SE405010B - IMPACT POLYMERS BASED ON SIDE CHAINS DERIVED FROM ANJONIC POLYMERIZABLE MONOMERS, VIKA IS TERMINATED WITH AN ASSOCIATION CONTAINING A CO-POLYMERIZABLE VINYLEN GROUP AND A BASIC SUBMARGE THAT INCLUDES ... - Google Patents

Description

vznz g 2 _ Most polymers; both natural and synthetic, are incompatible with each other. This has become more and more apparent as more and more polymers with particularly good properties for particular uses have become available and attempts have been made to combine pairs of these polymers with a view to incorporating the various good properties of each polymer in a product. These efforts have more often been unsuccessful than successful because the resulting blends have shown instability and, in many cases, the desired properties of the two polymers have been completely lost. For example, polyethylene is incompatible with polyisobutylene and a mixture of these two has poorer physical properties than either of the homopolymers. These failures were initially attributed to incomplete mixing procedures, but eventually it turned out that the failure was simply due to inherent incompatibilities. Although it is now considered that this is a correct explanation, the general nature of such incompatibilities has remained somewhat unclear even to this day. Polarity seems to be a factor, ie. two polar polymers are more likely to be compatible than a polar polymer and a non-polar polymer. The two polymers must also be somewhat similar in structure and composition if they are to be combinable. Furthermore, a particular pair of polymers may be compatible only within a certain range of relative proportions of the two polymers; outside this area they are incompatible.

Despite the general acceptance of the fact that incompatibility prevails for polymer pairs, there is great interest in developing methods by which the advantageous properties of combinations of polymers can be combined in one product.

One way in which attempts have been made to accomplish this involves the preparation of block or graft polymers. In this way, two different polymer segments are chemically combined which are normally incompatible with each other and give a kind of forced compatibility. Thus, in many cases, the block or graft polymer has a combination of properties not normally found in a homopolymer or a random copolymer. However, reliance on block polymer or graft polymer has its limitations when it comes to block polymer since only those monomers that allow anionic polymerization can be used and this eliminates a lot of potential polymeric segments. In the case of the graft polymers which have previously been available, these are always characterized by the presence of a substantial amount of homopolymer, either by the original homopolymer backbone or by the graft monomer. To the extent that such a homopolymer is present, it not only serves as a diluent but also significantly reduces the efficiency of the desired properties sought to be incorporated into the graft polymer. The object of the present invention is to achieve. graft polymers which have side chains of predetermined molecular weight, which are relatively free of homopolymers and which have new combinations of physical properties.

A further object of the present invention is to provide a process for the preparation of such graft polymers.

The present invention also provides controlled molecular weight polymerizable monomers having only one polymerizable group per monomer unit, which monomers are reactive for free radical, ionic or condensation polymerization reactions.

These objects of the invention are achieved by a graft polymer having a linear copolymer backbone and polymeric side chains of relatively uniform molecular weight, the bonding sites of adjacent pairs of said side chains to the backbone being separated by continuous segments of said backbone of at least about 20 recurring monomers. .

The present graft polymers differ from those previously available in that the polymeric side chains are first prepared by the anionic polymerization method. Such a method gives a living polymer which can be terminated by reaction with a halogen-containing compound and by selecting a suitable terminating agent a polymer having a polymerizable end group can be obtained. This polymer itself can be further polymerized to produce graft polymers of the type described above. Alternatively, copolymerization of this high molecular weight polymerizable compound with a second compound, usually of relatively low molecular weight, also yields a graft polymer of this type.

Particularly suitable graft polymers of this type are those in which the copolymer backbone and the polymeric side chains are thermodynamically incompatible. Such graft polymers are obtained when the continuous polymer segments in the copolymer backbone and in the polymeric side chains are large enough to impart to the graft polymer the physical properties characteristic of the polymers corresponding to these polymeric segments. In general, for this purpose, the polymeric segment, whether it forms part of the backbone or the side chain, should consist essentially of at least 20 continuous recurring monomeric units and preferably at least about 30 recirculating monomeric units.

The graft polymers of the present invention assume a "T" type structure when only one side chain is copolymerized into the copolymer backbone. However, when more than one side chain is copolymerized into the backbone polymer, the graft polymer may be characterized as having a comb-type structure illustrated as follows: wherein "a" denotes a substantially linear polymer or copolymer having a uniform molecular weight having a sufficient molecular weight to produce the physical properties of at least one of the substantially linear polymers; "b" denotes a reacted and polymerized end group chemically bonded to the side chain, "a", which is integrally polymerized into the backbone polymer, and "c" is the backbone polymer having continuous segments of sufficient molecular weight so that they The physical properties of the polymer are obtained.7 The preparation of these graft polymers begins, as stated above, with anionic polymerization of a polymerizable monomer.

In most cases, such a monomer is one having an olefinic group.

The monomers prone to anionic polymerization are well known and the present invention encompasses the use of anionically polymerizable monomers selected from styrene, 4-methylstyrene, isoprene and butadiene.

The catalyst for these anionic polymerizations is an alkali metal alkyl wherein the alkylene is a lower alkyl, i.e. an alkyl containing 8 or fewer carbon atoms. The butyllithium compounds are preferred, especially secondary butyllithium. Lower alkyl lithium compounds and lower alkyl sodium compounds are particularly suitable. Other suitable catalysts include isopropyl lithium, ethyl sodium, n-propyl sodium, n-butyl potassium, n-octyl potassium, n-butyllithium, ethyl lithium, t-butyllithium and 2-ethylhexyl lithium. The alkali metal alkyls are either commercially available or can be prepared by known methods. Phenyllithium, phenyl sodium, etc. can also be used as a catalyst and they are likewise conveniently available by reacting bromobenzene and the appropriate alkali metal.

The amount of catalyst is an important factor in anionic polymerization due to the fact that it determines the molecular weight of the living polymer. If a small proportion of catalyst is used, with respect to the amount of monomer, the molecular weight of the living polymer will be greater than if a large proportion of catalyst were used.

In general, it is advisable to add the catalyst dropwise to the moments (when this constitutes the selected addition order) until the characteristic color of the organic anion persists, and then add the calculated amount of catalyst. The preliminary dropwise addition serves to destroy impurities and thus allows better control of the polymerization.

The anionic polymerization must be carried out under carefully controlled conditions so that moisture and other impurities are excluded. The monomer and catalyst must be freshly purified and the apparatus in which the polymerization is to be carried out must be thoroughly cleaned. Procedures for cleaning the reactants and cleaning the reaction equipment are well known and need not be described here. The alkali metal catalyst can be added to the monomer or the monomer can also be added to the catalyst. One solvent was usually used to facilitate heat transfer and suitable mixing of catalyst and monomer. The solvent must be inert. Hydrocarbons and ethers are preferred including benzene, toluene, dimethyl ether, diglyme, glyme, diethyl ether, tetrahydrofuran, N-hexane, cyclohexane and N-heptane. The temperature of the polymerization will depend on the monomer. The polymerization of styrene is usually carried out at a temperature slightly above room temperature; the polymerization of ck-methylstyrene is preferably carried out at -80 ° C. The temperature of the anionic polymerization is not a critical feature of the present invention.

The polymeric product constitutes a so-called "living polymer", i.e. it is not terminated in the usual sense that this term is used in polymer chemistry but is susceptible to further reaction involving further polymerization. The anionic polymerization is illustrated by the following equation in which styrene is polymerized with secondary butyllithium: sec-BuL1 + n CH2 = CH _¿.sec-Bu C CH CHZCH Li ö nl '? 2fl20 ~ 75-3 pi 6 About styrene If the above living polymer is added, the polymerization is renewed and the chain grows until no additional monomeric styrene remains. Alternatively, if another differently polymeric polymerizable monomer is added, such as butadiene, the above living polymer initiates the polymerization of the butadiene and the final living polymer obtained as a result consists of a polystyrene segment and a polybutadiene segment. The living polymer can be terminated by reaction with a halogen-containing compound. Termination of the above living polystyrene with methyl iodide is illustrated by the following equation: _ f + se? -Bu-CHèCH_ CHZCH + CH3I-9880-Bu CHéCH .CHÉCHCH3 + Lil n-l n-1 Living polymers are characterized by relatively uniform molecular weight, ie. the molecular weight distribution in an average living polymer is really narrow. This is in sharp contrast to the typical polymer in which the molecular weight distribution is really wide.

An important feature of the present invention is the molecular weight unit for the side chains of the graft polymer and this molecular weight unit is present in the living polymer which is prepared as the first step in the overall synthesis of these graft I polymers. A particularly preferred embodiment of the invention consists of graft polymers containing side chains having an average molecular weight of from about 5,000 to about 50,000.

The present living polymers are terminated by reaction with a halogen-containing compound which also contains a polymerizable olefinic group. Suitable halogen-containing terminating agents include vinyl haloalkyl ethers wherein the alkyl groups contain 6 or fewer carbon atoms, vinyl esters of haloalkanoic acids wherein the alkanoic acid contains 6 or fewer carbon atoms, allyl halides, acrylyl halides, methacrylyl halides. The halogen group may be chlorine, fluorine, bromine or iodine, preferably chlorine. Termination of the living polymer by any of the above types of terminating agent is carried out simply by adding the terminating agent to the living polymer solution at the temperature at which the living polymer is prepared, the reaction is immediate and the yield is theoretical. A slight molar excess of the terminating agent, with respect to the amount of catalyst, was used even if the reaction proceeds on a molar-to-molar basis.

The following equations illustrate tynical reactions in accordance with the practice of the present invention: i r i -__ 1 e- e. _-1_ '- 1 r a? _ R ..... CH2 _CH_ + CS7 + L¿L @ Termination agent: H3 'v (a) xa --0-G ~ - <_ 1ß * 2 h, n _ “. 0Z _ hi fl im" m.nH ll i '' i * za x-: ïxßrt-ncdefeneovr fsëzf _ _ .___......_..., _....._......; ..... _ _- ..-.- _. ._ ._ l.., _ '. R4 _-- ll (d) X-- cc = cuz ii ~ ~ inf. -k ja) 3 -f- fl - «l: ~ --- «- c * .r2 ~ -__- '- m3» c-çg n GHz R2_n LZ R-'w. 111 nl F »I ¿3s- (e). .N-Ecfzï- (lzz n c.12-Ti-a - <|: 4-i C112 nn 'R _ dvznzovs-3 ie 8 1 -'1 n _ RO' i 1 _ e | u (a) n caf-c csfT-c R 2 In the above equations, R 1, R 1, R 2, R 3 and R 4 are all selected from the group consisting of hydrogen and lower alkyl and aryl groups. R will preferably be lower alkyl, such as secondary butyl. ; R 1 will be either hydrogen or methyl; R 2 will be phenyl; R 3 will be hydrogen or lower alkylene group and R 4 will be either hydrogen or lower alkyl group. "In some cases, depending on the nature of the living polymer, and these monomers from which it is made, or depending on the character of the terminating agent, it is advisable to seal the living polymer with a reactant, such as a lower alkylene oxide, i.e. one containing 8 or fewer carbon atoms, or diphenylethylene.

This closure reaction produces a product which is still a living polymer but which is less susceptible to reaction with functional groups or any active hydrogen atoms of a terminating agent. Thus, while serving as a terminating agent due to the presence of the chlorine atom in its structure, acrylic chloride also provides a carbonyl group in the terminated polymer chain and this carbonyl group can provide a center for attack by a second living polymer. The use of acrylic chloride as a terminating agent is greatly facilitated if the living polymer is first sealed, then reacted with the acrylic chloride. The resulting living polymer is a substantially pure vinyl ester, i.e. a living polymer which has been terminated with a molecule of acrylic chloride.

If no sealant is used in this intermediate step, the resulting polymer either has twice the expected molecular weight or contains some chlorine, indicating that a portion of the living polymer has been terminated by reaction with a second living polymer or with one of the active hydrogen atoms of the acrylic chloride; A particularly preferred sealant is ethylene oxide.

It reacts with the living polymer during decomposition of its oxirane chain as follows: six-nu Harbor CHZÉH åäö n ~ l 7202075-3 __ + Li + cëínè -> sek-Bugagor: "Pgon-caacsao m 'o Û nl' Above equation shows the reaction of the ethylene oxide as a sealing reagent with a living polymer prepared by polymerizing styrene with secondary butyllithium.

The sealing reaction is carried out simply, as is the case with the termination reaction, by adding the sealing reagent to the living polymer at polymerization temperature.

The reaction occurs immediately. As with the termination reactant, a negligible molar excess of the closure reactant was used with respect to the amount of catalyst; The reaction occurs on a molar-to-molar basis.

It should be noted that the reaction of the living polymers with the above termination reagents gives products which, while not constituting living polymers, are themselves further polymerizable. Such further polymerization can proceed through the double bonding of the terminating agent so that the terminating agent thus serves as a Y in the formation of a graft polymer. It should further be noted that these graft polymers, while their structure generally adheres to that of the prior art graft polymers, are prepared in a truly different manner from the prior art graft polymer production process. In addition, they are significantly different structurally. Prior to the present invention, graft polymers were prepared by synthesizing a linear "backbone", after which growing polymer chains were grafted to this backbone and the final result was a backbone having a plurality of adhering polymer chains. The graft polymers of the present invention are prepared. on the other hand, by first synthesizing these adherent polymeric chains (the living polymers) after which the end portions of these polymeric chains are polymerized into a backbone, i.e. the adhering chains, i.e. the side chains, are synthesized first, then the backbone. While apparently the two types of graft polymers are generally similar, the different compositions are not only due to the fact that they are prepared by significantly different methods but also due to the fact that the adhering polymer chains of the graft polymers according to the present invention is of relatively e uniform, minimum length and all form an integral part of the base frame and due to the fact that the base frame contains polymeric segments of a certain minimum length, these properties contribute greatly to the advantageous properties belonging to these new graft polymers.

As previously stated, the graft polymers of the present invention have unique properties and unique combinations of properties. These unique properties and combinations of properties are made possible by the present new process which produces the compatibility of otherwise incompatible polymer segments. The advantageous properties of a polystyrene can thus be combined with the advantageous properties of a polymethyl acrylate, although these two polymers are normally incompatible with each other and only physical mixtures of these have very little strength and are not usable. In order to combine these advantageous properties in a product, it is necessary that the different polymer segments are present as relatively large segments. The properties of polystyrene do not become apparent until the polymer consists essentially of at least about 20 recurring monomer units. The same relationship applies to the polymeric segments present in the graft polymers referred to herein, i.e. if a polystyrene block comprising a graft polymer is to be characterized by the advantageous properties of polystyrene, these polystyrene segments must then individually consist of substantially at least about 20 recurring monomer units. This relationship between the physical properties of a polymeric segment and its minimum size is applicable to all the polymeric segments of all graft polymers referred to herein.

In general, the minimum size of a polymeric segment associated with the appearance of the physical properties of said polymer in the graft polymers referred to herein is that of about 20 recurring monomer units. The polymeric segments, both of the copolymer backbone and of the side chains, should preferably, as previously indicated, consist essentially of more than about 30 recurring monomer units. These polymeric segments may themselves be homopolymeric or they may be copolymeric.

The graft polymers comprising polymeric segments having less than about 20 recurring monomeric units are no less useful for many applications, but the preferred graft polymers are those in which the various polymeric segments contain at least about 20 recurring monomeric units. Although, as indicated, the graft polymers referred to herein are characterized by a wide variety of physical properties, depending on the particular monomers used in their preparation and also on the molecular weight of the various polymeric segments within a particular graft polymer, all of these graft polymers are suitable, as a minimum, as tough, flexible, self-supporting films. These films can be used as packaging materials for foodstuffs, drip protection during painting, protective covers for commercial products that are signposted and the like.

The invention is further illustrated by the following examples.

In all cases all materials must be clean and care must be taken to keep the reactant mixtures dry and free from impurities. All parts and percentages are by weight unless otherwise indicated.

Example 1

A solution of a drop of diphenylethylene at 40 ° C is treated portionwise with a 12% solution of t-butyllithium in pentane until a residual light red color is obtained at which point 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 living polystyrene is terminated by treatment with 8 ml (0.08 mol) of vinyl 2-chloroethyl ether. The resulting polymer is precipitated by adding the benzene solution to methanol and the polymer is separated by filtration. Its number average molecular weight, determined by vapor phase osmometry, is 7,200 (theoretical value: 7870) and the molecular weight distribution is very narrow, ie. Mw / Mn is less than 1.06.

Example 2. Preparation of polystyrene terminated with vinyl chloroacetate.

A solution of 1 drop of diphenylethylene in 2,500 ml of cyclohexane at 40 ° C is treated portionwise with a 22% solution of sec-butyllithium in cyclohexane until a residual light red color is obtained at which point an additional 18 ml (0.024 mol) of sec. butyllithium 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 living polystyrene is sealed by treatment with 8 ml (0.040 mol) of diphenylethylene, after which it is terminated by treatment with 6 ml (0.05 mol) of vinyl chloroacetate. The resulting polymer is precipitated by adding the cyclohexane solution to methanol and the polymer is separated by filtration. Its number average molecular weight, determined by vapor phase osmometry, is 12,000 (theoretical value: 13,265) and the molecular weight distribution is very narrow, ie. Mw / Mn is less than 1.06.

Example 3. Preparation of polystyrene terminated with epichlorohydrin.

A benzene solution of living polystyrene is prepared in Example 1 and terminated by treatment with 10 g (1.0 mol) of epichlorohydrin. The resulting terminated polystyrene precipitates with methanol and is separated by filtration. Its molecular weight, obtained by vapor-phasosmometry, is 8,660 (theoretical value: 7,757) and its number-average molecular weight distribution is very narrow. Example 7 Preparation of poly («$ - methylstyrene) terminated with vinyl chloroacetate. 5 gp A solution of 357 g (3.0 mol) of 04-methylstyrene in 2,500 ml of tetrahydrofuran is treated dropwise with a 12% solution of t-bntyllithium in pentane until a residual light red color is obtained.

Then an additional 15.0 ml (0.03 mol) of the t-butyl solution is added, resulting in the development of a bright red color. The temperature of the mixture is then 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 (<$ - methylstyrene) is precipitated with methanol and separated by filtration. Its number average molecular weight, determined by vapor phase osmometry, is 14,280 (theoretical value: 12,065) and the molecular weight distribution is very narrow.

Example 5. Preparation of poly (ppmalkylstyrene) terminated with allzyl chloride.

A solution of 472 g (4.0 moles) of d-methylstyrene in 2,500 ml of tetrahydrofuran is treated dropwise with a 12% solution of n-butyllithium in hexane until a residual light red color is obtained.

An additional 30 ml of this n-butyllithium solution is added, resulting in the development of a bright red color. The temperature of the mixture is then lowered to -80 ° C and after 30 minutes at this temperature 4.5 g (0.06 mol) of allyl chloride are added. The red color disappears almost immediately, indicating termination of the living polymer. The resulting colorless solution is poured into methanol to precipitate the terminated poly (o-methylstyrene) which by vapor phase osmometry is shown to have a number average molecular weight of 11,000 (theoretical value: 12,300).

Example Sa).

The procedure of Example 1 is repeated except that instead of vinyl 2-chloroethyl ether, an equivalent amount of metalallyl chloride is used as the terminating agent to produce a metalyll terminated polystyrene having the following structural formula: CHBCHZ (C33) CH ÄH - CH CH CH ; ° 2 2 'DT =' _ L Û “ß '_41 3> 7202075-3 Example 6. Preparation of polystyrene terminated with methacrylyl chloride. To a solution of 0.2 ml of diphenylethylene in 2,500 ml of benzene is added dropwise a 12% solution of n-butyllithium in hexane until a residual light reddish brown color is obtained. An additional 24 ml (0.03 mol) of this n-butyllithium solution is added and then 416 g (4.0 mol) of styrene, resulting in the development of an orange color. A temperature of 40 ° C is maintained at all times by external cooling and by controlling the rate at which the styrene is added. This temperature is maintained for a further 30 minutes after all the styrene has been added and then lowered to 20 ° C, whereupon 4.4 g (0.1 mol) of ethylene oxide are added, which causes the solution to become colorless. The living polystyrene is terminated by reaction with 10 ml (0.1 mol) of methacrylyl chloride. The resulting polymer has a number average molecular weight of 10,000 determined by vapor phase osmometry.

Acrylyl chloride can be used instead of methacrylyl chloride in the above process to give an acrylic acid ester end group on the polystyrene chain.

Examples 1-6 show the preparation of terminated living polymers. These were used as starting materials in the procedures of Examples 7 to 14 for the preparation of graft polymers. The terminated living polymers appear as chain sides in the graft polymer, the polymerizable end group of the terminated living polymer ending as an integral part of the backbone of the graft polymer.

Example 6 (a). Preparation of polybutadiene terminated with allyl chloride. C.P. grade 1,3-butadiene (99.0% purity) is condensed and collected in 0.47 liter soda bottles. These bottles had been oven dried for 4 hours at 150 ° C, purged with nitrogen under cooling and encapsulated with a perforated metal crown capsule using butyl rubber and polyethylene film spacers. These bottles containing butadiene are stored at -10 ° C with a nitrogen pressure (0.70 kp / cm 2) in a laboratory freezer before use. Hexane solvent is charged to the reactors and heated to 50 ° C, followed by the addition of 0.2 ml of diphenylethylene by means of a syringe. Secondary butyllithium is added dropwise via syringe to the reactor until the red diphenylethylene anion paint remains for at least about 10-15 minutes. The reactor temperature is lowered to 0 ° C and 328.0 g of butadiene is charged to the polymerization reactor, followed by the addition of 17.4 ml (0.02-187 mol) of a 12% secondary butyllithium solution in hexane when half the butadiene charge has been added to the reactor. The butadiene is polymerized for 18 hours in hexane at 50 ° C. After the polymerization, 400 ml batches of the anionic polybutadiene solution are transferred into the reactor under nitrogen pressure into encapsulated bottles. Allyl chloride (0.48 mL, 0.00588 mol) is injected into each of the vials. The bottles are fixed in a water bath at temperatures of 50 ° C and 70 ° C for times varying up to 24 hours.

The samples in each of the bottles are stopped in a short time with methanol and Ionol solution and analyzed by gel permeation chromatography. Each of the samples is water clear and analysis of the gel permeation chromatography scans shows that each of the samples had a narrow molecular weight distribution.

Several comparative tests were performed on vials coming from the same batch of live polybutadiene, which were encapsulated with 1-chlorobutane (0.4 ml, 0.00376 mol) as a terminating agent. The resulting polymers terminated with 2-chlorobutane were yellow in color and, after standing for 24 hours at 70 ° C, were found to have a broad molecular weight distribution as revealed by the gel permeation chromatography scan. It is obvious that the reaction and reaction product of 2-chlorobutane with anionic polybutadiene differs from the reaction and reaction product of allyl chloride and anionic polybutadiene. Example 6 (b). Preparation of methacrylate terminated polyisoorene.

A 3.78 liter Chemco glass reactor is charged with 2.5 liters of purified heptane pre-dried with a Linde molecular sieve and calcium hydride, followed by the addition of 0.2 ml of diphenylethylene as an indicator and the reactor is sterilized by dropwise addition. of tertiary butyllithium solution (12% in hexane) until the characteristic light yellow color is obtained. The reactor is heated to 40 ° C and 19.9 ml (0.025 mol) of a 22% solution of tertiary butyllithium in hexane is injected into the reactor via syringe, followed by the addition of 331.4 g (4.86 mol) of isoprene. The mixture is allowed to stand for 1 hour at 40 ° C and 0.13 mol of ethylene oxide is charged to the reactor to encapsulate the living polyisoprene. The encapsulated living polyisoprene is kept at 40 ° C for 40 minutes after which 0.041 mol of methacrylyl chloride is charged to the reactor to terminate the encapsulated living polymer. The mixture is kept for 13 minutes at 40 ° C followed by removal of the heptane solvent by vacuum stripping. Based on gel permeation chromatography scans for polystyrene, the molecular weight of the methacrylate terminated polyisoprene according to gel permeation chromatography was approximately 10,000 (theoretical value: 13,000). The methacrylate terminated eng \ c - c. (m3 ./ 'CH \\ H n 3 Example 6 (c) Preparation of QL-olefin-terminated polyisoprene.

In a 3.78 liter Chemco glass reactor is charged 2.5 liters of purified heptane which has been pre-dried with a Linde molecular sieve and calcium hydride, followed by the addition of 0.2 ml of diphenylethylene as an indicator. The reactor and solvent are sterilized by the dropwise addition of tertiary butyllithium solution (12% in hexane) until the characteristic light yellow color is obtained. The reactor is heated to 40 ° C and 19.03 ml (0.02426 mol) of tertiary butyllithium solution is injected into the reactor via syringe, followed by the addition of 315.5 g (4.63 mol) of isoprene. The polymerization is allowed to proceed at 50 ° C for 66 minutes and at this time 2.0 ml (0.02451 mol) of allyl chloride is added to the living polyisoprene. The terminated polyisoprene is kept at 50 ° C for 38 minutes after which the polymer is removed from the reactor for use in copolymerization reactions. The polymer was analyzed by gel permeation chromatography and had a very narrow molecular weight distribution, i.e. a fi w / A less than about 1.06.

The theoretical molecular weight of the polymer is 13,000. The polymerizable macromolecular monomer has a structural formula corresponding to the following: 1 CH 5 CH 2 (CH 3) CH GHz cag one-ca = ena 1 = C - _ jCH 3 \\ H n 'Exemnel_6 (d).

Acrylyl chloride was used in place of methacrylyl chloride in the procedure of Example 6 to give an acrylic acid ester-terminated polystyrene having the following structural formula: "3 2 2 2 2 i 2 2 2 __. ! Example 7. Preparation of graft polymers from polystyrene terminated with vinyl 2-chloroethyl ether and ethyl acrylate.

To a solution of 18 g of octylphenoxy polyethoxyethanol (emulsifier) in 100 g of deionized water is added with vigorous stirring in a Waring-Blender apparatus a solution of 30 g of the polystyrene product of Example 1 and 70 g of ethyl acrylate. The resulting dispersion is purged with nitrogen and then heated with stirring at 6500 whereupon 0.1 g of ammonium persulphate is added to initiate the polymerization.

Then 200 g of ethyl acrylate and 0.5 g of 2% aqueous ammonium persulfate solution are added portionwise over a period of 3 hours, keeping the temperature at 65 ° C at all times. The resulting graft polymer emulsion is cast on a glass plate and allowed to air dry at room temperature to form a flexible, self-supporting film. The film is found to contain polystyrene segments by extraction with cyclohexane which dissolves polystyrene; the cyclohexane extract gives no residue on evaporation. _ _ '.

Example 8. Preparation of polymer polymer of poly (4-methylstyrene) terminated with vinyl chloroacetate and butyl acrylate.

A solution of 50 g of poly (ac-methylstyrene) macromer terminated with vinyl chloroacetate and having an average molecular weight of 12,600 and 450 g of butyl acrylate in 100 g of toluene is purged with nitrogen at 70 DEG C. and then treated with 1 g of azobisisobutyronitrile. The temperature is maintained at 70 ° C for 24 hours to give a solution of graft polymer which is cast as a film on a glass plate. The dried film is slightly tacky and is found to contain polystyrene segments by extraction with cyclohexane and evaporation of the cyclohexane extract as above. In Example 9. Preparation of graft polymer. of polystyrene macromer terminated with methacrylyl chloride and ethyl acrylate.

A mixture of 21 g of polystyrene macromer terminated with methacrylyl chloride and having an average molecular weight of 10,000 is prepared in the same manner as in Example 6. 28 g of ethyl acrylate and 0.035 g of azobisisobutyronitrile are prepared at room temperature and kept for 18 hours under nitrogen. at 67 ° C. The resulting product is a tough, opalescent material that can be formed at 160 ° C to produce clear, tough, transparent sheets.

Example 10 Preparation of a graft polymer of poly (O {-methylstyrene) terminated with allyl chloride and ethylene.

A solution of 20 g of poly (OK-methylstyrene) macromer terminated with allyl chloride and an average molecular weight of 27,000 prepared in the same manner as in Example 5 in 100 ml of cyclohexane is prepared and treated with 17 ml of vzozovsez 5.5 ml of 0.645 M-diethylaluminum chloride in hexane and 2 ml of vanadium oxytrichloride, then pressurized with ethylene to 3.1 kp / cm 2. This system is stirred gently for about 1 hour at 30 ° C after which a polymeric material precipitates from solution. It is recovered by filtration and pressed into a thin transparent film, which is tough and flexible.

Claims (14)

'f? -2 fl207'5 -3. t 1.81 'Z i i' PATENT CLAIMS Graft polymer suitable for the production of belts having a backbone and side chains therefrom, characterized in that (a) the side chains have a narrow molecular weight distribution and molecular weights in the range of 5,000-50,000, which side chains comprise a residue of an anionic alkali metal alkyl polymerization initiator, at least 20 polymerized units of at least one anionically polymerizable monomer selected from styrene, o (-methylstyrene, butadiene and gisoprene, optionally a closure agent selected from a lower alkylene oxide and 1.1 -diphenylethylene, and a terminating group having a copolymerizable vinyl end group derived from vinyl haloalkyl ethers wherein the alkyl group contains 6 or fewer carbon atoms, vinyl esters of haloalkanoic acids wherein the alkanoic acid contains 6 or fewer carbon atoms, allyl halides, methallyl halides, acrylic halides, acrylic halides; b) t the backbone comprises polymerized units of the copolymerizable the vinyl end group of the side chains and at least one ethylenically unsaturated backbone-forming monomer selected from ethyl acrylate, butyl acrylate, isobutylene and ethylene, the side chains being located 2. With spaced spaces at substantially regular intervals along the backbone and separated by at least about 20 continuous units of the backbone forming monomer. A graft polymer according to claim 1; k-ä n n e t e c k n a d in that the remainder of the anionic polymerization initiator is a secondary butyl group. 'l J The graft polymer according to claim 1, characterized in that the sealing agent is an ethyleneoxy group. Inoculum polymer according to Claim 1, characterized in that the anionically polymerizable monomer is styrene, the termination group is -CH 2 CH 2 OCH = CH 2 and the backbone-forming compound is ethyl acrylate. 'f t5. polymer according to claim 1, k ä n n e t e c k n a d 5. The terminating group is -CH 2 -C-O-CH = CH 2 and the backbone-containing compound is butyl acrylate. Inoculum polymer according to Claim 1, characterized in that the anionically polymerizable monomer is d-methyl, in that the anionically polymerizable monomer is demethyl. Styrene, the terminating group is -Cäå-CH = CH2 and the backbone-forming compound is ethylene. Inoculum polymer according to Claim 1, characterized in that the anionically polymerizable monomer is styrene, the sealant is ethylene oxide, the terminating group is E - -C = CH 2 H 2 Cs and the backbone compound is ethyl acrylate. A process for preparing a graft polymer according to claim 1, characterized in that a living polymer is prepared by polymerization in an inert solvent of at least one anionically polymerizable, ethylenically unsaturated monomer selected from the type, d-methylstyrene, butadiene and isoprene, in the presence of an anionic alkali metal alkyl polymerization initiator for the production of monofunctional living polymers having a molecular weight in the range of 5,000-50,000 and a narrow molecular weight distribution, react the monofunctional living polymer which may eventually a sealant selected from a lower alkylene oxide and 1,1-diphenylethylene, having a halogen-containing vinyl compound selected from vinyl haloalkyl ethers wherein the alkyl group contains 6 or fewer carbon atoms, vinyl esters of haloalkanoic acids wherein the alkanoic acid contains 6 or fewer carbon atoms, allyl halides , methallyl halides, acrylyl halides and methacrylyl halide for producing a macromolecular monomer having a copolymerizable vinyl end group and then copolymerizing said copolymerizable vinyl end group with at least one ethylenically unsaturated backbone-forming monomer selected from ethyl acrylate, butyl acrylate, isobutylene and ethylene, the side chains having at least 20 the anionically polymerizable monomer and are spaced at substantially regular intervals along the backbone and are separated by at least about 20 continuous units of the backbone-forming monomer. 9. A process according to claim 8, characterized in that the anionic polymerization initiator is secondary butyllithium. 10. A method according to claim 8, characterized in that the sealing agent is ethylene oxide. 11. ll. Process according to Claim 8, characterized in that the anionically polymerizable monomer consists of styrene, the halogen-containing vinyl compound consists of vinyl 2-chloroethyl ether and the backbone-forming monomer consists of ethyl acrylate. 12. -12. A process according to claim 3, wherein the anionically polymerizable monomer is α-methylstyrene, the halogen-containing vinyl compound is vinyl chloroacetate and the backbone monomer is butyl acrylate. 13. A process according to claim 8, characterized in that the anionic polymeric monomer is α-methylstyrene, the halogen-containing vinyl compound is allyl chloride and the backbone monomer is ethylene. 14. A process according to claim 1, wherein the anionically polymerizable monomer is styrene, the sealant is ethyleneoxy, the halogen-containing vinyl compound is methacrylyl chloride and the backbone compound is ethyl acrylate. l '. PROMISED PUBLICATIONS: US 3,029,221 (260-45.5), 3,078,254 '(26Ü-45.5), 3,135,716 (260-45.5), 3,135,717 (260-4S¿5), 3,235,626 (260- 881), 3 627 837 (260-836)