Double-end-functionalized ternary copolymer rubber and preparation method thereof

A ternary copolymer rubber, double-ended technology, which is applied in the field of new ternary copolymer rubber, can solve the problems of low functionalization degree of alkoxy groups, low functionalization degree, and insignificant improvement of the dispersion effect of rubber and silica, etc. , to achieve the effect of good solubility

Active Publication Date: 2016-07-06
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 s

Method used

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

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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 ternary copolymer rubber with both double ends of a macromolecular chain being functionally modified. In the invention, a functionalization initiator and an end terminating method are employed so that different functional groups are formed on two ends of the molecular chain and meanwhile the two ends of the molecular chain have excellent binding force with carbon black/white carbon black. On one end, an organic lithium initiator having a protecting group is employed to enable the molecular chain to contain a [-Si-(OR)3] group, which is beneficial to nano dispersion of a filler in a rubber substrate; and on the other end, a carboxylic group is included so that interaction with carbon black is promoted, thereby promoting dispersion of the carbon black in the rubber substrate. Meanwhile, the two ends of the macromolecular chain act on the carbon black/white carbon black to reduce the freedom degree of a chain section between a final crosslinked point and a chain terminal in the rubber network, so that the macromolecular chain effectively participates in elastic recovery of the whole crosslinked network, thereby reducing energy loss during periodic deformation and improving heat generation and rolling resistance. The double-end-functionalized ternary copolymer rubber has low rolling resistance and high anti-moisture sliding performance, so that the rubber is an excellent high-performance tyre rubber.

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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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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