KR910006959B1 - Compatibilized polyphenylene etherpolyamide composition - Google Patents

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Description

Compatible Polyphenylene Ether-Polyamide Compositions and Methods for Making the Same

The present invention relates to a process for the preparation of polyphenylene ether-polyamide compositions, and more particularly to a process for the preparation from carboxylated polyphenylene ethers.

Various compositions consisting of polyphenylene ethers (also known as polyphenylene oxides) and polyamides (such as nylon-6 and nylon-66) have attracted attention because of their high solvent resistance and potential high impact strength. . However, such compositions typically have large and incompletely dispersed polyphenylene ether particles and lack of phase interaction between the two resin phases, resulting in phase separation and interlayer separation.

Compatibilization of polyphenylene ethers with polyamides is possible by using carboxy functionalized polyphenylene ethers, which results in improved properties. For example, in addition to the method of functionalizing polyphenylene ethers with polycarboxylic acid compounds such as maleic anhydride and fumaric acid, high-performance compositions of the functionalized polyphenylene ethers and polyamides are disclosed. Co-pending, patent application No. 885,497, filed Jul. 14, 1986. US Pat. No. 4,600,741 describes polyphenylene ethers functionalized by reaction with polycarboxylic acid compounds such as anhydrous trimellitic acid chlorides and polyphenylene ether-polyamide compositions prepared therefrom.

The present invention finds and is based on the fact that polyphenylene ethers having structural units containing a single carboxylic acid moiety can be advantageously mixed with polyamides. The resulting composition is highly compatible and also has excellent properties including high impact strength and solvent resistance.

Accordingly, the present invention provides at least one structural unit comprising (A) at least one polyamide and (B) a direct unit or at least one structural unit containing a single carboxylic acid moiety separated by a carbon atom of one aromatic ring. It includes the manufacturing method of the resin composition which melt-mixes polyphenylene ether. In addition, the resin composition thus prepared is also included in the present invention.

In the process of the invention, any known polyamide can be used as reagent A. Examples thereof include at least two carbon atoms between an amino group and a dicarboxylic acid group, in addition to the monoamino-monocarboxylic acid or its lactam having at least two carbon atoms between the amino group and the carboxylic acid group. Diamines or monoaminocarboxylic acids or their lactams as defined above are prepared by reacting substantially equimolar ratios of diamines and dicarboxylic acids (the term "substantially equimolar ratios" is precise And some deviation from the exact equimolar ratio and belong to conventional techniques for stabilizing the viscosity of the resulting polyamides). Dicarboxylic acids can be used in the form of their functional derivatives, for example in the form of esters or acid chlorides.

Examples of such monoamino-monocarboxylic acids or lactams thereof useful for preparing polyamides include compounds containing 2 to 16 carbon atoms between amino and carboxylic acid groups, and in the case of lactams, the carbon atoms are represented by -CO- Together with the NH group form a ring. Specific examples of aminocarboxylic acids and lactams thereof include ε-aminocaproic acid, butyrolactam, pivaloractam, ε-caprolactam, capryllactam, enantholactam, undecanolactam, dodecanolactam and 3- and 4- Aminobenzoic acid is mentioned.

Suitable diamines for use in the preparation of the polyamides include straight and branched chain alkyl, aryl and alkali diamines. As an example of such a diamine, what is represented by the following general formula is mentioned, for example.

H ₂ N (CH ₂ ) n NH ₂

In formula, n is an integer of 2-16.

Examples of the diamines include trimethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, hexamethylenediamine (which is often preferred), trimethylhexamethylenediamine, m-phenylenediamine and m-xylenediamine.

Dicarboxylic acid can be represented by the following formula.

HOOC-Y-COOH

In the formula, Y is a divalent aliphatic or aromatic group having at least two carbon atoms. Examples of aliphatic acids include sebacic acid, octadecanedioic acid, subberic acid, glutaric acid, pimelic acid and adipic acid. Aromatic acids such as isophthalic acid and terephthalic acid are preferred.

Typical examples of polyamides or so-called nylons include polyamides derived from terephthalic acid and / or isophthalic acid and trimethylhexamethylenediamine, as well as polyamide-6,66,11,12,63,64,6 / 10 and 6/12. Polyamide derived from dific acid and m-xylenediamine, adipic acid, azelaic acid and polyamide derived from 2,2-bis- (p-aminocyclohexyl) propane, and terephthalic acid and 4,4'-diaminodicy Polyamides derived from clohexylmethane. Mixtures and / or copolymers of two or more such polyamides or prepolymers thereof are also included in the scope of the present invention. Preferred polyamides are polyamide-6,66,11 and 12, most preferably polyamide-66.

Reagent B is at least one polyphenylene ether having a specific type of carboxylic acid functional group. It can be produced by the method described below with known polyphenylene ether as starting material.

Suitable known polyphenylene ethers are widely used industrially, particularly in fields such as engineering plastics requiring toughness and heat resistance. Since their discovery, they are not limited to those described herein, but many changes and modifications have been applied to the present invention.

Polyphenylene ether consists of a plurality of structural units represented by the following general formula.

In each of the above units, each Q ¹ is independently a primary or secondary lower alkyl group (ie, an alkyl group having up to 7 carbon atoms), a phenyl or a hydrocarbonoxy group, and each Q ² is independently hydrogen, Halogen, primary or secondary lower alkyl, phenyl or a hydrocarbonoxy group as defined in Q ¹ above.

Suitable examples of primary lower alkyl groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3 Or 4-methylphenyl group and the corresponding heptyl group. Examples of secondary lower alkyl groups include isopropyl, sec.-butyl and 3-pentyl. The alkyl group is preferably straight rather than branched. Usually, each Q ¹ is an alkyl group or a phenyl group, especially a C _1-4 alkyl group, and each Q ² is preferably hydrogen. Suitable polyphenylene ethers are known in many patents.

Both homopolymers and copolymer polyphenylene ethers are included. Suitable homopolymers are, for example, homopolymers having 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers are random copolymers in which such units are combined with (eg) 2,3,6-trimethyl-1,4-phenylene ether units. In addition to homopolymers, many suitable random copolymers are known from the patent literature.

Polyphenylene ethers generally have a number average molecular weight in the range of about 3,000-40,000 and a weight average molecular weight in the range of about 20,000-80,000 as measured by gel permeation chromatography. Intrinsic viscosity is about 0.2-0.6 dl / g when it is measured in 25 degreeC and chloroform.

Typically, polyphenylene ethers are prepared by oxidatively coupling at least one of the corresponding monohydroxy aromatic compounds. Particularly useful and readily available monohydroxyaromatic compounds are 2,6-xyleneols, wherein each Q ¹ is methyl and each Q ² is hydrogen, thus the polymer is poly (2,6,- Dimethyl-1,4-phenylene ether), and 2,3,6-trimethylphenol, wherein each Q ¹ and one Q ² is methyl and the remaining Q ² is hydrogen.

Various catalyst systems are known for producing polyphenylene ethers by oxidative coupling. There is no particular limitation on the choice of catalyst, and any known catalyst can be used. In most cases the catalyst system typically contains at least one heavy metal compound such as copper, manganese or cobalt compounds in admixture with various other materials.

The first group of preferred catalyst systems consists of those containing copper compounds. Such catalysts are described, for example, in US Pat. Nos. 3,306,874, 3,306,875, 3,914,266 and 4,028,341. These are usually mixtures of monovalent copper ions and divalent copper ions, halogenated ions (ie chlorine, bromine or iodine), and at least one amine.

Catalyst systems containing manganese compounds constitute a second preferred group. These are generally alkaline systems in which divalent manganese is mixed with anions such as halides, alkoxides or phenoxides. Usually, manganese is one or more dialkylamines, alkanolamines, alkylenediamines, ο-hydroxyaromatic aldehydes, ο-hydroxyazo compounds, ω-hydroxyoximes (monomer and polymer forms), ο It exists as a complex with complexing agents and / or chelating agents, such as -hydroxyaryl oximes and (beta) -diketones. Also, catalyst systems containing cobalt are known to be useful. Suitable catalyst systems for preparing polyphenylene ethers containing manganese and cobalt are known in the art as described in numerous patents and publications.

Particularly useful polyphenylene ethers for the purposes of the present invention are those consisting of molecules having at least one terminal group represented by the following formula.

Wherein Q ¹ and Q ² are as defined above, each R ¹ is independently hydrogen or an alkyl group, with the total number of carbon atoms of only two R ¹ groups of 6 or less, and each R ² is independently hydrogen or C _{1- 6} primary alkyl group. Preferably, each R ¹ is hydrogen and each R ² is an alkyl group, in particular a methyl group or n-butyl group.

Polymers containing aminoalkyl substituted end groups of general formula II can be obtained by mixing suitable primary or secondary monoamines as one of the constituents of the oxidative coupling reaction mixture, especially when using copper or manganese containing catalysts. have. Such amines, in particular dialkylamines and preferably di-n-butylamine and dimethylamine, usually have at least one Q.^OneOne of the gaseous α-hydrogen atoms is substituted, often chemically bonded to the polyphenylene ether. The theoretical reaction site is Q adjacent to the hydroxy group on the terminal unit of the polymer chain.^OneQi. During the subsequent treatment and / or mixing process, the aminoalkyl substituted end groups may proceed in a variety of reactions, presumably including quinone metide intermediates of Formula IV, with increasing impact strength and compatibility with other mixed components. A number of advantageous effects are obtained, including.

References incorporated herein by reference are U.S. Patent Nos. 4,054,553, 4,092,294, 4,477,649, 4,477,651, 4,517,341, and the like.

Polymers having end groups of 4-hydroxybiphenyl of general formula III are typically obtained from reaction mixtures, in particular copper-halide-secondary or tertiary amine systems, in which diphenoquinones represented by the following formula V are present as by-products: Lose.

This is more appropriately described in US Pat. Nos. 4,234,706 and 4,482,697, as well as US Pat. No. 4,477,649, which are also incorporated herein by reference. In mixtures of this type, diphenoquinones are finally incorporated in significant proportions into the polymer, usually as end groups.

In many polyphenylene ethers obtained under these conditions, a substantial proportion of polymer molecules, ie, polymer molecules that typically make up about 90% of the weight of the polymer, have end groups having either or often both of formulas II and III. It contains. However, it is to be understood that other end groups may also be present and that, in the broadest sense, the present invention may not depend on the molecular structure of the polyphenylene ether end groups.

To prepare Reagent B, polyphenylene ether is carboxylated. Various carboxylation reactions can be used. One of them consists of metallizing the polyphenylene ether followed by carbonation with carbon dioxide, which reaction is performed by Chalk et al., J.Poly. Sci. , part A-1,7,691-705 (1969). Typical degrees of metallization are about 0.01-0.1 gram atoms of metal, preferably about 0.02-0.08 gram atoms, per structural unit of the polyphenylene ether.

Another method of carboxylation is the redistribution of polyphenylene ethers to carboxylated phenols such as 4-hydroxyphenylacetic acid. Redistribution or equilibration methods are described in US Pat. No. 3,496,236, although the use of carboxylated phenols is not mentioned. In addition, the molecular weight of the product is substantially reduced. For the purposes of the present invention a relatively small proportion of carboxylated phenols are used, typically about 1.5-3.0 moles per mole of polyphenylene ether. As a result, the molecular weight decreases further.

The redistribution reaction typically takes place in a solution at a temperature of about 50-150 ° C. and free radicals or precursors thereof, preferably 3,3 ′, 5,5′-tetramethyl-4,4′-diphenoquinone (hereinafter “ Preferably in the presence of diphenoquinone, such as TMDQ ". The proportion of diphenoquinone is, for example, about 0.1-0.5 mole per mole of carboxylated phenol. This method for producing carboxylated phenols is known in the co-pending application serial number [RD-16697].

From the stoichiometric point of view, carboxylation via metallization-carbonization is often preferred because relatively high levels of carboxylation can be obtained. However, redistribution reactions are generally more convenient to conduct. The carboxylation method can be selected with such a point in mind.

The preparation of carboxylated polyphenylene ethers suitable for use as Reagent B is described in the Examples below. Intrinsic viscosity was measured in 25 degreeC and mololoform. The molecular weight is a number average molecular weight and measured by gel permeation chromatography.

Example 1

Poly (2,6-dimethyl-1,4-phenylene ether) having an inherent viscosity of 0.49 dl / g and a molecular weight of about 15,000 was washed with hexane and dried in vacuo. A slurry of 200 g (13 mmol, or 1.67 mol based on structural units) of dried polyphenylene ether in 1.5 liter of cyclohexane dried with phosphorus pentoxide was stirred under a nitrogen atmosphere, and 42 millimoles of n-butyllithium (lithium per structural unit) 0.025 gram atom) was added as a 20% by weight solution in tetrahydrofuran, followed by 42 mmol of N, N, N ', N'-tetramethylethylenediamine. The mixture turned pale yellow within minutes, which was stirred for 3 hours. Next, solid pulverized carbon dioxide, which was immediately pulverized, was added, and the slurry was acidified with a 50% aqueous hydrochloric acid solution. The liquid phase was decanted, the solids were collected by filtration, washed with methanol and dried in a vacuum oven. The presence of carboxylic acid functional groups was confirmed by Fourier transform infrared spectroscopy.

Example 2-4

In the method of Example 1, polyphenylene ether metallized with lithium 0.05, 0.075 and 0.1 gram atoms per structural unit was prepared and carbonated.

Example 5

30 g (1.5 mmol) of poly (2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of about 0.57 dl / g and a molecular weight of about 20,000, 0.608 g (4 mmol) of 4-hydroxyphenylacetic acid, A mixture of 0.3 g (1.25 mmol) of TMDQ and 120 ml of toluene was heated at 110 ° C. under a nitrogen atmosphere for 2 hours with stirring. The liquid phase was decanted from the undissolved TMDQ and the functionalized polymer was precipitated by adding methanol, dissolved in chloroform, reprecipitated with methanol and dried.

According to the process of the invention, components A and B are melt mixed in a conventional manner. Often extrusion is preferred. Generally, the mixture contains about 5-75% by weight of component B and about 25-95% of component A. Typical mixing temperatures range from about 230-390 ° C.

While the present invention does not depend on theory or reaction mechanisms, the reaction is believed to occur between at least a portion of the carboxylic acid groups on the polyphenylene ether and the amine groups of the polyamide under melt mixing conditions, which groups already exist Or end groups formed by "chain biting" decomposition with functionalized polyphenylene ethers. Such degradation obviously does not occur to the extent that adversely affects the properties of the composition of the present invention. The copolymer formed in the reaction is inherently self compatible and also compatible with any unreacted polyphenylene ether and polyamide.

It is advantageous to contain impact modified resins in the mixture. Impact modifiers suitable for polyphenylene ether-polyamide compositions are well known in the art. They are typically derived from one or more monomers selected from the group consisting of olefins, vinyl aromatic monomers, acrylic acid, alkyl acrylic acid and ester derivatives thereof and conjugated dienes. Particularly preferred impact modifiers are high molecular weight rubbery materials, including natural and synthetic polymeric materials that exhibit elasticity at room temperature. These include both homopolymers and copolymers, including random, block, radial blocks, graft and core-shell copolymers and mixtures thereof. .

Polyolefins or olefin based copolymers usable in the present invention include low density polyethylene, high density polyethylene, linear low density polyethylene, isotactic polypropylene, poly (1-butene), poly (4-methyl-1-pentene), propylene-ethylene copolymer Etc. Additional olefin copolymers include one or more α-olefins, in particular ethylene and for example vinyl acetate, acrylic acid and alkylacrylic acid and their ester derivatives (e.g. ethylene-acrylic acid, ethylacrylate, methacrylic acid, methyl methacrylate). Copolymerizable copolymers, etc.) are mentioned. Also suitable are ionomer resins which can be neutralized in whole or in part using metal ions.

Particularly useful impact modifier groups are those derived from vinyl aromatic monomers. Examples thereof include modified or unmodified polystyrenes, ABS type graft copolymers, AB and ABA type block copolymers and radial block copolymers, and vinyl aromatic conjugated diene core shell graft copolymers. Modified and unmodified polystyrenes include homo polystyrenes and rubber modified polystyrenes such as butadiene rubber-modified polystyrene (or also referred to as high impact polystyrene or HIPS). Additional useful polystyrenes include copolymers of styrene with various monomers, such as poly (styrene-acrylonitrile) (SAN), styrene-butadiene copolymers and modified alpha- and para-substituted styrenes and for reference herein. There are any of the styrene resins described in US Pat. No. 3,383,435. The ABS type graft copolymer is at least one selected from the group consisting of conjugated dienes alone or monoalkenylarene monomers and substituted derivatives thereof and acrylic monomers (e.g. acrylonitrile, acrylic acid and alkylacrylic acid and esters thereof), preferably The following is represented as consisting of a rubbery polymer backbone derived from a mixture of two monomers grafted and copolymerizable with diene.

Particularly preferred among resins derived from vinyl aromatic monomers are block copolymers comprising monoalkenyl arene (usually styrene) block copolymers and conjugated diene (e.g. butadiene or isoprene) block copolymers as AB and ABA block copolymers. Is displayed. The conjugated diene block copolymer can be partially or wholly hydrogenated.

Suitable AB type block copolymers are described, for example, in US Pat. Nos. 3,078,254, 3,402,159, 3,297,793, 3,265,765 and 3,594,452, and 1,264,741, all of which are described herein by reference. do. Typical types of AB block copolymers include the following.

Polystyrene-Polybutadiene (SBR)

Polystyrene-polyisoprene and

Poly (alpha-methylstyrene) -polybutadiene

Such AB block copolymers are commercially available from a number of manufacturers, including Philips Petroleum under the trade name SOLPRENE.

In addition to the ABA triblock copolymer and a method for producing the same, the hydrogenation method may be further described in US Pat. The contents of which are incorporated herein by reference.

Examples of triblock copolymers include the following.

Polystyrene-polybutadiene-polystyrene (SBS),

Polystyrene-polyisoprene-polystyrene (SIS),

Poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene), and

Poly (α-methylstyrene) -polyisoprene-poly (α-methylstyrene).

KRATON D

및 KRATONG

이다.Particularly preferred triblock copolymers are CAROFLEX available from Shell.

KRATON D

And KRATONG

to be.

Other impact modifiers are derived from conjugated dienes. Although many copolymers with conjugated dienes have already been discussed above, as additional conjugated diene modifier resins, for example, polybutadiene, butadiene-styrene copolymers, isoprene-isobutylene copolymers, chlorobutadiene polymers, butadiene-acrylics Homopolymers and copolymers of one or more conjugated dienes, including ronitrile copolymers, polyisoprene, and the like. It is also possible to use rubber of ethylene-propylene-diene monomer (EPDM). These EPDMs are mainly represented as being ethylene units, appropriate amounts of propylene units and up to about 20 mole% nonconjugated diene monomer units. Many such EPDMs and methods for their preparation are described in US Pat. Nos. 2,933,480, 3,000,866, 3,407,158, 3,093,621 and 3,379,701, which are incorporated herein by reference.

Other suitable impact modifiers are core-shell graft copolymers. In general, they are mainly conjugated diene rubber cores or predominantly crosslinked acrylate rubber cores and one or more shells derived from polymerized monoalkenylarene and / or acrylic monomers alone or preferably in mixtures with other vinyl monomers. Has Such core-shell copolymers are commercially available, for example, under the trade names KM-611, KM-653 and KM-330 from the Rohm and Hass Company, U.S. Patent Nos. 3,808,180, 4,034,013. 4,096,202, 4,180,494 and 4,292,233.

Also useful are core-shell copolymers in which the interpenetrating network of resins used characterizes the interface between the core and the shell. Particularly preferred in this respect are ASA type copolymers sold by General Electric Company under the trade name GELOY ^™ resin, which is described in US Pat. No. 3,944,631.

It is also possible to use copolymers having monomers copolymerizable or grafted with the polymers and functional groups and / or monomers having polar or active groups. Finally, other suitable impact modifiers include Thiokol rubbers, polysulfide rubbers, polyurethane rubbers, polyether rubbers (e.g. polypropylene oxide), epichlorohydrin rubbers, ethylene propylene rubbers, thermoplastic polyester elastomers.

The proportion of impact modifiers varies widely. Generally, about 1-150 parts by weight per 100 parts of polyphenylene ether is used. If the impact modifier is a diblock or triblock copolymer, it is usually present in amounts up to about 50 parts per 100 parts of polyphenylene ether.

The following example demonstrates the manufacturing method of the resin composition of this invention. All parts are parts by weight.

Example 6-10

45 parts functionalized polyphenylene ether of Examples 1-5, 45 parts commercial polyamide-66 and partially hydrogenated styrene-butadiene-styrene tree having a styrene-butadiene ratio of 27:73 and a number average molecular weight of about 74,000. A mixture of 10 parts of the block copolymer was tumble mixed for 30 minutes with a roll mill, extruded at 288 ° C. using a full vacuum vent in a twin-screw extruder at 400 rpm and quenched with water The pellet was made into pellets and dried at 90-110 ° C. for 3-4 hours. Test pieces were prepared by extrusion molding and tested for notched Izod impact strength (ASTM method D256). The results are shown in the table below and compared to a control similarly prepared from unfunctionalized polyphenylene ethers.

Claims (20)

Fusing one or more polyphenylene ethers comprising (A) at least one polyamide and (B) structural units directly attached to the aromatic ring or having a single carboxylic acid separated from the aromatic ring by at least one carbon atom The manufacturing method of the resin composition to mix. The method according to claim 1, wherein the polyphenylene ether is composed of a plurality of structural units represented by the following formula (I).

Wherein each Q ¹ is independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy or halohydrocarbon in which the halogen and oxygen atoms are separated by two or more carbon atoms Oxy and each Q ² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or a halohydrocarbonoxy group as defined in Q ¹ above. The method of claim 1 wherein the polyamide is nylon-6 or nylon-66. The method of claim 1 wherein the carboxylic acid moiety is bonded directly to the aromatic ring. The method of claim 1 wherein the carboxylic acid moiety is separated from the aromatic ring by one carbon atom. The method of claim 1 wherein the mixing temperature is in the range of about 230-390 ° C. 3. The method of claim 2 wherein the polyphenylene ether is a poly (2,6-dimethyl-1,4-phenylene) ether. The method of claim 3 wherein the polyamide is nylon-66. The method of claim 1, wherein the mixture further contains an impact modifying resin for the polyphenylene ether-polyamide composition. 10. The impact modifier of claim 9, wherein the impact modifying resin is a styrene-conjugated diene diblock copolymer or a styrene-conjugated diene-styrene triblock copolymer and is present in an amount of up to about 50 parts by weight per 100 parts of polyphenylene ether. How to. The method of claim 10, wherein the conjugated diene block copolymer is partially or wholly hydrogenated. 10. The method of claim 9, wherein the mixing temperature is in the range of about 230-390 ° C. 10. The method of claim 9, wherein the carboxylic acid moiety is bonded directly to the aromatic ring. 10. The process of claim 9, wherein the carboxylic acid moiety is separated from the aromatic ring by one carbon atom. The resin composition prepared by claim 1. The resin composition prepared by claim 3. The resin composition prepared by claim 7. The resin composition prepared by claim 8. Resin composition prepared by claim 10. The resin composition prepared by claim 11.