SU992533A1 - Vulcanizable polymeric composition - Google Patents

Description

The invention relates to α-polymer compositions based on oil-filled rubbers and rubbers and can be used primarily in the tire and rubber industry, as well as other areas of the national economy.

A known method for producing oil-filled rubbers by introducing non-emulsified oil into polymer latex, where the latex in the pipeline or the first coagulation apparatus is continuously mixed with sodium chloride solution and t oil. The disadvantage of the known method is that the introduction of non-emulsified oil into latex is possible only with a powerful mixing equipment, which leads to the partial release of rubber in the form of coagulum, uneven distribution of oil in rubber and deterioration of its properties.

The closest to the proposed technical essence is the method p} of obtaining butadiene-methyl-styrene rubber SK (MS) -30 APKM-15, where the PN-6 oil introduced into the latex is used as a plasticizer filler of the following composition, parts:

oil PN-6 100, stearic acid 7.2 ,. triethanolamine 3.52 water 220.

The latex is coagulated with calcium chloride 5 and acetic acid, the coagulation and washing regime of rubber is serial.

However, the chemical heterogeneity of the oil PN-6 leads to a significant

10 scatter; - values of specific weight, viscosity, flash point and refractive index. According to the conditions of the preparation (by compounding the extract from the phenols from the phenol purification of the asphalt-freezers or by compounding them with low-viscosity extracts from the phenol to the viscous distillation fraction, or from the residues obtained by stripping the head fractions from the indicated

20 extracts, or their mixtures) and the composition of the oil PN-6 is a non-standard product: high viscosity up to 0.35, relatively low content of 78% by weight (sum of light and medium aromatics).

The high resin content (up to 8 May.%) Leads to worse compatibility of the oil with rubber and reduced stability during aging. In addition, the introduction of PN-6 oil into latex in the form of an emulsion increases latex foaming and is associated with an additional consumption of expensive products, while the emulsion with oil Pn is not sufficiently stable and stratified during storage, which creates technological difficulties when introducing oil into rubber . The purpose of the invention is to improve the plastic-elastic properties of the composition and the physico-mechanical properties of rubber from it. The goal is to achieve that the vulcanizable polymer composition, including diene rubber and oil plasticizer-filler, contains, as a plasticizer for the filling, an oil fraction that is distilled by vacuum distillation of a mixture of distillate and residual aromatic extracts in a ratio of 1: 2 and boiling point of 420 to 5 containing 10-20 wt.% of yellow aromatic hydrocarbons, in the amount of 17-50 wt.h. on 100 ma.ch. rubber ka. . The physicomechanical properties of the oil fraction used in the proposed composition, in comparison with oil PN-6, are listed in Table 1. These tables show that the proposed oil filler is more standard in composition than oil PN-6: fractional composition of 420-500 oil instead of 460-600s is characterized by low viscosity (0.165 instead of 0.35 which facilitates the introduction of oil into rubber , contains 2 times less resin (4.0 instead of 8.0 wt.%), high aroma content (10-20 wt.% of heavy aromatic hydrocarbons) provides better compatibility with rubber, contributes to better dispersion of soot in rubber. Example 1. To obtain an oil-based composition based on About styrene-butadiene rubber SKS (MS) -ZOARKM-15, use latex synthesized according to the following recipe, parts per 100 parts per part monomers: C, -methylstyrene or 32 Styrene 30 Butadiene 68 or 7 (respectively) Rosin soap 4, 1 Synthetic fatty acid soap1,1 LeukanolO, 3 Rongalit0,1 Trilon B0.05 Ferrous sulphate ferrous sulphate 0.025 Hydroperoxide isopropylbenzene 0,2 Tertiary dodecylmercaptan Til 0.15 Water180 Neozone d1.5 Oil fraction in the amount of 17 m.ch. polymer is introduced into flocculate (a mixture of latex with sodium chloride at. The oil-latex mixture is coagulated with sodium chloride (concentration 24-26 wt.%) and diluted (concentration 0.3 wt.%) solution of sulfuric acid at pH 3, 5-4.5 The resulting composition based on oil-filled rubber SKS MS ZOARKM-15 is tested in a standard rubber compounding according to GOST (I-38-78. In the control example, the composition based on oil-filled rubber SKS (MS) -30 ARKM-15 contains oil filler PN-6 (see table-. 2). Plastoelastic and physicomechanical the properties of the compositions are given in Table 2. From Table 2 it can be seen that the polymer composition based on SCS MS ZOARKM-15 rubber, containing the proposed oil fraction, is characterized by a better complex of the plastoelastic and physicomechanical properties compared to the control one. The preparation of an oil-filled composition based on butadiene-methylstyrene rubber SKMS {с) -ОАРКМ-27 uses latex synthesized according to the following recipe, ma.h. per 100 mph monomers: oC Metylethyrol or 32 Styrene. 30 Butadiene 58 or 70 (correspondingly) Disproportionate Rosin 2.45 Synthetic Fatty Acid Soap 2.45 Leikanol0.3 Rongalite0.07 Trilon B0.020 Ferrous sulfate acidic 0.101 hydroperoxide isopropylcyclohexylbenzene and 01:00, and it is a part of the sequence. containing 1020 wt.% heavy aromatic hydrocarbons, in the amount of 37.5 wt.h. on 100 ma.ch. the polymer is introduced into the flocculus at 25-30 ° C. The oil-latex mixture is coagulated with a saturated solution of sodium chloride and diluted (o, 3-1, o may.% Solution of sulfuric acid at pH 3.5-4.5. The resulting composition based on oil-filled SKMS rubber (C) ZOARKM-27 is tested in the standard rubber compounding according to GOST 15628-70 (Table 3).

Obtaining a control sample described in example 1.

The plastoelastic and physicomechanical properties of compositions based on SKMS (C) -ZOLRM-27 rubber are given in Table. 3

The results table. 3 shows that the proposed rubber composition based on CKMC (G) ZOARKM-27 rubber has the best complex of plastoelastic properties.

Example 3. To obtain an oil-filled composition based on SCS (MS) -OAPKM-33 rubber, a latex was synthesized according to the recipe given in Example 2, with the adjustment of the initiator of the polymerization process and the regulator of molecular x-ray polymer distribution molecules.

As an initiator, a mixture of isopropylcyclohexylbenzene hydropereoxide and isopropylbenzene hydroperoxide (in a 1: 1 ratio) in an amount of 0.065 parts per hour per 100 parts per hour of monomers is used.

The molecular weight regulator is tertiary dodecyl mercaptan up to 0.2 wt.h. on 100 ma.ch. monomers.

The oil fraction in the amount of 50 wt. on 100 ma.ch. the polymer is introduced into the flocculated at 50-55 ° C. The maleo-latex mixture is coagulated with a saturated solution of sodium chloride and diluted (0.3-1.0 wt.% solution of sulfuric acid at pH 3.5-4.5;

The resulting composition based on oil filled rubber SKS (ARKM-33 is tested in a standard rubber compounding according to GOST 15628-70. (Table 4).

Obtaining a control sample described in example 1.

Plastoelastic and physicomechanical evoyetva compositions based on rubber SKS (MS) -OARKM-33 are given in Table. four

The results table. 4 show that the proposed composition based on the SCS (MS) -30 rubber ARPM-33 has the best complex of the flame-elastic properties.

Example 4. To obtain an oil-filled composition based on emulsion butadiene rubber SKD, latex synthesized according to the following recipe, wt.h. on 100 ma.ch. monomers

Butadiene100

Soap rosin 2.45 Soap eintetichee fatty acids 2.45 Leukanol0.3

Rongalit0.07

Trilon B0.04

Ferrous sulphate ferrous sulphate 0.02 Hydroperoxide from 0 propyl benzene +

+ hydroisol of isopropyl cyclohexylbazole (1: 1 by weight) 0.06 5 Tertiary dodecyl mercaptan, 3.

Water180

Neozon D.1,5

Polymerization temperature is about.

Oil fraction in the amount of 17 wt. on 100 ma.ch. polymer is introduced into the mixture of latex with sodium chloride at 25-30 ° C. Oil-latex 5 mixture is coagulated with sodium chloride (24-26 wt. Dil. (0.3 - .1 wt.%) Solution of sulfuric acid. The resulting composition based on oil-filled butadiene cueQ SKDM-15 is tested in a standard rubber compounding according to GOST 149- 24-75 (tab. 5),

Paleoelectric and physicomechanical properties of compositions based on oil-filled rubber 5 SKDM-15 are listed in the tabl. five.

The results table. 5 show that the vulcanizate on the basis of the proposed CS ptosis compared with the control one has the best complex of physical and mechanical properties. Polymer composition on the basis of SCS (MS) -30 ARKM-15, SCS (MS) 30 ARKM-27 and SCS (MS) -30 ARKM-ZZ based rubbers, with the proposed oil fraction in the amount of 17- 50 ma.ch. on 100 ma.ch. polymer, allows to reduce the rubber compound by 8%, increase the plasticity of the rubber mixture by 10%, to increase the elasticity of the rubber mixture by rebound by 12% and to increase the life of rubber products.

The polymer composition on SKFM-15 rubber on a new oenove 5 makes it possible to increase the conditional strength by 9i and tear resistance by 20%, to increase the resistance to multiply by a factor of 1.5, as well as the service life of rubber products.

T a b l and c a

Density at 2SRc, kg / m Refractive indices at 50 ° C, Viscosity at 100 s, cm Vc Aniline point, ° C Group chemical composition,% Hydrocarbons: paraffin-naphthenic aromatic, including: light medium heavy resins Fractional composition From 420-500

Elastic recovery of rubber compound, mm

Rubber hardness

Nominal tensile strength, MPa 960 1,540 0.165 53.2 81.5 27.2 39.7 14.6 4.0

table 2

1.25 65

26.5 960 1.5200 0.350 67 arb. 8.0 60-600

Relative extension

at break,%

Relative residual

deformation after rupture,

Rebound elasticity

at 20 ° С,%

Resistance multiple times

stretching thous.

Glass transition temperature,

with

Heat generation, €

Growth resistance

ths

Plasticity of rubber

Elastic recovery of rubber, mm

Plasticity rubber compound

Restorability of rubber mix, mm

Elastic recovery of rubber compound, mm

f

Rubber hardness

Conventional tensile strength, MPa

Relative lengthening. At break,%

Relative residual deformation after rupture

Rebound elasticity at 20 ° С,%

Continued table. 2

646 20 30 52.0

-54 94

18,8

Table 3

0.29

W, 4 0.35

2.6

1.64

61

24.0

617

15 32

Glass transition temperature, with

Thermodynamic stability (creep),%

Resistance to crack propagation, thous.

Indicators

Plasticity of rubber

Elastic resistance of rubber, mm

Plasticity rubber compound

Composition of rubber compoundability, mm

Elastic recovery of rubber compound, mm

Rubber hardness

Conventional tensile strength, MPa

Relative elongation at break,%

/

Relative residual deflation after rupture,%

Elartichnost on rebound at 20 "C,%

Glass transition temperature, with heat generation, With

Resistance to multiple dilution, thou. C.

Hysteresis loss at c 100 20

Continued table. 3 b

-49

76.0

15.0

Table 4

Predlagae 4a composition based on rubber SKS (MS) -30 ARKM-33

0.20 3.2 0.39 1.9

1.34 50

22.5

686

20

27

-52.

88

13.7

0.23 0.33

Claims (1)

SUMMARY OF THE INVENTION A vulcanizable polymer composition comprising diene rubber and an oil filler plasticizer, characterized in that, in order to improve the plastoelastic properties of the composition and the physical and mechanical properties of the rubbers from it, it contains an oil fraction isolated by vacuum distillation of a distillate mixture as a plasticizer filler and residual aro1210 57,545.8 104106 -73-72 0.35 0.43 0.38 0.47 27.4 19.7 0.23 0.25 - 0.28 0.30 fifty fifty math extracts in a ratio of 1: 2 and a boiling point of 420 500 ° C _g containing 10-20 wt.% heavy aromatic hydrocarbons, in 55 quantities of 17-50 wt.h. per 100 parts by weight rubber.