DK160151B - COPOLYMER WITH LINEAR CHAIN AND LINEAR POLYMER SIDE CHAIN APPLICABLE FOR MAKE MOVIES AND PROCEDURES FOR PRODUCING THEM - Google Patents

Description

The present invention relates to a copolymer with a linear main chain and linear polymeric side chains. Furthermore, the invention relates to a process for preparing such a polymer. The copolymer according to the invention is characterized by the method of claim 1.

Most polymers, both natural and synthetic, are not compatible. This became increasingly evident as more and more polymerisates with particularly good properties and special applications became available, and as efforts were made to combine these polymerisates in pairs to combine the various good properties for each. polymerized in a product. In most cases, the efforts were unsuccessful as the mixtures obtained were unstable and in many cases had completely lost the good properties of both polymerisates. Thus, polyethylene is not compatible with polyisobutylene and a mixture of these substances exhibits poorer physical properties than the homopolymers. These errors were first attributed to unsuitable mixing methods, until it was finally determined that the poor results are a consequence of incompatibility, whereby the polarity appears to play a role, ie. two polar polymers can be more compatible with each other than a polar and a non-polar polymer. In addition, both polymers for their composition or structure must exhibit some similarity to be compatible. Furthermore, a particular polymer pair can only be compatible with each other within certain ranges of relative proportions.

30

Despite these facts, there is still a great interest in combining the beneficial properties of combined polymerisates in one product. For this purpose, e.g. block or graft copolymers to chemically join two different polymeric segments

2 DK 160151B

each other, thus eliciting a "forced conciliation."

However, these possibilities are limited, and in the case of block copolymers, e.g. only use such monomers that can be polymerized anionically, which excludes a large number of potential polymeric segments. In the case of known graft copolymers, there is a considerable amount of homopolymers that originate either from the original homopolymer main chain or from the grafted monomer. To the extent that such homopolymer polymers are present, they not only act as a diluent but significantly impair the desired properties to be incorporated into the graft copolymer.

This disadvantage is largely related to the method of preparation of these grafted copolymers, whereby e.g. by a process described in "Die Macromolecular Chemie", 59, 1963, pages 174-183 first prepares a polymeric main chain, introduces reactive sites therein by reaction with sodium metal and finally provides side chains by an anionically grafted poly-20 polymerisation.

In contrast, according to the invention, opener polymers having graft copolymerized structure containing side chains and a main chain segment with specific molecular weights are obtained which are relatively free of homopolymerizates and exhibit a novel combination of physical properties.

Copolymers of the present invention exhibit a linear copolymerization chain obtained and at least a side chain formed by polymerization, in the presence of multiple side chains, these have substantially the same molecular weight and the bonding points of adjacent side chains at the main chain are at least separated by segments. comprising approx. 20 repeating monomer-35 units.

DK 160151B

3

The process of the present invention is characterized by the method of claim 2 and differs from known processes for producing graft copolymers in that the polymeric side chains are first obtained by anionic polymerization to form a living polymer. which is interrupted by reaction with a halogen-containing compound with polymerizable end groups. By free radical, ionic or condensation copolymerization of the obtained high molecular weight polymer having polymerizable end groups with a comonomer of usually relatively low molecular weight, the copolymer of the invention is obtained. As comonomers, it can be the same monomer used to make the side chains or a different monomer therefrom.

Particularly useful copolymers of the invention are those in which the main chain polymers and the side chain polymers are thermodynamically incompatible. Such copolymers are obtained when the neighboring side chain bonding segments of the copolymer head cushion and the polymeric side chains are sufficiently large to impart to the copolymer the physical properties characteristic of the particular polymerate. For this purpose, these segments in the main chain or side chains, respectively, consist of at least 20 repeating monomeric units, preferably at least 30 repeating monomeric units.

The copolymers in question can be assumed to have a T-structure when only a single side chain is copolymerized in the copolymer main chain. When more than one side chain is copolymerized in the polymeric main chain, the graft copolymer will have a structure as a comb as set forth below:

DK 160151 B

4 c-c-c-b-c-c-c-b-c-c-c-b-c-c-c

III

a a a

III

"A a a

5 I I 'I

aaa where a represents a substantially linear side chain polymer or copolymer of uniform molecular weight such that the physical properties of at least one of the linear polymers are dominant, b represents one with the live polymer reacted and copolymerized end group which is chemically bonded to the side chain, a which is polymerized together with the monomer units of the main chain polymer, and c is the main chain polymer of continuous segments 15 having such molecular weight that the physical properties of the polymer are dominant.

Monomers which can be subjected to anionic polymerization, 2Q are well known, and any of such anionically polymerizable monomers can be used in the invention. Examples of such compounds are styrene, α-methylstyrene, acrylamide, N, N-di-lower alkyl acrylic amides, acenaphthalene, 9-acrylic carbazole, acrylonitrile and methacrylonitrile, organic isocyanates such as lower alkyl, phenyl, lower alkylphenyl - and halogenophenyl isocyanates, organic diisocyanates such as lower alkylene, phenylene and tolylene diisocyanates, lower alkyl and allyl acrylates and methacrylates, lower olefins, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl propionate, vinyloctate, vinyl , vinyl benzoate, vinyl lower alkyl ethers, vinyl pyridine, isoprene, butadiene and lower alkylene oxide. The term "lower" is used to refer to organic groups of up to 8 carbon atoms.

35

DK 160151B

5

A catalyst for these anionic polymerizations may be used an alkali metal alkyl, wherein the alkyl group is eight or less carbon atoms. Preferably, butyl lithium is used especially secondary butyl lithium. Lower alkyl lithium compounds and lower alkyl sodium compounds are particularly useful. Suitable catalysts are e.g. isopropyl lithium, ethyl sodium, n-propyl sodium, n-butyl potassium, n-octyl potassium, n-butyllithium, ethyl lithium, t-butyllithium and 2-ethylhexyllithium. These alkali metal alkyls are either freely available or can be prepared by known methods. Phenyllithium and phenyl sodium are also useful as catalysts and can e.g. is obtained by reaction of bromobenzene with the alkali metal concerned.

Catalyst amounts are an important factor in the anionic polymerization as it determines the molecular weight of the living polymer. When a small amount of catalysts is used in relation to the amount of monomer, the molecular weight of the living polymer becomes higher than if a larger quantity of catalyst is used. In general, it is preferable to drop catalysts to the monomer (if this is the order of choice for the addition) until the characteristic color of the organic anion remains constant, after which the calculated amount of catalyst is added. The foregoing theorem droplets serve to neutralize impurities, thereby enabling better control or control of the polymerization.

The anionic polymerization must be carried out under carefully controlled conditions to exclude moisture and other impurities. The monomer and catalyst must be freshly cleaned, and apparatus for conducting the polymerization must also be carefully cleaned, which is done in a manner known per se. The alkali metal catalyst can be added to the monomer or the monomer can be added to the catalyst. Generally

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6, a solvent is used to facilitate the heat transfer and a suitable mixture of the catalyst and the monomer. The solvent must be inert, and hydrocarbons and ether such as benzene, toluene, dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, dimethyl ether, tetrahydrofurene, n-hexane, cyclohexane and n-heptane are preferred. The polymerization temperature depends on the monomer. Polymerization of styrene generally occurs at a temperature slightly above room temperature 10 and polymerization of α-methylstyrene is preferably carried out at -80 ° C. The temperature of the anionic polymerization is not a critical feature of the invention.

The product obtained is a so-called "living polymer", ie.

It is capable of reacting at one end further to polymerization. The anionic polymerization can be illustrated by the following equation when styrene is polymerized by secondary butyl lithium: 20 sec-BuLi + n CH 2 = CH> sec-Bu-PCH 2 CH 2 - CH 2 CH Li ό 6L6 25

Upon addition of styrene to the aforementioned live polymer, polymerization continues and the chain grows until no more monomer styrene is left. Alternatively, adding a second one from the first different anionic polymerizable monomer, e.g. butadiene, the aforementioned live polymer will initiate polymerization of the butadiene and the resulting live polymer consists of a polystyrene segment and a polybutadiene segment. Normally, the living polymer is terminated by reaction with a halogen-containing compound, which can be illustrated by the use of methyl iodide as the disruptive agent.

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7 means with reference to the following equation:

5 sec-Bu-pCflhCH-j-CH2CH Li + CHjJ -► sec-Bu CH2CH CHjCHCHj + LiJ

16L 6 16L, 6 10 Such terminated polymers are not the subject of the present invention.

The living polymers recovered in the manner described have practically the same molecular weight, viz. the molecular weight distribution is rather narrow. This practically constant molecular weight for the side chains is an important feature of the present invention, which can be traced back to the living polymer produced in the first step of the process of the invention and exhibits an average molecular weight of between 5000 and 50000.

According to the invention, the living polymer is reacted with a halogen-containing compound which exhibits either a polymerizable olefinic group or an epoxy or thioepoxy group. Suitable halogen-containing compounds are e.g. vinyl haloalkyl ether having 6 or fewer carbon atoms in the alkyl group, vinyl ester of haloalkanecarboxylic acid with 6 or fewer carbon atoms in the alkanecarboxylic acid, allyl halide, epihalogen hydrine, acrylyl halide, methylacrylyl halide, halo maleic anhydride, halo halide anhydride, halo halide The halogen may be chlorine, fluorine, bromine or iodine, but chlorine is preferred.

The reaction of the living polymer with one of the aforementioned compounds is induced by adding the halogen-containing compound to the solution of the living polymer at the temperature at which the living polymer

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is prepared. The reaction occurs immediately and the yield corresponds to the theoretically possible. A small molar excess of the halogen-containing compound relative to the amount of catalyst is used, although the reaction is based on 5 1 moles of each component. The following equation typically illustrates such reactions: 10 Γ R1! R1 in 1

Live polymer: R-ch2-c— ¢ (¾— (U + Li®

I I

r + i · - 1 R J «R2 + halogen-containing compound, -, (a) X-R3-O-C = CH2

.... R4 O

3 II

(b) X - R3 - C - O - C = CH2 R4 (c) X - R3 - C = CH2 in *

ISLAND

Cd) X-R3-C-CH2 14 R4

ISLAND

II

(e) X-CC = CH2

(0 X -C-CO 30

ISLAND

R4-C-CO

(g) X - C - COOR 4

II

R4-C-COOR4 (h) X-SiRRC = CH2 i.

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9 R1 Ψ (a) R - - CH2 - C - CH2 - C - R3 - OC = CH2 R2 .. R2 R4

R1] R1 O

! I II

(b) R CH2 - C CH2 - C - R3 - C - OC = CH2 R2. R 2 R 4 R 1 R1

I I

(c) R CH2-C- -GH2-C-R3-C = CH2

I I I

r2J "r2 r4 [R'l Ψ o 1 1, / \" 1) R - CH2 - C - CH2 - c - R5 - C-CH1

I I I

I I I

R2 J2 R2 R4

R'l R1 O

I I II

(E) R CH2 - C CH2 - C - C - C = CH2 I I!

I I I

r2J „r2 r4 Rl R1 i i

(f) R - CH2 - C - CH2 - C - C - CO

I I \ I, I \

R2 R2 R2 O

/

R4-C-CO

R'1 R1

I I

(g) R - CH2 - C - CH2 - C - C - COOR4

I I II

30 [. R2Jn R2 R4-C-COOR4 R'l R 'I i (h) R CH2-C' CH2-C-SiRRC = CH2 l2 i2!

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In the above equations, the groups R, R, R, R and 4 R represent hydrogen or lower alkyl, lower alkylene or aryl groups. Preferably, R will be lower alkyl such as 1,2 sec-butyl, R may be hydrogen or methyl, R is 3

Phenyl, R is hydrogen or lower alkyl groups, and R

are either hydrogen or lower alkyl groups. n is a positive integer and X is halogen.

In some cases, because of the nature of the living polymer and the monomer from which it is recovered, and because of the nature of the halogen-containing compound used, the living polymer is first reacted with a reaction component such as a lower alkylene oxide with 8 or fewer carbon atoms or diphenylethylene.

This reaction referred to herein as "masking reaction" yields a product which, while still a living polymer, is less accessible for reaction with functional groups or active hydrogen atoms in the halogen-containing compound. Thus, for example, 20 is introduced. with the halogen-containing compound acrylyl chloride a carbonyl group in the polymer thus reacted, and this carbonyl group may constitute a center of the undesired attack of another living polymer. The use of acrylyl chloride as a halogenated compound is strongly favored if the living polymer is first masked and then reacted thereby to form a practically pure vinyl ester. Without this prior masking, the resulting polymer can either exhibit twice the expected molecular weight or contain some chlorine, ie. that a reaction may occur with another live poplomer or with one of the active hydrogen atoms in the acrylyl chloride.

A preferred masking agent is ethylene oxide which, during opening of the oxirane structure, reacts with the living polymer according to the following reaction equation:

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11 sec-Bu - [- CH2CH -] - CH2CH Li 5. 6L 6 + CH2-CH2 -► sec-Bu-pCH2CH v 16t ό In the above equation, the starting material is a living polymer which was prepared by polymerization of the secondary butyl lithium catalyst catalyst. The masking reaction, like the reaction with the halogen-containing compound, is carried out by adding the masking agent to the living polymer at the polymerization temperature. The reaction occurs immediately and, as with the reaction with the halogen-containing compound, a slight molar excess of the masking agent is used relative to the amount of catalyst. The reaction proceeds on a mole: mole basis.

If an epihalohydrin is used as a halogen-containing compound, the resulting polymer will contain a terminal epoxy group. Such a terminal epoxy group can be converted into the corresponding glycol by heating with aqueous sodium hydroxide. Such a glycol can be converted to a copolymer by reaction with a high molecular weight compound, e.g. is prepared by polymerization of a glycol or diamine with a molar excess of a dicarboxylic acid, e.g. in the form of phthalic anhydride, maleic anhydride or succinic anhydride. Furthermore, it can be reacted with a diisocyanate to produce a polyurethane. The diisocyanate may e.g. be the reaction product of a polyethylene glycol having an average molecular weight of 400,

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with a molar excess of the phenylene diisocyanate used.

According to another embodiment of the invention, an organic epoxide is copolymerized with the polymerizable polymer containing an epoxy or thioepoxy group to form a copolymer with a main chain containing at least 20, preferably at least 30, repeating monomer units of the organic epoxide. Preferred organic epoxides are ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, cyclohexene epoxide and styrene oxide, i.e. compounds with a maximum of 8 carbon atoms. When a haloalkylmaleic acid anhydride or haloalkylmalea ester is used as the terminating agent, the resulting terminal groups can be converted by hydrolysis to carboxyl groups. The dicarboxyl polymer formed can be copolymerized with glycols or diamines to form polyesters and polyamides having a graft copolymer structure.

Thus, the reaction of the living polymer with the halogen-containing compound yields products which are further polymerized without being a living polymer, whereby the additional polymerization occurs either over the resulting double bonds or the epoxy group or glycol group 25 from the halogen-containing compound to form the copolymer. according to the invention, the structure of which is in some respects comparable to the structure of known graft copolymers, which are admittedly made in a completely different way. Their structure is widely different in that the known graft copolymers are prepared by synthesizing a linear main chain and subsequently grafting growing polymeric side chains onto this main chain, whereas the copolymer of the invention is prepared by first synthesizing the polymeric side chains of living polymers, after which these polymer chains are polymerized at the terminal polymerizable groups in a main chain.

These side chains are in this way built into the main chain

DK 160151B

13 over the terminal groups formed by reaction with the halogenated compounds. The difference also consists in the fact that the polymeric side chains of the copolymer according to the invention have a relatively similar minimum length and because its main chain has polymeric segments of a certain minimal length.

These characteristic features significantly contribute to the advantageous properties of the copolymer of the invention. These unique properties and the combination of properties are made possible by the method of the invention, thereby forcing a compatibility of otherwise non-compatible polymeric segments. Thus, e.g. combine the advantageous properties of polystyrene with the advantageous properties of a polymethyl ethyl acrylate, although these two polymerisates are usually mutually incompatible and simple physical mixtures thereof exhibit very little strength and are useless. In order to combine these advantageous properties into one product, it is necessary that the various polymeric segments be relatively large. The typical properties of polystyrene do not emerge until the polymeric material consists essentially of at least approx. 20 repeating monomer units. The same is true for the copolymeric polymer segments present, i.e. if a copolymer containing segments of polystyrene is to exhibit the advantageous properties of polystyrene, these polystyrene segments must in practice consist of at least approx. 20 repeating monomeric units. This relationship between the physical properties of a polymeric segment and its minimum size applies to the polymeric segments of all the copolymers in question. Preferably, the polymeric segments in the main chain as well as in the side chains consist in practice of more than 30 repeating monomeric units. The copolymer segments may themselves be homopolymers or copolymers. Thus, a copolymer of the invention can be prepared by copolymerizing methyl methacrylate and lauryl methacrylate with a

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14 polystyrene which exhibits a polymerizable olefinic terminal group such that the polymeric segments in the main chain are copolymers of methyl methacrylate and lauryl methacrylate.

Copolymers containing polymeric segments having less than 20 repeating monomeric units are useful for many applications, but are not preferred. The copolymers of the invention, because of their particular physical properties, which depend on the monomers used for the preparation 10 and, moreover, on the molecular weight of the various polymeric segments within a particular copolymer, are versatile and all these copolymers are suitable for the production of tough , flexible, self-supporting foils. These films can be used for the packaging of 15 foodstuffs, cover materials for painters, for protective wrapping for merchandise and the like.

The invention will be further illustrated in the following by some exemplary embodiments. In all cases, the 20 materials used must be clean and the mixture of reaction components must be dry and free of impurities. Unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE 1 a) For the preparation of polystyrene, terminated with vinyl 2-chloroethyl ether, a solution of a drop of diphenylethylene at 40 ° C is treated portionwise with a 12% solution of t-butyllithium in pentane until a pink is maintained. color, after which an additional 30 ml (0.04 mol) of the t-butyllithium solution is added, followed by 312 g (3.0 mol) of styrene. The temperature of the polymerization mixture is maintained at 40 ° C for 30 minutes, after which the live polystyrene is terminated by treatment with 8 ml (0.08 mol) of vinyl-2-chloroethyl ether. The polymer formed is precipitated by the addition of benzene.

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The solution is dissolved in methanol and the polymer is filtered off. The average molecular weight by number, determined by vapor phase osmometry, is 7200 (theoretical 7870) and the molecular weight distribution is very narrow until Mw / Mn is less than 1.06.

B) To prepare a copolymer with ethyl acrylate as a comonomer, a solution of 18 g of octylphenoxypolyethoxyethanol as emulsifier in 300 g of deionized water is added under vigorous stirring in a Waring 10 stirrer, a solution of 30 g of the above polystyrene product and 70 g of ethyl acrylate. The resulting dispersion is vented with nitrogen, then heated with stirring to 65 ° C, then 0.1 g of ammonium persulfate is added to initiate the polymerization. Then 200 g of ethyl acrylate and 0.5 g of the above 2% aqueous ammonium per sulfate solution are added portionwise over a period of 3 hours during which the temperature is maintained at 65 ° C. The resulting copolymer emulsion is cast on a glass plate and dried in open air at room temperature to a flexible, self-supporting foil. By extraction with cyclohexane dissolving the polystyrene, it can be shown that the film exhibits polystyrene segments, the cyclohexane extract leaving no residue on evaporation.

EXAMPLE 2 a) To prepare polystyrene terminated with epichlorohydrin, a benzene solution of live polystyrene is prepared as set forth in Example 1 and terminated by treatment with 10 g (0.10 mol) of epichlorohydrin.

The polymerizable polystyrene formed is precipitated with methanol and separated by filtration. The average molecular weight by number is, as evidenced by vapor phase osmometry, 8660 (theoretical 7757), and the molecular weight distribution is very narrow.

B) To prepare a copolymer with isobutylene as a comonomer, a solution of 20 g of it is added.

DK 160151 B

16 section 1) recovered polystyrene product with an average molecular weight of 10000 in 1000 ml of toluene at -70 ° C 80 g of isobutylene. 45 ml of boron trichloride-ethyl ether complex are slowly added, keeping the temperature at -70 ° C.

The polymerization starts upon addition of the catalyst and is practically completed immediately after the addition of the catalyst is completed. The resulting copolymer is recovered by evaporation of the toluene and washing of the solid residue with methanol.

C) To 1000 ml of methylene chloride is added at -70 ° C 10 g of the polystyrene product recovered according to section a) with an average molecular weight of 10000. To the resulting solution kept at -70 ° C is added simultaneously and dropwise. show a solution of 2 g of aluminum chloride in 400 ml of methylene chloride and 90 g of isobutylene. The time required for this addition is 1 hour, and then the polymerization is practically complete. The resulting insoluble copolymer is isolated by evaporation of methylene chloride.

D) To prepare a copolymer using polytetramethylene ether diisocyanate, first polytetramethylene ether dissocynate is obtained by dissolving 290 g of polytetramethylene ether glycol with an average molecular weight of 25 2900 in 600 ml tetrahydrofuran, rinsing this solution with nitrogen and adding 14.4 g (0.05 mol) of a liquid diisocyanate similar in structure to diphenylmethane diisocyanate and sold under the trade name "Isocyanate 143L" (Upjohn Company). The flask containing contents 30 is closed, introduced into a water bath at 50 ° C and rotated therein at 30 rpm. minute. After 8 hours, an additional 7.2 g (0.025 mol) of the above-mentioned liquid diisocyanate is added and the reaction is continued for an additional 8 hours. After this time, 4.35 g (0.05 mol) of 2,4-tolulene diisocyanate is added and the polymerization is continued under the same conditions for an additional 8 hours.

17 DK 160151 B

To a solution of 200 g of the polystyrene recovered according to section a) with an average molecular weight of 12000 in 100 ml of water is added dropwise dilute sulfuric acid to adjust the pH to 2.0. The resulting solution 5 is stirred for 8 hours at 65 ° C, giving complete hydrolysis of the epoxide groups to glycol groups.

A mixture of a solution of 60 g of the above-described polytetramethylene ether diisocyanates in 60 ml of tetrahydrofuran, 60 g of the above polystyrene glycols and 100 ml of tetrahydrofuran is introduced into a polymerization vessel together with 0.6 g of tin (II) octoate. The flask is closed, rinsed with nitrogen and placed in a 65 ° C water bath to form the copolymer. Part of this is cast on a glass plate and allowed to dry in open air to a flexible elastic film. This is cut into small pieces and molded at 150 ° C and 2.4-3.1 bar into a foil having a tensile strength of 106 bar.

E) A reaction flask containing a mixture of 87 g of polytetramethylene ether glycol having an average molecular weight of 2900 and 4.3 g (0.015 mole) of the liquid diisocyanates described in section d) is sealed, rinsed with nitrogen and placed in a water bath at 65 ° C for 8 hours. The high molecular weight polyurethane glycol formed is cooled to room temperature, and 43 g of section d) of recovered polystyrene glycol having an average molecular weight of 8600 and 350 ml of tetrahydrofuran are added. After rinsing with 30 nitrogen, 5.8 is added. g (0.023 mol) of the above-described liquid diisocyanates and the flask is rotated for 8 hours at 65 ° C. The copolymer formed is isolated by plating on a glass plate and drying in air in the form of a flexible elastic film. The tensile strength is 70.3 bar.

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EXAMPLE 3 a) To prepare poly (α-methylstyrene), terminated with vinyl chloroacetate, a solution of 357 g of 5 (3.0 mol) of α-methylstyrene in 2500 ml of tetrahydrofuran is treated by dropwise addition of a 12% solution of t-butyllithium in pentane until a pink color is maintained. Then, an additional 15 ml (0.03 mole) of t-butyllithium solution is added, precipitating a clear red color. The temperature of the mixture is lowered to -80 ° C and after 30 minutes at this temperature 5.6 ml of diphenylethylene are added. The resulting mixture is poured into 5.0 ml (0.04 mol) of vinyl chloroacetate and the thus terminated poly (α-methylstyrene) is precipitated with methanol and filtered off.

The average molecular weight by number as determined by vapor phase osmometry is 14280 (theoretical 12065) and the molecular weight distribution is very narrow.

b) To prepare a copolymer with butyl acrylate as 20 comonomers, a solution of 50 g of the poly (α-methylstyrene) recovered according to section a) having an average molecular weight of 12600 and 450 g of butyl acrylate in 1000 g of toluene is rinsed with nitrogen at 70 ° C and then treated with 1 g of azobisisobutyritrile. The temperature is maintained for 25 hours at 70 ° C to form a solution of the copolymer cast as a film on a glass plate. The dried film is slightly sticky and can be shown to contain polystyrene segments by extraction with cyclohexane and evaporation of the cyclohexane extract.

EXAMPLE 4 a) To prepare poly (α-methylstyrene) terminated with allyl chloride, a solution of 472 g (4.0 35 moles) of α-methylstyrene in 2500 ml of tetrahydrofuran is treated by dropwise addition of a 12% solution of n butyl lithium in hexane until a pink color is maintained.

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An additional 30 ml (0.0383 mol) of this n-butyllithium solution is added to give a clear red color. The temperature of the mixture is then lowered to -80 ° C and after 30 minutes at this temperature 4.5 g of 5 (0.606 mol) of allyl chloride is added. The red color disappears almost immediately, indicating termination of the living polymer. The colorless solution formed is poured into methanol to precipitate the "olefin-terminated poly (α-methylstyrene) which, by vapor phase osmometry, is found to have an average molecular weight by number of 11000 (theoretical 12300).

b) To prepare a copolymer with ethylene as a comonomer, a solution of 20 g of the poly (a-methystyrene) recovered according to section 15 is treated with an average molecular weight of 27000 in 100 ml cyclohexane with 5.5 ml 0.645 M diethyl aluminum chloride in hexane and 2 ml of vanadium oxychloride, after which ethylene is introduced under a pressure of 2.11 bar. The system is maintained for 1 hour at 30 ° C with movement, whereby the copolymer is precipitated by the solution. It is expanded by filtration and pressed into a thin, transparent film which is tough and flexible.

EXAMPLE 5 a) To prepare polystyrene terminated with methacrylyl chloride, a solution of 0.2 ml of diphenylethylene in 2500 ml of benzene is added dropwise to a 12% solution of n-butyllithium in hexane until a light reddish brown is maintained. color. An additional 24 ml of 0.031 mole of said n-butyllithium solution is added and then 416 g (4.0 mole) of styrene is added to give an orange color. A temperature of 40 ° is maintained under external cooling by controlling the speed at which the control grid is added. This temperature is maintained for an additional 30 minutes after all the styrene is added, after which the temperature is lowered to 290 ° C, whereupon 4.4 g (0.1 mole) of ethylene is added.

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20 oxide is added, which makes the solution colorless. The polystyrene obtained is reacted with 10 ml (0.1 mole) of methacrylyl chloride. The polymer formed has an average molecular weight by number, determined by vapor phase osmometry, of 10000.

If acrylic chloride is used instead of methacrylyl chloride in the above procedure, acrylic acid ester end groups are obtained on the polystyrene chain.

B) To prepare a copolymer with ethyl acrylate as a comonomer, a mixture of 21 g of the polystyrene reacted with methacrylyl chloride having an average molecular weight of 10000, 28 g of ethyl acrylate and 0.035 of azobisisobutyronitrile at room temperature is first formed and the mixture is maintained for 18 hours under nitrogen. at 67 ° C. This copolymer formed is a tough opal-like material, which at 160 ° C can be molded into a clear tough and transparent article.

EXAMPLE 6

Preparation of a copolymer of allyl chloride terminates a poly-α (methylstyrene) and ethylene as a comonomer.

25

To prepare the copolymer, a solution of 20 g of poly (α-methylstyrene) terminated with allyl chloride having an average molecular weight of 10000 formed according to Example 4 a) is first formed in 100 ml of cyclohexane and treated with 5.5 ml of a 0.645 (9.1% solution) of diethyl aluminum choride in hexane and 2 ml of vanadium oxytrichloride. Subsequently, a pressure treatment with ethylene follows a pressure of 3.1 bar. The system is gently stirred for a period of approx. 1 hour at 30 ° C, upon which a polymeric material of the solution is precipitated. It is separated by filtration and pressed into a thin, transparent film which is tough and flexible.

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EXAMPLE 7

Preparation of a copolymer with a polyethylene main chain and polystyrene side chains.

5 a) For the production of polystyrene, terminated with allyl chloride, a stainless steel reactor 76.56 parts A.C.S. benzene (thiophene-free) produced by a molecular sieve of the type Linde and calcium hydride. The reactor is heated to 40 ° C and 0.015 parts of diphenylethylene is added to the reactor by means of a syringe. 12.1% solution of secondary butyllithium in hexane is added portionwise to the reactor until a permanent orange-yellow color is formed, after which 15.885 parts (1.67 moles) of secondary butyllithium solution followed by 22.7 parts (218 moles) of styrene are added. within 44 minutes. The reactor temperature is maintained at 36-42 ° C. The live polystyrene is terminated by adding 0.127 parts of allyl chloride to the reaction mixture. The resulting polymer is precipitated by addition of α-olefin-terminated polystyrene-benzene solution in methanol, and then the polymer is precipitated by the solution. The α-olefin-terminated polystyrene is dried in a circulating air atmosphere at 40-45 ° C and then in a fluidized layer to remove trace 25 of methanol. The methanol content after purification is 10 parts per liter. million. The molecular weight of the polymer as determined by membrane phase osmometry is 15400 (theoretical 13400), and molecular weight advantage none is very narrow, ie. Mw / Mn is less than 1.05.

B) To prepare the copolymer, 1 g of the α-olefin-terminated polystyrene described in Example 7 a) is dissolved in 1500 ml of cyclohexane and transferred to a 2 liter reactor.

This is rinsed with pre-purified nitrogen for a period of 35 30 minutes, then 22 ml of a 25% ethyl aluminium sesquichloride solution (in heptane) is added. The reaction is carried out under a pressure of 2.8 bar using 20 g

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22; ethylene introduced into the solution. Next: add 0.1 ml of vanadium trichloride, after which the ethylene pressure drops from 2.8 bar to 0.07 bar in 1 minute. The reaction is terminated in 3 minutes by the addition of 5 isopropanol. The copolymer is filtered off and suspended in cyclohexane and then in isopropanol. The yield is 18.0 of a fluffy white copolymer with a side chain content of 15.8%, as evidenced by IR examination. An extraction and analysis of the extract shows that the polymer is copolymerized with 17.0 g of the ethylene.

c) The working method described in Example 7 b) is repeated with the change that 2.0 g polystyrene is used instead of 1.0 g. The yield of copolymer is 20.5 g, whereby the content of side chains determined by IR analysis is 10%.

EXAMPLE 8 a) Preparation of graft copolymer with a polyethylene main chain and polystyrene side chains.

A 2-liter Chemco reactor is charged with 1500 ml of purified cyclohexane. 20 grams of α-olefin-terminated polystyrene made in Example 7 (a) are added and dissolved in purified cyclohexane. The reactor is then flushed with purified nitrogen for 1 hour with simultaneous slow stirring. Ethylene is introduced into the reactor at a rate of 5 liters per liter. per minute and a pressure of 0.35 bar. The contents of the reactor are heated and adjusted to a temperature of 25 ° C, after which a fast-running stirrer is started. Ethyl aluminum sesquichloride (22.8 ml, 25% in heptane) is used as a catalyst and injected into the reactor by means of a syringe, and then 0.1 ml of vanadium oxychloride is added. The polymerization begins immediately and the ethylene pressure in the reactor drops to almost zero in one minute. At this point, the ethylene feed rate is reduced to 0.5 liters per liter. minute, and

23 DK 160151 B

cooling is used to maintain a temperature of 25 ° C. After one hour, a total of 43 grams of ethylene was introduced into the reactor, which is full of a downy polymer slurry. The reactor is stopped by adding 50 ml of isopropanol to inactivate the catalyst.

The copolymer is recovered by filtration, slurried and boiled in 1.5 liters of benzene for 1 hour, then filtered again to remove all unreacted α-olefin-terminated polystyrene from the copolymer. The polymer is then slurried in 1.5 liters of isopropanol and 0.03 g of Irganox 1010 antioxidant is added, then the mixture is filtered and the filtered off is dried in a vacuum oven at 50 ° C. The yield is 49 g of a fluffy white copolymer with a content of 16% alpha-olefin-terminated polystyrene, determined by infrared analysis on a pressed film.

(b) Preparation of a copolymer with a polyethylene backbone and poly (/ 5-methylstyrene) side chains 20

The macromolecular monomer used to prepare the side chains is first solidified by repeating the procedure of Example 6 (a) with the change that instead of n-butyllithium as initiator, 14 25 ml (0.0178 mol) of secondary butyllithium ( 12% dissolved in heptane). The average molecular weight by number, as determined by gel permeation chromatography, is 26,000 (theoretical (26,500)) and the molecular weight distribution is very narrow, with Mw / Mn being less than 1.05.

30

Four liters of cyclohexane and 200 g of α-olefin-terminated poly (α-methylstyrene) macromolecular monomer produced as described above are introduced into a reactor. The mixture is heated to 70 ° C while simultaneously stirring to dissolve the macromolecular monomer.

DK 160151 B

24

The reactor is flushed with high purity nitrogen for 1 hour with stirring. Gaseous ethylene is introduced into the reactor to a pressure of 0.35 kg / cm 2 followed by 228 ml of ethyl aluminum sesquichloride (25% in heptane) and 1.0 ml of vanadium oxychloride. Stirring is increased and the polymerization begins immediately, as evidenced by the pressure in the reactor falling to near zero. The feed rate of the ethylene is set to 5 liters per liter. and the temperature of the reactor is set to 70 10 ° C. After 1 hour, the reaction is quenched by the addition of 500 ml of isopropanol to inactivate the catalyst.

The polymer is isolated by centrifugation, slurried with benzene for 1 hour and centrifuged again. The copolymer is then slurried in 5 ml of methanol and 0.3 g of antioxidant for 1 hour, centrifuged and dried in an oven at 50 ° C.

The yield is 260 g and contains 22% α-olefin-terminated poly (α-methylstyrene), as determined by infrared analysis of a pressed film.

EXAMPLE 9

Preparation of graft copolymer with an ethylene-propylene copolymer backbone and polystyrene side chains

A 2 liter reactor is charged with 1.5 liters of dry benzene and 50 g of poly (α-methylstyrene) terminated with allyl chloride (prepared according to Example 6a). The macromolecular 30 monomer is dissolved by stirring and then rinsed with nitrogen. The reactor is then charged with ethylene and propylene gas at a rate of 200 ml / minute 2 and 800 ml / minute, respectively, to build up a pressure of 0.7 kg / cm in the reactor. While maintaining a reaction temperature 35 of 25-30 ° C, 2 ml of vanadium oxychloride and 4 ml of aluminum sesquichloride solution (25% in heptane) are added to the reaction mixture by means of a syringe to

DK 160151 B

25 initiation of the polymerization. As soon as the polymerization is started, additional macromolecular monomer (335 ml of a 10% macromolecular solution) is added in solution, i.e. 70 g of the macromolecular monomer 5 is dissolved in 630 ml of dry benzene and pumped in by means of a micro-membrane pump. During the reaction, the velocity of the gas is constantly checked to ensure that the ethylene and propylene supply has the same velocity as originally. More catalyst, EtgA 2 Clg 10 (27 ml in 25% heptane) and VOClg (1.8 ml) is added by means of a syringe during the reaction as the rate of polymerization decreases, which is observed by building an internal pressure in the reactor. After 1 hour, the polymerization is stopped by the addition of 20 ml of isopropyl alcohol. The product is precipitated in methanol and 51 g of a white elastomeric polymer is obtained.

EXAMPLE 10 Preparation of graft copolymer with ethylene-propylene copolymer backbone and polystyrene side chains

A 3.8 liter reactor is charged with 3 liters of cyclohexane and 10 g of polystyrene terminated with allyl chloride (prepared according to Example 7 a). The solution is rinsed with nitrogen for 30 minutes. 20 ml of tri-n-hexyl aluminum (25% solution) are added, followed by 139.5 g of propylene to give a pressure of 1.8 bar and 20.4 g of ethylene to give a pressure of 3.4 bar. Finally, 0.2 ml of vanadium oxychloride is added and a pressure drop is observed. The polymerization is stopped after 10 minutes by adding 10 ml of isopropanol.

The terpolymer solution is slowly added with stirring 35 to a 4-liter beaker containing methanol to coagulate the polymer. The separated polymer is air dried for 18 hours. To remove traces of catalyst residue,

DK 160151B

26, the gray-colored polymer is dissolved in 500 ml of cyclohexane and introduced into a 2-liter plastic flask together with 1 liter of distilled water containing 0.1 g of sodium hydroxide and refluxed at 80 ° C for 2 hours. The contents are transferred by a 2-liter separating funnel and the lower water layer is led away. The top cyclohexane layer is slowly added to methanol with stirring to coagulate the polymer. The recovered polymer is dried in a vacuum oven. Unreacted macromolecular monomer is recovered from the dried polymer by first dissolving the cyclohexane and by dropwise addition to methyl ethyl ketone with stirring. The terpolymer which is insoluble in methyl ethyl ketone is filtered off and dried in a vacuum oven. A yield of 52 g is obtained. The terpolymer has an increased tensile strength in comparison with ethylene-propylene copolymers prepared in the same way, but without poly- (α-methylstyrene).

EXAMPLE 11 20

Preparation of a copolymer with polyisoprene main chain and polystyrene side chains 500 ml of dry cyclohexane is introduced into a reactor, followed by the addition of 100 ml (68 g) of freshly distilled isoprene together with 17 g of polystyrene terminated with allyl chloride (prepared according to Example 7 a). The reactor is closed and then 2.5 ml of tri-n-hexyl aluminum solution (25% in the hapten) and 0.16 ml of titanium tetrachloride are added by means of a syringe. The reactor is stirred at 55 ° C for 16 hours, then slowly, while stirring, the contents are poured into a 4-liter beaker containing 2 liters of a 1% solution of an antioxidant in isopropanol. A tough, elastomeric copolymer is obtained.

35

DK 160151 B

EXAMPLE 12

Preparation of Copolymer with a Polystyrene Main Chain and Polyoxyethylene Side Chains 5 a) To prepare a side chain polymer, the procedure described in Example 7 a) is repeated, using an equivalent amount of ethylene oxide instead of styrene to produce a living crystalline polyoxyethylene. Polymer. The living polymer is terminated by the addition of a molar equivalent amount of vinyl benzyl chloride.

b) To prepare the copolymer, equal parts of polyoxyethylene terminated with vinyl benzyl chloride 15 prepared according to Example 7 a) and styrene monomer are charged to a reactor containing 1000 ml of benzene. The reactor is heated to 60 ° C and a part by weight of azobisisobutyronitrile acting as a free radical polymerization catalyst is added. The polymerization is completed within 3 hours to give a graft copolymer with hydrophilic, hydrophobic properties. The graft copolymer also reduces hydrostatic charges and can be used as an alloy for polystyrene and polyoxyethylene.

EXAMPLE 13

Preparation of a Copolymer with a Polypropylene Main Chain and Cis-1,4-Polyisoprene Side Chains 30 a) To prepare the polymeric side chain, the working method described in Example 5 a) is repeated, using an equivalent amount instead of styrene. isoprene as well as n-butyllithium instead of using an equivalent amount of sec-butyllithium to obtain a substantially elastomeric cis-1,4-polyisoprene. The low Tg live polymer is terminated by the addition of a molar equivalent, calculated on sec-butyl lithium, ethylene oxide as a brake.

DK 160151B

28, and by subsequent addition of an equivalent allyl chloride to recover the polymer.

b) Into a four liter reactor with 3 liters of heptane and 5 grams of allyl ether-terminated cis-1,4-polyisoprene (prepared according to Example 13 a). The macromolecular monomer is dissolved with stirring, after which the solution is flushed with nitrogen for 30 minutes.

10 10 ml of diethyl aluminum chloride (25% solution in heptane) are added, followed by the addition of 0.3 g of titanium chloride. 139.5 g of propylene are added to give a pressure of 1.8 bar. The reactor is heated to 60 ° C and the polymerization is stopped after 18 hours, after which the reactor content is slowly poured into a 4-liter beaker containing 2 liters of a 1% solution of Ionol antioxidant in isopropanol. The copolymer has higher impact strength than polypropylene homopolymer.

EXAMPLE 14

Preparation of a copolymer with polyisobutylene backbone and polystyrene side chains 25 For a solution of 20 g polystyrene terminated with epichlorohydrin and having an average molecular weight of 10,000, cf. Example 2 a), in 1000 ml of toluene at -70 ° C is added 80 g of isobutylene. 45 ml of boron trichloride-ethyl ether complex are slowly added while maintaining the temperature at -70 ° C throughout the addition. The polymerization proceeds as the catalyst is added and is completely completed almost immediately after all the catalyst is added. The copolymer formed is obtained by evaporation of the toluene and washing of the solid residue with 35 methanol.

DK 160151 B

EXAMPLE 15

Preparation of a copolymer with polyisobutylene main chain and polystyrene side chains 5

To 1,000 ml of methyl chloride at -70 ° C is added 10 g of polystyrene terminated with epichlorohydrin, with an average molecular weight of 10,000. To the resulting solution maintained at -70 ° C is added simultaneously and dropwise a solution of 2 g of aluminum chloride in 400 ml of methyl chloride and 90 g of isobutylene. The addition time is 1 hour and after this time the polymerization is essentially complete. The insoluble copolymer formed is isolated by evaporation of the methylene chloride.

Similar results are obtained using either a methallyl or methacrylyl end group on the polystyrene ((see Example 5a)).

EXAMPLE 16 a) For the preparation of polystyrene, modified with butadiene and terminated with allyl chloride, 2.5 liters of benzene (thiophene-free) are introduced into a reactor and heated to 40 ° C. 0.2 ml of diphenylethylene is added as the initiator and the reactor is sterilized by dropwise addition of a 12% solution of secondary butyllithium until an orange-red color is maintained. At this point, an additional 18 ml (0.024 mol) of secondary butyllithium solution (12% in hexane) is added, followed by 416 g of 30 (4.0 mol) of styrene. The temperature of the polymerization mixture is maintained at 40 ° C for 5 minutes, then the live polystyrene is modified with butadiene by bubbling butadiene gas into the reactor until the color of the solution changes from dark red to orange. The living polymer is terminated by treatment with 4.1 ml (0.05 mol) of allyl chloride. The macromolecular monomer thus prepared is precipitated with methanol and filtered off. mean

DK 160151 B

The number molecular weight as determined by gel permeation chromatography is 25000 (theoretical 18000) and the molecular weight distribution is very narrow.

B) To prepare a copolymer with a polyethylene backbone and polystyrene side chains, 2 g of polystyrene from Example 16 a) is dissolved in 1500 ml of cyclohexane and introduced into a 2-liter reactor. The reactor is flushed with pre-purified nitrogen for 30 minutes and 22 mm 25% ethyl aluminum-sesquichlorido dip solution (in heptane) is added. The reactor is pressurized with 21 g of ethylene to 2.8 bar. Then, 0.1 ml of vanadium oxychloride is added and the ethylene pressure drops from 2.8 bar to 0.07 bar over approx. 1 minute. The reaction is quenched within 3 minutes by the addition of isopropanol. The polymer is recovered by filtration.

It is known that the physical properties of high density linear polyethylene depend on the degree of crystallisation, molecular weight and molecular weight distribution. These 20 values determine the properties of the finished items. The copolymers in question, especially those with a polyethylene backbone and polystyrene side chains, modify the physical properties of polyethylene without affecting the favorable crystalline properties of polyethylene.

To demonstrate these beneficial properties of the graft copolymers as well as their crystalline nature, several tests have been performed. In the following, properties of copolymers having a polyethylene backbone and polystyrene side chains illustrated in the form of methacryloyl and maleic acid terminated polymers are illustrated in the copolymer.

35

DK 160151 B

31

Determination of macromolecular monomer content by infrared spectroscope!

Calibration curve for ethylene-polystyrene copolymers.

5

High density technical polyethylene, U.S.I. The Microthene ML 708 and Dow-Polystyrene, Styron 666u are mixed in the ratios: 80/20, 70/30, 60/40 and 50/50 and extruded twice through an extruder of Killion. The extruded 10 mixtures are pressed into thin films (about 0.025 mm) and the infrared spectrogram was performed on a Beckman I.R. infrared spectrophotometer. 12. Benzene ring absorption at 710 cm and the methylene absorption at 1480 cm are measured and the ratio calculated. The calibration curve is plotted as a function of the absorption ratio relative to the styrene content in percent.

Determination of the Polymer Content of the Copolymers 20 The copolymer is pressed into thin films and their infrared spectra determined by a Beckman I.R. spectrophotometer. The absorption at 710 cm for the polystyrene product is compared to the absorption at 1480 cm 2 and the polymer content is determined by the calibration curve. The infrared spectra show that a copolymer with a polyethylene backbone and polystyrene side chains (molecular weight 27000) has been formed. with a 20% incorporation by weight.

30 Sample Preparation and Testing

The copolymer compression molds are molded to sheets of approx. 80 am for voltage-impact testing. The mold consists of two 178 x 178 x 1 mm steel plates, 35 spaced apart with a 178 x 178 x 0.5 mm steel spacer, so as to form a center space of 127 x 127 x 0.5 mm. Lubricate the surface with an abrasive, Dow

DK 160151B

32

Corning R-671.

Ca. 8 grams of polymer are placed in the mold and molded at 204 ° C for 10 minutes at a pressure of 30 tons and cooled by 5 of running water.

Three specimens are cut from the plate using a standard stamp "C" (ASTM D412-67T) and the dimensions are measured with a micrometer.

10

Strength properties are determined using an Instron tester in accordance with ASTM D638 at a pulling speed of 50 mm / minute.

The bending modulus of the copolymer is determined on rods using Instron tests in accordance with ASTM D790.

The heat deformation is determined on rods in accordance with ASTM D640.

The crystalline nature of copolymers with polyethylene-high-chain is studied from the following: Crystallinity X-ray diffraction,

Melting Properties Differential scanning calorimetry, Crystallite orientation X-ray diffraction, and

Spherulite Formation Light Microscopy.

Crystallinity The measurement of crystallinity by X-ray diffraction can be done in many ways, but an effective and simple method is 35

DK 160151 B

33 to calculate a crystallinity index (CrI) as follows:

I I

* • 110 - am

CrI = -x 100, 5 ± 110

Where I · £ 10 is above the background scatter of the 110 diffraction peak, taken at 21.6 0 2Θ. IQm, the amorphous dispersion is 19.8 ° 2Θ.

10

For polyethylene, the separation of the X-ray scattering due to the crystalline and amorphous fractions is simplified since the amorphous peak is clearly different from the crystalline peak in the diffraction pattern. A diffractometer measurement is illustrated for a polyethylene with 12% internally copolymerized α-olefin-terminated polystyrene exhibiting separation of the two fractions and measurement of the peak heights. When applied to published diffraction patterns for polyethylene, the method yields crystallinity values according to the values in which the authors used integrated intensity measurements for the respective crystalline and amorphous material.

The CrI values of many polyethylene materials ranged from 72 to 77. The CrI of polyethylene decreased for copolymers relative to the content of side chain polymer (6-30%). It is evident that the CrI values within the experimental errors are not lower than the expected values by a simple dilution of the polyethylene crystallinity with a 30 amorphous macromolecular monomer.

The diffractometer measurements for the CrI measurements have also been inspected for crystal lattice changes and diffraction line extensions upon addition of polymer. Changes in the crystal lattice have not been observed, which means that the macromolecular monomer is not incorporated

DK 160151 B

34 in the polyethylene crystal lattice, but in the amorphous portions of the sample. Measured half-widths of the 200 diffraction peak show no increase in crystal size upon addition of polymer. Thus, diffraction measurements, such as of a 12% macromolecular copolymer, and diagramed by CrI against the content of the macrometer will demonstrate a particular effect of the invention, namely that the crystallinity of the polyethylene fraction is maintained in the presence of the side chain polymer.

10

Melting properties of the side-chain polymer polyethylene copolymer 15 A differential scanning calorimeter (DSC) is used to determine the melting properties of the copolymers and to confirm the non-interference of the polymers with polyethylene crystallites. A typical endothermic DSC diagram for a copolymer that melts during a programmed temperature rise is illustrated. The polymer is an α-olefin-terminated polystyrene having a molecular weight of 27000. The copolymer contains 20% of the polymer internally copolymerized in the polymeric polyethylene backbone. The melting properties of the copolymer are quite similar to those of the literature for high density unidified polyethylene, although the sample contains 20% of that polymer. Eg. there is no premature melting in the copolymers and the melting point (Tm) © is the same for both 100% polyethylene and copolymer samples. On 30 basis of comparable polyethylenes prepared without macromolecular monomers using the same polymerization method, the original softening temperature (89 ° C) was on average 7 ° higher for samples containing the polymers. In a single sample, the temperature is increased 19 ° C over the corresponding polyethylene.

DK 160151 B

35

Crystallinity measurements are calculated from the heat of melt (ΔΗ), which is determined from the area under the DSC curve. The calculations are based on a ΔΗ of 68.4 cal / gel for 100% crystalline polyethylene. Although at a different level, the 5 crystallinity values of this method generally correspond to those obtained by X-ray examinations.

Thus, the thermal data upon melting and for the crystallinity confirm the X-ray data and all the integrity of the polyethylene crystallites is maintained in the copolymer of the invention. However, the reverse effect is generally observed for previously known epolyethylene copolymers or for polyethylene with side chains simply attached to polyethylene. In these cases, crystallinity will not only often decrease by more than a simple dilution factor, but the polyethylene crystallites will also exhibit low values of T and ΔΗ.

m

Crystal X-ray Orientation 20 X-ray diffraction charts were recorded on stretched samples by an Instron sample to determine the crystal lith orientation and the effect of adding macro-molecular monomers on the crystallites' ability to orient. The degree of orientation is determined from the size of the angle between the arcs of the 110 and 200 diffraction peaks that appear on oriented samples. High density, unstretched and stretched polyethylene (500%) is shown for comparison with a copolymer of a 20% polyethylene backbone after weight incorporation of polystyrene side chains, stretched 800%. A stretched homopolymer exhibits a small 110 arc describing an arc of 17 °, while the arc of the copolymer is 48 °, although it is stretched more than the homopolymer. Thus, the polymers will act within 35 amorphous regions to bond and hold the crystallites together at high extensions.

DK 160151 B

36

For molded films, on the other hand, another effect is noted, with copolymers exhibiting higher degrees of crystal plane orientation than homopolymers. The ratio of the 110 peak to the height of the 200 peak is used in these 5 cases. When the ratio of the peak intensities is of the order of 3.3, the polyethylene sample is considered to have a random orientation. For homopolymer polyethylenes, 110/200 peak ratios of 3.0 to 4.6 have been prepared and tested. The orientation ratio of co ~ 10 polymers ranged from approx. 3 to up to 7.3 for samples mounted in the diffractometer, with its foil surfaces parallel to the sample holder. However, molded samples reacted the opposite with subsequent heating and cooling, but without pressure during casting. Under these conditions, a copolymer is reduced from 7.3 to 4.8, while the polyethylene phase is increased from 4.6 to 5.0 in orientation. Similar changes are shown in other tests. These observations of changes in orientation further show the differences in the properties of the polyethylene due to the presence of the polymer which is integrally copolymerized in the polyethylene backbone.

Spherulite formation 25

The spherulite structure was observed by microscopic examination of several of the polyethylene and ethylene copolymers produced. For cast samples, large (10-30 mm) spherulites are observed in some of the samples with 100% polyethylene, which are reduced in size and in optical perfection by the addition of polymers. This behavior is confirmed by solvent crystallization (tetrahydronaphthalene) where large and individually separated spherulite units can be observed. Polarized light 35 is used and images of spherulites are taken from a monopolymer and copolymer containing 6.8 and 20% macro-molecular styrene. The majority of the spherulites obtained

DK 160151 B

37 from the copolymers are smaller and exhibit more structure defects than those from the homopolymers. Similar effects are likely to occur in samples where the spherulite structure is of a size of 1.0-3.0 µm in diameter but where it is difficult to clearly distinguish structural changes.

To demonstrate that the observed effects are functions of copolymerization, images of THN crystals were obtained which were obtained from physical mixtures with 5, 10 and 20% macromolecular monomer content. The spherulite structure of the blends was unchanged from the homopolymer.

Thus, yet another feature of copolymers of the invention has been demonstrated, that although the polyethylene crystals are not themselves affected, the polymer molecules will affect the aggregation of the crystallites into larger morphological units such as spherulites. This effect 20 agrees that they are part of the amorphous region of the sample and affect the crystallite aggregation, but do not contribute as binding molecules to increase the strength and elongation.

A number of copolymers with polyethylene head chains and polystyrene side chains have been prepared using the procedure of Examples 7 and 8 a). Also, a number of polyethylene homopolymers are prepared in the same manner as described for the copolymers, but without the use of polymer. Chain transfer agents are not used to control molecular weight. Products formed by continuous addition of ethylene have a wide molecular weight distribution, while those formed by batch polymerization have narrow molecular weight distribution.

Copolymers and homopolymers of polyethylene are pressed into foils, each subjected to assays for determination 35

DK 160151B

38 of the buoyancy, elongation, tensile strength, modulus of elasticity and other properties as set forth below to determine improved properties of the graft copolymers relative to polyethylene homopolymers. The results of these tests are shown in subsequent Tables I - III.

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ft ΰ) (B CD

H U -pin o O 01 -

ft "" <4H Φ CO

ΗΛΟ) J, ^ 1-1 H ft - C g HO I "H Λ β * 0 Φ μ vococMO ^ rHinin x Ο Φ a φ Όβ (ΰ νοηιηωσιΟ ^ 1 ^ η μ> ω ό> ι (Β Λ cm cm cm cg cm co cm csi · -µ cq fB h ft— - ^ 2 5 *

* £ id ft CO φ · Ρ G G

Lake -μ Φ Η -H

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1 μι - 'H i — IH CQ Φ Ό O

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Η & · Η iH ftO

5- H 4-> CO 'O νί Φ

X! o ft '- * co tN-µ E

p ft (Bo ro η οι μ Φ> o inininininintsiN μ Otdid HH HHHHHHCMCM ft Pi Xl ^ h o'— 'ε .¾ a s' s u w .pro 1Q / N »Cd Q O)

! * ft iSS

• ^ hwcoojsoh µ - c-µ

flj Q (1) · Η CQ

μ,. WD CO CO CM 'tf O Φε φ ft HHHHHHHH μ CQ S § £ ro tu ε ε s X3 η ε h -s <d (d ts

o ^ CO X C O CM

d (d o 'co cd in h

o - H CMCOE "OCO! SOiO C I

o coooocom'M'ooco ro µ µ x SI X CMiOCMCMCOCO'tfCM ft 0) 0)

u φ P H IS

O 3 H -

4-1 CD ft O CM

"" CO H ^ CO O 00 CM H CO X ε η H

µ (do V ». *. *. *. *. *«. co o

φ w H lOOCTilSvDC ^ 'M'CO -η ϋ = i X

XJ fi— H CO Η H CM CM CO CM 01

td s X> 1 O 00 CM

X m ft o ·> m U ^ co G · ro Φ co in vo is oo σι o h is h

ft Μ ΟΟΟΟΟΟΟΟΟΟ ^ '^' Μ 'HldXJO

ωΐ ω - <- - -

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42

The data provided is for non-heat treated compression molded specimens and is therefore typical of the physical properties. To obtain optimum physical properties, synthesis of a copolymer having a balanced molecular weight, MWD, polymer content and gauge cooling weight of the polymer is required.

5

It can be seen from Table I that the physical properties of the polyethylene homopolymers as a function of molecular weight and molecular weight distribution (MWD) f follow the expected values. Furthermore, the yield stress does not vary significantly, neither with the molecular weight or MWD. The elongation and tensile strength increase with increasing molecular weight, while the modulus, heat deformation and melt index decrease with increasing molecular weight. Examples 17 and 18 have a narrower MWD and show a significant increase in the elongation ice and tensile strength relative to the corresponding average molecular weight by weight polyethylenes with a wide MWD.

The summation of data for the copolymers is divided into two groups, those with a polydispersity (P.D.) less than 9Π10, given in Table II, and a P.D. greater than 10, given in Table III, to obtain a logical comparison of the properties as evidenced by the corresponding differences in properties of polyethylene homopolymers.

By comparing the different properties of the copolymers with homopolymers of the same average molecular weight, it is clear that the incorporation of the polymer into the skeleton of the polymeric hydrocarbons, such as polyethylene, significantly improves many of the properties of polymer without going beyond the advantageous properties of the homopolymer. Such an improvement in the properties must be considered surprising given that the polymer is actually copolymerized in the polyethylene backbone and breaks off the polyethylene segments. Generally, such a copolymerization with polyethylene

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43 result in deterioration of the good properties.

Furthermore, it is evident from the indicated data that the use of very low concentrations after molar percentages of the polymer does not change the content of crystalline polyethylene. The spherulite structure is significantly reduced in the copolymers but is not affected by simple mixtures of polyethylene homopolymer with the polymer. It can be seen from this that the polymeric side chain segments are found in the elastomeric amorphous regions of polyethylene. In other words, the crystalline portion of the polyethylene matrix has an elastomeric dispersed phase which in turn has a glassy dispersed phase. The high Tg amorphous polystyrene apparently reinforces the low Th 15 elastomeric phase at low polymer content in the same way that the polystyrene domains behave in block polymers such as Kraton.

As the content of polymer increases, the nature of the matrix and dispersed phase of the amorphous regions of the polyethylene 20 will change until a phase inversion occurs. Now, the crystalline matrix of polyethylene will have a plastic amorphous dispersion phase, which in turn will have an elastomeric dispersion phase of such size as the chain configurations of the amorphous and crystalline portions of polyethylene will allow.

The relationship between the property values in Tables I - III of polyethylene homopolymers and graft copolymers (polyethylene backbone and polystyrene side chains with a uniform molecular weight of 15400) is shown in Figures 1 and 2 as normalized values relative to the polymer content. .

These charts show a decisive effect of the polymer to increase all the measured physical properties relative to the corresponding properties of polyethylene homopolymers having the same molecular weight and molecular weight distribution. As can be seen from the diagram (Fig. 1), the yield stress exhibits a sharp increase in the area of

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44 4-12% polymer content and then a gradual increase with higher polymer content. The elongation and tensile forces increase to a maximum of approx. 12% polymer. The modulus of elasticity has a sharp increase up to 4% incorporation of side chain polymer, then stays constant to 14-16% polymer and rises again, but less sharply at higher concentrations of the polymer. The heat deformation shows a steady increase with increasing polymer content from 5%.

10

The above data and illustrations show some of the advantages obtained by graft copolymers with polyethylene head chain and polystyrene side chains integrally copolymerized in the polyethylene head chain. Similarly advantageous results are obtained by using polymerizable hydrocarbon monomers other than ethylene to give polymers of high Tm and low Tg, e.g. lower α-olefins such as propylene, butene-1 and pentene-1.

As shown in Example 16, high chain Tg side chain polymers, such as polystyrene, can be replaced by low Tg polymers such as polybutadiene and mainly cis-polyisoprene.

For example, isoprene can be polymerized anionically with secondary butyllithium, preferably to a molecular weight of 15,000 and terminated with allyl chloride. Instead, the elastomeric living polymer may be modified with an alkylene oxide such as ethylene oxide, followed by termination with allyl chloride, methallyl chloride or methacrylyl chloride to obtain polymers having lower Tg. The terminated 30 alpha-olefin (allyl chloride and anionic polymerized isoprene) can be used to prepare highly impact-resistant polyethylene or polypropylene copolymers by methods known in the art. For example, the aforementioned α-olefin-terminated polyisoprene can be copolymerized with ethylene using a Ziegler catalyst or with propylene using a Natta catalyst.

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45

Yet another alternative illustrated in the Examples comprises the use of monomeric hydrocarbons which produce elastomeric polymers in the main chain of the copolymer. Among these monomers are isobutylene, butadiene, isoprene and ethylene-propylene comonomers. The physical properties of the elastomeric backbone polymers can be enhanced by copolymerizing or incorporating in the backbone a large number of macromolecular monomers such as linear polymers, anionic polymerized from 10 styrene, α-methylstyrene, ethylene oxide, 4-vinylpyridine, methacylonitrile, , Ν-dimethyl acrylamide or methyl methacrylate. A preferred example is the macromolecular monomer of Example 16 wherein the polystyrene, modified with butadiene or isoprene, is terminated with either 15 allyl chloride or 2-bromomethyl-5-norbornene. The last end group is particularly suitable for preparing ethylene-propylene main chain graft copolymer by the process of Examples 9 and 10.

As can be seen from the foregoing, the present invention provides a convenient and economical method for preparing copolymers using a large number of monomeric hydrocarbons to form main chain polymer blocks and many different anionic polymerizable monomers to form side chain polymers. polymers. The copolymerization is facilitated by careful selection of the terminal end group of the anionic polymerized polymer. Thus, the problem of copolymerizing incompatible polymers can be solved economically to produce 30 copolymers having a main chain and a side chain polymer selected for the particular application.

EXAMPLE 43 (a) For the preparation of polystyrene-polyisoprene side chains terminated with allyl chloride, feed into a 3.8 liter reactor 2.5 liters of purified benzene and mix

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46 is heated to 40 ° C. After sterilization with secondary butyllithium using diphenylethylene as indicator, 15.3 ml (0.0193 mole) of secondary butyllithium (12% in hexane) is added by syringe.

5,193 g of monomeric styrene are added over 5 minutes while maintaining the reactor temperature at 40 ° C. 6 minutes after the addition of the monomeric styrene, 193 g of monomeric isoprene are added over 4.5 minutes. The reactor is maintained at 40 ° C for 60 minutes, after which 2.4 ml of 10 allyl chloride is added to terminate the reaction. The α-allyl chloride terminated polystyrene-polystyrene-poly-isoprene macromolecular monomers have the following structure: CH3CH2 - CH - CH2 - CH --- CH2 ^ CH2 CH2CH = CH2 ·

CH3 / C = C

(J / \ L \ / \. LCH3 h Jm 20 \ where n has such a value that the molecular weight of polystyrene is 10,000, and m has such a value that the polyisoprene segment of the diblock macromolecular monomer is about 10,000.

B) To prepare a copolymer of an allyl chloride terminated polystyrene-polyisoprene diblock polymer and propylene, 60 g of α-olefin-terminated diblock-polystyrene polyisoprene prepared according to Example 43a are introduced into a 2-liter reactor. with 1.5 liters of dry N-heptane. The reactor is flushed with nitrogen for 40 minutes. 30 ml of diethyl aluminum chloride (25% in N-heptane) is added followed by 2.05 g of titanium trichloride. The reactor is heated to 75 ° C and gaseous propylene is introduced into the reactor at a rate of 1 liter / minute. The polymerization is carried out at 75 ° C and a pressure of 1.4-1.8 bar while supplying propylene at an average rate of 0.5 liters / minute. After 2 hours,

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The reaction is by adding ethanol. The resulting copolymer is washed with dilute sodium hydroxide solution and dried in a vacuum oven. By infrared analysis it is shown that the diblock polymer was incorporated into the polypropylene backbone. The physical properties of the copolymer have been tested with the following results:

Tensile strength 347 bar

Float voltage 330 bar 10% extension 810 5

Elastic modulus 0.1435 x 10 bar Heat deformation temperature 62 ° C

Izod impact strength 0.138 m-kg / 25 mm EXAMPLE 44 a) For the preparation of polystyrene-polyisoprene macromolecular monomer, 2.5 liters of 20 dry benzene heated in a 4 liter reactor are heated to 40 ° C. After sterilization with secondary butyllithium using diphenylethylene as indicator, 15.8 ml (0.0199 mole) of secondary butyllithium (13% in hexane) is added by injection. 80 g of monomeric styrene are added while maintaining the reaction temperature at 40 ° C. Then, 319 g of monomeric isoprene are added and the polymerization is carried out at 40 ° C for 1 hour, after which the living diblock macromolecular monomer has a formula of the following structure: 30 CH 3 CH 2 - CH CH 2 CH: - CH 2 CH 0 = 0 / \ L \ / J. CH 2 H J + where n has such a value that the molecular weight of polystyrene is 16; 48 networks is approx. 4,000 and m has such a value that the molecular weight of the polyisoprene is approx. 16,000. Analysis of the diblock polymer by gel permeation chromatography reveals that the molecular weight distribution of the polymer is very narrow, ie. the ratio Mw / Mn is less than 1.1. (b) For the preparation of copolymers of polystyrene-poly-isoprene diblock polymer terminated with allyl chloride and ethylene, 300 ml of a di-block polymer prepared according to Example 44a (40 g based on Example 44a) is introduced into a 2-liter reactor. of dry matter) together with 1.2 liters of dry cyclohexane. The reactor is flushed with pure nitrogen for 50 minutes. 22 ml of ethyl aluminum sesquichloride solution (25% in heptane) is added by syringe. Ethylene is introduced into the reactor until the pressure has risen to 3.1 kg / cm 2 and the mixture is stirred vigorously. 0.2 ml of vanadium oxychloride is injected and the polymerization is started immediately. During the addition of vanadium oxychloride, the temperature rises from 25 ° C to 60 ° C.

20 As the pressure drops, ethylene is supplied at a rate of 2 liters / minute. The polymerization is carried out over 12 minutes and terminated by the addition of 10 ml of ethanol. The polymer is purified by washing with cyclohexane, dilute sodium hydroxide solution and dried in a vacuum oven. Ultraviolet analysis of the copolymer shows that it contains 24% of the diblock polymeric monomer. The physical properties of the copolymer were tested and the results are as follows: 30 Flow stress 175 bar

Tensile strength 151 bar% extension 490 g

Elastic modulus 0.0425 x 10 bar Heat deformation

Temperature 37 ° C

Izod impact strength 1.77 m-kg / 25 mm (sample did not break)

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EXAMPLE 45 a) To prepare a polystyrene-polyisoprene diblock polymer terminated with allyl chloride, a 3.0 liter purified benzene is charged to a 4-liter reactor and heated to 40 ° C. After sterilization with secondary butyllithium using diphenylethylene as indicator, 46.5 ml (0.0585 mol) of secondary butyllithium (12% in hexane) is added by syringe. 761 g of monomer styrene is added over 15 minutes while maintaining the reaction temperature at 40 ° C. 5 minutes after the styrene addition is completed, 410 g of monomeric isoprene is added over 4 minutes. The reaction mixture is kept at 40 ° C for 1 hour, after which the reaction was quenched by the addition of 15 ml of allyl chloride. In the diblock polymer formation formed, the molecular weight of the polystyrene was approx. 13,000, and the molecular weight of the polyisoprene 7,000. The diblock polymer was analyzed by gel permeation chromatography and this analysis revealed that the molecular weight distribution of the polymer was very narrow, ie. Mw / Mn was less than 1.1.

b) To prepare a copolymer of polystyrene-polyisoprene diblock polymer, terminated with allyl chloride and 25 ethylene, 200 ml of the diblock polymer prepared in Example 45a (40 g of dry basis) together with 1.3 liters of cyclohexane. The reactor is vented with high purity nitrogen for 1 hour. Add 22 ml of ethyl aluminum sesquichloride solution (25% in heptane). Ethylene is introduced into the reactor until the pressure has risen to 3.1 bar. Then 0.2 ml of vanadium oxy-trichloride is added and the polymerization is started immediately, raising the temperature from 27 ° C to 55 ° C. As the pressure drops, ethylene is supplied at a rate of 2 liters / minute. The polymerization is carried out for 8 minutes and terminated by the addition of 10 ml of ethanol.

The polymer is purified by washing with dilute sodium

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50 hydroxide solution, cyclohexane and dried in a vacuum oven. Ultraviolet analyzes showed that the copolymer contained 38.5% diblock macromolecular monomer. The physical properties of the copolymer were tested with the following results;

Floating voltage 405 bar

Tensile strength 414 bar% extension 77 5 10 Elastic modulus 0.12 x 10 bar

Heat deformation temperature 49 ° C

Izod impact strength 0.1382 m-kg / 25 mm EXAMPLE 46 a) For the preparation of polystyrene-polyisoprene diblock polymer terminated with allyl chloride, 2.5 liters of purified benzene are introduced into a 4-liter reactor and heated to 40 ° C. After sterilization with secondary butyl lithium using diphenylethylene as indicator, 35.1 ml (0.044 mol) of secondary butyl lithium (12% in hexane) is added by means of a syringe. 442 g of styrene 25 is added over 13 minutes while maintaining the reactor temperature at 40 ° C. Ten minutes after the addition of the monomeric styrene, 88.4 g of isoprene is added over 4 minutes. The reactor is maintained at 40 ° C for 30 minutes, then 3.6 ml of allyl chloride is added to terminate the reaction. In the recovered diblock polymer, it had a molecular weight of 1,000, while the molecular weight of the polyisoprene was approx. 2000. The polymer was analyzed by gel permeation chromatography and the analysis revealed that the molecular weight distribution of the polymer was very narrow, ie. Mw / Mn was less than 1.1.

in

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B) To prepare a polystyrene-polyisoprene diblock polymer terminated with allyl chloride and a mixture of ethylene and propylene, 155 g of a 19.3% solution of diblock polymer are fed into a 2-liter reactor. prepared according to Example 46a (30 g on dry basis) together with 1.6 liters of purified cyclohexane. 22 ml of ethyl aluminum sesquichloride solution (25% in hexane) is added by syringe. Then 19 liters (35 g) of gaseous propylene are introduced into the reactor. After 0.2 ml of vanadium oxytrichloride is injected, polymerization is started by adding ethylene. Ethylene is added to the reactor at a rate of 2 liters / minute for 14 minutes (35 g). The polymerization is carried out for 24 minutes and terminated by the addition of isopropyl alcohol.

15

The copolymer solution is introduced into a stainless steel vessel and 1 liter of dilute sodium hydroxide solution and 1 g of antioxidant are added. The mixture is stirred with a mixer to remove catalyst residue from the polymer. The copolymer is coagulated and dried.

EXAMPLE 47 a) To prepare polystyrene-polyisoprene diblock polymer modified with ethylene oxide and terminated with methacrylyl chloride, 193.22 kg of purified benzene is introduced into a stainless steel reactor. The reactor is heated to 40 ° C and the solvent and reactor sterilized with secondary butyllithium using diphenylethylene as indicator. After sterilization, 126.58 g (1.9764 mol) of secondary butyllithium (12% in hexane) is added to the solution, followed by 19.47 kg of styrene over 30-45 minutes while maintaining the reactor temperature at 36-42 ° C.

After the addition of the styrene, 48.62 kg of isoprene 35 is added to the reactor, followed by the addition of 0.38 kg of ethylene oxide to modify the diblock-living polymer. The modified diblock polymer is terminated at i

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52 addition of 0.22 kg of methacrylyl chloride to form | methacrylic acid ester of the following formula:

. IN

5 II j CH3CH2-CH-fCH2-CH1 · -Pcft C Hr] -CH2CH2 -O-C - C = CH2 '

I I \ / I

CH 2 / V C = C CH 2 I

() / \ 1 \ / \. LcHi h J.

10 where n has such a value that the molecular weight of the polystyrene is approx. 10,000 and m has such a value that the molecular weight of the polyisoprene is approx. 25,000. Analysis of the 15 macromolecular diblock polymer by gel permeation chromatography reveals that the molecular weight distribution of the polymer is very narrow, ie. the ratio Mw / Mn is less than 1.1. After recovery of the macromolecular monomer, 68 g of Agerlite Superlite (antioxidant) is added to the 20 polymer for stabilization against premature oxidation.

b) The procedure of Example 47a is repeated, using an equivalent amount of maleic anhydride instead of methacrylyl chloride to form the maleic acid half-ester of the polystyrene-polyisoprene diblock polymer of the following formula:

ISLAND

CH 2 CH 2 - CH - pCH 2 - CH -] - PCH 2 CH 2] - CH 2 CH - O - C

30! i \ / \

CH3 / V C-C CH

U / \ ii

\ / \ n LCH3 H m CH

/

HOC

Λ 35 ° where n and m are positive integers as indicated above.

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C) The polymer formed in Example 47b is copolymerized by vinyl chloride (10 parts by weight of the polymer with 90 parts by weight of vinyl chloride and a chain transfer agent) to give it with improved properties in terms of formability 5 and strength.

d) To prepare a copolymer from methacrylate ester-polystyrene-polyisoprene polymer and styrene, a suspension copolymerization with a methacrylate ester-terminated polystyrene-polyisoprene diblock polymer prepared in Example 47a is carried out by the above procedure. An aqueous solution and a monomeric solution are both freshly prepared before use. The components of the aqueous stabilizing solution and the monomeric solution were as follows:

Aqueous stabilizing solution

Distilled water 375 g Polyvinylpyrrolidone 0.625 g

Monomer solution

Methacrylate-terminated 291 g (25.9% solid solution polymer (Example 47a) in benzene, 75.4 g)

Styrene 177 g

Benzene (solvent) 52 g AIBN (azobisisobutylronitrile) 1.33 g 30 (polymerization initiator)

The aqueous stabilizing solution is introduced into a rinsed 1-liter flask which is sealed with a butyl rubber package with a polyester film coating. The bottle 35 is rinsed with nitrogen by means of an injection needle before introducing the monomeric solution. The monomeric solution is then introduced into the bottle by means of an i

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54 syringe and the bottle is placed in a polymerization bath rotating at 30 rpm. per minute at 65 ° C for 20 hours. Then, the suspension which is filtered is cooled, washed with water, air dried and sieved at room temperature. 117 g of the copolymer is recovered, corresponding to a 95% conversion rate of the styrene.

The chemically bonded, phase-separated graft copolymer is compressed into a clear plastic having the following physical properties:

Elastic modulus 13,360 bar

Heat deformation j

temperature 77 ° C

15

Izod impact strength 0.1521 m-kg / 25 mm-j 1.3134 mm-kg / 25 mm j i

It is evident from the above data that the copolymer has 20 remarkable physical properties and is also clearly transparent.

EXAMPLE 48 (Comparative Example) 25

Homopolymerization of Methacrylate Terminated Polystyrene a) For the production of polystyrene terminated with methacrylyl chloride, a stainless steel reactor is charged with 120 30 1 A.C.S. benzene (thiophene-free), which is pre-dried by a molecular sieve according to system Linde and with calcium hydride. The reactor is heated to a temperature of 38-40 ° C and 10 ml of diphenylethylene is added to the reactor by means of a syringe. An 11.4% solution of secondary butyl lithium in hexane is added portionwise to the reactor until a permanent orange-yellow color (60 ml) is maintained, then

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55 additional 1.6 kg of secondary butyl lithium in hexane is added to the reactor and then 37 kg of purified styrene over 1 hour and 40 minutes. The reactor temperature is maintained at 38-40 ° C. The living polystyrene is modified by the addition of 0.13 kg of ethylene oxide and the reaction solution changes color from red orange to yellow. The resulting modified live polystyrene is then reacted with 260 ml of methacrylyl chloride and the solution changes color to a very pale yellow color. The methacrylate-terminated polystyrene is precipitated by the addition of the polymeric benzene solution in the methanol, whereby the polymer is precipitated by the solution. The polymer is dried in a circulating air dryer at 40-45 ° C and then in a fluidized layer to remove traces of methanol.

The molecular weight of the polymer, determined by membrane phase osmometry, is 13,400 and the molecular weight distribution is very narrow, with Mw / Mn being less than 1.05.

b) The methacrylate-terminated polystyrene formed is subjected to a homopolymerization by suspension polymerization under the following conditions:

Aqueous solution: 25% technical polyvinyl alcohol 3.0 g

Distilled water 300.0 g

Monomer solution: 30 Methacrylate-terminated polystyrene 20-, 0 g

Lauroyl peroxide 0.16 g

Benzene (thiophene-free) 30.0 g

The aqueous polyvinyl alcohol solution is introduced into a clean 35 liter flask which is vented with nitrogen for 15 minutes.

The methacrylate-terminated polystyrene polymer solution is added to the flask and sealed after rinsing with

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56 nitrogen for 2 minutes. The flask is placed in a polymerization bath at 70 ° C for 17 hours.

The product is filtered, dried and dissolved in tetrahydrofuran 5 (THF) for analysis by gel permeation chromatography (GPC).

No gel was found in the THF solution. In the GPC chromatogram, the ratio of the area of unreacted polymer to the total area showed that 75.9% of the macromolecular monomer remained unreacted. Thus, by analysis of 10 GPCs, only 24% of the polymer has reacted and this conversion resulted in only a low molecular weight polymer.

EXAMPLE 49 (Comparative Example 15

Polymerization of acrylates in the presence of polystyrene

This example illustrates that a conventional polystyrene does not adhere to an acrylate backbone of the polystyrene segment, showing that the polymers of the invention copolymerize with acrylates and other polymerizable monomers over the terminal double bond.

The desired polymerization is carried out in a 3-neck flask, equipped with a capacitor, with stirring according to the following procedure:

Polymerization Recipe 30

Polystyrene1 18.0 g

Ethyl acrylate 42.0 g AIBN 0.168 g

Benzene (thiophene-free) 120.0 g DMSO 120.0 g in 57

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Live polystyrene with a molecular weight of approx. 10,000, terminated with methanol.

This material is introduced into a flask and the clear solution is heated under a slow stream of nitrogen for 13 hours at a temperature of 61-80 ° C. Upon completion of the reaction, the polymeric solution has a total solids content of 19.6% (theoretically 20.0%).

The product mixture is precipitated and dissolved in THF for GPC analysis. Unreacted polystyrene is determined from the area of polystyrene peak in the GPC chromatogram of a known sample, using polystyrene peak area / gram of polystyrene standard calibration, as shown in the following table: GPC determination of -transformed polystyrene

Unreacted 20 Polystyrene Unreacted Weight Product Injected Polystyrene Injected Polystyrene Top Sample * In Product (grams) _Areal (grams) _ (grams) _% 25 0.008039 0.1778 0.00268 33.3 (a) Calculated from standard 66.5 g area / 1,000 g polymer monomer.

30

The above provisions show that the polymer product contains 33.3% unreacted polystyrene. Therefore, there is little or no grafting of ethyl acetate to polystyrene polymer that occurs during polymerization.

35

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EXAMPLE 50

Preparation of a copolymer with polystyrene side chains and poly (butyl acrylate) main chain 5 The following components are introduced into a 1 liter bottle which is washed, dried, capped and rinsed with nitrogen:

Methacrylate-terminated polystyrene 10 (prepared according to Example 48a except that Mn = 11,000) 15.0 g

Butyl acrylate 45.0 g AIBN 0.09 g DMSO 195.0 g Benzene (thiophene-free) 195.0 g

The methacrylate-terminated polystyrene is first dissolved in benzene / DMSO solution, followed by dissolution of the butyl acrylate and AIBN in the solution. The homogeneous solution 20 is introduced into the nitrogen filled bottle by means of a syringe. The flask is placed at 67 ° C in a polymerization bath at a speed of 30 rpm. Samples are taken using a syringe and interrupted with 10% MEHQ after, 75 minutes, 120 minutes and 25 210 minutes. After a polymerization of 300 minutes, the remainder of the polymerization mixture in the bottle is quenched by four drops of 10% MEHQ in ethanol.

Butyl acrylate conversion is determined by measuring the solids content of a sample. The remainder of the sample is precipitated with methanol, dried and dissolved in THF for GPC analysis. The methacrylate-terminated polystyrene has a peak at 31 units in a GPC chromatogram. The GPC chromatogram of the products of 75, 120, 210 and 300 minutes shows an offset of the peak at 31 units. Analysis of the GPC chromatogram reveals that 25.6% of the copolymer in polystyrene and 74.4% is poly (butyl acrylate).

59

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The above procedure is repeated several times using the same methacrylate-terminated polystyrene having a molecular weight of 11,000 and a Mw / Mn ratio of less than 1.1 by copolymerizing increasing amounts of butyl acrylate, replacing butyl acrylate with ethyl acrylate and methyl methacrylate. Table IV gives the results of these copolymerizations.

10 15 20 25 30 35

TABLE IV

60

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The composition of methacrylate-terminated polystyrene-acrylic copolymers prepared in DMSO / benzene solution δ 5)

% Polymer 1 Polymer Copolymer I

in polymer Polymer-Comonomer remanufacturing isation-conversion phrase]

Comonomer time hours%% (% polymer) - in 10 BA 25 2 36.2 37.2 25.6 j 3.5 62.3 65.7 26.0 j 5 75.6 85.5 27.4 i BA 50 2 13.5 18.4 57.7! 4.75 67.0 77.0 53.5. EA 25 2 23.2 30.1 30.2! 15 3.5 58.3 67.2 27.8 5 77.6 90.4 28.0 EA 50 4.75 69.0 80.7 53.9 MMA 25 2 15.5 10.3 18.2! 48.3 53.4 26.9 20 MMA 50 2 12.0 22.9 65.6 4.75 35.7 32.0 47.3 (a) SllMa = Methacrylate-terminated polystyrene, 11,000 Mn methacrylate terminal group EA = Ethyl Acetate BA = Butyl Acrylate MMA = Methyl Methacrylate 35

Preparation of a copolymer with polystyrene side chains and poly (methyl methacrylate) main chain 5 61

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EXAMPLE 51 The following ingredients are introduced into a clear 1 liter flask which is plugged, rinsed with nitrogen and polymerized for 17.5 hours at 74 ° C in a polymerization bath.

Methacrylate-terminated polystyrene (product of Example 48a) 27.5 g

Methyl methacrylate 110.0 g

Benzene (thiophene-free) 413.0 g of AIBN 1.1 g of t-dodecylmercaptan 0.7 ml.

The copolymer formed is recovered by precipitation of one part of the copolymer in methanol and the other part in cyclohexane to give an overall yield of 87%. 20 clear, brittle films are obtained from cyclohexane or methanol precipitated products. The methacrylate-terminated polystyrene alone has a peak at 32 units on the chromatogram of 6PC.

However, the GPC chromatogram on the unprocessed product of the copolymer shows that no unreacted methacrylate macromolecular monomer can be detected at 32 units. Therefore, it is believed that all methacrylate-terminated polystyrene copolymerizes with methyl methacrylate.

EXAMPLE 52 30

Preparation of a copolymer with polystyrene side chains and poly (butyl acrylate) main chain by suspension copolymerization 1

Using the same methacrylate-terminated polystyrene as set forth in Example 50 (i.e., molecular weight = 11,000 and Mw / Mn less than 1.1, is prepared by the process

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62 of Example 48a, the following ingredients are introduced into a clean, stuffed 1-liter flask with nitrogen:

Distilled water 150.0 g 5 A 5% solution of polyvinyl alcohol 3.0 g

Disodium phosphate 0.80 g

Monosodium phosphate 0.05 g 10 Then the following solution is introduced into the bottle by means of a syringe: | |

Methacrylate-terminated polystyrene 20.0 g

Butyl acrylate 30.0 g Lauroyl peroxide 0.1 g

The bottle is rotated for 16 hours at 65 ° C, then heated for 2-3 hours at 86 ° C. The resulting granulate is washed with water, filtered and dried. A molded 20 foil is produced that is clear, elastic and strong. This transparent film shows that there is little unreacted methacrylate-terminated polystyrene.

In contrast to copolymerization in DMSO / benzene solution 25, the reactivity of methacrylate-terminated polystyrene with acrylic monomer by suspension polymerization is the reactivity anticipated in the literature. It can be seen from Table V that the polymerizable macromolecular monomer has a greater relative reactivity than the monomeric butyl acrylate.

30

The relative reactivity ratio of the methacrylate-terminated polystyrene (M 2) with butyl acrylate (M 2) is about

0.4 (Table V). 1

This corresponds to the values given in the literature for 0.37 for methyl methacrylate / butyl acrylate.

TABLE V

63

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The composition of methacrylate-terminated polystyrene-butyl acrylate copolymers prepared by suspension polymerization

Copolymer ^ = mM% BA conversion% polymer Polymer-Butyl composition_10 in the position acrylate-Polymerization% Polymer-limer time, min. conversion conversion (% po conversion addition see%% glue) 30 90 29.2 47.0 41.5 0.6 15 135 60.4 79.6 35.6 180 68.9 81.9 33.1 50 45 7.0 15.5 68.9 0.45 90 10.1 26.3 71.9 0.38 135 67.4 81.0 54.6 20 180 79.0 85.6 52.0 EXAMPLE 53 25 Preparation of a copolymer with polystyrene side chains and ethyl acrylate / butyl acrylate backbone by suspension copolymerization

A suspension copolymerization using a methacrylate-terminated polystyrene, prepared according to Example 48a and having a molecular weight of approx. 16,000 and an Mw / Mn of less than 1.1 is accomplished by the procedure described below. An aqueous solution and a monomeric solution were prepared immediately prior to use.

The components of the two solutions are as follows:

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64

Aqueous stabilizer solution:

Distilled water 300.0 g of 5% technical polyvinyl alcohol solution 3.0 g

Disodium phosphate 1.6 g

Monomer solution: 10 Methacrylate-terminated polystyrene 30.0 g

Ethyl acrylate 35.0 g

Butyl acrylate 35.0 g

Benzene (thiophene-free) 14.0 g

Lauroyl Peroxide 0.084 g 15

The 5% polyvinyl alcohol solution is prepared by dissolving polyvinyl alcohol in distilled water. The aqueous stabilizer solution is transferred to a rinsed 1-liter flask, which is closed with a butyl-rubber gasket capsule, coated with a polyester film. The flask is rinsed off with nitrogen by means of a syringe prior to introduction of the monomeric solution.

The monomeric solution is then transferred to a flask 25 by means of a syringe and it is introduced into a polymerization bath and rotated at a speed of 30 rpm at 55 ° G for 16 hours. The polymerization reaction is terminated by the following temperature course. The bath temperature is raised to 65 ° C for 3 hours, 80 ° C for 1 hour and 4 hours at 92-95 ° C. The suspension is then cooled, filtered, washed with water and dried at room temperature.

The granulate is ground for 2 minutes at 145 ° C rolling temperature for analysis and physical testing. The yield is 91.6% 35 of theory (there is some loss of material during grinding). The amount of unreacted methacrylate-terminated polystyrene in the product is 3.3%.

65

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The samples are prepared for physical testing by briefly grinding the dried polymeric granules prior to casting the test pieces to eliminate insoluble gel. The ground products are dissolved in THF for GPC determination for 5 unreacted methacrylate-terminated polystyrene. The cast samples which were not subjected to shear stresses during grinding usually did not develop optimal physical properties. All the products for analysis are ground 2 minutes in a laboratory mill with a narrow gap and 10 at a temperature of 145 ° C. The specimens for the pressure samples are compression molded for 10 minutes at 170 ° C and a pressure of 77.3 bar. Only contact pressure is applied until the plates reach the required temperature, after which the mold is subjected to full pressure. The pressure is maintained during the cooling of the bubble-preventing mold.

The cast plates (470 µm) with 30% incorporated methacrylate-terminated polystyrene copolymer of this example are tough and transparent and the properties are described in subsequent Table VI.

25 30 35

TABLE VI

66

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Properties of 30% methacrylate-terminated polystyrene copolymer with 1: 1 EA: BA 5

Unreacted polymer (%) 3.3 THF insoluble gel content of ground and molded sample,% 0.4

Tg of acrylic elastomer component with 10 DSC, ° C -37

Water absorption, 24 hours,% approx. 0.3

Flow limit, bar (a) 25.2

Tensile strength, bar (a) 114

Fracture elongation,% (a) 475 15 Permanent elongation (% increase in initial length) (a) 35 (a) Tensile tests were performed with an Instron at 250 mm / min tensile speed.

EXAMPLE 54

Preparation of copolymer with polystyrene side chains and poly (butyl acrylate) main chain by suspension copolymerization Into a 2 liter glass flask (13 cm diameter) immersed in a controlled temperature water bath, 600 grams of an aqueous stabilizer solution is introduced. containing 600 30 grams of distilled water, 3 g of 5% Lemol 42-88 polyvinyl alcohol solution (Borden) and 3.20 g of disodium phosphate. The reactor is equipped with a capacitor, thermometer, nitrogen feed tube and an agitator with a 11 cm crescent shaped blade of 1 piece Teflon. While heating the aqueous solution, the reactor is flushed with nitrogen at a rate of 100-200 ml / min for 50 minutes. The nitrogen flow is reduced and 225.2 g of a monomer is obtained

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solution is introduced into the reactor.

The monomeric solution consists of 60.0 g of methacrylate-terminated polystyrene prepared according to Example 58 and having a molecular weight of approx. 11,000 and 140 g butyl acrylate, 28.0 g benzene (thiophene free) and 0.280 g lauroyl peroxide (Alperox or Lucido). The agitator is set so that the blade is 38 mm below the surface and agitation is started at 300 rpm, then reduced to 10,230 rpm (the monomer separates into an overall phase at slower agitation speed). The bath temperature is maintained at 62 ° C with an internal temperature of 60-61 ° C. After 1.5 hours, internal droplets are transformed into balls. The internal temperature is raised to 90 ° C after 5.5 hours and the polymerization is completed in a further 1.5 hours. The product is filtered through a 60 mesh screen, washed with distilled water and dried at room temperature.

The weight of the dried polymer beads (5-12 mm in length, 3-4 mm in diameter) is 190.7 g. After milling (2 minutes at 45 ° C) and subsequent molding of the product for 10 minutes at 170 ° C a transparent elastomer is obtained.

Subsequent Table VII illustrates the physical properties obtained by copolymerizing macromolecular 25 monomers of the invention prepared by suspension polymerization in the above manner.

30 35

TABLE VII

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Physical properties of styrene-acrylic copolymers v 5 Polymer-Float- Pull-Extend- Lasting Moment- ^) type of strength enhancement extendable gene (wt%) Comonomer (bar) (bar) (%) formation (%) finding (%) _____! S11MA 20 1: 1 EA: BA - 57.4 800 0-2 98.5 10 S11MA 25 1: 1 EA: BA 9.1 99.4 790 5 95 S11MA 30 1: 1 EA: BA 26.6 105, 0 810 40 87 S11MA 35 1: 1 EA: BA 39.2 135.1 560 50 77 S16MA 25 1: 1 EA: BA - 91.7 730 10 96.8 S16MA 25 2: 1 EA: BA - 126.0 700 23 91 15 S16MA 30 1: 1 EA: BA 18.9 116.2 550 22 91 S16MA 40 1: 1 EA: BA 85.4 151.9 400 108 S16MA 45 1: 1 EA: BA 123.2 174, 3 350 128 S11MA 45 EA 146.3 168.0 290 140 S16MA 53 BA 177.8 142.1 276 105 20 S16MA 50 1: 1 EA: BA 187.5 206.5 240 125 (a) Samples with a thickness of 441-465 µπι drawn on an Instrom at 250 mm / min.

(b)% recovery = [% extension -% permanent 25 extension /% extension] x 100.

(c) S11MA = Polystyrene, 11,000 molecular weight, methacrylate terminal group.

S16MA = Polystyrene, 16,000 molecular weight, methacrylate terminal group.

30

The above Examples 50 and 51 illustrate that the subject polymerizable polymer copolymerizes and is incorporated into the main chain polymer at a uniform rate that does not change with conversion (Table IV).

These data (Table IV) show that the original composition of the copolymer is the same as the original.

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even supply ratio = 1). The reason for this behavior of the methacrylate-terminated polymer cannot be explained, but the effect is reproducible. The results of these experiments show that with very large monomers, e.g. the macromolecular monomers at very low molar concentrations can obtain a Poisson distribution of the segments. This distribution allows a synthesis of predetermined, uniform copolymeric structures. Table V shows that the r values correspond to the r values given in the literature for this type of copolymerization.

It can be seen from Table VII that at low concentrations of macromolecular monomer (20-30%) products are obtained which are thermoplastic elastomers with good recovery. At a content of 30-45% macromolecular monomers, the products are flexible thermoplastic materials with increasing tensile strength and yield strength as well as decreasing elongation and recovery as the content of macromolecular monomer increases.

20

The acrylate copolymers with such polymers have many good applications as thermoplastic elastomers.

Eg. For example, immersion of a macromolecular monomer / EA / Ba terpolymer in machine oil for 5 days at room temperature will only give a weight gain of 0.9%. The strength and recovery of the sample is unchanged by immersion in oil. The operating temperature of these thermoplastic elastomers is estimated to be between -30 ° C and +50 ° C. The oil resistance and brittleness temperature can be modified by comonomer blend using the polymers in the copolymers. The use of polymers with higher glass transition temperatures than polystyrene will significantly increase the upper temperature limits of these products.

These products have been found to be suitable for numerous applications, such as gaskets, O-rings, seals.

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70 agents and adhesives, in contact with hydrocarbons and oils, water and glycols. The possibility of injection molding and the absence of extractable curing agents are among the advantages of the copolymers in question.

EXAMPLE 55

Preparation of a copolymer with polystyrene side chains and poly (butyl acrylate) backbone prepared by emulsion copolymerization

Stable emulsions or latexes can be prepared by copolymerizing a methacrylate-terminated polystyrene macromolecular monomer prepared according to Examples 48a, 15 and having a molecular weight of 13,000 with acrylic monomers in accordance with the following recipe:

Solution A; Distilled water (boiled, nitrogen rinsed) 476.0 g

Sodium bicarbonate solution (5%) 16.0 g 10% aqueous solution of Igepal Co-880 80.0 g

Solution B; 25

Butyl acrylate 280 g

Methacrylate-terminated polystyrene (M.W. = 13,000, Mw / Mn 1.1) 120 g

Toluene 40 g 60% active calcium dodecylbenzenesulfonate 13.6 g t-dodecyl mercaptan 0.20 ml

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Solution C:

Lauroyl peroxide solution (1.6 g in 20.0 g toluene) 21.6 g 5

The molecular weight of the copolymeric products can be increased by removing mercaptan in the prescription.

The emulsion is prepared in a 1.5 liter SS beaker, cooled in an ice bath and formed in an 8,000 rpm homogenizer. Solution A is placed in the beaker and flushed with nitrogen. The homogenizer is started and solution B is introduced over 1 minute and stirred for a further 10 minutes. Solution C is then added and the whole contents stirred for a further 2 minutes.

The emulsion is transferred to a 2-liter glass kettle equipped with four baffles, 16 x 0.6 cm and stirred with 7.6 cm 6-blade turbine stirrer. Rinse with 20 nitrogen and stir (500 rpm) while maintaining the temperature to 67 ° C.

After 5 minutes at 500 rpm the speed is reduced to 175 rpm. After 19 hours at the specified temperature, the reactor contents are cooled to room temperature.

25 The latex is filtered through cloth. The polymer formed has a solids content of 39.2% and a Brookfield viscosity at 25 ° C (LVI 60 rpm) of 11.9 cps, and a particle size of 2 micrometers, a pH of 7.6 and a freeze-melt stability of 2 cycles. Analyzes show that only 1.5% of the methacrylate-terminated polystyrene remains unchanged.

35

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EXAMPLE 56

Preparation of a copolymer with polystyrene side chains and poly (butyl acrylate) / poly (ethyl acrylate) head chains by emulsion copolymerization

An emulsion copolymerization is carried out by the same procedure as described in Example 55 using the following recipe:

Solution A:

Distilled water (boiled, nitrogen rinsed) 401.5 g

Sodium bicarbonate solution (5% solution) 17.6 g 10% aqueous solution of Igepal Co-880 77.0 g

Solution B:

Ethyl acrylate 154.0 g N-butyl acrylate 154.0 g

Methacrylate-terminated polystyrene (molecular weight = 13,000) 132.0 g

Xylene 44.0 g calcium dodecylbenzenesulfonate 12.9 g t-dodecyl mercaptan 0.07 ml

Solution C:

Lauroyl Peroxide Solution 30 (0.9 g in 22.0 g xylene) 22.9 g

As indicated above, the emulsion is prepared in the same manner as described in Example 55, but the polymerization is carried out at 55 ° C for 4 hours and terminated at 95 ° C for 2 hours.

The content of solids of butyl acrylate / ethyl acrylate / macromolecular monomer polymer latex is 43.6% and the particle size is 3.4 µm and pH = 7.5. There are 73

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no coagulate in the latex polymer, nor is there any coagulate in the polymer of Example 71.

The graft copolymers thus prepared according to Examples 55 and 56 have the same physical properties as the above-described products prepared by suspension polymerization.

EXAMPLE 57

Preparation of a copolymer with polystyrene side chains and polyacrylonitrile backbone 15 A solution consisting of 30.0 g of a methacrylate-terminated polystyrene prepared by the method of Example 48a, and having a molecular weight of 11,000, dissolved in 120.0 g of dimethylformamide containing 0.10 g of AIBN is introduced into a 1-liter bottle. Plug the bottle and rinse with nitrogen for 15 minutes. 31.5 g of acrylonitrile are injected into the bottle and the clear solution is rotated for 18 hours at 67 ° C in a polymerization bath. The bottle is then heated for 5 hours at 90-95 ° C. The viscous solution is diluted with dimethylformamide and the product is recovered as a powder by precipitation of methanol. A film molded for 5 minutes at 150 ° C had good flow properties and was yellowish but clear. The absence of opacity in the molded film clearly shows that no or little unreacted polystyrene macromolecular monomer was present when polyacrylonitrile products containing unreacted polystyrene are cloudy and opaque.

DK 160151 B; 74 EXAMPLE 58 j

Preparation of a copolymer with polystyrene side chains and polyvinyl chloride backbone 5

A methacrylate-terminated polystyrene, prepared by the method of Example 48a, and having a molecular weight of approx. 16,000 and an Mw / Mn of less than 1.1 are copolymerized essentially to end with vinyl chloride 10 by introducing the following ingredients in the order indicated in a 1-liter flask:

Distilled water 300.0 g 5% solution of polyvinyl alcohol 15 (PVAL) 3.0 g

Disodium phosphate 0.40 g

Lauroyl peroxide 0.34 g

Methacrylate-terminated polystyrene 14.56 g

Vinyl chloride 85.4 g 20

The methacrylate-terminated polystyrene and lauroyl peroxide are added to the aqueous solution of distilled water.

Lemol and disodium phosphate and the bottle is cooled in ice water. Vinyl chloride is condensed. in the bottle is caused to evaporate to obtain the correct weight and to expel air. Then the bottle is immediately sealed with a capsule with a polyester-coated butyl rubber gasket. The flask is rotated in a polymerization bath at 95 ° C, and after 19 hours of polymerization 30 excess vinyl chloride is blown off and the contents of the flask are filtered off in a Buchner funnel and rinsed with distilled water. A yield of 92.5 g of the copolymer is obtained which corresponds to a conversion of 91.2% vinyl chloride. A GPC chromatogram of the product reveals no detectable unreacted methacrylate-terminated polystyrene at 30.5 units. (The peak of the GPC chromatogram for methacrylate-terminated polystyrene with a molecular weight

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75 of 16,000 are found at 30.5 units). Accordingly, it is shown that the copolymerization of methacrylate-terminated polystyrene with vinyl chloride is substantially complete.

EXAMPLE 59

Preparation of a copolymer with polystyrene side chains and polyvinyl chloride backbone 10

A graft copolymer of methacrylate-terminated polystyrene having a molecular weight of approx. 11,000 prepared according to Example 8 with vinyl chloride is prepared by suspension copolymerization according to the following recipe: 15

Solution A:

Distilled water 150.0 g 5% solution of polyvinyl alcohol 1.5 g 20 Disodium phosphate 0.2 g

Solution B:

Methacrylate Terminated Polystyrene 50.0 g Lauroyl Peroxide 0.125 g

Vinyl Chloride 50.0 g In each of three 1-liter bottles, 150 g of the above stock solution A is introduced and the solution is rinsed with nine-trogen for 30 minutes. The methacrylate-terminated polystyrene and lauroyl peroxide are added and the bottle is cooled on ice water. A small excess of vinyl chloride is condensed in the bottle and evaporated until the correct amount of weight is obtained and to expel the air. Then the bottle is immediately closed with a polyester-coated butyl rubber gasket. The bottle is rotated in a polymerization bath at 50 ° C and 30 rpm. DK bottles are taken after 2.5 hours, 5 hours and 15.5 hours, and vinyl chloride is blown out immediately after removal of each bottle. The solids content of each bottle is filtered on a Buchner funnel and rinsed with distilled water. The product 5 is first dried in air and then in a vacuum oven at 50 ° C.

Each of the total mixtures is dissolved in tetrahydrofuran.

One portion of the tetrahydrofuran solution is used for GPC analysis and the other portion of the solution is added to 10 excess of 3: 2 cyclohexane: hexane to precipitate the copolymer. The precipitate is filtered and washed with 3: 2 cyclohexane: hexane solution to remove unreacted macro-molecular monomer. The purified copolymer is dried and subjected to a chlorine analysis. The composition of the copolymer, calculated from the chlorine content of diffraction; tioned products are given in subsequent Table j VIII.

i j i TABLE VIII | 20 |

Copolymer composition of 50:50 methacrylate-terminated polystyrene / vinyl chloride for various reactions:! VCI Copolymer Composition 25 Polymerization Conversion% Polymer% Polymer (time, hours see% (from Cl analysis) (by GPC) 2.5 4.6 94 87 5.0 9.8 88 89 30 15.5 55.4 54 63 (a) Calculated from the product yield.

Non-fractionated portions of tetrahydrofuran solution are filtered and measured. The volumes of the solutions of known substances are injected into GPC. The peaks for unreacted methacrylate-terminated polystyrene at 31.4 units of

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The chromatogram is cut, weighed, and unreacted polymer in the sample is determined. The composition of the copolymer calculated from GPC data corresponds well to the data calculated from chlorine analysis, and these calculations are also given in Table VIII.

It is seen from the above examples that the subject polymerizable macromolecular monomers provide a convenient route for preparing polystyrene copolymers with 10 vinyl chloride. These vinyl chloride copolymers do not require processing aids as the melting properties of the product are improved over the PVC homopolymers. Even at lower concentrations of polymer copolymerized with vinyl chloride, rolled sheets and 15 cast samples will have greater clarity than corresponding PVC homopolymers.

The present polymers can be copolymerized with vinyl chloride in solution, in bulk or by usual suspension polymerization under the influence of free radicals as initiators. For example, the methacrylate-terminated polystyrenes are copolymerized. with vinyl chloride by suspension polymerization at polymer concentrations of 10-50%. The copolymer mixtures of low and medium conversion samples are determined by GPC analysis of the polymeric mixture and by chlorine analysis of the fractionated samples.

A series of GPC chromatograms of the product mixtures by polymerizations with 50/50 macromolecular monomer / VCL monomer have been performed with various vinyl chloride conversions. Analyzes of these chromatograms show that the peak of the macromolecular monomer at 31.4 units disappears rapidly at the beginning of the polymerization.

In all these copolymerizations, it has been found that the major type of methacrylate-terminated polystyrene copolymerizes at 10-20% vinyl chloride conversion. Some low conversion copolymer mixtures of several monomeric starting mixtures, calculated from GPC and

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78 product performance data are given in Table IX. The last column of this table gives the theoretical instant copolymer composition, calculated from the Alfrey-Goldfinger copolymerization equation (2), assuming the r-values in the literature for methyl methacrylate (M 2) and vinyl chloride (M 2). for methacrylate-terminated polystyrene and vinyl chloride, respectively, r ^ -10 and r2 = 0.1. It is seen from these data that the copolymeric composition corresponds very well to the theoretical values within the limits of the experimental accuracy at very low molar concentrations of the macromolecular monomeric double bond.

The relative reactivities of vinyl chloride with vinyl ether-terminated polymers and with maleic acid-half-terminated polymers prepared according to Example 1a and as set forth below.

For the production of polystyrene, terminated with maleic anhydride, a stainless steel reactor filled with 2.5 liters of thiopen-free benzene is used, which is desiccated using a molecular sieve according to system Linde and with calcium hydride. The reactor is heated to 40 ° C and 0.2 ml of diphenylethylene is added to the reactor by means of a syringe. A 12.1% solution of secondary butyllithium in hexane is added portionwise to the reactor until a permanent orange-yellow color (0.7 ml) is maintained, after which an additional 22.3 ml of secondary butyllithium solution is added, followed by 221.7 g of styrene. for 30 minutes in 16 minutes. The reactor temperature is maintained at 40-45 ° C. Five minutes after the styrene addition is complete, ethylene oxide is added from a glass flask under the surface at intervals until the solution is clear.

One hour after the ethylene oxide addition is complete, 20.55 ml of maleic anhydride benzene solution is added (the maleic anhydride solution was prepared by dissolving 84 g of maleic anhydride in 55 g of purified

DK 160151B

79 benzene) for modifying the living polymer. One hour after addition of the maleic anhydride solution, the reactor contents which precipitate in methanol are discharged. The maleic acid half-ester-terminated polystyrene had a molecular weight of 5. 14,000, as determined by gel permeation chromatography. The vinyl chloride conversion and reactivity ratio of the various polymers are given in Table X. The vinyl ether terminated polymer is found to copolymerize uniformly with vinyl chloride (= 1). The methacrylate-terminated polymeric and maleic half-ester-terminated polymer copolymers with vinyl chloride, as can be predicted from the literature on the reactivity ratios of methyl methacrylate or maleic acid esters with vinyl chloride. Although the polymers are incorporated at a much greater rate than vinyl chloride and yield composition heterogeneous copolymers without the use of a particular polymerization technique, such as gradual addition, copolymerization studies of methacrylate or maleic acid half-terminated polymers with vinyl chloride will show that the terminal groups of the polymerizable polymers are controlled by the same copolymerization kinetics as the corresponding low molecular weight monomers.

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EXAMPLE 60

Preparation of a copolymer with polyisoprene side chains and polystyrene backbone in 5 a) To prepare methacrylate-terminated polyisoprene, a 3.8 liter glass flask is filled with 2.5 liters of purified hepatane, which is pre-dried with a molecular sieve according to system Linde and calcium hydride, followed by addition of 0.2 10 ml diphenylethylene as indicator and the reactor sterilized by dropwise addition of tertiary butyllithium solution (12% in hexane) until a durable characteristic of pale yellow color is obtained. The reactor is heated to 40 ° and 19.9 ml (0.025 mol) of a 12% solution of tertiary butyl lithium in hexane is injected into the reactor by injection syringe, followed by the addition of 331.4 g (4.86 mol) of isoprene. . The mixture is left at 40 ° C for 1 hour and 0.13 mole of ethylene oxide is introduced into the reactor to modify the live polyisoprene. The modified 20 live polyisoprene is maintained at 40 ° C for 40 minutes, after which 0.041 moles of methacrylyl chloride are introduced into the reactor to terminate the modified live polymer. The mixture is maintained for 13 minutes at 40 ° C, followed by removal of the heptane solution by vacuum evaporation. Based on gel permeation chromatography for polystyrene, the molecular weight of the methacrylate-terminated polyisoprene was determined to be approx. 10,000 (theoretically 13,000).

B) A 370 g portion of the 7.1% methacrylate-terminated polyisoprene comonomers prepared in Example 60a is evaporated in vacuo for 1.5 hours at 50 ° C on a rotary evaporator (6.1 g of heptane is not removed by afdrivningen).

The round bottom flask containing the concentrated 35 macromolecular monomers is closed with a septum and flushed with nitrogen. A solution of 61.2 g styrene, 6.1 g benzene (thiophene free) and 0.31 g AIBN (0.5 wt% styrene)

DK 160151 B

83 is introduced with a syringe and the macromolecular monomer is dissolved. The clear monomer solution is transferred to a syringe in a thoroughly flushed 350 ml vial containing an aqueous polyvinylpyrrolidone solution (300 g water, 0.24 g PVP, 0.3 wt%). The bottle is closed with a capsule, rinsed briefly with nitrogen and rotated at 65 ° C in a polymerization bath.

After 17.5 hours at 65 ° C, polymerize at 95 ° C for three hours.

10

The beads formed are filtered on a sieve, washed with distilled water and dried at 40 ° C under vacuum. The product is ground for 2 minutes at 150 ° C and 0.40 g of technical antioxidant is added to the rolling machine. A yield of 75.8 g of transparent rolling product is obtained. The styrene conversion is 98%.

20 25 30 1

Claims (8)

1. A copolymer with a linear main chain and linear polymeric 5 side chains, characterized in that it is made by: - a monofunctional living polymer is formed by anionic polymerization of at least one anionic polymerizable monomer in the presence of an anionic alkali metal alkyl having up to 8 carbon atoms or of phenyl-lithium or phenyl sodium as catalyst, whereby the amount of catalyst is selected such that the living polymer achieves a molecular weight of 5000-50000 and consists of at least 20 repeating monomeric units, - the living polymer reacting with a halogen-containing epoxide or thioepoxide or halogen-containing vinyl compound to form a polymer with a terminally polymerizable epoxide, thioepoxide or vinyl moiety, whereby, at least in the case of this compound, a carbonyl group is introduced into the living polymer, which is pre-reacted with 1,1-diphenyl-ethylene or a lower alkylene oxide, whereby in 2 In all cases, a small molar excess is used relative to the amount of catalyst, and - the polymer obtained is copolymerized over terminated epoxide, thioepoxide or vinyl units in a manner known per se with a comonomer. Process for the preparation of a copolymer according to claim 1, characterized in that 1 - that a monofunctional living polymer is formed by anionic polymerization of at least one anionic polymerizable monomer in the presence of an anionic alkali-alkali metal alkyl with up to 8 carbon atoms or of phenyl-lithium or phenyl sodium as catalyst, whereby the amount of catalyst is selected such that the living polymer achieves a molecular weight of 5000-50000 and consists of at least 20 repeating monomeric units, - reacting the living polymer with a halogen-containing one epoxide or thioepoxide or halogen-containing vinyl compound to form a polymer having a terminally polymerizable epoxide, thioepoxide or vinyl moiety, wherein, at least in the case of this compound, a carbonyl group is introduced into the living polymer, this is pre-reacted with 1,1-diphenyl-ethylene or a lower alkylene oxide, whereby in all cases, they use a small molar excess relative to the amount of catalyst, and - copolymerize the obtained polymer over terminated epoxide, thioepoxide or vinyl units in a manner known per se with a comonomer. Process according to claim 2, characterized in that polyoxyalkylene, vinyl polymer r polystyrene, poly (a-methylstyrene), polybutadiene or polyisoprene are produced as a living polymer. Process according to claim 3, characterized in that polystyrene is produced as a living polymer and as lithium or sodium alkyl as an anionic catalyst. Process according to claims 2-4, characterized in that for use with a living polymer, as a halogen-containing compound, epichlorohydrin or a chlorine-containing vinyl compound is used. DK 160151 B 86 Process according to claim 2, characterized in that ethylene oxide is used as lower alkylene oxide. Process according to claim 6, characterized in that segments of vinyl polymers, polydienes, polyolefins or condensation polymerisers are formed in the copolymerization of the comonomer with the polymer. Process according to claim 7, characterized in that, as a comonomer, a vinyl compound, a diene, a polyisocyanate or a polycarboxylic acid are used. 15 20 25 30 35