DE2011059B2 - Mixtures based on vinyl aromatic polymers for the production of moldings and coatings - Google Patents

Description

wherein R 'hydrogen atoms or methyl radicals and G are monovalent aromatic radicals which consist of one to three 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 in the o-position to the

—CR “- grouping

no aliphatic-organic substituents with more than one carbon atom are present, (B) 0.1 to 20 parts by weight of a block copolymer having a molecular weight of 7,000 to 1,000,000, consisting essentially of aromatic-organic blocks and diorganosiloxane blocks according to the general formula

CH ₃ CH ₃ CH ₃ R- (CH ₂ -CRVCH ₂ -CR'-SiO- (SiO ^ Si-Z

! I I I i

GG CH ₃ CH ₃ R "

4. Mixtures according to claim 1, characterized in that that in components (A) and (B) R 'is hydrogen and G is phenyl.

Vinyl aromatic polymers have useful and desirable properties, and therefore will used for the production of numerous articles for industry and household. These vinyl aromatic However, polymers are often in the form of mixtures used with other organic polymers or as a copolymer because of their properties certain limits are imposed, thereby affecting their use in many types of applications will. One of these limits is the lack of toughness, their poor impact resistance and their glassy character. Numerous attempts have been made to improve these properties. The toughness and impact resistance could be improved, but this is often done was associated with the loss of other desirable properties.

Surprisingly, it has now been found that small amounts of a block copolymer from Polydimethylsiloxane and vinyl aromatic polymer blocks in a vinyl aromatic polymer lead to tougher products.

According to the invention, therefore, mixtures based on vinyl aromatic polymers for Production of moldings and coatings claimed, which are characterized in that the for each (A) 100 parts by weight of a vinyl aromatic polymer composed of repeating units the general formula

where R 'and G have the meaning given, but are each the same in components (A) and (B), R monovalent hydrocarbon radicals having 1 to 30 carbon atoms, R "monovalent hydrocarbon radicals having 1 to 18 carbon atoms, Z monovalent Mean hydrocarbon radicals with 1 to 18 carbon atoms or hydroxyl groups, χ and y each have average values of 20 to 5000, is structured so that 20 to 70 percent by weight of diorganosiloxane units and 30 to 80 percent by weight of units of the organic block are present and where up to about S Percent by weight of one or the other homopolymer may be present.

2. Mixtures according to ^ ß claim 1, characterized in that that for every 100 parts by weight (A) they contain 0.5 to 10 parts by weight (B).

3. Mixtures according to claim 1, characterized in that the block copolymers used (B) have a molecular weight of 20,000 to 500,000.

40 in which R 'denotes hydrogen atoms or methyl radicals and G denotes monovalent, aromatic radicals consisting of one to three rings with an aromatic structure, each of which can be substituted by up to three alkyl, cycloalkyl or alkoxy radicals with 1 to 6 carbon atoms, but so that in the o-position to the 50

—CR “- grouping

no aliphatic-organic substituents with more than one carbon atom are present, (B) 0.1 to 20 parts by weight of a block copolymer with a Molecular weight from 7,000 to 1,000,000, consisting essentially of aromatic-organic blocks and diorganosiloxane blocks according to the general formula

CH ₃ CH ₃ R "

III

R-fCH ₂ -CRVCH ₂ -CR'-SiO -fSiO ^ Si-Z

I I I I I

GG CH ₃ CH ₃ R "

in which R 'and G have the meaning given, but are each the same in components (A) and (B)

2 Oil

IO

are χ R monovalent hydrocarbon radicals having 1 to 30 carbon atoms, R "are monovalent hydrocarbon radicals having from i to 18 carbon atoms, T monovalent hydrocarbon radicals init 1 to 18 carbon atoms or hydroxyl groups and y are each average values 20-5000 have so is constructed in that 20 to 70 percent by weight of diorganosuoxane units and 30 to 80 percent by weight of units of the organic block are present and up to about 5 percent by weight of one or the other homopolymer can be present.

The block copolymers which can be used according to the invention can best be obtained by polymerization a vinyl aromatic compound of the formula

CH ₂ = CRO

with an organolithium compound in an organic solvent. The respective to a certain amount of the vinyl aromatic compound used amount of the organolithium compound determines the size of the organic block. The smaller the amount of the organolithium compound to 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 that are free from contamination by water, air, oxygen, inhibitors, acids and fats. The mixture of the vinyl aromatic compound and the organolithium compound in the solvent solution is kept at a temperature below the reflux temperature during the polymerization and the reaction product thus obtainable is above the freezing point of the mixture is a terminal Li-atom polymer of the following formula

R- (CH ₂ -

wherein R, R ', G and χ have the meaning given. This solution of the polymer with terminal Li atoms is mixed with hexamethylcyclotrisiloxane, dissolved in an organic solvent, in a sufficient amount that at least one hexamethylcyclotrisiloxane molecule is available for each terminal Li atom; however, the amount of hexamethylcyclotrisiloxane should not exceed 40% of the total amount of hexamethylcyclotrisiloxane to be added. In addition, the addition must be made in such a way that the above-mentioned impurities cannot enter. Most of the product obtained consists of the polymer of the formula

CH ₃ CH ₃ CH ₃

R-tCH ₂ -CRVCH ₂ -CR'-Si-O-Si-O-Si-OLi

CH ₃ CH,

CH ₃

consist, in which R, R ', G and χ have the meaning given. The reaction temperature is kept between -50 ⁰ C and the reflux temperature of the mixture. After sufficient time has passed, ie at least 30 minutes, preferably 1 to 4 hours, which can be determined by the disappearance of the color characteristic of the terminal Li atoms having polymers, hexamethylcyclotrisiloxane is again dissolved in an organic solvent and a promoter supporting the polymerization in a Amount of at least 1%, based on the weight of the mixture, added. The amount of hexamethylcyclotrisiloxane added results in the desired siloxane block size. To increase the rate of reaction, the reaction mixture is advantageously refluxed for 3 to 4 hours. However, the reaction can also be carried out between ⁰ -5o C and the reflux temperature for at least 30 minutes or longer. The product obtained corresponds to the formula

CH ₃ CH,
R- (CH ₂ - CRVCH ₂ -CR'-SiO

GG CH ₃ CH ₃

60

wherein R, R ', G, χ and y have the meaning given. In this block copolymer, the terminal Li atoms are then replaced by hydroxyl groups by adding acetic acid or by —SiR ₂ ”Z groups _{by adding triorganosilanes of the formula ZR 2 'SiCl.}

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

The vinyl aromatic compounds which are suitable for producing the copolymers which can be used according to the invention include aromatic compounds having one to three rings with an aromatic structure which have a CH ₂ = CH - or on one of the rings

CH ₃

CH ₂ = C group

bound included.

According to the definition, these aromatic rings can contain up to three substituents, which include alkyl ", cycloalkyl and alkoxy radicals. These substituents contain no more than 6 carbon atoms, and each substituent which is ortho to the CH ₂ = CH - or

CH ₃

CH ₂ = C group

is located, contains no more than 1 carbon atom, since larger aliphatic substituents in this position Sterically hinder polymerization; this can therefore only be a methyl or methoxy radical. examples for Such vinyl aromatic compounds are styrene, α - methyl styrene, ο - vinyl toluene, m - methoxystyrene, 9-vinylanthracene, 4-phenylstyrene, 3,5-diphenylstyrene, 3-methyl-5-hexylstyrene, 4-cyclohexylstyrene, 1-vinylnaphthalene, 3,4 - diphenoxystyrene, 4 - hexoxystyrene,

4,5 - dimethyl - 1 - vinylnaphthalene, 4 - propylstyrene, 3-p-tolyl-1-vinylnaphthalene and

CH = CH ₂

IO

The organolithium compounds used in the production of the block copolymers correspond to the general formula RLi, where R is a monovalent hydrocarbon radical having 1 to 30 carbon atoms. Examples of such compounds are ethyl lithium, octadecyl lithium, CH ₃ (CH ₂ ] I ₂₉ Li, naphthyl lithium, benzyl lithium, η - decyl lithium, cyclohexyl lithium, 4-cyclohexyl butyl lithium and octyl lithium.

Organolithium compounds, vinyl aromatic compounds and organic solvents should be present Can be dried, washed and / or distilled to remove possible impurities, such as water, To remove inhibitors and the like. 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.

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

RLi + (x + I) CH ₂ = CRO

(D
Li

Are defined. examples for this are

CH,

15th

25th

30th

35

40

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.

By definition, R 'is a hydrogen atom or a methyl group.

The aromatic radicals G are monovalent radicals which contain one, two or three rings with an aromatic structure, it being possible for these to be substituted by up to three organic radicals, each of which does not contain more than 6 carbon atoms, and by the specified condition with regard to the substitution in the o-position m of the grouping

—CR-

60

CH ₃

(CH ₂ ) ₅ CH ₃

CH ₂ -CH ₂

CH ₂

O (CH ₂ ) _S CH ₃

(CH ₂ J ₃ CH ₃ -CH ₂ CH ₂ CH ₂ CH ₂ -

(CH ₂ J ₄ CH ₃ CH (CH ₃ ),

CH ₂ -CH ₂

The amount of the organolithium compound to be used can easily be determined by dividing the weight of the vinyl aromatic compound by the molecular weight of the desired organic block can be determined approximately. These results lead to the number of moles of organolithium compound to be employed. Since the implementation is almost 100% runs, and if the unwanted impurities are carefully ruled out, that will obtained number average molecular weight the desired molecular weight, the to determine the moles of the organolithium compound was used, come very close. It should be noted that certain combinations of the organolithium compounds and vinyl aromatic compounds and certain conditions are minor

A, «Γ

Deviations in these calculated results can cause the percentage of implementation can vary. It should also be pointed out that mixtures of the vinyl aromatic compounds can be polymerized or a vinyl aromatic compound Compound can be polymerized and then another vinyl aromatic compound is added and can be polymerized.

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

The triorganosilxanes of the formula ZR ₂ "SiCl can be any monochlorosilanes, in which R" and 2 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 ß- phenylethyl radicals.

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

R- (CH ₂ -I

CH ₃ CH ₃ R "CR'-Si— 0- (SiO ^ - Si-Z G CH ₃ CH ₃ R"

where R, R ', R ". G, χ and y have the meaning given.

When trying vinyl aromatic polymers such as polystyrene and polydimethylsiloxane to one To mix certain intended uses, great difficulties arise, since these two homopolymers are completely incompatible. Self when using a common solvent, such as toluene, in which the two homopolymers are soluble, the obtainable mixture consists of two phases, e.g. B. from a toluene-polystyrene phase and a toluene-polydimethylsiloxane phase. Since when trying to unite polydiorganosiloxanes with such homopolymers, such as polystyrene, the Results either unsatisfactory or complicated techniques were required to achieve this feat; the results also failed brought special benefits; the plastics industry showed no interest in this. However, there were Numerous attempts have been made to make copolymers of vinyl aromatic compounds and Manufacture polydiorganosiloxanes. So were z. B. vinyl aromatic compounds such as styrene, with vinyl group-containing silanes or siloxanes, styrene polymerized with siloxanes or silanes containing Si-bonded Η atoms or grafted styrene onto polyorganosiloxanes or silanes and siloxanes onto polystyrene and even certain types of Block copolymers made from styrene and siloxanes.

For example, US Pat. No. 3,051,684 describes a process for producing block copolymers from macromolecular hydrocarbon and organosiloxane segments, that of prepolymerized hydrocarbons with terminal potassium, sodium, rubidium or cesium atoms, which are linked with diorganocyclo- siloxanes are implemented. However, these special alkali metal atoms cause an extended one Equilibration of the diorganosiloxanes, i.e. one of the -like polymerization process that is based on the cleavage of the siloxane rings and subsequent union of the fragments to form chain-like molecular associations is completely disordered, as there is also a rearrangement of the siloxane bonds in the fragments or their recycling is favored in the same way. The resulting products persist therefore made from chain-like polymers of various molecular sizes, in addition to cyclic siloxanes and the block copolymers contain considerable borrowed amounts of homopolymer fractions. Together In summary, it can therefore be stated that the block copolymers produced so far contain unusually large amounts of one or both homopolymers in the copolymer mixture. held. Because the homopolymers are so incompatible such copolymers showed the same

Disadvantages such as a mixture of the homopolymers 1-

th.

The mixed poly-

Merisate, on the other hand, are extremely pure and rarely contain more than 5 percent by weight of the one or other homopolymer in the block copolymer mixture, and usually the Amount of homopolymers less than 2 weight percent. The block that can be used according to the invention Copolymers 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 also have unusual solubility properties; they are formed in toluene soluble in clear solutions, although they are equivalent

409509/42 (

Quantities of the homopolymers in toluene are completely immiscible. Solutions of the invention usable block copolymers with solvents in which only one of the blocks dissolves well, remain clear and neither a precipitate nor a phase separation can be observed.

According to the invention, these block copolymers can now be used to produce mixtures with vinyl aromatic homopolymers, for their preparation the same vinyl aromatic monomers as Mentioned above for the preparation of the block copolymers, can be used, can be used. The vinyl aromatic polymers obtained in this way show extraordinary improvements in terms of the physical properties compared to the basic structure. So, small amounts of the Block copolymers distributed in a vinyl aromatic homopolymer, the tensile strength and elongation compared to the vinyl aromatic homopolymers without this block copolymer addition. These improvements are made with 0.1 to 20 percent by weight of the block copolymer, based on the weight of the homopolymer achieved. Preferably 0.5 to 10% and in particular 0.5 to 1.5% of the block copolymer, each based on the total weight of the homopolymer used. Such blends also have significantly improved toughness and impact resistance with respect to the homopolymers without this block copolymer addition. the Mixtures according to the invention are those consisting of aromatic vinyl polymers and block copolymers have been prepared in which the vinyl aromatic polymers are made up of the same repeating units exist, such as the

R-tC'H ₂ -CRVCH ₂ -CR 'blocks
GG

of the block copolymer. The improvement in the toughness of the mixtures according to the invention is from the adaptation of the vinyl aromatic polymer to the vinyl aromatic blocks of the block copolymer addicted. For this reason, in a given mixture, the repetitive Units of the formula

—CH ₂ -CR'-

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

The vinyl aromatic polymers (A) can be prepared by reacting the vinyl aromatic compounds with an organolithium compound dissolved in an organic solvent, as described above, getting produced. However, the vinyl aromatic polymers (A) can also be purchased commercially or by other known methods.

The mixtures are best prepared in that the vinyl aromatic polymers and 0.1 to 20 percent by weight of the block copolymer and 0.1 to 20 percent by weight of the block copolymer in an organic solvent in which the vinyl aromatic polymers are soluble are to be resolved or distributed. Suitable solvents for this are hydrocarbon solvents, as mentioned above. The solvent is then removed to form the mixtures. The solvent solution or dispersion can be used for casting a film or for producing moldings be used. The mixtures can also be prepared by other known methods

ίο be.

The mixtures according to the invention are suitable for the production of coatings and moldings, which have improved toughness and impact resistance. The mixtures according to the invention can used as such or they can be cured by processes customary for vinylaromatic polymers will.

The mixtures according to the invention can contain further additives and fillers which are customary for vinylaromatic polymers use, may also contain polydimethylsiloxanes are added to increase the amount of siloxane in the polymer, since the block copolymers can dissolve a considerable amount of diorganopolysiloxanes. To this Way it is possible, which usually occurs when mixing incompatible materials To overcome difficulties.

example 1

a) Production of the block copolymers used according to the invention

Freshly distilled styrene mixed with dilute sodium hydroxide to remove inhibitors washed and dried prior to distillation, was passed through in cyclohexane for 15 minutes a weak stream of purified nitrogen

heated to reflux. The styrene was obtained by heating the solution over calcium hydride for 30 minutes further dried under reflux. The styrene solution dried in this way was then turned into a Transfer the reaction vessel that had previously been purged with pure nitrogen and gently Nitrogen pressure is maintained without access to the atmosphere. The polymerization of the styrene was through Addition of a 1.6 molar solution of butyllithium in hexane triggered. At the beginning of the polymerization

_S o the reaction vessel was cooled After 3 to 4 hours at room temperature, the polymerization of the styrene was complete

A solution of hexamethylcyclotrisiloxane in cyclohexane was refluxed for 15 minutes under a gentle stream of nitrogen and then refluxed over calchimhydride for 30 minutes. A portion of this dried hexamethylcyclotrisiloxane solution was then introduced into the reaction vessel containing the polymerized styrene without admitting the atmosphere. After about an hour of vigorous stirring at 50 to 6O ⁰ C the characteristic orange-red coloration of the terminal lithium atoms having polystyrene was completely disappeared. Then the remaining was dried

Solution of hexamethylcyclotrisiloxane added and then tetrahydrofuran. The thus obtained The reaction mixture was then refluxed with vigorous agitation for 4 hours, after which time

7-.7Π

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 to form a terminal block copolymer having dimethylvinylsiloxy groups or with 1.0 ml of acetic acid and then 1.0 g of sodium bicarbonate to form a block copolymer having 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 remaining solvent was passed through. 19 hours heating at 5O ⁰ C and 0.1 mm Hg (abs.) Removed. The product was a block copolymer corresponding to the formula

CH3 CH ₃ C> ri ₃

CH ₃ CH ₂ CH ₂ Ch ₂ - (CH ₂ CH) TCH ₂ CH - Si- O- (SiO) ₇ - Si-CH = CH ₂ J \ J \ CH ₃ CH ₃ CH ₃

in the case of the block copolymer having terminal dimethylvinylsiloxy units and of the formula

CH ₃ CH ₃ CH ₂ CH ₂ CH ₂ - (CH ₂ CHk-CH ₂ CH - SiO CH ₃ CH ₃

- (SiO) ₇ - SiOH

CH ₃ CH ₃

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

The procedure was varied in batch no. 12 as follows: The mixture was after addition of the dimethyl sulfoxide Heated under reflux for 1 hour and then left to stand for 48 hours before adding 1.0 g Dry ice has been neutralized. The block copolymer was made by distilling off 200 ml of the solvent and then adding methanol failed. The infrared analysis was consistent 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 system in carbon tetrachloride. The one with this Process amounts used and the results are summarized in the following Table I:

b) Use according to the invention

A block copolymer was obtained by the process described under a) according to batches 1 to 11 made from 35 weight percent polystyrene blocks and 65 weight percent polydimethylsiloxane blocks was built up and had a molecular weight of 142,000.

Then a 20 weight percent solution of a commercially available polystyrene in toluene prepared and this solution with the amounts of the block copolymer indicated in Table II offset. The solutions were poured underneath on a mercury surface in a crystallizing dish Formation of a film of 0.0127 mm.

Before removing the film from the mercury surface, the toluene was allowed to evaporate for 48 hours ditched. Then the

40

45 films 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 tensile strength at break and elongation at break were determined. The tensile strength and the elongation at break were determined with a tension of 0.0254 cm / min at room temperature

The toughness of the blends is reported in Table II as the "Toughness Index," which is a numerical value that corresponds to the relative toughness of the material. The calculation is based on the following equation:

Toughness index = (tension at the yield point
+ Tensile at break) · (elongation in%): 2.

Further details on the toughness index can be found in the book "Testing of Polymers" by John V.

Schmitz, Interscience Publishers, New York. 1965, vol. 1, can be found.

In those cases that show no yield point under tension or elongation, the yield point and breaking point are the same.
55

Example 2

Films were cast according to the procedure described in Example 2 with the exception that the nacl Example 1 produced polystyrene - polydimethylsiloxane - block copolymer one molecular weight of 142,000 and of 40.8 weight percent polystyrene blocks and 59.2 weight percent poly dimethylsiloxane blocks end-blocked with dimethylvinylsiloxy groups was built up. In Ta belle III is the improved toughness of polystyrene by adding small amounts of the polystyrene-poly dimethylsiloxane block copolymer shown

Λ * V't / '.

13th

B e i s ρ i el 3

The following mixtures, which are compiled in Table IV, were used to produce films according to that in the example 2, these had a higher toughness index than films made from deft corresponding homopolymers !! alone.

Table I.

approach Styrene Styrene, dissolved jn mole total quantity [(ClIi) ₂ SiO] ₃ , ml cyclohexane
f * / Ali i% * ^ * ^^ Ί ml tetra ' No. in g ml of cyclohexane n-Bulyllilliium [(CH ₃ J ₂ SiO] ₃ solved in
ml of cyclohexane [(CHj) ₂ SiO] ₃ -
solution, 1st train. liydrofuran 1 140 466 0.0280 60 159 50 120 2 140 466 0.0070 60 159 60 120 3 104 400 0.0054 166.6 400 50 150 4th 90 288 0.0030 67 192 55 120 5 90 288 0.0030 67 192 40 120 6th 90 288 0.0030 67 192 55 120 7th 80 275 0.0026 120 350 100 120 8th 80 275 0.0026 120 350 100 120 9 20th 95 0.00064 30th 95 50 60 10 80 400 ») 0.0010 168 672 *) 100 20 *) 11th 140 400 0.00133 60 200 40 10 12th 69.4 350 0.0064 50 75 10 2 ****) 13th 70 350 0.0014 130 950 100 120 14th 50 200 *) 0.0015 127 804 *) 50 25 **) 15th 60 300 ·) 0.0014 130 656 *) 100 25 **)

(Continuation)

approach

Yield of Mixed polymer in%

96.0 84.0 84.0 78.0 80.0 94.0 91.0 91.0 8Z8 80.0 84.0

81.0 90.0 82.0

Arguably Molecular weight (counts) of the block nnschpolymensat ** ·)

7060 30 600 48 800 47 600 41.400 65 400 80000 80000 72 600 170000 129 000

44 200 140 227 169 300

independent groups Weight percent
the Sewn on ι value of Siloxane blocks X V -Si (CH ₃ J ₂ CH = CH ₂ 28.4 25th 47 -Si (CHj) ₂ CH = CH ₂ 29.1 118 207 -Si (CHj) ₂ OH 61.6 404 179 -Si (CHj) ₂ CH = CH ₂ 32.0 204 310 -Si (CHj) ₂ CH = CH ₂ 33.0 182 265 St (CHj) ₂ OH 36.9 324 WS -Si (CHj) ₂ OH 58.7 632 -Si (CHj) ₂ CH = CH ₂ 58.7 632 316 -Si (CHj) ₂ OH -Si (CHj) ₂ CH = CH ₂ 53.6 1229 • ^ 7 -Si (CHj) ₂ CH = CH ₂ 27.4 475 899 -Si (CH ₃ J ₂ OH -Si (CHj) ₂ CH = CH ₂ 26.8 310 158 -Si (CHj) ₂ CH = CH ₂ 58.2 562 1101 -Si (CHj) ₂ CH = CH ₂ *****) 60 651 1370

*) Benzene was used instead of cyclohexane.

* ·} Instead of tetrahydrofuran, bis (2-methoxyethyi) ether was used. ***) Determined by membrane osmometry.

*** ♦) Instead of tetrahydrofuran, dimethyl sulfoxide was used. · * ♦ · ♦) After 85% [(CHj) ₂ SiO] _{3 had been} consumed, 5 g

CH = CH ₂ (CH ₃ SiO) ₃

admitted.

SS ^ 9

Table II

aiock copolymer
in % To, .- at the stretch
limit ir. kg / cnr Elongation at the
Yield strength in% Train at break
in kg / cnj ² Elongation at break Toughness index 0.0 183 to 257.4 2.2 to 2.1 2860 to 3857 0.13 - 245.2 2.7 4709 0.38 - 238.6 2.6 4415 0.58 232.5 2.0 231.3 9.3 30 671 1.10 212.2 2.0 225.5 13.0 40456 2.20 236 2.0 239 4.0 13 500 10.10 183 2.0 246 6.0 15 300

Table HI

Block copolymer
in % Train at the track
limit in kg / cm ² Elongation at the
Yield strength in% Train at break
in kg cm * Elongation at break
in % Toughness index 0.1 292.9 2.2 4,587 0.3 289.7 2.0 284.5 3.9 15 937 0.5 283.8 2.0 281 4.0 16080 1.0 257.6 2.0 255.4 6.4 23 357 2.0 198.8 2.5 202.9 7.0 19 985 0.3 *) - - 176 1.6 2000 0.3 **) - - 246 1.9 3,325

*) A polydimethylsiloxane homopolymer was mixed with the polystyrene on the stem of the block copolymer. · *) Instead of the block copolymer, a styrene-butadiene elastomer was mixed with the polystyrene.

Table IV

Block copolymer x = 100, Ji = 200 Weight
percent
Block mix
polymer Formula unit des
Homopolymer CH ₃ CH ₃ CH ₃ 9 ^H3 CH ₃ CM ₃ CH ₂ CH ₃ CH ₃ - (CH ₂ -CHb-CH ₂ -CH SiO - (SiO) ₇ - SiC ₆ H ₅ / "V- (CH ₂ -CH) T CH ₂ -CH SiO - (SiO) ₅ - Si-CH ₂ CH = CH ₂ \ 0.15 - (CH ₂ -CH) - J \ - _CH J \ _ _CH CH ₃ CH ₃ CH ₃ CH ₃ rY \ rY \ ^{CHa CH3 CHjCH3} / V-CH ₃ χ = ■ 1000, y = 1000 χ - 250, y = 1220 CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ -iCH ₂ ) ₇ (CH ₂ -C) r CH ₂ -C SiO - (SiO) J-SiOH 0.5 - (CH ₂ -C) - A J \ CH ₃ CH ₃ CH ₃ 0 1.0 - (CHi-CH) - v0

continuation

18th

Block copolymer

CH ₃ CH ₃ CH ₃ CH ₃ (CH ₂ te-f CH ₂ -CHfe- CH ₂ - CH - SiO - (SiO) ₇ - Si (C ₆ H ₅ ) ₂

CH ₃ CH ₃

(CH ₂ J ₂ CH ₃ (CH ₂ J ₂ CH ₃

χ = 300, y = 146

CH ₃ CH ₃ CH ₃

I I I

CH ₃ (CH ₂ ) J ₅ - (CH ₂ - CH ^ - CH ₂ CH - SiO - (SiOJj-SiCH = CH ₂

CH ₃ CH ₃ C ₆ H ₅

'L-CCH ₃ LJ) -OCH ₃

χ = 4000, y = 2132

Weight percent block copolymer isal

CH ₃ CH ₃ CH ₃

^ CH ₂ -CHfe- CH ₂ -CH - SiO -fSiOJjr SiQ ₈ H ₃₇ "CH ₃ CH ₃ CH ₃

JC = 365, y = 2000

CH ₃ CH ₃ CH ₃ <\ ~ \ - CH ₂ - (CH ₂ -CHb CH ₂ CH - SiO - \ SiOJj-Si ~ ^ ~~ ^

CH ₃ CH ₃ CH ₃

CH ₃ (CH ₂ J ₅ CH ₃ CH ₃ (CH ₂ J ₅ CH ₃ χ = 2500, y = 1500

CH ₂ -CH ₂ CH ₃ CH ₃ CH ₃ CH ₂ CH - (CH ₂ - CHJr — CH ₂ —CH —SiO- (SiOJjT Si-

CH ₂ -CH ₂ CH ₃ VS CH ₃ -A CH ₃ CH ₃ CH ₃

χ = 20, y = 53

-CH ₃

CH ₃ CH ₃ CH ₃ CH ₃

CH ₃ CH ₃ CH ₃

CH ₂ -CHJ ₇ - CH ₂ —CH SiO - (SiOJ ₅ T Si-CH ₂ CH ₂ -

CH ₃ CH ₃ CH ₃

χ = 25, y = 20

CH ₃ CH ₃ CH ₃ CH ₃ (CH ₂ J ₃ (CH ₂ -CHJj CH ₂ CH -SiO- (SiO ^ SiCH = CH ₂

IL

I I 'I

CH ₃ CH ₃ CH ₃

CH ₃ ^ (CH ₂ J ₅ CH ₃ CH ₃ ^ (CH ₂ J ₅ CH ₃ x = 4000, y = 3130

1.5

1.9

2.0

1.7

0.7

1.2

1.1

Foimekinheil of the homopolymer

- (CH ₂ -CHJ-

(CH ₂ J ₂ CH ₃

- (CH ₂ -CHJ-

-OH,

- (CH ₂ -CHJ-

- (CH ₂ - CHJ-

CH ₃ (CH ₂ J ₅ CH ₃

- (CH ₂ -CHJ-

CH ₃ CH ₃

- (CH ₂ -CHJ-

- (CH ₂ -CHJ-

CH ₃ C j (CH ₂ J ₅ CH ₃

19th

Continued 20

Block copolymer

Weight percent Block copolymers

Formula unit of the homopolymer

CH ₃ CH ₃ CH _{3 2} - CH - SiO - (SiO) J - SiC ₆ H ₁₃ CH ₃ CH ₃ CH ₃

CH ₂ -CH ₂ CH ₃ CH ₃ CH ₃ CH ₂ CH - (CH ₂ J ₄ (CH ₂ -CHb-CH ₂ CH-SiO - (SiO ^ SiOH

CH ₂ -CH ₂ / \ / \ CH ₃ CH ₃ CH ₃

-CH ₂

CH ₂

-CH ₂

CH ₂

CH ₂ -CH ₂ CH ₂ -CH ₂

x = 430, y = 1000

CH ₃ CH ₃ CH ₃

I I i

CH ₃ (CH ₂ J ₃ - (CHiCHfe- CH ₂ CH-SiO - (SiO ^ SiCH = CH ₂

CH ₃ CH ₃ CH ₃

χ = 5000, Ji = SOOO

1.5

0.9

1.0

- (CH ₂ -CH) -

- (CH ₂ -CH * -

CH ₂

/ CH ₂ -CH ₂

- (CH ₂ -CHI-

L Il

Claims (1)

Patent claims: 1. Mixtures based on vinyl aromatic polymers for the production of shaped bodies and coatings characterized by that they are based on (A) 100 parts by weight of a vinyl aromatic polymer repeating units of the general formula -CH ₂ -CR'-