Preparation of surface functionalized nano SiO2 and its application in solution polymerized styrene butadiene rubber-polybutadiene rubber
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摘要: 采用液相原位修饰技术,制备了表面接枝有机硅烷的纳米SiO2(HB-2200)、表面接枝氨基的纳米SiO2(HB-2205N)、表面接枝不饱和双键的纳米SiO2(HB-2205D)、表面接枝氨基和双键的纳米SiO2(HB-2205ND)。利用TEM、SEM、流变仪对纳米SiO2/溶液聚合丁苯橡胶-顺丁橡胶(SSBR-BR)复合材料的结构和性能进行表征。结果表明:与未改性的纳米SiO2相比,表面功能化纳米SiO2与橡胶基体相容性改善,Payne效应降低,纳米SiO2之间的相互作用减弱,其在SSBR-BR复合材料中的分散性提高。HB-2200/SSBR-BR复合材料的混炼扭矩降低了35.7%,混炼能耗降低了15%,结合胶含量增加,填料/橡胶之间的界面结合作用增强,拉伸强度提高了60%。动态热力学和磨耗性能分析表明:纳米SiO2表面引入可反应性双键(HB-2205D),使HB-2205D/SSBR-BR复合材料的抗湿滑性能提高了40%,滚动阻力降低了43%。纳米SiO2表面接枝可反应性双键,可在不牺牲HB-2205D/SSBR-BR复合材料耐磨性能的基础上,降低其滚动阻力,提高其抗湿滑性能,为高性能轮胎的制备提供基础原材料。Abstract: A series of nano SiO2 grafted with organosilane (HB-2200), nano SiO2 grafted with amino (HB-2205N), nano SiO2 grafted with double bond (HB-2205D) and nano SiO2 grafted with amino-double bond (HB-2205ND) groups were prepared through liquid phase in-situ surface modification method. The structure and properties of nano SiO2/solution polymerized styrene butadiene rubber-polybutadiene rubber (SSBR-BR) composites were characterized by TEM, SEM and rheometer. The results show that compared with the unmodified nano SiO2, the compatibility between surface functionalized nano SiO2 and rubber matrix is improved, Payne effect is reduced, the interaction between nano SiO2 is weakened, and the dispersion of nano SiO2 in SSBR-BR is improved. Compared with nano SiO2/SSBR-BR composite, the mixing torque of HB-2200/SSBR-BR composite is reduced by 35.7%, the mixing energy consumption is saved by 15%, the interfacial bond between the filler and the rubber is strengthened due to the increase in the content of bound rubber, and its tensile strength is increased by 60%. The dynamic mechanical and abrasion performance analyses show that the reactive double bond group grafted on the surface of SiO2 could improve the wet slip resistance of HB-2205D/SSBR-BR composite by 40% and reduce the rolling resistance by 43%. Nano SiO2 surface grafted with reactive double bond could reduce its rolling resistance and improve its resistance to wet slip, without sacrificing the wear resistance of HB-2205D/SSBR-BR composite. It provides the basic raw materials for the preparation of high-performance tires.
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Key words:
- in-situ modification /
- SiO2 /
- interfacial interaction /
- rubber /
- Payne effect
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表 1 纳米SiO2/溶液聚合丁苯橡胶-顺丁橡胶(SSBR-BR)复合材料混炼配方
Table 1. Mixing formula of nano SiO2/solution polymerized styrene butadiene rubber-polybutadiene rubber(SSBR-BR) composite
Material Amount/g SSBR 96.25 BR 30 SiO2 70 Si69 7 ZnO 3 Stearic acid 1.5 6PPD(4020) 1.5 Paraffin wax 1.5 CBS 1.5 DPG 2 Sulfur 1.4 Notes:6PPD(4020)—N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine;CBS—N-cyclohexylbenzothiazole-2-sulphenamide;DPG—1,3-diphenyl guanidine. 表 2 纳米SiO2表面官能团种类和含量
Table 2. Contents of functional groups on surface of nano SiO2
Sample Nano SiO2/wt% Methyl/wt% Double bond /wt% Amino /wt% Z-1165MP 100 0 0 0 HB-2200 80 20 0 0 HB-2205D 80 15 5 0 HB-2205N 80 15 0 5 HB-2205ND 80 15 2.5 2.5 Notes: HB-2200—SiO2 surface grafted with methyl functional groups; HB-2205D—SiO2 surface grafted with methyl functional groups and polymers containing double bonds groups; HB-2205N—SiO2 surface grafted with methyl functional groups and polymers containing amino groups; HB-2205ND—SiO2 surface grafted with methyl functional groups and polymers containing double bonds and amino groups. 表 3 5种纳米SiO2物性参数
Table 3. Physical parameters of 5 types of nano SiO2
Structure parameter Z-1165MP HB-2200 HB-2205D HB-2205N HB-2205ND Apparent density /(g·mL−1) 0.28 0.15 0.16 0.16 0.13 Thermal mass loss at 400℃/% 3.13 4.82 4.27 6.31 5.84 Thermal mass loss at 950℃/% 5.54 6.50 5.97 9.58 8.24 Specific surface area/(m2·g−1) 159 124 142 108 119 Adsorption aperture/nm 18.4 21.2 25.4 19.6 20.9 Particle size D50/μm 11.2 10.3 10.0 10.7 10.0 表 4 纳米SiO2/SSBR-BR复合材料的最大混炼扭矩和能耗
Table 4. Max mixing torque and energy consumption of nano SiO2/SSBR-BR composites
Sample Max mixing
torque/(N·m)Energy consumption/kJ Z-1165MP/SSBR-BR 78.9 336 HB 2200/SSBR-BR 50.7 288 HB 2205D/SSBR-BR 50.8 301 HB 2205N/SSBR-BR 51.8 303 HB 2205ND/SSBR-BR 51.6 301 -
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