改性纳米二氧化硅的制备及其在溶聚丁苯橡胶/顺丁橡胶并用胶中的应用

用偶联剂KH570作修饰剂,采用液相原位表面修饰技术制备改性纳米二氧化硅,并考察其在溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)并用胶中的应用。结果表明:与未改性纳米二氧化硅相比,改性纳米二氧化硅在橡胶基体中的分散性较好,与橡胶的相容性提高,团聚减弱;改性纳米二氧化硅/SSBR/BR复合材料的物理性能和耐磨性能提高,Payne效应减弱;修饰量为50 mmol·kg~(-1)的改性纳米二氧化硅/SSBR/BR复合材料物理性能、耐热老化性能和耐磨性能最好。     

“胶乳共混法”制备天然橡胶／二氧化硅纳米复合材料及其性能

采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）改性纳米二氧化硅（SiO2）,然后通过乳液聚合接枝上聚甲基丙烯酸甲酯（PMMA）,再将其与甲基丙烯酸甲酯（MMA）改性的天然胶乳,通过胶乳共混法制备天然橡胶／二氧化硅纳米复合材料,结果显示,纳米二氧化硅表面接枝上了PMMA,二氧化硅在橡胶基体中分散良好,粒径在60～100nm之间,得到的胶膜力学性能有很大的提高。     

LMPB-g-KH-570改性纳米氮化硅/丙烯酸酯橡胶复合材料的制备与性能研究

采用溶液聚合法将硅烷偶联剂KH-570接枝到低相对分子质量的聚丁二烯液体橡胶(LMPB)分子长链中,合成了新型大分子表面处理剂LMPB-g-KH-570,用其对纳米氮化硅进行表面改性,制备改性纳米氮化硅/丙烯酸酯橡胶(ACM)复合材料,并对其结构和性能进行研究。结果表明:LMPB-g-KH-570与纳米氮化硅发生了化学键合;在复合材料中加入适量LMPB-g-KH-570,可以改善纳米氮化硅在复合材料中的分散性,提高复合材料的物理性能。     

纳米Si_3N_4/ACM复合材料的力学性能和硫化性能研究

采用大分子表面处理剂LMPB-g-KH570对纳米Si_3N_4表面进行修饰。利用共混技术制备了纳米Si_3N_4/ACM复合材料。利用RPA-8000、SEM、TEM等测试技术,对纳米复合材料的微观结构和性能进行了分析和评价。结果表明,大分子表面改性剂能有效改善复合材料的微观界面结构,促进纳米Si_3N_4在橡胶基体中的有效分散,橡胶硫化性能得到改善,力学性能得到提高。添加2.0份改性纳米Si_3N_4/ACM复合材料,胶料正硫化时间减少38 s,拉伸强度提高24.8%,撕裂强度提高3.39%。     

硅烷偶联剂改性阳离子水性聚氨酯的研究

以硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH550)为封端剂对阳离子型水性聚氨酯进行杂化改性,并以KH550和γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)为原料合成新型偶联剂D,对聚氨酯进行复合改性,分别合成了纳米SiO2/PU杂化材料和纳米SiO2/PU复合材料.通过FT-IR、粒径分析、AFM对样品的结构进行表征,并对样品的力学性能和耐水性、耐溶剂性进行测试.结果表明:两种体系均生成了二氧化硅相,二氧化硅相在杂化体系中的分散性好于其在复合体系中的分散性.对提高产品性能而言,化学封端改性比物理共混改性更有效.     

纳米Si3N4/ACM复合材料的力学性能和硫化性能研究

采用大分子表面处理剂LMPB-g-KH570对纳米Si₃N₄表面进行修饰。利用共混技术制备了纳米Si₃N₄/ACM复合材料。利用RPA-8000、SEM、TEM等测试技术,对纳米复合材料的微观结构和性能进行了分析和评价。结果表明,大分子表面改性剂能有效改善复合材料的微观界面结构,促进纳米Si₃N₄在橡胶基体中的有效分散,橡胶硫化性能得到改善,力学性能得到提高。添加2.0份改性纳米Si₃N₄/ACM复合材料,胶料正硫化时间减少38 s,拉伸强度提高24.8%,撕裂强度提高3.39%。     

纳米二氧化硅颗粒表面设计及其填充聚氯乙烯复合材料的性能

利用表面原位接枝聚合在纳米二氧化硅颗粒表面引入聚甲基丙烯酸甲酯(PMMA)高分子链段,用共混法制备了nano-SiO2/PVC复合材料,研究了不同界面特性时SiO2/PVC复合材料的力学性能.研究结果表明通过表面原位接枝聚合反应可以在纳米二氧化硅颗粒表面接枝聚甲基丙烯酸甲酯;表面接枝PMMA的nano-SiO2/PVC复合材料在力学和加工性能等方面都优于偶联剂处理和表面未处理样品.在纳米二氧化硅颗粒填充量为0%～8%(wt)时,复合材料的拉伸强度和冲击强度随着填充量的提高先上升后下降,并在4%～6%(wt)达到最大值.经PMMA表面接枝后SiO2/PVC具有更强的界面作用,偶联剂KH570处理的次之,表面未处理样品的最差.     

MoS_2/PVC/橡胶复合材料的制备及其性能研究

采用KH570/CTAB复配改性MoS2,并将改性MoS2与不同用量的PVC和橡胶进行共混,制备MoS2/PVC/橡胶复合材料,并研究了其力学性能和耐磨性能。结果表明,随着PVC用量的增加,NBR/PVC/MoS2和CNBR/PVC/MoS2复合材料的力学性能不断提高,SBR/PVC/MoS2复合材料的力学性能保持不变或略有下降;MoS2/PVC/橡胶复合材料的摩擦因数和阿克隆磨耗均不断降低。     

纳米SiO2增强TPS/PVA复合材料的研究

以甲酰胺／己内酰胺为复配增塑剂，添加纳米二氧化硅（SiO2）熔融制备了热塑性淀粉／聚乙烯醇／纳米二氧化硅（TPS／PVA／SiO2）复合材料，研究了复合材料的力学性能、流变性能和耐水性能。结果表明：添加1phr的表面改性SiO2，TPS／PVA的拉伸强度和断裂伸长率以及耐水性能均有所提高，但过量的纳米SiO2对材料的力学性能有损害；经KH560表面改性的纳米SiO2的团聚明显减少，因而对TPS／PVA性能的改善更明显；TPS／PVA／SiO2复合材料具有优良的加工性能，熔体表现出假塑性流体的特征。     

硅烷偶联剂的种类与结构对二氧化硅表面聚合物接枝改性的影响

在超细二氧化硅表面接枝聚合改性工艺的基础上,通过透射电子显微镜、红外光谱、X射线光电子能谱等检测手段,并结合模型计算,研究了硅烷偶联剂(silane coupling agent)对超细二氧化硅表面聚合物接枝改性的影响及其机理。认为硅烷偶联荆KH570和KH858都是有效的预处理剂,硅烷偶联剂的种类对改性影响很大。由于KH570中含有的双键与羰基形成了离域II4^4键,使其双键结合力减弱;而在KH858中由于硅原子的供电子效应,使其双键结合力有所加强;使用KH570预处理的超细二氧化硅表面含有的聚合物更多,分散性更好。KH570更适合用作超细二氧化硅表面接枝聚合改性的预处理剂。     

Vulcanization accelerator functionalized nanosilica: Effect on the reinforcement behavior of SSBR/BR

The application of nanosilica in high performance tire highly depends on its uniform dispersion in rubber matrix. A series of dispersible nanosilica (denoted as DNS) modified by diphenyl guanidine (denoted as DPG, a vulcanization accelerator) were synthesized by liquid phase in situ surface chemical modification. The structure of the as‐obtained DNS‐DPG fillers was investigated in relation to Fourier transform infrared spectrometric analysis, thermogravimetric analysis, dynamic light scattering test, and transmission electron microscopic observation. It was found that the rubber vulcanization accelerator DPG was successfully grafted onto the surface of nanosilica, thereby effectively preventing the silica nanoparticles from agglomeration and significantly reducing the average particle size. The reinforcing effect of the DPG‐modified DNS nano‐fillers for the solution polymerized styrene butadiene rubber/butadiene rubber (denoted as SSBR/BR) was dependent on the fraction of the modifier DPG; in particular, when the amount of modifier DPG is 135.25 mmol/kg (denoted as DNS‐DPG‐3), silica exhibited very homogeneous dispersion in the SSBR/BR matrix, which contributed to significantly enhancing the filler‐rubber compatibility. As a result, SSBR/BR/DNS‐DPG‐3 nanocomposite exhibited the best mechanical properties, integrated high abrasion resistance and low rolling resistance. The modified silica not only possessed the effect of accelerating the crosslinking reaction, but also showed the reinforcing effect. This could make it feasible for SSBR/BR/DNS‐DPG nanocomposite to find promising application in green tire tread. POLYM. ENG. SCI., 59:1270–1278 2019. © 2019 Society of Plastics Engineers     

Some interesting phenomena in silica‐filled HNBR with the addition of silane coupling agent

Hydrogenated nitrile rubber (HNBR)/silica nanocomposites were prepared by in‐situ modification dispersion technology, and the silane coupling agent γ‐methacryloxypropyl trimethoxy silane (KH570) was chosen to promote the interfacial strength between silica particles and HNBR matrix and further improve the dispersion of silica particles. Rubber Process Analyzer (RPA2000) was used to test the Payne effect of HNBR/silica compounds, from which some interesting phenomena were found: the Payne effect became stronger after KH570 was added to HNBR/silica compound at room temperature, which was a contrary result compared to SBR/silica system. However, after stored for a month at room temperature, the Payne effect weakened, which was contrary to the traditional phenomenon of storage hardening of filled rubber. All these results are related to filler–filler interaction and filler–rubber interaction. The modulus at small strain amplitude of HNBR/silica compound with KH570 gradually decreased with the increase of times of circulatory strain sweep but that of compound without KH570 had almost no change, which was explained by Fourier Transform Infrared (FTIR) results that the reaction between silica and KH570 almost completed at the test condition: 80°C and about 1 h. The effects of silane amount, heat‐treated temperature and time on the Payne effect of compounds and the mechanical properties of vulcanizates were also investigated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

有机杂化纳米CaCO3/SiO2复合粒子对硅橡胶性能的影响

以纳米碳酸钙（CaCO3）为原料,采用溶胶沉积法制备出具有核/壳结构的纳米CaCO3/SiO2复合粒子,并将其原位有机杂化。用纳米CaCO3/SiO2复合粒子替代部分气相法白炭黑作为硅橡胶的补强填料,采用扫描电子显微镜、拉力试验机、热失重仪等对改性硅橡胶的力学性能和热稳定性能进行表征。结果表明：有机杂化剂的种类不同,纳为CaCO3/SiO2复合粒子对硅橡胶的补强效果不同;与用未杂化的纳米CaCO3/SiO2复合粒子取代部分气相法白炭黑的硅橡胶相比,用经A-151杂化的复合粒子取代部分气相法白炭黑的硅橡胶,其拉伸强度、断裂伸长率得到明显改善,耐热性也得到提高;但撕裂强度大大降低。同时还发现,硅橡胶的力学性能及耐热性能在很大程度上也与复合粒子的取代量有关;即使是经KH-570杂化的复合粒子,当取代量小于10%时,其硅橡胶的性能也优于全部用气相法白炭黑补强的硅橡胶。     

硅藻土/白炭黑复合填料的补强性研究

为拓展硅藻土在高分子复合材料中的应用,将硅藻土/白炭黑填充到天然橡胶/丁苯橡胶/顺丁橡胶中制备了复合材料。通过RPA2000和扫描电镜分析了复合填料的Payne效应和分散性,考察了硅藻土用量对复合材料工艺性能、力学性能、耐磨耗性能影响。结果表明:少量硅藻土的加入有利于白炭黑在橡胶中的分散,能降低复合材料的门尼粘度和Payne效应,提高复合材料的硫化速度,缩短硫化时间,复合填料的补强效果较好;随着硅藻土用量的增加,复合填料容易聚集,其力学性能呈下降趋势,而磨耗性能变化不大;当硅藻土用量10~20份时,复合材料的综合性能最好。     

Application of nano‐zinc oxide master batch in polybutadiene styrene rubber system

The properties of nano‐zinc oxide master batch filled butadiene styrene rubber (SBR) systems were researched in comparison with those of common zinc oxide and nano‐zinc oxide filled systems. First, the nano‐zinc oxide master batch was prepared and the cure characteristics of three different kinds of zinc oxide filled SBR composites were studied; second, the mechanical properties and wear resistance were compared; then, the improved mechanical properties were confirmed by dynamic mechanical properties and transmission electron microscopy. Finally, the zinc oxide amount reducing mechanism was analyzed. Results show that nano‐zinc oxide master batch filled SBR system has better mechanical properties than those of nano‐zinc oxide and common zinc oxide filled systems, which is due to the improved dispersion by master batch mixing technology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 922–930, 2006     

改性剂种类对白炭黑补强阻尼硅橡胶性能的影响

以阻尼硅橡胶母胶、气相法白炭黑、改性剂为原料,制成了热硫化阻尼硅橡胶。研究了羟基硅油、六甲基环三硅氮烷、乙烯基三乙氧基硅烷(A-151)、γ-氨丙基三乙氧基硅烷(KH 550)、γ-环氧丙氧基丙基三甲氧基硅烷(KH 560)及其并用对阻尼硅橡胶硫化性能、分散性能、力学性能和黏弹性能的影响。结果表明,硅烷偶联剂类改性剂能显著加快混炼胶的硫化速度、缩短硫化时间;羟基硅油、六甲基环三硅氮烷和KH 560作改性剂时白炭黑的分散效果良好,而采用A 151作改性剂时白炭黑填料网络的Payne效应较明显,但在宽温域(-120~100℃)范围内具有温度稳定性;不同改性剂并用对改善白炭黑分散性没有明显的协同作用;改性剂种类对硫化胶的力学性能影响不大;六甲基环三硅氮烷与KH 560并用时,硅橡胶的阻尼性能最高。     

淀粉改性及其在胶料中的应用

将淀粉进行表面醚化和酯化疏水改性,研究改性淀粉在胶料中的应用。结果表明:改性淀粉替代部分炭黑对胶料物理性能有一定影响,采用酯醚淀粉替代部分炭黑的胶料物理性能明显优于采用轻质碳酸钙替代部分炭黑的胶料,与白炭黑替代部分炭黑的胶料物理性能接近;改性淀粉与偶联剂KH550和KH570配合的胶料物理性能较好;轮胎胎面胶中用8~10份改性淀粉替代部分炭黑可以明显提高胶料的耐屈挠性能并降低生热。     

不同种类低共熔溶剂对白炭黑填充丁苯橡胶物理机械性能的影响

以低共熔溶剂（DES）为白炭黑的改性剂,通过与双[3-（三乙氧基硅）丙基]四硫化物（TESPT）并用进行原位反应改善白炭黑在丁苯橡胶中的分散性,研究了不同种类DES对白炭黑/丁苯橡胶复合材料硫化特性、加工性能、物理机械性能和微观形貌的影响。结果表明,氯化胆碱/尿素与TESPT并用可以明显改善白炭黑在丁苯橡胶中的分散性,使Payne效应减弱,并提升白炭黑/丁苯橡胶硫化胶的力学性能和压缩疲劳性能;氯化胆碱/乙二酸与TESPT并用对提高白炭黑与丁苯橡胶界面结合力效果显著,所得白炭黑/丁苯橡胶复合材料的耐磨性能优异;而当DES用量较大时改性效果不佳。     

Silica‐modified SBR/BR blends

The purpose of this article is that the silica‐modified SBR/BR blend replaces natural rubber (NR) in some application fields. The styrene‐butadiene rubber (SBR) and cis‐butadiene rubber (BR) blend was modified, in which silica filler was treated with the r‐Aminopropyltriethoxysilane (KH‐550) as a coupling agent, to improve mechanical and thermal properties, and compatibilities. The optimum formula and cure condition were determined by testing the properties of SBR/BR blend. The properties of NR and the silica‐modified SBR/BR blend were compared. The results show that the optimum formulawas 80/20 SBR/BR, 2.5 phr dicumyl peroxide (DCP), 45 phr silica and 2.5 mL KH‐550. The best cure condition was at 150°C for 25 min under 10 MPa. The mechanical and thermal properties of SBR/BR blend were obviously modified, in which the silica filler treated with KH‐550. The compatibility of SBR/BR blend with DCP was better than those with benzoyl peroxide (BPO) and DCP/BPO. The crosslinking bonds between modified silica and rubbers were proved by Fourier transform infrared analysis, and the compatibility of SBR and BR was proved by polarized light microscopy (PLM) analysis. The silica‐modified SBR/BR blend can substitute for NR in the specific application fields. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Grafting hydroxy‐terminated polybutadiene onto nanosilica surface for styrene butadiene rubber compounds

Hydroxy teminated polybutadiene (HTPB) was grafted onto the surface of nanosilica particles via toluene di‐isocyanate (TDI) bridging to reduce filler–filler interactions and improve dispersion of nanosilica in rubber. Also, this prepolymer as modifier contains double bonds which participate in sulfur curing of styrene butadiene rubber (SBR) matrix to enhance filler/polymer interaction and reinforcement effects of silica. The reactions were characterized by titration and Fourier transforms infrared spectroscopy. Thermogravimetric analysis was utilized to evaluate the weight percentage of grafted TDI and HTPB. About 60% of the hydroxyl sites of silica were reacted with excess TDI in the first reaction. In the second reaction, HTPB as desired reactive coating was grafted on the functionalized nanosilica to constitute about 24 wt % of the final modified silica. The sedimentation experiments showed good suspension stability for the modified nanosilica in the organic media. Scanning electron microscopy revealed nanoscale dispersion of modified silica aggregates in the SBR matrix at concentration of about 14 phr. Also, vulcanization characteristics and mechanical properties of compounds demonstrated that HTPB grafting improved dispersion of nanosilica as well as its interaction to the rubber matrix as an efficient reinforcement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011