JPH0380180B2 - - Google Patents

Description

Claim 1: A composition comprising a blend of (a) a fluorinated polyolefin or copolymer thereof and (b) a polyetherimide having the formula: [In the formula, a represents an integer greater than 1, and the group -O
-A< is

【formula】

【formula】

[Formula], R' is hydrogen, lower alkyl group or lower alkoxy group, and Z is (1)

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

and (2) general formula (In the formula, X is −C _y H _2y −,

【formula】

[Formula] One member selected from the group consisting of divalent groups -O- and -S-, q is 0 or 1, and y is 1
R is one member selected from the group consisting of (1) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative, (2 ) alkylene and cycloalkylene groups having 2 to 20 carbon atoms, C ₂ to C ₈ alkylene-terminated polydiorganosiloxanes, and
(3) Formula (In the formula, Q is -O-,

【formula】

[Formula] One member selected from the group consisting of -S - and -C _x H _2x -, where x is an integer from 1 to 5). 2. The composition according to claim 1, wherein the fluorinated polyolefin contains fluorinated polyethylene. 3 Fluorinated polyethylene has a repeating structural formula (In the formula, b is an integer of 50 or more, Y ₁ to _{Y 4} may be the same or different and are selected from the group consisting of hydrogen, chlorine, bromine and fluorine, provided that Y ₁
3. The composition according to claim 2, wherein at least one of ~ _Y4 is fluorine. 4. The composition according to claim 3, wherein at least two of _Y1 to _Y4 are fluorine. 5. The composition according to claim 4, wherein at least three of _Y1 to _Y4 are fluorine. 6. The composition according to claim 5, wherein _Y1 to _Y4 are fluorine. 7 Polyetherimide is the formula is a polyetherimide in which the divalent bonds of -O-Z-O- are 3,3';3,4';4,3' and 4,
A composition according to claim 1 in the 4' position. 8 Z is and R is

【formula】

【formula】

8. A composition according to claim 7, which is selected from the formula: 9 Polyetherimide is the formula 9. The composition according to claim 8, which is a polyetherimide. Description This invention relates to polyetherimide-fluorinated polyolefin blends. These blends have good flexural strength and modulus, and have impact strengths greater than those associated with the polyetherimides of the blends. The blend of the invention has the formula Contains polyetherimide. In the formula, a represents an integer greater than 1, for example, an integer from 10 to 10,000 or more, and the group -O-A< is

【formula】

【formula】

Preferably, the polyetherimide is selected from the formula -O of the latter where R′ is hydrogen as in
-A<, and the divalent bond of the -O-Z-O- group is 3,
3′; 3,4′; 4,3′; or 4,4′ position;
Z is (1)

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 and (2) general formula (In the formula, X is the formula −C _y H _2y −,

【formula】

[Formula] One member selected from the group consisting of divalent groups -O- and -S-, q is 0 or 1, and y is an integer from 1 to 5). is one of the group, R
(1) aromatic hydrocarbon groups having 6 to 20 carbon atoms and halogenated derivatives thereof; (2) alkylene groups and cycloalkylene groups having 2 to 20 carbon atoms;
_C2 - _C8 alkylene-terminated polydiorganosiloxane, and formula (3) (In the formula, Q is -O-,

【formula】

[Formula] is a divalent organic group selected from the group consisting of one member selected from the group consisting of -S - and -C _x H _2x -, where x is an integer from 1 to 5. Particularly preferred polyetherimides for the present invention are polyetherimides in which -O-A< and Z are each

[expression] and

【formula】 and R is

【formula】

【formula】

A polyetherimide selected from the formula: Most preferred are polyetherimides in which R is metaphenylene. As mentioned above, the blends of the present invention also include thermoplastic fluorinated polyolefins. Such thermoplastic fluorinated polyolefins generally have an essentially crystalline structure and a melting point of about 120°C or higher. The fluorinated polyolefin is preferably a polymer of one or more fluorinated monomers containing ethylenically unsaturated bonds and optionally one or more other compounds containing ethylenically unsaturated bonds. The fluorinated monomer can be a perfluorinated monoolefin, such as hexafluoropropylene or tetrafluoroethylene, or a partially fluorinated monoolefin, which may contain other components such as chlorine or perfluoroalkoxy, such as vinylidene fluoride, chloro It can be trifluoroethylene and perfluoroalkyl vinyl ethers (in which case the alkyl group contains up to 6 carbon atoms), such as perfluoro(methyl vinyl ether). Monoolefins are preferably linear or branched chain compounds having terminal ethylenic double bonds and containing less than 6 carbon atoms, especially 2 to 3 carbon atoms. When units derived from monomers other than fluorine-containing monomers are present, their amount is preferably less than 30 mol%, generally 15 mol%.
less than Such other monomers include, for example, olefins containing less than 6 carbon atoms and having terminal ethylenic double bonds, especially ethylene and propylene. Suitable fluorinated olefins have the structural formula (In the formula, b is an integer of 50 or more, Y ₁ to _{Y 4} may be the same or different and are selected from the group consisting of hydrogen, chlorine, bromine or fluorine, provided that Y ₁
~ _Y4 , at least one of which is fluorine). Preferred fluorinated polyethylenes for the present invention include poly(vinyl fluoride), poly(vinylidene fluoride), polytrifluoroethylene, polychlorotrifluoroethylene, polybromotrifluoroethylene, polytetrafluoroethylene and their co-forms. Contains polymers. A particularly preferred fluorinated polyethylene is polytetrafluoroethylene. Other suitable fluorinated polyolefins include polyperfluoropropene, polyperfluorobutadiene, and polyhexafluoropropylene. In particular, polytetrafluoroethylene contains about 76 fluorine
Basic chemical formula (−CF ₂ −CF ₂ −) containing wt% _o
fully fluorinated polyethylene. These polymers are highly crystalline and have crystalline melting points of over 300°C. Commercially available polytetrafluoroethylene is available from EI du Pont de Nimois & Company under the trade name Teflon and from Imperial Chemical Industries under the trade name Fluon. Polychlorotrifluoroethylene and polybromotrifluoroethylene are also available in high molecular weights and can be used in the blends of the present invention. Other preferred fluorinated polyethylenes are vinylidene fluoride homopolymers and copolymers. Poly(vinylidene fluoride) homopolymer is a partially fluorinated polymer with the chemical formula ( _-CH2 - _CF2- ) _o . These polymers are tough linear polymers with crystalline melting points at 170°C. A commercially available homopolymer is available from Pennwalt Chemicals Corporation under the trade name Kynar. As used herein, the term "poly(vinylidene fluoride)" refers not only to normally solid homopolymers of vinylidene fluoride, but also to at least 50 mole percent, preferably at least 70 mole percent, polymerized vinylidene fluoride units, and more preferably at least 70 mole percent polymerized vinylidene fluoride units. Refers to a normally solid copolymer of vinylidene fluoride containing at least about 90 mole percent.
Suitable comonomers are halogenated olefins containing up to 4 carbon atoms such as dichlorodifluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride, perfluoropropene, perfluorobutadiene, chlorotrifluoroethylene, trichloroethylene, tetrafluoroethylene, etc. be. This group of commercially available fluorinated polyolefins includes Viton, commercially available by E.I. Dupont;
A. Copolymers of vinylidene fluoride and hexafluoropropylene such as Vuitton A35 and Vuitton AHV; vinylidene fluoride, hexafluoropropylene and tetrafluoropropylene such as Vuitton B and Vuitton B50 marketed by E.I. Dupont. copolymers of ethylene; and copolymers of vinylidene fluoride and chlorotrifluoroethylene such as Kel-F, commercially available from the Minnesota Mining and Manufacturing Company. include. Polyetherimide has the formula Reaction of any aromatic bis(ether anhydride) of the formula (wherein Z is as described above) with an organic diamine of the formula H ₂ NR-R-NH ₂ (wherein R is as described above) It can be obtained by any method well known to those skilled in the art, including. The aromatic bis(ether acid anhydride) of the above formula includes, for example, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propanedic anhydride;
4,4'-Bis(2,3-dicarboxyphenoxy)diphenyl ether diacid anhydride; 1,3-bis(2,3-dicarboxyphenoxy)benzenedic anhydride; 4,4' -bis(2,3-dicarboxyphenoxy)diphenylsulfide diacid anhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzenedic anhydride; 4,4'-bis( 2,
3-dicarboxyphenoxy) benzophenone diacid anhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfone diacid anhydride; 2,
2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propanedioic anhydride; 4,4'-bis(3,4'-dicarboxyphenoxy)diphenyl ether diacid anhydride; 4,4′-bis(3,4-
dicarboxyphenoxy) diphenylsulfide diacid anhydride; 1,3-bis(3,4-dicarboxyphenoxy)benzenedic anhydride; 1,4-
Bis(3,4-dicarboxyphenoxy)benzenedic anhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenonedic anhydride; 4
-(2,3-dicarboxyphenoxy)-4'-(3,
4-dicarboxyphenoxy)diphenyl-2,
2-propanedic anhydride and the like and mixtures of such dianhydrides. Furthermore, the aromatic bis(ether diacid anhydrides encompassed by the above formula also include coton, em, em,;
Florinsky, F.S. ; Besonov, M.
Rudakov, A., P., et al. (Institute of Heteroorganic Compounds of the Academy of Sciences of the Soviet Union), filed on May 3, 1967, Soviet Patent No. 11, November 1969. No. 257010. Furthermore, diacid anhydrides are shown by M.M.Coton, F.S. Florinsky in Zh.Org.Khin.4(5), 77 (1968). Examples of organic diamines of the above formula include m-phenynediamine, p-phenynediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl Sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2, 4-bis(β-amino-t-butyl)toluene, bis(p-β-amino-t-butylphenyl)ether, bis(p-β-methyl-o-aminopentyl)benzene, 1,3-diamino-4
-isopropylbenzene, 1,2-bis(3-aminopropoxy)ethane, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, bis(4-diaminotoluene)
-aminocyclohexyl)methane, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine,
2,2-dimethylopropylene diamine, octamethylene diamine, 3-methoxyhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,5-dimethylheptamethylene diamine,
3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine, 1,12-octadecanediamine, bis(3-aminopropyl)sulfide, N-methyl-bis(3-aminopropyl)amine, These include hexamethylene diamine, heptamethylene diamine, nonamethylene diamine, decamethylene diamine, bis(3-aminopropyl)tetramethylenedisiloxane, bis(4-aminobutyl)tetramethyldisiloxane, and the like. Generally, well-known solvents such as o-dichlorobenzene, m-cresol/
This can be advantageously carried out using toluene or the like.
Alternatively, a polyetherimide can be produced by simultaneously mixing a mixture of any of the above diacid anhydrides and any of the above diamine compounds and melt-polymerizing both components while heating at a high temperature. Generally about 200-400
Melt polymerization temperatures of 230-300°C can be used. The reaction conditions and proportions of each component can vary widely depending on the desired molecular weight, intrinsic viscosity, and solvent resistance. Generally equimolar amounts of diamine and dianhydride are used for high molecular weights, however in some cases a small molar excess of diamine (approximately 1-5 mol%) can be used and the terminal amino groups resulting in the formation of a polyetherimide having a Generally useful polyetherimides are
0.2 dl/g when measured in m-kusol at 25°C
greater than, preferably 0.35-0.60 dl/g, or 0.7
It has an intrinsic viscosity [η] greater than dl/g. Among the many ways to make polyetherimide,
There are methods described in US Pat. No. 3,847,867 to Heath et al., US Pat. No. 3,847,869 to Williams, US Pat. No. 3,850,885 to Takekoshi et al., and US Pat.
These descriptions are incorporated herein by reference in their entirety to teach, by way of example, general and specific methods for making polyetherimides suitable for the blends of the present invention. A large number of fluorinated polyolefins are available on the market for use in the blends of the present invention, and methods of making them are well known to those skilled in the art. For example, methods for producing fluorinated polyethylene are described in The Kirk-Othmer Encyclopedia of
Science and Technology, Volume 9, No.
805 to 847 (1966) and the literature cited therein, and is generally performed in the presence of an initiator at high pressures, e.g. 2 to 600 atmospheres, and at moderate temperatures, e.g. 30 to 100°C. polymerize the polymer or
Alternatively, it includes emulsion polymerization using a free radical initiator. Another method for making fluorinated polyolefins is described in U.S. Pat. No. 2,968,649, no.
No. 3051677, No. 3053818, No. 3069401, No.
No. 3080347, No. 3707529, and No. 3845024, all of which are incorporated herein by reference. According to the invention, blends of polyetherimide and fluorinated polyolefin are generally obtained in any proportion of the two polymers to each other. Therefore about 1
Blends comprising from about 99% by weight polyetherimide and from 99% to about 1% by weight fluorinated polyolefin are included within the scope of this invention. By controlling the proportions of the polyetherimide and fluorinated polyolefin with respect to each other, blends with certain predetermined properties that are improved over those of the polyetherimide or fluorinated polyolefin alone are readily obtained. Blends of polyetherimide and fluorinated polyolefins are generally prepared in small proportions, e.g., from about 0.5 to about 30% by weight, so as to maintain the high strength properties of the polyetherimide component of the blend while improving the impact strength of the blend. % of fluorinated polyolefin. The polyetherimide-fluorinated polyolefin blends of the present invention contain fillers, stabilizers,
It is contemplated that other additive materials such as plasticizers, softeners, surfactants, pigments, dyes, and toughening agents may also be included. The blend of the present invention also includes two or more polyetherimides and one or more fluorinated polyolefins, or two or more fluorinated polyolefins and one or more fluorinated polyolefins.
It is also contemplated that combinations of more than one polyetherimide may also be included. The method of forming polyetherimide-fluorinated polyolefin blends can vary considerably. Conventional mixing techniques are generally satisfactory. A preferred method is to mix the polymer and additives such as reinforcing agents in powder, particle or filament form and extrude the mixture by methods conventionally used to form normally solid thermoplastic compositions. It consists of cutting the extrudate into pellets suitable for molding. The polyetherimide-fluorinated polyolefin blends of the present invention have applications in a variety of physical forms, including applications such as films, molding compositions, coatings, and the like. When used as films or made into molded articles, these blends, including the laminates made from them, not only have good physical properties at room temperature, but they also have good performance at high temperatures for long periods of time. Retains excellent response to loads and their strength. Films formed from the blends of the present invention can be used in applications for which films are traditionally used. For example, the blend of the invention is
Can be used in automobiles and aircraft for decoration and protection, can be used as high temperature electrical insulation for motor slot liners, transformers, dielectric capacitors, coil and cable packaging (forming wound coil insulation for motors), containers and container liners. Blends can also be made by applying a film or solution of the blend to various heat-resistant or other types of materials such as asbestos, mica, fiberglass, etc., stacking sheets one on top of another, and then subjecting the sheets to high temperature and pressure treatment. It can also be used in laminated structures by pouring the resin blend and curing it to create an adhesive laminated structure. Films made from the polyetherimide-fluorinated polyolefin blends of this invention can also be used for printed circuit applications. Alternatively, the solution of the blend described here is
Can be coated on conductive materials such as copper, aluminum, etc.
The coated conductor can then be heated to a high temperature to remove the solvent and form a continuous coating of the resin composition thereon. If desired, polyamide, polyester, silicone, polyvinyl formal resin,
Additional overcoats can be applied over such insulated conductors, including using polymeric coatings such as epoxy resins, polyimides, polytetrafluoroethylene, and the like. It is also not excluded to use the blends of the invention as overcoats over other types of insulation. Other uses contemplated for these blends include use as binders for asbestos fibers, carbon fibers, and other fibrous materials in making brake linings. Furthermore, asbestos, glass fiber, talc, quartz,
Molding compositions and molded articles can be formed from the polymer blends of this invention by incorporating fillers such as powders, finely divided carbon, silica, and the like.
The molded article can be formed under heat or under heat and pressure by methods well known to those skilled in the art. The following examples illustrate specific polyetherimide-fluorinated polyolefin blends according to the present invention.
It should be understood that the examples are given by way of illustration and not as a limitation on the invention. In the examples, parts and percentages are by weight unless otherwise specified. EXAMPLES Polyetherimide-fluorinated polyolefin blends according to the present invention were made, the blends were formed into specimens, and the specimens were tested for various physical properties. The polyetherimide of the blend consists of essentially equimolar amounts of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane prepared at elevated temperatures from about 250 to about 300°C under a nitrogen atmosphere. Made from the reaction product of an acid anhydride and m-phenylenediamine. The polymer was extruded at approximately 300°C to form strands and mechanically cut into pellets. The polyetherimide test piece has a temperature of approximately 362 to 371℃ (approximately 685℃).
It was injection molded from pellets at a temperature of ~700°C.
The physical properties of polyetherimide are shown in the table below. The fluorinated polyolefin used was polytetrafluoroethylene sold under the trade name Teflon DLX-600 by EI DuPont de Nimois & Company, Inc. About 85 parts of the above polyetherimide is mixed with about 85 parts of polytetrafluoroethylene.
Mixed with 15 parts. Next, the mixture of two polymers is approx.
It was extruded in a Warner & Puchidler extruder with a temperature profile varying from 323-343°C (approximately 615-650°C). The formed extrudate is cut into pellets and the pellets are heated to about 362-371°C (about 685°C).
The specimens were injection molded in a batten field molding machine at a temperature of ~700°C. The impact strength of these test pieces was measured by unnotched and notched Izot impact tests, and the results are shown in the table below. The heat deflection temperature and bending properties of the blends were also measured and are shown in the table. EXAMPLE The method of the example was repeated except that about 90 parts of polyetherimide were mixed with about 10 parts of polytetrafluoroethylene to make a blend according to the invention. The results of heat deflection temperature, flexural properties and flexural modulus as well as unnotched and notched Izot impact tests for the blends are shown in the table. EXAMPLE The method of the example was repeated except that about 88 parts by weight of polyetherimide were mixed with about 12 parts of polytetrafluoroethylene and contained about 0.5% internal lubricant to make a blend according to the invention. . The internal lubricant used is a trade name from Union Carbide.
It is commercially available as PCL-700. The results of heat deflection temperature, flexural properties and flexural modulus as well as unnotched and notched Izot impact tests for the blends are shown in the table.

[Table] As is clear from the above results, the blend according to the invention with a small proportion of fluorinated polyolefin
Exhibits good bending properties and heat deflection temperatures and improved impact strength over polyetherimide itself. Substituting other polyetherimides and/or other fluorinated polyolefins for the polyetherimides and/or fluorinated polyolefins in the blends of each of the above examples results in the formation of polymer blends with similar properties. be able to. Although the invention has been described in terms of specific embodiments, it will be appreciated by those skilled in the art that many modifications can be made without departing from the scope of the invention as defined in the claims.