用1G／2G复合调节剂进行丁二烯阴离子聚合的研究

在环已烷中，以正丁基锂引发的丁二烯阴离子聚合，采用１Ｇ／２Ｇ复合调节剂，研究了１Ｇ／２Ｇ复合调节剂对聚丁二烯微观结构及聚合动力学的影响。实验结果表明：１Ｇ与２Ｇ复合调节剂对聚丁二烯微观结构的调节能力强于１Ｇ或２Ｇ单一调节剂。聚合速度与单体浓度呈一次方关系，并分别求得不同温度下的单体一级反应速度常数（Ｋ″ｐ）及表观增长活化能（Ｅ′ｐ）。     

2G／THF二元调节体系对丁二烯阴离子聚合产物微观结构的研究

研究了二乙二醇二甲醚（２Ｇ）／四氢呋喃（ＴＨＦ）二元调节体系对丁二烯阴离子聚合产物微观结构的影响。实验表明，当２Ｇ和ＴＨＦ混合加入时，除产物的１，２－结构介于两者单独加入时之间外，它能使产物的微观结构产生新的变化：在相同浓度下，从１，２－结构的数值上降低了强调节剂２Ｇ的作用，而增加了较弱的调节剂ＴＨＦ的影响；更重要的是，在相同和不同聚合温度时，当分别固定２Ｇ浓度（〔２Ｇ〕）或ＴＨＦ浓度（〔ＴＨＦ〕）与活性聚丁二烯基锂浓度（〔ＰＢＬｉ〕）比后，对调节上述另一种路易氏碱的浓度达到一定值条件后，发现产物的１，２－结构不再随后者加入量的增加而发生变化，即其微观结构进入了一个“稳态阶段”。这无疑在理论和实际应用上均有重要意义。     

改进型中乙烯基聚丁二烯橡胶的研制：IV.丁二烯聚合动力学

对ｎ－ＢｕＬｉ／ＧＤＥＥ（醚基微观结构调节剂）／环己烷体系丁二烯聚合动力学进行了研究。发现ＧＤＥＥ的加入提高了聚合速率，随ＧＤＥＥ／Ｌｉ（摩尔比）增大和反应测试的升高，反应速率加快；单体浓度与聚合速率呈一次方关系；在５０℃，ＧＤＥＥ／Ｌｉ为１．４时，引发剂浓度与聚合速率呈一次方关系，当ＧＤＥＥ／Ｌｉ１．４时，聚丁二烯基锂几乎完全解缔为单量体。     

异戊二烯阴离子聚合机理的研究

研究了以环己烷为溶剂、正丁基锂为引发剂，异戊二烯阴离子聚合微观结构随ＴＨＦ极性调节剂用量的变化情况。结果表明：（１）异戊二烯在非极性溶剂中聚合时，所得产物的３，４－结构含量较低，仅为５％～８％；１，４－结构含量为９２％～９５％；（２）随ＴＨＦ用量的增加，３，４－结构含量逐渐增加，并且当Ｒ≥１２时，会出现１，２－结构，其变化趋势也是随ＴＨＦ用量增加而增加。根据以上结果，并以金关泰、李天虎的丁二烯阴离子聚合机理［１］为基础，提出了适用于异戊二烯阴离子聚合的σ－烯丙基型，π－烯丙基型活性中心的聚合机理；同时用公式ｌｇ（ａ－ｂａ－Ｉｖ－１）＝ｎｌｇ［ＴＨＦ］＋ｌｇＫ′对所得微观结构数据进行处理，结果线性关系很好，从而验证了机理的正确性。     

改进型中乙烯基聚丁二烯橡胶的研制 Ⅳ.丁二烯聚合动力学

对ｎ－ＢｕＬｉ／ＧＤＥＥ（醚类微观结构调节剂）／环己烷体系丁二烯聚合动力学进行了研究。发现ＧＤＥＥ的加入提高了聚合速率，随ＧＤＥＥ／Ｌｉ（摩尔比）增大和反应温度的升高，反应速率加快；单体浓度与聚合速率呈一次方关系；在５０℃，ＧＤＥＥ／Ｌｉ为１．４时，引发剂浓度与聚合速率呈一次方关系。当ＧＤＥＥ／Ｌｉ为１．４时，聚丁二烯基锂几乎完全解缔为单量体。     

以2G－（i—Bu）_3Al为复合调节剂合成中乙烯基聚丁二烯

本文是以３－ＢｕＬｉ为引发剂，以２Ｇ和（ｉ－Ｂｕ）３Ａｌ为调节剂，环己烷为溶剂的丁二烯阴离子聚合．以合成中乙烯基型聚丁二烯。研究了Ａｌ／Ｌｉ与聚合反应速率及聚合物微观结构的关系。结果表明：随Ａｌ／Ｌｉ的增加，聚合速率下降，而对聚合物的微观结构影响较小。求得了聚合假一级表观增长速率常数ｋｐ及表观增长活化能Ｅｐ     

以ZnEt2为调节剂的阴离子聚合合成聚丁二烯的研究（Ⅱ）

丁二烯在ｎ－ＢｕＬｉ或ｎ－ＢｕＬｉ／２Ｇ引发的阴离子聚合体系中，以环已烷为溶剂，在不同程度下，研究添加ＺｎＥｔ２调节剂对聚丁二烯结构的影响。结果表明：在ｎ－ＢｕＬｉ引发体系中，ＺｎＥｔ２的加入对聚合物的微观结构含量、分子量及分子量分布无影响。在ｎ－ＢｕＬｉ／２Ｇ引发体系中，ＺｕＥｔ２的加入导致聚合物的１，２－结构含量及分子量下降，但不影响聚合物的立构规整性和序列分布。     

1,1,4,4,—四苯基—1,4—二锂丁烷引发丁二烯合成三嵌段聚合物的研究

用１，１，４，４－四苯基－１，４－二锂丁烷（ＤｉＬｉ－ＴＰＢ）为引发剂，二哌啶乙烷（ＤＰＥ）为结构调节剂，环己烷为溶剂，合成了１，２－１，４－１，２立构三嵌段聚丁二烯。研究了ＤＰＥ用量和聚合温度对聚丁二烯１，２－结构的影响和两种引发体系聚合动力学行为，求得了各种反应条件下的假一级增长速率常数和表观活化能。三嵌段聚丁二烯存在两个Ｔｇ和内耗能，呈微观相分离，且分相时融体流动性最小，屈服强度最大。     

Ni(naph)_2-Al(i-Bu)_3-(BF_3·OEt_2+C_8H_(17)OH+MeCOOBu)体系催化丁二烯聚合

探讨了正辛醇／乙酸丁酯混合溶剂对ＢＦ３·ＯＥｔ２在加氢汽油中的增溶情况，考察了Ｎｉ（ｎａｐｈ）２－Ａｌ（ｉ－Ｂｕ）３－（ＢＦ３·ＯＥｔ２＋正辛醇＋乙酸丁酯）体系催化丁二烯聚合活性和水对该体系聚合活性、聚合物特性粘数、聚合速率、微观结构和相对分子质量的影响。结果表明，该混合溶剂是ＢＦ３·ＯＥｔ２的良好增溶剂。当Ｈ２Ｏ／Ａｌ（摩尔比）≤２．３时，用其增溶的催化体系聚合活性高，可制得门尼粘度高、相对分子质量分布宽、顺－１，４结构含量大于９６％的聚丁二烯。     

异戊二烯／THF负离子聚合产物的微观结构

研究了２０～５０℃下,以ｎ－ＢｕＬｉ为引发剂,环己烷为溶剂,ＴＨＦ为极性调节剂的异戊二烯负离子聚合产物的微观结构。结果表明：随聚合温度升高,聚异戊二烯的３,４－结构含量降低;在同一温度下,随ＴＨＦ用量的增加,３,４－结构含量增加。［ＴＨＦ］／［ｎ－ＢｕＬｉ］（Ｒ,摩尔比）大于１２时,才会出现１,２－结构,且聚合温度越高,出现１,２－结构时的Ｒ值越高,并随Ｒ值的继续升高,１,２－结构含量也不断增加。此外,还建立了４个微观结构含量与ＴＨＦ用量的定量关系式。     

苯乙烯的间歇-半连续RAFT细乳液聚合

进行了苯乙烯的间歇-半连续RAFT细乳液聚合,考察了半连续段的起点、单体滴加速率及最终胶乳固含量的影响。结果发现：从最终胶乳的稳定性考虑,半连续聚合的起点选择在间歇聚合的高转化率时期更好;若综合考虑胶乳的稳定性、分子量及其分布、固含量、乳化剂及共稳定剂在胶乳中的残留率等因素,半连续聚合的起点可适当提前,但必须在间歇聚合成核期结束后。过早容易引起乳液的失稳;过迟会延长反应时间,降低聚合物的制备效率,导致死聚物链含量升高。聚合体系的稳定性与胶乳的固含量密切相关,最终固含量不宜超过40％。采用间歇-半连续二段聚合工艺可以制得窄分子量分布(PDI＝～1.3),低乳化剂及共稳定剂残留量（～1.5%,质量）的高分子量聚合物(≈8×10⁴g•mol^-1)。     

Chemospecific ring-opening polymerization of α-methylenemacrolides

α-Methylenemacrolides having various groups, such as aromatic, ether, and amine, were enzymatically, anionically, and radically polymerized. The polymerization with the lipase catalyst successfully afforded polymers only through the ring-opening process, whereas the vinyl polymerizations selectively proceeded by using anionic and radical initiators. The polyesters obtained by the enzymatic polymerization have a polymerizable methacrylic methylene group in the main-chain, in addition to the aromatic and polar groups, and were further radically polymerized to quantitatively produce a cross-linked polymer gel.     

Accelerated pressure synthesis and characterization of 2-oxazoline block copolymers

The cationic ring-opening polymerization of 2-oxazolines in acetonitrile was investigated under pressure conditions utilizing methyl tosylate as initiator of which the single crystal X-ray structure is described as well. The polymerization kinetics were studied and compared with previously reported microwave-assisted pressure polymerizations. Moreover, a series of block copolymers was synthesized in an automated parallel synthesis robot utilizing this pressure polymerization method. The resulting block copolymers were characterized with both differential scanning calorimetry and contact angle measurements to determine the effect of copolymer composition on glass transition temperature, melting point and surface energy. Atomic force microscopy was applied to further investigate the possible phase separation.     

Particle formation mechanism in radical polymerization in miniemulsion based on in situ surfactant formation without high energy homogenization

Conventional radical polymerization of styrene at 70 °C in aqueous miniemulsion generated using the in situ surfactant technique, without use of high energy mixing, has been investigated in detail. The surfactant potassium oleate was formed in situ by reaction between oleic acid and potassium hydroxide at the styrene/water interface. The particle formation mechanism was investigated by use of pyrene as a probe, revealing that under suitable conditions with an oil-phase initiator, particle formation occurs primarily via monomer droplet nucleation. The droplet/particle stability is however inferior to that in a typical miniemulsion generated employing ultrasonication, as manifested by a marked increase in droplet/particle size with conversion and a bimodal droplet/particle size distribution by weight. The droplet/particle stability increases with increasing amount of oleic acid, hexadecane, water, and the ratio potassium hydroxide:oleic acid, respectively.     

Synthesis of latex particles by ring-opening metathesis polymerization

This paper reviews the recent discoveries that were achieved by our group in the field of particle synthesis via ring-opening metathesis polymerization (ROMP). Both polynorbornene and polybutadiene-based particles were prepared by the respective ROMP of norbornene and cyclooctadiene initiated by (PCy₃)₂Cl₂RuCHPh using several methods of polymerization in dispersed media, such as dispersion, suspension and miniemulsion. Depending upon the process implemented, particles size was found to range from 300 nm to 20 μm.     

微乳液聚合研究新进展

对微乳液聚合的特点、聚合机理及动力学影响因素进行了总结和评述，指出了今后微乳液聚合研究的几个关键问题。     

等离子体引发丙烯酸(2-乙基)已酯乳液聚合

采用等离子体引发聚合的方法 ,进行了丙烯酸 ( 2 -乙基 )已酯 (简称 EHA)的乳液聚合。考察了后聚合时间、放电功率、乳化剂浓度对聚合转化率及特性粘数的影响。并对丙烯酸酯等离子体引发本体、乳液聚合进行了比较     

Microwave-Assisted RAFT Polymerization

Advances in controlled radical polymerization (CRP) have facilitated access to well-defined polymers with controlled molecular weight, topology, and functionality. However, despite the benefits afforded by many CRP techniques, control over these key polymer attributes often comes at the expense of polymerization rate. One method proposed for accelerating chemical synthesis is microwave heating. This review highlights recent examples of microwave heating being applied during reversible addition-fragmentation chain transfer (RAFT) polymerization. In addition to successfully leading to homopolymers from a variety of monomers, block copolymers have also been prepared by microwave-assisted RAFT, which suggests that the high polymerization rates observed do not necessarily lead to significant end group loss from termination. Despite significant debate regarding the origin of rate enhancement observed during microwave-assisted reactions, the reports included herein provide insight into mechanisms by which well-defined functional polymers can be prepared in an accelerated fashion.     

超声引发聚合反应的研究

综述了超声波在一些聚合方法中的应用。     

水性含硅聚合物涂料的制备与应用

乳液聚合法是制备水性含硅聚合物最常见、最有效的方法。介绍了种子乳液聚合、核/壳乳液聚合、无皂乳液聚合、微乳液聚合、互穿网络聚合等制备水性含硅聚合物的方法,并对水性含硅聚合物涂料的应用做了探讨。