DE2011059A1 - Mixtures based on vinyl aromatic polymers which can be hardened to give moldings and coatings - Google Patents

Description

iu_shaped bodies_and_coverings_härtbare_Geinlsche

Vinyl aromatic polymers are useful and desirable valuable properties and are therefore used in the manufacture of numerous items for industry and households. These Vinyl aromatic polymers, however, are often in the form of mixtures with other organic polymers or used as a mixed polymer because of their properties There are limits to their use in many types of applications is impaired »One of these limits is their lack of toughness, their poor impact resistance and their more vitreous Character. Numerous attempts have been made to improve these properties. So could the tenacity and impact resistance can be improved, but often with the loss of other desirable properties i was connected.

Surprisingly, it has now been found that small amounts of one Block copolymer made from polydimethylsiloxane and vinyl aromatic polymer blocks lead to tougher products.

According to the invention, therefore, moldings and coatings are hardenable Mixtures based on vinyl aromatic polymers claimed, which are characterized by the fact that they are based on each

009838/2260

(A) 100 parts by weight of a vinyl aromatic polymer from itself repeating units of the general formula

"CHpCR -,
G

wherein R ^{1 is} hydrogen or methyl and G is monovalent, aromatic radicals consisting of 1 to 3 rings with an aromatic structure, each with up to three alkyl. Cycloalkyl or alkoxy radicals can be substituted with 1 to 6 carbon atoms, but in such a way that no aliphatic-organic substituents with more than one carbon atom are present in the o-position to the -CR'-grouping,

(B) 0.1 to 20 parts by weight of a block copolymer having a molecular weight of 7,000 to 1,000,000, which is essentially from aromatic-organic blocks and diorganosiloxane blocks according to the general formula

CH3 CH3 R

Rf CH ₂ -CR '4-CH ₂ -CR ^! - ^ GG CH ₃ CH ₃ R "

where R ^f and G have the meaning given, but are each the same in components (A) and (B), R monovalent hydrocarbon radicals with 1 to 30 carbon atoms, R "monovalent hydrocarbon radicals with 1 to 18 carbon atoms, Z monovalent Mean hydrocarbon radicals with 1 to 18 carbon atoms or hydroxyl groups,

χ £ are each and average values 20-5000, 1st constructed so that 20 to 70 parts by weight Ji diorganosiloxane units and 30 to 80 wt -.% of units' of the organic blocks are present, included.

009838/2260

The block copolymers which can be used according to the invention can best be seen by polymerizing a vinyl aromatic Compound of the formula

CH ₂ = CR ¹ G

be prepared with an organoIithiumverbindungen in an organic solvent. The amount of organo-lithium compound used in each case for a certain amount of the vinyl-aromatic compound determines the size of the organic block. The smaller the amount of the organolithium compound for a given amount of the vinyl-aromatic compound, the greater the number of vinyl-aromatic units in the polymer formed. The reaction between the organolithium compound and the vinyl aromatic compound should be carried out under conditions free from contamination by water, air, oxygen, inhibitors, acid components and fats. The mixture of the vinyl aromatic compound and the organolithium compound in the solvent solution is kept during the polymerization at a temperature which is below the reflux temperature and above the freezing point of the mixture. The reaction product obtained in this way is a polymer of the following formula which has terminal Li atoms

^CRf > ^Li

wherein R, R ¹ , G and χ have the meaning given.

This solution of the polymer with terminal Li atoms is with hexamethylcyclotrisiloxane, dissolved in an organic solvent, added in sufficient quantity that at least 1 hexamethylcyclotrisiloxane molecule is available for each terminal Li atom stands) the amount of Hexamethylcyclotrisiloxan should be 4oji of Total amount of hexamethylcyclotrisiloxane to be added does not exceed

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rise. In addition, the addition must be made in such a way that the above-mentioned impurities cannot enter. The received The product is for the most part made from the polymer of the formula

CH3 CH3 CH3 R (-CH ₂ -CR '4 ^ CH ₂ -CR' -Si-0-Si-0-Si-OLi

I ^X II! I.

GG CH ₃ CH ₃ CH ₃

consist, in which R, R ', G and χ have the meaning given. The reaction temperature is kept between -5O ⁰ C and the reflux temperature of the mixture. After sufficient time has passed, i.e. at least 50 minutes, preferably 1 to 4 hours, which can be seen from the disappearance of the coloring characteristic of the terminal Li atoms, hexamethylcyclotrisiloxane is again dissolved in an organic solvent and a promoter which supports the polymerization added in an amount of at least 1% based on the weight of the mixture. The amount of hexamethylcyclotrisiloxane added leads to the desired siloxane block size. To increase the rate of reaction, the reaction mixture is advantageously refluxed for between 5 and 4 hours. However, the reaction can also be carried out between -50 ° C. and the reflux temperature for at least 30 minutes or longer. The product obtained corresponds to the formula

CH ₃ CH ₃ R (CH ₂ -CR'4-CH ₂ -CR'-SiO-f SiO -) - Li

ι χ ti 1 y '

GG CH ₃ CH ₃

in which R, R ¹ , G, χ and j $ r have the meaning given. In this block copolymer, the terminal Li atoms are then replaced by hydroxyl groups by adding acetic acid or by Z groups by adding triorganosilanes of the formula ZRgSiCl.

- 5 009i3l / 22S0

For this purpose, at least 1 mol of this agent providing the terminal groups must be added per gram atom of the lithium atoms. -

The vinyl aromatic compounds which are suitable for the production of the copolymers which can be used according to the invention include aromatic compounds having 1 to 3 rings with an aromatic structure which have a C ₂ = GH or C 2 = GH or

9V

CH ₂ = C- group contain bound.

According to the definition, these aromatic rings can have up to 3 sub < contain substituents, the alkyl, cycloalkyl and alkoxy radicals include. These substituents contain no more than 6 carbon atoms,

and every substituent which is in the e-position to the CHo = CH- or CH., * ■

CH ^ = C- group, contains no more than 1 Cr atom, so this can only be a methyl or methoxy radical. Examples of such vinyl aromatic compounds are styrene, oe-methylstyrene, o-vinyltoluene, m-methoxystyrene, 9-vinylanthracene, ^ -phenylstyrene, 3,5-di-phenylstyrene, ^ -methyl-S-hexylstyrene, 4-cyclohexylstyrene rol, 1-vinylnaphthalene, J>, 4-diphenoxystyrene, 4-hexoxystyrene, 4,5-dimethyl-1-vinylnaphthalene, 4-propylstyrene, ^ -p-Tolyli.-l-vinylnaphthalene and, CH = CH ₂ '

The ones used in the production of the block copolymers. Organolithium compounds correspond to the general formula RLi, in which R is a monovalent hydrocarbon radical with 1 to: JQ carbon atoms. Examples of such compounds are Ethylltthiüm, Öc.tadecyllithium, CH, (CH _o ) _o QLi, Naphthyllithium, Be.nzyliithium, 'n-Deoyllithium, Cyclöhexyllithium, 4-CyclohexylbutyllithiumJujtid » _v -, _% Octyllithium» - ^ t

uf

Organolithium compounds, vinyl aromatic compounds and Organic solvents should be dried, washed and / or before use distilled to remove possible impurities such as water, inhibitors and the like. The organic solvents are hydrocarbon solvents in which the vinyl aromatic compounds dissolve, such as cyclohexane, Toluene, benzene, η-hexane, petroleum ether, methylcyclohexane, xylene, η-butane, n-heptane, isooctane and cyclopentane are suitable.

As the organolithium compound with the vinyl aromatic compound reacts according to the following equation I:

(I) RLi + (x + i) CH ₂ = CR'G > RfCH ₂ -CR '^ - -Li

G ^{(X + 1)}

R, R 'and G can be illustrated by the following examples: Examples of radicals R are therefore methyl, ethyl, n-propyl, isopropyl, η-butyl, amyl, n-hexyl, octadecyl, triacontyl -, naphthyl, anthracyl, benzyl, phenyl, tolyl, xylyl, n-decyl, cyclohexyl, 4-butylphenyl, 4-cyclohexylbutyl, 4-phenylbutyl and octyl radicals. According to the ^{definition, R 1} is a hydrogen atom or a methyl group.

The aromatic radicals G are monovalent radicals which contain 1, 2 or 3 rings with an aromatic structure, whereby these can be substituted with up to J organic radicals, each of which contains no more than 6 carbon atoms, and by the specified condition with regard to the substitution in the o-position to the grouping -CR ¹ -. "Examples are

- 7 w

09838/2260

CHi

OCH ₃

CH ₃

(CHa) ₅ CH ₃

.CH ₂ -CH ₂ ^ CH ₂ - ^ "^

). ₅ SHs,

(CH2) 3CH3

^ VcH ₂ CH ₂ CH ₂ CH ₂ - ^ 7 >

(CHa) ₄ CH ₃

H (CH ₃ ).

and

CH ₂ -CH ₂ cH ₂ -CH ₂

The amount of the organolylum compound to be used can be easily by dividing the weight of the vinyl aromatic compound by he approximates the molecular weight of the desired organic block be averaged. These results lead to the number of moles of Organo! ithlum connection to be used. Since the implementation is almost lOOJiig runs, and if the unwanted impurities are carefully excluded becomes the average molecular weight obtained (Number average) the desired molecular weight, which is

009838/2260

averaging the moles of the organolithium compound was used, come very close. It should be noted that certain combinations of organolithium compounds and vinyl aromatic Connections and certain conditions can cause slight deviations from these calculated results, as the percentage of Implementation can vary. It should also be noted that mixtures of vinyl aromatic compounds can be polymerized or a vinyl aromatic compound can be polymerized and then another vinyl aromatic compound is added and polymerized can be.

The organic solvent used to dissolve the hexamethylcyclotrisiloxane is used can be any of those mentioned above for the vinyl aromatic compounds. As polymerization promoters can, for example, dimethyl sulfoxide, tetrahydrofuran and bis (2-methoxyethyl) ether be used.

The triorganosilxanes of the formula ZRgSiCl can be any monochlorosilanes be, where R "and Z are monovalent hydrocarbon radicals with 1 to 18 carbon atoms, such as methyl, ethyl, vinyl, allyl, Cyclohexyl, phenyl, xenyl, tolyl, octadecyl, naphthyl, isopropyl, Butyl, hexyl, decyl and / Ϊ-phenylethyl radicals.

The block copolymers which can be used according to the invention correspond the general formula

CH ₃ CH ₃ R "

R (CH ₂ -CR '4-CH ₂ -CR' -Si-C ^ SiCM

1 1 t t y t

G ■ G CH ₃ CH ₃ R "wherein R, R ¹ , R", G, χ and. ^ the given meaning applies.

When trying to mix vinyl aromatic polymers such as polystyrene and polydimethylsiloxane for a specific purpose, great difficulties arise because these two homopolymers are completely incompatible. Even with the use of a common

■ '- 9 -

. With a common solvent, such as toluene, in which the two homopolymers are soluble, the obtainable mixture consists of 2 phases, for example a toluene-polystyrene phase and a toluene-polydimethylsiloxane phase. Since when trying to unite polydiorganosiloxanes with such homopolymers, such as polystyrene, the. If the results were either unsatisfactory or complicated techniques were required to achieve this feat, and the results were not particularly beneficial, the plastics industry showed no interest in them. However, numerous attempts have been made to produce copolymers from vinyl aromatic compounds and polydiorganosiloxanes. So .Z , for example, vinyl-aromatic compounds such as styrene, with * vinyl group-containing silanes or siloxanes, styrene with Sig-bonded Η-atoms containing siloxanes or silanes or styrene on polyorganosiloxanes or silanes and siloxanes were polymerized. Polystyrene grafted on and even certain types of Blockmisehpolymerisaten made from styrene and siloxanes. The block copolymers produced so far, however, contained unusually large amounts of one or both homopolymers in the copolymer mixture. Since the homopolymers are so incompatible, such copolymers showed the same disadvantages as a mixture of the homopolymers. /

The copolymers which can be used according to the invention, on the other hand, are | ausserordentllch pure and rarely contain more than 5 wt -.% of one or other of the homopolymer in Blockmischpolymerisatmischung, and usually the amount of the homopolymers is less than 2 wt -.%. The block copolymers which can be used according to the invention are therefore practically free from homopolymers and have a narrow molecular weight distribution. They preferably have molecular weights from 20,000 to 500,000. ·

The block copolymers which can be used according to the invention have • They also have unusual solubility properties, they are in

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0 09138/2260

- ίο -

Toluene soluble with formation of clear solutions, although equivalents Quantities of the homopolymers in toluene are completely immiscible. Solutions of the block copolymers which can be used according to the invention with solvents in which only one of the blocks dissolves well remain clear and there is neither a precipitate nor a precipitate to observe a phase separation.

These block copolymers can now be used according to the invention for the production of mixtures with vinyl-aromatic homopolymers, for the production of which the same vinyl-aromatic monomers as mentioned above for the production of the block copolymers can be used. The vinyl-aromatic polymers obtained in this way show exceptional improvements with regard to the physical properties compared to the basic structure. Thus, small amounts of the block copolymers distributed in a vinyl-aromatic homopolymer improve the tensile strength and elongation compared to the vinyl-aromatic homopolymers without this block copolymer addition. These improvements are with 0.1 to 20 wt -% of the obtained block copolymer, based on the weight of the homopolymers.. It is preferred to use 0.5 to 10% and in particular 0.5 to 1.5% of the block copolymer, based in each case on the total weight of the homopolymer. Such mixtures also have a considerably improved toughness and impact resistance compared to the homopolymers without this block copolymer addition. The mixtures according to the invention are those which have been produced from vinylaromatic polymers and block copolymers, in which the vinylaromatic polymers consist of the same repeating units as the RC-C

G G

Blocks of the block copolymer. The improvement in the toughness of the mixtures according to the invention depends on the adaptation of the vinyl aromatic polymer to the vinyl aromatic blocs of the block copolymers. For this reason, in a given mixture, the repeating units of the formula -CHg-CR ¹ -

009838 ^ 2160

- li -

of the vinyl aromatic polymer the same as that repeating units in the blocks of the block copolymer.

The vinyl-aromatic polymers (A) can by reaction of vinyl aromatic compounds with an organoIithium " compound dissolved in an organic solvent as described above '; getting produced. The vinyl aromatic However, polymers (A) can also be purchased commercially or prepared by other known processes.

The mixtures are best made by having the | Vinyl-aromatic polymers and 0.1 to 20 wt .- ^ of the block copolymer dissolved or distributed in an organic solvent in which the vinyl-aromatic polymers are soluble will. Suitable solvents for this are hydrocarbon solvents, as already mentioned above. Then will removes the solvent to form the mixtures. the Solvent solution or dispersion can be used to cast a film or used for the production of moldings. The mixtures can also be prepared by other known methods.

The mixtures of this invention are coatings g for the preparation of over- and molded articles suitable with improved toughness and impact resistance. The mixtures according to the invention can be used as such or they can be cured by processes customary for vinyl-aromatic polymers.

The mixtures according to the invention can contain further additives and Fillers commonly used for vinyl aromatic polymers Find use included. Polydimethylsiloxanes can also be used are added to increase the amount of siloxane in the polymer, since the block copolymers a considerable Can dissolve amount of diorganopolyslloxanes. In this way it is possible, which is usually the case when mixing with to overcome the difficulties encountered with incompatible materials.

example 1

Freshly distilled styrene made with dilute sodium hydroxide Washed to remove inhibitors and dried before distillation was taken in cyclohexane for 15 minutes Heated to reflux through a weak stream of purified nitrogen. The styrene was further dried through The solution is refluxed over calcium hydride for 30 minutes. The styrene solution dried in this way was then transferred to a reaction vessel which had previously been filled with pure nitrogen had been flushed through and kept under slight nitrogen pressure without access to the atmosphere. The polymerization The styrene was released by adding a 1.6 molar solution of butyllithium in hexane. At the beginning of the polymerization the reaction vessel was cooled. After 3 to 4 hours at The polymerization of the styrene was complete at room temperature.

A solution of hexamethylcyclotrisiloxane in cyclohexane was refluxed for 15 minutes under a gentle stream of nitrogen and then refluxed over calcium hydride for 30 minutes. A portion of this dried hexamethylcyclotrisiloxane solution was then introduced into the reaction vessel which contained the polymerized styrene without access to the atmosphere. After about an hour of vigorous stirring at 50 ° - 6O ⁰ C the characteristic of the organgerote7ärbung terminal lithium atoms having polystyrene was completely disappeared. Then the remaining dried solution of hexamethylcyclotrisiloxane was added and then tetrahydrofuran. The reaction mixture obtained in this way was then heated under reflux for 4 hours with vigorous agitation, after which time the originally cloudy solution had become clear. The product obtained was then neutralized with 1.0 ml of dimethylvinylchlorosilane and then with 1.0 g of sodium bicarbonate with the formation of a terminal dimethyl «»

- 13 009838/2260

block copolymer containing vinylsiloxy groups or with 1.0 ml of acetic acid and then 1.0 g of sodium bicarbonate to form a block copolymer containing terminal silanol groups, »The solutions of the product were washed with water and precipitated with methanol. The precipitates were washed several times with methanol, then the residual solvent by 19 hours heating at 5O ⁰ C and 0.1 mm Hg (abs.) Removed. The product was a block copolymer corresponding to the formula

CH ₃ CH ₃ ^V CH ₃

in the case of terminal dirnethylvinyisiloxyo units Block copolymer and the formula

. CH ₃ CH ₃ CH ₃

CH ₃ CHaCHaCH ₂ —fCHaCH ^ -CHaCK-

^x r

CH ₃ CH ₃ CH ₃

CH C

in the case of the block copolymer having terminal silanol groups. The values of χ and j depend on the molecular weights and weight percentages of each block.

The procedure was carried out in batch no. 12 varies as follows: The | The mixture was refluxed for 1 hour after the addition of the methyl sulfoxide and then left to stand for 48 hours before it was neutralized with 1.0 g of dry ice. The block copolymer was precipitated by distilling off 200 ml of the solvent and then adding methanol. The infrared analysis agreed with this structure, and the block copolymer formed a single solution phase in carbon tetrachloride, while a mixture of polystyrene and polydimethylsiloxane formed a two-phase eyetem in carbon tetrachloride. The amounts used in this process and the results are summarized in Table I below! ^;

§09138 / 2260

Example 2

After in Example 1 according to the batches 1 to 11-described method, a block copolymer was prepared which ausL35 wt -.% ■ polystyrene blocks and 65 wt -.% Polydimethylsiloxanblöcken was constructed and had a molecular weight of 142,000.

A 20% strength by weight solution of a commercially available polystyrene in toluene was then prepared and the amounts of the block copolymer indicated in Table II were added to this solution. The solutions were poured onto a mercury surface in a crystallizing dish to form a 0.0127 µm P (0.5 mil.) Film. Before removing the film from the mercury surface, the toluene was left to evaporate for 48 hours. The films were then held in a vacuum oven at 0.2 mm Hg for 24 hours at room temperature. The oven temperature was then slowly increased to 70 ^° C. over the course of 24 hours. The films were held for 48 hours and 0.2 mm Hg before the tensile strength at brueh and the elongation at break were determined. The tensile strength and elongation at break were measured with a tension of 0.0254 om / min. determined at room temperature.

The toughness of the blends is shown in Table II as the "Toughness Index" given, that is a numerical value that corresponds to the relative toughness of the material. The calculation is based on the following-P Equation:

Toughness index = (tension in psi at the yield point + tension in psl at break) χ (elongation in %) : 2.

Further details about the toughness index can be found in the book "Testing of Polymers" by John V. Schmitz, Interscience Publishers, New York, 1965 * Vol.

In those cases that show no yield point under tension or elongation, the yield point and breakpoint are the same.

Example 3

! ,, films were cast by the process described in Example 2 with the exception that the polystyrene-polydimethylsiloxane Biockmischpolymerisat prepared according to Example 1 had a molecular weight of 142,000 and from 40.8 wt -.% Polystyrene, and blocks 59.2 wt -.% Polydimethylsiloxanblöcken that were end-blocked with dimethylvinylsiloxy groups, constructed wars Tn Table III is the improved toughness of polystyrene by adding small amounts of the polystyrene-polydimethylsiloxane block copolymer shown.

Example 4 -

Were made from the following mixtures, which are compiled in Table IV are, films produced according to the method described in Example 2, these had a higher toughness index than films the corresponding homopolymers alone.

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TABLE I.

Approach styrene-styrene dissolved in moles of total amount [(CH,) j, SiO], dissolved cyclohexane + £ <CH,) _p tetrah

Xr. In g ml of cyclohexane butyllithium [(CT, TgSiO], in ml of Cyclottexan SiOU solution,! »; Addition of drofur

0.0280 60 159 50 120

0.0070 60 159 60 120

0.0054 166.6 400 50 150

0.0030 67 192 55 120

0.0030 67 I92 40 120

0.0030 67 I92 55 120

0.0026 120 350 100 120 y

0.0026 120 350 100 12a *

0.00064 30 95 50 * 60

0.0010 I68 672 ⁺ 100 20

0.00133 6Ö 200 40 10

0.0064 50 75 '10 2

0.0014 130 950 100 120

0.0015 127 8o4 ⁺ 50 25

0.0014 130 656 ⁺ 100 25

1 ^ 3 140 466 2 O 140 466 ■ χ CO 104 400 4th OO 90 288 5 U9
OO 90 288 6th "**» 90 288 7th fs> 80 275 .8th cn
0 80 275 9 20th 95 10 80 40O ⁺ 11 140 400 12th .69.4 350 13th 70 350 14th 50 20O ⁺ 15th 60 30O ⁺

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TABLE! (Port setting)

approach

Aiis loot of the mixed average MoIepolymerlsats in % kulargew. (Number average). . _, the block copolymer

■ & * ■

96.0
84.0
84.0
78.0
80.0
94.0
91.0
91.0
82.8
80.0
84.0

82.0

7.O6O 3O.6OO 48,800 47,6OO 41,400 65,400 80,000 80,000 72,600 170,000 129,000

44.200 140.227 I69.3OO

Benzene was used instead of cyelohexane.

Instead of tetrahydrofuran, bis (2-methoxyethyl) ether was used.

Determined by membrane osmometry. ] Instead of tetrahydrofuran, dimethyl sulfoxide was used

'. ■■■■■ '' ■ ■ '. . ■■■■■. ■,, '.....,' C ₂

After 8556 t (CH ₃ ) ₂ SiO] had been consumed, 5 g (CH _{3) 3 were} added

Weight% approximate from Z the value 47 Terminal groups Siloxane blocks χ 207 -Si (CH ₃ J ₂ CH = CH ₂ 28.4 25th 179 -Si (CH ₃ J ₂ CH = CH ₂ 29.1 118 310 -Si (CH ₃ J ₂ OH 61.6 404 265 -Si (CH ₃ J ₂ CH = CH ₂ 32.0 204 395 -Si (CH ₃ J ₂ CH = CH ₂ 33.0 182 316 -Si (CH ₃ J ₂ OH 36.9 324 316 -Si (CH ₃ J ₂ OH 58.7 632. - -Si (CH ₃ ) ₂ CH = CH ₂ 58.7 632 757 -Si (CH ₃ J ₂ OH 899 -Si (CH ₃ J ₂ CH = CH ₂ 53.6 1229 - -Si (CH ₃ J ₂ ^{CH = CH} ₂ 27.4 475 158 -Si (CH ₃ J ₂ OH - «-.- --- 1101 -Si (CH ₃ J ₂ CH = CH ₂ 26.8 310 1370 -Si (CH,) pCH = CH _p
. • -III 58.2 562 -Si (CH ₃ J ₂ CH = CH ₂ ⁺ 60 651 CD CD -ether. used. cn
CO 'wenuc Jj
CH ³⁰ CHp

I. ιη oil OO • Ρ ΙΛ • Η ι Φ K ο VO bOO 00 • Η β CVJ , Li Π Nl.

O H

m r ?!

- = t νο

VO

ιη
· = * Ο

Jt

ο ο

ο ο

ιη ιλ

ιλ ιη

H ιΗ

H H

(U Q) XJ N

cvT

VO ΙΛ O O O

νο

Cu CVi CVi σ \ γλ
·> Η

CVl

ο Λ

-CVi ΐΛοο νο σ \ ι> -

• ^ co σ \ οο ο _ _

^ r Jt ιλ Cu CU Jt ιη

· »ΙΛ KN ΚΛ ΙΛ ίΛ CV)

ιη

CVi CVi νο - ιλ m

ιλ ιη οο η ιη σ \ νο

^ t KN ΙΛ CVl ΙΛ - ^

H CU CU CVI CVJ CVI CVJ

O O O O

CV) CVI CVI CVI

t- t- O Q

ο η ιη ο

KN O KN VO

KN KN KN CU

in Cu

CU CU VD ΙΛ

KN H KN OO

CU CU CU H

OO O O O

in η cj η

O .. O O H CVJ O H

C *? CO

Train at the Elongation at TABLE III Stretching at Tough £ block Stretch limit
in kg / cm the stretch sizes
ze in % Train at Break in ability
index mixed poly
merisat • Fraction ^ in
kg / cm ² (psi) 2.2 .j ■■■ 4,587 0.1 289.7 (4124) 2.0 292.9 (4170) 3.9 y 15,937 0.3 283.8 (4040) 2.0 284.5 (4049) 4.0 16,080 0.5 257.6 (3665) 2.0 281 (4000) 6.4 23,357 1.0 198.8 (2825) 2.5 255.4 (3634) 7.0 · 19,985 2.0 202.9 (2885) 1.6 ^% 2,000 o, 3 ⁺ ---- 176 (25OO) 1.9 3,325 0.3 "^ ⁺ 246 (35OO)

⁺ Instead of the block copolymer, a polydimethylsiloxane homopolymer was mixed with the polystyrene. ■ .. ■■■ '■ -

⁺⁺ Instead of the block copolymer, a styrene-butadiene elastomer was mixed with the polystyrene.

TABLE IV

Block copolymer wt. %
Block copolymer

Formula unit des
Homopolymer

^ CH ₂ -CH) -CH ₂ -CH-

CH3 CH3 CH3 f)

CH

VCH ₃ CH ₃ CH ₃ CH ₃ 0.15

f CH ₂ -CH)

x = 1000,

y = 1000

CH ₃

CH ₃ CH ₃ CH ₃ CH ₃

H ₂ ) τ (GH ₂ -C) CH ₂ -C SiOfSiO) SiOH

^x · ι ι y!

CH ₃ CH ₃ CH ₃

0.5

CH ₃
(.CH ₂ -C) -

X = 100,

y =

CH ₃

H ₂ -CH) -CHa-CH

CH ₃

CH ₃ CH ₃ CH ₂ CH ₃ JiOfSiO) -Si-CH ₂ CH = CH ₂ CH ₃ CH ₃ CH ₂ CH ₃ I ₁ O

f CH ₂ -CH)

x = 250,

y = 1220

TABLE IV (continued)

Block polymerizate by weight J6
Block copolymer

Formula unit des
Homopolymers

-CK) --— CH ₂ -CH-

CH ₃ CH ₃ CH ₃ -SiOfSiO) -Si (C ₆ H ₅ ) ₂

t .1 y

CH ₃ CH ₃

11

(CHs) ₂ CH ₃ (Clk) ₂ CH ₃ 1.5

(-CH ₂ -CH)

(CH2) ₂ CH ₃

x - 300, y =

CH ₃ \ CH ₂ -

.-C CH ₂ -CH-

¹ CH ₃

CH ₃ CH ₃ CH ₃ -SiOfSiO ^ -SiCH = CH ₂ CH ₃ CH ₃ CoH ₅

x = 4000, y = 2132 (-CH ₂ -CH) -

OCH;

H ₂ -CH ^ -T-CH ₂ -C

CH ₃ CH ₃ CH ₃

iOfSiO) "SiC 1 _S H _3T 11 Vt

CH ₃ CH ₃ CH ₃

x- 565- , y = 2000 2.0

(-CH ₂ -CH) -

CD CJl CO

- 22 -

TABLE IV (continued) Block copolymer.

Weight %
Block copolymer

Formula unit des
Homopolymer

cH ₂ (-CH ₂ -CH)

CH3 CH3 CH3 I t T

-OXi ₂ —Ort blood olLH — ο

t 1 y _T ν = / ν = /

CH3 CH3 CH ₃

CH ₃ (CHs) ₅ CH ₃ CH ₃
x = 2500, y = 150

1 * 7

f CH ₂ -CH)

CH3 (CH2J5CH3

,, CH ₂ -CH ₂ ,

"CH ₂ -CH ₂

CHfCH ₂ -CH) - CH ₂ -CH-

CH ₃ CH ₃ CH ₃

CH;

CH ₃ '

x = 20,

CH
H ₃ CH 3

y = 55

1 \ Ύ \ CH ₃ CH ₃ CH ₃

H ₃

0.7

VCH ₂ -CH)
CH ₃ ^ s ₁

CH ₃ CH ₃

_v JH ₂ -CH 810-4SiO) -Si-CH ₂ CH ₂ -

χ t f f y 1

X = 25,

fCH ₂ -CH)

TABLE IV (continued)

Block copolymer wt. % -;.
Block copolymer

Pormel unit des
Homopolymers

CH ₃ (CHa) ₃ (CH ₂ -CH-):

Tl

_CH2) 5CH3

CH ₃ CH ₃ CH ₃ -CH ₂ -CH-SiOfSiO) -SiCH = CH ₂

t t y ι

with CH ₃ CH ₃ CH ₃ (CH ₂ ) SCH ₃ (-CH ₂ -CH) -

'CH ₃ ^ (CHb) ₅ CH ₃

x = ^ 000, y = 3130

CH3 CH3 CH3

-CH) _x CHb -CH — SiOfSiO) -SiC ₆ Hi ₃ (-CH ₂ -CH) -

CH ₃ CH ₃

χ = 95, y = CH ₃

CD cn co

TABLE IV (continued)

Block copolymer wt. %
Block copolymer

Formula unit of the homopolymer

CH ₂ -CH ₂

"CH.2 - CH2

CHfCH ₂ ) ₄ (CH ₂ -CH)

H ₂ -CH-

x = 450,

CH ₂ y = 1000

CH ₂

CH ₂

-CH ₂

CH3 CH3 CH3

-SiOfSiOf-SiOH

CH3 CH3 CH3

CH ₂ - CH ₂ 0.9

(-CH ₂ -CH) -.

CH ₂

CH ₂ "- ~ - CH ₂

CH3 CH ₃ CH ₃ CH ₃ (CH _{2) 2} CH SfCH) -CH ₂ CH-SiOfSiO) SiCH = CH ₂

co 00 Ca) OO

CH ₃ CH ₃ CH ₃

χ = 5000, y = 5000 I ₁ O

f CH ₂ -CH) -

cn ο

Claims (4)

Claims Basis of vinyl aromatic polymers, d a - characterized by that they are on respectively · (A) 100 parts by weight of a vinyl-aromatic polymer composed of repeating units of the general Formula - -CH ₂ -CR ¹ -, wherein R 'is hydrogen or methyl and G denote monovalent, aromatic radicals consisting of 1 to 5 rings with an aromatic structure, each with up to three alkyl, cycloalkyl or alkoxy radicals with _: ^ 1 to 6 carbon atoms can be substituted, but in such a way - "that in the o-position to the -CR ¹ - group no'.aliphatic-organic substituents with more than one carbon atom exist j. (B) 0.1 to 20 parts by weight of a block copolymer with a molecular weight of 7,000 to 1,000,000, consisting essentially of aromatic-organic blocks and chlorganosiloxane blocks according to the general formula • β 2 ^m ■ ' 90983e / 2269 CH, CH, R " t j> ι j ι R (-CH ₀ -CR'4Tr-CH ₀ -CR'-SiO (-. SiO) - Si-Z, £ -! Λ eleven ι ι Jt G G CH, CH, R " wherein R 'and G have the meaning given, but in the Components (A) and (B) are each the same, R monovalent hydrocarbon radicals with 1 to J> 0 carbon atoms, R "monovalent hydrocarbon radicals with 1 to 10 carbon atoms, Z monovalent hydrocarbon radicals with 1 to 18 carbon atoms or mean hydroxyl groups, χ and ^ each have averages from 20 to 5000, is constructed so that 20 to 70 wt -.% diorganosiloxane units and JJO to 80 wt -.% of units of the organic block are included. 2. Mixtures according to claim 1, characterized in that that for every 100 parts by weight (A) they contain 0.5 to 10 parts by weight (B). 5 · Mixtures according to claim 1, characterized in c h η e t that the block copolymers (B) used are those with a molecular weight of 20,000 to 500,000 will. 4. A mixture according to claim 1, characterized gekennzeizeichnet, be that as components (A) and (B) those in which R 'are hydrogen atoms and G Phenylrr te means used. 009838/2260