SU870400A1 - Carbochain oligomers with terminal p-chloromethylbenzoate groups as vulcanizing agents of dienic rubbers - Google Patents

Description

(54) CARBON CHAIN OLIGOMERS WITH END

P-TRICHLOROMETHYL-VENZOATOUSHEMI GROUPS AS VOLCANO-ORDING AGENTS OF DIEN RUBBES ..., mi groups, and can be used in the petrochemical industry, ClCHjH C-O-f CH2-JH CIl- H2i7Jr ОО

Polymers of such a structure are cured with amine hardeners and give vulcanizers, possessing a number of valuable physicomechanical properties. However, they cannot be used as oligomeric vulcanizing agents that can vulcanize conventional high molecular weight rubbers.

C-0- (CH2-CH CH-CHjVKH2-CH- where m 31-85 and n 0-10, with a molecular weight of 2000-5000 as vulcanizing agents of diene rubbers. 30

ABOUT .

The aim of the invention is to impart the ability of functional chain-chain oligomers to vulcanise .. diene rubbers.

. Carbo-chain oligomers with terminal P-trichloromethylbenzoate groups of total form 20 are suggested.

I CN

(I)

about oligomers - as vulcanizing agents of diene rubbers Functional caroceptic oligomers, carbon-chain oligomers are known. a solvent in the presence of an initiator — L-trichloromethylbenoeloyl peroxide of the formula) - 3-oo - (; - / oV-CCu - / 11 v / a o; butadiene-or its mixture with acrylic acid nitrile is used as monomer, solvent is he or toluene. The polymerization is carried out at 6080 ° C, the duration is 20-40 hours. At the end of the polymerization, the unreacted monomer is degassed and the polymer is precipitated with alcohol. After re-precipitating with alcohol, the polymer is dried in vacuum at 60-80 ° C to contain no volatile more than 0.5%. The structure of the polymers and copolymers obtained and the terminal I-trichloromemethylbenzoate groups is confirmed by the data of IR spectroscopy and NMR spectra. In the IR spectrum, the following absorption bands are observed: at .1730, the corresponding stretching vibrations of -C AO-P are 2250 cm,. corresponding to C5N stretching vibrations. In the ICspectra there are characteristic C – H vibrations of the polybahadiene part of the chain: 730 1, .c; 910 cm 1,2-links, 867 1, 4-trans. In the NMR spectrum, the multiplet of the proton-phenyl core is centered at S 8.1 ppm. corresponds to the grouping. In the NPR spectra of copolymers with acrylic acid nitrile, there are multiplets of methine prone at sG 2.8 ppm. associated with the CzN group. The acryl nitrile content is consistent with the analytical determination of nitrogen. In the diene portion, the amount of 1.2 units averages 15%, 1,4-units .85%. Example 1. Preparation of a carboxy chain oligomer of the formula I, where m is 35 and p 6, 0.12 kg of initiator — peroxide I.-trichlorometh benzoyl, 2.23 kg of butadiene, 0.28 acrylic acid nitrile, 4.30 kg atse.tono and with stirring soak vaky when within 24 hours. The output of the sample is 27%. Analyzes found:. Molecular weight 2700 Chlorine content, wt.% 7 Nitrogen content, hr. May.% 3 Heppler viscosity at 25 ° C, P 1200 The structure of the obtained copolymer was confirmed by IR spectroscopy and NMR spectra, as described above. Example 2. Preparation of a chain-chain oligomer of the formula (where m is 76 and p 10. The autoclave is charged with 0.54 kg of the initiator - peroxide i-trichloromethylbenzoyl, 9.30 kg of butadiene, 1.20 kg of acrylic acid nitrile, 19.58 kg of toluene and incubated under agitation and hydrogenation for 18 hours. Polymer yield 34.3%. Analyzes revealed: Molecular weight 5100 Chlorine content, may.% 3.9 Nitrogen, May.% 2.8 Heppler viscosity at 25C, P3800 The structure of the obtained copolymer was confirmed by the data of NMR and IR spectroscopy, as indicated above Example 3. Preparation of the chain-chain oligome and of formula I, where m 31 and p 0. 0.9 g of peroxide I-trichloromethylbenzoyl initiator, 29.8 g of butadiene, 26.1 g of toluene are loaded into a 150 ml glass vial. The ampule is kept under stirring for 32 hours Polymer yield 21.4%. Analyzes revealed: Molecular mass 2140 Chlorine content, may.% 9.0 Heppler viscosity at, P1090 The structure of the obtained polymer was confirmed by IR spectroscopy and NMR spectra, as described above. Example 4. Getting chain-chain oligomer of formula I, where m 85, p 0. In a steel autoclave load 0.1 kg of initiator - peroxide And-trichloromethylbenzoyl, 3.0 kg of butadiene, 2.6 kg of toluene and incubated for 32 hours Polymer yield 25%. It was established by the analyzes: Molecular weight 5080 Chlorine content, wt.% 3.92 Heppler viscosity at, P1040 The structure of the obtained polymer was confirmed by the data of IR-spectroscopy and NMR-spectrum, as indicated above. The vulcanizing ability of polymeas with terminal AND-trichloromethyl benzoate groups is evaluated, based on the composition of the composition, wt.h .: 100 uadiened styrene polymer SKS-30

ARKP; 50 carbon black PM-75, 20 2PO; 20 of the proposed polymer.

The vulcanization is carried out at within 0.5 hours. The resulting vulcanizate has the following characteristics:

Module at 10p% elongation, kgf / cm Module at 300% elongation, kgf / cm

 / kgf / cm Elongation,%

Residual elongation,%

Tear resistance, kgf / cm

The above properties of the specified composition. Confirm the vulcanizing ability of the proposed polymers.

Viscosity of conventional black-filled high-molecular-mass cusps at and shear rates 3 10

 C-0- (CH2-CH (J-CH2-LH N, -CH-} (Jl5

 N. V /.

where m 31-85 and p 0-10, Sources of information

with a molecular weight of 2000–5000 per case, taken into account when examining the quality of diene curing agents. .one. USSR author's certificate

Kauchukov.№513988, class. C 08 F 136/06, 1972.

is 400-600 thous. The viscosity of the composition based on the polymer SCS-30 with the addition of 25-30 parts by weight. this polymer under the same conditions is 200 thousand units.

. -;

Thus, the use of the proposed polymers as vulcanizing agents in α-rubber mixtures of the type SCS-30 allows 2-3 times

reduce the viscosity of these mixtures, i.e. They can be used as a temporary plasticizer, improving technological properties at the stage of processing mixtures using

standard equipment, which confirms the advantages of the proposed polymers as vulcanizing agents.

Claims (1)

Invention Formula Chain-chain oligomers with terminal 1-trichloromethylbenzoate groups of the general formula (one) € K