高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (11): 2388.doi: 10.7503/cjcu20190378
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
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:
CAI Lei1,ZHAO Yuanjin1,ZHANG Xingping1,HE Aihua1,*(),DING Tao2,LI Xiaohong2,ZHANG Zhijun2
Received:
2019-07-07
Online:
2019-11-10
Published:
2019-10-24
Contact:
HE Aihua
E-mail:aihuahe@iccas.ac.cn
Supported by:
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.
中图分类号:
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.
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 |
Table 1 Basic parameters of four kinds of SiO2
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 |
Table 2 Physical and mechanical properties of the SSBR/BR/SiO2 compounds
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 |
tc10/min | 6.24 | 2.40 | 2.48 | 2.40 |
tc90/min | 28.9 | 18.9 | 18.1 | 17.4 |
Swelling ratio, Q | 1.75 | 1.45 | 1.52 | 1.45 |
Table 3 Cross-linking characteristics of the SSBR/BR/SiO2 compounds
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 |
tc10/min | 6.24 | 2.40 | 2.48 | 2.40 |
tc90/min | 28.9 | 18.9 | 18.1 | 17.4 |
Swelling ratio, Q | 1.75 | 1.45 | 1.52 | 1.45 |
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 |
Table 4 Filler dispersion of SSBR/BR/SiO2 vulcanizates
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 |
Fig.3 Stress-strain curves of SSBR/BR/SiO2 vulcanizates before(A) and after hot air ageing(100 ℃, 72 h)(B) a. S/B-1165MP; b. S/B-HB 2105N; c. S/B-HB 2205N; d. S/B-HB 2200D.
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 |
Table 5 Physical and mechanical properties of SSBR/BR/SiO2 vulcanizates
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 |
Fig.4 DMA curves of SSBR/BR vulcanizates filled with different SiO2 (A) tanδ versus temperature with a strain of 0.5%; (B) tanδ versus strain at 60 ℃. a. S/B-1165MP; b. S/B-HB 2105N; c. S/B-HB 2205N; d. S/B-HB 2200D.
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