Wide-distribution polyisocyanate-coupled multi-arm star random butadiene-styrene copolymer and preparation method thereof

A technology of polyisocyanate and random copolymer, which is applied in the field of multi-arm star-shaped random styrene-butadiene copolymer and its preparation, can solve the problem that white carbon black cannot be effectively melted in the rubber compound, raw rubber has low elastic memory, dynamic Issues such as heat generation and reduced rolling resistance

Active Publication Date: 2014-10-15
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The present invention aims at the narrow molecular weight distribution of solution-polymerized styrene-butadiene rubber in the prior art, the elastic memory of the raw rubber is not high, and the Weissenbery effect is also low, and the high-cis-rare-earth polymer with high molecular chain regularity and large cold fluidity Butadiene rubber and white carbon black have low frictional heat generation during the mixing process in the internal mixer, white carbon black cannot be effectively melted in the rubber compound, and the rubber compound cannot be mature

Method used

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  • Wide-distribution polyisocyanate-coupled multi-arm star random butadiene-styrene copolymer and preparation method thereof
  • Wide-distribution polyisocyanate-coupled multi-arm star random butadiene-styrene copolymer and preparation method thereof
  • Wide-distribution polyisocyanate-coupled multi-arm star random butadiene-styrene copolymer and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0092] (1) In a clean and dry 1000mL three-necked bottle under the protection of nitrogen, add anhydrous 425mL toluene, TMP80g, TDI290.58g respectively, at this time TMP / TDI=1:3.02 (mass ratio), in After stirring at a constant temperature of 75-80°C for 6-8 hours, the measured solid content was 49.6wt%, and the concentration of isocyanate was 0.83mol / L. The average functionality of the adduct molecule contains 3 -NCO.

[0093] (2) Add anhydrous 425mL toluene, TMP80g and TDI239.60g respectively in a clean and dry 1000mL three-necked bottle under the protection of nitrogen gas. At this time, TMP / TDI=1:2.52 (mass ratio), constant temperature After stirring for 6-8 hours at 75-80°C, the measured solid content was 50.3wt%, and the concentration of isocyanate was 0.74mol / L. The average functionality of the adduct molecule contains 4 -NCO.

[0094] (3) Add anhydrous 425mL toluene, TMP80g and TDI219.87g respectively in a clean and dry 1000mL three-necked bottle under the protection ...

Embodiment 2

[0100] Steps (1) to (6) are the same as in Example 1,

[0101]Take 2mL of chemically pure TDI with a mass content of 99%, 15mL of the prepolymer in (1), 20mL of the prepolymer in (2), 35mL of the prepolymer in (3), 15mL of the prepolymer in (4), Inject 18mL of the prepolymer in (5) and 3mL of the prepolymer in (6) into a 100mL dried volumetric flask, then add an appropriate amount of toluene and mix well to make a polyisocyanate with an isocyanate concentration of 0.85mol / L. Isoacid coupling agent.

Embodiment 3

[0103] Under the protection of nitrogen, add 3.5 L of hexane-cyclohexane mixed solvent and 0.98 g of tetrahydrofurfuryl alcohol ethyl ether into a 5-liter polymerization kettle, start stirring within 40 minutes, and continuously and uniformly add 0.5 mol / L of n-butyl Lithium 13mL, and 132.5g of styrene and 397.5g of butadiene mixed monomers, the polymerization is carried out at 50-75°C, after the addition of the monomers, react for 25min, and then add the isocyanate concentration in Example 1. 9.5mL of 0.68mol / L prepolymer was subjected to coupling reaction, the coupling reaction temperature was 60-75°C, and the time was 25min. The obtained one-arm to eight-arm SSBR was filled with 198.1g of TDAE oil, condensed and dried to obtain SSBR filled Oil raw rubber, in which the number average molecular weight of single-arm polymer is 8.1×10 4 , the average number average molecular weight of the conjugate is 42×10 4 , molecular weight distribution index 2.23, vinyl content 74.6%, Moo...

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Abstract

The invention discloses a wide-distribution polyisocyanate-coupled multi-arm star random butadiene-styrene copolymer and a preparation method thereof. The preparation method comprises: mixing butadiene and/or isoprene with styrene, continuously adding into a solvent within 40-60 min, under the effect of a C2-6 alkyl ether of tetrahydrofurfuryl alcohol and butyllithium, performing polymerization at 45-75 DEG C, so as to obtain an active butadiene-styrene random copolymer; and performing coupling on the obtained butadiene-styrene random copolymer with a polyisocyanates prepolymer coupling agent at 50-75 DEG C, and after coupling is finished, terminating with water, so as to obtain the copolymer. The random butadiene-styrene copolymer has high molecular weight distribution, the middle ends have a relatively large number of polar groups, and the main chain has a high short-branched-chain content. When being matched and mixed with rare earth BR (rare earth-based cis-1,4-polybutadiene rubber) with high linearity and white black carbon, the random butadiene-styrene copolymer has extremely good compatibility with white carbon black, the mechanical properties and the wet skin resistance of the rubber material are both improved, dynamic heat build-up and rolling resistance are substantially reduced, and the random butadiene-styrene copolymer is a relatively ideal high-performance tyre surface rubber material. The simple rapid preparation method for the random butadiene-styrene copolymer is suitable for industrialized production.

Description

technical field [0001] The invention relates to a multi-arm star-shaped random styrene-butadiene copolymer coupled with wide-distribution polyisocyanate and a preparation method thereof, belonging to the field of synthesis of modified styrene-butadiene rubber. Background technique [0002] Styrene and conjugated diene can be directionally polymerized into a random copolymer under the trigger of butyllithium in a solvent. This material is especially suitable for making tires. As an ultra-high performance tire compound, SSBR with high vinyl content, high cis-butadiene rubber and white carbon black are its main components. However, due to the low Weissenbery effect and elastic memory effect of general-purpose SSBR, during the mixing process of high-cis-rare-earth polybutadiene rubber and white carbon black with high molecular chain regularity and high cold flow in the internal mixer, the rubber The shear force of the material in the mixing process is insufficient, the friction...

Claims

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Application Information

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IPC IPC(8): C08F236/10C08F236/06C08F236/08C08F212/08C08C19/22C08L9/06C08L15/00
Inventor 张建国蒋文英
Owner CHINA PETROLEUM & CHEM CORP
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