The method of obtaining stabilizer elastomers

 

(57) Abstract:

The invention relates to the production of stabilizers on the basis of substituted amines and can be used to obtain rubber, vulcanization agents and other polymeric materials. In the method of producing a stabilizer elastomers alkylation of diphenylamine vinylaromatic compounds when heated in the presence of a catalyst of the Friedel-crafts alkylation is carried out in the presence of N,N - diethylhydroxylamine, or 4 - oxydiphenylene, or alkylphenol with chain length WITH8-C12the dosage of 0.01 to 50.00 wt.% in the calculation of the diphenylamine. The method allows to simplify the technology of production and application of the resulting stabilizer. table 1.

The invention relates to the preparation of stabilizers for elastomers, in particular stabilizers on the basis of substituted amines and can be used to obtain rubber, vulcanization agents and other polymeric materials.

In the world practice widely used stabilizers elastomers obtained by alkylation of diphenylamine with styrene and alpha-methylstyrene [1] These products are known under the trade name Wangsta 29 (firm Goodyear, USA), stabilizer DDA (firm BA is avodat in the presence of acid catalysts Freescripts [3] Recommended acidic clay (natural aluminum silicate), treated base [4] sulfuric acid [5] aluminium chloride [7]

Closest to the present invention is a method of obtaining a stabilizer elastomers by alkylation of diphenylamine with styrene in the presence of aluminosilicate at a temperature of 190-220o(U.S. Patent N 4263456).

Industrial exploitation of the production of stabilizers alkylation of diphenylamine with styrene or methylstyrene showed that the irreproducibility of quality stabilizers on the viscosity of the product, which further complicates the technological use of the stabilizer in the preparation of emulsions and solutions. Due to new product often used in vacuum distillation of the product of alkylation of diphenylamine with styrene, thus remain difficult recyclable waste. The use of other, in addition to these, the well-known acidic catalysts of the Friedel-type benzosulfimide, oxalic acid also does not solve the above task in obtaining a standard low-viscosity stabilizer.

The aim of the invention is to simplify the production technology of the stabilizer and its application by reducing the viscosity of the stabilizer obtained by alkylation of diphenylamine with stiroporovaya of diphenylamine with styrene or methylstyrene when heated in the presence of a catalyst of the Friedel-crafts alkylation is carried out in the presence of N, N-diethylhydroxylamine, or 4-oxydiphenylene, or alkylphenol with chain length WITH8-C12at a dose of from 0.01 to 50.0 wt. in the calculation of the diphenylamine.

It is known the use of diethylhydroxylamine as a stopper emulsion polymerization [8] 4-oxydiphenylene as antioxidant for gasoline stabilizer turbine and transformer oils, etc. [9] of alkyl phenols in the production of ethoxylated monoalkylphenols, lubricating oil additives, resins [10] as well as a softener for rubber for various purposes [11]

P R I m e R 1. The mixture 253,5 g of diphenylamine (1,5 mol) of 25.3 g of aluminosilicate, of 2.53 g of N,N-diethylhydroxylamine heated in a three-neck flask with reflux condenser to 204oWith and within 45 min add 312 g (3 mol) of styrene. The reaction was poured into water, extracted with toluene, the organic portion is dried, distilled toluene. Get the stabilizer with dynamic viscosity of 1.7 P 80oWith residual diphenylamine 4%

The resulting stabilizer have to prepare aqueous emulsions according to the following recipe, wt.h. the stabilizer 100; potassium soap disproportionating rosin 5; water 200.

Get the emulsion with resistance to delamination, equal to 1,Tomo recipe with sulfuric acid and sodium chloride. After drying the rubber feel on heat aging at 140oC for 30 min and measure the index of conservation of plasticity (COI) using plastometer Wallace. COI samples of rubber was equal to 51%

The resulting stabilizer has significant advantages over the prototype, which was not used N,N-diethylhydroxylamine (example 2).

P R I m m e R 2 (prototype). The mixture 253,5 g (1.5 mol) of diphenylamine, to 25.3 g of aluminosilicate (the content of SiO273% of Al2O219%) is heated in a three-neck flask with reflux under stirring to 204oWith and within 45 min add 312 g (3 mol) of styrene. The reaction was poured into water, extracted with toluene, the organic portion is dried, distilled toluene. Get a mixture of alpha-methylbenzhydrylamine in the form of a viscous liquid dark brown color with a dynamic viscosity of 2.5 N at 80oWith residual diphenylamine 8%

The stability of the emulsion stabilizer prepared according to example 2, 0.5 h, and the effectiveness of the rubber SKS-ARC in terms of index save plasticity is 27%

P R I m e R 3. The reaction of alkylation of diphenylamine spend styrene or methylstyrene in example 1 with iSlate, the dihydrate of oxalic acid, sulfuric acid (experiments 2,3,5,7, 9,11 in the table). Measure the viscosity of the stabilizer after removal of unreacted styrene, the stability of the emulsion obtained stabilizers and their effectiveness. Parallel conduct the alkylation of diphenylamine (experiments 1,4,6,8, 10,12) using N, N-diethylhydroxylamine, 4-oxydiphenylene, ALKYLPHENOLS with chain length WITH8-C12.

Obtained by the proposed method stabilizers have considerable advantages in viscosity, stability, emulsion stabilizers and higher efficiency in the stabilization of rubbers.

The method of obtaining stabilizer elastomers by alkylation of diphenylamine with styrene or methylstyrene when heated in the presence of a catalyst of the Friedel of crafts, characterized in that the alkylation is carried out in the presence of N, N-diethylhydroxylamine, or 4-oxydiphenylene, or alkylphenol with chain length WITH8WITH12at a dosage of 0.01 to 50.0 wt. in the calculation of the diphenylamine.

 

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