CAJ | 학술논문

采用新癸酸钕(简称 Nd)/烷基铝[Al(i - Bu)2 H 或 Al(i - Bu)3(简称 Al)]/二异丁基氯化铝(简称 Cl)催化剂对丁二烯(Bd)/异戊二烯(Ip)进行共聚合,考察了 Al 种类及单体配比对 Bd/ Ip 共聚合的影响,通过凝胶渗透色谱(GPC)、傅里叶变换红外光谱和核磁共振氢谱表征了共聚物,研究了2种催化剂体系聚合过程中单体的竞聚率及所得共聚物的序列分布。结果表明,2种催化剂体系所得共聚物中聚丁二烯(PB)和聚异戊二烯(PI)链节的顺式-1,4-结构摩尔分数均超过97%,且 Al(i - Bu)2 H 催化体系的活性明显高于 Al(i - Bu)3催化体系,但前者所得共聚物的数均分子量相对较低,分子量分布较宽, GPC 曲线呈双峰,而后者所得共聚物的 GPC 曲线呈单峰；随着单体 Bd 用量的增加,2种催化剂体系所得共聚物中 PB 链节的顺式-1,4-结构摩尔分数均超过99%,而 PI 链节的顺式-1,4-结构摩尔分数则随着单体 Ip 用量的增加而略有降低,且 Al(i - Bu)3催化体系所得共聚物中2种链节的摩尔分数与单体用量基本一致,而 Al(i - Bu)2 H 催化体系所得共聚物中 PB 链节含量略高于单体 Bd 用量；在2种催化体系中,Bd 易于自身均聚,Ip 更容易与 Bd 共聚合,以 Al(i - Bu)3为助催化剂时,所得产物为无规共聚物；随着单体中 Bd 加入比例的增加,PB 链节数均序列长度增加；随着 Ip 加入比例的增加,PI链节数均序列长度增加。
채용신계산녀(간칭 Nd)/완기려[Al(i - Bu)2 H 혹 Al(i - Bu)3(간칭 Al)]/이이정기록화려(간칭 Cl)최화제대정이희(Bd)/이무이희(Ip)진행공취합,고찰료 Al 충류급단체배비대 Bd/ Ip 공취합적영향,통과응효삼투색보(GPC)、부리협변환홍외광보화핵자공진경보표정료공취물,연구료2충최화제체계취합과정중단체적경취솔급소득공취물적서렬분포。결과표명,2충최화제체계소득공취물중취정이희(PB)화취이무이희(PI)련절적순식-1,4-결구마이분수균초과97%,차 Al(i - Bu)2 H 최화체계적활성명현고우 Al(i - Bu)3최화체계,단전자소득공취물적수균분자량상대교저,분자량분포교관, GPC 곡선정쌍봉,이후자소득공취물적 GPC 곡선정단봉；수착단체 Bd 용량적증가,2충최화제체계소득공취물중 PB 련절적순식-1,4-결구마이분수균초과99%,이 PI 련절적순식-1,4-결구마이분수칙수착단체 Ip 용량적증가이략유강저,차 Al(i - Bu)3최화체계소득공취물중2충련절적마이분수여단체용량기본일치,이 Al(i - Bu)2 H 최화체계소득공취물중 PB 련절함량략고우단체 Bd 용량；재2충최화체계중,Bd 역우자신균취,Ip 경용역여 Bd 공취합,이 Al(i - Bu)3위조최화제시,소득산물위무규공취물；수착단체중 Bd 가입비례적증가,PB 련절수균서렬장도증가；수착 Ip 가입비례적증가,PI련절수균서렬장도증가。
Nd ( vers )3 ( simplied as Nd ) /Al(i-Bu)2 H or Al(i-Bu)3 ( simplied as Al ) /Al(i-Bu)2 Cl(simplied as Cl) catalyst systems were applied to butadiene(Bd) / isoprene(Ip) copolymeri-zation. The effects of different Al and comonomer feed ratio on the polymerization behaviors were inves-tigated, the obtained copolymers were characterized by gel permeation chromatography ( GPC), Fourier transform infrared spectroscopy and nuclear magnetic resonance, and the monomer reactivity ratios during polymerization with the catalyst systems and sequence distributions of the obtained copolymers were further studied. The results showed that the mole fraction of cis-1,4-unit in both polybutadiene(PB) and polyiso-prene(PI) units exceeded 97% . The activity of the Al(i-Bu)2 H-based system was obviously higher than that of Al(i-Bu)3-based system, the former afforded copolymers with lower number average molecular weights and broader molecular weight distributions and the GPC curves were bimodal, while the GPC curves of the copolymer obtained with the later system was monomodal. With increase of Bd in monomer feed, the mole fraction of cis-1,4-unit in PB of the copolymers were above 99% , whereas the cis-1,4-unit contents in PI slightly decreased with increase of Ip in monomer feed, and the composition of the co-polymer obtained by Al(i-Bu)3-based system practi-cally coincided with the comonomer composition. In the case of Al(i-Bu)2 H-based system, the PB con-tent in the copolymer was slightly higher than that in monomer feed. In both catalyst systems, the monomer reactivity ratios exhibited similar tendency, Bd ten-ded to homopolymerization while Ip tended to copoly-merization with Bd. When Al(i-Bu)3 was used as co-catalyst, the copolymer was random. With the in-crease of Bd content in monomer feed, the number average sequence lengths of PB increased, and the number average sequence lengths of PI increased with an increase of the Ip content in monomer feed.