Wide-distribution, high-elasticity and functionalized solution polymerized styrene-butadiene rubber, preparation method and application thereof in tire tread rubber

A solution-polymerized styrene-butadiene rubber, high-elasticity technology, used in special tires, tire parts, transportation and packaging, etc. Issues such as literature submission

Pending Publication Date: 2020-10-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Carlo kanz, Mamer (LU) US2012 / 0123018A1 describes the use of amine-containing silicon compounds to couple butyllithium-initiated butadiene-styrene polymers. Such coupling agents include N,N-bistrimethylsilyl -Aminopropylene-triethoxysilane, N,N-bistrimethylsilyl-aminoethylene-triethoxysilane, N,N-bistrimethylsilyl-aminopropylene- Methyldimethoxysilane, N,N-bistrimethylsilyl-aminopropylene-methyldimethoxysilane and other compounds, the described high-performance tread rubber formula contains aminosiloxane In addition to the alkane-coupled SSBR, it also contains high cis-BR, white carbon black, tackifying resin, etc., but the end group blocking rate of this aminosiloxane-coupled SSBR is less than 50%, and the molecular weight distribution index of the prepared polymer is Both are less than 1.6, the melt elasticity is small, and the processing performance of rubber in the white carbon black formula is not good
[0006] Up to now, there is no complete literature report on the preparation of wide molecular weight distribution, high melt elasticity, and functionalized solution-polymerized styrene-butadiene rubber by discontinuous method.

Method used

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  • Wide-distribution, high-elasticity and functionalized solution polymerized styrene-butadiene rubber, preparation method and application thereof in tire tread rubber
  • Wide-distribution, high-elasticity and functionalized solution polymerized styrene-butadiene rubber, preparation method and application thereof in tire tread rubber
  • Wide-distribution, high-elasticity and functionalized solution polymerized styrene-butadiene rubber, preparation method and application thereof in tire tread rubber

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058]In a 10-liter polymerization kettle under the protection of nitrogen, add 7000 mL of cyclohexane solution with a mass fraction of 10% n-hexane, start stirring, then add 3 mL of 99.0% tetrahydrofurfuryl alcohol ethyl ether ETE, 0.8 mol / L of DVB 8ml of cyclohexane solution, 4.0mL of isoprene and 16mL of 0.72mol / L NBL, heated to 52°C and reacted for 15-20min; then added 1.0mL of DBU, followed by 200mL of styrene and 800mL of butanediol The mixed monomers of olefins are subjected to two-stage copolymerization reaction, and the temperature rise-time curve of random copolymerization reaction is shown in figure 1 , when the polymerization temperature rises to the highest temperature of 72°C, react for 28 minutes, then add 0.70mol / L N,N'-dimethylimidazolinone 12mL to the active glue in the polymerization kettle, Capping reaction 25 ~ 30min, that is. Finally, the glue is discharged, hydrolyzed, coagulated, and dried to become F-SSBR raw rubber.

[0059] The vinyl mass content o...

Embodiment 2

[0061] The relevant process conditions in Example 1 were kept unchanged, except that the DBU added was 0.8 mL. The second-stage polymerization state is as follows: the initial polymerization temperature of the second stage is 53.5°C, the heating time of the mixed monomer polymerization is 16min, the highest polymerization temperature is 69.5°C, and the total polymerization time of the second stage is 60min; then the active glue in the polymerization kettle Add 15mL of 0.70mol / L N,N'-dimethylimidazolidinone to the mixture, react at 55~60℃ for 20min, then add 0.70mol / L trimethylsilyl chloride to the polymerization glue 8mL can be condensed with lithium on dimethylimidazolinone for 15min.

[0062] After the glue is discharged, hydrolyzed, coagulated, and dried, it becomes F-SSBR raw rubber. The vinyl mass content of the butadiene segment in the F-SSBR molecule was measured to be 60.4%, the number average molecular weight of the polymer Mn=102700, the molecular weight distributio...

Embodiment 3

[0064] The relevant process conditions in Example 1 were kept unchanged, except that the added DBU was 1.2mL, DVB was 10mL, and NBL was 19mL. The second-stage polymerization state is as follows: the initial polymerization temperature of the second stage is 47.6°C, the heating time of the mixed monomer polymerization is 20min, the highest polymerization temperature is 66°C, and the total polymerization time of the second stage is 70min; then the active glue in the polymerization kettle Add 15 mL of 0.70 mol / L N,N'-dimethylimidazolidinone to the polymer solution, and react at 66°C for 20 min, then add 0.70 mol / L trimethyl-chlorosilane 8 mL and Lithium on the dimethylimidazolinone can be condensed for 15 minutes.

[0065] After the glue is discharged, hydrolyzed, coagulated, and dried, it becomes F-SSBR raw rubber. The vinyl mass content of the butadiene segment in the F-SSBR molecule was measured to be 66.4%, the number average molecular weight of the polymer Mn=86300, the mole...

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Abstract

The invention discloses a wide-distribution, high-elasticity and functionalized solution polymerized styrene-butadiene rubber, a preparation method and application thereof in tire tread rubber. The preparation method includes: firstly adding divinyl benzene, conjugated diene and an alkyl lithium initiator into an anionic polymerization solution system for polymerization reaction; sequentially adding a diazo reagent and a styrene / butadiene mixed monomer, and carrying out random copolymerization reaction; finally, adding a polar end-capping reagent for end-capping reaction, and conducting hydrolysis and coagulation, thus obtaining the solution polymerized styrene-butadiene rubber (SSBR) with wide molecular weight mass distribution (D is greater than or equal to 1.8), long and short branchedchains, wide molecular fraction and high melt elasticity, wherein functional groups at the tail ends of molecular chains are closed in a head-tail mode, and the end capping rate is larger than 75%. The rubber replaces existing conventional SSBR to be used for tire tread rubber, the processability can be obviously improved, and the rolling resistance of a tire is reduced.

Description

technical field [0001] The invention relates to an elastomer material, in particular to a wide distribution, highly elastic and functionalized solution-polymerized styrene-butadiene rubber, and also relates to its application in tire tread rubber, which belongs to the field of tire tread rubber elastic material preparation. Background technique [0002] Since solution polystyrene-butadiene rubber (SSBR) adopts anionic polymerization method, the product structure is easy to adjust and the brand is rich. Compared with ESBR, SSBR can reduce the rolling resistance of tires by 20-30%, and improve the wet skid resistance by 30-40%. The development trend of SSBR used as the main material of tires is to have intelligent processing, and high performance of safety, comfort and energy saving when the tire is running. Functionalization is the most effective way to achieve high performance of SSBR. That is to say, the development trend of today's SSBR is that the content of vinyl units...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F297/04C08F212/08C08F212/36C08F236/10C08F2/38C08L9/06C08L9/00C08K13/02C08K3/36C08K3/04C08K3/22C08K5/09C08K3/06B60C1/00
CPCB60C1/0016C08F2/38C08F212/08C08F212/36C08F236/10C08F297/04C08F297/046C08K2003/2296C08L9/06C08L9/00C08K13/02C08K3/36C08K3/04C08K3/22C08K5/09C08K3/06Y02T10/86
Inventor 邢立江张建国王旭蒋文英
Owner CHINA PETROLEUM & CHEM CORP
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