JPS62246957A - Thermoplastic molding material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Industrial applications The present invention A) at least 5% by weight of holJ phenylene ether and B] At least 5% polyamide Thermoplastic molding material containing.

Furthermore, the invention relates to a molded article containing the above-mentioned molding material as a main component.

Prior Art Polyphenylene ethers have excellent thermal, mechanical and dielectric properties, but are extremely difficult to process in pure form. Mixtures of polyphenylene ether and styrene polymers are also known. However, Mixture 9/J suffers from the disadvantage that its solvent stability is extremely low. Therefore, its field of use is severely limited.

Furthermore, from U.S. Pat.
It is known that the amount (') can be improved by adding polyamide. However, this publication further states that additions of more than 20% by weight of polyamide significantly deteriorate other properties of the polyphenylene ether.

From GB 2,054,623 a molding composition consisting of polyphenylene ether and a high proportion of polyamide is also known. However, producing the molding material requires a long mixing process at melt temperature.

However, when mixed at melting temperature for a long time, decomposition phenomena easily occur.

EP-A-24120 describes liquid diene polymers and/or compounds consisting of polyphenylene ethers and polyamides containing carbon-carbon double bonds and carboxylic acid groups and/or epoxy compounds. The epoxy compound is an epoxy resin produced by condensation of a polyhydric alcohol or phenol with epichlorohydrin, a glycidyl derivative of an amino compound, or &X
It is an epoxidation product of A-class olefins or cycloalkanes. The molding material produced in this way does indeed have good mechanical properties, although laminar cracks (delaminations) can be observed in the molded body.

Problems to be Solved by the Invention Therefore, the object of the present invention is to provide a material having good thermal, mechanical and dielectric properties in addition to good processing properties, and having particularly high impact resistance and good solvent stability. The object of the present invention is to provide a thermoplastic molding material that has excellent properties and does not cause delamination.

Means for Solving the Problems The above-mentioned problem is solved by the invention, in a thermoplastic molding material containing A) at least 5% by weight of polyphenylene ether, B) at least 5% by weight of polyamide, C) C1) styrene and/or General formula (I): [wherein R and R'+!
at least 3 tIL-substituted styrenes representing an alkyl group having 1 to 8 carbon atoms, a hydrogen atom and/or a halogen atom, and n is 0, 1.2 or 3
0% by weight, 0° at least 0.5% by weight of a polymerizable monomer containing epoxy groups and/or 03) General formula (■): [wherein X&X represents a halogen atom and R2 and Ha are 1 to 8 At least 0.05% by weight of a polymerizable monomer containing a halogen benzyl group, which has a structural unit represented by an alkyl group containing one carbon atom or a hydrogen atom, and n is 1.2 or 3. and/or R4) at least 0.05% by weight of oxazoline-based polymerizable monomers and 5) at least 0.05% by weight of acrylonitrile, methacrylnitrile and/or other comonomers. 1% by weight and D) 0-35% by weight of impact-modifying rubber.

Advantageous embodiments of a molding material of this type are evident from the dependent claims.

Operation and Effects of the Invention The thermoplastic molding material of the invention has the advantage of being well processable, having good mechanical properties and high impact resistance and solvent stability. Moreover, no delamination is observed in molded articles made from the material.

The advantageous properties of the molding composition according to the invention are that, as is evident, for example, from DE 30 27 104 A1, phase separation occurs in most cases when molding mixtures of polyphenylene ether and polyamide. This contradicts the prevailing opinion that compatibility between the two plastics does not occur in the mixture.

The polyphenylene ethers A) contained in the molding compositions according to the invention are known per se. Compounds based on substituted, disubstituted polyphenylene oxides are suitable, in which the ether oxygen atom of one unit is bonded to the benzene nucleus of the adjacent unit. Polyphenylene oxides substituted in the 2 to 6 positions relative to the oxygen atom are preferably used, in which case at least 50 units are preferably bonded to one another. Examples of substituents include halogen atoms, such as chlorine atoms or bromine atoms, and alkyl groups having 1 to 4 carbon atoms Z, preferably alkyl groups without a tertiary hydrogen atom in the alpha position, such as methyl, ethyl group, propyl group or butyl group. Furthermore, alkyl groups may be substituted by halogen atoms, such as chlorine or bromine atoms, or by hydroxy groups. Another example of possible substituents is fI!, preferably by an alkoxy group having up to 4 carbon atoms or optionally a halogen atom and/or an alkyl group. t, a substituted 7-enyl group. Similarly, different phenols, l-1,
1 mer, for example 2,6-dimethylphenol 2.3.
6- To! J Methylphenol fuvolimer is also added as appropriate. Of course, it is also possible to use mixtures of different polyphenylene ethers.

Examples of polyphenylene ether &X, Ho IJ (2,5-
dilauryl-1,4-phenylene) oxide, poly(diphenyl-1,4-phenylene oxide, poly(2,
6-Simethoxy1,4-phenylene)oxide, poly(2,6-dinitoxy1,4-phenylene)oxide, poly(2-methoxy-6-nitoxy1,4-phenylene)oxide, poly(2-methyl-6 ,
6-dichloro-1,4-7 enylene) oxide, poly(
2-Methyl-6-7enylene-1,4-phenylene] oxide, poly(2,6-dibensyl-1,4-)unisine] oxide, poly(2-ethoxy-1,4-phenylene) oxide, Poly(2-chloro-1,4-phenylene) oxide, poly(2,5-dibromo-1,4-phenylene oxide).The R substituent is an alkyl group containing 1 to 4 carbon atoms. Polyphenylene ethers, such as poly(2,6-dimethyl-1,4-phenylene oxide, poly(2,6-dinityl-1,4-7 enylene)
Oxide, poly(2-methyl-6-nityl-1.4-
phenylene] oxide, poly(2-methyl-6-broby-1,4-phenylene) oxide, poly(2,6-
Preference is given to using diprobyl-1,4-phenylene) oxide and poly(2-ethyl-6-propyl-1.4-phenylene) oxide.

Regarding the physical properties of polyphenylene ether, 30
0.4-0.7 di, measured in chloroform at
Preference is given to those having a limiting viscosity of /f.

The proportion of polyphenylene ether in the molding material according to the invention is not critical, provided that it is at least 5% by weight, based on the total weight of components A) to D], preferably &'! , 10~
It should be 89% by weight. Particular preference is given to molding compositions containing 20 to 70% by weight, especially 35 to 60% by weight, of polyphenylene ether.

The polyphenylene ether used as component A) is
Styrene polymers can be partially substituted. It is advantageous to replace up to half of the polyphenylene ether component with such styrene polymers. Examples of such styrene polymers include polystyrene, poly-α-
methylstyrene or poly-p-methylstyrene;
Among them, polystyrene is advantageous. Also advantageous are styrenic polymers which have been backchanneled in the presence of 2 to 20 t% by weight of rubber-elastic polymers. Rubber-like polymers based on butadiene, such as styrene-butadiene polymers, polybutadiene and also butadiene-styrene block copolymers, are suitable in this case. When using styrene-diene-block copolymer,
It has proven advantageous to substitute up to 20% by weight of the polyphenylene oxide content with butadiene- or isopre/-styrene block polymers or hydrogenated products thereof.

The molding composition according to the invention comprises as component B) at least 1
Contains various thermoplastic polyamides. Although no particular restrictions have to be taken into account with respect to the structure of the polyamides, preference is given to polyamides derived from lactams with 7 to 13 ring members, such as polycaglolactam, polycapryllactam or polylaurinlactam. , as well as polyamides obtained by the reaction of dicarboxylic acids and diamines. Dicarboxylic acids which can also be used in combination include alkanedicarboxylic acids containing 6 to 12, especially 6 to 10 carbon atoms, and terephthalic acid and isophthalic acid. Examples of diamines which can likewise be used in combination are alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms, furthermore m-xylylene diamine, bis(4-aminophenylnopropane-2
, Al at 2.

It is likewise possible to use mixtures of polyamides produced in this way. From an industrial point of view, polyamides composed of polycaprolafterne and polyhexamethylene sebacamide, as well as hexamethylene diamine and hysoheptalic acid and/or terephthalic acid, are of greater importance.

As for the physical properties, there are likewise no particular limitations, but it is nevertheless possible to obtain a linear viscosity with a relative viscosity of 2.2 to 4.5, measured as a 1% solution in 96% sulfuric acid at 23°C. Polyamides are preferred.

The proportion of component B) in the molding composition according to the invention also includes component A]
As with , there are no special restrictions, but A) ~
Based on O), at least 5% by weight, preferably from 10 to 89% by weight of polyamide is used. Particularly preferred molding materials are thermoplastic polyamides 15 to 70, very particularly preferably 2.
5~60i1F! Contains %. All % values are for component A
) to D) are taken as the reference.

As a further component, the molding composition according to the invention comprises C1) styrene and/or general formula (I): in which R and R1 are an alkyl group having 1 to 8 carbon atoms, a hydrogen atom and/or At least 3 t11-enhanced styrenes representing a halogen atom and n being 0.1.2 or 3
0% by weight, 0° at least 0.5% by weight of polymerizable monomers containing epoxy groups and/or 03) of the general formula (It
): [In the formula, X represents a halogen atom, R2, p, and a represent an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, and n is 1.2 or 3] at least 0.05% by weight of polymerizable monomers containing halogen benzyl groups and/or 0.4) at least 0.05% by weight of polymerizable monomers containing oxazoline groups having structural units of acrylonitrile, methacrylonitrile and and/or other nonionic fumonomers, and at least 0.11% by weight of copolymers thereof.

Monomers containing epoxy groups, halogenbenzyl groups or oxazoline groups improve the adhesion between components A) and B] and thus overall improve the properties of the molding compositions produced therefrom. The adhesion improving effect is probably due to the epoxy group,
This is due to the interaction of the halogen benzene/I/ groups and/or oxazoline groups with components A) and B). It is not yet possible to say with certainty whether this interaction forms a covalent bond or whether it is a physical interaction.

As mentioned above, component C) is styrene and/or of general formula I
C1) containing at least 30, preferably at least 80% by weight of substituted C1). Additionally, up to 20% by weight of acrylonitrile and/or (emethacrylonitrile and other nonionic comonomers a5) may be contained. However, comonomers which omit the component Os) are advantageous.

As substituted styrenes of the general formula I, α-methylstyrene and p-methylstyrene are particularly preferred; however, examples include liver, various ethyl- and chlorostyrenes (m-10-1p), to name a few. -) is also appropriate.

As the epoxy group-containing monomer 01), all compounds having an epoxy group in the molecule are suitable in principle. However, preference is given to using monomers carrying glycidyl groups, especially glycidyl acrylate and glycidyl methacrylate.

However, glycidyl derivatives and glycidyl allyl and vinyl ethers of other acids are also suitable. These are generally characterized by the structural formula in the molecule:

If monomers containing epoxy groups are used, comonomer C) is styrene and/or substituted styrene, preferably 80 to 99.5 iti%, W! Interest 1C is 90-9
8% by weight and from 0.5 to 20, particularly preferably from 2 to 10% by weight, of monomers containing epoxy groups. The proportion of further copolymerizable monomers, if used, is preferably less than 10 ii 11%, particularly preferably 8% by weight.

The molecular weight of the comonomer a) containing epoxy groups is generally from 20,000 to 1,000,000, preferably from 40,000 to
It is within the range of 250,000.

According to another embodiment, the copolymer used is a copolymer composed of styrene and/or substituted styrene <1) and a monomer having halogen benzyl groups. In the following, the following structural units according to the invention are used as halogenbenzyl groups: It is to be understood that R1 and R2 can be an alkyl group having 1 to 8 carbon atoms or a hydrogen atom. The halogen benzyl group is advantageously (echloromethyl-vinylbenzene (meta, rose or mixtures of these isomers)
introduced by However, as in compounds containing epoxy groups, the halogen benzyl group itself is important, so in principle it can be copolymerized with 0,
All compounds in which the above structural units are π are suitable.

used! Regarding the substituted styrene and possible substitution with other monomers, what has been said above regarding the epoxy group-containing copolymers also applies.

According to a particularly advantageous embodiment, the copolymer C) comprises styrene and/or styrene with 1% to 99.5%,
Particularly preferably from 95 to 99.5% by weight and from 0.05 to 20, particularly preferably from 0.05 to 20, of monomers having halogen benzyl groups.
．． It consists of 5 to 5% by weight. The proportion of other copolymerizable monomers, if present, is 10% by weight or less.

Contains a halogen benzyl group. Acupoint +) Mark C) is
Generally 5000-10000001 preferably 2oooo
~250,000 S, particularly preferably 40,000 to 2,000
It has a molecular weight of 0.0.

According to another embodiment, the copolymer C) comprises component C
4) It has at least one oxazoline group-containing polymerizable monomer Z@.

The cholera heptads are preferably those represented by the general formula (1): [wherein 2 contains a polymerizable double bond].

Preferred substituents 2 have the formula: %Formula % where R2 is a hydrogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms, to name a few methyl groups, 1 - and n-probyl or butyl groups.

Particularly preferred monomers 04) are vinyloxazolines of the general formula 1:t, in which R2 is as defined above and preferably represents a hydrogen atom or a methyl group.

The copolymers used according to the invention can be prepared in a continuous batchwise manner by bulk, solution, emulsion or suspension polymerization in a manner known per se. Advantageously, the monomers are polymerized in a suitable solvent, for example ethylbenzene. In a particularly advantageous embodiment, seven polymers, such as styrene or chlormethylvinylbenzene, can be used continuously with a radical initiator or with a radical initiator, i.e. without an initiator. Polymerize at high pressure.

Component O) may also be impact-modified.

Such polymers are generally known to those skilled in the art as high-impact polystyrenes or corresponding styrene derivatives. + in this case! The polymer is prepared in the presence of impact-modifying rubber or is grafted and mixed with a rubber. Rubber-like polymers include, for example, polybutadiene, styrene-butadiene, styrene-b-butadiene, acrylonitrile-butadiene, ethylene-propylene, polyacrylate and polyisoprene rubber. C) is preferably not modified for impact resistance. They can also be used in ungrafted form for the impact modification of component A).

In this case, in addition to components A) and B), it is also possible to add impact-modifying rubber D).

In this case, examples are polybutadiene rubber, acrylate rubber, styrene-butadiene rubber, polybutene rubber, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, polyisoprene rubber. - Rubbers, styrene-grafted ethylene-propylene rubbers, thermoplastic ethylene-propylene 7-f rubbers, h-flexible polyester-elastomers, ethylene rubbers and ionomers, styrene-butadiene block copolymers, e.g. AB ,ABA,
AEA-tapering and star block copolymers and similar isoprene-block copolymers and hydrogen 1
hydrogenated or partially hydrogenated block copolymers. Among these, block copolymers containing styrene and butadiene are preferred.

The proportion of rubber D) which is modified to be 1iiv resistant is not critical. However, the proportion is generally below 35% by weight, preferably between 4 and 20% by weight, based on the total weight of components A) to D).
It is.

Thermoplastic molding according to the invention! On the scale, as separate ingredients,
Conventional additives and processing aids can be included in effective amounts. The proportion is preferably less than 40i-11%, particularly preferably less than 20% by weight. To name a few: heat and light stabilizers, lubricants and mold release agents, colorants such as dyes and pigments, reinforcing agents such as glass fibers, asbestos fibers, carbon fibers, aromatic polyamide fibers and/or light moulds. agent,
Mention may be made of orthogonal fibers, synthetic calcium silicate, kaolin, calcined kaolin, wollastonite, talc, chalk, and also fireproof materials such as inorganic and organic phosphorus compounds. Furthermore, further low-molecular weight or high-molecular weight polymers can be included as additives in the molding compositions according to the invention.

The thermo-OTfable molding material according to the invention is preferably processed by mixing the components in a conventional mixing apparatus such as a kneader, a Banbury mixer and a screw extruder, preferably a twin-screw extruder, at a temperature of 250 to 320°0'. ) produced by mixing at temperatures within the range. Intensive mixing is necessary in order to obtain a molding material that is as homogeneous as possible. The mixing order of each component can be varied; two or optionally more components can be mixed first, or all components can be mixed together.

Molded bodies having good mechanical properties can be produced from the thermoplastic molding compositions according to the invention by injection molding or extrusion.

Example Next, the present invention will be explained in detail with reference to Examples.

Example 1 A molding composition according to the invention was prepared using the following components: Component A Relative viscosity 0.61 (measured in chloroform at 30° C.)
B1 Polycaprolactam having a relative viscosity of 3.2 and B2 Polycaprolactam having a relative viscosity of 3.9 and 96 at 23°C, respectively. Styrene-butadiene-styrene-block copolymer prepared by rubber (DJ anionic main polymerization, r, 9; 32% by weight of styrene and butadiene 6s !it% included: MW-11000
0 (weight average molecular weight) Component C Styrene-chloromethylstyrene-copolymer (95ift% styrene, 3t!% m-chloromethylstyrene, p-produced by continuous solution polymerization at 0.135°C and residence time 6 hours) -2% by weight of chloromethylstyrene;
%-80000 (weight average molecular weight) 02 Produced in the same manner as component C1, except that the molecule it M
.

A styrene-chloromethylstyrene polymer (97% by weight of styrene, 2% by weight of m-chloromethylstyrene, 1% by weight of p-chloromethylmethy9) having a molecular weight of -5sooo <weight average molecular weight) Screw extruder (Fa.

Werner &, Pfleidsrer) at 28
Mix at 0°C, granulate the resulting molding material, and process it into a molded body by injection molding. All the samples according to the invention showed no laminar cracks (delamination), whereas the comparative example showed cracks.

The measurement results of impact strength and notched impact strength are summarized in Table 1. Examples 14 to 25 Using the following components A) to C), the polymer was A molding material was produced by mixing at °C, the molding material obtained was granulated and processed into molded bodies by injection molding.

Components A Same components as in Example 1 B B1 polycaprolactam with relative viscosity [3, CIN and B2 polycaprolactam with relative viscosity 4.0 each in a solution containing 1% heavy gold in 96% sulfuric acid at 23'C Styrene-glycidyl methacrylate tofu polymer (styrene 93w 4#%, GII sidyl methacrylate 1 ll) prepared by continuous solution reaction with the same components as in measurement example 1 and a residence time of 5 hours. (%): MW-105000 a4) Produced in the same manner as component C3, but with molecular weight i□
-75,000 styrene-glycidyl methacrylate tofu polymer (96% by weight of styrene, 4% by weight of glycidyl methacrylate) The results of impact strength and notched impact strength measured based on D Engineering N 53453 are as follows: They are summarized in Table 2.

Examples 26-35 Molding compositions according to the invention were prepared using the following components: Component A Same components as in Examples 1-16 B B4 Polycaprolactam with relative viscosity 3.0 and B5 Relative viscosity 4°0 Polycaprolactam with 23"C respectively measured in a solution containing 1% monofilament in 96% sulfuric acid @Rubber (D) to increase impact resistance (Component D) Styrene produced by anionic polymerization Butadiene-styrene-block fuborimer; 32 wt% styrene and 68 N'rt% butadiene stone: Mw-ttOOoo 1 molecular weight ilc weight average] Component O 05 Styrene-vinyl oxazoline having a molecular weight (weight average) M, -200000 -Fholima- (99 mol% styrene, 1 mol% vinyloxazoline) The above polymer was extruded using a twin screw extruder (F&.

Werner & Pfleiderer) at 280
The molding material obtained was granulated and processed into molded bodies by injection molding. All samples according to the invention exhibit laminar cracking (delamination), whereas cracking occurred in the comparative example.

The composition of each molding material and the measurement results of impact strength and notched impact strength are summarized in Table 3. rate and good notch placement yf,
@ Indicates excellence in quality.

Claims (1)

[Scope of Claims] In a thermoplastic molding material containing A) at least 5% by weight of polyphenylene ether, B) at least 5% by weight of polyamide, C) C_1) styrene and/or general formula (I): ▲ mathematical formula, chemical formula, There are tables etc.▼(I) [In the formula, R and R^1 represent an alkyl group having 1 to 8 carbon atoms, a hydrogen atom and/or a halogen atom, and n is 0, 1, 2 or 3. C_2) at least 0.5% by weight of a polymerizable monomer containing epoxy groups and/or C_3) general formula (II): ▲The mathematical formula, chemical formula, table, etc. Yes▼(II) [In the formula, X represents a halogen atom and R^2 and R^3
represents an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, and n is 1, 2 or 3. % by weight and/or C_4) at least 0.05% by weight of polymerizable monomers containing oxazoline groups and C_5) acrylonitrile, methacrylnitrile and/or
or D) 0-35% by weight of a rubber modifying impact resistance.