DE2255930A1 - THERMOPLASTIC MASS - Google Patents

Description

PATENT ADVOCATE DR. HANS-GUNTHER EGGERT, DIPLOMA CHEMIST

5 COLOGNE 51, OBERLÄNDER UFER 90 2255930

Cologne, November 4th, 1972 Eg / Ax

General Electric Company, 1 River Road, Schenectady 5,

New York (USA)

Thermoplastic mass

The invention relates to new resin compositions, in particular Polymer compositions containing a polyphenylene ether, an elastomer Block copolymer of a vinyl aromatic compound and a conjugated diene and optionally contain a styrene homopolymer or random (randon) styrene copolymer resin »

The polyphenylene ethers are known and are described in numerous publications, e.g. U.S. Patents 3,306,874, 3,306,875, 3,257,357, and 3,257,358. The high molecular weight polyphenylene ethers are technical high-performance thermoplastics, which have relatively high melt viscosities and softening points above 275 ° C and are suitable for numerous technical applications that require high heat resistance, including suitable for the production of foils, fibers and standard parts.

In addition to the desirable properties noted above However, the polyphenylene ether resins have certain properties that are undesirable for some technical applications are. For example, molded parts made from polyphenylene ethers are poor in impact strength somewhat brittle. Furthermore, the relatively high

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Melt viscosities and softening points for many applications viewed as a disadvantage. Films and fibers can be made from the polyphenylene ethers on an industrial scale are produced by solution processes, but processing in the melt is technically uninteresting Because of the high temperatures required to soften the resin and related problems such as Instability, discoloration and the need for specially designed processing equipment and machines, who have to work at high temperatures. Molded parts can be produced by processing the masses as melts but here, too, the high temperatures required are undesirable.

Ea is known that the properties of the polyphenylene ether resins can be changed significantly by adding other resins. A process for improvement the processability of the polyphenylene ethers in the melt is for example in US Pat. No. 3,379,792 described by the applicant. According to this patent specification the flow properties of the polyphenylene ethers are improved, by giving them about 0.1 to 25 parts by weight of a Polyamides are added. Applicant's U.S. Patent 3,361,851 describes one based on polyphenylene ethers based molding compound that contains a polyphenylene ether mixed with a polyolefin »The polyolefin is added to improve impact strength and resistance to aggressive solvents In a third patent by the applicant, US Pat. No. 3,383,435, ways of improving the processability of the polyphenylene ether resins in the melt with simultaneous improvement of many properties of styrene homopolymers and random styrene copolymer resins. The one in the United States patent The invention described in 3,363,435 is the finding based on the fact that the polyphenylene ether resins and

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these polystyrene resins including the rubber-modified polystyrene resins in all proportions can be combined and lead to molding compounds that have numerous properties compared to those of each individual component are improved.

A preferred embodiment of US Pat. No. 3,383 is a molding compound which contains a high-impact, rubber-reinforced polystyrene and a poly (2,6-dialkyl-1,4-phenylene) ether. This molding compound is preferred because it includes the aforementioned Objectives of improving the processability of the polyphenylene ether resin in the melt are achieved and the further advantage of improving the impact strength of molded parts produced from the mixture is achieved Adjustment of the quantitative ratio of the two polymers are put together so that predetermined properties between those of polystyrene and those of polyphenylene ether are achieved. The reason for this is that the mixture has an, as is typical of known mixtures having a single combination of thermodynamic properties and not two different combinations of properties, ie, _e for each component of the mixture.

Those described in Applicant's U.S. Patent 3,383,435 Styrene resins are either homopolymers or random copolymers, i.e. copolymers with random distribution of the monomer units. For example, the crystalline polystyrenes are the examples 1 and 9 homopolymers. The polymer "Lustrex HT-88" mentioned in Example 7 is a commercially available, high impact polystyrene grafted with styrene and modified with butadiene rubber. In these Products is part of styrene in side chains

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homopolymerized a rubber main chain. Those described in column 3 of U.S. Patent 3,383,435 Atyrene-containing copolymer resins are random copolymers, namely copolymers of styrene with acrylonitrile, Copolymers of styrene with butadiene, copolymers of styrene with acrylonitrile and α-alkylstyrene, copolymers of styrene with acrylonitrile and butadiene (ABS), copolymers of ethylvinylbenzene and divinylbenzene and the like, with the exception of the styrene-acrylonitrile-α-methylstyrene copolymer in Example 17, the terminology in this United States patent can in no way be construed as such that it describes a block copolymer of type A-B-A. Since the monomers are in terminal blocks and are not grafted into side chains, A-B-A block copolymers and their properties are more linear differ considerably from the grafted rubber copolymers used according to US Pat. No. 3,383,435. Furthermore, since no copolymers with an elastomeric middle block are described, they include Mixtures and molding materials of this US patent no combinations of polyphenylene ethers with elastomers Block copolymers of vinyl aromatic compounds and conjugated dienes

Regarding the preferred embodiments in the United States patent 3,383,435 is assumed that the impact resistance of the polyphenylene ethers is due to the diene rubber content in random grafted high impact polystyrene and ABS resin is improved, and in this regard The improvement in impact strength turns out to be directly proportional to the diene rubber content of the polystyrene resin or the ABS resin, with increasing concentrations of diene rubber leading to increased impact strength to lead. However, it has also been found to be a disadvantage that the gloss of molded articles made of the polyphenylene ether resin and the high-impact polystyrene resin

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be assumed inversely proportional demDienkautsehu ^1, is content and therefore nit increasing content of Dienkatri, gloss and appearance -schuk the surface dor UW; ~ parts worse v; erdon _o Consequently performs Erböhi> t »· * of. Dienkautschukgohalta animal ^ molding compounds to increased impact strength, but "on ICoö.ten appearance and 0- <v nature of the surface and shine Uin.'io]. oli .- u results in a reduction dcß'Dicnkautschuk / iehaltn?" beiüniel ■ ■ -. wisely by using unprepared (ki'i ;: to.ll.i ■ υ.) polystyrene moldings that have a good gloss, jtV.ooh at the expense of sleep oil capacity. Since both impact strength and gloss are, from a commercial point of view, important properties in the production of moldings, it turned out to be despite the fact that the advantages mentioned above are achieved with the "preferred Pormraasson dor US Pat. No. 3,383,435"'Difficult to manufacture molding compounds with which both optimum impact strength and an optimum appearance and surface texture can be achieved »

In addition, as already mentioned, US Pat. No. 3,383,435 states that the polyphenylene ether-styrene resin compositions mentioned therein are produced by copolymerization of the styrene resin with an alkenyl cyanide compound. , for example acrylonitrile (Examples 10 to 12), can only be improved in the resistance to aggressive organic solvents. There is thus still a need for ways to more easily make porramaoos with excellent resistance to gasoline «

It has now been found that an elastomeric block copolymer a vinyl aromatic compound (A) and (A) and a conjugated diene (B) of type A-B-A, where A and A are the same or different and the middle block has a higher molecular weight than the terminal block Blocks, both the PolyphenylenlitHerharzon as well as the geniuses of polyphenylene ether resins

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BATH ORIGINAL

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and styrene homopolymers and random copolymer resins surprisingly high impact strengths and chemical properties Gives constancy. For example, a molded part made from a molding compound had the 45 parts of polyphenylene ether resin, 27.5 parts of an elastomer Block copolymer of styrene, butadiene and styrene and 27.5 parts of a modified polybutadiene Styrene resin contained, a notched Izod impact strength 1.19 mkg / 25i4 mm notch. When this molding is in a Jig that exerted an elongation of 1%, was clamped and immersed in gasoline, no hairline cracking or cracking occurred after 5 minutes. Further a molding compound made of 4-5 parts of poly (2,6-dimethyl ~ 1,4-phenylene) ether, 13 parts of an elastomeric styrene buta * diene-styrene block copolymer, 13.5 parts of a rubber-modified, high-impact polystyrene resin and 28 parts of a crystalline styrene homopolymer are processed into a molded part which has notched Izod impact strength of 0.57 mkg / 25 »4 mm notch and a similar, excellent resistance to gasoline would have. These blends can also be used with glass fibers to improve their properties without deterioration the excellent resistance to gasoline. All of these blends had higher impact strengths, higher elongations and a much improved resistance to attack by organic Solvents than the corresponding known - "standard masses, which contain a rubber, but not in the form of a block copolymer. For example, had a mixture of 45 parts of polyphenylene ether resin and 55 parts of a rubber-modified high impact strength Polystyrene has a notched Izod impact strength of 0.28 mkg / 25.4 mm notch and was catastrophically destroyed after 5 seconds in gasoline · In addition, the new molding compounds according to the invention an unusually good dimensional stability in the warmth.

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The invention normally relates to solid thermoplastics Masses containing the following components:

a) A polyphenylene ether resin or a mixture of a polyphenylene ether resin and a styrene homopolymer or random styrene copolymer resin and

b) an elastomeric block copolymer of a vinyl aromatic compound (A) and (A) and a conjugated one Diene (B) of type A-B-A, the middle block B having a higher molecular weight than the combined ones has terminal blocks A and A,

and component (b) is present in an amount of from about 10 to 80 percent by weight of the total resin components of the composition is.

Thermoplastic compositions in which the polyphenylene ether is at least 1% by weight of the total resin components are preferred matters in the crowd.

Of course, the thermoplastic compositions according to the invention can also contain customary amounts of customary additives, which the processability, flame retardancy, Improve stability, etc. '

Preferred embodiments of the invention are reinforced thermoplastic compositions containing reinforcing amounts of reinforcing agents, for example powder, whiskers, fibers or flakes of metals, for example aluminum, bronze, iron and nickel, and non-metals, for example carbon threads, needle-shaped CaSiO, asbestos, TiO ₂ , titanate whiskers, glass flakes and fibers and "like _e. contain. These reinforcing agents are present in amounts of, for example, 2 to 90% by weight, preferably 10 to 60% by weight. Glass fibers are particularly preferred as reinforcement.

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The preferred thermoplastic compositions contain in the Component (a) Polyphenylene ether resins with repeating structural units of the formula

in which the oxygen ether atom of one unit is connected to the benzene ring of the next adjacent unit is, η is a positive integer of at least 50 and each Q is a monovalent substituent selected from Hydrogen atoms, halogen atoms, hydrocarbon radicals ^ Halocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halocarbon oxy radicals having at least 2 carbon atoms between the halogen atom and the Phenyl nucleus is an existing group. The preparation of polyphenylene ether resins of the above formula is described in U.S. Patents 3,306,874, 3,306,875, 3,257,357, and 3,257,358, cited above. Polyphenylene ether resins containing alkyl substituents in carry the two o-positions to the oxygen ether atom, i.e. those in which each radical Q is an alkyl radical, preferably having 1 to 4 carbon atoms. Most preferred as a polyphenylene ether resin for the purposes of the invention is poly (2,6-dimethyl-1,4-phenylene) ether (wherein each Radical Q is a methyl radical).

The elastomeric block copolymers used as component (b) vinyl aromatic compounds and conjugated dienes are prepared by known processes and are also commercially available from a number of sources.

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Block copolymers of vinyl aromatic compounds and conjugated dienes are described by Kennedy et al in "Polymer Chemistry of Synthetic Elastomers", Interscience, Volume 23, Part II, 1969, pages 553 bis 559. In general, they are of the type A-B-A, wherein the middle block and the end blocks are vari-; can ieren. In the thermoplastic compositions according to the invention, the middle block B is always a block of one conjugated diene, e.g. butadiene, isoprene, 1,3-pentadiene and 2,3-dimethylbutadiene or mixtures of these dienes.

The terminal blocks A. and A are identical or different, but are always vinyl aromatic Compound, e.g. styrene, α-methylstyrenes vinyltoluene, Vinyl xylene, vinyl naphthalene or mixtures of these compounds derived. The block copolymer is contained in the particularly preferred thermoplastic compositions terminal blocks A and A made of polystyrene and one middle block B made of polybutadiene.

The proportion of the comonomers can be used within wide limits as long as the middle block has a higher molecular weight than the end blocks together. This proves necessary to achieve maximum impact strength and solvent resistance. Under With the above limitation in mind, the terminal blocks each have a molecular weight of about 2000 to 100,000, while the middle block has a molecular weight of about 25,000 to 1,000,000.

The block copolymers are made according to an organic " metallic compounds triggered polymerization process, in which, for example, organic Sodium or lithium derivatives can be used. The diene monomers can be monofunctional or difunctional Initiator can be polymerized as described in the above-referenced publication by Kennedy et al.

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In a known method, the block mixture is polymerized prepared as follows: The conjugated diene, e.g. Butadiene, is dissolved in an aromatic hydrocarbon such as xylene and toluene used as a solvent. The solution is 0.3 to per 100 parts of the monomer 7.5 mmoles of an organodilithium initiator, e.g., dilithiobutane and Dilithiostilben. The polymerization of the diene is completed, whereupon the vinylareate Compound added and the polymerization of this compound to form the block copolymer is brought to completion. The product is precipitated and deactivated, e.g. with an alcohol such as ethanol or Isopropanol, and by redissolving in a hydrocarbon and reprecipitation cleaned with alcohol 3 251 905.

In another process, the block copolymer is built up one after the other, using, for example, a secondary or tertiary alkyllithium compound in an amount based on the total weight of the monomers of about 100 to 2000 parts per million and a polymerization temperature in the range from 20 to 65 ° C. For example, styrene is dissolved in cyclohexane at 32 ⁰ C and treated with 5530 parts of sec-butyllithium per 1,000 000 parts. When the polymerization is complete, isoprene is injected and the polymerization is continued at 55 to 57.degree. Finally, styrene is added and the third block is polymerized. The product can be isolated in the manner described above. Such a process is fully described in U.S. Patent 3,231,635.

Styrene-butadiene-styrene block copolymer resins of this type alone and in admixture with rubber-modified styrene resins are also commercially available, e.g. the designations "Kraton" X-4119, K-1102, K-1101,

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XT-Ot55- and ΧΪ-Ο4Ο1 (manufacturer Shell Chemical Company, Polymers Division),

As mentioned earlier, the block elastomeric polymer resin a polyphenylene ether resin or a mixture a polyphenylene ether resin with an additional resin, preferably a styrene homopolymer or random Styrene copolymer resin, especially a high impact one Polystyrene resin can be added. As in the TJSA patent writ. 3 383 435 mentioned, styrene resins can most easily be combined with the polyphenylene ether resin contain at least 25% by weight of polymer units, the of vinyl aromatic monomers of the formula

RC ¹ Ss,

in which R is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms or a halogen atom, Z a vinyl group Hydrogen atom or an alkyl radical with 1 to 4 carbon atoms and ρ is a number from 1 to 5. These mixtures contain 1 to 99 wt .- ^ of the Polyphenylenätherkomroaente and 99 to 1% by weight polystyrene resin. Pure the purposes of the invention are considered to be either styrene resins Styrene homopolymers or rubber-modified polystyrenes preferred, for example with about 3 to 30% by weight, preferably 4 to 12% by weight, of a polybutadiene oder.a rubber-like random copolymer for example about $ 70 butadiene and $ 30 styrene are mixed or grafted.

The amount which is added to the polyphenylene ether with polystyrene or its mixture of the elastomeric Blockmisc'npolymerharzes, can lie within fairly wide limits, but is preferably about 10 to 80 wt _o - $ of the resin components,

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In a preferred group of thermoplastic compositions, the proportion of polyphenylene ether is between about 1 and 90 wt .->, the proportion of the elastomeric block copolymer of the vinyl aromatic compound with the conjugated Diene between about 10 and 80 wt .- ^ and the proportion of the styrene homopolymer or random copolymer resin between 0 and the remainder of the total weight of the resin components in bulk. Thermoplastic ones are particularly preferred Masses that are called polyphenylene ethers, poly (2,6-dimethyl-1,4-phenylene) ether in an amount of about 20 to 90% by weight, as component (b) an elastomeric block copolymer of styrene and butadiene of the styrene-butadiene-styrene block copolymer type in an amount of about 10 to 80 wt .- ^ and as styrene homopolymer or random styrenic copolymer resin is a rubber modified polystyrene in an amount of from 0 to about 60% by weight Total weight of resin components included in the mass.

Of course, other additives, e.g. plasticizers, pigments, flame retardants, can also be used in the thermoplastic masses Agents and stabilizers, present in amounts between about 1 and 30% by weight of the total composition be. The above range of amounts for the elastomeric block copolymer resin, the polyphenylene ether resin and, if present, the polystyrene resin is based solely on these resin components in the polymer mixture and excludes other additives.

The method of making the polymer blends is not critically important. Known mixing processes are suitable. Preferred is a process in which the polymers and, if used, the additives, e.g. mixes reinforcing agents in powder, granulate and fiber form, the mixture is extruded and crushed to granulate, which is suitable for the production of molded parts by processes that are normally used for deformation solid thermoplastic masses applied

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Preferred embodiments of the invention are shown in Examples described below illustrate these examples the advantages of mixtures that are an elasto-

meres A-B-A block copolymer resin composed of a vinyl aromatic compound with a conjugated diene and a Polyphenylene ether resin alone or in combination with another resin.

example 1

The ingredients listed below are mixed mechanically, then on a 19.05 mm Wayne extruder extruded and on an 85 g Newbury injection molding machine processed to test specimens Das Blockmischpolyraerisat and the rubber-modified polystyrene are first premixed. The physical properties are according to determined by the following test methods? Notched Izod Impact Strength (1/8 inch) according to ASTM D 256-56, tensile strength and elongation according to ASTM D-639-61T. The determined physical Properties are mentioned below «,

Poly (2,6-dimethyl-1,4-phenylene) ether *. 20 parts by weight Elastomeric block copolymer resin ** 40 "

High impact, rubber modified Polystyrene resin *** 40 "

♦ Product "PPO" from the applicant in powder form, intrinsic viscosity 0.40 to 0.65 dL / g.

** Kraton X4119 "(manufacturer Shell Chemical Company), Styrene-butadiene-styrene block copolymer ($ 66 Butadiene units and $ 33 styrene units).

*** »Polystyrene 324E» (manufacturer Shell) (12 $ polybutadiene rubber)

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properties

Notched Izod impact strength 0.97 mkg / 25.4 mm notch

Tensile strength at the 2nd

Yield strength 288 kg / cm

Tensile strength at break 260 kg / cm elongation

Example 2

In the manner described in Example 1, a mixture is obtained manufactured, molded and tested with the following composition. The mix ingredients and the Properties of the test specimens are given in the following table.

Poly (2,6-dimethyl-1,4-pbenylene) ether

(as in Example 1) 20 parts by weight

Block copolymer elastomeric resin

(as in example 1) 20 "

High impact, rubber modified polystyrene resin (as in
Example 1) 20 "

Crystalline polystyrene * 40 "

* Styrene homopolymer "Monsanto HH-101 ^M" for pressing purposes.

properties

Notched Izod impact strength 0.705 mkg / 25.4 mm notch

Tensile strength at the _2nd

Yield strength 464 kg / cm

Tensile strength at break 400 kg / cm

strain

These values show that thermoplastic compositions with good impact strength were obtained when part of the Graft copolymer is replaced by the styrene homopolymer.

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45 Gew " Parts 27 , 5 I! 27 , 5 Il

Example 5

In the manner described in Example 1 "a mixture manufactured, pressed and tested with the following composition. The composition of the mixture and the properties are listed in the following table.

Poly (2,6-dimethyl-1,4-phenylene) ether (as in example 1)

Block copolymer elastomeric resin (as in example 1)

High impact, rubber modified polystyrene (as in Example 1)

properties

Notched Izod impact strength 1.19 mkg / 25.4 mm notch Tensile strength at the ' ₂ yield point 485 kg / cm

Tensile strength at break 515 kg / cm elongation 8T />

A product excellent in impact resistance and elongation is obtained.

Example 4

In the manner described in Example 1, a mixture is obtained manufactured, molded and tested with the following composition. The composition of the mixture and the physical properties are given below.

Poly (2,6-dimethyl-1,4- ^! Phenylene) ether

(as in Example 1) - 45 parts by weight

Block copolymer elastomeric resin

(as in example 1) 13.5 "

High impact rubber modified polystyrene (as in Example 1) 13.5 "

Crystalline polystyrene

(as in Example 2) 28 "ι

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properties

Notched Izod impact strength 0.56 mkg / 25.4 mm notch tensile strength at yield point 654 kg / cm

2 Tensile strength at break 584 kg / cm

Elongation 77 #

These values show that by adding substantial amounts of crystalline polystyrene thermoplastic compositions with excellent impact strength and very good elongation properties can be obtained.

For comparison purposes, a mixture is prepared in which the block copolymer resin is replaced by a rubber-modified one Polystyrene resin is replaced. The composition of the mixture and the physical properties of the product are listed in the following table.

Poly (2,6-dimethyl-1,4-phenylene) ether 45 parts by weight

Rubber modified high impact styrene resin * 55 "

* "Cosdon 825-TV", contains about 8 wt .- # polybutadiene with styrene-grafted side chains.

properties

Notched Izod impact strength 0.283 mkg / 25 _t 4 mm notch

Tensile strength at the ₂

limit 661 kg / cm

Tensile strength at break 563 kg / cm ² elongation 3996

In comparison with Example 3, these values show that when a polystyrene resin is used which is not in the form of the Block copolymers is present, a thermoplastic mass was obtained which had only 1/4 of the notched impact strength of the mass containing the block copolymer (Example 3).

Example 5

In the manner described in Example 1, a mixture is obtained of the following composition, molded, and checked:

Poly (2,6-dimethyl-1 _t 4-phenylene) ether

(as in Example 1) 55 parts by weight

Block copolymer elastomeric resin

(as in example 1) 45. "

Such a thermoplastic mass has high impact strength (0.76 mkg / 25.4 mm notch) and high tensile strength

(436 kg / cm) and elongation ($ 44). This mass is an example for a polyphenylene ether alone with a styrene-butadiene-styrene block copolymer.

Example 6

In the manner described in Example 1, a mixture is obtained of the following composition, molded, and checked: ■

Poly (2,6-dimethyl-1,4-phenylene) ether

(as in Example 1) 20 parts by weight ₀ ■

Block copolymer elastomeric resin

(as in example 1) 30. '· -...

Rubber modified styrene resin

(as in example 1) 30 ^sts

Reinforcing glass fibers 3.2 mm 20 "

The reinforced thermoplastic mass has good tensile strength

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speed (570 kg / cm) and good elongation ($ 7) and notched impact strength (0.4 mkg / 25.4 mm notch).

To determine the resistance of the thermoplastic compositions according to the invention against crazing by environmental influences test specimens are kept under 1 $ elongation and submerged at about 21 ⁰ C in gasoline. In the case of the ¹¹ thermoplastic compositions according to the invention, no hairline cracking or cracking can be observed even after a relatively long time, a sign of excellent resistance to this aggressive one

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Solvent. In particular, the product of Example 3 shows no visible sign of cracking after 5 minutes. The glass fiber reinforced composition produced according to Example 6 also shows the same excellent result Resistance to gasoline.

In contrast to this, the product produced in the manner described above for a comparative owl (without at least 10 Cc \ i. ~ '/> Styrene-butadiene-styrene-IP.iu ·' »copolymer) not only has achlochto lüoii-llca ¹ ·! ) - · Impact strength and schlochto elongation, but also a much lower resistance to attack by botinin · Under the same conditions, this product is completely destroyed by cracking in 5 seconds.

Example 7

The experiment described in Example 3 is repeated, but using a polystyrene with a butadiene-styrene copolymer (78 '/' 5 Butadiene, $ 22 styrene) is modified instead of with Polybutadiene rubber modified high impact polystyrene resin. This is a thermoplastic Masao obtained according to the invention.

The experiment described in Example 3 is repeated, but instead of the polystyrene-polybutadiene-polystyrene block copolymer the following block copolymers can be used:

Polystyrene-polyisoprene-polystyrene
Polystyrene-polyisoprene-poly (a-methylstyrene)

Here, high-impact thermoplastic materials are used obtained according to the invention.

The experiment described in Example 3 is repeated, however, instead of the block copolymers, the following block copolymers with the additions mentioned (in wt .- ^ i) can be used:

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Polystyrene-polybutadiene-polystyrene 50-90-5

Polystyrene-Polybntadiene-Polystyrene 10 - 80 - 10

Polystyrene-polybutadiene-polystyrene 15 - 75 - 15

Polystyrene-polybutadiene-polystyrene 12.5 - 75 - 12.5

Here, high-impact thermoplastic compositions are obtained according to the invention.

Example 8

The following polyphenylene ethers are used instead of Poly (2,6-dimethyl-1,4-phenylene) ether in the example 3 "described thermoplastic mass used:

Poly (2,6-diethyl-1,4-phenylene) ether Poly (2-methyl-6-ethyl-1 _t 4-phenylene) ether Poly (2-methyl-6-propyl-1,4-pbenylene) ether Poly (2,6-dipropyl-1,4-phenylene) ether Poly (2-ethyl-6-propyl-1,4-phenylene) ether

The thermoplastic compositions obtained in this way have properties similar to those produced according to Example 5 Dimensions.

Claims (3)

2 2 5 b 9 3 U claims 1) Containing thermoplastic masses that are solid under normal conditions a) a polyphenylene ether resin or a mixture of a polyphenylene ether resin with a styrene homopolymer or random styrene copolymer resin and "b) an elastomeric ABA block copolymer of a vinyl aromatic compound (A) and (A) and a conjugated diene (B), the middle block B having a higher molecular weight than the terminal blocks A and A combined and component (b) in an amount of about 10 "to 80 of the total resin component of the thermoplastic composition is present ₀ 2) Thermoplastic compositions according to claim 1, characterized in that that as component (a) it is a polyphenylene ether of the formula in which the oxygen ether atom of one unit is attached to the benzene ring of the next adjacent units is bonded, η is an integer of at least 50 and each radical Q is a monovalent substituent from that of hydrogen atoms, halogen atoms, hydrocarbon radicals, halogenated hydrocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halocarbon oxy radicals having at least 2 carbon atoms between the halogen atom and the phenyl nucleus existing group. _ ₂₁ _ 225593Ü 3) Thermoplastic compositions according to claim 1 and 2, characterized in that each radical Q- in the formula des Polyphenylene ether is an alkyl radical with 1 "to 4 carbon atoms. 4) Thermoplastic compositions according to claim 1 to 3, characterized characterized in that each radical Q in the formula of the polyphenylene ether is a methyl radical. 5) Thermoplastic. Compositions according to Claims 1 to 4, characterized in that the polyphenylene ether is at least 1% by weight of the total resin components in the thermoplastic composition. 6) Thermoplastic compositions according to claim 1 to 5, characterized in that component (b) is in the form of blocks (A) and (A) ^{1 contains} styrene, α-methylstyrene, vinyltoluene, vinylxylene or vinylnaphthalene and, as block (B), butadiene, isoprene, 1,3-pentadiene or 2,3-dimethylbutadiene. 7) Thermoplastic compositions according to claim 1 to 6, characterized in that in · the component (b) the block (A) a styrene block, the block (B) is a butadiene block and the block (A) is a styrene block. 8) Thermoplastic compositions according to claim 1 to 7, characterized in that in component (b) the terminal blocks A and A each have a molecular weight of 2,000 to 100,000 and the middle block B has a molecular weight of 25,000 to 1,000,000 _o 9) Thermoplastic compositions according to claim 1 to 8 _$ characterized in that component (a) consists of the following components: I) 1 to 99 wt .-? & Of a polyphenylene ether of formula 3 f) 'J ι? . · '/ Ι Π 4 4 Q / η in which Q is an alkyl radical with 1 to 4 carbon atoms and η is an integer of at least 50, and II) 99 to 1 wt .-% of a styrene homopolymer or random styrene copolymer resin in which at least $ 25 of the polymer units from a vinyl aromatic Compound of formula RC ⁼ in which R is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms or a halogen atom, Z is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms or a vinyl group and ρ an integer from 1 to 5 is derived. 10) Thermoplastic compositions according to claim 1 to 9, characterized in that they contain as styrene resin is a Styrolnomopolymerharz or a styrene resin having a diene rubber or a kautsehukartigen Copolyrnerisat of butadiene and styrene in an amount of about k to 12 weight - modified% of the resin. is included. 11) Thermoplastic compositions according to claim 1 to 10, characterized in that they are polyphenylene ethers Contain poly (2,6-dimethyl-1,4-phenylem) ether. 12) Thermoplastic compositions according to claim 1 to 11, characterized in that they contain the polyphenylene ether in one Share of about 1 to 90 wt .- ^ S, the elastomeric block copolymer the vinyl aromatic compound and 3 Ü y ti "/ 2/1 0 · 4 U of the conjugated diene in a proportion of about 10 to 80 wt .- ^ and the styrene homopolymer or random styrene copolymer resin in a proportion between 0 wt .- $ and the remainder of the total weight of the resin components ^{: contained} in the thermoplastic composition. Ij5) Thermoplastic compositions according to claim 1 to 12, characterized in that they contain as Polyphehylenäther poly (2, 6- dimethyl-l, 4-phenylene) ether in an amount of about 20 to 90 percent - as component (b%). an elastomeric block copolymer of styrene and butadiene, styrene-butadiene-styrene type in an amount of about 10 to 80 wt -.%, and the styrene homopolymer or rule-free styrene copolymer resin is a homopolymer of polystyrene or a rubber-modified polystyrene present in an amount up to about 60 wt -.% of Contained total weight of the resin components in the thermoplastic composition. 14) Reinforced thermoplastic compositions according to claim 1 to 15, characterized in that it is a reinforcing Amount of fiberglass included. 3 Π ■■ - 'i -A) LL