SU491236A3 - The method of obtaining graft copolymers - Google Patents

Description

The invention relates to a method for the preparation of H | ri1weaved sololimbres, e.g. acrylo. Nitrile butadiene styrene (ABS).

The known method of i-no-ABS by priiivki airilonitrile and styrene. On latex and black polybutadiene and / or rubber-like copolymer of styrene and butadiene. Prior to grafting, latex is usually mixed with monomers, “which must be grafted on, and the mixture is mixed several times to emulsify: monomers and absorb I.x. by H: ast, its.x rubber. Before grafting. This enhances the physical properties of the grafted C01 polimer. The grafting reaction is carried out periodically with or without pre-absorption of the monomers on the latex polymer, and my measurements are added to the reactor in portions.

With the aim of improving technology P | re (for example, a method for obtaining a graft copolymer, including immersion; the addition of one or more vinyl aromatic monomer and one or more unsaturated nitrile monomar with latex rubbery polymer, selected, 113 groups of lolibutadiene and Snooper monomers, and I have I’m in front of I-tos and I and I will be in front of I-lines and I will be in front of I-lines and I will be in front of I-lines and I will be in front of I-lines and I will be in front of I-lines and I will be in front of I-lines and I will have I-to-I-lines and I will be out of I-lines and I will have I’m going to have I-I-lines and I will have I / I to go with I-lines and I will have I and I will have I have I, I will be able to do it. characterized in that the mixture is prevented from falling into the first reactor and copolymerizing in the topmost reactor until a conversion reaches no more than 65% by weight of iMOiHQMepQB, the transfer of the reaction mixture from the first reactor to the second, in which the copolymer is continued until the end reaches at least 80% by weight of the monomers, and the temperature in each reactor is from 50 to 100 ° C.

Before copolymerilization, the monomer mixture can be absorbed for 90 minutes at a temperature of 20-90 ° C under the condition of a continuous stream of a mixture of latex and epoiB monom.

L: Atex rubber polymer, which is used according to the invention as a starting material, can be obtained in several ways, usually obtained by emulsion polymerization. When using butadiene and styrene (SBR) KO.TOI copolymer latex, the quality of styrene in the soiolimer can be up to 30% by weight of all monomers, but it is usually 5-15%. You can use a mixture of latex polybutadiene and SBR. They prefer sredinnech and spruce latex particle diameter, according to

at least 1500 A, preferably 2000-

about

2800 A. srednezozoy diameter 2500-

about

3000 A. The swelling index of polymer particles (in toluene, mesh 200 mesh.) 10-30. better than 12-20, the gel content when dissolved 3 toluene for 24 hours or more at

20 ° C and filter I-1I through a metal grid with a 200-mesh diameter, at least 50%, preferably 60-90%.

, In the quality of the monomer vinyl monomer according to the proposed method, styrene, a-1methyl carbon and VI-1Nto are different, and styrene and α-methyl styrene are better; as nanosychen1 10RO nitrile - al. phytic acid iiirils with: KOTA chain, for example, aisrilonitrol or leta1, kryloi nitrile. Change the number and type of viiiilar; monomer and non-saturated & nitrile MOZH1IO to obtain a wide range of properties s of the grafted copolymer, and the weight ratio of symromolithic monomer and non-saturated satrill varies from 1: 1: 1, 1 to 3, 1 to 1, 1 to 1, 2 to 1), 1 to 2, 1 to 1), 1 to 1), 2 to 1), and to a non-saturated satrill will vary from 1: 1, will be: 1;

To prepare a thermoplastic | Icheoki sopol imvr, use is made of a mixture in which rubber is squeezed regularly but in the range of 1–5–40 iBec. % vinylaromatic monomers 40-80 weight. % and unsaturated nitriles 15-40 weight. % To obtain rubber-grafted graft sapolis, merle is usually used to blend with vitreous | M thermoplastic, such as styrene and acryloyitrile copolymer (SAN), the grafted graft monomer is lower in less than, measures 60–40 wt. % motiver instill to 40-60 weight. % rubber

It is desirable to increase the stability of rubber latex before mixing with monomers that are 1P | p 1 1 V1, since insufficient stability may result in coagulation. On the other hand, radial, lateral stabilization of the latex can lead to “insufficient vaccination, TaiK” ak (the monomers copolymerise between themselves, and this is reflected in the physical properties of soyolimer. In some cases, the latex stability is sufficient and an additional emulsifier is not required. However, it is desirable mix with latex to 4 parts by weight (dry) per 100 parts by weight of the latex monomer of one or more alionic emulsifiers, na; nRI | Mer, the salt of the silk metal (usually potassium or sodium) carbonic acids with 12-20 or more carbon atoms. Ta It is preferable to use salts with secondary, emulsifier, such as the alkali metal salt of derivatives of naphtha-insulfonic acid (nalime / p, n-naphtalic acid naphthalate acid sulfonate with naphtalic acid sulfide). Examples of carboxylic acid salts of new acid are salts Unsaturated fatty acids are acidified with 15–18 carbon atoms, such as salt and palmitic acid (Cis), better than the potassium salt of oleic acid or a mixture of the potassium salts of oleic acid and. acids with a small amount of other salts. The emulsifier is in the amount of 2.5-4.5 wt. hours at 00 weight. including polymer.

The anti-oxidant or stabilizer is preferably dissolved in the monomers before mixing: with latex and, if desired, with the modifier takiM as t-dodeyl-mercapga: n. iB if you can, from 0.03 to 0.50 of you. h. “a

100 weight. including monomer and rubber. The fluidity and impact resistance of the final graft copolymer can be changed, in 1 minute of the amount of the CTiBO modifier.

The content of the following: The usual solids in the latex-lumer mixture is 25-30% (the solids content is calculated by the end of the reaction). The solids content below 20% is undesirable because of the | Iinshen solubility and loss of water-soluble nitrile (for example, a11-: | rilonitrile), but their content above 35% leads to instability of the mixture.

The mixture of latex-monomer is emulsified and abs. Is boiled for 90 minutes at a temperature of 20-90 ° C in a continuous circulation. In some cases, the absorption process may be excluded. Absorption can be carried out with an iB / flow mixer or a flow mixer, connecting one; io: m with a single tube (preferably vertical), or a cascade of vessels, preferably with mixing devices. The duration of absorption varies inversely with temperature. The reaction of the primed poly1merization is preferably carried out in two stages, preferably in a relatively short period, for example, 10-40 minutes. However, up to 10 stages can be applied, but this is usually impractical. The stages can proceed in separate reactors, preferably with mixing and temperature control. When two reactors are used, they are connected in a cascade and the temperature (T) is maintained at 70-90 ° C in the first stage, and in the second stage the temperature (G-3) is equal to or.

is below the temperature T ,. At the same time, the conversion of monomers “is more than 65% in the first reactor, in the second (or last) reactor a higher conversion is better, for example, 80-90%. Usually, in the production of ABS it is impossible to achieve a conversion above 95% due to the water dissolving of acry. Tonitrile. The polymerization time in the first reactor, i.e. the time of the nerve stage, may be 10 minutes at a temperature of 75-80 ° C and in the second reactor (the time of the second stage) 20 minutes. with the same temp. temperature. It is desirable that the rate of conversion of monomers does not exceed 5% per minute. The grafting reaction of the exothermicheoca and, if desired, the polyp; 1 o of polymerization is retained in the reaction mixture. The reaction speed can be changed by adjusting its temperature.

The graft copolymerization reaction can be, for example, initiated by 0.1-1% (in terms of monomer and rubber) of a radical polymerization initiator, for example potassium persulfate, treg; percoctoate, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide / hydroperoxide | Diisopropyl benzene, which can be activated, for example,

D1vuh | valenny1m iron. Prefer activated cumene hydroperoxide. The initiator is mixed with a rubber latex and an activator, which is introduced into the first reactor, during slow initiation, and the initiator can be added during the absorption procedure.

By changing the type and the CO.PHI & S-BVI myogram U-Lovi absorption and graft, one can obtain primed copolymers having different physical cBofiCTiBa. . You can get ABS with modeling fluidity and heat,: bone.

After prizivka, the graft sapolimer can be removed by coagulating the latex, and then: washed and dried. The grafted copolymer obtained by the method can be combined by using a lubricant, a nalimer, a lubricant (With oils, lubricants and / or thermoplastics, MOZHPO use it as a material for molding and products.

EXAMPLE 1 A polybutadiene latex containing 25% solids, And the mixing average particle diameter of 2237 A, and the average particle diameter of 2800 A, and including 95% of the gel with ibitex 12 (measured, described). Get known spssobom. Without further processing, styrene and acrylolitrile are continuously subjected to grafted tulilization on the indicated latex by the method of emulsion polymerization, iodine latex through the pipeline / (see Fig. 1) and the copolymer through pipeline 2, and they are combined, after mixing, in the absorber 3 with double walls, iKQTOpOM supports a temperature of 65-70 ° C.

The absorber 3 is connected to the reactor 4 (with a displacing device and double steels. 1CaMi), the temperature in which support is left at 80 ° C. The capacity of the a-ctizer is connected by pipe 5 to the reactor 4. The realtor 4 is connected to the second stage reactor 6, having a jacket whose temperature is also equal to approximately SOС. Hence, the grafted sopo. Iiler; get rid of and direct — on Xipai i; iHe to the vessel 7.

A mixture of latex and monomarosis gotoz tlz ingredients indicated in the table. 1. Emulsification of monomers and latex components is carried out at 65 ° C 3 for 30 minutes and then supplied with IB reagent 4. into which is continuously added. And: nitsiato, p - glucose. And ferrous sulfate (see 2) to provide approximately 40% of 1KON | Monomer Versions in 10 minutes at 80 ° C (7 |). Partly lre; in, raw materials 1 Napra; is Got zo-second reactor 6,

where iB Follow 1D 1e 30 minutes the condenser reaches 8C - 85% 1% and 80 ° С (:).

P-; in: that latex-o-coagulated at 95 ° C with a diluted solution of calcium chloride, g: 3 | D; MSLEG:, NS; 1M EDTA. and dried s vacuum pec. at 65 ° C for 12 hours. After displaciveness at 180 ° C with lubricants - barium stearinous oxides and Armogel (hydrirosis oil) and with a stabilizer (phosphorite;) GOG05YT compression test specimens. The following results are obtained: Impact-on Strength of samples with a cut-off (/ 8 bar) at 23 ° C, pound-inch7.5

Rozkell Ptsi

23 ° С 97

 oasplaz

200 ° C5 kg), g / 10 min0.5

And what are the results obtained with Pavtoania: Primer 1, about | MWN equipment, P0 | ;; aza.n-nu na FIG. 2, in which the absorber is parastasally a vertical tube 9 with dzoynymi walls, the equipment in which 65-70 ° C, one of the tubes has a perimeter device.

The power

24 2

OSTGL 0

 Lkt1v. Vlyuchao (svoy. H. With gluko.Ig 2,4; tetranatryp - G rofosfta 2; sulph g: -lc: O.C4 II pod ICO.

Conduct a series of experiments in accordance with example I. Amount of components of the components and conditions of pr-o-tsaos, for example, -: s for table. 2

Stage i

Time, min

Latex consists of 2 weight. h. polnbstadiene and 3 months. h SBR.

30 j S5 I

ten ; 80

So

The properties of the lrisite sapoli of the measures obtained from 3. 1; 2; 3; n 4; the samples are as shown in Example 1 are listed in Table. 3

T a b l and c n 3

Impact strength, pound inch

For ic, paiB.HeiiiHH, Example 1 is repeated, wire | Polymer | C1Iu in one reactor (.reactor 4, fig. I), bypass, reactor 6. Temperature in reactor 4 is 85-90 ° С, reaction time B min Pr.iv, i; iB single stage gives the product; with worse properties: impact strength of 5.5 pounds per inch with Rockwell hardness of 90 and a melt index of 0.4 g / 10 min.

The optimal effect of the proposed supply of € 1 is achieved by monitoring in the reactor the rotation of the monomers into the polymer and the degree of polymerization of each station.

Subject matter of the invention; 1. The method of obtaining polyvinylchloride from polymers by mixing and impregnating copolymerisation of the vinylarmatic moyumer and nonsyash, e; NITR-il with the latex of rubbery polymer chosen from the group of polybutadiene and copolymer of butadiene n styrene, nt h olyme resin u with the fact that, in order to suspend the technology, to graft the copolymer of the gadget by uninterruptedly supplying the polymerization mixture to the first reactor, to carry out the copolymerization of IB with it until reaching a co-version of more than 65% by weight of Mo.H1More1B, ( Ames minutes from the first reactor and the second iBo further copolymerization in the second reactor

until a conversion reaches at least 80% iHO, the weight is low. The temperature in each reactor is 50-100 ° C.

2. A method according to claim 1, characterized in that prior to the grafting of the graft copolymerization

MOiHOiMepbi absorb on the polymer latex.

3. The method according to claim 1, which is based on the fact that 1VI | Nilaromatic1, lyuio, measures are chosen from the group consisting of α-of styrene and a-: methylstyrene, and yenaschiny yitryl - acrylo. nltrile, the weight ratio of vinyl aromatic monomer and unsaturated "itryl is 3-1; one.

4. The method according to claim 1, wherein the temperature in the first mode is preferably 70-90 ° C, and in the second one paiBHa or more than the temperature in the first cycle.

5. The method according to claim 1, wherein the conversion rate of monomer-to-and the first stage is not more than 5% per minute.