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Polybutadiene-isoprene rubber simultaneously containing micro-blocks and long-chain blocks and preparation method of polybutadiene-isoprene rubber

A technology of isoprene rubber and long-chain blocks, which can be used in transportation and packaging, tire parts, special tires, etc. It can solve the problems of poor processing performance, low T-1,4 content, high viscosity, etc., and achieve excellent performance effect

Pending Publication Date: 2021-01-12
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] In order to overcome the poor performance of the existing high-cis BR and NR composite materials, or the narrow molecular weight distribution of BR synthesized by lithium-based catalysis, poor processability, low T-1,4 content, easy crystallization, and the existing TBIR Due to the high viscosity, there are problems such as poor processability. The first object of the present invention is to provide a kind of polyisoprene micro-block and polyisoprene Polybutadiene-isoprene rubber (BIR) with long-chain blocks, and the 1,2-addition units of the butadiene segment and the 3,4-content addition units of the isoprene segment in the rubber are less than 10%, the cis (c-1,4) adduct content of isoprene unit and butadiene unit is less than 8%, and the trans T-1,4 adduct content is higher than 80%, which can improve The strength and melt elasticity of polymer raw rubber reduce its crystallinity; this rubber and natural rubber are used in radial tire treads, sidewalls, inner liners and belt layers. The two have good compatibility and strengthen vulcanization. The anti-aging and anti-cracking of the material can improve the force of the carcass and the impact resistance of the cushion, and reduce the rolling resistance of the tire; especially the compound rubber has the characteristics of good adhesion to the steel wire, anti-aging and anti-digging (winding) fatigue, etc. Replace BR or existing TBIR in the traditional formula (the composite of BR and NR has the disadvantages of poor matrix compatibility, easy aging and cracking)

Method used

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  • Polybutadiene-isoprene rubber simultaneously containing micro-blocks and long-chain blocks and preparation method of polybutadiene-isoprene rubber
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  • Polybutadiene-isoprene rubber simultaneously containing micro-blocks and long-chain blocks and preparation method of polybutadiene-isoprene rubber

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0060] Add 7000mL of n-hexane to a 10-liter polymerization kettle under the protection of nitrogen, start stirring, then add 0.05mL of anisole with a mass fraction of 99.0%, and then raise the temperature of the polymerization solution to 70°C; Press the pre-selected mixed monomer composed of butadiene, isoprene and divinylbenzene into the polymerization kettle (the mixed monomer consists of 1055g butadiene, 305g isoprene and 1.5mL divinylbenzene Benzene), while continuously adding 0.70mol / L of NBL12mL from the sight glass of the polymerization kettle, the polymerization time of monomer and NBL being continuously added to the polymerization kettle at the same time is 60min, and the polymerization reaction is carried out under adiabatic conditions. When the monomer and NBL After the addition, the polymerization temperature reaches 85-90°C. At this time, add 50mL of isoprene for the second molecular chain extension at one time, and react for 20 minutes at the temperature of the p...

Embodiment 2

[0064] Keep the relevant process conditions in Example 1 unchanged, only 0.08mL of anisole is added, and the mixed monomer used in the first stage is composed of 1055g of butadiene, 305g of isoprene and 1.8mL of divinylbenzene , The added butyllithium is 16mL, the continuous feeding time of mixed monomer and NBL is 70min, the amount of isoprene added in the second stage is 80mL, and the N,N'-dimethylimidazolinone used for capping the active chain lithium 15mL.

[0065] The results are measured: the number average molecular weight Mn=12.6×10 of raw rubber 4 , molecular weight distribution index D=1.83; the 1,2-addition unit content in the polybutadiene unit in the raw rubber is 7.87%, and the trans 1,4-addition unit content is 81.34%; the polyisoprene unit The content of 3,4-addition units is 5.64%, and the content of trans 1,4-addition units is 87.21%. The Mooney viscosity ML of raw rubber is 50.6; Tg is -78.8°C.

Embodiment 3

[0067] The relevant process conditions in Example 1 remain unchanged, only 0.10 mL of anisole is added, and the mixed monomer used in the first stage is composed of 800 g of butadiene, 533 g of isoprene and 2.2 mL of divinylbenzene , the added butyllithium is 14mL, the continuous feeding time of mixed monomer and NBL is 80min, the amount of isoprene added in the second stage is 100mL, and the amount of 0.71mol / L tributyltin chloride used for capping the active chain lithium is 14 mL of hexane solution.

[0068] The result is measured: the number average molecular weight Mn=14.2×10 of raw rubber 4 , molecular weight distribution index D=1.88; the content of 1,2-addition units in polybutadiene units in raw rubber is 8.54%, and the content of trans 1,4-addition units is 82.65%; the content of polyisoprene units in The content of 3,4-addition units is 7.48%, and the content of trans 1,4-addition units is 85.94%. The Mooney viscosity ML of raw rubber is 56.8; Tg is -81.4°C.

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Abstract

The invention discloses polybutadiene- isoprene rubber simultaneously containing micro-blocks and long-chain blocks and a preparation method of the polybutadiene isoprene rubber. Butadiene, isoprene and divinyl benzene are used as mixed monomers, alkyl lithium is used as a catalyst, and through the processes of slow initiation, slow growth, polar end capping and the like, the polybutadiene-isoprene rubber which has wide molecular mass distribution, high melt elasticity and good processability and simultaneously contains the micro-blocks and the long-chain blocks is obtained. In the polybutadiene-isoprene rubber, the number ratio of 1, 2-addition units of butadiene and the number ratio of 3, 4-addition units of isoprene are both less than 10%, and trans-addition number ratios of the isoprene units and the butadiene units are both higher than 80%. The polybutadiene isoprene rubber is suitable for rubber for tire treads, tire sidewalls, inside liners and belt plies, and especially shows excellent compatibility, cracking resistance and aging resistance and after being compounded with natural rubber.

Description

technical field [0001] The invention relates to a polybutadiene-isoprene rubber, in particular to a polybutadiene and isoprene as monomers and divinylbenzene as a branching agent, which is synthesized by lithium-based catalysis and contains Polybutadiene-isoprene rubber with polyisoprene micro-block and long-chain block, trans-1,4 structure, wide distribution, etc., especially suitable for tire tread, sidewall, inner liner The utility model relates to a rubber for a layer and a belt layer, belonging to the field of tire rubber. Background technique [0002] The BR-9000 in the prior art is a common tire rubber compound, but its Tg=-100°C, the polymer molecular chain is highly regular, and has a strong tendency to crystallize. It starts to harden at -35°C and is easy to lose elasticity. The belt layer, sidewall and other parts of the tire are usually made of natural rubber (NR) and BR together. Because the two are incompatible, the produced tire is prone to cracks, which affe...

Claims

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Application Information

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IPC IPC(8): C08F297/04C08L7/00C08L9/00C08L53/02C08K13/02B60C1/00
CPCC08F297/046C08L7/00B60C1/00C08L9/00C08L53/02C08K13/02
Inventor 张建国颜煜康铮姚琼蒋文英
Owner CHINA PETROLEUM & CHEM CORP