[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2022266289A1 - Procédé de fabrication de compositions de polyester/élastomère polyester - Google Patents

Procédé de fabrication de compositions de polyester/élastomère polyester Download PDF

Info

Publication number
WO2022266289A1
WO2022266289A1 PCT/US2022/033735 US2022033735W WO2022266289A1 WO 2022266289 A1 WO2022266289 A1 WO 2022266289A1 US 2022033735 W US2022033735 W US 2022033735W WO 2022266289 A1 WO2022266289 A1 WO 2022266289A1
Authority
WO
WIPO (PCT)
Prior art keywords
mole
weight
polyester
acid
mpa
Prior art date
Application number
PCT/US2022/033735
Other languages
English (en)
Inventor
Robert Erik Young
Marc Alan Strand
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
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Publication of WO2022266289A1 publication Critical patent/WO2022266289A1/fr

Links

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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/02—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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds

Definitions

  • the invention generally relates to a polyester composition comprising at least one rigid polyester and at least one polyester elastomer, at least one primary antioxidant, at least one secondary antioxidant, and at least one chain extending agent as well as articles produced from the polyester composition. Processes to produce the polyester compositions as well as processes to produce articles comprising the polyester compositions are also provided.
  • compositions comprising rigid polyesters and copolyester elastomer with improved thermal stability and improved physical and processing properties aredisclosed.
  • Thermoplastic polyesters are typically considered rigid thermoplastics with high tensile strength and modulus values.
  • Thermoplastic polyester elastomers are typically considered inherently flexible materials with lower tensile strength and modulus values.
  • processing techniques such as powder coating to have improved color, processing and thermal stability properties.
  • a polyester composition comprising: a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to produce a polyester composition comprising contacting a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive to produce a polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to produce a polyester composition comprising extruding a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive in an extrusion zone to produce a polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to produce a polyester composition comprising: a) polymerizing at least one dicarboxylic acid and at least one diol to produce a rigid polyester having a Tg greater than 60°C; b) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a Tg less than 50°C; and c) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less; wherein the polymerizing in steps a) and/or b) is conducted in the presence of at least one primary antioxidant; and wherein the polymerizing in steps 1) and/or 2) is conducted in the presence of at least one secondary antioxidant.
  • a process to produce a polyester composition comprising a) polymerizing at least one dicarboxylic acid and at least one diol to produce a rigid polyester having a Tg greater than 60°C; b) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol in the presence of 1) at least one primary antioxidant; and 2) at least one secondary antioxidant to produce a polyester elastomer having a Tg less than 0°C, and c) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process for making a polyester coated article comprising coating an article with a polyester composition to produce the polyester coated article; wherein the polyester composition comprises a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the composition has a enthalpy of melting of 3 cal/gm or less.
  • a process of manufacturing a molded article comprising: a) placing a polyester composition in a mold having mold surfaces; wherein the polyester composition comprises: 1) at least one rigid polyester;
  • composition has a enthalpy of melting of 3 cal/gm or less; b) heating the polyester composition until it becomes molten; c) dispersing the molten polyester composition to cover the mold surfaces; d) solidifying the molten polyester to form a solid molded article; and e) removing the molded article from the mold.
  • residue means any organic structure incorporated into a polymer through a polycondensation or ring opening reaction involving the corresponding monomer. It will also be understood by persons having ordinary skill in the art, that the residues associated within the various polyesters of the invention can be derived from the parent monomer compound itself or any derivative of the parent compound.
  • the dicarboxylic acid residues referred to in the polymers of the invention may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
  • 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, or mixtures thereof, useful in a polycondensation process with a diol to make a curable, aliphatic polyester.
  • branching agent refers to an alcohol or an acid molecule with three or more functional groups.
  • alcohol branching agents include glycerine, trimethylol propane and pentaerythritol. Trimellitic anhydride is an example of an acid based branching agent.
  • the enthalpy of melting of the polyester composition ranges from 0.1 to 3 cal/gm, 0.3 to 3 cal/gm, 0.5 to 3 cal/gm, 0.7 to 3 cal/gm, 1 to 3 cal/gm, 1 .2 to 3 cal/gm, 1 .5 to 3 cal/gm, 2 to 3 cal/gm, 0.1 to 2.5 cal/gm, 0.3 to 2.5 cal/gm, 0.5 to 2.5 cal/gm, 0.7 to 2.5 cal/gm, 1 to 2.5 cal/gm, 1 .5 to 2.5 cal/gm, 2 to 2.5 cal/gm, 0.1 to 2 cal/gm, 0.3 to 2 cal/gm, 0.5 to 2 cal/gm, 0.7 to 2 cal/gm, 1 to 2 cal/gm, 1 .2 to 2 cal/gm, 1 .5 to 2 cal/gm, 0.1 to 1 .5 cal//
  • the polyester composition exhibits a blister size of 6 or greater as determined by ASTM D714 after 500 hours of Salt Fog testing per ASTM B117.
  • the polyester composition exhibits a scribe rust value of 6 or greater as determined by ASTM D1654.
  • the polyester composition has an impact resistance of 160 ft-lbs or greater as measured by ASTM D2794 when applied to metal panels.
  • Other ranges for impact resistance is 170 ft-lbs or greater, 180 ft-lbs or greater, 190 ft-lbs or greater, or 200 ft-lbs or greater as measured by ASTM D2794.
  • 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, or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester.
  • modifying aromatic diacid means an aromatic dicarboxylic acid other the terephthalic acid.
  • modifying glycol means a glycol other than 1 ,4-cyclohexanedimethanol.
  • terephthalic acid may be used as the starting material.
  • dimethyl terephthalate may be used as the starting material.
  • mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and/or as an intermediate material.
  • polyesters and copolyesters of the present invention are readily prepared by methods well known in the art, for example, as described in U.S. Patent No. 2,012,267, incorporated herein by reference in its entirety. More particularly, the reactions for preparing the copolyesters are usually carried out at temperatures of about 150° C to about 300° C in the presence of polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, germanium or combinations thereof.
  • the catalysts are typically employed in amounts of 10 to 1000 ppm, based on total weight of the reactants.
  • Condensation polymers are also susceptible to hydrolytic degradation if not pre-dried or if they are held at elevated temperatures in moist air for a long period of time.
  • Condensation polymers are any polymers where monomers reacting during polycondensation to create a polymer and a by-product such as water or methanol is produced. The polymerization reaction is reversible; thus, condensation polymers are often pre-dried before processing.
  • the rigid 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 rigid polyester polymer as their corresponding residues.
  • the rigid polyesters of the present invention therefore, can contain substantially equal molar proportions of acid residues (100 mole%) and diol (and/or multifunctional hydroxyl compounds) residues (100 mole%) such that the total moles of repeating units is equal to
  • rigid polyesters with high amounts of terephthalic acid can be used in order to produce higher impact strength properties.
  • terephthalic acid and "dimethyl terephthalate” are used interchangeably herein.
  • dimethyl terephthalate is 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
  • the amount of one or more modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 30 mole%, from 0.01 to 20 mole%, from 0.01 to 10 mole%, from 0.01 to 5 mole%, or from 0.01 to 1 mole% of one or more modifying aromatic dicarboxylic acids.
  • 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.
  • modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, 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.
  • isophthalic acid is the modifying aromatic dicarboxylic acid.
  • dimethyl isophthalate is used.
  • dimethyl naphthalate is used.
  • esters of terephthalic acid and esters of the other modifying dicarboxylic acids 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, and phenyl esters.
  • the rigid polyesters useful in the invention can contain less than 30 mole% of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 20 mole% or less of one or more modifying glycols. In another embodiment, the rigid 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 rigid polyesters useful in the invention may contain 0 mole% modifying glycols. Certain embodiments can also contain 0.01 or more mole%, such as 0.1 or more mole%, 1 or more mole% of one or more modifying glycols.
  • ethylene glycol is excluded as a modifying diol.
  • the modifying glycol can be a glycol other than ethylene glycol and 1 ,4- cyclohexanedimethanol, for example.
  • the rigid polyesters useful in the polyester compositions of the invention can comprise from 0 to 10 mole% of at least one branching agent, for example, 0.01 to 5 mole% or 0.01 to 4 mole% or from 0.01 to 3 mole% or from 0.01 to 2 mole% or from 0.01 to about 1.5 mole% or from 0.01 to 1 mole% or from 0.1 to 5 mole% or 0.1 to 4 mole% or from 0.1 to 3 mole% or from 0.1 to 2 mole% or from 0.1 to about 1 .5 mole% or from 0.1 to 1 mole or from 0.5 to 5 mole% or 0.5 to 4 mole% or from 0.5 to 3 mole% or from 0.5 to 2 mole% or from 0.5 to about 1 .5 mole% or from 0.5 to 1 mole% or from 1 to 5 mole% or 1 to 4 mole% or from 1 to 3 mole% or from 1 to 2 mole% or from 0.5 to about 1 .5 mole% or from 0.5 to 1 mole% or from
  • branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, citric acid, tartaric acid, 3- hydroxyglutaric acid, pentaerythritol, sorbitol, 1 ,2,6-hexanetriol, glycerine tetra- maleaic anhydride, and trimesic acid, and the like or mixtures thereof.
  • multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, citric acid, tartaric acid, 3- hydroxyglutaric acid, pentaerythritol, sorbitol, 1
  • At least one of trimellitic acid, trimellitic anhydride, trimesic acid, pentaerythritol, glycerine, tetra-maleaic anhydride, and trimer acid can be used as the branching agent.
  • the branching monomer may be added to the rigid polyester reaction mixture or blended with the rigid polyester in the form of a concentrate as described, for example, in U.S. Patent Nos. 5,654,347 and 5,696,176.
  • the rigid polyesters useful in the invention can comprise residues of 1 ,4-cyclohexanedimethanol in any amount, included but not limited to at least one of the following amounts: from 0.01 to 100 mole%; from 0.01 to 100 mole%; from 0.01 to 99.99 mole%; from 0.10 to 99 mole%; from 0.10 to 99 mole%; from 0.10 to 95 mole%; from 0.10 to 90 mole%; from 0.10 to 85 mole%; from 0.10 to 80 mole%; from 0.10 to 70 mole%; from 0.10 to 60 mole%; from 0.10 to 50 mole%; from 0.10 to 40 mole%; from 0.10 to 35 mole%; from 0.10 to 30 mole%; from 0.10 to 25 mole%; from 0.10 to 20 mole%; from 0.10 to 15 mole%; from 0.10 to 10 mole%; from 0.10 to 5 mole%; from 1 to 100 mole%; from 1 to 99 mole%; 1 to 95 mole%; from 1 to
  • the rigid polyesters useful in the invention can be any of the traditional compositions described as polyethylene terephthalate (PET), acid-modified polyethylene terephthalate (PETA), glycol modified PET (PETG), glycol modified poly(cyclohexylene dimethylene terephthalate) (PCTG), poly(cyclohexylene dimethylene terephthalate) (PCT), acid modified poly(cyclohexylene dimethylene terephthalate) (PCTA), and any of the foregoing polymers modified with 2,2,4,4-tetramethylcyclobutane-1 ,3-diol.
  • the rigid polyester useful in the polyester compositions of the invention comprises residues of isosorbide.
  • the isosorbide polymer can also comprise residues of ethylene glycol and/or cyclohexanedimethanol.
  • the rigid polyester comprises residues of isosorbide and 1 ,4-cyclohexanedimethanol and optionally, ethylene glycol.
  • the rigid polyester comprises residues of isosorbide and ethylene glycol and optionally, 1 ,4-cycloehexanedimethanol.
  • terephthalic acid can be present in an amount of from 70 to 100 mole%.
  • Modifying dicarboxylic acids may be present in an amount of up to 30 mole%.
  • the modifying dicarboxylic acid can be isophthalic acid.
  • Aliphatic diacids can also be present in the terephthalic acid based polyesters of the invention.
  • the polyester compositions of the invention can include rigid copolyesters comprising residues of 70 to 100 mole% terephthalic acid, and optionally, 0.01 to 30 mole%, or 0.01 to 20 mole%, or 0.01 to 10 mole%, or 0.01 to 5 mole% of isophthalic acid, or esters there and/or mixtures thereof.
  • the polyester compositions of the invention can include rigid copolyesters comprising 1 ,4-cyclohexanedimethanol and, optionally, ethylene glycol.
  • the polyester compositions of the invention can include rigid copolyesters comprising residues of 99 to 100 mole% terephthalic acid and residues of 99 to 100 mole% 1 ,4-cyclohexanedimethanol.
  • the rigid polyester comprises residues of diethylene glycol.
  • the rigid polyester comprises residues of terephthalic acid, isophthalic acid and 1 ,4-cyclohexanedimethanol.
  • the rigid polyester comprises from 50 mole% to 99.99 mole% of residues of 1 ,4- cyclohexanedimethanol, 0.01 mole% to 50 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid. In embodiments, the rigid polyester comprises from 80 mole% to 99.99 mole% of residues of 1 ,4-cyclohexanedimethanol and 0.01 mole% to 20 mole% of residues of ethylene glycol.
  • the rigid polyester comprises from 90 mole% to 99.99 mole% of residues of 1 ,4-cyclohexanedimethanol and 0.01 mole% to 10 mole% of residues of ethylene glycol. In embodiments, the rigid polyester comprises from 95 mole% to 99.99 mole% of residues of 1 ,4- cyclohexanedimethanol and 0.01 mole% to 5 mole% of residues of ethylene glycol.
  • the rigid polyester comprises from 95 mole% to 99.99 mole% of residues of 1 ,4-cyclohexanedimethanol, 0.01 mole% to 10 mole% of residues of ethylene glycol, from 90 mole% to 100 mole% of residues of terephthalic acid, and 0.01 to 10 mole% of residues of isophthalic acid.
  • the rigid polyester comprises from 95 mole% to 100 mole% of residues of 1 ,4-cyclohexanedimethanol, 0.01 mole% to 5 mole% of residues of ethylene glycol, from 95 mole% to 100 mole% of residues of terephthalic acid, and 0.01 to 5 mole% of residues of isophthalic acid.
  • the rigid polyester comprises from 20 mole% to less than 50 mole% of residues of 1 ,4- cyclohexanedimethanol, greater than 50 mole% to 80 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid. In embodiments, the rigid polyester comprises from 20 mole% to 40 mole% of residues of 1 ,4-cyclohexanedimethanol, 60 mole% to 80 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid.
  • the rigid polyester comprises from 0.01 to 15 mole% 2, 2,4,4- tetramethyl-1 ,3-cyclobutanediol residues. In embodiments, the rigid polyester comprises from 15 to 40 mole% 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol residues and from 60 to 85 mole% 1 ,4-cyclohexanedimethanol residues.
  • the rigid polyester comprises from 20 to 40 mole% 2, 2,4,4- tetramethyl-1 ,3-cyclobutanediol residues and from 60 to 80 mole% 1 ,4- cyclohexanedimethanol residues. In embodiments, the rigid polyester comprises from 20 to 30 mole% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues and from 70 to 80 mole% 1 ,4-cyclohexanedimethanol residues and 70 to 100 mole% terephthalic acid residues.
  • the rigid polyester can comprise from 0.01 to 99.99 mole% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues and 99.99 to 0.01 mole% 1 ,4-cyclohexanedimethanol residues, or from 20 to 50 mole% 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol residues and 50 to 80 mole% 1 ,4- cyclohexanedimethanol residues, or from 20 to less than 50 mole% 2, 2,4,4- tetramethyl-1 ,3-cyclobutanediol residues and greater than 50 to 80 mole% 1 ,4- cyclohexanedimethanol residues, or from 15 to 40 mole% 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol residues and 60 to 85 mole% 1 ,4-cyclohexanedimethanol residues, or from 20 to
  • the rigid polyester can comprise 20 to 40 mole% 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol residues and 60 to 80 mole% 1 ,4- cyclohexanedimethanol residues and 70 to 100 mole% terephthalic acid residues, based on a total of 100 mole% acid residues and a total of 100 mole% diol residues.
  • the rigid polyester of the invention may can include copolyesters comprising diacids, wherein at least one diacid is selected from the group consisting of terephthalic acid and isophthalic acid, or esters there and/or mixtures thereof; and a diol component comprising: (a) from 20 to less than 50 mole% of 1 ,4-cyclohexanedimethanol and residues from greater than 50 to 80 mole% ethylene glycol residues; or from 20 to 40 mole% of 1 ,4- cyclohexanedimethanol residues and from 60 to 80 mole% ethylene glycol residues, or from 20 to 40 mole% of 1 ,4-cyclohexanedimethanol residues and from 60 to 80 mole% ethylene glycol residues, or from 25 to 40 mole% of 1 ,4- cyclohexanedimethanol residues and from 60 to 75 mole% ethylene glycol residues, or from 25 to 35 mole
  • the diol component can comprise from 18 mole% to 35 mole%, or from 20 mole% to 35 mole%, of residues of isosorbide; from 40 mole% to 58 mole%, or from 45 mole% to 55 mole%, of residues of 1 ,4-cyclohexanedimethanol; and, from 15 mole% to 25 mole%, or from 20 mole% to 25 mole%, of residues of ethylene glycol.
  • the rigid polyester can comprise residues of a branching agent.
  • the polyester or the polyester component of said polyesterether comprises 0.01 to 5 mole% or 0.01 to 4 mole% or from 0.01 to 3 mole% or from 0.01 to 2 mole% or from 0.01 to about 1 .5 mole% or from 0.01 to 1 mole% or from 0.1 to 5 mole% or 0.1 to 4 mole% or from 0.1 to 3 mole% or from 0.1 to 2 mole% or from 0.1 to about 1 .5 mole% or from 0.1 to 1 mole or from 0.5 to 5 mole% or 0.5 to 4 mole% or from 0.5 to 3 mole% or from 0.5 to 2 mole% or from 0.5 to about 1 .5 mole% or from 0.5 to 1 mole% or from 1 to 5 mole% or 1 to 4 mole% or from 1 to 3 mole% or from 1 to 2 mole% or from 0.5 to about 1 .5 mole% or from 0.5 to 1 mole% or from 1 to 5 mo
  • the polyfunctional branching agent has at least 3 carboxyl or hydroxyl groups.
  • the polyfunctional branching agent comprises residues of trimellitic acid, trimellitic anhydride, trimesic acid, trimethyol ethane, trimethyolpropane, pentaerythritol, glycerine, tetra-maleaic anhydride, and trimer acid.
  • the polyfunctional branching agent comprises residues of trimellitic anhydride, trimethyolpropane, pentaerythritol, glycerine, tetra-maleaic anhydride.
  • the polyester elastomer used in the polyester composition of this invention can be any known in the art having a Tg of 50°C or less.
  • the polyester elastomer comprises at least one dicarboxylic acid; at least one dihydroxy alcohol; at least one polyol; and optionally a multi- functionalized acid, alcohol or anhydride branching agent; wherein the polyester elastomer has a Tg of 50°C or less.
  • the Tg of the polyester elastomer can be 45°C or less, or 40°C or less, or 35°C or less, 30°C or less, 25°C or less, 20°C or less, 15°C or less, 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10°C or less, -15°C or less, -20°C or less, -25°C or less, -30C or less, -35C or less, -40C or less, -50C or less, -55C or less, - 60C or less, -70C or less, and -80 or less.
  • the polyester elastomer can have a flexural modulus ranging from 25 Mpa to 1000 Mpa, 50 Mpa to 1000 Mpa, 100 Mpa, to 1000 Mpa, 150 Mpa to 1000 Mpa, 200 Mpa to 1000 Mpa, 250 Mpa to 1000 Mpa, 300 Mpa to 1000 Mpa, 350 Mpa to 1000 Mpa, 400 Mpa to 1000 Mpa, 450 Mpa to 1000 Mpa, 500 Mpa to 1000 Mpa, 550 Mpa to 1000 Mpa, 600 Mpa to 1000 Mpa, 650 Mpa to 1000 Mpa, 700 Mpa to 1000 Mpa, 750 Mpa to 1000 Mpa, 800 Mpa to 1000 Mpa, 25 Mpa to 9000 Mpa, 50 Mpa to 900 Mpa, 100 Mpa, to 900 Mpa, 150 Mpa to 900 Mpa, 200 Mpa to 900 Mpa,
  • a diacid selected from the group consisting of cyclohexane dicarboxylic acid (CHDA), dimethylcyclohexane dicarboxylic acid (DMCD), and combinations thereof; b. 75 to 92 mole percent of cyclohexane dimethanol and 8 to 25 mole percent of polytetramethylene ether glycol based on the total glycol content of the polyester; c.
  • the polyester composition comprises at least one primary antioxidant of the hindered phenol type, at least one secondary antioxidant in the phosphite family and at least one chain extending agent with epoxide functionalities.
  • the free radicals can also, in the presence of oxygen, react to create hydroxy, peroxy, peroxide, and mono and di-hydroxy terephthalates which are also very reactive and will lead to further polymer degradation.
  • R3, R4, R5 are independently H or an organic residue. wherein: each X is independently selected from the group consisting of C1-C20 alkyl and C1-C20 alkenyl;
  • the primary antioxidant is selected from at least one hindered phenol, at least one secondary aryl amine, or a combination thereof.
  • the at least one hindered phenol useful in the polyestercompositions of the invention comprises one or more compounds selected from triethylene glycol bis[3-(3-t-butyl-5-methyl-4- hydroxyphenyl)propionate], 1 ,6-hexanediolbis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t- butylanilino)-1 ,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], 2,2-thiodiethylene bis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4
  • the phenolic antioxidants useful in the polyester compositions of the invention can be octadecyl-3-(3,5-di-tert.butyl-4- hydroxyphenyl)-propionate (CAS number 2082-79-3; pentaerythritol tetrakis[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate] (CAS# 6683-198, otherwise known as IrganoxTM 1010); N,N’-hexane-1 ,6-diyl-bis[3-(3,5-ditert-butyl-4- hydroxyphenyl]propionamide] (CAS# 23128-747-, lrganoxTM1098); benzenepropanoic acid 3,5-bis(1 ,1 -dimethylethyl)-4-hydroxyoctadecyl ester (lrganoxTM1076).
  • the phenolic antioxidant is present in the amount of from 0.01 to 5 weight%, or from 0.01 weight% to 4 weight%, or from 0.01 weight% to 3 weight%, or from 0.01 weight% to 2.0 weight%, or from 0.01 weight% to 1 .0 weight%, or from 0.01 weight% to 0.90 weight%, or from 0.01 weight% to 0.80 weight%, or from 0.01 weight% to 0.75 weight%, or from 0.01 to 0.70 weight%, or from 0.01 to 0.60 weight%, or from 0.01 weight% to 0.50 weight% or from 0.10 weight% to 5 weight%, or from 0.10 weight% to 4 weight%, or from 0.10 weight% to 3 weight%, or from 0.10 weight% to 2.0 weight%, or from 0.10 weight% to 1 .0 weight%, or from 0.10 weight% to 0.90 weight%, or from 0.10 weight% to 0.80 weight%, or from 0.10 weight% to 0.75 weight%, or from 0.10 weight% to 0.70 weight%, or from 0.10 weight% to 0.
  • the primary antioxidant can be present (total loading) in the polyester compositions of the invention in the amount of from 0.01 weight% to 5 weight% or from 0.01 weight% to 4 weight% or from 0.01 weight to 3 weight% or from 0.01 to 2.0 weight% or from 0.01 to 1 .5 or from 0.01 to 1 weight% or from 0.01 to 0.75 weight% or from 0.01 to 0.50 weight% or from or from 0.10 weight% to 5 weight% or from 0.10 weight% to 4 weight% or from 0.10 weight to 3 weight% or from 0.10 to 2.0 weight% or from 0.10 to 1 .5 or from 0.10 to 1 weight% or from 0.10 to 0.75 weight% or from 0.10 to 0.60 weight% or from, based on the total weight of the polymer composition equaling 100 weight%.
  • the primary antioxidant can be present (total loading) in the polyester compositions of the invention in the amount of from 0.01 to 1.0 weight%, 0.01 to 0.90 weight% or from 0.10 to 1.0 weight%, 0.10 to 0.90 weight% from 0.20 to 1 .0 weight%, 0.20 to 0.90 weight% from 0.25 to 1.0 weight% or 0.25 to 0.90 weight%, based on the total weight of the polyester composition.
  • a “hindered amine” as used herein refers to a compound or polymer comprising a substituted piperidinyl group.
  • the substituted piperidinyl group may comprise 1 , 2, 3, 4, 5, 6, 7, 8, or more substituents, such as, e.g., an alkyl, alkenyl, or alkoxy group.
  • the substituted piperidinyl group comprises 1 or 2 substituents (e.g., a C1 -C20 alkyl or C1 -C20 alkenyl group) at the 2- and/or 6-position of the piperidine ring.
  • the hindered amine light stabilizer is a polymer and comprises one or more (e.g., 1 , 2, 3, 4, 5, or more) substituted piperidinyl group(s) per repeating unit of the hindered amine light stabilizer.
  • an acrylic composition of the present invention may comprise a hindered amine light stabilizer that comprises one or more (e.g., 1 , 2, 3, 4, or more) 2, 2,6,6- tetraalkylpiperidinyl group(s) in the hindered amine light stabilizer.
  • the hindered amine light stabilizer may be a polymeric or oligomeric hindered amine light stabilizer, and may comprise one or more (e.g.,
  • Example hindered amine light stabilizers include, but are not limited to, those under the tradename Tinuvin® commercially available from BASF, such as, e.g., Tinuvin® PA 123, Tinuvin® 371 , Tinuvin® 111 and/or Tinuvin®
  • the polyester composition of this invention contains at least one secondary antioxidant.
  • the secondary antioxidant can be any that is known in the art. Molecular weight, reactivity and hydrolytic stability can be considered in the choice of secondary antioxidant. Some examples of secondary antioxidants are thiodipropionates, phosphites and metal salts. Thiopropionates are mostly used in polyolefins and are of limited use in condensation polymers. Phosphites are the most typically used in thermoplastics. A typical phosphite antioxidant structure is shown below: wherein R is selected from Ci to C2o_ alkyl groups. [000119] Molecular weight, reactivity and hydrolytic stability must all be considered in the choice of secondary antioxidant.
  • the secondary antioxidant can also be selected from an organophosphate or thioester, or a combination thereof.
  • the secondary antioxidant comprises one or more compounds selected from tris(nonyl phenyl)phosphite [WestonTM399, available from Addivant, Connecticut), tetrakis(2,4-di-tert-butylphenyl) [1 ,1 - biphenyl]-4,4'-diylbisphosphonite, tris(2,4-di-tert-butylphenyl)phosphite
  • the polyester composition of the invention contains at least one phosphite comprising an aryl phosphite or an aryl monophosphite.
  • aryl monophosphite refers to a phosphite stabilizer which contains:(1 ) one phosphorus atom per molecule;
  • the aryl monophosphite contains C1 to C20, or C1 to C10, or C2-C6 alkyl substituents on at least one of the aryloxide groups.
  • C1 to C20 alkyl substituents include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and iso-butyl, tertiary butyl, pentyl, hexyl, octyl, nonyl, and decyl.
  • Preferred aryl groups include but are not limited to phenyl and naphthyl.
  • the phosphites useful in the invention comprise tertiary butyl substituted aryl phosphites.
  • the aryl monophosphite comprises at least one of triphenyl phosphite, phenyl dialkyl phosphites, alkyl diphenyl phosphites, tri(nonylphenyl)phosphite, tris-(2,4-di-t- butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, (believed to be lrgafosTM38, available from BASF), 2,2,2- nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1 ,1 -biphenyl-diyl)phosphite (believed to be lrgafos
  • the aryl monophosphite is selected from one or more of tris-(2,4-di-t- butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, and 2,2,2-nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1 , 1 -biphenyl-diyl)phosphite.
  • an aryl monophosphite useful in the invention is tris-(2,4- di-t-butylphenyl)phosphite.
  • the secondary antioxidant is present in the polyester composition in an amount from about 0.01 weight% to about 3.0 weight%, or from 0.01 weight% to 2 weight%, or from 0.01 weight% to 1 weight% or from 0.10 weight% to 5 weight%, or from 0.10 weight% to 4 weight%, or from 0.10 weight% to 3 weight%, or from 0.10 weight% to 2 weight%, or from 0.10 weight% to 1 weight%, or from 0.25 weight% to 1 weight%, or from 0.25 weight% to 0.75 weight%, based on the total weight of the polymer composition.
  • the secondary antioxidant is present in the polyester composition in an amount from about 0.01 weight% to about 2.5 weight%.
  • the secondary antioxidant is present in an amount from about 0.5 weight% to about 2.5 weight%. In yet another aspect, the secondary antioxidant is present in an amount from about 0.5 weight% to about 2.0 weight% In still another aspect, the secondary antioxidant is present in an amount from about 0.05 weight% to about 0.75 weight%. In still another aspect, the secondary antioxidant is present in an amount from about 0.05 weight% to about 0.75 weight%. In certain embodiments, the secondary antioxidant is present in an amount from about 0.1 weight% to about 1.0 weight%, or about 0.2 weight% to about 0.8 weight%, or 0.25 to 0.75 weight%. In one embodiment, the secondary antioxidant is present in an amount from about 0.35 weight% to about 0.65 weight%.
  • the weight ratio of primary antioxidant to secondary antioxidant present in the polyester compositions useful in the invention can be from 5:1 to 1 :5. In certain aspects of the invention, the weight ratio of primary antioxidant to secondary antioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1 :1 or 1 :2 or 1 :3 or 1 :4 or 1 :5. In certain aspects of the invention, the weight ratio of primary to secondary antioxidant is 1 :1 or 1 :2 or 1 :3 or 1 :4 or 1 :5. In certain aspects of the invention, the weight ratio of primary antioxidant to secondary antioxidant is 2:1 to 1 :2, e.g., 2:1 .
  • the weight ratio of primary antioxidant to secondary antioxidant is in the range from 1.1 :1 to 4:1 , or 1 .2:1 to 4:1 , or 1 .5:1 to 4:1 , or 1 .6:1 to 4:1 , or 1 .8:1 to 4:1 , or 2:1 to 4:1 , or 1.1 :1 to 3:1 , or 1 .2:1 to 3:1 , or 1 .5:1 to 3:1 , or 1 .6:1 to 3:1 , or 1 .8:1 to 3:1 , or 2:1 to 3:1 , 1.1 :1 to 2.5:1 , or 1 .2:1 to 2.5:1 , or 1 .5:1 to 2.5:1 , or 1 .6:1 to 2.5:1 , or 1 .8:1 to 2.5:1 , or 2:1 to 2.5:1 .
  • the polyester compositions of the invention can comprise at least one chain extending agent.
  • Suitable chain extending agents include, but are not limited to, multifunctional (including, but not limited to, bifunctional) isocyanates, multifunctional epoxides, including for example, and phenoxy resins.
  • the chain extending agents have epoxide dependent groups.
  • the chain extending additive can be one or more styrene- acrylate copolymers with epoxide functionalities.
  • the chain extending additive can be one or more copolymers of glycidyl methacrylate with styrene.
  • Chain extending additives include compounds such as bisanhydrides, bisoxaolines, and bisepoxides which react with -OH or -COOH end groups caused by hydrolytic degradation. Chain extending additives can also be added during melt processing to build molecular weight through ‘reactive extrusion’ or ‘reactive chain coupling’. Another effective type of chain extending additive are styrene-acrylate copolymers with epoxide functionalities.
  • chain extending agents are added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, chain extending agents can be incorporated by compounding or by addition during conversion processes such as injection molding or extrusion.
  • the amount of chain extending agent used can vary depending on the specific monomer composition used and the physical properties desired but is generally about 0.01 percent by weight to about 10 percent by weight, 0.1 percent by weight to about 10 percent by weight, from about 0.01 to about 5 percent by weight, from about 0.1 to about 5 percent by weight, from about 0.01 percent by weight to about 3 percent by weight, from about 0.1 to about 3 percent by weight, from about 0.01 percent by weight to about 2 percent by weight, from about 0.1 to about 2 percent by weight, from about 0.01 percent by weight to about 1 percent by weight, from about 0.1 to about 1 percent by weight, from about 0.01 percent by weight to about 0.5 percent by weight, and from about 0.1 to about 0.5 based on the total weight of the polyester.
  • Chain extending additives can also be added during melt processing to build molecular weight through ‘reactive extrusion’ or ‘reactive chain coupling or any other process known in the art.
  • Chain extending agents useful in the invention can include, but are not limited to, copolymers of glycidyl methacrylate (GMA) with alkenes, copolymers of GMA with alkenes and acrylic esters, copolymers of GMA with alkenes and vinyl acetate, copolymers of GMA and styrene.
  • Suitable alkenes comprise ethylene, propylene, and mixtures of two or more of the foregoing.
  • Suitable acrylic esters comprise alkyl acrylate monomers, including, but not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations of the foregoing alkyl acrylate monomers.
  • the acrylic ester can be used in an amount of 15 weight% to 35 weight%, based on the total amount of monomer used in the copolymer, or in any other range described herein.
  • vinyl acetate can be used in an amount of 4 weight% to 10 weight% based on the total amount of monomer used in the copolymer.
  • the chain extending additive comprises acrylic esters comprising monomers selected from alkyl acrylate monomers, including, but not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations thereof.
  • the chain extending additive is a copolymer comprising at least one acrylic ester and styrene.
  • Illustrative examples of suitable chain extending agents comprise ethylene-glycidyl acrylate copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-vinyl acetate copolymers, ethylene-glycidyl methacrylate-alkyl acrylate copolymers, ethylene-glycidyl methacrylate-methyl acrylate copolymers, ethylene-glycidyl methacrylate-ethyl acrylate copolymers, and ethylene-glycidyl methacrylate-butyl acrylate copolymers.
  • Examples of useful chain extending agents include but are not limited to Joncryl 4368, JoncrylTM4468 (copolymers of glycidyl methacrylate with styrene), JoncrylTM4368, JoncrylTM4470, JoncrylTM4370, JoncrylTM 4400, JoncrylTM4300, JoncrylTM4480, JoncrylTM4380, JoncrylTM4485, JoncrylTM4385, and mixtures thereof commercially available from BASF Corporation, New Jersey.
  • the chain extending agents can be styrene- acrylate copolymers with glycidyl groups.
  • the chain extending agent can be a copolymer of glycidyl methacrylate and styrene.
  • the polymeric chain extending agent can have an average of greater than or equal to 2 pendant epoxy groups per molecule, greater than or equal to 3 pendant epoxy groups per molecule; or an average of greater than or equal to 4 pendant epoxy groups per molecule; or an average of greater than or equal to 5 pendant epoxy groups per molecule; or an average of greater than or equal to 6 pendant epoxy groups per molecule; or an average of greater than or equal to 7 pendant epoxy groups per molecule; or more specifically, an average of greater than or equal to 8 pendant epoxy groups per molecule, or, more specifically, an average of greater than or equal to 11 pendant epoxy groups per molecule, or, more specifically, an average of greater than or equal to 15 pendant epoxy groups per molecule, or, more specifically, an average of greater than or equal to 17 pendant epoxy groups per molecule.
  • the chain extending agent can be present (total loading) in the polymer composition of the invention in the amount of from 0.25 weight% to 0.75 weight%, or from 0.30 weight% to 0.70 weight%, or from 0.4 weight% to 0.6 weight%.
  • the chain extending agent is present (total loading) in the polyester composition of the invention in the amount of from 0.01 weight% to 1 .5 weight% or from 0.10 weight% to 1 weight% or from based on the total weight of the polyester composition.
  • the weight ratio of chain extending agent to primary antioxidant present in the polyester compositions useful in the invention can be from 5:1 to 1 :5.
  • the weight ratio of chain extending agent to primary antioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1 :1 or 1 :2 or 1 :3 or 1 :4 or 1 :5.
  • the weight ratio of chain extending agent to primary antioxidant is 3:1 to 1 :2, or 2.5-3:1 .
  • the weight ratio of chain extending agent to primary antioxidant is 1 :2 or 3:1 .
  • the weight ratio of chain extending agent to secondary antioxidant present in the polyester compositions useful in the invention can be from 5:1 to 1 :5.
  • the weight ratio of chain extending agent to secondary antioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1 :1 or 1 :2 or 1 :3 or 1 :4 or 1 :5.
  • the weight ratio of chain extending agent to secondary antioxidant is 3:1.
  • the weight ratio of chain extending agent to secondary antioxidant is 1 :1 or 1.5:1 or 1.3:1.
  • the weight ratio of chain extending agent to secondary antioxidant is 1 :1 to 3:1 , or 1 :1 to 2:1.
  • the polyester composition comprises: (1 ) at least one hindered phenolic antioxidant that comprises one or more compounds selected from pentaerythritol tetrakis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)- propionate, N,N’-hexane-1 ,6-diyl-bis[3-(3,5-ditert-butyl-4- hydroxyphenyl)propionamide, benzenepropanoic acid 3,5-bis(1 ,1 - dimethylethyl)-4-hydroxyoctadecyl ester, and octadecyl-3-(3,5-di-tert.butyl-4- hydroxyphenyl)-propionate (CAS number 2082); (2) at least one phosphite that is chosen from
  • the polyester composition comprises at least one hindered phenolic antioxidant that is pentaerythritol tetrakis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate; at least one phosphite that is tris(2,4-di-tert- butylphenyl)phosphite; and at least one chain extending agent that is JoncrylTM4468 additive.
  • hindered phenolic antioxidant that is pentaerythritol tetrakis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate
  • at least one phosphite that is tris(2,4-di-tert- butylphenyl)phosphite
  • at least one chain extending agent that is JoncrylTM4468 additive.
  • a primary antioxidant is incorporated in the hindered phenol family, i.e., lrganox tm 1010 commercially available from BASF Corporation, New Jersey, in the amounts of 0.01 to about 2.0 % by weight, a secondary antioxidant in the phosphite family, i.e, lrgafosTM168 commercially available from BASF Corporation, New Jersey, in the amounts of 0.01 to 2.0 % by weight, and a chain extending agent in the styrene-acrylate copolymer family, i.e., JoncrylTM4468 commercially available from BASF Corporation, New Jersey, in the amounts from .01 to 2.0 % by weight into a polyester or copolyester.
  • lrganox tm 1010 commercially available from BASF Corporation, New Jersey
  • a secondary antioxidant in the phosphite family i.e, lrgafosTM168 commercially available from BASF Corporation, New Jersey
  • the polyester composition comprises (1 ) at least one phenolic antioxidant in the amount of from 0.01 weight% to 2.0 weight%, (2) at least one phosphite in the amount of from 0.10 weight% to 1 .0 weight%, and (3) said chain extending agent in the amount of from 0.25 weight% to 2.0 weight percent, based on the total weight of the polyester composition.
  • the polyester composition comprises (1 ) at least one phenolic antioxidant in the amount of from 0.10 weight% to 1.5 weight%, or from 0.10 weight% to 1 .0 weight%, or from 0.50 weight% to 1 .5 weight%, or from 0.75 weight% to 1 .25 weight%, (2) at least one phosphite in the amount of from 0.10 weight% to 1.0 weight%, or 0.10 weight% to 0.75 weight%, or from 0.25 weight% to 0.75 weight%, and (3) at least one chain extending agent in the amount of from 0.10 weight% to 1 .0 weight%, or 0.25 weight% to 1 .0 weight, or from 0.25 weight% to 0.75 weight% based on the weight of the polyester composition.
  • the polyester composition comprises (1 ) at least one phenolic antioxidant in the amount of from 0.75 weight% to 1 .25 weight%, (2) at least one phosphite in the amount of 0.10 weight% to 1.0 weight%, or from 0.25 weight% to 0.75 weight%, and (3) at least one chain extending agent in the amount of 0.10 weight% to 1.0 weight%, or from 0.25 weight% to 0.75 weight% based on the weight of the polyester composition.
  • the polyester composition comprises a primary antioxidant in the hindered phenol family, preferably Irganox ® 1010 commercially available from BASF, in the amounts of 0.01 to about 2.0 % by weight, a secondary antioxidant in the phosphite family, preferably Irgafos ® 168 commercially available from BASF, in the amounts of 0.01 to 0.5 % by weight or Doverphos ® 9228 in the amounts of 0.01 to 0.5 %, and a chain extending agent in the styrene-acrylate copolymer family, preferably Joncryl ® 4468 commercially available from BASF, in the amounts from 0.01 to 2.0 % by weightwherein the % by weight is based on the weight of the polyester composition.
  • a primary antioxidant in the hindered phenol family preferably Irganox ® 1010 commercially available from BASF
  • a secondary antioxidant in the phosphite family preferably Irgafos ® 168 commercially available from BASF,
  • the present invention can employ a primary antioxidant of the hindered phenol type, a secondary antioxidant in the phosphite family and a chain extending agent with epoxide functionalities.
  • the weight percentages specified herein can also be combined with the ratios of additives to each other that are specified. They can also be combined with the particular classifications of additives that are described herein. The weight ratios of one additive to another or weight percentages of additives are calculated based on the weight of the additive compared to the total weight of the polyester composition at the time of loading the additive into the composition (total loading) wherein all components equal 100 weight%.
  • the polyester composition comprises at least one rigid polyester, at least one polyester elastomer, from about 0.1 to about 2% by weight of at least one hindered phenol primary antioxidant, from about 0.01 to about 0.5 % by weight of at least one phosphite secondary antioxidant, and from about 0.01 to about 2.0% by weight of at least one styrene-acrylate cpolymer; wherein the weight percent is based on the total weight of the polyester composition.
  • the stabilizer compositions useful in the invention can improve or maintain color, reduce the loss of number average molecular weight, and/or inherent viscosity, and/or reduce the total number of carboxyl end groups, under the conditions as specified herein.
  • thermal oxidative and hydrolytic stability can be measured by any method known in the art, for example, through using gel-permeation chromatography and through visual color observations, colorimeter, and/or spectrophotometry. Viscosity improvements can be measured by any method known in the art, for example, using parallel plate rheometry or inherent viscosity measures. Numbers of carboxyl end groups can be measured by titration.
  • polyester compositions useful in this invention may also contain at least one other additive selected from colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, other stabilizers (including but not limited to, UV stabilizers, thermal stabilizers, hydrolytic stabilizers), fillers, and impact modifiers.
  • additives selected from colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, other stabilizers (including but not limited to, UV stabilizers, thermal stabilizers, hydrolytic stabilizers), fillers, and impact modifiers.
  • the polymer compositions can contain from 0.01 to 25% by weight or 0.01 to 20% by weight or 0.01 to 15% by weight or 0.01 to 10% by weight or 0.01 to 5% by weight of the total weight of the polyester composition of common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
  • common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
  • Examples of 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 copolymer impact modifiers and various acrylic core/shell type impact modifiers.
  • UV additives can be incorporated into articles of manufacture through addition to the bulk, through application of a hard coat, or through coextrusion of a cap layer. Residues of such additives are also contemplated as part of the polymer composition.
  • Reinforcing materials may be useful in the polyester 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 are glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • the polyester compositions of this invention can be blended with any other polymers known in the art.
  • the polyester compositions of the invention can comprise at least one polymer chosen from at least one of the following: poly(etherimides), polyphenylene oxides, poly(phenylene oxide)/polystyrene blends, polystyrene resins, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly(ester- carbonates), polycarbonates, polysulfones, polysulfone ethers, and poly(ether- ketones).
  • certain additional polymers other than the ones described in the polyester compositions of the invention can be present in an amount of 50 weight% or less, or 40 weight% or less, or 30 weight% or less, or 20 weight% or less, or 10 weight% or less, or 5 weight% or less; in another embodiment, 0.01 to 50 weight%, or 1 to 50 weight%, or 5 to 50 weight%, or 0.01 to 40 weight%, or 0.01 to 30 weight% or 0.01 to 20 weight%, or 0.01 to 10 weight% or 0.01 to 5 weight%.
  • the polyester compositions of the invention can comprise at least one other polymer.
  • the at least one other polymer is selected from liquid crystalline polyesters/amides/imides, polyesteramides, polyimides, polyetherimides, polyurethanes, polyureas, polybenzimidazole, polybenzoxazoles, polyimines, polycarbonates, other polyesters, other copolyesters, and polyamides.
  • the polyester composition does not include polycarbonate.
  • the polyester composition does not include bisphenol polycarbonate.
  • the polyester composition does not include polybutylene terephthalate.
  • the polyester composition does not include polyarylene ethers.
  • the polyester composition does not include cellulose esters.
  • the at least one other polymer is present in the composition in the amount of 50 weight% or less, or 40 weight% or less, or 30 weight% or less, or 20 weight% or less, or 10 weight% or less, or 5 weight% or less, based on the total weight of the polyester composition equaling 100 weight%.
  • the at least one other polymer is present in the polyester composition in the amount of 0.01 to 50 weight%, or 1 to 50 weight%, or 5 to 50 weight%, or 0.01 to 40 weight%, or 0.01 to 30 weight% or 0.01 to 20 weight%, or 0.01 to 10 weight% or 0.01 to 5 weight%, based on the total weight of the polyester composition equaling 100 weight%.
  • the polyester compositions described herein do not contain carbon nanotubes.
  • An effective amount of the primary antioxidant, secondary antioxidant, and the chain extending additive can be determined by understanding fitness for use requirements, target properties and/or target criteria for various applications and/or thermoplastic processing conditions and/or when the chosen property is preserved during processing.
  • the polyester composition of this invention can be produced by any method known in the art.
  • blends of the primary antioxidant, secondary antioxidant, chain extending agent, rigid polyester and polyester elastomer can either be prepared directly during the polymerization process or compounded to produce pellets using typical plastics compounding and extrusion techniques.
  • a process to produce a polyester composition comprising contacting a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive to produce a polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • the rigid polyester, the polyester elastomer, the primary antioxidant, the secondary antioxidant, and the chain extending additive additive can be melt compounded in either a twin screw compounding extruder, a single screw extruder, a BanburyTM type mixer or a Farrell Continuous MixerTM to produce a homogenous blend.
  • the rigid polyester and the polyester elastomer melts at 240°C or below, 230°C or below, 220°C or below, 210°C or below, 200°C or below, 190°C or below or 180°C or below.
  • a process to produce a polyester composition comprising extruding a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive in an extrusion zone to produce a polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • the extrusion zone comprises at least one extruder. Examples were previously provided in this disclosure.
  • a process to produce a polyester composition comprising 1) polymerizing at least one dicarboxylic acid and at least one diol; and b) at least one secondary antioxidant to produce a rigid polyester having a Tg greater than 60°C; 2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a Tg less than 0°C, and 3) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less; wherein the polymerizing in steps 1 ) and/or 2) is conducted in the presence of at least one primary antioxidant; and wherein the polymerizing in steps 1) and/or 2) is conducted in the presence of at least one secondary antioxidant.
  • a process to produce a polyester composition comprising 1 ) polymerizing at least one dicarboxylic acid and at least one diol in the presence of a) at least one primary antioxidant; and b) at least one secondary antioxidant to produce a rigid polyester having a Tg greater than 60°C; 2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a Tg less than 0°C, and 3) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to produce a polyester composition comprising 1 ) polymerizing at least one dicarboxylic acid and at least one diol to produce a rigid polyester having a Tg greater than 60°C; 2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol in the presence of a) at least one primary antioxidant; and b) at least one secondary antioxidant to produce a polyester elastomer having a Tg less than 0°C, and 3) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • polyesters and copolyesters of the present invention are readily prepared by methods well known in the art, for example, as described in U.S. Patent No. 2,012,267, incorporated herein by reference in its entirety. More particularly, the reactions for preparing the polyesters are usually carried out at temperatures of about 150° C to about 300° C in the presence of polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, or combinations thereof. The catalysts are typically employed in amounts of 10 to 1000 ppm, based on total weight of the reactants.
  • the primary antioxidant can be in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one rigid polyester, the primary antioxidant, and optionally the secondary antioxidant.
  • the secondary antioxidant can be in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one rigid polyester, the secondary antioxidant, and optionally, the primary antioxidant.
  • the primary antioxidant can in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one polyester elastomer, the primary antioxidant, and optionally, the secondary antioxidant.
  • the secondary antioxidant is in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one polyester elastomer, the secondary antioxidant, and optionally, the primary antioxidant.
  • the amount of primary antioxidant and/or secondary antioxidant in a masterbatch concentrate is that which is sufficient to supply the level of antioxidant as previously described in this disclosure.
  • An article comprising a polyester composition; wherein the polyester composition comprises a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the composition has a enthalpy of melting of 3 cal/gm or less.
  • polyester compositions of this invention can have usefulness in multiple applications.
  • the polyester of the present invention is suitable for use in low shear polymer melt processes such as rotational molding, powder slush molding, powder coating and 3D printing processes.
  • the article of manufacture can comprise at least one light emitting diode (LED) assembly housing, or reflector.
  • the article of manufacture comprises at least one 3D powder or material used to make a different article of manufacture.
  • the article of manufacture is a molded or extruded article.
  • the article of manufacture is a fiber or a filament.
  • the article of manufacture is a film or sheet [000182] Lower shear melt viscosities are very useful for 3-D printing applications where fast polymer flow from the rapid heat up of the polymer from a laser or infrared heat source is helpful to ensuring a well-formed and fused article.
  • HSS High Speed Sintering
  • SLS Selective Laser Sintering
  • IR infrared
  • C02 laser is used to heat the powders.
  • the powders are often held at very high temperatures just below their melting point for up to 24 hours to minimize the heat output from the IR lamp.
  • Polymers held at these high temperatures and times can undergo thermal oxidative degradation and hydrolytic degradation, if they are a condensation polymer. This can cause the molecular weight to drop and the polymer to discolor and render it unrecyclable and un-processable.
  • LED light emitting diodes
  • Compounded plastic materials are used as reflector materials in the construction of LEDs both to provide control over the direction of emitted light as well as to protect the actual diode from damage.
  • These compounded plastic materials can be thermoplastic or thermoset based on the needs of the LED in the application. For example, high power LEDs, with energy input requires >1.0 watts typically use thermoset materials due to the heat generated in use.
  • Lower wattage LEDs can use thermoplastic materials that can be injection molded. These injection molded materials are cheaper to process and can include a range of conventional materials. During the assembly of LEDs, the diode is soldered to the LEAD frame and this soldering process requires that the thermoplastic materials are dimensionally stable during the soldering process. This requires that material to be semi-crystalline with a crystalline melting point in excess of 280°C. Additionally, since these molded thermoplastic parts reflect the LED light from the diode, they can provide high reflectivity during the lifetime of the application. Low color and high color stability, measured via color measurements as described herein, before and after aging, is often used as a proxy for reflectivity.
  • these parts also have high mechanical properties because they protect the diode from damage and survive various processing steps without breaking.
  • the properties of reflectivity and high mechanical strength can be improved by compounding various base resin with other additives.
  • These additives can provide enhanced “whiteness” as is the case for titanium dioxide and they can provide high toughness as is the case for inorganic fillers like glass fiber.
  • Stabilizers and nucleating agents can also be added to improve stability and increase the rate of crystallization respectively. Due to the high demands of the thermoplastic materials in these applications, PCT is currently used in large amounts for the thermoplastic LED applications. PCT has a crystalline melting point of 285°C and is manufactured carefully to produce a material with very low color (high reflectivity).
  • PCT can be compounded with titanium dioxide and glass fiber along with various stabilizers and additives to optimize the performance of this material in these applications.
  • US Patent Application 2007/0213458 discloses the use of PCT compounds in Light-Emitting Diode Assembly Housings. [000186] During the manufacture of injection molded articles, the thermoplastic resin undergoes thermal and shear induced degradation. Additionally, waste material that is not converted into usable parts should be recycled to reduce to overall cost of the material. For these reasons, the compounded thermoplastic material much be stable to processing without significant loss of the original performance. Additionally, the molded parts should maintain high reflectivity and high mechanical strength throughout the lifetime of the application, which in the case of LEDs, could be as long as 20+ years.
  • This invention describes an optimized combination of additives that improves the process robustness of the compounded PCT resins. Improvements in reflectivity are measured via color and color stability using the color measurement as described herein.
  • Reprocessability is measured via inherent viscosity (IV) before and after an extrusion or processing step.
  • the invention further relates to articles of manufacture comprising any of the polyester compositions described above.
  • the methods of forming the polyester compositions into articles of manufacture, fibers, films, molded articles, containers, and sheeting are well known in the art.
  • the polyester compositions are useful in articles of manufacture including, but not limited to, fibers, filaments, films, sheets, containers, 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.
  • 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 polymer compositions and/or polymer blend compositions can be useful in forming fibers, films, light diffusing articles, light diffusing sheets, light reflecting articles, light reflecting sheets, light emitting diodes, 3D powders or other materials, 3D articles containing powders or other materials.
  • the extruded sheet can be further modified using typical fabrication techniques such as thermoforming, cold bending, hot bending, adhesive bonding, cutting, drilling, laser cutting, etc. to create shapes useful for application as light reflectors and/or light diffusers.
  • the light reflector article comprising the polymer compositions of the invention can comprise at least one inorganic light reflecting additive, for example, titanium dioxide, barium sulfate, calcium carbonate or mixtures thereof.
  • polyester compositions of the invention include but are not limited to: (1) membrane backing. It can be a film or a woven or nonwoven (wetlaid or melt blown/melt spun) mat. Improved temperature, chemical resistance, and/or hydrolytic resistance would be relevant to it as well; (2) spun-laid nonwoven webs using processes well known in the art such as meltblowing and spun bond processes, wherein the continuous PCT fiber is spun from a pellet and laid into a nonwoven fabric in a single processing step; dry-laid or wet-laid nonwoven webs using processes well known in the art such as carding or air-laid processes, wherein PCT fiber is first spun in one process, chopped into staple fiber and laid into nonwoven fabric in a secondary step, using dry-laying technologies; Such nonwoven webs can be useful for air and liquid filtration media, particularly those filtration applications which are routinely exposed to high temperatures (80- 200 C) or corrosive chemicals. Wet laid webs is a common method for producing
  • Machine clothing comprising monofilament, multifilament fibers, films or sheet, with improved thermal stability over existing PCT, PCT copolymers and additive formulations, to enable use in high temperature manufacturing environments, including for example belts used in the dryer section of paper and tissue making processes.
  • Dry-laid media can include high temperature and/or chemically resistant bag house filters and variation thereof used to capture pollutants, such as those in in coal burning power plants, and various manufacturing processes.
  • Certain embodiments would include using the polyester compositions of the invention in film application.
  • High temperature processes may include variations of lead free soldering processes on films requiring good registration, flexibility, and/or optical clarity, as standalone or part of a multilayer system that may include inks, coatings, and/or other functionality.
  • wt means "weight”.
  • the inherent viscosity of the polymers, for example, the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.
  • the following examples further illustrate how the compositions of matter of the invention can be made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope thereof. Unless indicated otherwise, parts are parts by weight, temperature is in degrees C or is at room temperature, loading level is measured in units of weight percentage based on the total weight of the initial polymer composition equaling 100 weight%; and pressure is at or near atmospheric.
  • the present invention could have usefulness in multiple applications. Areas that could benefit are applications that are at high temperatures and humidity levels for extended periods of time. These could include applications in the 3D printing of thermoplastic powders, powder coating of metal articles, LED lighting, electrical and electronic, under the hood automotive applications, maritime, aerospace, thermoplastic powder coatings and the chemical process industries, surgical simulation devices, and orthotic and prosthetic devices.
  • a process of making a polyester coated article comprising coating an article with a polyester composition to produce the polyester coated article; wherein the polyester composition comprises a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to coat a surface is providedcomprising : a. providing the polyester composition in powdered form to produce a powdered polyester composition; b.
  • a process to coat a metal article comprising: a. providing the polyester composition in powdered form to produce a powdered polyester composition; b. Spreading the powdered solid polyester composition onto a metal surface; c. Heating the powdered polyester composition on the metal surface to form a molten polyester coating; and d. Cooling the molten polyester coating on the metal surface to form a solid polyester coating on the metal surface.
  • the metal surface can be any type of appliance, such as, dishwasher racks.
  • a process of manufacturing a molded article comprising:
  • polyester composition placing a polyester composition in a mold having mold surfaces; wherein the polyester composition comprises a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the composition has a enthalpy of melting of 3 cal/gm or less;
  • Samples for powder coating were prepared by cryogenically grinding pellets of each formulation in an attrition mill with liquid nitrogen until a particle size of approximately 100 to 150 microns was achieved. This powdered material was then spray coated using an electrostatic coating applicator to cold rolled steel panels. The panels were then heated above the melting point of each formulation to form a film on each panel. Hot Stage Microscope Method:
  • the hot stage microscope method is a method developed to monitor the visual changes in a material with a microscope as the material is subjected to increased temperatures.
  • the system was designed around an existing stereo microscope, the Nikon SMZ1000.
  • a Point Grey Research Flea3 color camera was used to capture images from the microscope’s objective.
  • the camera has a 1/1.8 inch CCD sensor with 1928x1448 pixel resolution with a 3.69 pm pixel size.
  • a 1” CCD C-mount adapter from SPOT Imaging Solutions was used to combine the camera with the microscope.
  • a Linkam DSC 600 hot stage system was used for controlling heating and cooling cycles during experiments. Additionally, a fiber optic halogen lamp system was used for sample illumination. No sample prep was needed, samples were placed as received in 5 mm aluminum DSC pans.
  • a Durometer Type D Hardness method was used on testing instrument Rex Durometer Model OS-1 Stand. The method allows sample to be indented by an indenter on the tip of the instrument, and the load is recorded.
  • Sample dimension The standard ASTM D 2240 type specimen shall be a minimum of 6.0 mm thick
  • test specimen is cut from either a molded flex or tensile bar, and loaded into the cantilever beam for impact.
  • IZOD the bar is held in place such that the energy will be focused on the vertex of the notch.
  • a calibrated hammer is released to swing and impact the mounted specimen, and the energy required to cause the “break” is recorded along with the “break type” - Non-break, Partial, Hinged, and Complete.
  • Partial - A break that presents with less than 10% of the specimen width remaining at the break, and able to support itself above a 90° axis.
  • Hinged - A break that presents with less than 10% of the specimen width remaining at the break, and unable to support itself above a 90° axis.
  • Complete - A break that presents as two pieces completely separated.
  • Tritan® DX4000 - amorphous copolyester obtained from Eastman Chemical Company.

Landscapes

  • 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)

Abstract

L'invention concerne un procédé de production d'une composition de polyester consistant à mettre en contact a) au moins un polyester rigide ; b) au moins un élastomère polyester ; c) au moins un antioxydant primaire ; d) au moins un antioxydant secondaire ; et e) au moins un additif allongeur de chaîne pour produire une composition de polyester ; cette composition de polyester ayant une enthalpie de fusion inférieure ou égale à 3 cal/gm.
PCT/US2022/033735 2021-06-17 2022-06-16 Procédé de fabrication de compositions de polyester/élastomère polyester WO2022266289A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202163202598P 2021-06-17 2021-06-17
US63/202,598 2021-06-17

Publications (1)

Publication Number Publication Date
WO2022266289A1 true WO2022266289A1 (fr) 2022-12-22

Family

ID=84526761

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2022/033735 WO2022266289A1 (fr) 2021-06-17 2022-06-16 Procédé de fabrication de compositions de polyester/élastomère polyester

Country Status (1)

Country Link
WO (1) WO2022266289A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636528A (en) * 1985-09-26 1987-01-13 Pennwalt Corporation Foaming of unsaturated polyester resin at elevated temperatures
US20100292352A1 (en) * 2009-05-18 2010-11-18 Armacell Enterprise Gmbh Preparation and application of chain-extending concentrates for polyester foaming process
US20130210949A1 (en) * 2012-02-10 2013-08-15 Kimberly-Clark Worldwide, Inc. Renewable Polyester Compositions having a Low Density
US20160168374A1 (en) * 2014-12-12 2016-06-16 Eastman Chemical Company Flame retardant copolyester compositions
US20200157342A1 (en) * 2017-07-20 2020-05-21 Eastman Chemical Company Polymer compositions having improved properties of thermal stability, color, and/or flow

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636528A (en) * 1985-09-26 1987-01-13 Pennwalt Corporation Foaming of unsaturated polyester resin at elevated temperatures
US20100292352A1 (en) * 2009-05-18 2010-11-18 Armacell Enterprise Gmbh Preparation and application of chain-extending concentrates for polyester foaming process
US20130210949A1 (en) * 2012-02-10 2013-08-15 Kimberly-Clark Worldwide, Inc. Renewable Polyester Compositions having a Low Density
US20160168374A1 (en) * 2014-12-12 2016-06-16 Eastman Chemical Company Flame retardant copolyester compositions
US20200157342A1 (en) * 2017-07-20 2020-05-21 Eastman Chemical Company Polymer compositions having improved properties of thermal stability, color, and/or flow

Similar Documents

Publication Publication Date Title
US11492484B2 (en) Polymer compositions having improved properties of thermal stability, color, and/or flow
KR101870616B1 (ko) 폴리에스테르 엘라스토머용 난연제 배합물 및 이로부터의 난연처리된 압출 또는 성형 조성물
JP2008163334A (ja) ポリエステル系樹脂組成物及びプラスチック成形品
WO2022266292A1 (fr) Procédé de fabrication d'articles comprenant des compositions d'élastomère de polyester/polyester
WO2022266300A1 (fr) Procédé de fabrication d'articles moulés
WO2022266289A1 (fr) Procédé de fabrication de compositions de polyester/élastomère polyester
WO2022266284A1 (fr) Compositions de polyester/élastomère polyester
WO2022266297A1 (fr) Articles comprenant des compositions de polyester/élastomère polyester
WO2022266299A1 (fr) Procédé de fabrication de compositions élastomères de polyester/polyester
US11629224B2 (en) Polymer compositions comprising crystalline polymers and a stabilizer composition
JP2011132293A (ja) 基板収納容器ガスケット用熱可塑性エラストマー樹脂組成物および基板収納容器用ガスケット成形体
JP5549902B2 (ja) ポリエーテルエステルブロック共重合体組成物
US20220049069A1 (en) Polymer compositions with improved weathering resistance
JP2018168212A (ja) 熱可塑性エラストマー組成物
JP2014133810A (ja) 複合成形体用ポリエステルブロック共重合体樹脂組成物および複合成形体
JPH10287791A (ja) 帯電防止性アクリル系樹脂組成物およびその成形品
JP3212848B2 (ja) 難燃性ポリエチレンテレフタレート系樹脂組成物
WO2024158786A1 (fr) Compositions de copolyester ignifuges
JPH10287739A (ja) 帯電防止用ポリエーテルエステルおよびその製造方法
JP2012126832A (ja) 薄肉成形用ポリエステルブロック共重合体樹脂組成物及び成形体
JPH07304959A (ja) 難燃性ポリマ組成物および成形物品
JP2000053848A (ja) 熱可塑性ポリエステル樹脂組成物
JPH0873717A (ja) 熱可塑性樹脂組成物
JPH0853612A (ja) 難燃性芳香族ポリエステル樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22825791

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22825791

Country of ref document: EP

Kind code of ref document: A1