SU694078A3 - Method of preparing crafted copolymers - Google Patents

Description

one

This invention relates to the synthesis of high molecular weight compounds, in particular, to the preparation of graft copolymers, and can be used in the chemical and petrochemical industries.

A known method for producing graft copolymers by polymerization or copolymerization of 5-99 parts by weight of monomers selected from the group containing ethylenically unsaturated compounds and eocyanat in an aqueous medium or organic solvent under the action of free-radical polymerization initiators or catalysts in the presence of 1-95 weight. h functional polymers containing polymerizable end groups 1, with the said groups being vinyl and functional polymers having a molecular weight distribution greater than 1.1,

The disadvantage of this method is the relatively low physicomechanical properties of the polymers obtained, since Along with grafted polymers, homopolymers are formed and the lateral grafted polymer units have a wide molecular weight distribution.

The aim of the invention is to improve the physicomechanical properties of the polymers obtained. This is achieved by the fact that in the known process for the preparation of graft copolymers by polymerization or copolymerization 99-5 parts by weight monomers, monomers selected from the group containing ethylenically unsaturated compounds and isocyanates in an aqueous medium or organic solvent medium under the action of free-radical initiators or polymerization catalysts in the presence of 1-95 parts by weight. functional polymers containing polyepylene end groups, as the latter, use chain-chain or alkylene oxide polymers containing one terminal olefin, epoxy or thioepoxy group per macrompector, with a molecular weight of 5,000 to 50,000 and a molecular weight distribution of 1.0- 1.1.

The functional polymers are monofunctional polymerizable macromolecular monomers of the general formula:

,, X,

where R is a lower alkyl group.

iZh

macromolecule of carboxylic or alkylene oxide polymer is a positive integer,

n is a value equal to at least about 20, and

X polymerizable end group containing a unit selected from a series of olefinic, epoxy, and thioepoxy groups. This macromolecular monomer has a substantially uniform molecular weight distribution, so that its ratio has a value less than about 1.1, where MNJV is the weight average molecular weight of the macromolecular monomer, and M is the average molecular weight of the macromolecular monomer. These macromolecular monomers are obtained by anionic polymerization or copolymerization of ethylenically unsaturated compounds and / or alkylene oxides in the presence of, for example, alkyl lithium catalysts followed by chain termination by the interaction of the living polymers with halogen-substituted ethylenically unsaturated compounds, epoxides or thioepoxides.

Monomers to be anionically polymerized include, for example, vinyl aromatic compounds, in particular styrene, c-methyl styrene, vinyl toluene and its isomers; vinyl unsaturated amides, in particular acrylamide, methacrylamide, N, N-dialkylacrylamide E, for example N, Y dimethylacrylamide; acenaphthalene; 9-acrylcarbazole; acrylonitrile and methacrylonitrile; alkyl and allylacrylates and methacrylates, including methyl, tert. . butyl acrylates and methacrylates; lower olefins, such as ethylene, propylene, butylene, isobutylene, pentene, hexene, etc .; vinyl ether rxj of aliphatic carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl octoate, vinyl oleate, vinyl stearate, vinyl benzoate; lower vinyl alkyl esters; vinshiryridine, vinylpyrrolidone; dienes, including isoprene and butadiene. Preferred ethylenically unsaturated compounds are conjugated dienes containing 1-12 carbon atoms per molecule, and vinyl-substituted aromatic hydrocarbons containing up to 12 carbon atoms.

The macromolecular monomer obtained can be mixed with a suitable monomer and polymerization catalyst so that graft copolymerization can be carried out in the same system in which the macromolecular monomer was obtained, provided that the solvent and materials present are present; the reactor to produce the macromolecular monomer will not serve as catalyst for the catalyst or cause adverse

effect on the graft copolymerization process. Thus, careful selection of the solvent and purification of the reactor system during the process of producing macromolecular monomer is necessary, since this can lead to significant savings in the production of graft copolymers.

Preferred monomers which are subjected to the PRIVATO cono-i liquefaction with the macromolecular monomers described above are preferably used:

Ct-olefins, of the general formula where R is hydrogen, alkyl or aryl C -C radical, mixture of ethylene and propylene, butadiene and / or isoprene, vinyl monomers, such as acrylic acid, methacrylic acid, alkyl esters of acrylic and methacrylic acid, acrylonitrile , methacrylonitrile akpila vlida, methacrylamide, N, N-dimethylacrylamide, vinyl chloride, vinylidene chloride, vinylidene cyanide, vinyl acetate, vinyl propionate, vinyl chloroacetate, maleic anhydride and fumaric, maleic and fumaric acids and their esters.

The resulting products are thermoplastic graft copolymers consisting of a copolymer backbone containing a plurality of uninterrupted repeating units of the base polymer, and at least one copolymerized whole unit per chain of the base polymer, having a chemical polymer bonded to it forming a copolymerized side chain grafted to the main chain, each of the polymer side chains having essentially the same molecular weight and polymer side chain of chemical and is associated with only one BASIC1-1 polymer.

Graft copolymers refer to

type structure

if only one side chain is copolymerized with the main polymer. However, in the case when more than about; the side chain is copolymerized with the base polymer, the graft copolymer can be characterized as having a comb structure, which can be described as follows cc-bc-cc-c -in ss-in-ss

but

II

ahh

where a is a substantially linear polymer of uniform molecular weight. HJTH g: a polymer having sufficient molecular weight in order to develop

the physical properties of at least one of the substantially linear polymers; c is a reacted or polymerized end group chemically bound

with side chain

which is polymerised into one with the skeletal polymer, and c is a skeletal polymer having uninterrupted segments of sufficient molecular weight, in order to develop the physical properties of the polymer.

The main chain of graft copolymers preferably consists of at least about 20 uninterrupted repeating monomer units in each segment. It was found that this condition results in a graft copolymer with polymer properties. In other words, the presence of segments containing at least about 20 uninterrupted repeating qy-dimensional units makes it possible to obtain graft copolymers with physical properties intrinsic to this polymer, such as melting point) and structural integrity.

Chemically bonded, split-phase, skeletal polymer segments of thermoplastic graft copolymers are prepared from starting monomers selected from the group of ethylenically unsaturated compounds and isocyanates.

Polymeric side chains, having a substantially uniform molecular weight, are linear polymers and copolymers and are formed from the macromolecular monomers described above. Preferably, the side chain of the polymer is different from that of the skeletal chain.

It is recommended that at least one polymer segment is a serviceable side chain, the graft copolymers have a molecular weight sufficient to demonstrate the beneficial properties of the respective polymer. In other words, such side-chain polymer properties as the glass transition temperature should be fore, v. Typically, the average molecular weight of the polymeric side chain segment required to manifest the physical characteristics of the polymer should be between about 5,000 and 50,000.

Control of the structure of the graft copolymer can be carried out by any of the methods; determining the ratio between the reactivity of the macromolecular monomer and the second monomer during the copolymerization reaction, and a pure graft copolymer can be obtained without

homopolymer impurities; controlling the rate of addition of the monomers during the copolymerization of the macromolecular monomer and the second monomer, which makes it possible to control the distance between the side chains in the polymer structure; the size of the graft chain can be preset and controlled at the anionic polymerization stage, which serves

0 to prepare macromolecular monomer.

The copolymerization of polymerizable macromolecular monomers with comonomers can be given in a wide range of ratios. At all

5, in order to create a chemical bond for at least one of the polymer side chains of uniform molecular weight with each skeletal polymer, a sufficiently precise amount of macromolecular monomer is required so that the properties of the graft copolymer are noticeably affected. Due to the fact that the molecular weight of the polymerized

The 5 macromolecular monomer, as a rule, exceeds the molecular weight of the polymerized comonomers, it is possible to use a relatively small amount of polymerized macromolecular monomer. However, chemically bound, having separate phases / graft copolymers. Can be prepared by copolymerizing a mixture containing up to 95% by weight.

5% by weight of IL15 even more than polymerized macromolecules of monomers, although it is recommended to use mixtures containing up to 60% by weight of polyetheuvromic macromolecular monomer. In other words, gum formation, thermoplastic, graft copolymers having separate phases, contain from 1% to 95% by weight of a polymerizable macromolecular monomer having a narrow distribution interval.

5 molecular weights (e.g., the ratio, / MT is less than 1.1) and from 99% to about 5% by weight of the copolymerizable seed meter.

0

The polymerisable macromolecular monomers are copolymerized with the block monomers described above with the block monomers, in solution, in aqueous suspension and in aqueous emulsion, i.e. in systems

5 suitable for individual polymerizable macromolecular monomer, its end group and comonomer used. When using a catalyst, one should use

0 polymerization medium acceptable for this catalyst. For example, oil-soluble or soluble peroxides in solvents, which are called benzoyl peroxide, usually are 5 pg effective at copolymerisation

full ri 3 y S m o m o m ro romol ak l ph o monomer with ethylenically unsaturated and G – OMO numbers and when copolymerization is carried out using a block method, in a solution of organic solvents, gaih, like benzene; cyclohexane, hexac, toluene, xylene and so on, nl B water suspension. Such water soluble peroxides as sodium persulfate, kelk; lithium and ammonium, etc., are very poor in polymerisation from aqueous suspension and in emulsion. In the copolymerization of many polymerizable macromolecules: street monomers, for example, they have (dich ethylenically unsaturated end groups, with repeated polystyrene; -, polybutadiene and: polyisoprenyl, in the aqueous suspension system; the theme can be used by the template. : l.ch systems, a special advantage can be achieved by dissolving in the macrodeptorium with the rhomogenus from the macroscopic, pekuli; rsnom monomer Eebob o, only to OLI t; s on dx some Go solvent, such as Hanpnjvsepf carbon When this method is applied, the comonomer is h; polymerizes with polymers, macromolecule rn / MbBCiMepOM in a solvent medium, in an aqueous system, okru: kaush, it is a solvent polymer polymer, and the polymerization agent is chosen such so that it grows, thins in the organic phase of the polymerization system, 51

Different catalyst sets can be used for the conoJrMNsepn-gase. The individual system used for copolymerisation of the cattle is 3Eii; Opa varies depending on the type of monomer being loaded and KOi-nie-vop group of macromole curlotch; 1 monomer, for example, when using macromolecular monomer having vinclaceral end group of the most - 11,: no results are usually obtained when using the system of free-radical catalyst, On the other hand, pr, and carried out, and “cont. , pimerizad, and using loaded and gobouti, a foam monomer with macromolecules, a monomer, a monomer, eluent -:, terminal allyl, a high metal epoxy group, the best results are obtained when using the method of cation-E polymerization ,. In SBS with tm; that the individual polymerisable end groups of the macromomer monomer are dependent on this single comonomer, the user should: use the individual polymerization mechanism “For example, ethylene polymerizes at a rate; x, free radical, cationic and coordinated, field of ionic ion and omexaci and: sma: propylfl and higher s, - o.lefins polymerization under coordination polymerization; isobutylene is polymerized only under free radical and coordination post-limiting conditions; styrene is polymerized under free-radical, cationic,., anionic and coordinating conditions of half-gmerization; Vinylidene:; loride polymerizes under conditions of a water-free polymer; vnylfluoride ps is primed by free radical polymerization, tetrafluoroethylene is polymerized under free-radical conditions and coordinated by-product polymerization; simple vinyl ethers submeasured under cationic and coordination conditions, polymerisation; vinyl esters of polymerization E conditions of free-radical polymerization, esters of acrylic and methacrylic acid, and Triche g; cryolitrile field has a comfort in conditions of free-radical, anionic and coordinated:.

The solvent used, the reaction conditions and the rate of introduction of the charge partly depend on the type of catalytic system used, which is used for. of this copolymerisation, It is preferable that the m-acromolecular m-one number is a padTOR. To dissolve in the system used, Hoj need to be identified. This is what: The loaded monomer is soluble in the system, ke solvent. But, if such conditions occur when the copolymer is formed by it, then the graft copolymer is precipitated from the solvent / and isolated from the known methods

Te / .ters, tour and daze during r,; coprocessing processes vary according to the order of E. 1-. 1 with the type of application used 1 ::. E, t.l.l.zator5 Tak.,., Upon receipt The polyolefied skeleton chain of DC flesh t. 1-3 in the free radixlone noJ.rHMepMaanJ-iH should be used in TWO. high € 5 pressure, on the other hand., semi-armored using u: atalkks.ators., 13 coordination type, “pinned sk.pex at A: noji glol efi F-IOB yu. chain view Total quotas, as a rule, in accordance with relatively low pressures of PIP,

When prigotovklvni. grafted sopoli; Merov, sh-g. poly skeleton, new skeleton, 4z ttnlena or .JieKa or copolyglylene ethylene and propylene together with macromolecules monomer, it is recommended to use coordinator CEE (Ziegler-Natta catalysts}

The solvent system used is up to 10kn, it is preferable to be such a ke, as used by the manufacturer. .-: i macromolecular monomer. K -1.Slu r eOr, fits-gx dlg; Almost all of them belong to the field of polystyrene, which are soluble in polystyrene from tyrol macromolecules. To number

typical solvents for polystyrene include cyclohexac, benzene, toluene, xylene, decalin, tetraclic, etc.

The r-ioxno copolymerization reaction is carried out at any acceptable temperature, depending on the specific catalyst, the macromolecular monomer charged with the t number, the graft copolymer formed and the solvent used. In general, graft copolymerization can be carried out at a temperature between 10 ° C and preferably between about 20 ° C and 100 ° C.

The graft coping reaction is preferably carried out by placing the pre-calculated amount of macromolecular monomer dissolved in the approach where the solvent is in the reactor. Thereafter, a solvent of the polymerization catalyst and a monomer for TorOf is introduced into the solvent system to cause a graft copolymerization reaction.

It is usually desirable to obtain a graft copolymer containing at least 2% macromogent; a monomer monomer embedded in a skeletal polymer material, satisfactory results are also obtained with the introduction of up to 40% weight,% macromolecular MOHOMSPEI, Pre-respectfully, grafted sopo.ymer5 contain from 5 to 20 weight. katsromol-aul monomer, that Pu: -1water 5gg to optimally achieve - with fnccchaskk characteristics, as in full-ora; forming a side chain, and the polymer, which serves as the skeleton of the copolymer.

Chemically bound, having separate phases, the graft copolymers, when deposited under a microscope, possess an controlled dispersion of macromolecular side chains in the skeleton polymer phase (matrix). Due to the fact that the side chain regions consisting of the macromolecular monomer are a common part or are located between the KpynHbiNM segments of the skeleton polymera, the resulting graft copolymer has the characteristics of a cross-linked polymer, if there is a big difference between the T-hek / h, T, and h segments of the skeletal polymer and the polymer that forms the side chains. This is true only when the temperature increases and to the point required for the destruction of the thermodynamic cross-links of the dispersed phase. In essence, it is possible to obtain polymers with crossgroups of bonds of a physical type (as opposed to having crosslinks of a chemical type), which can be created by simple

cooling, not by vulcanization, or by chemical introduction of transverse ev.

Graft copolymers differ from macroscopic opaque and 5 fragile blends of incompatible polymers. The graft copolymers contain separate phases, interconnected by the chemical dispersion of one segment in the polymer, which, on a matrix, is at the microscopic level. The graft copolymers are therefore transparent, durable and truly thermoplastic.

Example 1. Getting vaccinated; r-o copolymer from poly- (x-methylethiol), the chain growth of which is interrupted by allyl chloride, serving as a macromolecule p1 monomer, and from stylen.

A solution of 20 g of poly- (o-methylstyrene), which serves as a macromolecular molecular number, whose chain growth is broken, and with chloride, and has an average molar weight of 10,000, prepared in 100 ml of cyclohexane, is treated with 5.5 ml of 0.645 M (9, 1% solution of dketylaluminium chloride chloride; -exa.ne and 2 ml of trichloride vanadium, increase the excess pressure with ethylene to 2.1 kg - / - m-. This system is carefully mixed; from 1 hour at temperature , as a result of which a polymeric material is precipitated from a solution, it is separated by filtration, pressed in the form of Coy transparent, iiOK film, durable and flexible.

EXAMPLE 2. A. Preparation of lHBHToiro copolymer, which is located in a loose chain made of polyethylene and side chains, ns polyester,

. Grams of polystyrene, the chain growth of which the halo gene and the house of OS-sleftgene are distributed, and the molecular weight of the cathodogue, are restbed in 1500 ml of inclohexane and loaded into a 2-liter reactor. The reactor is flushed with purified nitrogen for 30 minutes, and injected into it.

5 22 g-s of a solution of ethyl halomino sesquint in heptane, B 1: 20 g of ethyl Hut pr 6 are given Cfl ml of trichloroquate and the reaction mixture is injected. vanadium and the pressure created by ethyl HQMf is reduced from 2.8 kg / cm to

Oro kg / cm, for a period of about 1 minute. P, the reaction is terminated after 3 minutes by the addition of isopropanol, the complete is filtered and treated with cyclohexane and isopropanol. The copolymer yield is 18.0 g, this copolymer has side chains of macromolecular monomer, the amount of which is 5.8%, according to the 0 III spectrum. Extraction and analysis of the extracts show that the whole macromolecular monomer reacts in a copolymerization reaction, and the amount of copolymerized ethylene is 17.0 g.

B. Similarly to the procedure of Example 2A, the experiment is repeated, except that 2.0 g are used instead of 1.0 g of macromolecular monomer. The copolymer yield is 20.5 g, and the content of side chains consisting of macromolecules monomer, according to the IR spectrum is 10%. Example Z.A. Preparation of a graft copolymer consisting of polyethylene in the main chain and polystyrene side chain,

Into a 2 liter reactor, 1500 ml of purified cyclohexane are charged with 20 g of polystyrene, the chain growth of which is interrupted by a halogonide with α-olefin, mol.v. 15400 with molecular weight distribution, / M p, 1.05, is dissolved in B purified cyclohexane. The reactor is flushed with purified nitrogen for one hour with slow stirring. Ethylene is introduced into the reactor at a rate of 5 liters / minute to a pressure increase of up to 0.35 kg / cm2-. The mixture is heated and maintained at a temperature of 25 ° C, with rapid stirring; A 22.8 ml of a 25% solution in heptane of ethyl one and a half ethyl chloride MINININ is injected into the reactor using a medical syringe, and then 0.1 ml of trichloroxy vanadium is added. Polymerization: begins quickly, the pressure of ethylene in the reactor drops to almost zero in one minute. The ethylene feed rate is reduced to 0.5 L / min, cooled to maintain the temperature in the reactor at 25: C. After the enchantment, 43 g of ethylene are charged into the reactor, the reactor is filled with polymer. The reaction is terminated by the addition of 50 ml of isopropanol to deactivate the catalyst.

The polymer is filtered, boiled with 1.5 liters of benzene for one hour, then filtered again to remove all unreacted polystyrene from the copolymer. Then the polymer is treated with 1.5 l of isopropanol with 0.03 g of antioxidant Irganox 1010, after which it is filtered and dried in a dryer at a temperature of 50 ° C. The yield of a copolymer containing 16% polystyrene is 49 g by B. IR spectroscopy. Preparation of a graft copolymer consisting of polyethylene in the main chain and poly (c-methylstyrene) side chain.

4 liters of cyclohexane and 200 g of poly (c-methylstyrene), whose chain growth was interrupted by the addition of the oL-Olefin helogenide, which is a macromolecular monomer having a molecular weight of 26,000 with a 1.05 equilibrium molecule distribution, is loaded into the reactor. The mixture is heated to 70 ° C while stirring to dissolve the macromolecular monomer. The solution is rinsed.

high purity nitrogen for one hour without mixing. Ethylene gas is fed to the reactor to increase the pressure to 0.35 kg / cm, after which 228 ml of ethyl aluminum sesquint (25% solution in heptane) and 1.0 ml of vanadium trichloride oxide are introduced. The stirring rate is increased and the polymerization starts immediately, which is indicated by the pressure drop in the reactor almost to zero. The ethylene feed rate is 5 l / min, and the internal temperature is maintained at 70 ° C. After an hour, the reaction is terminated by the addition of 500 ml of isopropanol,

The polymer is isolated by centrifugation, boiled in benzene for one hour and again centrifuged. After that, the copolymer is treated with 5 liters of methanol with the addition of 0.3 g Irganox 1010 for one hour, centrifuged and dried in an oven at 50 ° C. The product yield is 260 g, the content of poly- (o-methylethylene) is 22%,

Example 4. Preparation of a graft copolymer consisting of a polyethylene propylene copolymer and a polystyrene side chain in the main chain.

In the reactor with a volume of 2 l load

11/2 l of anhydrous benzene and 50 g of poly- (c-methylethyrene). the chain termination is carried out with allylchloride, the macromolecule monomer is dissolved with stirring, and then the reactor is purged with nitrogen. Then ethylene and propylene are fed into the reactor at a rate of 200 ml / min and 800 ml / min to create pressure in the reactor.

Of 70 kg / cm. At a reaction temperature of 25-30 ° C, injected with a syringe

2 ml vanadium trichloroxide and 4 ml of ethyl aluminum sesquint chloride solution to initiate the polymerization reaction. After the start of polymerization, 335 ml of a 10% aqueous solution of a macromolecular monomer obtained by dissolving are additionally introduced into the solution using a pump.

70 g of macromolecular monomer in 630 ml of anhydrous benzene,

. To maintain an equal reaction rate, an additional 110 catalysts are injected with a syringe: 110 ml of a 25% solution in heptane of ethyl aluminum sesquint and 1.8 ml of vanadium trichloride. After one hour, the polymerization is completed by adding 20 ml of isopropyl alcohol. The product is precipitated in methanol and 51 g of a white, aucid-like copolymer are obtained.

Example 5 Preparation of a graft copolymer consisting of an ethylene-propylene copolymer in the main chain and a side chain of polystyrene are charged with 3 liters of anhydrous cyclohexane and 10 g of polystyrene, the chain growth of which has been terminated by ally chloride. The solution is purged with nitrogen for 30 minutes. 20 ml of a 25% trihexyl aluminum solution are added, then 139.5 g of propylene is added to reach a pressure of 1.83 kg / cm and 20.4 g of ethylene to reach a pressure of 3.37 kg / cm. Oj2 ml of vanadium trichloroxide is added and pressure decrease is observed. The polymerization is terminated after 10 minutes by the addition of 10 isopropanol. The terpolymer solution was added slowly, with stirring, into a 4-liter beaker containing methanol to coagulate the polymer. The polymer that has been isolated is dried overnight in air, and to remove traces of catalyst, the polymer is dissolved in 500 ml of cyclohexane and placed in a 2-liter flask, together with 1 l of distilled water containing 0.1 g of sodium hydroxide, and then The mixture is heated at reflux temperature, i.e. with oOC for 2 hours. The contents are then transferred to a 2-liter long funnel and the lower aqueous layer is drained. The upper cyclohexane layer is slowly, with stirring, added to methanol to coagulate the polymer. The selected polymer is dried in a vacuum dryer. Unreacted macromolecular monomer is removed from the dried polymer by dissolving it in cyclohexane, dripping dropwise, with stirring, to methyl ethyl ketone. The terpolymer, insoluble in methyl ethyl ketone, is filtered off and dried under vacuum, yield 52 g. The terpolymer has improved tear resistance. Example 6, Preparation of a graft copolymer consisting of polyisoprene in the main chain and a polystyrene side chain. 500 ml of anhydrous cyclohexane is loaded into the reactor, 100 ml (68 g) of freshly concentrated isoprene are introduced with 17 g of polystyrene, the chain growth of which was cut off using allyl chloride. The reactor is sealed, after which 2.5 ml of a solution (25% solution in heptane) of trihexylaluminum and 0.16 ml of titanium tetrachloride are injected with a medical syringe. The contents of the reactor are stirred at 55 ° C for 16 hours, after which the contents of the reactor are slowly poured, with stirring, into a 4-liter beaker containing 2 liters of a 1% solution of an antioxidant ion in isopropanol. A solid rubber copolymer is obtained. Example 7: Preparation of a graft copolymer consisting of polystyrene in the main chain and polyoxyethylene side chain. Polyoxyethylene, the chain of growth of which was interrupted by vinyl benzyl chloride, styrene is placed in a reactor containing 1000 ml of benzene. The reactor is heated to 60 ° C and 1 part of the free radical polymerization catalyst, azobisiobutyronitrile, is added. The polymerization is completed in 3 hours and a graft copolymer is obtained, which has hydrophilic hydrophobic properties and properties. Example 8. Preparation of a graft copolymer consisting of polypropylene in the main chain and cis-1,4-polyisoprene side chain. The reactor was loaded with 3 l of heptane and 10 g of cis-1,4-polyisoprene, the chain of growth of which was cut off by halo allyl ether-sm. The macromolecular monomer is dissolved by stirring, and the solution is purged with nitrogen for 30 minutes. 10 ml of a 25% solution of diethylaluminium chloride in heptane are added, followed by 0.3 g of titanium trichloride. 139.5 grams of propylene is added to an increase in pressure of 26 psi. The reactor is heated to and the polymerization is finished after 18 hours, the contents of the reactor are poured, with stirring, into a 4-liter beaker containing 2 liters of a 1% solution of anti-oxidant ionol in isopropanol. The graft copolymer has a higher impact strength than the polypolypropylene homopolymer. Example 9: Preparation of a graft copolymer consisting of a polyisobutlene and a polystyrene side chain. To a solution of 20 g of polystyrene, the chain of growth of which was cut off by epichlorohydrin, having an average mole in 10000 in 1000 ml of toluene at a temperature of -70 ° C was added 80 g of isobutylene. Then 45 ml of a complex of boron trichloride with diethyl ether are slowly added, while maintaining the temperature at -70 ° C. The polymerization proceeds with the addition of catalysis. lysator. The resulting graft copolymer is isolated by evaporation of toluene and washing the remaining solid with methanol. Example 10 Preparation of a graft copolymer consisting of: polyisobutylene and a polystyrene side chain. To 1000 MP of methyl chloride - 10 g of polystyrene is added, the chain's growth is cut off with the help of epichlorohydrin, having an average mol. 10,000, To the resulting solution at a temperature of -70 ° C a solution of 2 g is added dropwise within an hour

aluminum chloride in 400 ml of methyl chloride and 90 g of isobutylene. The resulting graphener copolymer was isolated by extracting methylene chloride. Similar results are obtained when using a metal or methacryl end group of polystyrene.

Example 11 Preparation of Accepted Copolymer, from Polyisoprene Polystyrene Block, Growth of the Chain of which Is EaSh Chloride Torn With Allyl and Propylene

60 g having terminal Sb-olefinic groups of block polystyrene-polyisoprene are placed in the reactor; a polystyrene segment in mol. 10000 I; polyisoprene segment with mol.v. 1000 in anhydrous heptane. The reactor is flushed with nitrogen for 40 min., Stimulated with 30 ml of a 25% strength solution of diethylaluminium chloride in heptane; then 2.05 g of titanium trichloride are added. The reactor is heated to 75 ° C and propylene gas is introduced at a rate of 1 l / min. The polymerization is carried out at 75 ° C and a pressure of 1.4-1 / 8 kg / cm with propylene feed at a rate of 0.5 l / min , 2 hours, the reaction is terminated by the addition of ethanol. The resulting copolymer is washed with a dilute solution of sodium hydroxide and dried in vacuo. Analysis by spectrometry in the infra-red region showed; that the diblock macromolecular monomer has been incorporated into the polypropylene skeleton chain.

The resulting copolymer has the following properties: tensile strength 349 kg / cm; yield strength of 325 kg / cm, an elongation of 810%; bending modulus 1.44-10 kg / cm-; deformation temperature 6 2.1 С; Izod impact viscosity 0.0531 kgm / cm, Example 12, Preparation of a graft copolymer from a block polypropylene roll of polyisoprene, the chain growth of which was interrupted by allyl chloride and ethyleneMe

300 ml of diblo: it is a macromolecular monomer, having a polystyrene segment with a mole c. about 4000 and polyisoprene segment with a mole, in. about 16000 at the molecules of the pH of the aces of the distribution of r: 1,1; (40 g per dry substance) together with 1.2. Of anhydrous cyclohexane. The reactor is purged with high purity nitrogen for 50 minutes. Using a medical syringe, 22 ml of ethyl aluminum sesquint chloride (2b% solution in heptane) are injected. Ethylene is introduced into the reactor until the pressure reaches 44 psig. inch and the mixture is stirred. Then, 0.2 ml of vanadium hydrochloride is injected,

this temperature rises from 25 to 60 ° C. Due to the decrease in pressure, the flow of ethylene is carried out at a rate of 2 l / m. The polymer is washed with cyclohexanr with a dilute solution of sodium hydroxide and dried in vacuo. The copolymer contains 24% diblock macromolecular monomer. The resulting copolymer has the following properties: yield strength of 175.8 kg / cm; tensile strength 151 kg / cm; relative lengthening of 490%; bending modulus 3,510 kg / cm; deformation temperature Зб, 7С; Izod impact strength 0.68 kgf / cm (sample did not break).

Example 13. Obtaining a graft copolymer from a block polystyrene-polyisoprene, the growth of the chain which was cut off by allyl chloride and ethylene.,

200 ml of a diblock macromolecular monomer with a polystyrene segment with a mole, B, 13000 and a polyisoprene segment with a molar concentration of about 7000 with a molecular weight distribution, / MD 1.1 (40 g based on dry substance, together with 1.3 liters of cyclohexane. The reactor is purged with high purity nitrogen for one hour. 22 ml of ethyl aluminum sesquint chloride solution (25% solution in heptane) are added. Ethylene is introduced into the reactor until such time, noKdi pressure will not reach 3.1 kg / cm. Of 2 ml of vanadium trichloroxide is added, the temperature rises from 27 ° C to 55 ° C, ethylene pressure reductions are started at a rate of 2 liters, the polymerization is carried out for 6 minutes and stopped by the addition of 10 ml of ethanol, the half-meter is washed with a dilute sodium hydroxide solution , cyclohexane and dried in vacuum. The copolymer contains 38.5% diblock macromolecular monomer., The resulting copolymer has the following properties: yield strength 406 kg / cm; tensile strength 418 kg / cm 2; relative lengthening of 77%; bending modulus 1.12 10 kg / cm; The deformation temperature of the impact viscosity of the Izod 0.053 to gm / cm.

Example 14 “Preparation of a graft copolymer from a block of polystyrene polyisoprene, the chain growth is interrupted by the addition of allyl chloride, and from a mixture of ethylene and propylene.

155 g of a 19.3% by weight solution of the diblock macromolecular monomer is introduced into the reactor. having a polystyrene segment with mol.v. 10,000 and polyisoprene segment with mol. In,. about 2000 with molecular weight

the distribution of Mjj / Mn.l, l (30 g based on dry substance), together with 1.6 l of purified cyclohexane. Using a medical syringe, add 22 ml of a solution of ethyl aluminum sesquint (solution in heptane). Then 19 liters (35 g) of propylene gas are introduced into the reactor. As soon as 0.2 ml of vanadium chloroxide is introduced, ethylene is continuously supplied. Ethylene was introduced into the reactor at a rate of 2 L / min for 14 minutes (35 g). The polymerization is carried out for 24 minutes, and is cut off by the addition of isopropyl alcohol.

The copolymer solution is placed in a stainless steel beaker and 1 l of diluted sodium hydroxide solution and 1 g of an, Irgonox 1010 thiooxidant are added to it. The copolymer is coagulated and dried.

Example 15. A diblock macromolecular monomer with a maleic semi-ester terminal group, having a polystyrene segment having a mol. about 10,000 and polyisoprene segment with a mole, in. about 25,000 at molecular weight ratios and ida 1.1 is copolymerized with vinyl chloride (10 parts by weight of macromolecular monomer with SO weight, h, vinyl chloride and chain transfer agent) to produce a chemically bound graft copolymer.

Example 16, Obtaining a graft copolymer of diblock polystyrene-polyisoprene with terminal groups of methacrylate ether and styrene.

Copolymerization was carried out in suspension, using diblock polystyrene-polyisoprene having terminal groups of motoacrylate ester, polystyrene segment mol, about 10,000 and polyisoprene mol mol. about 25,000 with molecules of the equilibrium distribution Msw / Mf, 1 L,. The aqueous solution and the monomer solution are prepared immediately before use.

Aqueous stabilizer solution. 375 g of distilled water, 0.625 polyrinylpyrrolidone.

Monomer solution.

291 g of macromolecular monomer with a methacrylate terminal group (25.9% solution of solid in benzene), 177 g of styrene, 52 g of benzene, 1.33 g of azobisisobutyronitrile,

An aqueous solution of the stabilizer is loaded into a washed container, covered with a gasket lid, made of butyl rubber and lined with a mylar film. The tank is flushed with a syringe with a syringe before the monomer solution is introduced into it. Then the monomer solution is introduced into the tank with a syringe and the tank is placed in a bath and rotated at a speed of 30 rpm at 65 ° C for 20 hours. After that, the suspension is cooled and the precipitate is filtered. washed with water, air dried. 117 g of copolymer are obtained, which corresponds to the degree of conversion of styrene.

The transparent polymeric material obtained after pressing has

10 the following properties: bending modulus 13360 kg / cm; deformation temperature 77 ° C; Izod impact viscosity 0.058-0.50 kgm / cm.

Example 17. The preparation of a copolymer of privatized from polystyrene, the chain growth of which is interrupted by vinyl 2-chloroethyl ether and from ethyl acrylate.

To a solution of 18 g of octylphenoxypent150 ethoxyethanol (emulsification agent) in 300 g of deionized water was added, with vigorous stirring in a Waring mixer, a solution of 30 g of polystyrene with allyl chloride ends, and macromolecular monomer having mol.v. about 15400 ° C with molecular weight distribution, j ,, / Mn 1.05 and 70 g of ethyl acrylate. The resulting dispersion is purged with nitrogen, then heated with stirring, 0.1 g of ammonium parsulfate is added to initiate the polymerization process. 200 g of ethyl acrylate and 0.5 g of a 2% 5% aqueous solution of ammonium persulfate are added in portions over a period of 3 hours, while maintaining the temperature at 65 ° C. The resulting graft copolymer, in the form of an emulsion, is poured onto a glass plate, dried in air at room temperature, to form a flexible film. The film was found to contain polystyrene segments.

Example 18. Obtaining a graft copolymer from poly (ci-methylstyrene), the chain of growth of which is cut off using vinyl chloroacetate and from butyl acrylate.

A solution of 50 g of poly- (methyl methyl styrene), which is a macromer having end groups, the formation of which} -: is associated with a p-octyl chain of Eninyl chloroacetate having an average mole, 12600, and 450 g butyl acrylate in 1000 g of toluene is purged with nitrogen at 70 ° C, then 1 g of azobisisobutyronitrile is treated. The temperature is maintained at 70 ° C for 24 hours to obtain a solution of the graft copolymer.

0

The finished dried film has some tackiness to it contains polystyrene-a segments.

PRI me R 19. Obtaining a graft copolymer from polystyrene

5 macromer, the growth of the chain of which is broken with methacryl chloride and ethyl acrylate,

A mixture consisting of 21 g of polystyrene macromer, the chain growth of which was interrupted by methacrylyl chloride, having an average mol. 10,000 g, 28 g of ethyl acrylate and 0.035 g of azobisisobutyronitrile, prepared at room temperature and held for 18 hours under nitrogen at. The resulting product is an opalising material, which is pressed into transparent, durable, colorless sheets.

Example 20: Preparation of a graft copolymer consisting of polybutyl acrylate and a polystyrene side chain in the main chain.

A 1.14 l container is loaded pre-rinsed, the vessels are washed with nitrogen and closed with a stopper.

15.0 g of polystyrene (mol. 11000), whose rust is torn off with chloride: methacrylate, is dissolved in a mixture of 195.0 benzene and 195.0 g of dimethyl sulfoxide in the resulting solution is dissolved 45.0 g of butyl acrylate and azobisisobutyronitrile. The homogeneous solution is injected into a container filled with nitrogen with a syringe. The tank is placed in a bath and

rotate with a speed of 30 rpm. Samples are taken at a speed of 30 rpm. Samples are taken with a syringe and the reaction is terminated by the addition of 10% methyl ethyl hydroquinone (ENH) after 75 minutes, 120 minutes and 210 minutes. After 300 minutes, the residue in the flask was treated with 4 drops of MEGC in ethanol, the reaction was terminated.

The conversion rate of butyl acrylate is determined by the solids content of the sample samples. The rest of the samples are precipitated with methanol, dried, dissolved in terahydrofuran and analyzed by gel chromatography.

The presence of 25.6% grafted polystyrene and 74.4% polybutyl acrylate is shown.

Similarly, using polystyrene with a methacrylate end group, mol. equal to 11,000 and with a ratio of less than 1.1, copolymerization is carried out with increasing amounts of butyl acrylate, ethyl acrylate and methyl methacrylate.

In tab. 1 shows the results of copolymerization of polystyrene with the indicated monomers in a mixture of dimethyl sulfoxide and benzene.

Table 1

Example 21: Preparation of a graft copolymer consisting of polymethyl methacrylate and

in a polystyrene side chain. A nitrogen purged container is loaded with 65.27.5 g of polystyrene with methacrylate

terminal groups having mol.v. 13400 with molecular weight distribution, 1.05, 110.0 g of methyl methacrylate, 413.0 g of benzene (not containing thiophon), 1.10 g of azobisiobutyronitrile, 0.70 ml of tert. dedecyl mercaptan. The polymerization was carried out for 17.5 hours at a temperature of

 in the bath.

The resulting graft copolymer is separated by precipitating a portion of the copolymer in methanol, and another portion is in cyclohexane, the total yield is 87%. Transparent fragile films are obtained from products precipitated by both cyclohexane and methanol. Chromatography has shown that all polystyrene with terminal methacrylate groups is copolymerized with methyl acrylate.

Example 22: Preparation of a graft copolymer consisting of polybutyl acrylate in the main chain, and polystyrene in the side chain using copolymerization in suspension.

It was shown that the polymerized macromolecule monomer has a relatively large reactivity than monomeric butyl acrylate.

Example 23: Preparation of a graft copolymer consisting of ethyl acrylate (butyl acrylate) in the main chain and a polystyrene side chain with copolymerization in suspension.

 In a clean, nitrogen-flushed capacity; aqueous stabilizer solution containing 300.0 g of distilled water, 3 g of 5% polyvinyl alcohol, 1.6 g of disodium phosphate

An aqueous solution of the stabilizer is loaded into the container, closed with a lid with a gasket of butyl rubber. The monomer solution is injected with a syringe of 30.0 g of polystyrene with methacrylate terminal groups in mol.v. 16000, M-W / M p 1.1, 35.0 g of ethyl acrylate.

A clean, blown azo 1KhZM capacity of 150.0 g of distilled water is loaded; 3 g of a 5% aqueous solution of 1% alcohol (Lemol 48-88), 0.80 g of disodium phosphate.

Then, 20.0 g of polystyrene with terminal methacrylate groups (mol 110000, M xf / Mf 1.1), 30.0 g of butyl acrylate, 0.1 g of lauroyl peroxide are injected with a syringe.

The container is placed on a bath and rotated for 16 hours at 65 ° C, then heated at 86 ° C for 2-3 hours. The product is washed with water, filtered, and dried. Compress strong and transparent films. Transparency

5 films indicates the presence of a very small amount of unreacted polystyrene with methacrylate terminal groups.

In tab. 2 shows the composition of copolymers derived from methylacrylate polystyrene and butyl acrylate, when carrying out the polymerization in suspension.

Table 235, 0 g of butyl acrylate, 14.0 g of benzene (not containing thiophene) 0.084 lauroyl peroxide. The container is placed in a bath g, l of carrying out polymerization, rotated at a speed of 30 rpm at a temperature of 16 hours. Then the bath temperature is raised to 65 ° C for 3 hours, to 80 ° C for 1 hour to withstand 4 hours at 92-95 s. The suspension is cooled, filtered, the precipitate is washed with water and dried at ambient temperature. Yield 91.6% of the theoretical. The amount of unreacted polystyrene from the ends .. with methacrylate groups in the finished product was 3.3%.

Test specimens - prepared by rolling for 2 minutes at 145 ° C. Until Loka, the temperature of the press plates did not reach the set level, only contact pressure is applied, and then full pressure is applied to the press. The pressure is maintained during the time. cooling the mold to prevent the formation of a bubble. To determine the tensile strength, sheet 0.5 mm thick must be removed. Pressing is carried out for 10 minutes at a temperature of 170 ° C, under a pressure of 7.7 kg / cm. The pressed sheets contain 30% of polystyrene introduced into the copolymer with methacrylate terminal groups.

Below are the properties of copolymegpai containing 30% polystyrene with terminal methacrylate groups to ethyl acrylate and butyl acrylate in a 1: 1 ratio,

Unreacted macromolecular monomer 3.3%; gel content not soluble in tetrahydrofuran in samples pressed after rolling 0.4%; water absorption for 24 hours 0, -3%; yield strength 25j3 kg / cm -; tensile strength 114 kg / cm2; ultimate elongation of 475%; a gain after stretching of 35%.

Mechanical tests were carried out on the instrument Instron Tester,

Example 24. Preparation of a graft copolymer consisting of polybutyl acrylate and a side chain of polystyrene in the main chain using the suspension copolymerization method.

The reactor with a rubber lining of 2 liters (diameter of 12.7 cm) ,, becoming. t per bath, load 600 g of an aqueous stabilizer solution containing 600 g of distilled water, 3.0 g of a 5% aqueous solution of polyvinyl alcohol and 3.20 g of disodium phosphate. When the stabilizer water solution is heated, the reactor is flushed with nitrogen at a feed rate of 100–200 ml / min for 50 minutes. Then, 225.2 g of monomer solution is charged to the reactor. The monomer solution consists of g polystyrene with methacrylate terminal groups, with mol, 11000 and

140 (.0 g of butyl acrylate, 28.0 g of benzene (not containing thiophene) and 0; 280 g of lauryl peroxide. The mixture is stirred at 300 rpm and then 230 rpm. Bath temperature is 62 ° C, npfi temperature inside the reactor is 60 - After 7 hours, the temperature inside the reactor rises to 90 ° C and the polymerization is completed after 1.5 hours. The product is filtered through a 0.25 mm sieve, washed with distilled water, and dried at a fritted temperature. The weight of the dried pearl copolymer (length 5-12 mm, diameter 3-4 mm) is 190.7 g. Copolyure is rolled for 2 minutes at 145 ° C and pressed for 10 minutes. at 170 ° C to give a clear elastomer.

At measure 25. The training is grafted from copolymers consisting in the main chain of polybutylcrylate and a side chain of polystyrene using a copolymer with a diameter of 3 a c i and l and those of ca.

Latexes are prepared by copolymerizing polystyrene with the methacrylate konde BbEv-iH groups f mol. at . 13000, with acrylic MO nomerami,

Three solutions are prepared in advance.

Solution and .. 476.0 i-distilled water (boiled, blown nitride 16.0 g of 5% diluted sodium bicarbonate g 80.0 g 10% aqueous

Yxpala 00 2880.

solution

Solution S. 280.0 g of butyl acrylate, 120.0 g of polystyrene with me and rig; and terminal ones: opynnai.iH (mol. 13000 Mvja / Mn 1; 1) J 40.0 g of toluene, 13.6 g of calcium dodecylbenzo. calcium sulfonate

(Ninat 401), cit.p.me pk apta on

Solution C, 21, 6

Kisi Lauroyl (1.6 to 20.0 g of toluene) „

The molecular weight of the copolymer may be increased by exclusion from the formula me pj with a pt anna.

The emulsion is prepared in a 1.5 liter homogenizer glass, cooled in an ice bath. Solution A is placed in a beaker and purged with nitrogen. The homogenizer is put into operation and after 1 micron solution B is introduced and mixed for 10 minutes. Solution C is then added and another 2 minutes is stirred.

The resulting zmulse; The gas is loaded into a 2-liter glass pan) - a rubber-lined reactor equipped with four reflective partitions with a turbine-type agitator with six blades, flushed with nitrogen and mixed with 500 gb / min at 6-7 ° C. After five minutes mixing speed of the stirrer is reduced to 175 rev / mic. After 19 hours, the contents of the reactor are cooled to room temperature. Latex is filtered through a cloth. The polymer obtained has a 39.2% solids Begdspes-E.CHKKOST by Brookfmld, measured at 2 5 C 11-9 with n C, particle size 2 µm, pH 7.6, stability under freezing conditions thawing corresponds to 2 cycles. Shown that 1.5% of polystyrene with methacrylate terminal groups did not react ,.

Example 26. Preparation of a graft copolymer in a main chain consisting of polybutyl acrylate (polyethylacrylate) and a side chain of polystyrene, during latex copolymerisation.

The copolymerization of latex may be analogous to the example. Three solutions are prepared in advance. Solution A. 401.5 g of distilled water {boiled, purged nitrogen 17.6 g of 5% sodium bicarbonate solution, 77.0 g of 10% aqueous solution, Ipepal Ce-880 solution, Solution B, 154 , 0 g of ethyl acrylate, 154.0 g of butyl acrylate, 132.0 g of poly styrene with methacrylate terminal groups (mol, W. 13000), 44.0 g of xylene, 12.9 g of calcium dodecylbenzenesulfonate Kinat 401 0.07 g of tert . dodecyl apan a, Solution C. 22.9 g of a solution of lauroyl peroxide {0.9 g in 22.0 g of xyl la). The polymerization is carried out at 55 ° C for 4 hours and finished at 95 ° C, the mixture is kept for 2 hours. The content of solids in the polymer latex is 43.6%, the particle size is 3-4 µm, pH 7; Coagulation of the latex polymer is not observed. Example 27. Preparation of a graft copolymer consisting of a polyacryloitrile in the main chain to a polystyrene side chain. A solution consisting of 30.0 g of polystyrene with methacryl-terminated groups prepared analogously to example 8 mol. 1100, dissolved in 120.0 g of dimethylformamide, containing 0.10 g of azobisisobutyronitrile, is loaded into a container with a volume of 1.14 l. Capacity closes, purge with nitrogen for 15 minutes. Syringe is injected with 31/5 g of acrylonitrile and placed in a bath at 67 ° C and rotated for 18 hours, then heated for 5 hours at 90-95 ° C. The solution is diluted with dimethylformamide, salted with methanol, isolated in the form of a powder. Films made by pressing at 150 ° C, not transparent, yellow. Example 28: Preparation of a graft copolymer consisting of polyvinyl chloride main chain and polystyrene side chain. Polystyrene with methacrylate terminations, having mol.v. about 16000, (/ Mp 1.1, with about for l comforting with vinyl chloride. Load a capacity of 300; About g of distilled water, 3.0 g of 5% polyvinyl alcohol, o, 40 g of disodium phosphate, 0.34 g of lauroyl peroxide, 14.56 g of polystyrene with methacrylate terminal 1 and group w of 85.4 g of vinyl chloride. Polystyrene with methacrylate terminal groups and lauroyl peroxide are added to an aqueous solution consisting of distilled water, polyvinyl alcohol and sodium vapor in the sodium solution, and also in a sodium vapor of polyvinyl alcohol and a sodium vapor that is dispersed in a sodium solution and consisting of distilled water, polyvinyl alcohol and a sodium vapor, and a sodium vapor, and a sample of sodium polyacrylate, and sodium sulfate and lauroyl peroxide are added to an aqueous solution consisting of distilled water, polyvinyl alcohol and sodium acetate and an amount of distilled water and polyvinyl alcohol and sodium sulfate and sodium nitride, and a sodium sulfate and hydrogen sulfide peroxide groups. water, where vinyl chloride is condensed. Capacity is closed with a stopper with a gasket from butyl rubber, is placed in a bath and rotated at 55 ° C for 19 hours, the excess vinyl chloride is distilled off in air, the solid products are filtered on a Büchner funnel and washed with distilled water. The graft copolymer 92, -5 g corresponds to 91.2% the degree of conversion of vinyl chloride. Gelchromatographically shows the absence of polystyrene macromolecular monomer with methacrylate end groups and it can be considered that copolymerization of polystyrene with methacrylate HbuvH end groups with vinyl chloride occurs completely stew. Example 29. Preparation of a graft copolymer consisting of polyvinyl chloride in the main chain and a polystyrene side chain. Prepare the solutions. Solution A. 150.0 g of distilled water, 1.5 g of a 5% aqueous solution of polyvinyl alcohol (Lemol 48-88), 0.2 g of disodium phosphate. Solution B. 5О, -O g of polystyrene with methacrylate ends. ha groups, 0.125 g of lauroyl peroxide, 50.0 g in AI Il chloride. 150 g of solution A are placed in each of the 1.14 liter tanks with a track. The mixture is flushed with nitrogen for 30 minutes. Polystyrene with methacrylate terminal groups and lauroyl peroxide are added, the contents are cooled in ice-water, and excess chlorine chloride is condensed into it. The container is closed KRYSH.KSY with a gasket of butyl rubber. The container is placed in a water bath at a temperature and rotated at a speed of 30 rpm. The container is then removed from the bath after 2.5 hours-: 5 hours, and 15.5 hours and the excess vnichloride is removed. The solids are filtered on a Buchner funnel and washed with distilled water. The product is dried in air and then in a vacuum oven at 50 ° C. The mixture is dissolved in tetrahydrofuran. One part of the tetrahydrofuran solution was used for analysis by gel chromatography (method A), and another part of the solution was added to an excess of cyclohexane and hexane (3: 2) to displace 1 copolymer. The precipitate is filtered off, washed with a mixture of cyclohexane and hexane {3: 2) cl to remove unreacted macromolecular core. The copolymer is dried and analyzed to determine the chlorine content (method B). The composition of the copolymers obtained by polymerization of polystyrene with vinyl chloride in a ratio of 50:50 is given in Table 3.

27

Duration of polymerization, hours Example 30. Preparation of a graft copolymer consisting of polystyrene in the backbone and a side chain: polyisoprene. 370 g of 7.1% polypoprene with methacrylate terminal groups with mol. 10,000, 1.1 during 1.5 hours is evaporated in vacuo at -iO ° on a rotary evaporator. A round bottom flask containing a concentrated macromolecular monomer is sealed with a biological septum and purged with nitrogen. A syringe is injected with a solution of 61.2 g of styrene, 6.1 g of benzene (not containing tisfen) and 0.31 g of azobisisobutyronitol sludge (0.5% based on the weight of styrene). A clear solution of monomers of rarenos t with a syringe into a nitrogen-flushed container containing 0, aqueous jiacTBOp of polyvinylpyrrolidone (300 g IODINE, 0.24 g of luvisiol K-90). The container is closed, rinsed with nitrogen and placed in a bath with temperature and rotated to accelerate the polymerization process. Withstand 17.5 CHs1s at 65 ° Cf and then 3 hours with ELS. The product is filtered, washed with distilled water and dried at 40 ° C in vacuo. The product is subjected to rolling for 2 minutes at 150 ° C, 0.40 g of anti-oxidant Ionol CP is added to the rolled product. The yield of the rolled product is 75.8 g. The degree of styrene conversion is 98%. Example 31. Preparation of graft copolymer of tetrametre ether of diisocyanate and polystirol macromer, the growth of chains is broken by epichlorohydrin, 290 g of polytetramethylene glycol ether, mol.v. 2900, dissolved in 600 ml of tetrahydrofuran, purged with nitrogen, and 14.4 i {0.05 mol) of liquid diisocyanate was added. The container is closed, placed in a water bath with a temperature of 50 s and rotated at a speed of 3 rpm. After 8 hours, 7.2 g (0.025 mol) of liquid di-isocyanate was added and the reaction was continued for another 8 hours. Enter t

28

Claims (1)

Table 3 4.35 g (0.05 mol) of 2,4-tc) lylene diisocyanate and polymerization is continued for another 8 hours. To a solution of 200 g of polystyrene, the chain growth of which was interrupted by epichlorohydrin (mol 12000) in 100 MP of tetrahydrofuran was added dropwise dilute sulfuric acid to a pH of 2.0. The resulting solution is stirred at 8 hours, which leads to complete hydrolysis of the epoxy groups. A mixture of a solution containing 60 g of polytetrazmethylene ether of diisocyanate in 60. ml of tetrahydrofuran, 60 g of polystyrene with glycol end groups and 100 mp of tetrahydrofuran is placed in a container for carrying out the polymerization, together with 0.6 g of bivalent hydrochloride octate. The container is sealed, purged with nitrogen and placed in one bath with a temperature of 8 hours to obtain a graft copolymer. Samples of the film are prepared, pressed at a temperature of 150 ° C and an overpressure of 1.4 - 2.1 kg / cm. It is established that the resistance to stretching is 105 kg / cm. Example 32. Preparation of a graft copolymer from polytetramethylene diisocyanate and polystyrene ether with terminal glycol groups. A mixture of 87 g of polytetramethylene glycol ether, mol.v, 2900, and 4.3 g (0.015 mol) of liquid diisocyanate, is purged with nitrogen and placed in a water bath at 65 s for 8 hours, then cooled to room temperature, added 43 g of polystyrene with terminal glycol groups with mol. 8600, and 350 MP of tetrahydrofuran are closed, the container is closed. Purge with nitrogen. 5.9 g (0.023 mol) of diisocyanate are added and the container is rotated for 8 hours at 65 ° C. The graft copolymer is obtained, the film samples obtained from it have a tensile strength of 70 kg / cmH. Based on the above examples, it can be concluded that the use of polymerizable macromolecular monomers is a convenient way to prepare grafted polystyrene copolymers with vinyl chloride. The graft copolymers with vinyl chloride do not require the use of processing aids as the melt flow rate of the graft product is improved compared to that of the vinyl chloride homopolymer. Even at low levels of macromolecular monomer copolymerized with vinyl chloride, rolled sheets and extruded products are more transparent than control samples of homopolymerized vinyl chloride. The proposed method allows to obtain graft copolymers of a wide class with high physicomechanical indicators. The invention The method of obtaining graft copolymers by polymerization or copolymerization of 99-5 parts by weight monomers selected from the group containing ethyl wine-saturated compounds and isocyanates, in an aqueous medium or organic solvent medium under the action of free-radical initiators or polymerization catalysts in the presence of 1-95 parts by weight. functional polymers containing polymerizable end groups, characterized in that, in order to improve the physicomechanical properties of the copolymers obtained, carbon-chain or alkylene oxide polymers containing one terminal olefin epoxy or thioepoxide group per macromolecule with a molecular weight of 500050000 are used as functional polymers and molecular weight distribution of 1.0-1.1. Sources of information taken into account in the examination 1. US patent 3235626, cl. 260-881, published. 1966.