表面改性SiO2对SSBR/BR绿色轮胎胎面胶结构与性能的影响

doi:10.7503/cjcu20190378

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (11): 2388.doi: 10.7503/cjcu20190378

表面改性SiO₂对SSBR/BR绿色轮胎胎面胶结构与性能的影响

蔡磊¹,赵远进¹,张新萍¹,贺爱华^1,^*(),丁涛²,李小红²,张治军²

^1. 山东省烯烃催化与聚合重点实验室, 橡塑材料与工程教育部重点实验室, 青岛科技大学高分子科学与工程学院, 青岛 266042
^2. 纳米杂化应用技术国家地方联合工程中心, 河南大学, 开封 475001

收稿日期:2019-07-07 出版日期:2019-11-10 发布日期:2019-10-24
通讯作者: 贺爱华 E-mail:aihuahe@iccas.ac.cn
基金资助:
国家重点基础研究发展计划(2015CB654700(2015CB654706));山东省重大基础研究(ZR2017ZA0304);泰山学者工程项目资助.

Structure and Properties of SSBR/BR/Surface-modified SiO₂ Green Tire Tread Stock ^†

CAI Lei¹,ZHAO Yuanjin¹,ZHANG Xingping¹,HE Aihua^1,^*(),DING Tao²,LI Xiaohong²,ZHANG Zhijun²

^1. Shandong Provincial Key Laboratory of Olefin Catalysis and Polymerization, Key Laboratory of Rubber-plastics(Ministry of Education), School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
^2. National & Local Joint Engineering Research Center for Applied Technology of Hybrid Nanomaterials, Henan University, Kaifeng 475004, China

Received:2019-07-07 Online:2019-11-10 Published:2019-10-24
Contact: HE Aihua E-mail:aihuahe@iccas.ac.cn
Supported by:
? Supported by the National Basic Research Program of China(2015CB654700(2015CB654706));The Major Program of Shandong Province Natural Science Foundation, China(ZR2017ZA0304);The Taishan Scholar Program, China

摘要/Abstract

摘要：

采用4种含不同官能基团修饰剂改性的二氧化硅SiO₂增强溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)共混体系, 制备了SSBR/BR/SiO₂橡胶纳米复合材料, 研究了其结构与性能. 结果表明, 在混炼胶体系中, 与未改性SiO₂填充的SSBR/BR相比, 改性SiO₂填充的SSBR/BR门尼黏度及结合橡胶含量显著增大, 表明填料-橡胶相互作用显著提高; 硫化焦烧时间缩短60%, 硫化速度增大了35%~40%. 在硫化胶体系中改性SiO₂填充的SSBR/BR具有更大的交联密度, 填料分散性明显改善, 同时也表现出更为优异的物理机械性能, 100%和300%定伸模量提高47%以上, 旋转滚筒式磨耗机法(DIN)磨耗降低5%~12%, 生热降低了约7%~13%, 热空气老化性能提升4%~22%, 代表滚动阻力的tanδ在60 ℃降低8%~13%. 此外, 与SSBR/BR/1165MP硫化胶相比, 用90 mmol/kg氨基改性SiO₂填充的SSBR/BR硫化胶的抗湿滑性能提高6.9%, 表现出最优的综合性能. 填料的良好分散及填料与聚合物的相互作用增强对于提高SSBR/BR/SiO₂胎面胶综合力学性能具有重要意义.

关键词: 二氧化硅, 表面改性, 胎面胶, 溶聚丁苯橡胶/顺丁橡胶, 物理机械性能

Abstract:

SiO₂ is deemed as one of the most important reinforcing materials in tread stocks of green tires. The surface modification of SiO₂ and interactions between hydrophilic SiO₂ and hydrophobic rubbers are closely related to the properties of rubber vulcanizates. In this work, four kinds of SiO₂ modified with different functional groups were incorporated into the solution polymerized styrene butadiene rubber/butadiane rubber(SSBR/BR) stocks, and the structures and properties of the SSBR/BR/SiO₂ rubber nanocomposites were systematically studied. Compared with the compound filled with unmodified SiO₂, the Mooney viscosity and bound rubberof the SSBR/BR/SiO₂ compounds filled with modified SiO₂ increased significantly indicating the greatly enhanced filler-rubber interaction. The scorch time and the optimum curing time of the SSBR/BR/SiO₂ compounds filled with modified SiO₂ reduced by 60% and 35%—40%, respectively. The SSBR/BR vulcanizates filled with modified SiO₂ exhibited higher cross-linking density, remarkably improved filler dispersion and excellent mechanical properties including the modulusat 100% and 300% increased by 50%—63% and 48%—57%, the wear resistance improved by 5%—12%, and heat built-up decreased by 7%—13%, the hot air aging properties increased by 4%—22%, and tanδ at 60 ℃ indicating rolling resistance decreased by 8%—13%. In addition, the wet-skid resistance of SSBR/BR/HB 2105N vulcanizate filled with 90 mmol/kg amino-modified SiO₂ was 6.9% higher than that of SSBR/BR/1165MP vulcanizate filled with unmodified SiO₂. Surface modification of SiO₂ could significantly improve the filler-rubber interaction and filler dispersion in the rubber matrix, and therefore contribute to the excellent comprehensive properties of the composites.

Key words: SiO₂, Surface-modified, Tire tread stock, Solution polymerized Styrene butadiene rubber/Butadiene rubber, Physical-mechanical propery

中图分类号:

O631

TrendMD:

蔡磊,赵远进,张新萍,贺爱华,丁涛,李小红,张治军. 表面改性SiO₂对SSBR/BR绿色轮胎胎面胶结构与性能的影响. 高等学校化学学报, 2019, 40(11): 2388.

CAI Lei,ZHAO Yuanjin,ZHANG Xingping,HE Aihua,DING Tao,LI Xiaohong,ZHANG Zhijun. Structure and Properties of SSBR/BR/Surface-modified SiO₂ Green Tire Tread Stock ^†. Chem. J. Chinese Universities, 2019, 40(11): 2388.

图/表 10

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SiO₂Brand	1165MP	HB 2105N	HB 2205N	HB 2200D
Functional group in the modifier	None	Amino	Amino	Double bond
Contents of modifier/(mmol·kg^-1)	0	90	140	260
Apparent density/(g·mL^-1)	0.88	0.28	0.13	0.16
Mass loss at 950 ℃(%)	4.50	7.52	8.17	5.61
Oil absorption/(mL·100 g^-1)	160	168	196	207
Specific surface area(BET)/(m²·g^-1)	155	151	125	121

SiO₂Brand	1165MP	HB 2105N	HB 2205N	HB 2200D
Functional group in the modifier	None	Amino	Amino	Double bond
Contents of modifier/(mmol·kg^-1)	0	90	140	260
Apparent density/(g·mL^-1)	0.88	0.28	0.13	0.16
Mass loss at 950 ℃(%)	4.50	7.52	8.17	5.61
Oil absorption/(mL·100 g^-1)	160	168	196	207
Specific surface area(BET)/(m²·g^-1)	155	151	125	121

System	S/B-1165MP	S/B-HB 2105N	S/B-HB 2205N	S/B-HB 2200D
Mooney viscosity	72	79	74	80
Boundrubber(%)	16	23	20	22
Green strength/MPa	0.41	0.40	0.39	0.41
Modulus at 100%/MPa	0.40	0.39	0.36	0.41
Modulus at 300%/MPa	0.36	0.37	0.35	0.32
Elongation at break(%)	935	1119	662	695
Shore A hardness/(°)	32	32	33	31

System	S/B-1165MP	S/B-HB 2105N	S/B-HB 2205N	S/B-HB 2200D
Mooney viscosity	72	79	74	80
Boundrubber(%)	16	23	20	22
Green strength/MPa	0.41	0.40	0.39	0.41
Modulus at 100%/MPa	0.40	0.39	0.36	0.41
Modulus at 300%/MPa	0.36	0.37	0.35	0.32
Elongation at break(%)	935	1119	662	695
Shore A hardness/(°)	32	32	33	31

System	S/B-1165MP	S/B-HB 2105N	S/B-HB 2205N	S/B-HB 2200D
ML/(dN·m)	2.53	2.96	2.83	3.10
MH/(dN·m)	20.2	24.7	23.7	24.4
MH-ML/(dN·m)	17.7	21.8	20.8	21.3
t_c10/min	6.24	2.40	2.48	2.40
t_c90/min	28.9	18.9	18.1	17.4
Swelling ratio, Q	1.75	1.45	1.52	1.45

表面改性SiO₂对SSBR/BR绿色轮胎胎面胶结构与性能的影响

Structure and Properties of SSBR/BR/Surface-modified SiO₂ Green Tire Tread Stock ^†

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参考文献 44

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System	S/B-1165MP	S/B-HB 2105N	S/B-HB 2205N	S/B-HB 2200D
Tensile strength/MPa	19.9	19.5	17.7	17.6
Modulus at 100%/MPa	1.8	2.9	2.7	3.0
Modulus at 300%/MPa	7.2	11.2	10.7	11.3
Elongation at break(%)	613	487	460	438
Shore A hardness/(°)	63	72	70	72
Tear strength/(kN·m^-1)	45.3	44.2	43.3	40.7
DIN abrasion/(cm³·40 m^-1)	0.135	0.123	0.119	0.128
Rebound(%)	37.0	40.2	39.0	42.5
Heat built-up/℃	31.5	29.4	27.8	29.0
Compression set(%)	5.00	5.19	4.93	5.69
Tensile fatigue at 125%	193×10⁴	>500×10⁴	>500×10⁴	>500×10⁴
tanδ at 60 ℃	0.142	0.130	0.123	0.131
tanδ at 0 ℃	0.233	0.249	0.212	0.230
	Properties after hot air ageing(100 ℃, 72 h)
Tensile strength/MPa	18.0	18.1	17.1	17.4
Modulus at 100%/MPa	3.1	4.4	4.1	4.6
Modulus at 300%/MPa	13.3	17.4	15.5	17.1
Elongation at break(%)	386	311	330	304
Swelling ratio, Q	1.66	1.41	1.35	1.36
Ageing coefficient(%)	56.9	69.3	68.7	59.3

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System	S/B-1165MP	S/B-HB 2105N	S/B-HB 2205N	S/B-HB 2200D
Dispersion(%)	99.3	99.7	99.8	99.7
White area(%)	1.0	0.1	0.1	0.2

System	S/B-1165MP	S/B-HB 2105N	S/B-HB 2205N	S/B-HB 2200D
Dispersion(%)	99.3	99.7	99.8	99.7
White area(%)	1.0	0.1	0.1	0.2