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通过在较低温度下的乳液聚合制备出共聚物SIBR,研究影响其聚合速率的因素。结果表明,温度的变化,以及乳化剂、引发剂用量的不同,聚合速率影响较大;而调节剂用量的变化对聚合速率影响较小。 相似文献
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以自制的4种苯乙烯-异戊二烯-丁二烯橡胶(SIBR)为增韧组分,采用本体聚合工艺,以过氧化苯甲酰为引发剂进行苯乙烯接枝聚合以制备高抗冲聚苯乙烯,考察了用量、相对分子质量及分子链结构不同的SIBR对苯乙烯聚合速率的影响,并比较了用不同橡胶改性聚苯乙烯时的聚合动力学行为。结果表明,SIBR的用量越大聚合速率越小,相对分子质量越大则聚合速率越大;按SIBR分子链序列结构的不同聚合速率还呈现出从大到小依次为线型嵌段SIBR、线型无规SIBR、星形嵌段SIBR及星形无规SIBR的规律。用不同橡胶增韧聚苯乙烯时的聚合速率从大到小依次为SIBR、丁苯橡胶及顺丁橡胶。苯乙烯的表观接枝率随着SIBR用量或其相对分子质量的增大而减小,且远大于使用顺丁橡胶。 相似文献
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以多官能度锂(简称Li)为引发剂,在不同条件下合成了3种星形苯乙烯(St)-异戊二烯(Ip)-丁二烯(Bd)三元共聚物,分析了共聚物的结构。结果表明,两次投料法的产物为两嵌段共聚物,低R[四氢呋喃(THF)与Li的摩尔比]值合成的聚异戊二烯(PI)链段的玻璃化转变温度(Tg)为-58.3℃,1,4-结构为83.8%;高R值合成的无规共聚段的Tg为-36.2℃。低R值一次投料法产物为多嵌段共聚物,-69℃为Bd-Ip无规共聚段的Tg,1,4-结构含量高;22.7℃为Ip-St共聚段的Tg,含摩尔分数为6.6%的PS嵌段。高R值一次投料法的产物为三元无规共聚物,1,4-结构含量低,只有1个Tg,为-28.9℃。 相似文献
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锡偶联型充油苯乙烯-异戊二烯-丁二烯三元共聚物的合成 总被引:3,自引:0,他引:3
以正丁基锂为引发剂、环己烷为溶剂、自制的二元复配调节体系为调节剂、四氯化锡为偶联剂,采用负离子聚合法合成了锡偶联型苯乙烯(St)-异戊二烯(Ip)-丁二烯(Bd)三元共聚物(SIBR),并用湿法充油技术制备了充油SIBR,研究了调节剂对SIBR三元共聚动力学的影响,考察了单体配比和微嵌段含量对SIBR及充油SIBR性能的影响,并对比了充油SIBR与3种通用胶(溶聚丁苯橡胶2305、乳聚丁苯橡胶1502和1712)的性能。结果表明,在SIBR三元聚合过程中,不添加调节剂时,Bd、Ip、St的聚合速率依次减慢,且St的聚合速率远小于前两者;在添加复配调节剂后,St的聚合速率大幅度提高,并超过Ip的聚合速率;当St/Ip/Bd(质量比)为20/40/40时,SIBR的300%定伸应力和拉伸强度呈现最大值;当St微嵌段质量分数小于1.0%时,充油SIBR具有良好的物理机械性能及优异的动态力学性能;充油SIBR的物理机械性能基本与3种通用胶相当,抗湿滑性优于3种通用胶,且滚动阻力小于3种通用胶。 相似文献
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以n-BuLi为引发剂、乙基四氢糠基醚(ETE)和十二烷基苯磺酸钠(SDBS)二元复合调节体系为调节剂、己烷/环己烷为混合溶剂,在聚合温度为50 ℃时采用负离子聚合法进行苯乙烯-异戊二烯-丁二烯(SIBR)三元共聚合,考察了ETE/n-BuLi(摩尔比)和SDBS/n-BuLi(摩尔比)对SIBR微观结构含量和玻璃化转变温度(Tg)的影响。结果表明,当ETE/n-BuLi从0.5增加到2.0、SDBS/n-BuLi为0.1时,SIBR中聚丁二烯的1,2-结构质量分数和聚异戊二烯的3,4-结构质量分数分别增加了5.4和7.6个百分点,Tg上升了28.84 ℃左右;当SDBS/n-BuLi从0.1增加到0.8、ETE/n-BuLi为0.5时,SIBR中聚丁二烯的1,2-结构含量、聚异戊二烯的3,4-结构含量和Tg变化很小;ETE调节SIBR中聚丁二烯的1,2-结构和聚异戊二烯的3,4-结构的能力远远大于SDBS。 相似文献
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以正丁基锂(n-BuLi)为引发剂,双四氢糠丙烷(DTHFP)为极性调节剂,环己烷为溶剂,采用负离子聚合法合成了线型苯乙烯(St)-异戊二烯(Ip)-丁二烯(Bd)三元共聚物,考察了三元共聚合总反应速率的影响因素,研究了三元共聚合反应动力学,并与传统极性调节剂四氢呋喃(THF)体系进行了比较。结果表明,在单体质量分数为12%,St/Ip/Bd(质量比)为20/40/40,设计单臂相对分子质量为10×104的条件下,随着聚合反应温度的升高或DTHFP/n-BuLi(摩尔比)的增加,总转化率和总反应速率逐渐增大,聚合反应的假一级表观增长反应速率常数增大;表观增长反应活化能和频率因子均随DTHFP/n-BuLi值的增加而减小;DTHFP在用量较小的情况下与较大THF用量的效果相当,促进聚合反应速率的能力明显高于THF。 相似文献
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通过对兰州石化公司合成橡胶厂50kt/a ABS改造装置EBR单元工业试验的总结,分析了影响EBR聚合及其产品质量的主要因素,从而为全面消化吸收该项技术提供了一定的参考和帮助。 相似文献
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This paper examines the important dimensionless numbers that control emulsion polymerization in a tubular reactor. It was found that the activation energy of polymerization was of major importance, while the role of monomer diffusion was not very significant. By selecting certain combinations of the dimensionless numbers, changes occurring during scaleup from a small tubular diameter to a larger diameter can be approximated. 相似文献
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Summary The kinetics of seeded batch emulsion polymerization of n-butyl acrylate (BA) have been investigated at 50°C using potassium persulfate (KPS) as the thermal initiator. The variations in the average number of radicals per particle (ñ) and termination rate constant (kt) have been determined as a function of conversion for particles of different sizes using established kinetic equations. Contrary to expectations, the values of ñ were found to be unusually high and the values of kt were found to be very low for all the reactions studied. The high values of ñ are consistent with the low rates of termination. An explanation has been proposed for the low values of kt based on preliminary computations of the energy barrier for rotation about the terminal C-C bond of the polymer chain end of polybutyl acrylate (PBA). 相似文献
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Seeded emulsion polymerization of methyl methacrylate (MMA) or styrene (ST) was carried in the presence of different vinyl‐containing polysiloxane latices (SV‐*) and the core‐shell particles with poly(methyl methacrylate) (PMMA) or polystyrene (PST), as the shells were obtained under different polymerization conditions. Besides the compatibility of the vinyl monomer and its polymer with polysiloxane and the reaction between vinyl monomer with vinyl group of polysiloxane, the content of vinyl group of seed polysiloxane has influence on the morphology and component of the resulted composite particles. The mechanism for the formation of core‐shell structure is discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2752–2758, 2001 相似文献
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醋酸乙烯乳液聚合的影响因素探讨 总被引:1,自引:0,他引:1
研究了聚合温度和电解质对醋酸乙烯(AVc)乳液聚合反应的影响,对以聚乙烯醇(PVA)为保护胶体的系统而言,乳液粘度随聚合温度的升高而增大,随电解质用量的增加而减少。 相似文献
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The rate coefficient for entry of radicals into the polymer particles and the radical exit rate coefficient were estimated in seeded emulsion polymerization of styrene. The dependence of both coefficients on the particle size was used in an attempt to discriminate between the models proposed for these coefficients. The results obtained were found to be consistent with a model in which the entry of radicals into the polymer particles occurs by the propagational mechanism and the radicals desorb from the polymer particles by diffusion. A comparison between the estimated values of the coefficients and those calculated theoretically using the equations derived from the corresponding mechanisms was performed. 相似文献
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The effects of various components in an emulsion polymerization system on the dissociation rate coefficient of persulfate at 50 °C are examined using iodometry. Styrene monomer is found to enhance greatly the dissociation, while there is either no effect or possibly a slightly reduced rate of dissociation with methyl methacrylate monomer. The saturated analogues of these monomers (ethylbenzene and methyl isobutyrate) also enhance the dissociation, although not as much as styrene. Thus, such analogues should not be used as model compounds for determining the effect of a monomer on decomposition rate. The presence of metal parts in the reactor (e.g. as part of the agitation system) also could enhance the dissociation. The accelerations are consistent with literature mechanisms involving transfer reactions of aqueous-phase species. These results have significant implication for the interpretation and prediction of entry efficiencies and particle formation rates in emulsion polymerization systems. 相似文献
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