1-Chloro-1,3-butadiene copolymers. I. Synthesis of copolymer with 1,3-butadiene and physical properties of its vulcanizate

Emulsion copolymerization of 1-chloro-1,3-butadiene and 1,3-butadiene was carried out using potassium persulfate at 50°C. The thus synthesized 1-chloro-1,3-butadiene copolymer was possible to be cured with 2-mercaptoimidazoline (MI) as well as with sulfur. The tensile strength of the MI vulcanizate of the copolymer compounded with 30 phr HAF black reached 100 kg/cm² and was higher than that of the sulfur vulcanizate. Moreover, these two vulcanizates showed higher tensile strengths than the sulfur vulcanizate of emulsion butadiene rubber. The addition of the copolymer to the blend of chloroprene rubber (Neoprene GRT) and butadiene rubber extremely improved the elongation and the tensile strength. Dynamic measurements of the vulcanizates showed that the glass transition temperature of the copolymer was situated at the region between that of butadiene rubber and that of chloroprene rubber.     

Synthesis of poly(chloroprene-co-isobutyl methacrylate) and its compatibilizing effect in polychloroprene/poly(isobutyl methacrylate) blends

A copolymer of chloroprene (CP) and isobutyl methacrylate (iBMA) [poly(CP-co-iBMA)] was prepared in benzene by radical copolymerization. For comparison, the graft copolymer of iBMA onto polychloroprene (CR) [poly(CR-g-iBMA)] was also prepared. The glass transition temperature of the poly(CP-co-iBMA) was about ?32.4°C. The monomer reactivity ratios determined by the Finneman-Ross method were given as r₁ (CP) = 1.80 and r₂ (iBMA) = 0.74 in the copolymerization of CP and iBMA, respectively. Miscibility of blends of CR and poly(isobutyl methacrylate) (PiBMA), prepared by casting from tetrahydrofuran (THF) solution, was investigated by their glass transition temperature behaviors and morphologies. Although the blends of CR and PiBMA were incompatible, the addition of poly(CP-co-iBMA) or poly(CR-g-iBMA) enhanced miscibility between the two base polymers. It was found that the extent of partial miscibility becomes larger when adding poly(CP-co-iBMA) than poly(CR-g-iBMA) as a third component to the CR/PiBMA blend of 50/50 wt % composition. © 1993 John Wiley & Sons, Inc.     

氯丁二烯与2，3－二氯丁二烯－1，3硫调共聚物（DCR－114）的研制

采用硫黄为分子量调节剂，进行了氯丁二烯与２，３－二氯丁二烯－１，３硫调共聚物聚合配方、聚合工艺条件及断链工艺条件的研究。结果表明．产品不仅有优良的抗结晶性能，而且兼有良好的物理机械性能，低温制品质软，各项性能与美国Ｄｕｐｏｎｔ公司相应牌号的ＧＲＴ氯丁胶的技术性能相当。     

高温溶液法制备SBR的结构和性能研究

以正丁基锂（n-BuLi）为引发剂、醚类化合物为调节剂、环己烷／正己烷为溶剂,采用阴离子高温聚合工艺合成了溶聚丁二烯／苯乙烯橡胶（SSBR）。通过GPC、NMR分别测试了SSBR的相对分子质量及其分布和微观结构;并对硫化胶性能和门尼粘度进行了测定。考察了调节剂、温度等因素对SSBR的相对分子质量及其分布、共聚物微观结构、序列分布以及动态力学性能和物理机械性能的影响。研究结果表明：所用调节剂是有效的SSBR高温聚合调节剂,可很好地调节SSBR中的乙烯基含量,获得微观结构适中的中高乙烯基丁苯共聚物;n（调节剂）／n（Li）对聚合速率及共聚物的1,2-结构含量有明显的影响,但对共聚物的相对分子质量分布无明显影响;温度对共聚物的转化率及微观结构均有一定的影响。     

Studies on graft copolymerization of cyclohexyl methacrylate onto chloroprene rubber

Graft copolymerization of cyclohexyl methacrylate (CMA) onto chloroprene rubber (CR) was carried out in toluene using benzoyl peroxide as an initiator. The graft copolymer was isolated from the gross polymer by extracting it with a butanone solution. Infrared (IR) spectra of the graft copolymer showed the occurrence of grafting. Optimization of various parameters of the grafting, namely, time, temperature, and initiator concentrations, was performed. The mechanical adhesive properties of the graft copolymer, CR-g-CMA, were measured and compared with those of the graft copolymer of methyl methacrylate (MMA) onto CR, CR-g-MMA. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1733–1737, 1997     

UHMWPE纤维用氯丁橡胶粘合剂的制备及应用研究

研究了丙烯酸丁酯(BA)和氯丁橡胶(CR)粘合剂的接枝共聚合反应。用正交设计方法探讨了引发剂用量、丙烯酸丁酯用量、温度和时间对产物性能的影响；用红外光谱(FT-IR)和示差扫描量热仪(DSC)对产物的结构和性能进行了表征。结果表明，改性氯丁橡胶粘合剂可用于超高相对分子质量聚乙烯纤维的上胶。     

丁二烯/苯乙烯阴离子连续溶液共聚合研究

在2L的搅拌釜式反应器中，对以正丁基锂（n-BuLi)、THF和环己烷分别为引发剂、调节剂和溶剂的丁二烯／苯乙烯阴离子连续溶液共聚合进行了实验研究。用气相色谱、凝胶渗透色谱和核磁共振仪分别实测了单体转化率、共聚物的分子量分布和共聚物的微观结构。考察了平均停留时间和THF／Li^ 比值对丁苯连续共聚合的转化率、分子量及分子量分布和共聚物微观结构的影响。研究结果表明，在THF存在下，由n-BuLi引发的丁苯阴离子连续溶液共聚合可获得微观结构较合适的丁苯无规共聚物；平均停留时间对转化率有明显影响，而对共聚物的微观结构的影响较小；THF／Li^ 比值对聚合速率及共聚物中的结合苯乙烯含量有明显影响，对共聚物的微观结构如1，2－结构 1，4－结构及顺反结构也有一定程度的影响，THF／Li^ 比值对共聚物的平均分子量有显著的影响，因而共聚物的分子量分布无明显影响。研究表明合适的THF／Li^ 比值为70。     

Controlled radical polymerization of conjugated 1,3-dienes with methyl 1,3-butadiene-1-phosphonate

Preparation of new tailor-made phosphorus-containing polydiene materials via controlled radical copolymerization of dimethyl 1,3-butadiene-1-phosphonate (BP^Me) with chloroprene (CP) or isoprene (IP), by using, respectively, AIBN or an alkoxyamine derivative as initiator, is reported. The corresponding materials have been microstructurally characterized by ¹H and ³¹P NMR spectroscopies.     

多单体固相接枝共聚物对废聚丙烯/稻糠复合体系结构与性能的影响

用固相接枝法接枝合成了聚丙烯(PP)与甲基丙烯酸甲酯(MMA)／马来酸酐(MAH)／丙烯酸丁酯(BA)的多单体接枝共聚物(GPP)，将其应用于废聚丙烯(RPP)／稻糠(RC)复合体系，研究了接枝共聚物对体系的力学性能、微观形态、热性能的影响。结果表明，在RPP／RC复合体系中加入固相接枝共聚物，可有效提高复合材料的拉伸强度、弯曲强度、弯曲模量和维卡软化点。     

丁苯负离子共聚物大分子峰的成因及抑制

采用正丁基锂引发反应制备了丁苯负离子共聚物。氧及二氧化碳对活性聚合液的作用、单体与残留聚合液活性链接触、极性添加剂以及聚合温度等,均是形成高于设计相对分子质量的大分子结构分布峰的重要原因,抑制这些因素,可合成出Ｍｗ／Ｍｎ小于１．１的窄分布丁苯共聚物,经ＧＰＣ测定,观察不出大分子峰。