SU382293A1 - - Google Patents

Description

Method of producing ethylene copolymers

one

Isoorhetia refers to the production of ternary coagulmers on the basis of ethylene and vinyl acetate.

It is known for the preparation of ethylene SO1OL1 copolymers by 1xing it from 10 to 85% by weight of vinyl acetate in bulk, in the aqueous phase of an organic solvent medium at elevated pressure and in an atomic temperature of 10-250 ° C in the presence of radical initiators.

The purpose of combining sastoite in the increase of the index and the improvement of the thermal stability of copolymers of ethylene with viyl acetate, especially for copolymers with a high content of pilacetate.

The purpose of the invention is achieved by the polymerization of ethylene and 10-85% by weight of vinyl acetate at pressures up to 20 at and temperatures above in the presence of radical initiators with third carbon monomer — winnallyl compounds, ethers or substituted amides of unsaturated carboxylic acids, unsaturated derivatives of inorganic acids containing several double bonds, or with unsaturated organometallic compounds containing several double bonds. In this case, the resulting copolymer is easily crosslinked according to the centernote method.

The initial concentration of the third component (comonomer) is 0.05-10 wt.%

(15 calculation; ia in 1 1 acetate). mildly I) J-5 pes.%.

Of the vinylallyl compounds as the third component, the most suitable is the 1H production; {preliminarily aromatic or aliphatic) tcarboxylic acids, polyhydric alcohols or urea acid, or iuuni} - .po, oi K11; slots, preferably phthalate:; ; 1pi, 1al, 1ila. Oxllt vi.ila.tlila, ikol

viillall.la, ethylene glycol diacrylate. Dimeta krilat et; 1leng.I1KOL. allyl ether N:; and P lkarba .M Pyuva kis.toty. ester ethanol; chol-bis (X-in INlcarbamoNvon acid) and allylvinyl cyanamide a.

The polymerisation of ethers and substituted amides of unsaturated carboxylic acids (allyl acrylate, allyl methacrylate, allyl crotonate, vinyl crotonate, methyl vinyl maleate, N-alL, 1-acrylamide, as well as used in the production of inorganic groups, as well as in the inorganic acid, as well as in the inorganic acid, as well as in the production of inorganic acrylamide, as well as with the use of inorganic acid, n-alL, 1-acrylamide, as well as with the use of inorganic milamide. for example, divinyl. methyl phosphate.

As unsaturated organometallic compounds, DI1Sh1N1IL diethylsilane and divatildiethoxysilane are used mainly. It turned out that for this polymerization process the most suitable are also compounds with nonconjugated, asymmetric

structure, which contain in the molecule at least two prostrate-unobstructed polymerized double bonds. Water or organic solvents (carbon tetrachloride, toluene, K; sy.1ol, cyclohexan, hexane, methol, greta-butauyul, tsclohexanol or dioxane) can be used as solvent. In the Wooded Systems, they operate mainly at pH 4 to 7 and also use both persulfates and various oxidizing systems as initiators. With solvent free solvents, to achieve a high content of double bonds, the polymerization depth is 10–20%, ii in the opposite case, partly strongly network products can be formed, whereas with nomerization in the presence of a solvent, almost all concrete and products are obtained. Considerable ow: I5G11ie ia The course of the radical polFMERICATION is provided by the initial concentration of the investigator. The higher this concentration, the greater the possibility of increasing the degree of snngvani. At a polymerization in solution, it is 0.01-2.5 wt.% (Calculated on B: nl lcene g). In block-copolymerization, a favorable concentration is 50% of this amount. But even here, it is possible to obtain an H1It is a very large number of connections for the non-hospital Stapling by selecting the initial concentration of the third component and the initiator concentration. Such radical inoculants are acceptable, such as, for example, reversing, hydroperoxides and these azo compounds or solutions of unreacted salts for: 1 yudnyh systems. Advantageously used nerokisn dnatsiLa (peroxide bepzo 1la, Laurana, acetyl, dichlorobenzyl.) And nerekisn dialkyl (nerekns di mp tbutila) n peraksidkarboiaty, such as peroksidkarbonat diisopropyl, and such compounds KaiK «nerester (e.g." perester t / W-butylbenzoia K: isslota, or hydroperoxide (cumene hydroperoxide). The polymerization is carried out depending on the dyeing initiator at temperatures of 10-250 ° C and pressures above 20 a.t. depending on the desired ethylene content. components, get paternally, rubbery and even resinous LOlimers. With an increase in the content of vinlacetate, an elastic product is obtained, and with a higher initial concentration of the third co.noneite, more rigid and hrunk products can be obtained: noBbiHieiHiijiM melt index. the product varies the absolute amount of the added third component in accordance with the differences in the contents of vaylacetate in polymers. The initial content of the third component B of the initial monomer mixture MUST. Not more than 10 wt.%. Due to the content of unsaturated bonds, further curing of the polymer is possible. After this kind of treatment, the polymerizates are insoluble in ordinary organic solvents and become tuto-melts. If curing occurs at temperatures above 240 ° C, this may cause discoloration of the polymer. These terpolymers can be vulcanized with a gray mixture, similar to natural or synthetic rubber, which, as is well known, also contain double bonds in the molecule. The resulting elastomers have good mechanical properties and are therefore of great industrial interest. In addition, non-vulcanized triple copolymers do not, in contrast to pro- tected copolymers, have increased thermal stability, enhanced ice melts, and increased stiffness and softening points. The refined polymers are characterized by increased heat resistance, frost resistance, and resistance to atmospheric influences. They can be used in the manufacture of elastomers, sponge masses, films and foils, na.npHiMep, in the cable industry and construction as a means of insulation, compaction, and lining, as well as profiles resistant to weathering, window gaskets, hoses and rubberized textile materials. The invention is illustrated by the following examples. Example 1. In a 2 liter stainless steel autoclave, 750 ml of benzene, 275 ml of viiiyl acetate and 0.7 g of azobiscnobutyronitrile are mixed, and allylacryne / pc is added to this solution in the amounts shown in the table. The mixture is then heated to 70 ° C and served under a pressure of 300 at. Ethylene. After 6 hours, the mixture is cooled and relieve pressure. The solution of polymerization is purified by precipitation in eta.nol or petroleum ether, the solid is sucked off, rinsed by EXPLOSION in vacuum at 60 ° C. The table shows the results of experiments.

The amount of added allylacrylate, g (wt.% In the calculation of vinyl acetate)

Output, g

The content of vinlacetate in TpOHHOiM copolymer, Ex.%

Iodine number

The third component in the tron copolymerization, wt.%

Spreading point, SYNEX rasilava, s / .npk

Viscosity, dl / g

1 IBR - the method with the review of Cyclns and 1 disappears. ASTM-E 28-58 T, 190 ° C. THL 20996. 80 ° С, tetralia. Example 2. Under the condition of the product, as described in Example Y, 750 ml of ni-cyclohexane, 400 ml of ethyl acetate and 5 g (1.34% by weight, based on vinyl acetate) of the allyl acrylate, are polymerized. 34 g of ternary copolymer are obtained with the following indicators: Saderl aa1ie in hydroacetate, wt.% Content of the third component in triple.m co-copolymer: measure, wt.% Iodine value Point or softening point, ° C Iidex, g / 10 min. Viscosity, dl / g Example 3. Under the conditions described in example 1, 750 ml of begool, 275. l of vipl acetate, 3 g of H-allylacrylamnd and 0.8 g of benzoyl peroxide are polymerized for 8 hours. After drying, 35 g of polymer are obtained. On the basis of elemental analysis and by the number of saponification, it was found that the mp: oyno11 copolymer contains 4.8 Bvs.% N-allylacrylamide, 26.3% by weight of vinyl acetate and 68.9% by weight of ethylene. Example 4. Under the conditions of x and ir 1dep.c. and example 1, 1000 m g of toluene, 300 ml of vinyl acetate, 15 g of divi-methyl methyl phosphate and 1 g of lauryl peroxide are polymerized for 10 hours. On the basis of elementary analysis, we can assume the following composition: 6.1% by weight of divinylmethyl phosphate, 31.3% by weight of vinyl acetate and 62.6% by weight of ethylene. The limits of the melt temperature obtained from Uni noos No. Nimer are 78-88 ° C. Example 5. In a 2-liter autoclave with a capacity of 2 liters, 500 ml of vinyl acetate, 0.3 g of azobasis and 3 g of allyl acrylate are mixed. Then it is heated and the ethylene pressure is increased to 350 at. After 5 hours, the mixture is cooled and the pressure is dropped (15,85)

20 (7.8)

29

26

25.1

27.0 30.8 36.4

13.6

16.0 140 140

55 0.57

oo 0.56 vie. The resulting ternary copolymer is only difficult to dissolve in boiling benzene, it is somewhat easier to dissolve in tetrachloride carbon. 60 g of ternary copolymer are obtained with the following indicators: Content of vniil acetate, wt.% 58.8 Third component in ternary copolymer of carbonate, wt.% 4.3 Submarine number 6.8 Softening point, ° С 140 Melt index, g / 10 min5 V viscosity, dl / g Everything is described; 1st in at: 1ram 1-5 volatile ternary copolymer derivatives are sulfur. PRI mea 6. When calculated for 100 parts of the ternary copolymer, 2 parts of sulfur are mixed in the rollers, 1 part of a vulcanization accelerator, 5 parts of zinc oxide, 1 part of an activating auxiliary agent and 30 parts of carbon black. Pure vulcanization of the mixture under pressure at a temperature of 150 ° C for 1 hour: its strength, stretch, hardness 11 elasticity. Elastic are obtained. H 1st substances with a weak chi .p. Proof. Mp (in example 1, data from the experiment 5 are used): Example I Example 2 Tensile strength, kg / cm 120110 Stretch,% 250300 Hardness, ° Shore A 7165 Elasticity,% 3845 EXAMPLE 7. By heating to 200 ° C of the ternary copolymer obtained in Example 1 with the number 14 iodine for 14 hours, the softening point can be raised from 105 ° C to 130 ° C. For comparison, a copolymer of ethylene and vinyl acetate, but under the same conditions, has a softening point of 81 ° C. However, it does not change iiivii luirpcuse. 7 II p e: L m ete 11 3 about b ete e li ii CONCERNING the preparation of ss; goli: measures of utterly calming it with 10--85 wt.% Viniladetate in Maioce, the aqueous phase or the organic solution 1g: 1 with a lower daslen and also by: - a culture of 10-250 0 in the presence of radical initiators, characterized in that. For example, the properties of the final nodhk8 to.h, proc-ss are carried out in the presence of the quality ;; e of the third cr., my-} K) measure of polyethylene-syschennyh, kyor-any of gruppy , containing 1; 1: 1. 1all; |, -1b.chysydsheny, esters or for / meshsplle aiMi-mbi peredsarlyh carboxy acids, inorganic acid esters and unsaturated organometallic compounds, nos. 0.05-W weight .% of vinyl acetate.