SU481631A1 - The method of producing oligomers - Google Patents

Description

one

The invention relates to a method for producing g-etero chain peroxidation of Igomeriv having high thermal stability (13O-15O C). Such oligomers can be used in the synthesis, graft and network polymers, lacquer coatings, sulfur-free vulcanizates, and also as additives diesel fuel.

A known method of producing oligomers by cationic polymerization in bulk and in solutions of epoxy compounds.

However, the obtained oligomers do not contain peroxide groups and, therefore, cannot be used in the synthesis of network polymers, lacquer coatings, and sulfur-free vulcanizates.

For the synthesis of heat-resistant hetero-chain, chemically active peroxide-functional oligomers, epoxy-1-alkyl peroxide p6iijefi formulas are used as starting epoxy compounds

HsFCH-OHg-O.-O-K

about

where R С (СНз) д,

) 2 5 3 2Сз7- 3 2 lead to a temperature from -5 to -1 ° C.

Epoxy-dialkyl peroxides contain two reaction centers in lightning cones: the peroxide-0: O group and the relatively fragile three-unit epoxy-alcohol. When opening it, its polypolymerization (subfinely non-first kisic epoxysidene) with the reactionary profile pbr onnroNtepoB, which can be represented by the following equation:

CH-CH-O: 0-R -} - H2 C - CH-CH O: O-R.2 ± J ±

 O-CH - CH-O-CH-I 2I 2

SNR

CH2

I

OOFj 00-R

where R is tertalkyl radicals.

Thus, in the case of cationic polymerization and epoxyperoxides, saturated hetero-chain peroxide-functional oligomers are formed.

When conducting experiments on a particular method using the following source Eresra:

1. 1.2 zyuks1 -3 tert, butylperoxypro

Sn, Sn - Sn, -0: 0 -c (cil

 i. i- 3 -J

about

contains 10.9% of active oxygen; TP-4O-410C at 3 mm Hg;

il, 4179,

, 9609. D

2. 1,2 enox (1-3-tert, amylperoxypro-

CH, -SI-SI, -0: 0-С pan-

jGD

 /

I

 from 2li5

ABOUT

contains 9.54% of active oxygen (theoretically 9.99%) j so bp. at O, 3 mm PT.SL1. 1.4243,

 -0.9569.

four

3.1.2 - .. e110xy-3 - tert.-hexyl peroxpropane CIl2-Cli-Cli2 0: 0- .C {CH.5) -СзН-, contains 8.94% of the active acid; hydrogen (theoretically 9.18% ), 429

fi -0,9518.D

-t

4,., 2-epoxy 3-tert-heptaugaeroxy

propane-CHg-CH-CH -OrO-CCCH) contains 8.31% of active oxygen

ri 2 (-1.4324, (theoretically 8.50%); D

20 0.9446

The carbon tetrachloride used has the following constants:

, 0.595. , 4630 (litas, 4631);

D

Tin tetrachloride is purified by boiling with RuO for 2 hours and vacuum neret-onca. For polymerization, a solution of SfzCI in a tenfold amount of carbon tetrachloride is used,

with

The depth of the ohm;

Active oxygen is determined by iodometrically polarographic method.

PRI me R 1. In a 150 ml reactor equipped with a magnetic stirrer, a thermostatic jacket, a dropping funnel and a thermometer, purified nitrogen is passed through and 29.24 g of epoxy peroxide (1) and 32 MP of purified carbon tetrachloride are placed. When moving, 18–6 ml of tin tetrachloride – 1 in CC1 are gradually added.

(0.1 g, mol of the catalyst per 1 gm monomer). The mixture was heated for 8 hours at a temperature of from -11 to 0, nitrogen was constantly passed. At the end of the reaction, the catalysts are neutralized with a 5% sodium hydroxide solution and the mixture is separated.

The aqueous layer is separated, and the organic is washed several times with distilled water and dried with anhydrous sodium sulfate. After distilling off the solvent, the liquid residue is evacuated for 10-12 hours in a bath at a temperature of 50--60 ° C and a pressure of 0.5-1 mm Hg. I get 2O, 2 g of peroxide-fudic-diol oligomer (yield 68.5% per monomer).

The product is an oily liquid with a molecular weight of 740 (KpHocKoniwecKH in benzene is determined) and an active oxygen content of 10.37% (theoretically 10.95%).

PRI mme R 2. 29.4 g of peroxide (1) dissolved in 32 ml of C1 are placed in the reactor. While stirring, add 18, about 1 ml of the catalyst solution (see Example 1). The mixture thermostatic for 8 hours at a temperature of from 6 to + 0.2 ° C in nitrogen atmosphere. Thereafter, 2 g of pyriine is added to the reactor to precipitate the catalyst. The precipitated Sphidine precipitate with catalyst is filtered off. The solvent is distilled off and the desired product is purified as described in Example 1. 22.4 g of peroxide oligomer is obtained (yield 76.4%) with a molecular weight of 650 (determined cryoscopically in benzene) and a content of 1O, 69% active oxygen (theoretically 10.95%). PRI me R 3. 29.4 g of epoxyperoxide (1) and 32 ml of CC1 are placed in a reactor. With stirring, 22 catalyst solutions are added (0.12 g. Mol of FFLChA to 1 gm. Of monomer). The mixture was thermostatic at a temperature of from -9 to + 0 for 8 hours, constantly skipping nitrogen. The desired product is isolated and purified as described in Example 1. Obtain 2O, 9 oligomers (71.6% yield per monomer) with a molecular weight of 6VO (determined cryoscopically in benzene) and a content of 10.63% active oxygen (theoretical 10 , 95%), Example 4. When transferring the reactor, 11.5 g of epoxyperoxide (P) and 32 ml of CC14 are placed. Then 11 ml of tin tetrachloride solution is added. To CCli (0.15 g mol kata; mol monomer). The mixture is incubated for 8 hours at a temperature of from -8 to + 0.2 ° C, and passes pure nitrogen. Isolation and purification of the oligomeric product is carried out as in Example 1. 8 g (yield, 69.7%) of an oily peroxide oligomer with a molecular weight of 550 (increased cryoscopically in benzene) and a content of 94.1% active oxygen ( theoretically 9.99%). Example 5, 10.46 g of epoxyperoxide (IJ1) and 11.5 ml of SDS are added to the reactor. When moving, 11 catalyst solutions (0.155 gmole Sna. Per 1 gmole monomer) are added. The mixture thermostatic for 8 hours at a temperature of from -8 to O, 2-C, skip nitrogen. The peroxidation oligomer was isolated and purified as described in Example 1. 7.22 g (69.9% yield) of a peroxide oligomer with a molecular weight of 530 and a content of 8.85% active oxygen (theoretically 9.18%) are obtained. Example 37.2 g of epoxy peroxide (IV) and 32 ml of solvent are placed in the reactor and 18.6 ml of catalyst are added thereto (see Example 1). Isolation and purification of the oligomer is carried out as in Example 1. 26.3 g are obtained (yield 7O, 7%); a thick oily liquid with a molecular weight of 780 (determined cryoscopically in benzene) and a content of 8.29% active oxygen (theoretically 8.5%). Thus, in cationic polymerization of epoxy dialkyl peroxides, peroxide functions can be obtained in solutions; oligomers with a yield of the target product of 68-77%. I Reactive oligomers of this type I are non-volatile, non-toxic, safe to use, soluble in monomers and organic solvents, and upon thermal decomposition they are able to sequentially i generate free radicals. the production of oligomers by polymerization of epoxy compounds in a solvent medium in the presence of cationic catalysts, characterized in that, in order to synthesize heat-resistant heterochain chemically active. In the first peroxide-functional oligomers, epoxy-dialkyl peroxides of the general form of the formula HgC-HHH-C O C S /, p L ;; 1 C C 5H. CH5 are used as starting epoxy compounds. C. (CH3) 2C3H7 or C (CH3) “the process is carried out at a temperature of from -5 to -1O ° C.