Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to polyetherimide- -polyamide compositions having improved resistance to moisture as manifested by reduced water absorption and swell in moist environments. More specifically, polyetherimide-polyamide compositions are rendered less susceptable to weight gain and expansion in moist environments by incorporating therein certain phenolic compounds and polymers.
• Polyamides are well known and have enjoyed tremendous commercial demands, particularly in the fiber and bristle industries, as a result of their generally excellent processability and solvent resistance.
• their utility as molding compositions has been hindered as a result of their poor tolerence to moist environments, particularly with respect to their tendency to absorb water, thus gain weight, and to swell or expand.
• Polyetherimides are a more recent class of high performance specialty thermoplastics. Because of their high continuous-use temperatures, inherent flame resistance, low smoke evolution, good electrical properties and generally good physical properties, they are becoming more and more desirable for a wide range of applications requiring such characteristisc, particularly in the high tech electronics industries and in the manufacture of aircraft and the like. However, because of their high temperature characteristics, very high temperatures are needed to process the thermoplastic, e.g. from about 680 to 820°F. Such high temperatures may have a tendency to adversely affect the properties of the polymer. Furthermore, while the polyetherimides have numerous beneficial characterisitics, they are susceptible to premature failure in certain environments.
• polyetherimide-polyamide blends may be prepared having reduced water absorption characteristics and improved dimensional stability with little, if any, adverse impact on the physical properties of the blend by incorporating therein one or more phenolic compounds capable of manifesting said improvements.
• polyetherimide-polyamide blend compositions are rendered less susceptible to water absorption and expansion due to moisture by incorporating therein at least one phenolic compound, oligomer or polymer selected from the group consisting of a) mono-, di- and polyphenols of the formula:
• n 1, 2 or 3
• m 3
• (n+m) 6
• p 1 or 2
• each r is independently equal
• each R is independently hydrogen; halogen, e.g. bromine, chlorine, fluorine, etc.; a C..-C.., alkyl, a Cg-C.g aryl or a C_-C 20 arylalkyl radical, any of which
• 2 ⁇ 5 may be substituted with a C--C. 2 alkyl group or with a halogen atom and whereby the aryl radical, if present, may be bonded by a -0-, C--C, alkylene or alkylidene, or -SO-- bridge member; or a hydroxy aryl or alkyl hydroxy aryl radical; and each R' is independently
• a direct carbon-carbon bond or a bridge member selected from the group consisting of divalent alkyl, aryl, arylalkyl, hydroxy aryl or alkyl hydroxy aryl radicals, including halogen substituted derivatives of each; divalent ester and amide radicals; and hetero containing bridges including:
• polyetherimide component of the blends of this invention contain repeating groups of the formula:
• the group -0-A is selected from:
• the polyetherimide includes the latter -O-A ⁇ group where R' is hydrogen, such that the polyetherimide is of the formula:
• X is a member selected from the class consisting of divalent radicals of the formulas,
• R is a divalent organic radical selected from the class consisting of (1) aromatic hydrocarbon radicals having from 6 to about 20 carbon atoms and halogenated derivatives thereof, (2) alkylene radicals and cycloalkylene radicals having from 2 to about 20 carbon atoms, C 2 to C Pain alkylene terminated polydiorganosiloxane, and (3) divalent radicals included by the formula
• x is a whole number from 1 to 5 inclusive.
• Particularly preferred polyetherimides for the purposes of the present invention include those where -0-A ⁇ and Z respectively are:
• R is selected from:
• polyetherimide may be a copolymer which, in addition to the etherimide units described above, further contains repeating units of the formula
• R is as previously defined and M is selected from the group consisting of
• polyetherimides can be obtained by any of the methods well known to those skilled in the art including the reaction of an aromatic bis(ether anhydride) of the formula:
• Aromatic bis(ether anhydride)s of the above formula include, for example, 2-bis[4-(2,3-dicarboxy- phenoxy) ⁇ henyl]propane dianydride; 4,4'-bis(2,3-dicar- boxyphenoxy)diphen 1 ether dianhydride; 1,3-bis(2,3-di- carboxyphenoxy)benzene dianhydride; 4,4'-bis(2,3-dicar- boxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-di- carboxyphenoxy)diphenyl sulfone dianhydride; 2,2-bis- [4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis (3,4-dicarboxy)dipheny1 ether dianhydride; 4,4'-bis (3,4-dicarboxy)diphenyl sulfide dianhydride; 1,3-bis(3,4-dicarbox
• aromatic bis(ether anhydride)s included in the above formulas are shown by Koton,
• Organic diamines of the above formulas include, for example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'diaminodiphenylmeth- ane, benzidine, 4,4'-diaminodipheny1 sulfide, 4,4'- diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5 diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'- dimethoxybenzidine, 2,4-bis(B-amino-t-butyl)toluene, bis (p-B-amino-t-butylphenyl)ether, bis (p-B-methyl-o- aminopentyl)benzene, 1,3-diaminotoluene, 2,6-diamino- toluene, bis(4-a
• N-methyl-bis (3-aminopropyl)amine N-methyl-bis (3-aminopropyl)amine, hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, deca ethylenediamine, bis (3-aminopropyl)tetra ethyl- disiloxane, bis(4-aminobutyl)tetramethyldisiloxane, etc. and mixtures of such diamines.
• the reactions can be carried out by employing well-known solvents, e.g., o-dichlorobenzene, m-cresol/toluene, etc. to effect interaction between the dianhydrides and the diamines, and temperatures of from about 100°C to about 250°C.
• the polyetherimides can be prepared by melt polymerization of any of the above dianhydrides with any of the above organic diamines while heating the mixture of the ingredients at elevated temperatures with concurrent intermixing. Generally, melt polymerization temperatures between about 200°C to 400°C and preferably 230°C to 300°C can be employed.
• the conditions of the reaction and the proportions of ingredients can be varied widely depending on the desired molecular weight, intrinsic viscosity, and solvent resistance.
• equimolar amounts of diamine and dianhydride are employed for high molecular weight polyetherimides, however, in certain instances, a slight molar excess (about 1 to 5 mole percent) of diamine can be employed resulting in the production of polyetherimides having terminal amine groups.
• useful polyetherimides have an intrinsic viscosity greater than 0.2 deciliters per gram, preferably 0.35 to 0.60, or 0.7 deciliters per gram or even higher when measured in m-cresol at 25°C.
• useful polyetherimides include those disclosed in U.S. Patent to Heath et al., 3,847,867, Williams 3,847,869, Takekoshi et al., 3,850,885, White 3,852,242 and 3,855,178, etc. These disclosures are incorporated herein in their entirety by reference for the purpose of teaching, by way of illustration, general and specific methods for preparing polyetherimides suitable for the blends of this invention.
• Polyamides suitable for use in the practice of the present invention are well known and widely available. Basically they may be obtained by polymerizing a monoamino-monocarboxylic acid or a lacta thereof having at least 2 carbon atoms between the amino and carboxylic acid group; or by polymerizing substantially equimolecular proportions of a diamine which contains at least 2 carbon atoms between the amino groups and a dicarboxylic acid; or by polymerizing a monoaminocar- box lic acid or a lactam thereof as defined above together with substantially equimolecular proportions of a diamine and dicarboxylic acid.
• the dicarboxylic acid may be used in the form of a functional derivative thereof, for example an ester or acid chloride.
• substantially equimolecular proportions (of the diamine and of the dicarboxylic acid) is used to cover both strict equimolecular proportions and slight departures therefrom which are involved in conventional techniques for stabilizing the viscosity of the resultant polyamides.
• Examples of the aforementioned monoamino-mono- carboxylic acids or lactams thereof which are useful in preparing the polyamides include those compounds con ⁇ taining from 2 to 16 carbon atoms between the amino and carboxylic acid groups, said carbon atoms forming a ring with the -CO-NH- group in the case of a lactam.
• Examples of aminocarboxylic acids and lactams there may be mentioned 6-aminocaproic acid, butyrolactam, pivalolactam, caprolactam, capryllactam, enantholactam, undecanolactam, dodecanolactam and 3- and 4- aminobenzoic acids.
• Diamines suitable for use in the preparation of the polyamides include alkyl, aryl and alkyl-aryl diamines.
• Such diamines include, for example, those represented by the general formula: wherein n is an integer of from 2 to 16, such as tri- methylenediamine, tetramethylenediamine, pentamethyl- .enediamine, octamethylenediamine and especially hexa- methylenediamine; trimethyl hexamethylene diamine; meta-phenylene diamin; meta-xylylene diamine and the like, as well as those mentioned above..
• the dicarboxylic acids may be aromatic, for example isophthalic and terephthalic acids or aliphatic wherein the aliphatic dicarboxylic acids are of the formula HOOC-Y-COOH wherein Y represents a divalent aliphatic group con ⁇ taining at least 2 carbon atoms, and examples of such acids are sebacic acid, octadecanedoic acid, suberic acid, glutaric acid, pimelic acid and adipic acid.
• polycapryllactam polyhexamethylene adipamide (nylon 6,6) polyundecanolactam (nylon 11) polydodecanolactam (nylon 12) polyhexamethylene azelaiamide (nylon 6,9), polyhexamethylene sebacamide (nylon 6,10) polyhexamethylene isophthalimide (nylon 6,1) polyhexamethylene terephthalamide (nylon 6,T) polyamide of hexamethylene diamine (nylon 6,12) and n-dodecanedioic acid as well as polyamides resulting from terephthalic acid and/or isophthalic acid and trimethyl hexamethylene diamine, polyamides resulting from adipic acid and meta xylylenediamines, polyamides resulting from adipic acid, azelaic acid and 2,2-bis-(p-aminocyclohexyl)pro ⁇ pane- and polyamides resulting from terephthalic
• Copolymers of the foregoing polyamides or prepoly- mers thereof are also suitable for use in the practice of the present invention.
• Such copolyamides include copolymers of the following: hexamethylene adipamide/ (nyl ⁇ .i 6,6/6) caprolactam hexamethylene adipamide/hexa- (nylon 6,6/6, ) methylene-isophthalamide hexamethylene adipamide/hexa- (nylon 6,6/6,T) methylene-terephthalamide hexamethylene adipamide/hexa- (nylon 6,6/6,9) methylene-azelaiamide hexamethylene adipamide/hexa- (nylon 6,6/6,9 methylene-azelaiamide/caprolactam /6)
• Mixtures and/or copolymers of two or more of the foregoing polyamides or prepolymers thereof, respect ⁇ ively, are also within the scope of the present inven ⁇
• polyamides are the polyamides 6; 6,6; 11; 12 and mixture of at least one crystalline polyamide, e.g. 6; 6,6, and at least one amorphous polyamide, e.g. 6,1; 6,I,T; most preferrably polyamide 6,6.
• polyamides are intended to include the toughened or super tough poly ⁇ amides.
• Super tough polyamides, or super tough nylons, as they are more commonly known, are available commer ⁇ cially, e.g. from E.I. duPont (Zytel® ST resins), Wilson Fiberfill (NY resins) , Badische (ULTRAMID® resins) , Allied (CARPION® resins) and Celanese (7000 series resins), among others, or may be prepared in accordance with a number of U.S. Patents including, among others, Epstein - U.S. 4,174,358; Novak - U.S.
• these elastomeric polymers and copolymers may be straight chain or branched as well as graft polymers and copolymers. including core-shell graft copolymers, and are characterized as having incorporated therein either by copolymerization or by grafting on the preformed polymer, a monomer having functional and/or active or highly polar groupings capable of interacting with or adhering to the polyamide matrix so as to enhance the toughness of the polyamide polymer.
• the blending ratio of polyetherimide to polyamide will generally be from about 5 to 95% by wt. , preferably from about 30 to 70% by wt. , of the former to from about 95 to 5% by wt. , preferably from about 70 to 30% by wt., of the latter.
• the polyamide is less that 5 wt. percent, its effect to improve solvent resistance is small, while when it exceeds 95 wt. per ⁇ cent, thermal properties such as heat distortion tem ⁇ perature and dimensional stability tend to become poor.
• Suitable phenolic compounds, oligomers and polymers are selected from the group consisting of a) mono-, di- and polyphenols of the formula:
• p equals 1 or 2
• each r is independently equal to 0, 1 or 2
• each s is independently equal to 0, 1, 2, 3 or 4 as appropriate;
• t equals 0, 1, 2, 3 or 4;
• each R is independently hydrogen; halogen, e.g. bromine, chlorine, fluorine, etc.; a C.-C.
• each R 1 is independently selected from the group consisting of a direct carbon-carbon bond or a bridge member selected from the group consisting of divalent alkyl, aryl, arylalkyl, hydroxy aryl or alkyl hydroxy aryl radicals, including halogen substituted derivatives of each; divalent ester and amide radicals; and hetero containing bridges including: 0 0 0 0 0 0 0
• oligomeric and polymeric phenols characterized as having free (ie. unreacted) phenolic hydroxy groups along the oligomer or polymer chain or in pendant phenol radicals attached to the oligomer or polymer chain; provided that there are no phenolic hydroxy groups having two adjacent alkyl radicals on the phenol ring with tertiary alpha carbon atoms.
• decanaphthol 2-butyl phenol(sec and tert) , 4-t-butyl phenol, thymol, 4-t-pentyl phenol, octylphenols, nonyl phenols, dodecyl phenols, 4-hydroxy diphenyl, 2-hydroxy diphenyl, alkyl substituted hydroxy diphenyls (as dis ⁇ closed in German application 1943230) , 1-naphthol, 2-naphthol, benzy phenols, benzyl cresols, 2-phenyl-2- -(4-hydroxy phenyl) propane, 4-hydroxydiphenyl sulfone, 4-hydroxydiphenyl ether, 2- and 4-cyclohexylphenol, resorcinol, hydroquinone, 1,2,4-benzenetriol, phloroglucinol and mixtures thereof.
• decanaphthol 2-butyl phenol(sec and tert)
• Suitable bisphenols and polyphenols according to formula II there may be given 2,2-bis (4-hydroxyphenyl) propane; bis(4-hydroxy- phenyl)methane; 2,2-bis(4-hydroxyphenyl)heptane; 2,2-bis (3-chloro-4 hydroxyphenyl)propane;
• 2,2-bis(4-hydroxypheny1)propane is 2,2-bis(4-hydroxypheny1)propane.
• oligomeric and polymeric phenols there may be given the polyvinyl phenols and the phenol-formaldehyde resins (e.g. novolak and resol resins) .
• polymeric phenols will have a number average molecular weight of up to 40,000, preferably from about 400 to 30,000.
• the amount by which the phenol compound or polymer will be employed in the practice of the present invent ⁇ ion is that amount capable of providing dimensional stability and reducing water absorption in the poly ⁇ etherimide-polyamide composition, preferably at least 10% improvement as compared to similar compositions prepared without the phenol.
• the amount of the phenol will be from about 0.5 to about 30, preferably from about 1 to about 20, most preferably from about 1.5 to about 10 parts by weight per 100 parts by weight of the mixture of polyetherimide and polyamide.
• the specific amount of phenol compound or polymer employed will depend in part upon the efficacy of the phenol itself, the weight ratio of polyamide to polyetherimide in the resin mixture and the extractability of the phenol upon conditioning and/or processing of the material.
• the present invention is also applicable to polyetherimide-polyamide blends further comprising an additional thermoplastic polymer and/or a polymeric or copolymeric impact modifier resin.
• thermoplastic polymers that may be included in the blends contemplated by the present invention include polyimides, polyamideimides, polycarbonates, polyaklylene ethers, polyphenylene ethers, polyarylates, polyesteramides, polyesters and the like. All of these thermoplastic polymers are well known and widely available.
• Suitable rubbery impact modifiers are also well known and widely available.
• Exemplary of the many rubbery impact modifiers included within the scope of the present invention there may be given polyolefins and copolyolefins, e.g. polyethylenes, polypropylene, ethylene-propylene copolymer, copolymers of ethylene with acrylic acids and alkylacrylic acids, etc.; ethylene-propylene-diene monomer rubbers (EPDM) ; diene rubbers and copolymers, e.g.
• compositions of the present invention may also contain one or more fillers and/or reinforcing agents.
• fillers and/or reinforcing agents there may be given glass fibers, carbon fibers, glass spheres, mineral fillers, including mica and silica, carbon black, and the like. Where such fillers and/or reinforcing agents are employed they should constitute no more than up to about 50% by weight, preferably from about 5 to about 30% by weight of the composition based on the total composition.
• composition of the present invention may also contain such other ingredients as flame retardants, colorants, nucleating agents, drip inhibitors, stabilizers and the like in effective amounts known in the art for their conventionally employed purposes.
• composition of the present invention may be prepared by any of the known methods for melt blending.
• the ingredients may be dry blended and extruded or fluxed on a mill and comminuted or they may be prepared by extrusion compounding. Suitable equipment for such processes include extruders, Banbury mixers, rollers, kneaders and the like. Additionally, these compositions may be prepared by continuous or batch processing.
• the following examples are provided in order for those skilled in the art to better understand how to practice the present invention. These examples are for illustration only and are not intended to limit the invention thereto. Unless otherwise stated, all formulations are expressed in terms of parts by weight.
• Blends were prepared by extrusion on either a single screw or twin screw extruder at 250-300 ⁇ C. All ingredients were mixed and fed together. Blend compositions were injection molded after drying for preparation of test parts. Moisture absorption and expansion were measured on samples immersed in de-ionized water for approximately 40 hrs at 75°C. Samples were cooled to room temperature for testing.
• Examples 1-6, Comparative Examples A-B A series of polyetherimide-polyamide blend compositions were prepared demonstrating the ability of various phenolic compounds within the scope of the present invention to reduce water absorption and expansion in parts molded from said compositions.
• the formulations of the specific examples and the results achieved with each were as shown in Table 1.

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• 1987
  • 1987-02-12 JP JP62501420A patent/JPH01500274A/ja active Granted
  • 1987-02-12 WO PCT/US1987/000263 patent/WO1988006170A1/en not_active Application Discontinuation
  • 1987-02-12 EP EP19870901843 patent/EP0303598A1/de not_active Withdrawn

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