NL8700111A - POLYMER MIXTURE WITH POLYPHENYLENE ETHER AND FUNCTIONALIZED POLYOLEFINE. - Google Patents

Description

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General Electric Company of Schenectady, New York United States of America. The applicant mentions as inventor: Roelof VAN DER MEER.

Polymer mixture with polyphenylene ether and functionalized polyolefin.

The invention relates to a polymer mixture containing a polyphenylene ether and a functionalized polyolefin.

EP-A-0088293 describes polymer blends containing a polyphenylene ether and a small amount of an ethylene-methyl acrylate copolymer. All examples of this prior art describe polymer blends which additionally contain a relatively large amount of impact resistant polystyrene.

EP-A-0090523 describes polymer mixtures containing a polyphenylene ether and a small amount of an ethylene-based terpolymer with hydroxyl and carbonyl functional groups. All prior art examples relate to polymer blends which additionally contain a relatively high amount of impact resistant polystyrene.

The invention relates to polymer mixtures which contain no or a relatively small amount of impact-resistant polystyrene. The polymer mixtures according to the invention contain - in comparison with the above-mentioned patent applications - a relatively large amount of a functionalized polyolefin, namely a polyolefin functionalized with an unsaturated carbon acid or reactive derivative thereof. 1 ·· 'O. v '; T ^

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Polymer blends with approximately equal weight amounts of non-functionalized polyolefin and polyphenylene ether show a strong tendency to delamination and phase agglomeration. The invention relates to polymer mixtures containing a polyphenylene ether and a functionalized polyolefin / chosen within wide limits for the mutual amounts /. The polymer mixtures according to the invention have a lower tendency to delamination than the mixtures containing a non-functionalized polyolefin.

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The polymer mixtures according to the invention have a combination of favorable properties. In particular, they have reasonable impact strength and good chemical resistance.

The polymer mixtures according to the invention are characterized in that they consist of: 20 A. one or more polyphenylene ethers / in an amount of 2-74 wt.%; B. one or more polyolefins functionalized with an unsaturated carboxylic acid or reactive derivative thereof in an amount of 26-98% by weight; C. one or more bismaleimides / in an amount of 0-5 wt%; D. one or more impact improving agents / in an amount of 0-25 wt.% E. one or more additives in an amount of 0-20 wt. Parts per 100 wt. Parts A + B + C + D / where the percentages by weight are calculated relative to the sum of the parts by weight A + B + C + D.

Preferably, the polymer mixtures according to the invention consist of: A. one or more polyphenylene ethers / in an amount of 5-60% by weight; «Fc 1 - n / η ~ μ • '· ^? 8-CB-10,218 -3- B. One or more polyolefins functionalized with an unsaturated carboxylic acid or reactive derivative thereof in an amount of 40-95% by weight; C. a bismaleimide / in an amount of 0-5 wt%; D. an agent for improving impact strength, in an amount of 0-25% by weight; E. conventional additives in an amount of 0-20 parts by weight per 100 parts by weight A + B + C + Dy, the weight percentages being calculated relative to the sum of the parts by weight A + B + C + D.

The interaction between the components of the polymer mixture according to the invention can be enhanced by including a bismaleimide in the polymer mixture. This further suppresses the tendency to delamination.

When using a bismaleimide, it is preferably used in an amount of 0.1-2.0% by weight calculated relative to the sum of the parts by weight A + B + C + D.

A particularly suitable bismaleimide is N, 1, -4, 4'-diphenylmethane bis-maleimide.

25

As an agent for improving the impact strength (D), the polymer mixture according to the invention may contain an impact resistant polystyrene or a styrene-diene diblock or triblock copolymer in which the poly-diene blocks are selectively hydrogenated or not.

In addition to the above-mentioned components, the polymer mixture according to the invention as component E can, for example, contain one or more plasticizers / one or more agents for improving the flame-retardant f 7 (\ Γ * «fi * · * V v> 1 5» * 8-CB-10.218 -4- properties, one or more stabilizers, one or more fillers such as reinforcing fillers, one or more dyes or pigments and / or crystal clear polystyrene.

5

The polymer mixtures according to the invention in any case contain the following components: A. one or more polyphenylene ethers and B. one or more polyolefins functionalized with an unsaturated carboxylic acid or reactive derivative thereof.

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The polymer blends may additionally contain one or more of the following ingredients: C. one or more bismaleimides and / or D. one or more impact enhancers E. one or more additives.

20 A. Polyphenylene ethers.

The polyphenylene ethers (also known as polyphenylene oxides), which form component A in the polymer mixtures according to the invention, contain a large number of structural units of formula (I) (see 25 page 17).

In each of these units individually, each Q ^ individually represents a halogen, a primary or secondary lower alkyl (i.e., an alkyl of 1-7 carbon atoms), phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy or halohydrocarbonoxy, wherein at least two carbon atoms separate the halogen and oxygen atoms and each individually represents a hydrogen, a halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q - * -. Examples of suitable f, f; Primary lower alkyl groups, 21-methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, η-hexyl, 2, 3-dimethylbutyl, 2-, 3- or 4-methylpentyl and the corresponding heptyl groups.

Examples of secondary lower alkyl groups are isopropyl, sec-butyl and 3-pentyl. Preferably alkyl radicals, if present, have a straight chain instead of a branched chain. Usually each Q * is an alkyl or phenyl, in particular a 0-4 alkyl and every 10 is hydrogen. Suitable polyphenylene ethers have been described in a large number of patents.

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Homopolymeric and copolymeric polyphenylene ethers are suitable. Suitable homopolymets are those containing, for example, 2,6-dimethyl-1-4-phenylene ether units. Suitable copolymers are, for example, random copolymers containing such units in combination with, for example, 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable random copolymers and homopolymers have been described in the patent literature.

Also suitable are polyphenylene ethers, which contain parts that modify properties such as molecular weight, melt viscosity and / or impact strength.

Such polymers are described in the patent literature and can be prepared by grafting vinyl monomers such as acrylonitrile and vinyl aromatic compounds (eg styrene) or polymers such as polystyrenes and elastomers on the polyphenylene ether in a known manner. The product usually contains grafted and ungrafted parts. Further suitable polymers are the coupled polyphenylene ethers in which the coupling agent is reacted in a known manner with the hydroxy groups of two polyphenylene ether chains under f '· τ ν

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8-CB-10,218-6- formation of a higher molecular weight polymer containing the reaction product of the hydroxy groups and the coupling agent. Examples of coupling agents are low molecular weight / 5 quinone compounds polycarbonates, heterocyclic compounds and formal compounds

The polyphenylene ether usually has a number average molecular weight of about 3,000 to 40,000 and a weight average molecular weight of about 20,000-80,000 determined by gel permeation chromatography. The intrinsic viscosity is usually between about 15 and 60 and is preferably at least 25 ml / g measured in chloroform at 25 ° C.

Polyphenylene ethers are usually prepared by oxidative coupling of at least one corresponding monohydroxyaromatic compound. Particularly suitable and readily available monohydroxyaromatic compounds are 2,6-xylenol (wherein each Q1 represents a methyl and each Q2 represents a hydrogen), resulting in a poly (2,6-dimethyl-1,4-phenylene-ether) polymer and 2 3 6-trimethylphenol (wherein 25 each represents Q- * and a Q2 methyl and the second Q2 represents hydrogen).

A number of catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupling. There is no particular limitation on the choice of catalyst and any of the known catalysts can be used. For the most part, they contain at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with various other materials.

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A first class of preferred catalyst systems is that which contains a copper compound. Such catalysts are described, for example, in US-A-3,306 / 874; US-A-3,306,875; US-A-3,914,266 and US-A-4,028,341. It usually concerns combinations of cupro and cupric ions, halide (ie chloride, bromide or iodide) ions and at least one amine. Catalyst systems containing manganese compounds are a second preferred type. These are usually alkaline systems in which divalent manganese is combined with anions such as halide, alkoxide or phenoxide. Usually, the manganese is present in the form of a complex with one or more complexing agents and / or chelating agents such as dialkylamines, alkanolamines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds; omega-hydroxy oximes (monomeric and polymeric), 20 o-hydroxyaryl oximes and beta-diketone compounds.

Also known are known cobalt-containing catalyst systems. Suitable manganese and cobalt-containing catalyst systems for the preparation of polyphenylene ethers are well known in that they have been described in numerous patents and publications.

Polyphenylene ethers that can be used in the invention are also those containing molecules having at least one of the end groups of formulas II and III (see page 17), in which and have the same meaning as indicated above in which each R 2 is hydrogen or represents alkyl, wherein the total number of carbon atoms in both radicals is 6 or less; and each R ^ P "0 Γ '11

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* 8-CB-10,218 -8- individually represents hydrogen or a 6 primary alkyl radical. Preferably, each is hydrogen and each alkyl, especially methyl or n-butyl.

Polymers with end groups of formula II

(hereinafter "aminoalkyl end groups") can be formed by incorporating a suitable primary or secondary monoamine as one of the components of the oxidative coupling reaction mixture, especially when a copper or manganese containing catalyst is used. Such amines, in particular the dialkyl amines and preferably di-n-butylamine and dimethyl amine, are regularly chemically bound to the polyphenylene ether, usually by linking one of the alpha hydrogen atoms to one or more radicals to replace. The main reaction site is the Q1 radically located next to the hydroxy group on the terminal unit of the polymer chain. During further processing and / or mixing, the aminoalkyl end groups can undergo various reactions, probably involving a quinone-methide type intermediate of formula IV (see page 17), with numerous beneficial effects including often an increase in impact strength and a compatibility with other ingredients in a mixture.

Reference can be made for this to US-A-4,054,553; US-A-4,092,294; US-A-4,477,649; US-A-4,477,651 and US-A-4,517,341, the contents of which are incorporated by reference herein.

Polymers with 4-hydroxybiphenyl end groups of formula III are usually obtained from reaction mixtures containing a by-product diphenonquinone of formula V (see page 17), especially in a copper halide secondary or tertiary amine system.

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In this regard, the content of US-A-4,477,649 is of interest as well as that of US-A-4,234,706 and US-A-4,482,697, which are also incorporated herein by reference. In mixtures of this type, the diphenonquinone is ultimately incorporated into the polymer in relatively large amounts, largely as an end group.

In many polyphenylene ethers, which are obtained under the above-mentioned conditions, a large proportion of the polymer molecules, for example as much as 90% by weight of the polymer, contain end groups with one or sometimes both of formulas II and III. It will be clear that other end groups may also be present and that the invention in its broadest form does not depend on the molecular structure of the polyphenylene ether end groups.

Those skilled in the art will appreciate that the polyphenylene ethers useful in the invention include any polyphenylene ethers currently known, regardless of variations in structural units or further chemical aspects.

B. Polyolefins functionalized with an unsaturated carboxylic acid or reactive derivative thereof.

Polyolefins functionalized with unsaturated carboxylic acid are compounds known per se. Two types can be distinguished: a first type where one or more unsaturated carboxylic acids are included in the polymer chain (copolymer) and a second type where one or more unsaturated carboxylic acids are grafted on the polyolefin chain (graft polymer). Both types can be used in the polymer mixtures according to the invention.

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The polyolefin preferably contains ethylene, propylene or butylene units or also a mixture of alkylene units such as ethylene propylene. Suitable polyolefins are, for example, low or high density polyethylene, linear low density polyethylene or polypropylene.

In addition to the units derived from the above-mentioned monomers, the polyolefin may also contain units derived from further copolymerizable monomers. Suitable copolymerizable monomers are, for example, unsaturated monomers such as alkyl acrylates or methacrylates, alkyl maleates, vinyl halides, vinyl ethers, N-vinyl lactam compounds and N-vinyl carbon amides.

The unsaturated carboxylic acid or reactive derivative thereof may be included in the polymer chain or may be grafted onto the polymer chain. As unsaturated carboxylic acid or reactive derivative thereof, one or more of the following compounds can be used: maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide, methylnadic acid, dichloromaleic anhydride, maleic amide, certain natural fats and oils such as, for example, soybean oil, acrylic acid, methacrylic acid, 2,3-dimethyl-3-butenoic acid, diallylacetic acid, linolenic acid, acid amides or anhydrides of unsaturated carboxylic acids.

30

The weight percentage of alkylene units is generally between 50 and 99.99; from the units derived from unsaturated carboxylic acids or reactive derivatives thereof between 0.01 and 25, and from any units present derived from further copolymerizable monomers between 0 and 50.

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A functionalized polyolefin commercially available under the ADMER® L 2100 brand is preferably used. This product is a maleic anhydride functionalized ethylene copolymer.

5 C. Bismaleimides.

The polymer mixtures according to the invention can contain one or more bismaleimides. The addition of bismaleimides leads to a stronger interaction between the different components, probably in particular between components A and B. This is evident from the reduction in the amount of extractable material and the increase in the melt viscosity of polymer mixtures containing a bismaleimide. .

Such an interaction further reduces the tendency to delamination.

Suitable bismaleimides are the compounds of formula VI of the formula sheet (page 17). In this formula, R 1 represents a divalent radical such as a radical derived from, for example, methane, butane, benzene, bis (benzene) methane. It is also possible to use a mixture of the precursors (precursors) of such bismaleids, for example a reaction product (such as an acid amide) of a suitable diamine and maleic or maleic anhydride.

D. Agent for improving impact strength.

The polymer mixture according to the invention can contain one or more agents for improving the impact strength. As such, any agents known for polyolefins and / or for polyphenylene ethers can be used.

Particular mention may be made of impact-resistant polystyrene and styrene-diene block copolymers. This £ ~ ’: ·; 1 * * Λ 8-CB-10.218 -12 block copolymers can be diblock or triblock copolymers or radial block copolymers. The diene blocks can be selectively hydrogenated. It is of course possible to use a mixture of one or two different block copolymers or, for example, a mixture of impact-resistant polystyrene and a block copolymer.

E. Additives.

The polymer mixture according to the invention can contain one or more of the additives customary for polyphenylene ethers and / or polyolefins.

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Particularly mentioned are plasticizers / agents for improving the flame-retardant properties / such as, for example, phosphates or halogen-containing styrene compounds / stabilizers such as phosphites / fillers such as reinforcing fillers, for example glass fibers / dyes or pigments; crystal clear polystyrene.

20

The polymer mixtures according to the invention can be prepared in a manner generally known for polymer mixtures. Preferably, the different polymers are melt-mixed together, for example in an extruder.

Examples 1 / II / III and IV and comparative example A _._

Several polymer blends were prepared having a composition as indicated in Table 1 below. As polyphenylene ether, a poly (2/6-dimethyl-1,4-phenylene) ether with an intrinsic viscosity of 46 ml / g was measured in chloroform at 25 ° C / prepared with a copper amine catalyst. As the functionalized polyolefin, a maleic anhydride functionalized ethylene. . . "F H · -p.

-8-CB-10.218-13-copolymer used / commercially available under the designation ADM ADR® L 2100. In Examples II and IV, a bismaleimide was used / namely NrN, -4,4, -diphenylmethane- bis-maleimide. Examples III and IV used an impact improving agent / a styrene-butadiene-styrene triblock copolymer with selectively hydrogenated butadiene blocks. The number molecular weight of the triblock copolymer is about 10 74,000 / with a polystyrene to polybutadiene ratio of from 27 to 73.

In comparative example A, a non-functionalized polyethylene was used / namely a low density polyethylene.

The components were extruded in the amounts indicated (see Table A) in a Werner Pfeiderer twin screw extruder at 300 revolutions per 20 minutes and at a temperature set at 285 ° C. The extrudate was chopped (pellets). The polymer blend extrudate of Comparative Example A gave a rough, very brittle beach, the grains of which occasionally exhibited clearly delaminated structures. The brittleness of the beach according to comparative example A was such that the beach already broke with a slight bend. Standardized test samples were injection-molded from the granules of the polymer mixtures according to the invention for determining the impact strength according to Izod with and without notch, for determining the instrumented falling dart impact (FDI), the tensile strength and the heat deflection temperature ( HDT).

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The instrumented Falling Dart Impact was determined on injection molded discs with a thickness of 3.2 mm and a diameter of 100 mm. In this test, a standard test body with a hemispherical 5 point and weighing 100 N is dropped on the disc from a height of 2.2 meters. The disc lies on a ring with a diameter of 95 mm. The energy absorbed by the disc until the time the disc breaks is measured. The energy value thus found is designated as "Falling Dart Impact" (DIN 53443). The tensile strength was measured on a Zwick tensile tester at a tensile speed of 50 ntm / min. The tensile yield strength and elongation at break were determined.

15

Furthermore, the percentage of extractable material was determined by extracting finely ground material with chloroform.

The melt viscosity was determined in a Göttfert Rheometer, at a constant shear rate of 1500 s - * - and a temperature of 282 ° C.

The results obtained are summarized in Table 1.

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Table 1

Example AI II III IV

5 Composition (parts by weight o polyphenylene ether 50 50 50 45 45 o functionalized - 50 50 45 45 10 polyolefin o bismaleimide - - 0.25 - 0.5 o triblock copolymer - - - 10 10 o unfunctionalized polyolefin 50 - - -

Properties o Izod impact strength - 611 422 - - 20 without notch (y / m) o Izod impact strength 43 25 412 325 with notch (Yy / ro) o Max. tensile strength - 19 17 17 17 (N / m2) 25 o Elongation at break (%) - 16 13 120 61 o Melt viscosity 63 338 352 321 332 (Pa.s) o Falling dart impact - 3 2 85 71 (J) 30 o % extractable - 48 46 - 45 material o HDT (° C) - 106 88 - o delamination yes no no no no (visually assessed on the extrudate) ί 7 i. - * f • ’τ- Α 8-CB-10 218 -16-

It can be seen from the table that the polymer blends of the examples have good mechanical properties. The addition of a bismaleimide leads to a decrease in the percentage of extractable material and an increased melt viscosity. This indicates an improved interaction between both main components.

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Claims (9)

Polymer mixture containing a polyphenylene ether and a functionalized polyolefin / characterized in that the polymer mixture consists of: A. one or more polyphenylene ethers, in an amount of 2-74 wt.% B. one or more with a unsaturated carboxylic acid or reactive derivative thereof functionalized polyolefins, in an amount of 26-98% by weight; C. one or more bismaleimides, in an amount of 10-5 wt%; D. one or more impact improving agents, in an amount of 0-25% by weight; E. one or more additives in an amount of 0-20 parts by weight per 100 parts by weight of A + B + C + D, 15 in which the percentages by weight are calculated relative to the sum of the parts by weight A + B + C + D. Polymer mixture according to claim 1, characterized in that the polymer mixture consists of: A. one or more polyphenylene ethers, in an amount of 5-60% by weight; B. one or more polyolefins functionalized with an unsaturated carboxylic acid or reactive derivative thereof, in an amount of 40-95% by weight; C. a bismaleimide, in an amount of 0-5 wt%; D. an agent for improving the impact strength, in an amount of 0-25 wt.% E, conventional additives in an amount of 0-20 parts by weight per 100 parts by weight of A + B + C + D, the weight percentages being calculated relative to the sum of the parts by weight A + B + C + D. Polymer mixture according to claim 1, characterized in that the polymer mixture as component B contains a copolymer or a graft copolymer of ethylene and maleic anhydride. Polymer mixture according to claim 1, characterized in that the polymer mixture as component C contains N, N'-4,4'-diphenylmethane-bis-maleimide. 0 · f * yr j> ï. - - I -¾. ^ Il Λ Polymer mixture according to claim 1, characterized in that component C is present in an amount of 0.1-2% by weight. 6. Polymer mixture according to claim 1, characterized in that the polymer mixture as component D contains an impact-resistant polystyrene or a styrene-diene diblock or triblock copolymer in which the polydiene blocks are selectively hydrogenated or not. Polymer mixture according to claim 1 / characterized in that the polymer mixture as component E comprises one or more plasticizers, one or more agents for improving the flame-retardant properties, one or more stabilizers, one or more fillers such as reinforcing fillers, one or more contains more dyes or 1 15 pigments and / or crystal clear polystyrene. Polymer mixture according to claim 1, characterized in that the polymer mixture as component A is poly (2,6-dimethyl-1,4-phenylene ether) or poly (2,6-dimethyl-co-2,3-6-trimethyl-). 1,4-phenylene ether). 8-CB-10.218 -19- 8-CB-10.218 -18- CONCLUSIONS. Articles formed from the polymer mixture according to one or more of the preceding claims. 25 30 35 r, - * f '