新型异戊二烯聚合体的研制
|
摘要
一、以自制双锂为引发剂，环己烷为溶剂，TMEDA为调节剂，研究
了异戊二烯均聚动力学，采用两次加料法合成了3,4-1,4-3,4-立构三嵌
段聚异戊二烯，并对立构嵌段聚异戊二烯的微观相态进行了研究。结
果表明：
（1）随着TMEDA/2Li的增加，聚合反应温度的降低，有利于
提高聚异戊二烯中的3,4-结构含量；当3,4-含量增加到约
35％时，开始出现1,2-结构，并且1,2-结构的含量随着
TMEDA/2Li的增加而增加；
（2）当TMEDA/2Li＞0.5时，随着TMEDA/2Li的增加，聚合
反应速度降低；
（3）当分子量大于20万时，立构嵌段聚异戊二烯才会出现微
观相分离；
（4）嵌段比（Br）和3,4-结构含量（Ip_(3,4-)）均对立构嵌段聚异
成二烯的玻璃化温度有影响，其关系式为：
Tg_1=-51.70－2.03×Br~2＋0.257×Br×Ip_(3,4-)
二、以自制双锂为引发剂，环己烷为溶剂，研究了在不加调节剂时苯
乙烯、异戊二烯共聚反应动力学行为。采用两次加料法合成了SIS。
同时，采用一次加料法合成了有过渡段的SIS（tapered SIS），对其微
观相态及力学性能进行了研究。将SIS和有过渡段SIS进行了对比。
实验结果表明：
（1）随着体系中异戊二烯含量的增加，聚合温度的升高，聚
合反应速度加快；
＿＿＿儿＿＿＿＿＊＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿。＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿
大连理工大学硕士学位论文
（2）随着聚合温度地降低，体系中苯乙烯含量的增加，苯乙
烯、异戊二烯共聚物中3，4－结构含量增加（无二，2－结构）；
一
（3）与SIS相比，有过渡段SIS的拉伸强度有所下降，但是
断裂伸长率增加、熔体流动速率增大。永久变形和透光率
稍有增加；
“（4）对有过渡段幻S的相态进行研究表明，有过渡段 SIS仍
。可出现微观相分离，但是其微观相分离的程度降低。
The anionic polymerization of isoprene was studied with dilithium as
initiator, TM~EDA as modifier and cyclohexane as solvent. The
stereotriblock 3,4-1,4-3,4-polyisoprene was synthesized by two step feed
with dilithium as. initiator, TMEDA as structure regulator and cyclohexane
as solvent. The microphase of stereotriblock polyisoprene was investigated.
The results showed that 1) With the increase of TMEDAI2Li and the
decrease of temperature, the 3,4-content of pOlyisoprene increase. When
3,4-content increase to about 35%, 1,2-structure appeared and increase
with the increase of TMEDAI2Li. 2) When TMEDAI2Li>0.2, with the
increase of TMIEDAI2Li, the polymerization rate decreased. 3) Only when
the molecular weight greater than 20 X 1 ~4, can the microphase separation
of the stereo-block polyisoprene appear. 4) The hard block/soft block (Br)
and 3,4-microstructure content influence the glass transition temperature of
the stereo-block polyisoprene.
The anionic copolymerization of styrene and isoprene was studied
with dilithium as initiator and cyclohexane as solvent. A tapered SIS was
synthesized by adding of isoprene and styrene simultaneously. The
microphase and mechanical properties were investigated. The results
showed that 1) With the increase of isoprene content and temperature, the
polymerization rate increase. 2) With the decrease of temperature or with
the increase of styrene content, the 3,4-structure of polyisoprene increased
(without 1,2-structure). 3) Compared with pure block SIS, the tensile stress
m
/
L
of tapered SIS decreased. But the elongation at break increased. 4) The
investigation of microphase shows that the tapered SIS is microphase
separation. The degree of microphase separation decreased.
了异戊二烯均聚动力学，采用两次加料法合成了3,4-1,4-3,4-立构三嵌
段聚异戊二烯，并对立构嵌段聚异戊二烯的微观相态进行了研究。结
果表明：
（1）随着TMEDA/2Li的增加，聚合反应温度的降低，有利于
提高聚异戊二烯中的3,4-结构含量；当3,4-含量增加到约
35％时，开始出现1,2-结构，并且1,2-结构的含量随着
TMEDA/2Li的增加而增加；
（2）当TMEDA/2Li＞0.5时，随着TMEDA/2Li的增加，聚合
反应速度降低；
（3）当分子量大于20万时，立构嵌段聚异戊二烯才会出现微
观相分离；
（4）嵌段比（Br）和3,4-结构含量（Ip_(3,4-)）均对立构嵌段聚异
成二烯的玻璃化温度有影响，其关系式为：
Tg_1=-51.70－2.03×Br~2＋0.257×Br×Ip_(3,4-)
二、以自制双锂为引发剂，环己烷为溶剂，研究了在不加调节剂时苯
乙烯、异戊二烯共聚反应动力学行为。采用两次加料法合成了SIS。
同时，采用一次加料法合成了有过渡段的SIS（tapered SIS），对其微
观相态及力学性能进行了研究。将SIS和有过渡段SIS进行了对比。
实验结果表明：
（1）随着体系中异戊二烯含量的增加，聚合温度的升高，聚
合反应速度加快；
＿＿＿儿＿＿＿＿＊＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿。＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿＿
大连理工大学硕士学位论文
（2）随着聚合温度地降低，体系中苯乙烯含量的增加，苯乙
烯、异戊二烯共聚物中3，4－结构含量增加（无二，2－结构）；
一
（3）与SIS相比，有过渡段SIS的拉伸强度有所下降，但是
断裂伸长率增加、熔体流动速率增大。永久变形和透光率
稍有增加；
“（4）对有过渡段幻S的相态进行研究表明，有过渡段 SIS仍
。可出现微观相分离，但是其微观相分离的程度降低。
The anionic polymerization of isoprene was studied with dilithium as
initiator, TM~EDA as modifier and cyclohexane as solvent. The
stereotriblock 3,4-1,4-3,4-polyisoprene was synthesized by two step feed
with dilithium as. initiator, TMEDA as structure regulator and cyclohexane
as solvent. The microphase of stereotriblock polyisoprene was investigated.
The results showed that 1) With the increase of TMEDAI2Li and the
decrease of temperature, the 3,4-content of pOlyisoprene increase. When
3,4-content increase to about 35%, 1,2-structure appeared and increase
with the increase of TMEDAI2Li. 2) When TMEDAI2Li>0.2, with the
increase of TMIEDAI2Li, the polymerization rate decreased. 3) Only when
the molecular weight greater than 20 X 1 ~4, can the microphase separation
of the stereo-block polyisoprene appear. 4) The hard block/soft block (Br)
and 3,4-microstructure content influence the glass transition temperature of
the stereo-block polyisoprene.
The anionic copolymerization of styrene and isoprene was studied
with dilithium as initiator and cyclohexane as solvent. A tapered SIS was
synthesized by adding of isoprene and styrene simultaneously. The
microphase and mechanical properties were investigated. The results
showed that 1) With the increase of isoprene content and temperature, the
polymerization rate increase. 2) With the decrease of temperature or with
the increase of styrene content, the 3,4-structure of polyisoprene increased
(without 1,2-structure). 3) Compared with pure block SIS, the tensile stress
m
/
L
of tapered SIS decreased. But the elongation at break increased. 4) The
investigation of microphase shows that the tapered SIS is microphase
separation. The degree of microphase separation decreased.
引文
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16．程钰，何辰凤，金关泰，异戊二烯阴离子聚合机理的研究，弹性体 1998,8(1)，12
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3．罗志河，发展异戊橡胶应当提上日程，合成橡胶工业，
4．姜晓明，吉林石油化工，1993,(4)，23
5.US5082906
6.US5151398
7.US5239023
8.US5356997
9.US5448003
10.US5300599
11.US5620939
12.US5677402
13．徐其芬、黄锡仁，异戊橡胶的发展前景及对策，弹性体，1991，1(3)，49
14．罗志河，关于发展异戊橡胶的探讨，合成橡胶工业，1990,13(2)，79
15．韩丙勇，金关泰，双锂引发剂研究异戊二烯阴离子聚合的动力学研究，化工学报 1997,48(3)，320
16．程钰，何辰凤，金关泰，异戊二烯阴离子聚合机理的研究，弹性体 1998,8(1)，12
17．韩丙勇，金关泰等，双锂引发剂合成热塑性弹性体SISIS，合成橡胶工业 1997,20(4)，218
18．韩丙勇，金关泰等，热塑性弹性体SISIS的微相分离、性能及应用，合成橡胶工业 1998,21(1)，25
19．严自力，金关泰，石化技术 1998,5(4)，327
20．李扬、张淑芬，我国锂系聚合物发展前景展望，合成橡胶工业 1995,18(5)，266
21．王德充，苯乙烯—异戊二烯—苯乙烯热塑性嵌段聚合物，合成树脂及塑料 1994,11(3)，62
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