不同金属离子中和的新型硫酸盐基顺丁橡胶离聚体的合成、表征与性质

用环氧化顺丁橡胶在二氯乙烷中与硫酸氢钾、硫酸氢钠或硫酸氢锂水溶液以N,N-二甲基苯胺和四乙基溴化铵为催化剂进行反应,合成了新型的含硫酸钾、硫酸钠或硫酸锂基的顺丁橡胶离聚体,还用钾离聚体与醋酸镁、钙、钡、锌或铅溶液反应并洗涤,生成相应的离聚体。离聚体经纯化,用红外光谱（FTIR）及透射电镜表征,确定了硫酸盐基离子及其微区的存在。研究了开环反应的一些条件,结果表明,开环率可达到36％,该离聚体具有相当好的乳化性、一定的吸水性及耐油性,其吸水率和乳化性随离子电位的增加而增大,一价离子的吸水率及乳化体积比二价离子的大;稀溶液粘度随离子电位的增加而增大,二价离子的粘度比一价离子的大;其作为增容剂能增加SBS和氯醇橡胶的相容性。     

含顺丁烯二酸钾基的顺丁橡胶离聚体的合成、表征与性质

用环氧化顺丁橡胶在甲苯中与顺丁烯二酸氢钾水溶液以N，N-二甲基苯胺和四乙基溴化铵为催化剂进行反应，合成了含顺丁烯二酸钾基的顺丁橡胶离聚体，研究了其开环反应条件。结果表明：开环率可以达到34．2％；该离聚体具有一定的乳化性、吸水性、耐油性；其稀溶液粘度随离子含量的增加而增大；其作为增容剂能增加SBS和氯醇橡胶的相容性。     

新型两亲性顺丁橡胶硫酸盐离聚体及其在共混中的增容作用

通过环氧化顺式1,4-聚丁二烯与硫酸氢钠开环反应制备了新型顺丁橡胶硫酸盐离聚体,该离聚体呈现较高的吸水性及突出的乳化性,并能作为氯醚橡胶(CHR)/苯乙烯-丁二烯一苯乙烯嵌段共聚物(SBS)共混物的增容剂.用透射电子显微镜研究了新型顺丁橡胶硫酸盐离聚体的形态,并用扫描电子显微镜分析了离聚体在共混中的增容原因.结果表明,离聚体中存在着黑色纳米级离子微区;离聚体明显改善了CHR与SBS两相界面作用.     

磺化丁基橡胶离聚体与其他聚合物的共混

研究了磺化丁基橡胶(IIR)离聚体与苯乙烯-丁二烯嵌段共聚物、聚丙烯、高密度聚乙烯、氯醚橡胶及顺丁橡胶的共混。结果表明，磺化IIR离聚体与苯乙烯-丁二烯嵌段共聚物或聚丙烯的共混物在拉伸强度方面呈现协同效应，随着磺化IIR离聚体质量分数的增加，聚丙烯的熔点下降。磺化IIR离聚体与高密度聚乙烯的共混物在拉伸强度方面呈现加和效应，而其与氯醚橡胶或顺丁橡胶的共混物在拉伸强度方面则呈现抵销效应。     

含磷酸钠基的SBS两亲离聚体的合成、表征及性质

环氧化SBS在甲苯中与磷酸氢二钠水溶液,以N,N-二甲基苯胺及四乙基溴化铵为催化剂,通过开环反应合成了含磷酸二钠基的两亲性SBS离聚体。离聚体采用FTIR进行表征。研究了开环反应条件及该离聚体的乳化性、吸水性、耐油性和稀溶液粘度。结果表明开环率可以达到32%,该离聚体具有很好的乳化性、明显的吸水性和耐油性,其乳化性、吸水性、耐油性及稀溶液粘度随离子含量增加而增大,随一价阳离子的离子电位增加而增加。     

不同金属离子及胺中和的磺化丁基橡胶离聚体的性能

研究了不同金属离子及胺中和的磺化丁基橡胶离聚体的熔融流动性及力学性能。结果表明,随着硬脂酸锌加入量的增加,锂离聚体的熔融黏度降低,拉伸强度增大;随离聚体中磺酸基含量的增加,锂离聚体的熔融黏度和拉伸强度增大。对于一价金属离子中和的离聚体,其熔融黏度及拉伸强度随着离子电位的降低而减小;对于二价金属离子中和的离聚体,随着离子电位的下降及共价性的增加,熔融黏度下降而拉伸强度增大。用胺中和的离聚体,硬脂酸锌的影响较小,未加硬脂酸锌的离聚体具有较高的扯断伸长率及较低的永久变形,是良好的热塑性弹性体;随离聚体中磺酸基含量的增加,乙胺离聚体的拉伸强度增大。对于不同胺中和的离聚体,其拉伸强度按下列顺序依次降低：乙胺,三乙胺,二乙胺;乙胺,己胺,十二胺,十八胺。     

环氧SBS开环制备磺酸钠离聚体及其部分性能研究

利用环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物（ESBS）的环氧基与亚硫酸氢钠在相转移催化剂、开环催化剂和pH调节剂（BS）存在条件下反应制得磺酸钠离聚体。研究了其反应条件，并采用FTIR及透射电镜确定了离聚体的存在，还研究了不同离子基团含量对磺酸离聚体的乳化性能、吸水率、吸油率及稀溶液粘度的影响。结果表明，ESBS开环反应制备磺酸钠离聚体的最佳条件为：ESBS在甲苯中的质量浓度为12g／100mL；n（NaHSO3）／n（Epoxy）：1．8；m（BS）／m（NaHSO3）=36％；m（TEAB）／m（ESBS）=5％；m（DMA）／m（ESBS）=5％；60℃搅拌反应7h，环氧基转化率达到90％。随着离聚体中离子基团的增加，离聚体的乳化性能增强，吸水性能增大，吸油性能明显增强，离聚体稀溶液粘度增大。     

磺化丁苯橡胶离聚体与一些聚合物的熔融共混及产物性能

将磺化丁苯橡胶镁离子交联聚合体（简称离聚体）在增塑剂硬脂酸锌存在下分别与聚丙烯（ＰＰ）、高密度聚乙烯（ＨＤＰＥ）、丁苯嵌段共聚物（ＳＢＳ）、聚苯乙烯（ＰＳ）、顺丁橡胶（ＢＲ）在Ｂｒａｂｅｎｄｅｒ塑性仪密炼机中熔融共混，考察了共混比对平衡扭矩及物理机械性能的影响。结果表明，磺化丁苯橡胶镁离聚体与ＳＢＳ或ＰＰ共混，其拉伸强度呈协同效应，与ＨＤＰＥ共混呈加和效应，而与ＰＳ或ＢＲ共混则呈抵销效应。透射电镜     

弹性离聚体的研究进展

总结及评述了近年来弹性离聚体的研究进展,包括羧基离聚体、磺化离聚体及遥爪离聚体等,介绍了最近用新方法合成的新型离聚体.     

用环氧化丁苯橡胶制备含顺丁烯二酸钾的丁苯橡胶离聚体

在聚乙二醇(PEG)为相转移催化剂、碱性促进剂存在下,用顺丁烯二酸氢钾(PHM)与环氧化丁苯橡胶进行开环反应,制备了环氧基转化率达100%的含顺丁烯二酸钾的丁苯橡胶离聚体,用傅里叶变换红外光谱及透射电子显微镜进行了表征,并研究了其吸水性、吸油性及稀溶液黏度。结果表明,随着离子含量的增加,离聚体的吸水率和稀溶液黏度增大,吸油率降低。     

Interaction of n-alkanes with crosslinked cis-1,4-polybutadiene

Permeation of n-alkanes through cis-1,4-polybutadine crosslinked using conventional, efficient, and peroxide vulcanizing systems was studied by a gravimetric method. Four alkanes from n-hexane to n-nonane were used. In n-octane, the studies were conducted in the temperature range of 27–70°C.The sorption data was used to estimate the diffusion and permeability coefficients, the activation energy for diffusion and permeation, the entropy and enthalpy of sorption, polymer–solvent interaction parameter, and the degree of crosslinking. The various parameters estimated indicate that permeability of the membranes depends more on the degree of crosslinking than on the nature of crosslinks. Increase in permeant chain length was found to lower permeability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2404–2413, 2001     

氯酯化顺T橡胶的基本性能

将顺丁橡胶胶液与次氯酸叔丁酯及甲酸反应,制得了舍氯和酯侧基的氯酯化顺丁橡胶(CEBR).研究了CEBR生胶的热稳定性能、玻璃化转变温度及门尼黏度,并测定了其硫化胶的力学性能.结果表明,随着结合氯质量分数的提高,CEBR的热稳定性逐渐降低,门尼黏度和玻璃化转变温度上升;CEBR的硫化速率低于顺丁橡胶,且结合氯质量分数越高,硫化速率就越小.必须使用超速硫化促进剂;氯和酯侧基的引入提高了分子的极性,破坏了分子链的规整性,CEBR为非结晶性橡胶;随着结合氯质量分数的增加,CEBR硫化胶的拉伸强度和耐油性提高,且用20份和50份炭黑增强CEBR.当氯的质量分数为3%时,CEBR硫化胶的扯断伸长率可达200%以上.     

Equation of state of cis-1,4-polybutadiene melt

Recent equation of state data are analyzed in terms of the hole theory of polymer melts. The good agreement between experimental and theoretical volume-temperature curves at atmospheric pressure, observed previously for a number of amorphous and crystallizable polymers, is again confirmed. Similarly, satisfactory theoretical results for the isotherms ensue, with deviations however becoming noticeable at elevated pressures and low temperatures. The linearity of the isochores observed experimentally is confirmed by the theory, however with somewhat different slopes. Departures of maximally 10 percent from the thermal pressure coefficients derived from the experimental PVT data are noted. Significant differences between theory and experiment apper only in the third derivatives of the partition function, as has also been observed with other pollymers. The characteristic scaling parameters of volume, temperature and pressure show the expected similarity with hevea rubber. Earlier correlations for scaling entropy and segmental volume with scaling temperature are found to be valid within the scatter of these relations. Finally, the applicability of the empirical Tait equation in the form applied to the equation of state in other polymer melts is confirmed. Although the resulting thermal pressure coefficient exhibits an explicit even if smal dependence on temperature, in disagreement with experiment or theory, the Tait equation remains a useful relation for the representation of PVT information.     

Time-dependent viscoelastic functions for cis-1,4-polybutadiene melts

Summary Relevant recent advances in slit die rheometry are discussed, and an error in the cited publication is corrected.     

Time-dependent viscoelastic functions for cis-1,4-polybutadiene melts

Summary Transient linear and nonlinear viscoelastic functions were measured on cis-1,4-polybutadiene melts and compared to the ROUSE theory and a nonlinear modification of the network theory. The latter was found to overestimate material nonlinearity, especially of the first normal stress coefficient at cessation of steady shear flow. Steady-state functions were recovered from the time dependent measurements. Single step strain experiments in the linear region were recorded by computer, up to 7 milliseconds after the sudden shear jump; a paradox arised in the interpretation of shear versus normal stress after a sudden shear strain.Financial support from DEUTSCHE FORSCHUNGSGEMEINSCHAFT and FONDS DER CHEMISCHEN INDUSTRIE is gratefully acknowledged. We thank CHEMISCHE WERKE HÜLS AG for providing the cis-1,4-polybutadienes. Finally, we are especially indebted to Dr. Michael KOWALSKI for intensive cooperation with ELECTRONICS.     

顺丁橡胶用量对官能化溶聚丁苯橡胶/顺丁橡胶

考察了顺丁橡胶用量对官能化改性溶聚丁苯橡胶与顺丁橡胶并用作为胎面胶时的硫化特性、加工性能、物理机械性能及动态力学性能的影响。结果表明,随着顺丁橡胶用量的增加,并用胶的网络化程度增强,硫化进程加快,填料的分散性得以提高,但其静态力学和动态力学性能均有一定程度的损失,其中顺丁橡胶用量为20份（质量）时官能化改性溶聚丁苯橡胶的抗湿滑性能降低了50%左右。     

Strain-induced crystallization of cis-1,4-polybutadiene containing dispersed 1,2-polybutadiene crystalline particles

Some grades of cis-1,4-polybutadiene contain dispersed crystalline particles made up of a block copolymer having amorphous cis-1,4- and crystalline 1,2 blocks. The particles are known to enhance the strain-induced crystallization of cis-1,4 matrix rubber. The deformational behavior was examined by dynamic shear measurements at small deformation and tensile stress–strain measurements at large deformation. In the shear measurements (linear behavior), the temperature dependence of the shift factor in the time-temperature superposition has been evaluated. The higher temperature dependence was observed for the lower crystalline particle content and higher degree of branching of the matrix rubber. The presence of the crystalline particles resulted in the viscosity enhancement like that expected from the dispersed particles. In the tensile measurements (non-linear behavior), the rubbers showed strain softening. The higher degree of strain softening was observed for the higher amount of the crystalline particles and lower degree of branching. The strain softening is a result of the crystalline particles facilitating the elongation. Because these particles posses the branches which are cis-1,4 chains of the block copolymer, the branches are lubricating the system during the stretching. The length of the branches must be short enough so as to produce no significant entanglement constraint. This observation is in accord with the previous one that a relatively long branch gives strain hardening, whereas a relatively short branch gives strain softening. The strain softening was found to enhance the strain-induced crystallization. This conclusion is opposite to what one might expect from the entanglement constraints by the long branches, forcing the orientation of the chains, and thus enhancing the strain-induced crystallization. © 1996 John Wiley & Sons, Inc.     

Toughened polystyrene containing high cis-1,4-polybutadiene rubber

High cis -1,4 -polybutadiene has been used to prepare toughened polystyrene in an attempt to improve its low temperature impact properties. A range of physical and mechanical properties was obtained by keeping the amount of rubber and the polymerization conditions constant, and varying the rate of agitation in a purpose -built reactor system. Although a good balance of tensile and impact properties is obtained at room temperature, the rubber partially crystallizes when the polyblends are cooled to below ?40°C. This should decrease the efficiency of rubber particles to create and terminate crazes. However, it is significant that the developed crystallinity decreases with the rubber phase volume, and is suppressed almost completely at about 21% rubber phase volume (RPV). The factors influencing the RPV are discussed, and a study of the phase inversion with three different types of rubber shows that its duration depends on the viscosity of the styrene/rubber system.     

Thermal crosslinking of cis-1,4-polybutadiene at ultrahigh pressures

cis-1,4-Polybutadiene (BR) samples, in the absence of crosslinking agents, were simultaneously compressed by ultrahigh pressures (>4.0 GPa) and annealed between 25 and 180°C. The BR samples were crosslinked when the annealing temperatures were above 100°C. The Vickers microhardness of the treated BR increased and the extent of swelling decreased rapidly as the annealing temperature increased, indicating that the crosslinking density increased. Solid-state carbon-13 nuclear magnetic resonance and Fourier transform infrared spectroscopy results showed that some C=C bonds in the BR were opened to form the crosslinking network structures with C—C linkages and that a partial cis–trans isomerization took place during the treatments. Differential scanning calorimetry studies revealed that the glass transition temperature increased and the crystallinity decreased as the annealing temperature increased. When the annealing temperature exceeded 140°C, the treated BR samples lost their rubbery elastic characteristics completely and became brittle materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2131–2140, 1998     

Measurement of the PVT behavior of cis-1,4-polybutadiene

The volume of cis-1,4-polybutadiene between 5 and 55°C and 1 and 3000 atmospheres was measured to within a relative error of 0.1 percent with an especially developed, bellows-type dilatometer. The presence of a small transition near 55°C was indicated by analysis of the data and confirmed by differential thermal analysis.