反式异戊橡胶合金改性溶聚丁苯橡胶/顺丁橡胶轿车胎面胶

doi:10.7503/cjcu20170152

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (11): 2095.doi: 10.7503/cjcu20170152

反式异戊橡胶合金改性溶聚丁苯橡胶/顺丁橡胶轿车胎面胶

王浩^1,², 张剑平¹, 马韵升², 王日国^2,³, 贺爱华¹()

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. 山东省烯烃催化与聚合重点实验室, 黄河三角洲京博化工研究院有限公司, 滨州 256500
3. 山东华聚高分子材料有限公司, 滨州 256500

收稿日期:2017-03-14 出版日期:2017-11-10 发布日期:2017-10-16
作者简介:联系人简介: 贺爱华, 女, 博士, 教授, 博士生导师, 主要从事可控定向聚合制备橡塑新材料的基础与应用研究. E-mail: aihuahe@iccas.ac.cn; ahhe@qust.edu.cn
基金资助:
国家“九七三”计划项目(批准号: 2015CB654700, 2015CB654706)、国家自然科学基金(批准号: 51473083)、泰山学者工程、山东省重大基础研究项目(批准号: ZR2017ZA0304)、山东省重点项目研发计划(批准号: 2015GGX102019)和黄河三角洲学者工程资助

Modification of SSBR/BR with Trans-1,4-Polyisoprene Alloy Rubber for High Performance Passenger Car Radical Tire Tread Stock^†

WANG Hao^1,², ZHANG Jianping¹, MA Yunsheng², WANG Riguo^2,³, HE Aihua^1,^*()

1. Shandong Provincial Key Laboratory of Olefin Catalysis and Polymerization,Key Laboratory of Rubber-plastics of Ministry of Education, School of Polymer Science and Engineering,Qingdao University of Science and Technology, Qingdao 266042, China
2. Shandong Provincial Key Laboratory of Olefin Catalysis and Polymerization,Chambroad Chemical Industry Institute Co., Ltd., Binzhou 256500, China
3. Shandong Huaju Polymer Material Co., Ltd., Binzhou 256500, China

Received:2017-03-14 Online:2017-11-10 Published:2017-10-16
Contact: HE Aihua E-mail:aihuahe@iccas.ac.cn
Supported by:
† Supported by the National Basic Research Program of China(Nos.2015CB654700, 2015CB654706)), the National Natural Science Foundation of China(No.51473083), the Taishan Scholar Program of China, the Significant Basic Research Program of Shandong Province, China(No.ZR2017ZA0304), the Shandong Provincial Key R&D Program(No.2015GGX102019) and the Yellow River Delta Scholar Program, China

摘要/Abstract

摘要：

研究了反式异戊橡胶合金(TPIR)的结晶性能、加工性能和力学性能及在轿车胎面胶溶聚丁苯橡胶/顺丁橡胶(SSBR/BR)中的应用. 研究结果表明, 与无定形SSBR和BR相比, TPIR生胶具有常温可结晶性, 因此TPIR具有较高的格林强度. 毛细管挤出行为研究结果表明, TPIR具有优异的挤出性能, 挤出物外观光滑, 挤出涨大比小. 与SSBR/BR混炼胶相比, 用TPIR改性后的SSBR/BR/TPIR混炼胶的格林强度与100%定伸应力随TPIR含量的增加而提高. 经150 ℃硫化反应后制备的SSBR/BR/TPIR硫化胶物理机械性能优异: 不仅耐湿滑性能、耐磨耗性能及压缩强度较对比胶提高, 其伸张疲劳性能较对比胶提高4倍以上. 透射电子显微镜(TEM)及填料分散仪表征结果表明, 与SSBR/BR硫化胶相比, SSBR/BR/TPIR硫化胶的填料聚集体平均尺寸降低2 μm, 填料分散性显著改善. 表明TPIR是一种应用于高性能轿车胎面胶的理想胶料.

关键词: 反式异戊橡胶合金, 溶聚丁苯橡胶/顺丁橡胶并用胶, 高性能轮胎, 胎面胶, 耐湿滑性能, 耐磨耗性能, 丁苯橡胶, 顺丁橡胶

Abstract:

The crystalline characteristics, processing and mechanical properties of trans-1,4-polyisoprene alloy rubber(TPIR) were studied. Then TPIR incorporated with solution polymerized butadiene-styrene rubber(SSBR)/cis-1,4-polybutadiene rubber(BR) blends were further investigated as passenger car radical(PCR) tire tread stocks. Compared with amorphous SSBR and BR, TPIR raw rubber showed improved green strength due to its crystallizability at room temperature. The capillary extrusion behavior of TPIR indicated that TPIR presented good extrusion behavior with smooth extrusion appearance and low extrusion swelling ratio. SSBR/BR/TPIR compounds showed increased green strength and 100% modulus with the increase in TPIR, when compared with SSBR/BR blends. After vulcanization, SSBR/BR/TPIR vulcanizes showed excellent physical and mechanical properties, such as increased wet skid resistance, wear resistance, compressive strength, and outstanding tensile fatigue resistance(increased by more than 4 times). Carbon blacks and silica were proved to be dispersed much more uniformly in SSBR/BR/TPIR vulcanizates with much smaller aggregates than in SSBR/BR vulcanizates. So comprehensive speaking, TPIR as a novel synthetic rubber has the potentional application in PCR tire tread stock with superor performance.

Key words: Trans-1,4-polyisoprene alloy rubber, Butadiene-styrene rubber/cis-1,4-polybutadiene rubber blend, High performance tire, Tread stock, Wet skid resistance, Wear resistance, Butadiene-styrene rubber, cis-1,4-Polybutadiene rubber

中图分类号:

O631.1⁺1

TrendMD:

王浩, 张剑平, 马韵升, 王日国, 贺爱华. 反式异戊橡胶合金改性溶聚丁苯橡胶/顺丁橡胶轿车胎面胶. 高等学校化学学报, 2017, 38(11): 2095.

WANG Hao, ZHANG Jianping, MA Yunsheng, WANG Riguo, HE Aihua. Modification of SSBR/BR with Trans-1,4-Polyisoprene Alloy Rubber for High Performance Passenger Car Radical Tire Tread Stock^†. Chem. J. Chinese Universities, 2017, 38(11): 2095.

图/表 11

Table 1 Rubber amount in SSBR/BR/TPIR(phr)

SSBR 4526	75	75	75	70	50
BR 9000	25	15	5	0	0
TPIR-04	0	10	20	30	50

Fig.1 Curves of DSC(A) and stress-strain(B) of TPIR-04(a), SSBR(b) and BR raw rubbers(c) Inset of (B): enlarged stress-strain curves of SSBR(b) and BR(c) raw rubber

Fig.2 Capillary extrusion behavior of TPIR(a), SSBR(b) and BR(c)(A) Shear viscosity(η) versus shear rate(γ); (B) die swell ratio versus γ. Insets images in (A): extrusion morphologies of SSBR and BR raw rubbers. Insets images in (B): extrusion morphologies of TPIR raw rubbers.

Fig.3 DSC curves(A) and stress-strain curves(B) of SSBR/BR/TPIR-04 compoundsm(SSBR):m(BR):m(TPIR-04): a. 75:25:0; b. 75:15:10; c. 75:5:20; d. 70:0:30; e. 50:0:50.

Table 2 Properties of SSBR/BR/TPIR vulcanizates

m(SSBR):m(BR):m(TPIR-04)	75:25:0	75:15:10	75:5:20	70:0:30	50:0:50
ML/(dN·m^-1)	2.58	2.25	2.15	2.05	2.15
MH/(dN·m^-1)	16.46	15.08	15.01	15.70	19.05
t₁₀/min	5.18	5.31	5.18	5.18	4.33
t₉₀/min	12.27	12.37	12.06	12.30	9.38
Vc/min^-1	14.10	14.16	14.53	14.05	19.80
10⁴Crosslink density/(mol·cm^-3)	1.21	1.23	1.28	1.35	1.49
Compressive strength/MPa	1.17	1.30	1.29	1.36	1.85
Tensile Strength/MPa	20.6	19.7	19.6	18.8	18.8
Modulus at 100%/MPa	2.42	2.38	2.58	2.55	3.39
Modulus at 300%/MPa	10.0	10.1	10.6	10.5	13.0
Elongation at break(%)	540	530	510	494	419
Tear strength/(kN·m^-1)	53.9	48.0	51.7	47.3	48.4
Hardness(Shore A)	64	64	65	67	73
Rebound(%)	24	20	16	15	21
DIN Abrasion/(cm³·40 m^-1)	0.175	0.160	0.164	0.170	0.145
Heat built-up/℃	22.5	23.2	22.8	23.4	25.0
10^-4Tensile fatigue life/times	150	810	860	690	720
Tensile strength/MPa	19.6	19.1	19.0	18.4	19.0
Elongation at break(%)	436	413	415	349	321
Ageing coefficient(%)	76.8	75.5	78.9	69.1	77.4

Fig.4 DSC curves of SSBR/BR/TPIR-04 vulcanizatesm(SSBR):m(BR):m(TPIR-04): a. 75:25:0; b. 75:15:10; c. 75:5:20; d. 70:0:30; e. 50:0:50.

Fig.5 Loss factor(tanδ) versus temperature of SSBR/BR/TPIR-04 vulcanizatesm(SSBR):m(BR):m(TPIR-04): a. 75:25:0;b. 75:15:10; c. 75:5:20; d. 70:0:30.

Fig.6 Filler dispersion images of SSBR/BR/TPIR-04 vulcanizatesScan size: 2.2 mm×1.6 mm. m(SSBR):m(BR):m(TPIR-04): (A) 75:25:0; (B) 75:15:10; (C) 75:5:20;(D) 70:0:30; (E) 50:0:50.

Table 3 Filler dispersion and mean aggregate size of SSBR/BR/TPIR-04 vulcanizates

m(SSBR):m(BR):m(TPIR-04)	75:25:0	75:15:10	75:5:20	70:0:30	50:0:50
Dispersion(%)	77.4	89.0	86.3	86.8	89.5
Mean aggregate size/μm	13.8	12.0	11.9	11.6	11.7

Fig.7 TEM images of SSBR/BR/TPIR-04 vulcanizatesm(SSBR):m(BR):m(TPIR-04): (A) 75:25:0; (B) 75:15:10; (C) 75:5:20.

Fig.8 Properties radar map of SSBR/BR/TPIR-04 vulcanizates

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反式异戊橡胶合金改性溶聚丁苯橡胶/顺丁橡胶轿车胎面胶

Modification of SSBR/BR with Trans-1,4-Polyisoprene Alloy Rubber for High Performance Passenger Car Radical Tire Tread Stock^†

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反式异戊橡胶合金改性溶聚丁苯橡胶/顺丁橡胶轿车胎面胶

Modification of SSBR/BR with Trans-1,4-Polyisoprene Alloy Rubber for High Performance Passenger Car Radical Tire Tread Stock†

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Modification of SSBR/BR with Trans-1,4-Polyisoprene Alloy Rubber for High Performance Passenger Car Radical Tire Tread Stock^†