RU2270211C2 - Additive for rubber mixture - Google Patents

Abstract

FIELD: organic chemistry, polymers.

SUBSTANCE: invention relates to production of rubber mixture containing sulfur as vulcanizing agent, and more particularly to additive for rubber mixture improving consumption characteristics thereof. Claimed additive contains salt of iron (II), cadmium, copper, nickel, cobalt, tin, lead, and zinc or mixture thereof in form of bromide, nitrate or chloride (10-40 mass %); mixture of organic ester(s) with polyglycol(s) having boil temperature not less than 150°C in ratio of ester: polyglycol from 1:4 to 4:1 (10-25 mass %); polyvinyl chloride (20-55 mass %) and if necessary stearin, kaolin, or aerosil or mixture thereof (0-45 %).

EFFECT: additive for rubber mixture capable to reduce vulcanizing agent odor from rubber mixture and to improve vulcanizing agent physical and chemical characteristics.

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Description

The invention relates to the field of creating a material used as an additive to a rubber compound containing sulfur as a vulcanizing agent.

A known additive to the rubber mixture based on esters [Products of the company "DOG", Rubber and Rubber, No. 3, 2002]. However, this additive does not increase the physical and mechanical properties of vulcanizates from the rubber compound.

The closest solution is to add to the rubber mixture based on ester and zinc and cadmium chlorides [SU 1010083 A, Bull. No. 13, 1983]. However, this additive is either poorly distributed in the rubber mixture (with cadmium chloride), or loses its activity during storage (with zinc chloride), and in addition it does not reduce the smell of vulcanizates.

The purpose of the invention is to create an additive to the rubber compound containing sulfur as a vulcanization agent, which is stable during storage, reduces the smell of vulcanizates from the rubber mixture and increases their physical and mechanical properties.

This goal is achieved in that the additive introduced into the rubber mixture in an amount of from 0.5 to 20.0 mass parts per 100.0 mass parts of rubber, has the following composition in% by weight:

1. A salt or mixture of salts of ferrous iron, cadmium, copper, nickel, cobalt, tin, lead and zinc in the form of bromide, nitrate, sulfate or chloride 10-40 2. The combination of organic ether or mixture esters with polyglycol or polyglycols with a boiling point not lower than 150 ° C and with the ratio of ether: polyglycol from 1: 4 to 4: 1 10-25 3. Polyvinyl chloride 20-55 4. The rest, if necessary separately or as a mixture - stearin, kaolin, or aerosil 0-45

Example 1. We make a rubber mixture of the following composition:

SKI-3 - 100.0; zinc oxide - 3.0; stearin - 2.0; acetonanil - 2.0; Diafen FP - 1.0; carbon black P 324 - 40.0; sulfur - 2.5; altax - 1.5; additive from 0 to 20.0. The composition of the additive is shown in table 1, the content of the additive in the rubber compound and the physical and mechanical properties of the vulcanizates are shown in table 2. Additive No. 6 (proposed) and additive No. 13 (prototype) were introduced into the rubber mixture immediately after its manufacture (*) and after 6 -monthly storage (**).

It can be seen from the above data that during storage of a known additive, it completely loses its properties, and the physicomechanical parameters of vulcanizates with this additive are even lower than from a mixture without an additive, while the proposed additive has completely retained its activity.

Example 2. We make a rubber mixture of the following composition:

SKMS-30ARKM-15 - 60.0; SKI-3 - 40.0; zinc oxide - 3.0; stearin - 1.0; diaphene - 0.5; acetonanil - 2.0; sulfur - 2.2; sulfenamide - 0.6; altax - 1.2; filler - 40.0; additive No. 6 (see table 1) —0 or 30. As a filler, mixture No. 1 contained P 324 without additives, No. 2 — P 324 with additive, No. 3 — P 514 with additive, No. 4 — P 702 with additive , No. 5 - a combination of P 324 - 20.0 and 20.0 chalk, No. 6 - a combination of P 324 (20.0) and T-900 (20.0), where P 324, P 514, P-702 - technical carbon of different brands.

Table 3 shows the physico-mechanical properties of the vulcanizates from this mixture. From the above data it is seen that vulcanizates from a mixture with an additive are superior in elastic strength to vulcanizates without an additive, even in the case of a 50% replacement of an active filler with an inactive filler.

Example 3. We make a rubber mixture of the following composition:

BNKS-18AMN - 100.0; zinc oxide - 3.0; acetonanil 3.0; P 514 - 50.0; DBP - 12.0; sulfur -1.0; sulfenamide C - 2.0; altax - 2.2; additive 0 or 4.0. The additive introduced into the rubber mixture had the following composition: diethylene glycol - 5.0; dibutyl phthalate - 10.0; salt - 35.0; polyvinyl chloride - 50.0. In the rubber mixture No. 1 of the additive, ZnCl _{2 was} contained as a salt; No. 2 - ZnNO ₃ 6H ₂ O; No. 3 - ZnSO ₄ 7H ₂ O; No. 4 — ZnBr ₂ , and mixture No. 5 — did not contain an additive. Table 4 shows the physical and mechanical properties of the vulcanizates. From the above data it is seen that the proposed additive reduces or eliminates the characteristic smell of vulcanizates and increases their hardness, conditional tensile strength, stress at a given elongation, reduces the swelling of vulcanizates in hydrocarbons and reduces residual deformation.

Table 1. The composition of additives to the rubber mixture,% by weight No. p / p Name of materials Suggested supplement Prototype one 2 3 four 5 6 * 7 8 9 10 eleven 12 13* one Salt SnCl ₂ 2H ₂ O thirty 10 CoCl ₂ 6H ₂ O twenty 10 Cdcl ₂ 40 10 CuCl ₂ 2H ₂ O twenty 10 10 NiCl ₂ twenty 10 PbCl ₂ thirty 10 ZnCl ₂ 40 10 10 10 80 FeCl ₂ 4H ₂ O thirty 2 Polyglycol Diethylene glycol 10 10 fifteen 10 fifteen 10 Glycerol 10 twenty fifteen 10 5 PEG-115 ¹ 5 10 5 5 5 3 Ether Dibutyl phthalate fifteen twenty 10 fifteen fifteen 5 10 10 fifteen twenty Polyester PDA-400 10 Ether LZ-7 5 Dibutyl phosphate 5 four Polyvinyl chloride 35 40 55 thirty 45 35 40 twenty 45 45 45 45 5 Rest Stearin 10 fifteen 10 5 twenty Kaolin 10 25 Aerosil 175 10 ¹ - polyethylene glycol; * - additives were used immediately after manufacture and after 6 months of storage.

Table 3 Physico-mechanical properties of vulcanizates Indicators Option No. one 2 3 four 5 6 1. ISO hardness, conv. units 63 67 66 65 62 65 2. Conditional tensile strength, MPa 17.4 20,2 18,4 18.0 17.3 16.8 3. Stress at 300% elongation, Kn / m 10.8 12.7 11.8 11.7 11.6 11.7 4. Indicators after aging in air of 100 ° × 72 hours hardness, conv. units 73 72 72 71 67 71 strength, MPa 16.7 19.8 17.0 17.1 16.5 16.6 residual deformation at 25% compression,% 22.9 19.6 19.3 18.0 16,0 17.0 Table 4 Physico-mechanical properties of vulcanizates Indicators Option No. one 2 3 four 5 1. ISO hardness, conv. units 67 63 61 65 58 2. Strength, MPa 13.8 13.9 13.5 3. Elongation,% 490 600 630 550 680 4. Stress at 300% elongation, Kn / m 9.6 8.4 7.9 9.1 7.0 5. The change in volume in a mixture of isooctane: toluene (70:30),% 68 90 93 87 106 6. The temperature of brittleness, ° C 57 56 56 56 55 7. The presence of odor in the vulcanizate - + - + - + - ++

Claims (1)

An additive to a rubber composition containing sulfur as a curing agent, including a salt or a mixture of salts of ferrous iron, cadmium, copper, nickel, cobalt, tin, lead and zinc in the form of bromide, nitrate or chloride, a combination of organic ether or ethers with polyglycol or polyglycols , with a boiling point not lower than 150 ° C and with an ether: polyglycol ratio of 1: 4 to 4: 1, polyvinyl chloride and, if necessary, stearin, kaolin or aerosil, taken individually or as a mixture, in the following ratio of the components of the additive , wt.%: Salt or salt mixture ferrous iron cadmium, copper, nickel, cobalt, tin, lead and zinc in the form of bromide, nitrate or chloride                                    10-40 Organic ester combination or esters with polyglycol or polyglycols with temperature their boiling is not lower than 150 ° С and with the ratio of ether: polyglycol from 1: 4 to 4: 1, respectively 10-25 Polyvinyl chloride 20-55 Stearin, kaolin or Aerosil 0-45