RU2028319C1 - Polymethyl-1-methylenesiloxy-4,4′-dipyridylium chloride of copper (ii) acetate (cobalt ii) as a modifying addition to the rubber mixture on the basis of nonpolar, unsaturated, carbon-chain rubbers - Google Patents

Abstract

FIELD: synthesis of organic compounds. SUBSTANCE: product - polymethyl-1-methylenesiloxy-4, 4′-dipyridilium chloride of copper (II) acetate (cobalt II) of the general formula where n=14,

Description

где n = 14, Мt = Cu²⁺, Co²⁺, которые могут быть использованы в качестве модифицирующей добавки в резиновые смеси на основе неполярного карбоцепного каучука СКМС-30 АРКМ-15 (бутадиен-альфаметилстрирольный) и комбинации каучуков СКИ-3 (полиизопреновый) СКД (полибутадиеновый), СКМС-30 АРКМ-15.The invention relates to new chemical compounds, namely polymethyl-1-methylenzyloxy-4,4'-dipyridylium chloride of acetic acid copper (II) and polymethyl-1-methylenzyloxy-4,4'-dipyridyl chloride of acetic acid cobalt (II), of the General formula

where n = 14, Mt = Cu ²⁺ , Co ²⁺ , which can be used as a modifying additive in rubber compounds based on non-polar carbochain rubber SKMS-30 ARKM-15 (butadiene-alphamethylstyrene) and a combination of rubbers SKI-3 (polyisoprene ) SKD (polybutadiene), SKMS-30 ARKM-15.

 In industry, the FP diaphhen is used as a modifying additive (1), which has insufficient modifying properties and is bought abroad.

 The aim of the invention is to obtain new modifying additives, providing an increase in the modifying properties of vulcanized rubber compounds.

где n=14, Mt=Cu²⁺, Co²⁺.This problem is solved by substances of the general formula:

where n = 14, Mt = Cu ²⁺ , Co ²⁺ .

 These substances are obtained by fusion of oligochloromethyl (methyl) siloxane with an excess of 4,4'-dipyridyl followed by precipitation and washing of the resulting polymer precipitate with hot butyl acetate and the interaction of the obtained dipyridylium siloxane with copper acetate (II) (substance I) and cobalt (II) (substance 2) in ethanol solution.

A comparison of the IR spectra of dipyridylium siloxane and its complexes showed that the groups (Si-0), (Si-CH ₃ ) do not participate in complexation. A significant change is observed in the nature of the absorption of dipyridylium groups. When metals are coordinated, the stretching vibration band of CH groups (3030 cm ^-1 ) is mixed by 10-13 cm ^-1 in the long-wavelength absorption region, the singlet of their deformation vibrations (713 cm ^-1 ) splits into a doublet (716, 724 cm-1) . Skeletal vibrations of pyridinium and pyridine rings are represented by a group of bands in the region of 1639-1520 cm ^-1 . Complexation leads to a change in their intensity and a shift of the bands 1639 and 1520 by 8-10 cm ^-1 to the short-frequency region of the spectrum, and the bands 1600 by 13 cm ^-1 to the high-frequency.

 Calculated,%: C 42.76; H 4.93; About 17.80; N, 6.23; Cl 7.89; Si 6.24; Cu 14.14.

C ₁₆ H ₂₂ O ₅ N ₂ ClSiCu.

 Found,%: C 42.96; H 5.03; O 17.66; N, 6.86; Cl 7.57; Si 6.31; Cu 14.23.

Calculated,%: C 37.40; H, 6.30; O 28.02; N 5.54; Cl 6.90; Si 5.46; C 11.47;
C ₁₆ H ₂₇ O ₉ N ₂ ClSiCo.

 Found,%: C 37.91; H 5.22; About 27.98; N, 5.40; Cl 5.99; Si 5.15; C 11.11.

 The invention is illustrated by the following examples.

In glass ampoules, 2 g (1.84 meq) of oligochloromethylmethyl) siloxane / kinematic viscosity according to VPZh-1 1.39 × 10 ³ mm / s, n _D ²⁰ = 1.4645, Mn = 1500 (determined on an EP-68 euliograph chloroform) and 8.51 (5.52 meq) of 4,4'-dipyridyl (mp mp 114 ^° C). The reaction is carried out for 0.5 h at 115 ^about C. After the reaction is complete, the mixture is planted in 100-150 ml of butyl acetate. To remove the starting monomers of the polymer precipitate was washed with hot (50-60 ° ^C) with butyl acetate. Dry in vacuo at ⁶⁰ C to constant weight.

A portion of 1 g of dipyridylium siloxane - polymethyl-1-methylenzyloxy-4,4'-dipyridyl chloride is dissolved in 20-25 ml of ethanol and added to a solution of 3 times the equivalent of copper or cobalt acetate in an Erlenmeyer flask with a magnetic stirrer. A copious precipitate of cheesy precipitate is observed (substance 1.2), it is filtered off and washed with small portions of ethanol to remove excess copper or cobalt acetate ions. Dry in vacuo at ⁶⁰ C to constant weight.

Yield: Substance 1 93%
substance 2 100%.

 Modification of elastomeric compositions.

Rubber compounds are prepared in a laboratory rubber mixer with a rotor speed of 30 rpm and a mixing chamber volume of 2x10 ^-3 m ³ . Sulfur is introduced on a laboratory roll. Modifying additives are administered in conjunction with bulk ingredients.

Rubber mixture in a machine for vulcanized at a temperature of 142 ± 2 ° ^C.

 To test the properties of rubber compounds, the compositions shown in Table 1.2 were made according to the well-known technology.

 Then, according to GOST 269-86, tests of vulcanizates were carried out, the results of tests of physical and mechanical properties are given in Table 3.4.

Claims (1)

POLY-METHYL-1-METHYLENE-SILOXY-4,4 ^1- DIPYRIDYLYCHLORIDE OF ACETIC COPPER (II) (COBALT II) AS A MODIFICATION ADDITIVE FOR RUBBER MIXTURES BASED ON HEAT-FREE SHEAR. Copper (II) (cobalt (II) poly (methyl) 1-methylenzyloxy-4,4 ^1- dipyridyl chloride of copper (II) acetate

where n = 14;
Mt = Cu ^{2 +} , Co ^{2 +} ,
as a modifying additive in rubber compounds based on non-polar, unsaturated, carbochain rubbers.

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