双锂体系丁二烯/异戊二烯/苯乙烯聚合物的研制
|
摘要
近年来烷基锂引发剂的发展已从单锂转向双锂、多锂和混合锂方向发
展，而其中双锂引发剂由于近年来在非极性溶剂中的溶解问题得以解决，
发展非常迅速，日益引起人们普遍关注。双锂引发剂用于制备锂系聚合物
具有单锂引发剂无法比拟的优势，其最大特点在于聚合物可以双端引发、
增长、终止，可以制备结构对称的聚合物，加之阴离子活性聚合的特点，
双锂引发丁二烯、异戊二烯、苯乙烯聚合领域已成为锂系聚合物新的技术
增长点。美国DOW化学公司的双锂引发剂是目前已知综合性能最为理想的
工业化产品，但仍存在诸如溶剂体系不单一、引发速度较慢、溶解性能不
理想、制备时间较长等问题。
本文在确保双官能团烷基锂引发剂具有很好的溶解性能、均一的官能
度、较快的引发速度、溶剂体系单一、制备工艺简单、合成时间短、成本
低的前提下，研制了两种双锂引发剂，其一为双烯加成型双锂齐聚物，各
项技术指标达到国际水平，并已形成专利技术；其二为双卤代烷烃取代型
双锂齐聚物，对双锂的认识从传统观念上有了新的突破，从工业化实用角
度出发，从产品立足于满足使用要求出发，从现实国产化条件出发，给双
卤代烷烃取代型双锂注入新的生机。本文始终贯穿高分子设计思想，以双
锂为引发剂、环己烷为溶剂、二乙二醇二甲醚/四甲基乙二胺为极性添加剂、
立足于三种大宗单体—丁二烯、异戊二烯、苯乙烯，制备了聚丁二烯、聚
异戊二烯、1，2-1，4-1，2-立构三嵌段聚丁二烯、3，4-1，4-3，4-立构三嵌段
聚异戊二烯、对称型双端过渡态丁二烯/苯乙烯嵌段共聚物、对称型双端过
渡态异戊二烯/苯乙烯嵌段共聚物、对称型双端过渡态丁二烯/异戊二烯/苯
乙烯嵌段共聚物，并对聚合反应过程动力学行为、热效应进行了较为系统
的研究，对聚合物的微观结构、序列结构、形态结构进行了较为深入的研
摘要
究，同时对聚合物的物理机械性能进行了较为全面的研穴。
纵观全文，结论如下：
l 双卤代烷烃取代型双理齐聚物是一种极具工业化前景的引发剂，其原料
价廉易得、制备工艺简单，使用极性较低的试剂乙醚为溶剂，严格控制引
发剂的浓度不低于04N，可不必按传统方式进行溶剂晋换，而确保聚合物的
微观结构无较大变化，制备工艺极大简化，引发剂官能度箔以保证，采用
齐聚技术可确保双钾的稳定和溶解性能，聚丁二烯的1，2－结构含量、聚异
戊二烯的 3，4－结构含量均小于 15％，产品性能均可满足使用要求。对双卤
代烷烃取代型双理有必要进行重新评价和认识，实事求是地对双狸引发剂
是否固执追求无醚化问题进行客观分析。
2以双理为引发剂，制备了聚丁二烯、聚异戊二烯、立构三嵌段聚丁二烯。
立构三嵌段聚异戊二烯、对称型双端过渡态丁二烯／苯乙烯嵌段共聚物、对
称型双端过渡态异戊二烯／苯乙烯嵌段共聚物、对称型双端过渡态丁二烯／
异戊二烯／苯乙烯嵌段共聚物，结果表明：采用双卤代烷烃取代型双理为引
发剂，可以实现对聚合物分子量的准确设计，分子量分布较窄并呈正态分
布。
3 在国内外首次以双钾为引发剂成功地制备了立构三嵌段聚异戊二烯、对
称型双端过渡态丁二烯／异戊二烯／苯乙烯嵌段共聚物，并对两类新型聚合
物的结构和物性进行了系统研究，发现具有双端过渡态的丁二烯／异戊二烯
／苯乙烯嵌段共聚物均具有优良的拉伸性能，在适宜的单体配比下，断裂强
度、断裂伸长率可达到较佳的平衡。
4采用mC和动态粘弹谱等技术，在国内外首次对丁二烯、异戊二烯立构
三嵌段聚合物和对称型双端过渡态丁二烯、异戊二烯、苯乙烯嵌段共聚物
的微观相分离结构进行研究，发现在适宜的结构参数下丁二烯、异戊二烯
立构三嵌段聚合物具有微观相分离结构，存在两个玻璃化转变温度，对札
2
人过理丁人学汹－DU门c生学位沦义
型双端过渡态丁二烯、异戊二－烯、苯乙烯嵌段共聚物只有微观川分离纸构，
在适宜的结构参数下存在三个玻璃化转变温度，即存在苯乙烯聚合物1＆段
相、共轭二烯烃聚合物嵌段川1、本乙烯／共轭二烯烃过渡态人聚物1＆段州，
这在国内外尚属首次发现。
5在国内首次对以双理为引发剂的丁二烯、异戊二烯、苯乙烯均聚和共聚过
程的聚合反应动力学行为、聚合反应过片热效应进行了系统研究，并对聚
合物的微观结构、序列结构进行了系统＊究。
6成功地研制出双烯加成型双挫齐聚物引发剂，彻底解决了双挫制备体系
和聚合体系溶剂一致性问题，通过加入适量的极性添加剂、控制双理齐聚
物的齐聚度很好地解决了双鲤制备反应速度较慢、溶解性能不理想、引发
活性较低等瓶颈问题，并形成专有技术，获得专利权，但山于双烯加成型
双钾制备工艺较复杂、控制步骤较多、成本较高、原材料立足囚内还有一
些问题需要解决，因此，与实用型的双卤代烷烃取代型双埋相比较，双烯
加成型双理的工业化时间安排可暂列其后。
7 以双?
During the last few years, the focus on development of alkyllithium
initiator gradually shafted from monolithium to dilithium or multilithium or
mixed-lithium initiators. Among them, the dilithium initiator was
developed very fast and increasingly attracted extensive attentions since
the dissolution problem of the dilithium initiator in non-polar solvent had
been overcome. Dilithium initiator possessed the incomparable
advantages over monolithium in preparing lithium-initiated polymers,
among them, the most important characteristic was that the symmetrical
polymer could be synthesized when the initiation, propagation and
termination of the chain occurred at two ends at the same time.
Combined with the features of anionic active polymerization, the dilithium
initiator already created a new growth point in technology of
lithium-initiated polymer through its application in the ternary
copolymerization field of butadiene-isoprene-styrene. At present, the
dilithium initiator manufactured by Dow Company, USA, was known as
the best commercialized product in comprehensive properties, however,
there still existed problems which remain to be resolved, such as
non-single solvent system, slow initiation speed, inferior solubility and
long preparation time,
Under the precondition of ensuring the advantages such as good
solubility, uniform functionality, fast initiation speed, single solvent
system, simplified preparation technology, short synthesis time and low
cost, the present thesis developed two kinds of dilithium initiators. One
was the dilithium oligomer prepared via addition reaction of diene,
named as diene addition type dilithium; the novel initiator reached the
current international level in the technical indexes and formed proprietary
technology. The other was dilithium oligomer prepared through
substitution reaction of dihalogenated alkane, named as dihalogenated
alkane substitution type dilithium. Thanks to the breakthrough in the
understanding against the traditional concept of dilithium, the
development of the dihalogenated alkane substitution type dilithium was
injected with the fresh vigor proceeding from facilitating the practical
application on industrial scale, making the initiator meet the
requirements in application and realizing the localization of the initiators.
Based on the philosophy of macromolecular design throughout the
thesis, the author fully utilized the monomers of butadiene, isoprene and
styrene produced in bulk to synthesize a series of novel copolymers with
the dilithium as initiator, cyclohexane as solvent and diethylene glycol
dimethyl ether / tetramethyl ethylenediamine as polar additive.
Following were the typical block copolymers as prepared, including the
polybutadiene, polyisoprene, 1,2-1,4-1 ,2-stereo-triblock polybutadiene,
3,4-1 ,4-3,4-stereo-triblock polyisoprene, symmetrical two-end tapered
block copolymer of butadiene/styrene, symmetrical two-end tapered
block copolymer of isoprene/styrene and symmetrical two-end tapered
block terpolymer of butadiene/isoprene/styrene. Furthermore, this thesis
also studied systematically the kinetic behaviour and heat effect in the
polymerization process. The microstructure, sequential arrangement and
morphology as well as the mechanical properties of the polymers
mentioned above were also investigated in detail.
From the summary of the full thesis, it came to the conclusions that:
1. The dihalogenated alkane substitution type dilithium was one kind of
initiator that possessed pret
展，而其中双锂引发剂由于近年来在非极性溶剂中的溶解问题得以解决，
发展非常迅速，日益引起人们普遍关注。双锂引发剂用于制备锂系聚合物
具有单锂引发剂无法比拟的优势，其最大特点在于聚合物可以双端引发、
增长、终止，可以制备结构对称的聚合物，加之阴离子活性聚合的特点，
双锂引发丁二烯、异戊二烯、苯乙烯聚合领域已成为锂系聚合物新的技术
增长点。美国DOW化学公司的双锂引发剂是目前已知综合性能最为理想的
工业化产品，但仍存在诸如溶剂体系不单一、引发速度较慢、溶解性能不
理想、制备时间较长等问题。
本文在确保双官能团烷基锂引发剂具有很好的溶解性能、均一的官能
度、较快的引发速度、溶剂体系单一、制备工艺简单、合成时间短、成本
低的前提下，研制了两种双锂引发剂，其一为双烯加成型双锂齐聚物，各
项技术指标达到国际水平，并已形成专利技术；其二为双卤代烷烃取代型
双锂齐聚物，对双锂的认识从传统观念上有了新的突破，从工业化实用角
度出发，从产品立足于满足使用要求出发，从现实国产化条件出发，给双
卤代烷烃取代型双锂注入新的生机。本文始终贯穿高分子设计思想，以双
锂为引发剂、环己烷为溶剂、二乙二醇二甲醚/四甲基乙二胺为极性添加剂、
立足于三种大宗单体—丁二烯、异戊二烯、苯乙烯，制备了聚丁二烯、聚
异戊二烯、1，2-1，4-1，2-立构三嵌段聚丁二烯、3，4-1，4-3，4-立构三嵌段
聚异戊二烯、对称型双端过渡态丁二烯/苯乙烯嵌段共聚物、对称型双端过
渡态异戊二烯/苯乙烯嵌段共聚物、对称型双端过渡态丁二烯/异戊二烯/苯
乙烯嵌段共聚物，并对聚合反应过程动力学行为、热效应进行了较为系统
的研究，对聚合物的微观结构、序列结构、形态结构进行了较为深入的研
摘要
究，同时对聚合物的物理机械性能进行了较为全面的研穴。
纵观全文，结论如下：
l 双卤代烷烃取代型双理齐聚物是一种极具工业化前景的引发剂，其原料
价廉易得、制备工艺简单，使用极性较低的试剂乙醚为溶剂，严格控制引
发剂的浓度不低于04N，可不必按传统方式进行溶剂晋换，而确保聚合物的
微观结构无较大变化，制备工艺极大简化，引发剂官能度箔以保证，采用
齐聚技术可确保双钾的稳定和溶解性能，聚丁二烯的1，2－结构含量、聚异
戊二烯的 3，4－结构含量均小于 15％，产品性能均可满足使用要求。对双卤
代烷烃取代型双理有必要进行重新评价和认识，实事求是地对双狸引发剂
是否固执追求无醚化问题进行客观分析。
2以双理为引发剂，制备了聚丁二烯、聚异戊二烯、立构三嵌段聚丁二烯。
立构三嵌段聚异戊二烯、对称型双端过渡态丁二烯／苯乙烯嵌段共聚物、对
称型双端过渡态异戊二烯／苯乙烯嵌段共聚物、对称型双端过渡态丁二烯／
异戊二烯／苯乙烯嵌段共聚物，结果表明：采用双卤代烷烃取代型双理为引
发剂，可以实现对聚合物分子量的准确设计，分子量分布较窄并呈正态分
布。
3 在国内外首次以双钾为引发剂成功地制备了立构三嵌段聚异戊二烯、对
称型双端过渡态丁二烯／异戊二烯／苯乙烯嵌段共聚物，并对两类新型聚合
物的结构和物性进行了系统研究，发现具有双端过渡态的丁二烯／异戊二烯
／苯乙烯嵌段共聚物均具有优良的拉伸性能，在适宜的单体配比下，断裂强
度、断裂伸长率可达到较佳的平衡。
4采用mC和动态粘弹谱等技术，在国内外首次对丁二烯、异戊二烯立构
三嵌段聚合物和对称型双端过渡态丁二烯、异戊二烯、苯乙烯嵌段共聚物
的微观相分离结构进行研究，发现在适宜的结构参数下丁二烯、异戊二烯
立构三嵌段聚合物具有微观相分离结构，存在两个玻璃化转变温度，对札
2
人过理丁人学汹－DU门c生学位沦义
型双端过渡态丁二烯、异戊二－烯、苯乙烯嵌段共聚物只有微观川分离纸构，
在适宜的结构参数下存在三个玻璃化转变温度，即存在苯乙烯聚合物1＆段
相、共轭二烯烃聚合物嵌段川1、本乙烯／共轭二烯烃过渡态人聚物1＆段州，
这在国内外尚属首次发现。
5在国内首次对以双理为引发剂的丁二烯、异戊二烯、苯乙烯均聚和共聚过
程的聚合反应动力学行为、聚合反应过片热效应进行了系统研究，并对聚
合物的微观结构、序列结构进行了系统＊究。
6成功地研制出双烯加成型双挫齐聚物引发剂，彻底解决了双挫制备体系
和聚合体系溶剂一致性问题，通过加入适量的极性添加剂、控制双理齐聚
物的齐聚度很好地解决了双鲤制备反应速度较慢、溶解性能不理想、引发
活性较低等瓶颈问题，并形成专有技术，获得专利权，但山于双烯加成型
双钾制备工艺较复杂、控制步骤较多、成本较高、原材料立足囚内还有一
些问题需要解决，因此，与实用型的双卤代烷烃取代型双埋相比较，双烯
加成型双理的工业化时间安排可暂列其后。
7 以双?
During the last few years, the focus on development of alkyllithium
initiator gradually shafted from monolithium to dilithium or multilithium or
mixed-lithium initiators. Among them, the dilithium initiator was
developed very fast and increasingly attracted extensive attentions since
the dissolution problem of the dilithium initiator in non-polar solvent had
been overcome. Dilithium initiator possessed the incomparable
advantages over monolithium in preparing lithium-initiated polymers,
among them, the most important characteristic was that the symmetrical
polymer could be synthesized when the initiation, propagation and
termination of the chain occurred at two ends at the same time.
Combined with the features of anionic active polymerization, the dilithium
initiator already created a new growth point in technology of
lithium-initiated polymer through its application in the ternary
copolymerization field of butadiene-isoprene-styrene. At present, the
dilithium initiator manufactured by Dow Company, USA, was known as
the best commercialized product in comprehensive properties, however,
there still existed problems which remain to be resolved, such as
non-single solvent system, slow initiation speed, inferior solubility and
long preparation time,
Under the precondition of ensuring the advantages such as good
solubility, uniform functionality, fast initiation speed, single solvent
system, simplified preparation technology, short synthesis time and low
cost, the present thesis developed two kinds of dilithium initiators. One
was the dilithium oligomer prepared via addition reaction of diene,
named as diene addition type dilithium; the novel initiator reached the
current international level in the technical indexes and formed proprietary
technology. The other was dilithium oligomer prepared through
substitution reaction of dihalogenated alkane, named as dihalogenated
alkane substitution type dilithium. Thanks to the breakthrough in the
understanding against the traditional concept of dilithium, the
development of the dihalogenated alkane substitution type dilithium was
injected with the fresh vigor proceeding from facilitating the practical
application on industrial scale, making the initiator meet the
requirements in application and realizing the localization of the initiators.
Based on the philosophy of macromolecular design throughout the
thesis, the author fully utilized the monomers of butadiene, isoprene and
styrene produced in bulk to synthesize a series of novel copolymers with
the dilithium as initiator, cyclohexane as solvent and diethylene glycol
dimethyl ether / tetramethyl ethylenediamine as polar additive.
Following were the typical block copolymers as prepared, including the
polybutadiene, polyisoprene, 1,2-1,4-1 ,2-stereo-triblock polybutadiene,
3,4-1 ,4-3,4-stereo-triblock polyisoprene, symmetrical two-end tapered
block copolymer of butadiene/styrene, symmetrical two-end tapered
block copolymer of isoprene/styrene and symmetrical two-end tapered
block terpolymer of butadiene/isoprene/styrene. Furthermore, this thesis
also studied systematically the kinetic behaviour and heat effect in the
polymerization process. The microstructure, sequential arrangement and
morphology as well as the mechanical properties of the polymers
mentioned above were also investigated in detail.
From the summary of the full thesis, it came to the conclusions that:
1. The dihalogenated alkane substitution type dilithium was one kind of
initiator that possessed pret
引文
1 D. Lipkin;et al. ;Science, 117, 534(1953)
2 LO,Grace, Y. ;PCT, WO89/04843, 1989(DOW)
3 Lu H. Tung;et al. ;USP4169115, 1979(DOW)
4 Lu H.Tung;et al. ;USP4200718, 1980(DOW)
5 Lu H. Tung;et al. ,USP5057583, 1991(DOW)
6 Lu H.Tung;et al. ;USP4205016, 1980(DOW)
7 Lu H. Tung;et al. ;USP4201729, 1980(DOW)
8 Lu H. Tung;et al. ;USP4196154, 1980(DOW)
9 Lu H. Tung.et al. ;USP4169153, 1980(DOW)
10 Lu H.Tung;et al. ;EP0118572, 1984(DOW)
11 Gary R. Marchand;et al. ;EP0472749,1992(DOW)
12 Klaus Bronstert;et al. ;USP4861742,1989(BASF)
13 Hoecker Hartwig;et al.:EP0025942,1981(BASF)
14 V.Gnehl; E.Anton;et al. ;GB2124228(1982) (BUNA)
15 V. Griehl; E.Anton;et al. ;DD237669(1982) (BUNA)
16 Bernard Francois,et al. ;USP4048420,1977(France)
17 Pierre Sigwalt;et al;USP4161494, 1979(France)
18 岸本泰志等;JP63-5403，1988(Asahi)
19 J. E. Hall;EP0096875, 1983(Firestone)
20 John F. Vitkuske; et al. ;USP5100938,1992(DOW)
21 Vonk Willem Cornelis;et al. ;EP0280357,1988(SHELL)
22 JPl-53681(1989) (Asahi)
23 JP5008136603(1982) (Asahi)
24 JP6000155204(1984) (Asahi)
25 BW. Walther.Lu Tung;et al. ;EP0413294(1991) (DOW)
26 V.Griehl;E. Anton,et al. .GB2092163,FR2496673;1982(BUNA)
27 E. Anton,S.Keisenet al. ;DD154981 ;CS7803109(1977) (BUNA)
28 S. Keiser; E.Anton;et al. ;DD154982(1978) (BUNA)
29 E. Anton;HO Frohlich,et al. ;DD28272 (1984) (BUNA)
30 E. Anton;HO Frohlich;et al. ;DD229138(1984) (BUNA)
31 E. Anton;HO Frohlich;et al. ;DD233576(1985) (BUNA)
32 V.Griehl; E.Anton;et al. ;DD247455(1986) (BUNA)
33 E.Anton; V.Griehl;et al. ;GB2083041; FR2489337 (1980) (BUNA)
34 E.Anton;V. Griehl;et al. ;DD154610(1977) (BUNA)
35 E.Anton;V. Griehl;et al. ;DD154980;SU979367(1978) (BUNA)
36 E.Anton;V. Griehl;et al. ;KK155995(1978) (BUNA)
37 E.Anton;V. Griehl;et al. ;DD158781(1980) (BUNA)
38 E. AntoniV.Griehl;et al. ;GB2083041;FR2489337(1980) (BUNA)
39 N. Yanaihara;BE8899002;(1981) (Fillips)
40 K. Bronstert;S. Bohner;DE3711920(1987) (BASF)
41 DT2634391:US4048420(1975) (AGENCE)
42 VG Kulieva;et al;SU1535867(1987) (AS AZERB)
43 C. Foth;E.Anton;et al,DD151065(1977) (BUNA)
44 DT2521502;FR2279774(1974) (DENKI KAGAKU)
45 E. Z.Diner;et al. ,SU1070877 (1982)
46 A. Pleska;et al;DD154611(1977) (BUNA)
47 DD160062(1978) (BUNA)
48 E. Anton;A. Pleska;et al;DD204931(1982) (BUNA)
49 USP4182818;USP4196153(1977) (DOW)
50 USP4200718;USP4201729;USP4205016(1977) (DOW)
51 USP3668263(1972)
52 USP3776964(1973)
53 H.Eschway;et al. ;Makromol,Chem., 173,235(1973)
54 P. Lutz;et al. ;C. R. Acd. Sci., Series 0123(1976)
55 R. P. Foss;et al. ;Macromolecules, 10, 287(1977)
56 G. Beinert;et al. ;Makromol, Chem. , 179, 551(1978)
57 DD154609(1977) (BUNA)
58 N. L. Hofmann,GB1029451(1966)
59 USP2947793(1960) (Firestone)
60 M. Moton;et al. ;Rub. Chem. &Tech., 49, 303(1976)
61 W. N. Smith;et al. ;USP3886089(1975) (Foote Mineral Co)
62 K. C. Eberlyiet al. ;USP2947793(1960) (Firestone)
63 L.H.Tung;et al. ;Macromolecules, 11, 616(1978)
64 G. H. Schulz;et al. ;Makromol. Chem., 178, 2589(1977)
65 A. D. Broske;et al. ;Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. ,25(2) ,85(1984)
66 F. Bandermann;et al. ;Makromol. Chem., 186, 2017(1985)
67 G. Beinert;et al. ;Makromol. Chem., 186, 1351(1985)
68 L J.Fetters;et al. ;Macromolecules, 12(2) , 345(1979)
69 I.Obriotiet al. ;Polymer, 28, 2093(1987)
70 M. Fontanille;et al. ;FR2313389(1975)
71 P. Guyot;et al. ;Polymer, 22, 1724(1981)
72 L.J. Fetters;et al. ;Macromolecules, 2, 453(1969)
73 DE2042624(1971)
74 J. E. McGrath, Ph. D. Thesis, The University of Akron, Akron, Ohio (1967)
75 J.G.Balas,USP3448176(1969)
76 W. Cooper;et al.;Polymer, 15, 175(1974)
77 J. M. Guyon-Gellin;et al. ; J. Appl. Polym. Sci. , 19, 3173(1975)
78 Dunlop Co. Ltd., FR1566887(1969)
79 P. T. Hale;et al. ;Eur. Polym.J., 11, 677(1975)
80 J. H. Carter ;et al. ;Polym. Prepr., Am. Chem. Soc. , Div. Polym. Chem. ,5 (2) ,614 (1964)
81 R. P. Zelinski,USP3287333(1966)
82 Phillips Petroleum Co.,GB964478(1964)
83 J. W. Dean, J. Polym. Sci., Part B, 8, 677(1970)
84 General Electric Co., FR2134884(1973)
85 J.W. Dean, Ger.Offen. 2116837(1971)
86 Y. Minoura;et al. ;J. Polym. Sci., Polym. Chem. Ed., 7, 2753(1969)
87 F. X.Mueller;et al. ;USP3585257(1971)
88 R. P. Foss, Ger. Offen. 2307740(1973)
89 R. P. Foss;et al. ;Macromolecules, 9, 373(1976)
90 R. E. Cunningham;et al. ;J. Appl. Polym. Sci., 16, 163(1972)
91 Y.K.Wei ,Canadian Patent 786865(1968)
92 S. Horne;et al. ;JP75-133291(1975)
93 Polymer Corp.,FR1573989(1969)
94 V. P. Shatalov.et al. ;GB1409956(1975)
95 J. Furukawa;et al. ;JP72-08641(1972)
96 M. Morton ;et al. ; Polym. Prepr. , Am. Chem. Soc. , Div. Polym. Chem., 13(1) , 61 (1972)
97 E. Shiratsuchi;et al. ;JP70-01629(1970)
98 R. P. Zelinski;et al. ;USP3078254(1963)
99 R.P.Zelinski;USP325l905(1966)
100 H.L. Hsieh; et al.;USP3410836(1968)
101 L.J. Fetters;et al.;Macromolecules, 2,453(1969)
102 T. Inoue;et al.;Macromolecules, 4, 500(1971)
103 J.C. Saam;et al.;Ger. Offen. 2142595(1972)
104 T. Shimomura;et al.;Ger. Often. 2224616(1972)
105 T. Shimomura;et al.;JP73-00790(1973)
106 M. Morton;" Encyclopedia of Polymer Science and Technology", Vol. 15, p508, Wiley, New York, 1971
107 m. Morton, J. Polym. Sci., Polym Symp., 60, 1(1978)
108 M. Morton; et al. ;Int. Synth. RubberSymp., Lect., 4th, 1969, p70(1969)
109 G. Karoly, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 10(2), 837(1969)
110 Netherlands Patent Appl. 6405416(1964)(Shell)
111 R.G. Hayter;et al.;USP3639523(1972)
112 李光辉，大连理工大学硕士研究生学位论文，1987
113 马立人，谢洪泉，合成橡胶工业，1984，7(5)：365
114 佘万能等，高分子通讯，1983，(4)：299
115 杨万泰，金关泰，CN1070198(公开号)，1993
116 杨万泰，许铭，金关泰，合成橡胶工业，1992，2(4)：1
117 杨万泰，许铭，金关泰，弹性体，1992，2(4)：1
118 蒋硕健，刘怀兵，赵忠，弹性体，1992，2(2)：33
119 蒋硕健，刘怀兵，罗传秋，合成橡胶工业，1991，14(5)：339
120 蒋硕健，刘怀兵，罗传秋，弹性体，1992，2(2)：1
121 庞永新，王孟钟，合成橡胶工业，1986，9(2)：106
122 庞永新，王孟钟，合成橡胶工业，1986，9(3)：189
123 王玉荣，李光辉，顾明初，合成橡胶工业，1995，18(5)：290
124 王玉荣，李光辉，顾明初，合成橡胶工业，1997，20(1)：21
125 还振卫，刘卫国，白令君等，中国科学(B辑)，1994，24(11)：1127
126 薛联宝，金关泰，阴离子聚合的理论和应用，中国友谊出版社，1990
127 金关泰，高分子化学的理论和应用进展，中国石化出版社，1995
128 金关泰，金日光，汤宗汤等，热塑性弹性体，化学工业出版社，1983
129 M．Morton，余鼎声，范治群译，阴离子聚合的原理和实践，1988
130 应圣康，郭少华等，阴离子聚合，化学工业出版社，1988
131 应圣康，余丰年，共聚合原理，化学工业出版社，1984
132 DD220805(1984) (BUNA)
133 LH. Tung, AU8659830(1985)(DOW)
134 LO, Grace, Y. ;et al.;EP316857(1987)(DOW)
2 LO,Grace, Y. ;PCT, WO89/04843, 1989(DOW)
3 Lu H. Tung;et al. ;USP4169115, 1979(DOW)
4 Lu H.Tung;et al. ;USP4200718, 1980(DOW)
5 Lu H. Tung;et al. ,USP5057583, 1991(DOW)
6 Lu H.Tung;et al. ;USP4205016, 1980(DOW)
7 Lu H. Tung;et al. ;USP4201729, 1980(DOW)
8 Lu H. Tung;et al. ;USP4196154, 1980(DOW)
9 Lu H. Tung.et al. ;USP4169153, 1980(DOW)
10 Lu H.Tung;et al. ;EP0118572, 1984(DOW)
11 Gary R. Marchand;et al. ;EP0472749,1992(DOW)
12 Klaus Bronstert;et al. ;USP4861742,1989(BASF)
13 Hoecker Hartwig;et al.:EP0025942,1981(BASF)
14 V.Gnehl; E.Anton;et al. ;GB2124228(1982) (BUNA)
15 V. Griehl; E.Anton;et al. ;DD237669(1982) (BUNA)
16 Bernard Francois,et al. ;USP4048420,1977(France)
17 Pierre Sigwalt;et al;USP4161494, 1979(France)
18 岸本泰志等;JP63-5403，1988(Asahi)
19 J. E. Hall;EP0096875, 1983(Firestone)
20 John F. Vitkuske; et al. ;USP5100938,1992(DOW)
21 Vonk Willem Cornelis;et al. ;EP0280357,1988(SHELL)
22 JPl-53681(1989) (Asahi)
23 JP5008136603(1982) (Asahi)
24 JP6000155204(1984) (Asahi)
25 BW. Walther.Lu Tung;et al. ;EP0413294(1991) (DOW)
26 V.Griehl;E. Anton,et al. .GB2092163,FR2496673;1982(BUNA)
27 E. Anton,S.Keisenet al. ;DD154981 ;CS7803109(1977) (BUNA)
28 S. Keiser; E.Anton;et al. ;DD154982(1978) (BUNA)
29 E. Anton;HO Frohlich,et al. ;DD28272 (1984) (BUNA)
30 E. Anton;HO Frohlich;et al. ;DD229138(1984) (BUNA)
31 E. Anton;HO Frohlich;et al. ;DD233576(1985) (BUNA)
32 V.Griehl; E.Anton;et al. ;DD247455(1986) (BUNA)
33 E.Anton; V.Griehl;et al. ;GB2083041; FR2489337 (1980) (BUNA)
34 E.Anton;V. Griehl;et al. ;DD154610(1977) (BUNA)
35 E.Anton;V. Griehl;et al. ;DD154980;SU979367(1978) (BUNA)
36 E.Anton;V. Griehl;et al. ;KK155995(1978) (BUNA)
37 E.Anton;V. Griehl;et al. ;DD158781(1980) (BUNA)
38 E. AntoniV.Griehl;et al. ;GB2083041;FR2489337(1980) (BUNA)
39 N. Yanaihara;BE8899002;(1981) (Fillips)
40 K. Bronstert;S. Bohner;DE3711920(1987) (BASF)
41 DT2634391:US4048420(1975) (AGENCE)
42 VG Kulieva;et al;SU1535867(1987) (AS AZERB)
43 C. Foth;E.Anton;et al,DD151065(1977) (BUNA)
44 DT2521502;FR2279774(1974) (DENKI KAGAKU)
45 E. Z.Diner;et al. ,SU1070877 (1982)
46 A. Pleska;et al;DD154611(1977) (BUNA)
47 DD160062(1978) (BUNA)
48 E. Anton;A. Pleska;et al;DD204931(1982) (BUNA)
49 USP4182818;USP4196153(1977) (DOW)
50 USP4200718;USP4201729;USP4205016(1977) (DOW)
51 USP3668263(1972)
52 USP3776964(1973)
53 H.Eschway;et al. ;Makromol,Chem., 173,235(1973)
54 P. Lutz;et al. ;C. R. Acd. Sci., Series 0123(1976)
55 R. P. Foss;et al. ;Macromolecules, 10, 287(1977)
56 G. Beinert;et al. ;Makromol, Chem. , 179, 551(1978)
57 DD154609(1977) (BUNA)
58 N. L. Hofmann,GB1029451(1966)
59 USP2947793(1960) (Firestone)
60 M. Moton;et al. ;Rub. Chem. &Tech., 49, 303(1976)
61 W. N. Smith;et al. ;USP3886089(1975) (Foote Mineral Co)
62 K. C. Eberlyiet al. ;USP2947793(1960) (Firestone)
63 L.H.Tung;et al. ;Macromolecules, 11, 616(1978)
64 G. H. Schulz;et al. ;Makromol. Chem., 178, 2589(1977)
65 A. D. Broske;et al. ;Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. ,25(2) ,85(1984)
66 F. Bandermann;et al. ;Makromol. Chem., 186, 2017(1985)
67 G. Beinert;et al. ;Makromol. Chem., 186, 1351(1985)
68 L J.Fetters;et al. ;Macromolecules, 12(2) , 345(1979)
69 I.Obriotiet al. ;Polymer, 28, 2093(1987)
70 M. Fontanille;et al. ;FR2313389(1975)
71 P. Guyot;et al. ;Polymer, 22, 1724(1981)
72 L.J. Fetters;et al. ;Macromolecules, 2, 453(1969)
73 DE2042624(1971)
74 J. E. McGrath, Ph. D. Thesis, The University of Akron, Akron, Ohio (1967)
75 J.G.Balas,USP3448176(1969)
76 W. Cooper;et al.;Polymer, 15, 175(1974)
77 J. M. Guyon-Gellin;et al. ; J. Appl. Polym. Sci. , 19, 3173(1975)
78 Dunlop Co. Ltd., FR1566887(1969)
79 P. T. Hale;et al. ;Eur. Polym.J., 11, 677(1975)
80 J. H. Carter ;et al. ;Polym. Prepr., Am. Chem. Soc. , Div. Polym. Chem. ,5 (2) ,614 (1964)
81 R. P. Zelinski,USP3287333(1966)
82 Phillips Petroleum Co.,GB964478(1964)
83 J. W. Dean, J. Polym. Sci., Part B, 8, 677(1970)
84 General Electric Co., FR2134884(1973)
85 J.W. Dean, Ger.Offen. 2116837(1971)
86 Y. Minoura;et al. ;J. Polym. Sci., Polym. Chem. Ed., 7, 2753(1969)
87 F. X.Mueller;et al. ;USP3585257(1971)
88 R. P. Foss, Ger. Offen. 2307740(1973)
89 R. P. Foss;et al. ;Macromolecules, 9, 373(1976)
90 R. E. Cunningham;et al. ;J. Appl. Polym. Sci., 16, 163(1972)
91 Y.K.Wei ,Canadian Patent 786865(1968)
92 S. Horne;et al. ;JP75-133291(1975)
93 Polymer Corp.,FR1573989(1969)
94 V. P. Shatalov.et al. ;GB1409956(1975)
95 J. Furukawa;et al. ;JP72-08641(1972)
96 M. Morton ;et al. ; Polym. Prepr. , Am. Chem. Soc. , Div. Polym. Chem., 13(1) , 61 (1972)
97 E. Shiratsuchi;et al. ;JP70-01629(1970)
98 R. P. Zelinski;et al. ;USP3078254(1963)
99 R.P.Zelinski;USP325l905(1966)
100 H.L. Hsieh; et al.;USP3410836(1968)
101 L.J. Fetters;et al.;Macromolecules, 2,453(1969)
102 T. Inoue;et al.;Macromolecules, 4, 500(1971)
103 J.C. Saam;et al.;Ger. Offen. 2142595(1972)
104 T. Shimomura;et al.;Ger. Often. 2224616(1972)
105 T. Shimomura;et al.;JP73-00790(1973)
106 M. Morton;" Encyclopedia of Polymer Science and Technology", Vol. 15, p508, Wiley, New York, 1971
107 m. Morton, J. Polym. Sci., Polym Symp., 60, 1(1978)
108 M. Morton; et al. ;Int. Synth. RubberSymp., Lect., 4th, 1969, p70(1969)
109 G. Karoly, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 10(2), 837(1969)
110 Netherlands Patent Appl. 6405416(1964)(Shell)
111 R.G. Hayter;et al.;USP3639523(1972)
112 李光辉，大连理工大学硕士研究生学位论文，1987
113 马立人，谢洪泉，合成橡胶工业，1984，7(5)：365
114 佘万能等，高分子通讯，1983，(4)：299
115 杨万泰，金关泰，CN1070198(公开号)，1993
116 杨万泰，许铭，金关泰，合成橡胶工业，1992，2(4)：1
117 杨万泰，许铭，金关泰，弹性体，1992，2(4)：1
118 蒋硕健，刘怀兵，赵忠，弹性体，1992，2(2)：33
119 蒋硕健，刘怀兵，罗传秋，合成橡胶工业，1991，14(5)：339
120 蒋硕健，刘怀兵，罗传秋，弹性体，1992，2(2)：1
121 庞永新，王孟钟，合成橡胶工业，1986，9(2)：106
122 庞永新，王孟钟，合成橡胶工业，1986，9(3)：189
123 王玉荣，李光辉，顾明初，合成橡胶工业，1995，18(5)：290
124 王玉荣，李光辉，顾明初，合成橡胶工业，1997，20(1)：21
125 还振卫，刘卫国，白令君等，中国科学(B辑)，1994，24(11)：1127
126 薛联宝，金关泰，阴离子聚合的理论和应用，中国友谊出版社，1990
127 金关泰，高分子化学的理论和应用进展，中国石化出版社，1995
128 金关泰，金日光，汤宗汤等，热塑性弹性体，化学工业出版社，1983
129 M．Morton，余鼎声，范治群译，阴离子聚合的原理和实践，1988
130 应圣康，郭少华等，阴离子聚合，化学工业出版社，1988
131 应圣康，余丰年，共聚合原理，化学工业出版社，1984
132 DD220805(1984) (BUNA)
133 LH. Tung, AU8659830(1985)(DOW)
134 LO, Grace, Y. ;et al.;EP316857(1987)(DOW)