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Epoxy polysiloxane modified solution polymerized styrene-butadiene rubber, preparation and application thereof

A technology of epoxy polysiloxane and solution-polymerized styrene-butadiene rubber, which is applied in the fields of tire parts, rolling resistance optimization, transportation and packaging, etc. The effect of large group equivalent

Active Publication Date: 2018-11-23
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Compiled by Li Hantang. Modified synthetic rubber for white carbon black and carbon black filled tread rubber [J]. Modern Rubber Technology, 2012, 38(5): 12-17. In this article, some scholars suggest using less polar The polymer chain of the group constitutes a new main chain modification technology that can further reduce the hysteresis loss of the vulcanized rubber and reduce the rolling resistance of the tire. Polar groups such as 4-N-(trimethyl)silyl-methyl-ethyl-styrene are used as comonomers in an amount of 1-2% of the total monomer usage, unfortunately, additional Monomers often affect polymerization kinetics and thus alter the properties of the original unmodified polymer
Additionally, legacy polymer products are often difficult to remove unconverted backbone modifiers from conventional polymerization plant streams (e.g. from solvent streams), so tertiary monomers can accumulate and prevent switching between polymer grades, What is more worth considering is that the preparation process of this type of polar monomer is long and the process is difficult. In addition, the preparation of this kind of polar monomer is also difficult, expensive and not easy to obtain.
The polar compounds contained in the SSBR molecules in the above-mentioned prior art are used as SSBR modifiers. If the polar group has a small amount in the molecular chain, it is limited to reduce the heat generation and hysteresis loss of the vulcanized rubber in the cyclic deformation.

Method used

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  • Epoxy polysiloxane modified solution polymerized styrene-butadiene rubber, preparation and application thereof
  • Epoxy polysiloxane modified solution polymerized styrene-butadiene rubber, preparation and application thereof
  • Epoxy polysiloxane modified solution polymerized styrene-butadiene rubber, preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0091] Add 3,500mL of cyclohexane solution with a mass fraction of 10% n-hexane to a 5-liter polymerization kettle under nitrogen protection, heat the material to 45-50°C with hot water, and then mix the mixture in the monomer metering tank. 100g of styrene and 482mL of butadiene were injected into the polymerization kettle with nitrogen pressure, then 1mL of tetrahydrofurfuryl alcohol ethyl ether, 50mL of cyclohexane and 8mL of 0.5mol / L n-butyllithium were added into the feeding sight glass with a syringe, and Press nitrogen into the polymerization kettle to initiate polymerization, control the polymerization temperature at 50-80°C, and maintain the reaction for 40 minutes, then inhale 105-3 type epoxy polysiloxane with an epoxy value of 0.021mol / 100g (density 1.1 ) 17mL and put into the polymerization kettle for coupling reaction, and the coupling reaction was carried out at 55-80°C for 20-60min. Finally, remove the polymer from the polymerization kettle, add 10761.2 g of an...

Embodiment 2

[0097] With the relevant process conditions unchanged in Example 1, only the styrene used is 120g, butadiene is 358mL, tetrahydrofurfuryl alcohol ethyl ether 0.8mL, 0.5mol / L n-butyllithium 12mL, 105-3 ring 18 mL of epoxy polysiloxane with an oxygen value of 0.021 mol / 100 g. Finally, it is measured that the polymer Mn=64×10 4 , the molecular weight distribution index is 1.71, the polybutadiene segment 1.2-unit content is 58.8%, the raw rubber Mooney viscosity ML=120, and the mass content of the polysiloxane chain unit combined in the coupled SSBR is 5.47% (wt).

[0098] attached figure 2 It is the H-NMR spectrogram of the SSBR after epoxy polysiloxane coupling in embodiment 2.

[0099] attached image 3 It is the infrared spectrogram (IR) after the coupling of embodiment 2, wherein VSL5025-2 is the SSBR infrared spectrogram of general type (without modification), and its purpose is to carry out the IR spectrogram after modification with epoxy polysiloxane Compared.

[010...

Embodiment 3

[0103] The relevant process conditions in Example 1 were kept unchanged, only 1.2 mL of ditetrahydrofurfuryl propane was used, and 14 mL of 105-1 type epoxy polysiloxane with an epoxy value of 0.022 mol / 100 g (density 1.06). Finally, it is measured that the polymer Mn=62×104, the molecular weight distribution index is 1.64, the polybutadiene segment 1.2-unit content is 64.5%, the raw rubber Mooney viscosity ML=118, the polysiloxane chain unit combined in the coupled SSBR The mass content of is 3.57% (wt).

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Abstract

The invention discloses epoxy polysiloxane modified solution polymerized styrene-butadiene rubber, which belongs to polymerized styrene-butadiene rubber modified by polysiloxane link sections and obtained by coupling tail end active lithium of styrene-butadiene random copolymers and epoxy polysiloxane. The invention also provides a preparation method of the solution polymerized styrene-butadiene rubber and application of the solution polymerized styrene-butadiene rubber to preparation of tire tread rubber. The solution polymerized styrene-butadiene rubber provided by the invention shows the good affinity and physical performance with white carbon black in the high-performance tire tread rubber. Compared with general SSBR, the epoxy polysiloxane modified SSBR has the advantages that the good ground grasping traction force is realized; meanwhile, the rolling resistance improvement rate is improved by 23 to 28 percent.

Description

technical field [0001] The invention belongs to the field of tire tread rubber material preparation, and in particular relates to a preparation and application method of modifying styrene-butadiene random copolymer with epoxy polysiloxane oligomer. Background technique [0002] Styrene butadiene rubber is divided into emulsion polystyrene butadiene rubber (ESBR) and solution polystyrene butadiene rubber (SSBR). Compared with ESBR, SSBR can reduce the rolling resistance of tires by 20-30%, and improve the wet skid resistance by 30-40%. In addition, SSBR adopts anionic polymerization method, the product structure is easy to adjust, and the brand is rich. The development trend of SSBR is ultra-high performance, and functionalization is the most effective way to achieve high performance of SSBR. The significance of high performance lies in the comprehensive balance of rolling resistance, wet skid resistance and wear resistance, so as to manufacture safe, comfortable and energy-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G81/02C08L87/00C08L9/00C08K13/02C08K3/36C08K3/04C08K5/548C08K3/22B60C1/00
CPCC08G81/024C08L87/005B60C1/0016C08K2003/2296C08L9/00C08K13/02C08K3/36C08K3/04C08K5/548C08K3/22Y02T10/86
Inventor 张建国贺卉昌陈移娇蒋文英
Owner CHINA PETROLEUM & CHEM CORP
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