) can be ramped down from 300 to 3 torr over 3 minutes to 180 minutes followed by up to 12 hours at 0.02 to 3 torr.
  • Reaction times for the esterification Step (I) of any of the processes of the invention are dependent upon the selected temperatures, pressures, and feed mole ratios of glycol to dicarboxylic acid.
  • the heating time of Step (II) may be from 1 to 6 hours or 1 to 5 hours.
  • the polyesters, polyester compositions and/or processes of the invention useful in the invention can comprise phosphorus atoms.
  • the polyesters, polyester compositions and/or processes of the invention useful in the invention can comprise tin atoms.
  • the polyesters and/or polyester compositions and/or processes useful in the invention can comprise titanium atoms and tin atoms.
  • any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one phosphorus compound.
  • any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one tin compound.
  • any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one titanium compound.
  • any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one titanium compound and at least one phosphorus compound.
  • any of the polyester(s), polyester compositions and/or processes of making the polyesters useful in the invention may comprise at least one tin compound and at least one titanium compound.
  • any of the polyester(s), polyester compositions and/or processes of making the polyesters useful in the invention may comprise at least one tin compound, at least one titanium compound, and at least one phosphorus compound.
  • the amount of tin atoms in the polyesters useful in the invention can be from 0 to 600 ppm tin atoms based on the weight of the final polyester.
  • the amount of tin atoms in the polyesters useful in the invention can be from 50 to 600 ppm tin atoms based on the weight of the final polyester.
  • the amount of tin atoms in the polyesters useful in the invention can be from 50 to 400 ppm tin atoms based on the weight of the final polyester.
  • the amount of titanium atoms in the polyesters useful in the invention can be from 0 to 100 ppm titanium atoms based on the weight of the final polyester.
  • the invention further relates to the polyester compositions made by the process(es) described above.
  • the invention further relates to a polymer blend.
  • the blend comprises: (a) from 5 to 95 weight % of at least one of the polyesters described above; and
  • Suitable examples of the polymeric components include, but are not limited to, nylon; polyesters different than those described herein; polyamides such as ZYTEL® from DuPont; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly(methylmethacrylate); acrylic copolymers; poly(ether-imides) such as ULTEM® (a poly(ether-imide) from General Electric); polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide)/polystyrene blends such as NORYL 1000® (a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resins from General Electric); polyphenylene sulfides; polyphenylene sulfide/sulfones; poly(ester-carbonates); polycarbonates such as
  • the blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.
  • polycarbonate is not present in the polyester composition. If polycarbonate is used in a blend in the polyester compositions of the invention, the blends can be visually clear.
  • polyester compositions useful in the invention also contemplate the exclusion of polycarbonate as well as the inclusion of polycarbonate.
  • Polycarbonates useful in the invention may be prepared according to known procedures, for example, by reacting the dihydroxyaromatic compound with a carbonate precursor such as phosgene, a haloformate or a carbonate ester, a molecular weight regulator, an acid acceptor and a catalyst.
  • a carbonate precursor such as phosgene, a haloformate or a carbonate ester
  • a molecular weight regulator such as phosgene, a haloformate or a carbonate ester
  • an acid acceptor such as sodium bicarbonate
  • Methods for preparing polycarbonates are known in the art and are described, for example, in U.S. Patent 4,452,933, where the disclosure regarding the preparation of polycarbonates is hereby incorporated by reference herein.
  • suitable carbonate precursors include, but are not limited to, carbonyl bromide, carbonyl chloride, and mixtures thereof; diphenyl carbonate; a di(halophenyl)carbonate, e.g., di(trichlorophenyl) carbonate, di(tribromophenyl) carbonate, and the like; di(alkylphenyl)carbonate, e.g., di(tolyl)carbonate; di(naphthyl)carbonate; di(chloronaphthyl)carbonate, and mixtures thereof; and bis-haloformates of dihydric phenols.
  • Suitable molecular weight regulators include, but are not limited to, phenol, cyclohexanol, methanol, alkylated phenols, such as octylphenol, para-tertiary-butyl-phenol, and the like. In one embodiment, the molecular weight regulator is phenol or an alkylated phenol.
  • the acid acceptor may be either an organic or an inorganic acid acceptor.
  • a suitable organic acid acceptor can be a tertiary amine and includes, but is not limited to, such materials as pyridine, triethylamine, dimethylaniline, tributylamine, and the like.
  • the inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
  • the catalysts used in making the polycarbonates useful in the invention that can be used include, but are not limited to, those that typically aid the polymerization of the monomer with phosgene.
  • Suitable catalysts include, but are not limited to, tertiary amines such as triethylamine, tripropylamine, N 1 N- dimethylaniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n- heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethyl ammonium chloride, tetra-methyl ammonium hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium chloride and quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.
  • quaternary ammonium compounds such as, for example, n-butyltriphenyl
  • the polycarbonates useful in the polyester blends of the invention also may be copolyestercarbonates such as those described in U.S. Patents 3,169,121 ; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465,820, and 4,981 ,898, where the disclosure regarding copolyestercarbonates from each of the U.S. Patents is incorporated by reference herein.
  • Copolyestercarbonates useful in this invention can be available commercially and/or may be prepared by known methods in the art.
  • polyester compositions and the polymer blends of the invention may also contain common additives such as colorants, toner(s), dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, and antioxidants, including but not limited to, UV stabilizers, thermal stabilizers other than the phosphorus compounds describe herein, and/or reaction products thereof, fillers, and impact modifiers.
  • the polyester compositions and the polymer blends can contain from 0.01 to 25 % by weight of one or more of these additives.
  • typical commercially available impact modifiers well known in the art and useful in this invention include, but are not limited to, ethylene/propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and/or glycidyl methacrylate, styrene-based block copolymeric impact modifiers, and various acrylic core/shell type impact modifiers. Residues of such additives are also contemplated as part of the polyester composition.
  • certain agents which colorize the polymer can be added to the melt.
  • a bluing toner is added to the melt in order to reduce the b* of the resulting polyester polymer melt phase product.
  • Such bluing agents include blue inorganic and organic toner(s).
  • red toner(s) can also be used to adjust the a* color.
  • Organic toner(s) e.g., blue and red organic toner(s), such as those toner(s) described in U.S. Pat. Nos. 5,372,864 and 5,384,377, which are incorporated by reference in their entirety, can be used.
  • the organic toner(s) can be fed as a premix composition.
  • the premix composition may be a neat blend of the red and blue compounds or the composition may be pre-dissolved or slurried in one of the polyester's raw materials, e.g., ethylene glycol.
  • the total amount of toner components added depends, of course, on the amount of inherent yellow color in the base polyester and the efficacy of the toner. Generally, in one embodiment, a concentration of up to about 15 ppm of combined organic toner components and a minimum concentration of about 0.5 ppm can be used. The total amount of bluing additive typically ranges from 0.5 to
  • the toner(s) can be added to the esterification zone or to the polycondensation zone.
  • the toner(s) are added to the esterification zone or to the early stages of the polycondensation zone, such as to a prepolymerization reactor
  • the aliphatic polyester composition of the invention also can comprise at least one hindered amine light stabilizer, abbreviated herein as "HALS".
  • HALS hindered amine light stabilizer
  • Many of the HALS of the present invention are known compounds and some are commercially available.
  • the HALS can include their salts, N-oxides and N- hydroxides.
  • the HALS can be described as having an amino nitrogen contained in a carbon-nitrogen-carbon chain which forms part of a non-aromatic heterocyclic ring where each of the two carbon atoms of the chain is bonded to two lower alkyl groups which may be the same or different, each lower alkyl group containing from 1 to 22 carbon atoms, or to an alicyclic group containing from 3 to 8 carbon atoms, which sterically hinder the amine.
  • the HALS can comprise
  • 2,2,6,6-tetraalkylpiperidines their acid addition salts or complexes with metal compounds.
  • hindered amine light stabilizers which can be used in the instant invention are represented by formulas (1-4):
  • R3, R 4 , Rs and R 6 are Ci-C 2 2 alkyl
  • R? and Rs are independently selected from hydrogen, C1-C22 alkyl, and C1-C22 alkoxy;
  • Y 1 is -O-
  • Li is the divalent linking group -C(O)-L 2 -C(O)-;
  • L 2 is C1-C22 alkylene;
  • Rg and Rio are independently selected from hydrogen, C1-C22 alkyl, C3-C8 cycloalkyl, and substituted C 3 -Ce cycloalkyl, or R9 and Rio collectively may represent a divalent group forming a morpholine and/or a piperidine ring; Z is a positive integer of up to 20;
  • Rn is selected from hydrogen, C1-C22 alkyl, substituted CT-C22 alkyl, and radical A, wherein radical A has the following structure:
  • C 1 -C 22 alkyl denotes a saturated hydrocarbon radical which contains one to twenty-two carbons and which may be straight or branched-chain.
  • Such C 1 -C 22 alkyl groups can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, tertbutyl, neopentyl, 2-ethy I heptyl, 2-ethylhexyl, and the like.
  • substituted C 1 -C 22 alkyl refers to C 1 -C 2Z a'M radicals as described above which may be substituted with one or more substituents selected from hydroxy, halogen, cyano, aryl, heteroaryl, C 3 -C 8 -cycloalkyl, substituted C 3 -C 8 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkanoyloxy and the like.
  • C 3 -C 8 cycloalkyl is used to denote a cycloaliphatic hydrocarbon radical containing three to eight carbon atoms.
  • substituted C 3 -C 8 cycloalkyl is used to describe a C 3 -C 8 cycloalkyl radical as detailed above containing at least one group selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy, halogen, and the like.
  • aryl is used to denote an aromatic radical containing 6,10 or 14 carbon atoms in the conjugated aromatic ring structure and these radicals substituted with one or more groups selected from Ci-C 6 alkyl; C 1 -C 6 alkoxy; phenyl, and phenyl substituted with C 1 -C 6 alkyl; Ci-C 6 alkoxy; halogen and the like; C 3 -C 8 cycloalkyl; halogen; hydroxy, cyano, trifluoromethyl and the like.
  • Typical aryl groups include phenyl, naphthyl, phenylnaphthyl, anthryl (anthracenyl) and the like.
  • heteroaryl is used to describe conjugated cyclic radicals containing at least one hetero atom selected from sulfur, oxygen, nitrogen or a combination of these in combination with from two to about ten carbon atoms and these heteroaryl radicals substituted with the groups mentioned above as possible substituents on the aryl radical.
  • Typical heteroaryl radicals include: 2-and 3-furyl, 2- and 3-thienyl, 2- and 3-pyrrolyl, 2-, 3-, and 4-pyridyl, benzothiophen-2-yl; benzothiazol-2-yl, benzoxazol-2-yl, benzimidazol-2-yl, 1, 3, 4- oxadiazol-2-yl, 1 , 3, 4-thiadiazol-2-yl, 1,2,4-thiadiazol-5-yl, isothiazol-5-yl, imidazol-2-yl, quinolyl and the like.
  • CrC 6 alkoxy is used to represent the groups -0-C 1 -C 6 alkyl, wherein “C 1 -C 6 alkyl” denotes a saturated hydrocarbon that contains 1-6 carbon atoms, which may be straight or branched-chain, and which may be further substituted with one or more groups selected from halogen, methoxy, ethoxy, phenyl, hydroxy, acetyloxy and propionyloxy.
  • halogen is used to represent fluorine, chlorine, bromine, and iodine; however, chlorine and bromine are preferred.
  • the polyester composition of the invention will comprise about 0.05 to about 2 weight percent of at least one HALS or, more typically, about 0.1 to about 1 weight percent.
  • HALS are compounds having formula (1), wherein R 3 , R4, Rs, and R 6 are methyl; R 7 is methyl, C 8 Hi 7 O-, or hydrogen; and L 2 is Ce alkylene.
  • the HALS may be represented by formula (1) above wherein R 3 , R4, R5, and Re are methyl, R 7 is hydrogen, and L 2 is C 8 alkylene.
  • R 3 , R 4 , R 5 , and R 6 are methyl, R 7 is an octyloxy radical, C 8 Hi 7 O-, and L 2 is C 8 alkylene.
  • R 3 , R 4 , R 5 , R 6 and R 7 are methyl, and L 2 is C 8 alkylene.
  • HALS are compounds can be represented by formula (2), wherein R 3 , R 4 , R 5 , and R 6 are methyl groups; R 8 is a methyl group or hydrogen; (Rg)N(Ri 0 ) collectively represents a morpholino group; and L 2 is Ce alkylene or, in another example, R 3 , R 4 , Rs, and R 6 are methyl groups; R 8 and R 9 are hydrogen; R 10 is 2,4,4-trimethyl- 2-pentyl; and L 2 is Ce alkylene.
  • the HALS can comprise at least one compound having formula (3), in which Rn is radical A; and R 3 , R 4 , R 5 , R 6 , and Re each are methyl.
  • the HALS can comprise a compound having formula (4), in which R 3 , R 4 , R 5 , and R 6 each are methyl and R 7 is hydrogen or methyl.
  • UVAs Ultraviolet light absorbers
  • UVAs Ultraviolet light absorbers
  • the term "ultraviolet light absorber” is defined as one compound or a mixture of compounds that absorb light in the range of 290-400 nm with a minimal absorbance between 400 and 700 nm, and that improves the weatherability of the polymer compositions.
  • the aliphatic polyesters of the present invention can have blended therein at least one UVA selected from triazines, cyanoacrylates, benzotriazoles, naphthalenes, and benzoxazinones and mixtures thereof.
  • UVA selected from triazines, cyanoacrylates, benzotriazoles, naphthalenes, and benzoxazinones and mixtures thereof.
  • UVAs useful for blending can be represented by the formula:
  • X represents a divalent aromatic residue in which the two bonds from X are at the 1- and 2-positions; n is 1 , 2 or 3; and R 1 represents a hydrocarbon residue having a valence of n which may further contain a hetero atom, or R 1 may be a direct bond when n is 2, in the unreacted state.
  • X is a divalent aromatic residue in which two bonds from X are at the 1- and 2- positions; n is 2, and R 1 is a hydrocarbon residue having a valence of n which may further contain a hetero atom, or R 1 may be a direct bond.
  • Preferred examples of X include 1 ,2-phenylene, 1 ,2-naphthylene, 2,3- naphthylene, and groups represented by formulas (a) and (b), wherein formula (a) is:
  • R for formulas (a) and (b) is -O-, -CO-, -S-, -SO 2 -, -CH 2 -, -(CH 2 ) 2 or - C(CHa) 2 -.
  • 1 ,2-phenylene is preferred.
  • the aromatic residue for X exemplified above may be substituted by substituents, for example, alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, hexyl and decyl; aryl groups 6 to 12 carbon atoms such as phenyl and naphthyl; cycloalkyl groups having 5 to 12 carbon atoms such as cyclopentyl and cyclohexyl; aralkyl groups having 8 to 20 carbon atoms such as phenethyl; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy and decyloxy; nitro; halogens such as chlorine and bromine; and acyl groups having 2 to 10 carbon atoms such as acetyl, propionyl, benzoyl and decanoyl.
  • R 1 is a hydrocarbon residue having 1 to 10 carbon atoms, such
  • unsubstituted aliphatic residues having 2 to 10 carbon atoms are ethylene, trimethylene, tetramethylene and decamethylene.
  • Examples of the unsubstituted aromatic residues having 6 to 12 carbon atoms are phenylene, naphthylene and p.p'-biphenylene.
  • Examples of the unsubstituted alicyclic residues having 5 to 12 carbon atoms include cyclopentene and cyclohexylene.
  • examples of the divalent hydrocarbon residue include groups represented by the following formula (c)
  • R 2 is any one of the groups of formulae (d)-(h) defined below:
  • R 4 represents an alkylene of 2 to 10 carbon atoms, phenylene or naphthylene
  • R 5 represents an alkyl having 1 to 10 carbon atoms, a phenyl or a naphthyl
  • R 4 and R 5 are as defined above, and R 6 is hydrogen atom or any one of the groups defined for R 5 and a group represented by formula (g) below
  • R 4 and R 6 are as defined above, and R 7 is hydrogen or any one of the ggrroouuppss defined for R 5 and substituted aliphatic or aromatic residues of formula (h) below
  • R 2 is as defined above
  • R 8 is any one of the groups defined for R 4 .
  • R 9 is any one of the groups defined for R 6 .
  • R 1 is preferably a direct bond or any one of the unsubstituted or substituted aromatic hydrocarbon residues in the first to third groups. Those unsubstituted or substituted aromatic hydrocarbon residues in the first or third group in which the two bonds extend from positions farthest from each other, above all p-phenylene, p.p'-biphenylene, and 2,6-naphthylene, are especially preferred.
  • R 10 represents a divalent aromatic hydrocarbon residue.
  • Particularly preferred compounds of formula (I) include 2,2'-p-[phenylene-bis(3,1-benzoxazin- 4-o ⁇ e), 2,2'-(4,4 l -diphenylene)-bis(3,1 -benzoxazin-4-one), and 2,2'-(2,6- naphthalene)bis(3,1 -benzoxazin-4-one) are especially preferred.
  • the compound, 2,2'-P-(phenylene)-bis(3,1 -benzoxazin-4-one) is even more preferred.
  • UVAs such as, for example: Cyasorb UV-2337 (Cytec Industries, CAS# 25973-55-1), Cyasorb UV-5411 (Cytec Industries, CAS# 3147-75-9), Cyasorb UV-5365 (Cytec Industries, CAS# 2440-22-4), Cyasorb UV-1164 (Cytec Industries, CAS# 2725- 22-6), Cyasorb UV-3638 (Cytec Industries, CAS# 18600-59-4), Tinuvin 213 (Ciba Specialty Chemicals, CAS# 104810-47-1), Tinuvin 234 (Ciba Specialty Chemicals, CAS# 70321-86-7), Tinuvin 320 (Ciba Specialty Chemicals, CAS# 3846-71-7), Tinuvin 326 (Ciba Specialty Chemicals, CAS# 3896-11-5), Tinuvin 327 (Ciba Specialty Chemicals, CAS# 3864-99-1),
  • the UVAs are chosen from benzotriazoles, triazines and benzoxazin-4-ones such as Cyasorb UV-1164 (Cytec Industries, CAS# 2725-22-6), Cyasorb UV-3638 (Cytec Industries, CAS# 18600-59-4), Tinuvin 1577 (Ciba Specialty Chemicals, CAS# 147315-50-2), Tinuvin 234 (Ciba Specialty Chemicals, CAS# 70321-86-7) and Tinuvin 328 (Ciba Specialty Chemicals, CAS#25973-55-1).
  • Cyasorb UV-1164 Cytec Industries, CAS# 2725-22-6
  • Cyasorb UV-3638 Cytec Industries, CAS# 18600-59-4
  • Tinuvin 1577 Ciba Specialty Chemicals, CAS# 147315-50-2
  • Tinuvin 234 Tinuvin 234
  • Tinuvin 328 Tinuvin 328
  • the UVAs are chosen from Cyasorb UV-1164 (Cytec Industries, CAS# 2725-22-6), Cyasorb UV-3638 (Cytec Industries, CAS# 18600-59-4) and Tinuvin 1577 (Ciba Specialty Chemicals, CAS# 147315-50-2.
  • Cyasorb UV-1164 Cytec Industries, CAS# 2725-22-6
  • Cyasorb UV-3638 Cytec Industries, CAS# 18600-59-4
  • Tinuvin 1577 Ciba Specialty Chemicals, CAS# 147315-50-2.
  • a combination of two or more of any of the UVAs may be used within the scope of this invention.
  • the benzotriazole compounds can be represented by the structure of formula Il below:
  • X 2 is an alkyl or aryl substituent or a halogen atom such as chlorine and R 11 is independently selected from alkyl or aryl groups having 1 to 20 carbon atoms.
  • the R 11 moiety may be located on the ring but is usually located para- to the hydroxyl grouping for greatest synthetic ease.
  • a representative structure from the class of triazine compounds is formula III below:
  • R 13 , R 14 , and R 15 are an alkyl or aryl group. Their position of substitution on the rings may be as desired but is generally ortho- and para- to the bond to the triazine ring for best synthetic ease. One or both of the two groups R 13 or R 14 may be hydrogen.
  • Tris-aryl-S-triazine UV absorbers have been found to provide low color and haze in the composition of the invention.
  • the aliphatic polyester composition also comprises at least one tris- aryl-S-triazine UV-absorber represented by formula (5):
  • RiS 1 Ri6, Ri7, and Ri 8 are independently selected from hydrogen, C1-C22 alkyl, substituted Ci-C22 alkyl, C3-C8 cycloalkyl, and substituted C 3 -Cs cycloalkyl;
  • Rig is selected from hydrogen, C 1 -C 22 alkyl, substituted C1-C 22 alkyl,
  • R20 is selected from hydrogen, C1-C22 alkyl, substituted Ci- C22 alkyl, C 3 -C 8 cycloalkyl, substituted C 3 -C 8 cycloalkyl, aryl, and heteroaryl.
  • UVAs are compounds represented by formula (5) above in which Ri 3 , Ru, R15, Ri 6 , R17, and R1 8 are hydrogen and R1 9 is -OC ⁇ Hi 3 ; and in which R 1 5 and Ri 6 are hydrogen; Ri 3 , Ri 4 , R 17 , and Ri 8 are methyl; and R 19 is -OC 8 Hi 7 .
  • compositions of the present invention can contain one or more compounds chosen from phenolic antioxidants, hindered phenols, phosphite stabilizers, phosphonite stabilizers and other stabilizers known to one skilled in the art.
  • phenolic antioxidants and "hindered phenol” are primary antioxidants that are known to those skilled in the art and may be represented by the structures listed on pages 98-108 in the Plastic Additives Handbook 5 th Edition (Hanser Gardner Publications, lnc. s Cincinnati, OH 1 USA, 2001), incorporated herein by reference in its entirety.
  • phenolic antioxidants are as follows: Irganox 1010 (Ciba Specialty Chemicals, CAS# 6683-19-8), Irganox 1330 (Ciba Specialty Chemicals, CAS# 1709-70-2) and Irganox 3114 (Ciba Specialty Chemicals, CAS# 27676-62-6)., [00286]
  • phosphite stabilizers and “phosphonite stabilizers” refer to secondary antioxidants that are known to those skilled in the art and may be represented by the structures listed on pages 109-112 in the Plastic Additives Handbook 5 th Edition (Hanser Gardner Publications, Inc., Cincinnati, OH, USA, 2001), incorporated herein by reference in its entirety.
  • Some common phosphite stabilizers are as follows: Ultranox 626 (GE Specialty Chemicals, CAS# 26741- 53-7), lrgafos 168 (Ciba Specialty Chemicals, CAS# 31570-04-4), Weston 619 (GE Specialty Chemicals, CAS# 3806-34-6) and Doverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).
  • alkyl phosphites may be combined with an ultraviolet light absorber.
  • aryl phosphites for example, lrgafos 168) can be combined with a hindered amine light stabilizer and optionally, an ultraviolet light absorber.
  • phenolic antioxidants for example, Irganox 1010 can be added during melt processing. Phenolic antioxidants are particularly useful when a polyglycol ether [for example, poly(tetramethylene glycol)] is present.
  • the amount of UV absorbing compound in the blend can be from about 0.1 weight % to about 10 weight %, preferably from about 0.5 weight % to about 5 weight % and more preferably from about 0.5 weight % to about 4 weight %, wherein the weight % are based on the total weight of the blend.
  • the UV absorbing compound may be incorporated into the copolyester and at the desired concentrations by suitable blending and/or mixing technology such as by preparation of a concentrate of the UV absorbing compound in a base copolymer followed by pellet blending of the concentrate with further copolyester pellets containing no UV absorber, such that the final extruded product will be the copolyester with the desired overall level of UV absorber.
  • the UV absorbing compound may be placed as the layer onto the plastic sheeting or film to be stabilized with the protective stabilized layer facing the light exposure shielding the sheeting from the effects of UV exposure.
  • the protective layer can be on both sides of the sheet or film either for purposes of attenuating the effect of reflected radiation in a particular application environment or to render installation of the product foolproof. Suitable means for application of this protective layer include, but are not limited to, coextrusion, extrusion coating, extrusion lamination, calendaring, hot press lamination, solvent coating, and the like.
  • the copolyesters blends of the present invention are suitable for use in both the protective layer (cap layer) and the substrate layer of film or sheeting to which the protective layer is applied.
  • the substrate layer can be composed of a polymer composition different than the protective layer.
  • the structure of a coextruded product can be a film, a solid sheet or can be a profiled article. Many other configurations of such structures are possible, such as, having two or more layers of the sheeting connected by ribbing.
  • the essential element of such structures is that they provide a great deal of rigidity of the final structure compared to the weight of the polymer employed therein. In these cases, the UV absorber containing layer is placed on either one side or both flat sides just the same as if it were a solid sheet.
  • the protective layer of film or sheeting need not be of the same copolyester composition as the substrate which does not contain the UV absorbing compound.
  • the thickness of the protective layer on the underlying film or sheeting can vary according to the desired technological ends of the coating. As a general rule, the thickness of the protective layer is chosen depending upon the UV absorber concentration in order to screen at least 99% of the incoming UV light in solar radiation and render the structure weathering resistant. The thickness can be further reduced by higher concentration of the UV absorber in the protective layer.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; optionally, at least one antioxidant as described herein, and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; and at least one antioxidant as described herein; and optionally, at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; and optionally, at least one antioxidant as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer (base layer) comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; and at least one antioxidant as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; optionally, at least one hindered amine light stabilizer as described herein, and optionally, at least one ultraviolet light absorbing compound.
  • This invention further relates to a thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; and at least one hindered amine light stabilizer as described herein; and optionally, at least one ultraviolet light absorbing compound.
  • a thermoplastic article comprising: a first layer comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; and optionally, at least one hindered amine light stabilizer as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic article comprising: a first layer (base layer) comprising a polymeric material; and a second layer (which can be a protective layer) comprising at least one of the polyesters of the invention; and at least one hindered amine light stabilizer as described herein, and at least one ultraviolet light absorbing compound.
  • thermoplastic articles of the invention can include but are not limited to polyesters useful in the invention, polyethylene terephthlate (PET); polyethylene terephthlate modified with glycols other than ethylene glycol, for example, PETG; polybutylene terephthalate (PBT), polycarbonate (PC), polycarbonate blends (for example, PC/ABS, PC/PVC, PC/PBT, PC/PETG and PC/PET), ABS and ABS blends, and acrylics.
  • PET polyethylene terephthlate
  • PC polyethylene terephthlate modified with glycols other than ethylene glycol
  • PETG polybutylene terephthalate
  • PC polycarbonate
  • PC/ABS PC/PVC
  • PC/PETG and PC/PET polycarbonate blends
  • ABS and ABS blends for acrylics.
  • ABS is the abbreviation for acrylonitrile butadiene styrene copolymers.
  • PVC is the abbreviation
  • polyester compositions comprising terephthalic acid, 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 1 ,4-cyclohexanedimethanol such as, for example, those described in United States Patent Application Publication No. 2006-0287493; Pub. dated December 21, 2006 and United States Patent Application Publication No. 2006-0293495, dated December 28, 2006, incorporated by reference in their entireties.
  • Reinforcing materials may be useful in the compositions of this invention.
  • the reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof.
  • the reinforcing materials include glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • the invention further relates to the film(s) and/or sheet(s) comprising the polyester compositions and/or polymer blends of the invention.
  • the methods of forming the polyesters and/or blends into film(s) and/or sheet(s) and/or multi- sheets are well known in the art.
  • Examples of film(s) and/or sheet(s) of the invention including but not limited to extruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s), compression molded f ⁇ lm(s) and/or sheet(s), solution casted film(s) and/or sheet(s).
  • Methods of making film and/or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.
  • Examples of potential articles made from film and/or sheet useful in the invention include, but are not limited, to uniaxially stretched film, biaxially stretched film, thermoformed sheet; multi-layer sheets, graphic arts film; building and construction articles, (for example, outdoor signs, skylights); auto panels, optical media, coating(s), coated articles, painted articles, laminates, laminated articles, and/or multiwall films or sheets.
  • the present invention also relates to shaped articles wholly or partially produced from the polymer containing the ultraviolet light absorbing compound.
  • Representative applications are for example; signs for businesses, both stationary mounted and also portable ones, luggage carriers for the tops of the vehicles, sign boards, marquees on stores, solar roof panels, skylights, highway sound barriers, greenhouse panels, both in the sidewalls and the roofing thereof, separation walls in aquariums, aquariums themselves, recreational vehicle windows and vents, snowmobile, jet ski, golf cart, motorcycle and other such recreation vehicle windshields, bug screens or air deflection screens on cars and trucks or other such vehicles, transparent or translucent awnings, formed letters to be applied to the sides of buildings, letters to be used on signs, particularly those where the letters are changed at some frequency to change what the sign says, airport runway and taxiway marker signs, multiwall sheeting for use in signs, greenhouses, glazing applications and fluorescent or other light covers, etc., facia for soft drink and juice dispensing machines, etc.
  • the product can be used either as a clear plastic part or it could be colored via producer added colors to give a clear, colored sheet or it could be printed on the back surface, in particular for sign and marquee applications to give the desired effects of highlighting letters, for example.
  • This list is not intended to be all inclusive but merely representative of the vast number of applications available for a material having suitable properties.
  • Graphic art film is a film having a thermally-curable ink (e.g., heat-curable ink or air-curable ink) or radiation-curable ink (e.g., ultraviolet-curable ink) printed thereon or therein.
  • thermally-curable ink e.g., heat-curable ink or air-curable ink
  • radiation-curable ink e.g., ultraviolet-curable ink
  • Cosmetic refers to capable of undergoing polymerization and/or crosslinking.
  • the graphic art film may optionally also include varnishes, coatings, laminates, and adhesives.
  • Exemplary thermally or air-cured inks involve pigment(s) dispersed in one or more standard carrier resins.
  • the pigment can be 4B Toner (PR57), 2B Toner (PR48), Lake Red C (PR53), lithol red (PR49), iron oxide (PR101), Permanent Red R (PR4), Permanent Red 2G (PO5), pyrazolone orange (PO13), diaryl yellows (PY12, 13, 14), monoazo yellows (PY3,5,98), phthalocyanine green (PG7), phthalocyanine Blue, ⁇ form (PB15), ultramarine (PB62), permanent violet (PV23), titanium dioxide (PW6), carbon black (furnace/channel) (PB7), PMTA pink, green, blue, violet (PR81 , PG1, PB1, PV3,), copper ferrocyanide dye complexes (PR169, PG45, PB62, PV27), or the like.
  • Pigmental identifications in the foregoing refer to the generic color index prepared by the Society of Dyers and Colourists.
  • Such pigments and combinations thereof can be used to obtain various colors including, but not limited to, white, black, blue, violet, red, green, yellow, cyan, magenta, or orange.
  • Examples of typical carrier resins used in standard inks include those which have nitrocellulose, amide, urethane, epoxide, acrylate, and/or ester functionalities.
  • Standard carrier resins include one or more of nitrocellulose, polyamide, polyurethane, ethyl cellulose, cellulose acetate propionate, (meth)acrylates, polyvinyl butyral), polyvinyl acetate), polyvinyl chloride), and the like.
  • Such resins can be blended, with widely used blends including nitrocellulose/polyamide and nitrocellulose/polyurethane.
  • Ink resin(s) normally can be solvated or dispersed in one or more solvents.
  • Typical solvents employed include, but are not limited to, water, alcohols (e.g., etha ⁇ ol, 1-propanol, isopropanol, etc.), acetates (e.g., n-propyl acetate), aliphatic hydrocarbons, aromatic hydrocarbons (e.g., toluene), and ketones.
  • Such solvents typically can be incorporated in amounts sufficient to provide inks having viscosities, as measured on a #2 Zahn cup as known in the art, of at least 15 seconds, such as at least 20 seconds, at least 25 seconds, or from 25 to 35 seconds.
  • the polyester have sufficient T 9 values to allow thermoformability, and to allow ease of printing.
  • the graphic art film has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, T 9 , and flexibility.
  • Graphic art films can be used in a variety of applications, such as, for example, in-mold decorated articles, embossed articles, hard-coated articles.
  • the graphic art film can be smooth or textured.
  • Exemplary graphic art films include, but are not limited to, nameplates; membrane switch overlays (e.g., for an appliance); point of purchase displays; flat or in-mold decorative panels on washing machines; flat touch panels on refrigerators (e.g., capacitive touch pad arrays); flat panel on ovens; decorative interior trim for automobiles (e.g., a polyester laminate) ; instrument clusters for automobiles; cell phone covers; heating and ventilation control displays; automotive console panels; automotive gear shift panels; control displays or warning signals for automotive instrument panels; facings, dials or displays on household appliances; facings, dials or displays on washing machines; facings, dials or displays on dishwashers; keypads for electronic devices; keypads for mobile phones, personal digital assistants (PDAs, or hand-held computers) or remote controls; displays for electronic devices; displays for hand-held electronic devices such as phones and PDAs; panels and housings for mobile or standard phones; logos on electronic devices; and logos for hand-held phones.
  • PDAs personal digital assistants
  • Multiwall film or sheet refers to sheet extruded as a profile consisting of multiple layers that are connected to each other by means of vertical ribs.
  • Examples of multiwall film or sheet include but are not limited to outdoor shelters (for example, greenhouses and commercial canopies).
  • extruded articles comprising the polyester compositions useful in this invention include, but are not limited to, thermoformed sheet, film for graphic arts applications, outdoor signs, skylights, multiwall film, plastic film for plastic glass laminates, and liquid crystal display (LCD) films, including but not limited to, diffuser sheets, compensation films, and protective films for LCDs.
  • the present invention comprises a thermoplastic article, typically in the form of sheet material, having a decorative material embedded therein which comprise any of the compositions described herein.
  • Outdoor sign refers to a surface formed from the polyester described herein, or containing symbols (e.g., numbers, letters, words, pictures, etc.), patterns, or designs coated with the polyester or polyester film described herein.
  • the outdoor sign comprises a polyester containing printed symbols, patterns, or designs.
  • the sign is capable of withstanding typical weather conditions, such as rain, snow, ice, sleet, high humidity, heat, wind, sunlight, or combinations thereof, for a sufficient period of time, e.g., ranging from one day to several years or more.
  • Exemplary outdoor signs include, but are not limited to, billboards, neon signs, electroluminescent signs, electric signs, fluorescent signs, and light emitting diode (LED) displays.
  • Other exemplary signs include, but are not limited to, painted signs, vinyl decorated signs, thermoformed signs, and hardcoated signs.
  • the outdoor sign has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and T 9 .
  • a "vending machine display panel,” as used herein, refers to a front or side panel on a vending machine that allows a customer to view the items for sale, or advertisement regarding such items.
  • the vending machine display panel can be a visually clear pane! of a vending machine through which a consumer can view the items on sale.
  • the vending machine display panel can have sufficient rigidity to contain the contents within the machine and/or to discourage vandalism and/or theft.
  • the vending machine display panel can have dimensions well known in the art, such as planar display panels in snack, beverage, popcorn, or sticker/ticket vending machines, and capsule display panels as in, e.g., gumball machines or bulk candy machines.
  • the vending machine display panel can optionally contain advertising media or product identification indicia. Such information can be applied by methods well known in the art, e.g., silk screening.
  • the vending machine display panel can be resistant to temperatures ranging from -100 to 120 0 C.
  • the vending machine display panel can be UV resistant by the addition of, e.g., at least one UV additive, as disclosed herein.
  • the vending machine display panel has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and T 9 .
  • Point of purchase display refers to a wholly or partially enclosed casing having at least one visually clear panel for displaying an item.
  • Point of purchase displays are often used in retail stores to for the purpose of catching the eye of the customer.
  • Exemplary point of purchase displays include enclosed wall mounts, countertops, enclosed poster stands, display cases (e.g., trophy display cases), sign frames, and cases for computer disks such as CDs and DVDs.
  • the point of purchase display can include shelves, and additional containers, such as holders for magazines or pamphlets.
  • the display can be as small as a case for jewelry, or a larger enclosed cabinet for displaying multiple trophies.
  • the point of purchase display has at least one property chosen from toughness, clarity, chemical resistance, T 9 , and hydrolytic stability.
  • appliance parts refers to a rigid piece used in conjunction with an appliance.
  • the appliance part is partly or wholly separable from the appliance.
  • the appliance part is one that is typically made from a polymer.
  • the appliance part is visually clear.
  • Exemplary appliance parts include those requiring toughness and durable, such as cups and bowls used with food processers, mixers, blenders, and choppers; parts that can withstand refrigerator and freezer temperatures (e.g., refrigerator temperatures ranging from greater than O 0 C (e.g., 2°C) to 5°C, or freezer temperatures, e.g., at temperatures less than 0 0 C, such as temperatures ranging from -20 to 0 0 C, e.g., -18°C), such as refrigerator and freezer trays, bins, and shelves; parts having sufficient hydrolytic stability at temperatures up to 90 0 C, such as washing machine doors, steam cleaner canisters, tea kettles, and coffee pots; and vacuum cleaner canisters and dirt cups.
  • refrigerator and freezer temperatures e.g., refrigerator temperatures ranging from greater than O 0 C (e.g., 2°C) to 5°C, or freezer temperatures, e.g., at temperatures less than 0 0 C, such as temperatures ranging from -20 to 0 0 C
  • these appliance parts have at least one property chosen from toughness, clarity, chemical resistance, T 9 , hydrolytic stability, and dishwasher stability.
  • the appliance part can also be chosen from steam cleaner canisters, which, in one embodiment, can have at least one property chosen from toughness, clarity, chemical resistance, T 9 , and hydrolytic stability.
  • the polyesters useful in the appliance part has a T 9 of 105 to 140 0 C and the appliance part is chosen from vacuum cleaner canisters and dirt cups.
  • the polyesters useful in the appliance part has a Tg of 120 to 150 0 C and the appliance part is chosen from steam cleaner canisters, tea kettles and coffee pots.
  • Skylight refers to a light permeable panel secured to a roof surface such that the panel forms a portion of the ceiling.
  • the panel is rigid, e.g., has dimensions sufficient to achieve stability and durability, and such dimensions can readiliy be determined by one skilled in the art.
  • the skylight panel has a thickness greater than 3/16 inches, such as a thickness of at least 1/2 inches.
  • the skylight panel is visually clear.
  • the skylight panel can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light.
  • the skylight panel comprises at least one UV additive that allows the skylight panel to block up to 80%, 90%, or up to 95% UV light.
  • the skylight has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and T 9 .
  • "Outdoor shelters," as used herein, refer to a roofed and/or walled structure capable of affording at least some protection from the elements, e.g., sunlight, rain, snow, wind, cold, etc., having at least one rigid panel.
  • the outdoor shelter has at least a roof and/or one or more walls.
  • the outdoor shelter has dimensions sufficient to achieve stability and durability, and such dimensions can readiliy be determined by one skilled in the art.
  • the outdoor shelter panel has a thickness greater than 3/16 inches.
  • the outdoor shelter panel is visually clear.
  • the outdoor shelter panel can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light.
  • the outdoor shelter panel comprises at least one UV additive that allows the outdoor shelter to block up to 80%, 90%, or up to 95% UV light.
  • Exemplary outdoor shelters include security glazings, transportation shelters (e.g., bus shelters), telephone kiosks, and smoking shelters.
  • the shelter is a transportation shelter, telephone kiosk, or smoking shelter
  • the shelter has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, and T 9 .
  • the shelter is a security glazing
  • the shelter has at least one property chosen from toughness, clarity, chemical resistance, and T 9 .
  • a "canopy,” as used herein, refers to a roofed structure capable of affording at least some protection from the elements, e.g., sunlight, rain, snow, wind, cold, etc.
  • the roofed structure comprises, either in whole or in part, at least one rigid panel, e.g., has dimensions sufficient to achieve stability and durability, and such dimensions can readiliy be determined by one skilled in the art.
  • the canopy panel has a thickness greater than 3/16 inches, such as a thickness of at least 1/2 inches.
  • the canopy panel is visually clear.
  • the canopy panel can transmit at least 35% visible light, at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light.
  • the canopy panel comprises at least one UV additive that allows the canopy to block up to 80%, 90%, or up to 95% UV light.
  • Exemplary canopies include covered walkways, roof lights, sun rooms, airplane canopies, and awnings.
  • the canopy has at least one property chosen from toughness, clarity, chemical resistance, T 9 , and flexibility.
  • a "sound barrier,” as used herein, refers to a rigid structure capable of reducing the amount of sound transmission from one point on a side of the structure to another point on the other side when compared to sound transmission between two points of the same distance without the sound barrier.
  • the effectiveness in reducing sound transmission can be assessed by methods known in the art. In one embodiment, the amount of sound transmission that is reduced ranges from 25 % to 90 %.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Selon l'un de ses aspects, l'invention concerne des compositions de polyester comprenant au moins un polyester qui comprend : (A) un composant acide dicarboxylique comprenant : i) 70 à 100 % en moles de résidus d'acide cyclohexanedicarboxylique, ou d'un ester de celui-ci comprenant : (a) 70 à 98 % en moles de résidus d'acide trans-cyclohexanedicarboxylique, ou d'un ester de celui-ci; et (b) 2 à 30 % en moles de résidus d'acide cis-cyclohexanedicarboxylique, ou d'un ester de celui-ci; ii) 0 à 30 % en moles de résidus d'acide dicarboxylique aliphatique, autres que des résidus d'acide cyclohexanedicarboxylique, ayant jusqu'à 16 atomes de carbone, ou d'esters de celui-ci, autres que des résidus d'acide cyclohexanedicarboxylique; et iii) 0 à 10 % en moles de résidus d'acide dicarboxylique aromatique ayant jusqu'à 20 atomes de carbone; et (B) un composant glycol comprenant : i) 1 à 99 % en moles de résidus de 2,2,4,4-tétraméthyl-1,3-cyclobutanediol; et ii) 1 à 99 % en moles de résidus de 1, 4-cyclohexanediméthanol, de résidus de 1,3-cyclohexanediméthanol, de résidus de 1,2-cyclohexanediméthanol, ou d'esters de ceux-ci ou de mélanges de ceux-ci, le pourcentage en moles total du composant acide dicarboxylique étant égal à 100 % en moles; le pourcentage en moles total du composant glycol étant égal à 100 % en moles; la viscosité inhérente dudit polyester étant de 0,35 à 1,2 dl/g telle que déterminée dans du phénol/tétrachloroéthane à 60/40 (poids/poids) à une concentration de 0,5 g/100 ml à 25°C; et le polyester ayant une Tg de 60 à 155°C. Les polyesters peuvent être fabriqués sous la forme d'articles.
PCT/US2007/015713 2006-10-27 2007-07-10 Certaines compositions de polyester qui comprennent du cyclobutanediol, du cyclohexanediméthanol, et de l'acide trans-cyclohexanedicarboxylique supérieur WO2008054560A2 (fr)

Applications Claiming Priority (46)

Application Number Priority Date Filing Date Title
USPCT/US06/42293 2006-10-27
US11/588,883 2006-10-27
US11/588,524 US20100096589A1 (en) 2005-10-28 2006-10-27 Polyester compositions containing low amounts of cyclobutanediol and articles made therefrom
US11/588,524 2006-10-27
US11/588,906 2006-10-27
US11/588,527 US20100087574A1 (en) 2005-10-28 2006-10-27 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
USPCT/US06/42291 2006-10-27
US11/588,907 US20070106054A1 (en) 2005-10-28 2006-10-27 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US11/588,554 US20070100125A1 (en) 2005-10-28 2006-10-27 Polyester compositions comprising minimal amounts of cyclobutanediol
PCT/US2006/041917 WO2007053434A1 (fr) 2005-10-28 2006-10-27 Compositions de polyester comprenant du cyclobutanediol et certains stabilisants thermiques et/ou des produits de reaction de ceux-ci
USPCT/US06/42069 2006-10-27
PCT/US2006/042291 WO2007053548A2 (fr) 2005-10-28 2006-10-27 Compositions de polyester comprenant des quantites minimales de cyclobutanediol
US11/588,906 US8193302B2 (en) 2005-10-28 2006-10-27 Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof
US11/588,554 2006-10-27
PCT/US2006/042292 WO2007053549A1 (fr) 2005-10-28 2006-10-27 Compositions de polyester contenant du cyclobutanediol qui presente une certaine combinaison d'indice logarithmique de viscosite et de temperature de transition vitreuse moderee et articles fabriques a partir de celles-ci
US11/588,527 2006-10-27
PCT/US2006/042293 WO2007053550A1 (fr) 2005-10-28 2006-10-27 Compositions de polyester contenant du cyclobutanediol qui presente une temperature de transition vitreuse elevee et articles fabriques a partir de celles-ci
US11/588,458 US20070100122A1 (en) 2005-10-28 2006-10-27 Polyester compositions containing cyclobutanediol and articles made therefrom
USPCT/US06/41917 2006-10-27
US11/588,883 US20070105993A1 (en) 2005-10-28 2006-10-27 Polyester compositions which comprise cyclobutanediol and at least one phosphorus compound
US11/588,907 2006-10-27
PCT/US2006/042069 WO2007053460A1 (fr) 2005-10-28 2006-10-27 Compositions de polyester comprenant du cyclobutanediol et au moins un compose phosphoreux
US11/588,458 2006-10-27
USPCT/US06/42292 2006-10-27
US11/635,433 US20070142511A1 (en) 2005-12-15 2006-12-07 Polyester compositions which comprise cyclobutanediol ethylene glycol, titanium, and phosphorus with improved color and manufacturing processes therefor
US11/635,434 US7737246B2 (en) 2005-12-15 2006-12-07 Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor
US11/635,434 2006-12-07
US11/635,433 2006-12-07
US11/706,791 US20070232779A1 (en) 2006-03-28 2007-02-14 Certain polyester compositions which comprise cyclohexanedimethanol, moderate cyclobutanediol, cyclohexanedimethanol, and high trans cyclohexanedicarboxylic acid
US11/706,476 US20070232778A1 (en) 2006-03-28 2007-02-14 Certain polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and high trans-cyclohexanedicarboxylic acid
US11/706,476 2007-02-14
US11/706,791 2007-02-14
USPCT/US07/07532 2007-03-27
PCT/US2007/007632 WO2007126855A1 (fr) 2006-03-28 2007-03-27 Compositions de polyester lesquelles comprennent du cyclobutanediol et certains agents stabilisants thermiques et/ou des produits de réaction de ceux-ci
PCT/US2007/007532 WO2007123631A1 (fr) 2006-03-28 2007-03-27 Compositions polyester comprenant du cyclobutanediol et au moins un compose phosphore
USPCT/US07/07632 2007-03-27
PCT/US2007/010551 WO2007139653A1 (fr) 2006-05-23 2007-05-02 Films de lcd ou feuilles comprenant des films comprenant des compositions polyester formées de 2,2,4,4,-tétraméthyl-1,3-cyclobutanediol et de 1,4-cyclohexanediméthanol
USPCT/US07/10551 2007-05-02
USPCT/US07/10590 2007-05-02
PCT/US2007/010590 WO2007139655A1 (fr) 2006-05-23 2007-05-02 Compositions de polyester comprenant un cyclobutanediol et un certain nombre de stabilisants thermiques et/ou des produits de réaction de ceux-ci
PCT/US2007/011150 WO2007139663A1 (fr) 2006-05-23 2007-05-09 Compositions de polyester comprenant du cyclobutanediol et certains stabilisants vis-à-vis de la chaleur et/ou des produits de réaction de ceux-ci
USPCT/US07/11150 2007-05-09
US91731607P 2007-05-10 2007-05-10
US60/917,316 2007-05-10
US11/773,275 US8586701B2 (en) 2005-10-28 2007-07-03 Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11/773,275 2007-07-03

Publications (2)

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WO2008054560A2 true WO2008054560A2 (fr) 2008-05-08
WO2008054560A3 WO2008054560A3 (fr) 2008-07-24

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PCT/US2007/015713 WO2008054560A2 (fr) 2006-10-27 2007-07-10 Certaines compositions de polyester qui comprennent du cyclobutanediol, du cyclohexanediméthanol, et de l'acide trans-cyclohexanedicarboxylique supérieur
PCT/US2007/015702 WO2008054559A1 (fr) 2006-10-27 2007-07-10 Certaines compositions de polyester qui comprennent du tétraméthylcyclobutanediol, du cyclohexanediméthanol et un acide trans-cyclohexanedicarboxylique supérieur
PCT/US2007/015701 WO2008051320A1 (fr) 2006-10-27 2007-07-10 Compositions de polyester comprenant tétraméthylcyclobutanediol, cyclohexanediméthanol et éthylèneglycol, et méthodes de production desdites compositions
PCT/US2007/015704 WO2008051321A1 (fr) 2006-10-27 2007-07-10 Compositions de polyester de couleur améliorée comprenant cyclobutanediol, éthylèneglycol, titane et phosphore, et méthodes de production desdites compositions

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PCT/US2007/015701 WO2008051320A1 (fr) 2006-10-27 2007-07-10 Compositions de polyester comprenant tétraméthylcyclobutanediol, cyclohexanediméthanol et éthylèneglycol, et méthodes de production desdites compositions
PCT/US2007/015704 WO2008051321A1 (fr) 2006-10-27 2007-07-10 Compositions de polyester de couleur améliorée comprenant cyclobutanediol, éthylèneglycol, titane et phosphore, et méthodes de production desdites compositions

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WO2008054560A3 (fr) 2008-07-24
BRPI0717761A2 (pt) 2013-03-12
EP2074158A1 (fr) 2009-07-01
CA2666571A1 (fr) 2008-05-02
TW200819497A (en) 2008-05-01
JP2010507717A (ja) 2010-03-11
TW200819496A (en) 2008-05-01
KR20090079212A (ko) 2009-07-21
BRPI0717755A2 (pt) 2013-03-12
JP2010507716A (ja) 2010-03-11
EP2074174A1 (fr) 2009-07-01
CA2666585A1 (fr) 2008-05-02
WO2008051321A1 (fr) 2008-05-02
KR20090079211A (ko) 2009-07-21
WO2008054559A1 (fr) 2008-05-08
WO2008051321A8 (fr) 2008-07-10

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