DE2211006C3 - Thermoplastic masses - Google Patents

Description

• J

22 Il 006

Styrene polymer consists, and 0.1 to 30 wt .-% of a disperse elastomeric phase, based on the weight, to a greater extent! from a butadiene polymer has been produced that has an Eis-1,4 content of at least 50% by weight and a vinyl group content of not more than 10% by weight.

The elastomeric phase is preferably made from a butadiene polymer with an cis-1,4 content of at least 85% by weight has been produced. According to a preferred embodiment of the invention the elastomeric phase contains a small proportion by weight of a rubber-like butadiene-styrene copolymer. The elastomeric phase preferably consists of a graft copolymer of styrene on one Butadiene polymer, which has an ice-1,4 content of has at least 85% by weight.

According to a further preferred embodiment, the elastomeric phases are in an amount of about 1.5 to 6% of the total weight of the thermoplastic composition and the styrene polymer in the tapped phase in an amount of 40 to 60% of the Total weight of styrene polymer and polyphenylene ether present. These thermoplastic masses can be processed into farmed parts by conventional pressing and spraying processes. Of course you can Polystyrene resin and the rubber the mixture with di: m polyphenylene ether as separate components may be added, but preferably the polystyrene resin and the rubber are added in combination.

The thermoplastic compositions according to the invention consist of a mixture of two phases, which under Magnification can be seen, the continuous or closed phase consisting of a matrix of a Polyphenylene oxide resin and a styrene resin, wherein a discontinuous one, consists of elastomer particles existing phase is dispersed. These particles can vary depending on how the thermoplastic Masses are produced, to varying degrees also polystyrene resins and polyphenylene ether resins contain. In either case, the microstructure of the elastomer in the particles can be determined by known methods be measured, e.g. B. by infrared analysis of the separated rubber. In addition, the microstructure is in the final thermoplastic mass basically that of the one used for its manufacture Rubber.

As mentioned above, the polystyrene resin and dis elastomeric polybutadiene can warden added together as separate components with the polyphenylene ether. However, since comparable impact strengths seem to be achieved with lower amounts of the elastomer, a polystyrene foam modified with a polybutadiene rubber is preferably combined with the polyphenylene ether. In the first method, the etomeric phase is dispersed by mechanical mixing of the rubber, the styrene resin and the polyphenylene oxide resin. In the second method, the elastomer is dispersed, for example, by polymerizing styrene in the presence of dissolved rubber under known conditions, whereby a dispersed microgel of, for example, grafted, crosslinked rubber particles is dispersed in a polystyrene matrix. The product is then combined with the polyphenylene ether and the microstructure of the polybutadiene in the particles remains essentially the same in the final mixture.

The closed phase polyphenylene ethers are discussed in detail in the publications cited above described. They are self-condensation products of monohydric monoeyclic phenols, the produced by reacting the phenols with oxygen in the presence of complex copper catalysts are, in general, the molecular weight is adjusted by the reaction time, with longer Times result in a higher average number of recurring units.

A preferred group of polyphenylene ethers consists of recurring structural units formula

in which the oxygen ether atom of a unit is bonded to the benzene ring of the next adjacent unit, η is a positive integer of at least 50 and each radical Q is one of the following monovalent substituents Si'bstituenten: hydrogen, halogen atoms, hydrocarbon radicals which have a primary or secondary a -Carbon atom, halogenated hydrocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halocarbon oxy radicals with at least 2 carbon atoms between the halogen atom and the phenyl nucleus.

Representative examples from this group of polyphenylene ethers are:

Poly (2,6-dilauryl-1,4-phenylene) oxide,
Poly (2,6-dlphenyl-1,4-p; enylene) ether,
Poly (2,6-dimethoxy-1,4-phenylene) ether,
Poly (2,6-diethoxy-1,4-phenylene) ether,
Poly (2-me'.hoxy-6-ethoxy-1,4-phenylene) ether,

Poly (2-ethy! -6-stearyloxyl, 4-phenylene) ether,
Poly (2,6-dichloro-1,4-phenylene) ether,
Poly (2-methyl-6-phenyl-1,4-phenylene) ether,
Poly (2,6-dibenzyl-1,4-phenylene) ether,
Poly (2-ethoxy-1,4-phenylene) ether,
Poly (2-chloro-1,4-phenylene) ether and
Poly (2,5-dibromo-1,4-phenylene) ether.
Examples of polyphenylene ethers corresponding to the above formula can be found in the above-mentioned USA patents.

A group which is particularly preferred for the purposes of the invention is formed by polyphenylene ethers which contain alkyl substituents in the two o-positions to the S5 oxygen ether atom, ie polyphenylene ethers of the above formula in which Q is an alkyl radical, of these polyphenylene ethers those in which this alkyl radical is 1 to Contains 4 carbon atoms, are particularly preferred. Examples of polvphemous ethers from this group are:
Poly (2,6-dimethy! -L, 4-phenylene) ether,
Poly (2,6-diethyl-1,4-phenylene) ether,
Poly (2-methyl-6-ethyl-1,4-phenylene) ether,
Poly (2-methyl-6-propyl-1,4-phenylene) ether.
(s poly (2,6-dipiopyl-1,4-phenylene) ether and

Poly (2-ethyl-6-propyl-1,4-phenylene) ethers.
Particularly preferred as the polyphenylene ether resin for the purposes of the invention is the poly (2,6-dimethy! -

22 Π

i, 4-phenylene) ether. This resin forms with polystyrene resins Easily compatible single-phase compounds over the entire range of proportions.

In the thermoplastic marsen according to the invention, the polyphenylene ether is 5 with the polystyrene and a rubber or a rubber-modified polystyrene combined. The expression nPolys'yrol « is used here in the same sense as in U.S. Pat. No. 3,383,435. These styrene polymers can be combined with the polyphenylene ether ι ο. In general, styrene polymers are used used in which at least 25% by weight of the polymer units are from a vinyl aromatic Monomers are derived, e.g. B. of a monomer of the formula ι?

R-C = CH,

Polybutadiene ^.

10

in which R is a hydrogen atom, a lower alkyl radical having, for example, 1 to 4 carbon atoms or a halogen atom, Z is a hydrogen atom, a vinyl radical, a halogen atom or a lower alkyl radical and ρ is O or an integer from 1 to 5. As representative examples of suitable polystyrenes are to be mentioned: Homopo'ymerisate of styrene, polychlorostyrene, poly-Ä-methylstyrene, styrene-containing copolymers, z. B. styrene-acrylonitrile copolymers, copolymers of ethylvinylbenzene and divinylbenzene and terpolymers of styrene, acrylonitrile and tx-methylstyrene. Of the styrene polymers from this group, preference is given to styrene homopolymers, poly-α-methylstyrene, styrene-acryloni-> 5 trile copolymers, styrene-ix-methylstyrene copolymers, styrene-methyl methacrylate copolymers and poly-α-chlorostyrene. The styrene homopolymer is particularly preferred (R is a hydrogen atom and ρ stands for O). ₄ <

In the thermoplastic compositions according to In accordance with the invention, the elastomeric phase can consist of a predominantly ir. The cis-1,4 configuration Polybutadiene alone or in a mixture with small proportions of other rubbers. When using ^ Preparation of mixtures, it is only necessary that the greater proportion, i.e. more than 50% by weight, of the elastomeric phase is a polybutadiene. that mostly has the cis-1,4 microstructure. The smaller portion of the mixture, i.e. H. less than 50% by weight. can thus consist of a different rubber and even, for example, a 1,4-polybutadiene, which is predominantly the has trans-1,4 microstructure.

The polybutadiene with a predominantly cis-1, ^{4-configuration} should be at least 50 wt contain ⁰ A cis-l / t groups and not (due to 1,2-addition) is more than 10 wt .-% vinyl groups. These rubbers are manufactured according to known processes, for example by stereospecific polymerization of butadiene in inert hydrogen hydrogen solutions using heterogeneous catalysts. /. IV Chromium compounds which are adsorbed on inorganic supports, or catalysts which are obtained from the reaction products of organometallic compounds, for example aluminum irialkvl. with bonds of transition metal. /. IV 1 lalojieniden, especially 1 itanchlonden, -iodide ii. Like. Or lithium halides! and the like. Kmiphon. In the vor / ugien PnWbutadienes lsi in natural and synthet.sche ^ py ^ ^ _{n &} ^ at room temperature. _natural rubbers

are. The term includes som ^ _n ^

or synthetic choke from VP · _{n is used}

Presentation of "Wagahen K y _{pd butadiene with} will. All these rubbers u ^ ^.

predominant C, s _d 1.4-Konf, gura ^ _{styrene polymers} .

^P - ^hase Ts ^e t2lSdie d continuous or disperse, nsat and make uic u "■ _po [ystyrene resin mas-

^fein i ^eili i, s ^Ph K ^a :, u ^ kfS 'die V ⁿ erwe ^y ndu ^y ng with the se. As KautscnuKc _cis .l, 4 configuration

Polybutadiene «mt ^^^ for the purposes of the invention σig _{diene rubbers} ke.

Natural rubber and rubber and copolymers

^Ζ /% ΐη ¹ : ΪΓν "yS-ren, eg 5nyl.rom.iid these dienes mn v» y examples of more suitable

see monomers «ie syrole. Ais *. _{sin (J}

Kauuchuke ^ f. ^ Gj ^ .uit SBR Kau, -

ctaken α for the production of the

Unur of ethylene, U ₁ ,,. s uj .- "^ '^ uifidkamscriuke.

^ tamscnike "tlyur" h ^ autsch'uke, Copo.ymcr, -Acrylkaulschuke ^ Koy _and , ^^ _{m | (}

sate of service, e.g. o. " _R """"ä.iiixten alkyl

Cloning.

for use with

the elastomeric phase is dispersed by ■ phenylene acid with a rubber-coated polystyrene resin. The expression "rubber-modified polystyrene resin" denotes compounds which have a two-phase structure in which the rubber in a polyol resin is used as a matrix in the form of individual n, coherent particles d .ispersed. The vision can be formed by mechanical mixing of the K utsc-huks and the PoUsumlhar / .cs. U ₁ OsSm lall they represent a dispersed elastomeric P; edr andm ^ eit consists in the preferred la das / 'emhasensYs. An interpolation of a vinylaronic monomer, for example with the above-mentioned formula, preferably a stymic monomer and an elastomer or rubber, which is formed by grafting the monomer onto the monomeric chain. Im, niche

22 1 I.

These similar polystyrenes are usually used as a yardstick produced by grafting rubber in the presence of polymcrisicrcndcm styrene. This Systems consist of a closed phase of the polymerized styrene monomer, in which the cheese Tschuk or the elastomer as a discontinuous elastomeric gel phase with or without grafted chains of polymerized styrene monomer is dispersed. Polymerized styrene monomer can also be present in the particles be included. ι ο

Methods for making polystyrenes with a dispersed elastomer are known. For example is according to the United States Patent 26 94 692 the polymerization of rubber in styrene monomer in Mass carried out, the mixture during the is Initially stirred vigorously and then weakened the stirring and the polymerization is completed. Another method, which is described in US Pat. No. 2,886,553, is a block prepolymer tion of rubber in styrene monomers jo carried out with stirring until the desired Degree of polymerization is reached, whereupon water and surfactants are added and the Polymerization in suspension is completed. It is also possible, as already mentioned, the rubber and the Polystyrene resin mechanically under the action of relatively strong shear forces, for example in one Intensive mixer of the Banbury type to mix until a polystyrene, the dispersed particles of the elastomer contains, has been received.

Preferred rubber-modified styrene polymers are those in which the elastomeric phase consists of elastomeric particles to which a vinyl aromatic polymer, e.g. B. polystyrene, is grafted. Polymers of this type preferably contain about 70 to 99 parts by weight of polystyrene and 1 to 30 parts by weight of the finely divided diene elastomer-styrene graft copolymer phase. Polymers of this type in which the elastomer consists of polybutadiene or a mixture of polybutadiene or a mixture of polybutadiene with a rubber-containing butadiene-styrene copolymer are particularly preferred. These materials can be prepared by known methods, e.g. B. the above.

As is stated in US-PS 33 83 435, Polypheriylenäthcr and styrene polymers can be used in all Quantities are combined, being a single combination of thermodynamic Have properties. The closed phase with the thermoplastic compositions according to the invention can thus consist of 1 to 99% by weight of polyphenylene ether resin and 99 to 1% of rubber-free polystyrene resin exist. These proportions fall within the scope of the invention. Generally will thermoplastic compositions preferred, in which the Styroipoiymerisai 20 to 80 in the closed phase % By weight of polystyrene plus polyphenylene ether because it is the best after molding Combination of impact strength. Surface appearance and solvent resistance. Especially Advantageous and preferred are thermoplastic compositions in which the closed phase Styrene polymer makes up 40 to 60% by weight of the total weight of polystyrene and polyphenylene ether. Properties such as flexural strength. Tensile strength, f <s Hardness and especially impact strength are in these preferred masses maximum.

The rubber content, i.e. H. the percentage by weight of the disperse elasiomeric phase in the thermoplastic Masses according to the invention can vary, but no benefit is obtained if over one A maximum of about 30% of the total weight of the mass is exceeded. If the proportion of elastomeric phase falls below about 0.1 wt .-%, the impact resistance and impact strength are poor. The proportion of the elastomeric phase is preferably in the range from about 1 to 15% by weight, with the higher Amount is used when the rubber is dispersed by mechanical mixing. If like this is preferred that the rubber is in the form of an elastomeric gel on which a vinyl aromatic Monomer is grafted, the low amounts can be advantageous. In all cases the amount is the elastomeric phase preferably in the range between 1.5 and 6% of the total weight of the mass. At higher Proportions, the impact strength is clearly optimized, but other properties, e.g. B. the Solvent resistance and the appearance of molded parts, impaired. Since the with grafted Rubber particles produced thermoplastic compositions have better impact strength and impact resistance than mechanical mixing, d. H. with ungrafted particles in an optimal amount of 1.5 to 6 Have wt .-% prepared masses, the thermoplastic masses according to the invention, the a finely divided elastomer phase with grafted vinyl aromatic! Monomer, e.g. B. styrene, contain, particularly preferred.

The process used for the preparation of the polyphenylene ether, polystyrene and elastomers, i.e. H. Rubber, existing thermoplastic compositions according to the invention is not applied critically important provided that there is effective dispersion of the particles of the elastomer enables. Preferred is a method in which the polyphenylene ether is mixed with polystyrene and a rubber or a rubber modified polystyrene is mixed in any conventional manner. That way formed thermoplastic mass is for example by extrusion. Hot deformation and the like to any desired molded parts processed.

Of course, the thermoplastic compositions according to the invention can also contain other additives, e.g. B. Plasticizers. Pigments, fire retardant additives. Reinforcement fillers, e.g. B. glass thread or fibers, and Stabilizers included.

In the context of the invention, the thermoplastic Masses also other polymers, eg. B. polyamides, polyolefins and polystyrene can be added. For example, it has been found that thermoplastic compositions made of polyphenylene oxide and equal parts of a Polystyrene and a rubber-modified polystyrene, the elastomer being predominantly the cis-1.4 microstructure has. in terms of impact resistance and impact strength with the known thermoplastic Masses are comparable which have the same content of polyphenylene ether, but in which the whole Polystyrene resin is rubber-modified and contains an elastomer that is predominantly made from polybutadiene trans-1.4 microstructure. The thermoplastic compositions according to the invention are not only more economical manufacture than the known thermoplastic masses, but also have a after injection molding better surface appearance.

A polyphenylene ether resin. that is used for manufacturing the thermoplastic masses according to the invention

suitable, can be made by the following process:

Procedure A

A complex catalyst is prepared by adding 100 ml of toluene, 0.42 g of anhydrous copper (II) bromide. 10.9 g of di-n-butylamine and 4 ml of a 55% solution of 2,6-xylenol in toluene are stirred together. The catalyst is transferred to a 1-1 flask, which is provided with cooling coils, thermometer pocket and inlet ι ο lines for oxygen and monomers. After adding 400 ml of toluene, the mixture is vigorously stirred at 1500 rpm with a single 51 χ 6.4 mm turbine mixer while oxygen is introduced into the mixture at a rate of 28.3 l / hour. 127 g of a 55% strength solution of 2,6-xylenol in toluene are then added over the course of 8 minutes. The temperature is kept ^{at 30 °} C. after cooling water has been circulated. After 1.75 hours the temperature is increased to 35 ° C., and after a further 15 minutes 30 ml of a 50% strength aqueous acetic acid solution are added to stop the reaction. The mixture is centrifuged and the polymer is precipitated from the upper toluene phase with methanol. The polymer is filtered off, washed with methanol and dried at 70 ° C. under vacuum. Here, poly (2,6-dimethyl-1,4-phenylene) ether is obtained in a yield of 90%. The resin has an intrinsic viscosity of 0.61 dl / g (measured in chloroform at 30 ° C.). y,

A styrene polymer. which contains an elastomeric phase, and for the manufacture of the thermoplastic Compositions suitable according to the invention can be prepared by the following process:

Procedure B ^3S

A solution of 90 parts of polybutadiene with a predominantly cis-1,4 configuration (90% cis-1,4 groups and less than 10% vinyl groups), 2 parts of tert-dodecyl mercaptan, 0.5 parts of benzoyl peroxide, 0.5 parts Dicumyl peroxide and 2 parts of butylated hydroxytoluene in 910 parts of styrene are slowly stirred under nitrogen at 85 to 95 ° C until about 30% by weight of the styrene has polymerized. 2000 parts of water containing 0.07% polyvinyl alcohol, 0.02% alkylarylsulfonate and 0.08% sodium chloride are added to this mixture. The polymerization is carried out in 16 to 20 hours at 130 to 14O ⁰ C to the end, being sufficient gtrührt, to keep the particles in suspension. The product is obtained in the form of pearls, which are washed and dried. Finally, the beads are extruded in a 25.4 mm laboratory extruder at 177 ° C. and then granulated.

Preferred embodiments of the invention are described in the following examples. Unless otherwise stated, all thermoplastic compositions are produced by passing mixtures of the polyphenylene ether, the styrene resin and the rubber or high-impact polystyrene and other optionally used ingredients through a single-screw press with a variable pitch, the extrusion temperature being kept between about 232 and 288 ° C . All parts are parts by weight. The exiting from the extruder strands are cooled by conventional methods, zn chopped granules, extruded chopped into pellets and molded into test bars.

Ei c i s ρ i e I 1

A mixture is au in an amount of 22.7 kg; the following components:

Poly (2,6-dimethyl-

1,4-phenylene) ether ") 45 parts

Rubber modified

Polystyrene ") 55 parts

Polyethylene 1.5 parts

Tridecyl phosphite 0.5 parts

Synth, glossy wax 0.25 parts

Titanium dioxide 2 parts

*) PPO polyphenylene ether in pellet form (manufactured by of the applicant).

**) Impact-resistant polystyrene in pellet form, which is modified with polybutadiene with a high cis-1,4 content dnd something Contains% by weight of a disperse elastomeric phase, ale am There is polybutadiene whose cis-1,4 content is greater than 9 ( % By weight and the vinyl group content of which is less than 1% by weight, and on which the polystyrene is grafted.

The mixture is extruded using a 63.5 mm Prodex extruder. The strands obtained will be cooled, chopped into granules and shaped into test sticks. The elastomeric phase makes up 4.75% by weight Mass off. The following physical properties are determined:

Izod impact strength

Garuner impact resistant ': eit
Elongation at break
Dimensional stability in
of heat (18.6 kg / cm ² )
Tensile strength at the
Stretch limit
Tensile strength at break
45 ° gloss value
Bending modulus!
Flexural strength

0.79 mkg / 25.4 mm notch 276.5 cmkg 48%

123 ° C

668 kg / cm ²

590 kg / cm ²

62

24620 kg / cm ²

1916 kg / cm ²

For comparison, that is described in example 1! Experiment repeated, but instead of de; impact-resistant polystyrene modified with rubber with a high cis-1,4-proportion, an impact-resistant polystyrene that is modified with polybutadiene with predominantly acr trans-1.4 structure and contains about ί "(° of ^a disperse elastomeric phase, di < consists of polystyrene, on which polybutadiene is grafted, the cis-1,4-content of which is about 35 to 40% by weight and the trans-1,4-content of which is about 55% by weight 4.75% by weight of the elastomeric phase upon mixing. The following physical properties are determined:

Notched Izod impact strength wedge

Gardner impact strength
Elongation at break

Dimensional stability in
of heat (18.6 kg / cm ² )
Tensile strength at the
Stretch limit

Tensile strength at break
· «-Vjianzwert
Bending modulus!

Flexural strength

0.249 mkg / 25.4 mm notch 230 cmkg 51%

131 ° C

682 kg / cm ²

577 kg / cm ²

59

26780 kg / cm ²

2142 kg / cm ²

A comparison of the results clearly shows a significant improvement in the impact strength, measured according to the Izod and Gardner method, as well as the appearance of the surface (recognizable by the gloss value) in the case of the thermoplastic mass, which contains particles of polybutadiene with a predominantly cis-1,4 structure, in contrast to the mass, which contains particles of polybutadiene with a high trans-1,4 content.

Example 2

A mixture weighing 22.7 kg is made up of the following ingredients:

Poly (2,6-dimethyl-

1,4-phenylene) ether (PPO)

Rubber modified

Polystyrene (90% cis-1,4-

see example 1)

Polyethylene

Triphenyl phosphate

Tridecyl phosphite

Zinc sulfite

30% soot premix

in styrene

50 parts

50 parts
1.5 parts
3.0 parts
1.0 parts
t, 5 parts

0.5 parts

Notched Izod impact strength,
mkg / 25.4mm notch
Gardner impact strength
Elongation at break
Dimensional stability in
of heat (18.6 kg / cm ² )
Tensile strength at the
Stretch limit
Tensile strength at break
Bending module
Flexural strength

0.705
202 cmkg
49%

122 ⁰ C

640 kg / cm ²
577 kg / cm ²
24030 kg / cm '
1829 kg / cm ^!

Notched Izod impact strength, mkg / 25.4 mm notch Gardner impact strength Elongation at break Dimensional stability in heat (18.6 kg / cm ² ) Tensile strength at the
Stretch limit
Tensile strength at break bending modulus! Flexural strength

0.249
138 cmkg
40%

121 ⁰ C

657 584 kg / cm ² 23852 kg / cm ² 2170 kg / cm ²

A comparison of the results reveals an essential one Improvement of the impact strength of thermoplastic compositions that are a dispersed elastomer contain, the; ms polybutadiene with predominantly eis-1,4-Struklui "stone.

Example 3

A flame retardant or self-extinguishing thermoplastic mass is made in an amount of 22.7 kg the following components:

After extrusion with a 63.5 mm Prodex extruder, the strands are conventionally Process cooled, chopped into granules and shaped into test bars. The elastomeric phase makes about 4.2% by weight of the mass and consists of polybutadiene, on which styrene is grafted, and one cis-1,4-content of more than 90%. The following physical properties are determined:

For comparison purposes, the experiment described in Example 2 is repeated, but instead of the impact-resistant, with a rubber with a high ice-1,4 content modified polystyrene a rubber-modified polystyrene is used, which is a disperse contains elastomeric phase with predominantly trans-1,4 microstructure (35 to 40% by weight cis structure). the the following physical properties are determined:

Polyphenylene ether (PPO)
Impact-resistant polystyrene
(90% cis structure,
see example 1)
Polyethylene
Tridecyl phosphite
Triphenyl phosphate
Polytetrafluoroethylene

40 parts

60 parts
1.5 parts
0.5 parts
9 parts
0.1 parts

After extruding on a 63.5mm Prodex extruder the strands are cooled by conventional methods, chopped into granules and shaped into test specimens. The elastomeric phase makes 4.8 % By weight of the mass. The following physical properties are determined:

Notched Izod impact strength,
mkg / 25.4mm notch
Gardner impact strength

Elongation at break

Dimensional stability in
of heat (18.6 kg / cm ² )
Tensile strength at the
Stretch limit

Tensile strength at break
45 ° gloss value

0.733

> 276.5 cmkg

55%

104 ⁰ C

562 kg / cm ²
522 kg / cm ²
61.5

For comparison purposes, the experiment described in Example: was repeated, but instead of de ¹ with the rubber with a high cis degree of modified polystyrene, the impact-resistant polystyrene used in Example 1 with the rubber with predominantly trans-1,4 configuration was used . The final thermoplastic mass contains a rubber phase, the cis-1,4 content of which is 35 to 40% by weight / l. The following physical properties are determined:

Notched Izod impact strength,
mkg / 25.4mm notch
Gardner impact strength
Elongation at break
Dimensional stability in
of heat (18.6 kg / cm ² )
Tensile strength at the
Stretch limit
Tensile strength at break

0.249
58 cmkg
42%

99 ⁰ C

605 kg / cm ²
506 kg / cm ²

A comparison of the results clearly shows one

6s significant improvement in impact strength b < thermoplastic masses that are dispersed elastomer

Contain particles that consist of polybutadiene with predominantly

gender cis-l, 4 microstructure exist.

example

A thermoplastic Ma ¹ .
is made by mixing the
manufactured:

Polyphenylene ether (I ⁵ IH))

Impact-resistant polystyrene

(90% cis share.

see example 1)

Polyethylene

Tridecyl phosphite

Triphenyl phosphate

e with a weight of 22.7 kg the following components

30 parts

70 parts
1.5 parts
0.5 parts
6 parts

The strands produced by extrusion in a 63.5 mm Prodex extruder are conventional Process cooled, chopped into granules and shaped into test specimens. This thermoplastic mass, which is about 68% by weight of styrene resin (on a rubber-free basis), based on the total weight of rubber-free Styrene resin and polyphenylene ether, and about 5.8% of a dispersed elastomeric phase composed of Styrene-grafted polybutadiene with 90% ice-1,4-content contains, has a higher notched impact strength (0.677 versus 0.235) than it is known for similar ones thermoplastic compositions are indicated, which are made from rubber-modified polystyrene, in which the disperse elastomeric phase of styrene-grafted polybutadiene with less than 50 wt .-% cis-1,4 groups (based on polybutadiene) exists (U.S. Patent 33 83 435). The following physical Properties are determined:

Notched Izod impact strength, mkg / 25.4 mm notch Dimensional stability when heated (18.6 kg / cm ² ) Elongation at break Tensile strength at the yield point

0.677

108 ° C
44%

527 kg / cm ^:

Example 5

A mixture weighing 22.7 kg is made from the following ingredients:

Polyphenylene ether (PPO) 25 parts Impact-resistant polystyrene (90% cis share, see example 1) 75 parts Polyethylene 1.5 parts Tridecyl phosphite 0.5 parts Triphenyl phosphate 6 parts

The strands made by extrusion in a 63.5 mm Prodex extruder are cooled to Granules chopped up and shaped to test specimens. The following physical properties are determined:

Izod impact strength. 0.553 mkg / 25.4mm notch 34% Elongation at break Dimensional stability in 106 ° C of heat (18.6 kg / cm ² ) Tensile strength at the 527 kg / cm ² Stretch limit 506 kg / cm ² Tensile strength wedge at break

I. a similar thermoplastic mass of the booth the technology, which, however, contained an impact-resistant polystyrene that was predominantly with a polybutadiene trans-1.4 syrup was modified (USA.Patent 33 83 435. Example 7 and Fig. 18). had a notched impact strength of only about 0.235 mkg / 25.4 mm notch.

Test bars which had been produced from the thermoplastic compositions of Examples 1 and 2 and in

lu gasoline was immersed at 1% elongation, showed no sudden destruction after 15 minutes if the elastomeric phase consisted of styrene-grafted polybutadiene, about 90% by weight of which had the cis-1,4 microstructure. In contrast, they failed

κ (sudden destruction) all test rods from the thermoplastic compositions were produced in which the elastomeric polybutadiene phase to less than 50 Wt% had the cis-1,4 microstructure in less than 15 seconds at 1% elongation in gasoline.

Example 6

A thermoplastic mass is produced that contains 50 parts of poly (2,6-dimethy! -L, 4-phenylene) ether, 45 parts crystalline polystyrene and 5 parts polybutadiene rubber

^ s chuk with about 95% cis-1,4-content and less than 5 Contains wt .-% vinyl groups. First of all, the rubber and the crystalline polystyrene are in one Banbury mixer mixed intensively until the rubber is dispersed as a finely divided, discontinuous phase.

w The mixture is then mixed together with the Polyphenylene ether extruded, whereby a uniform mixture is obtained. This mixture gives after cooling, chopping into granules and shaping into test specimens, molded parts with high impact strength

Toughness and improved gloss. Example 7

The experiment described in Example 1 is repeated, but instead of the polystyrene modified with 9% by weight of polybutadiene with> 0% cis-1,4 structure, a polystyrene is used which contains 5% by weight of an elastomeric phase is modified, the zi 25 wt .-% of a rubber-like styrene-butadiene copolymer. the 77 wt .-% butadiene unc 23 wt .-% of styrene units contains, and 75 wt ⁰ A from polybutadiene having 90% cis-1,4-structure is This composition has a high Kerbschlagzähigkeil. which is comparable to that mentioned in Example 1.

Example

The following polyphenylene ethers who instead of poly (2,6-dimethyl-1,4-phenylene) ethers used in the mixture of example 1:

Poly (2.6-diethyl-1.4-phenylene) ether. Poiy (2-methyi-b-äthyl-l, 4-phenylene) ether, Poly (2-methyl-6-propyl-1,4-phenylene) ether. Poly (2.6-dipropyl-1,4-phenylene) ether, Poly (2-ethyl-6-propyl-1,4-phenylene) ether.

The thermoplastic compositions obtained have properties similar to those according to the example manufactured thermoplastic mass.

Example 9

The following Styroipoiymerisatc are on Steii of the crystalline Styrofoam homopolymer in the i

15th

Example 6 used:

described «.hermoplustic mass

Poly-a-methylstyrene, Styrene-acrylonitrile copolymer (27% acrylonitrile), styrene-oc-methylstyrene copolymer, Styrene-methyl methacrylate copolymer,

Poly-ix-chlorostyrene,

Styrene-acrylonitrile-A-meth ^ lstyrening polymer.

The thermoplastic compositions of this composition have properties similar to those in Example 6 thermoplastic composition described.

Claims (1)

22 M. Polybutadiene with predominantly cis-U.Kon-.gurauon ¹ S Ä Patent claims: ! .Thermoplastic masses, consisting of: a) 70 to 99.9 wt .-% of a closed phase, which consists of a polyphenylene ether and a Styrene polymer consists, and b) 0.1 to 30 wt .-% of a disperse elastomeric phase, based on the weight to a major part has been made from a butadiene polymer which has a cis-1,4 content of at least 50% by weight and a vinyl group content of not more than 10% by weight has. 2. Thermoplastic compositions according to claim 1, characterized in that the elastomeric phase from a butadiene polymer with an ice-1,4- From the Polyphenv are due to the 15th - ^ · ■ u ohhäneen What the rubber type ren ^te ! ^{lche "8} YES technology is concerned, it is common derzeiugen S and the Technical ^ ^^ a Polybutadiene Cautery ™ ^UK _{0 /} ^ ₁₄ . _Group n, 55% ^Structure r ₄ groups "1 2 groups (vinyl groups). Trans-1,4-groups, ιυ / '■ _the trans configu-This polybutadiene _m " J * ™ "^ at the lowest Phase s low weight of a kau-Sanigen ^, ^ aiien.S.yrCCopCmeri, - ^dl "° ^ls J" ^ n _urde but erforverwende in higher quantities - ^, <* 2 £ <j £ £? elastomeric nose made of a ■ nu _H ..........., ._._, .... sat of styrene on a butadiene polymer which has a cis-1,4 content of at least 85 % By weight. 5. Thermoplastic compositions according to claim 1 to 4, characterized in that the elastomeric Phase in an amount of about 1.5 to 6% of the total weight of the thermoplastic composition and the styrene polymer in the closed phase in an amount of 40 to 60% of the total weight of styrene polymer and polyphenylene ether are present. 6. Thermoplastic compositions according to claim 1 to 5, characterized in that the polyphenylene ether from recurring units of the structure _{33 83} 435 describes. I.a. Mixtures of ^ ^,, "Polys.yroler., ⁴⁵ isis h J So contains ^ the preferred embodiment of the P tentc 33 435, for the _line .zod-Kerbsch.agzä- -Kateni- ->-> mkg / 25.4 mm Ksrbe (test- 256) is stated to be polybutadiene 1 4-GeS vo ^ less a.s half of the consists in which the oxygen ether atom of one unit is attached to the benzene ring of the next neighboring one Unit is bound, / 7 is a positive integer of at least 50 and each remainder Q for one monovalent substituents from the group consisting of hydrogen atoms, halogen atoms, hydrocarbon radicals, which have a primary or secondary <% carbon atom contain halogenated hydrocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halocarbon oxyresy with at least 2 carbon atoms are between the halogen atom and the phenyl nucleus. so "" It "has now been found that a surprising increase in the notched impact strength is obtained when d;. Elastomer phase in a mixture of a loading Polvphenylenäther and a Styrolpolymensat ° £ ^P" T. -in a larger part from a polybutadiene °. ■ ■ · · _ 1 .ι κ / ΐ; υ, - / -> <τίπι1ί · ίιΐΓ has The invention relates to ν ^; Tough thermoplastic masses consisting of a closed phase consisting of a polyphenylene ether and a polystyrene resin 25 have 4 mm notch, show representations according to the invention with the same rubber housing S however with more than 90 <> / o cis-1,4-microstructure zod notched impact strengths of 0.65 to 0.79 mkg / 25 4 mm notch. In addition, the appearance of the surface, especially the gloss, is surprising Dimensions improved as well as the resistance to aggressive solvents such as gasoline. The invention relates to thermoplastics Masses from 70 to 99.9% by weight of a closed phase that consists of a polyphenylene ether and a