Two-end functionalized ternary copolymer rubber and preparation method thereof

A ternary copolymer rubber and double-end technology, applied in the field of new ternary copolymer rubber, can solve the problems of low degree of functionalization of alkoxy groups, unstable functionalized initiator, unable to maintain the growth of active ends, etc., to achieve solubility good effect

Active Publication Date: 2018-06-01
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, multifunctional initiators have problems such as unstable storage and high system viscosity when initiating polymerization, resulting in a low degree of functionalization of siloxane groups. When preparing high-molecular-weight rubber materials, the degree of functionalization is only 40-60%. , the most important thing is to bring an excessive amount of functionalized end-capping agent and hydrogen chloride generated by the reaction into the polymerization system, which brings great difficulties for solvent refining and recycling, and limits its application in industrial production
[0006] From the existing report technology, there are mainly the following deficiencies: (1) some functional groups can only partially modify one end of the macromolecular chain, and usually only interact with carbon black or white carbon black, but cannot simultaneously improve the interaction with carbon black, Compatibility of white carbon black; (2) functionalized initiators are unstable and usually have relatively poor solubility in hydrocarbon solvents of the type usually used for anionic polymerization; (3) functionalized initiators are used for polymerization During the process, the viscosity of the system is too high to maintain the growth of the active end, which negatively affects the polymerization rate and efficiency; (4) the degree of functionalization of the alkoxy groups prepared by the end-capping agent method is not high, and the dispersion effect of rubber and silica is not improved. Obviously; (5) It is mainly used for the modification of butadiene and styrene copolymerization, but there are few reports for the modification of butadiene, styrene and isoprene copolymerization

Method used

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  • Two-end functionalized ternary copolymer rubber and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Under the protection of anaerobic, anhydrous, and argon, add 700ml of hexane and 3mol of metal lithium wire into a 1000ml three-necked flask equipped with a condenser, dropping funnel, and magnetic stirrer, raise the temperature to 50°C, and add Add 1.36 mol of trimethoxy (4-chlorobutoxy) silane solution slowly (dropping rate: 0.03 mol / min) into the three-necked flask, stir while adding, and use cold oil to lower the temperature, and control the reaction temperature at 50-60°C , the dropwise addition time is 1h, after the dropwise addition is complete, the constant temperature reaction is continued for 2h, the crude product is filtered under an inert atmosphere to obtain a functionalized initiator, and finally an organolithium initiator containing silicon ether is obtained for future use.

[0026] In a jacketed 15L stainless steel polymerization kettle, the system was replaced 3 times with argon gas. Add 2654g of cyclohexane, 400g of isoprene, and 0.12g of tetrahydrofur...

Embodiment 2

[0030] Under the protection of anaerobic, anhydrous, and argon, add 700ml of hexane and 3mol of metal lithium wire into a 1000ml three-necked flask equipped with a condenser, dropping funnel, and magnetic stirrer, raise the temperature to 50°C, and add Add 1.36 mol of triethoxy (4-chlorobutoxy) silane solution slowly into a three-necked flask (dropping speed 0.05 mol / min), stir while adding, and use cold oil to cool down, and control the reaction temperature at 50-60°C , the dropwise addition time is 1h, after the dropwise addition is complete, the constant temperature reaction is continued for 2h, the crude product is filtered under an inert atmosphere to obtain a functionalized initiator, and finally an organolithium initiator containing silicon ether is obtained for future use.

[0031] In a jacketed 15L stainless steel polymerization kettle, the system was replaced 3 times with argon gas. Add 1991 g of cyclohexane, 300 g of isoprene, and 0.08 g of tetrahydrofuran into the ...

Embodiment 3

[0035] The preparation of the functionalized catalyst was the same as in Example 1.

[0036] In a jacketed 15L stainless steel polymerization kettle A, the system was replaced 3 times by passing argon. Add 3318g of cyclohexane, 500g of isoprene, and 0.18g of tetrahydrofuran into the polymerization kettle, add 5.0mmol of n-butyllithium, raise the temperature to 70°C, and polymerize for 60min. After the monomer is completely converted, add 2674g of cyclohexane, butane Diene 240g, styrene 160g, tetrahydrofuran 0.24g, reaction temperature 70°C, polymerize for 70min, add cyclohexane 652g, butadiene 100g after complete monomer conversion, maintain reaction temperature 70°C, continue to react for 60min, after the completion of the reaction, pass Inject carbon dioxide gas to carry out capping reaction, and the reaction time is 20min. After the end-capping reaction is completed, add 10 g of antioxidant 1010 [tetrakis-(4-hydroxy-3,5-tert-butylphenylpropionic acid) pentaerythritol ester...

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Abstract

The invention provides a ternary copolymer rubber with functionalized modification at both ends of the macromolecular chain, which uses a functional initiator and an end-capping method to make both ends of the molecular chain contain different functional groups and simultaneously combine with carbon black / silica Good binding force: one end adopts the organolithium initiator of the protective group to make the molecular chain contain [—Si‑(OR)3] group, which is helpful to realize the nano-dispersion of the filler in the rubber matrix; the other end contains (—COOH ) group, which is beneficial to interact with carbon black, thereby promoting the dispersion of carbon black in the rubber matrix. At the same time, due to the interaction between the two ends of the macromolecular chain and carbon black / silica, the degree of freedom of the chain link between the final cross-linking point and the chain end in the rubber network is reduced, so that it can effectively participate in the elastic recovery of the entire cross-linking network , reduce energy loss in periodic deformation, improve heat generation and rolling resistance. The double-end functionalized ternary copolymer rubber of the present invention is an ideal rubber for high-performance tires due to its low rolling resistance and high anti-wet skid resistance.

Description

technical field [0001] The invention belongs to the technical field of synthetic rubber, and relates to a double-terminal functionalized ternary copolymer rubber and a synthesis method thereof, thereby obtaining a novel ternary copolymer rubber with excellent comprehensive performance, especially high wet skid resistance and low rolling resistance. Background technique [0002] With the technological progress of the automobile and tire industry, the performance requirements of synthetic rubber are getting higher and higher. Tire tread rubber should not only have low rolling resistance and good wet skid resistance, but also have excellent wear resistance, etc. . Solution-polymerized styrene-butadiene rubber (SSBR) has gradually become one of the preferred rubbers for high-performance tire treads due to its good balance of low rolling resistance and high wet skid resistance. Terpolymerized rubber (SIBR) is a new generation of polystyrene butadiene rubber. Its design concept i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F297/04C08F8/00C08L53/02
Inventor 董静赵旭涛张华强陈红宋同江崔英崔彦君陶惠平康安福龚光碧郑聚成李晶梁滔丛日新
Owner PETROCHINA CO LTD
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