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。     

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2G－（i—BU）_3Al为复合调节剂合成高乙烯基聚丁二烯橡胶

研究了在以环己烷作溶剂的２Ｇ－ｎ—ＢｕＬｉ体系的了二烯阴离子聚合中添加（ｉ一Ｂｕ）３Ａｌ对聚合的影响。结果表明：（ｉ—ＢＵ）３Ａｌ对聚丁二烯的微观结构、分子量分布无影响，但聚合物的立构规整度随Ａｌ／Ｌｉ的增加而增加，聚合速率随Ａｌ／Ｌｉ的增加而下降。求得了假一级表观增长速率常数与表观增长活化能。     

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。     

二乙烯基苯-丁二烯-苯乙烯负离子聚合动力学行为

用气相色谱法对正丁基锂为引发剂、环已烷为溶剂、ＴＦ为极性调节剂的二乙烯基苯－丁二烯－苯乙烯负离子聚合动力学进行了研究,求得了体系内各单体表观增长反应速率常数（ｋｐ＂）。结果表明,各单体ｋｐ＂的大小依次为：ｐ－ＤＢＶ,ｍ－ＤＢＶ,Ｂｄ,Ｓｔ,ｍ－ＥＶｇ,ｍ－ＥＶＢ,ｐ－ＥＶｂ。     

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。     

立构嵌段聚丁二烯的研制 Ⅴ．立构三嵌段聚丁二烯的合成及动力学行为

以α－甲基萘锂（α－ＭＮＬｉ）为引发剂、二哌啶乙烷（ＤＰＥ）为调节剂、环己烷为溶剂的丁二烯负离子聚合体系，研究了ＤＰＥ／α－ＭＮｌｉ、聚合温度与聚合物１，２－结构含量关系，合成出１，２一结构近１００％的１，２－聚丁二烯（１，２－ＰＢ）和１，２－１，４－１，２－ＰＢ。反应动力学研究表明：１，４－ＰＢ与１，２－ＰＢ中单体浓度与反应速率呈一级方程关系；４０℃时，生成１，４－ＰＢ的反应动力学方程式为－ｄ［Ｍ］／ｄｔ＝０．２８［Ｃ］￣０．５［Ｍ］；ＤＰＥ用量增大，表观增长反应过度常数Ｋ＿ｐ￣η减小；求得不同条件下的表观增长活化能。     

Ni（naph）2—Al（i—Bu）3—（BF3.OEt2＋C8H17OH＋MeCOOBu）体系催化丁二…

探讨了正辛醇／乙酸丁酯混合溶剂对ＢＦ３．ＯＥｔ２在加氢汽泡中的增溶情况，考察了Ｎｉ（ｎａｐｈ）２－Ａｌ（ｉ－Ｂｕ）３－（ＢＦ３．ＯＥｔ２＋正辛醇＋乙酸乙酯）体系催化下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，微观结构和相地分子质量的影响，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，可制得门尼龙粘度高，相对分     

以2G—（i—Bu）3Al为复合调节剂合成高乙烯基聚丁二烯橡胶

研究了在以环己烷作溶剂的２Ｇ－ｎ－ＢｕＬｉ体系的丁二烯阴离子聚合中添加（ｉ－Ｂｕ）３Ａｌ对聚合的影响。结果表明：（ｉ－Ｂｕ）３Ａｌ对聚丁二烯的微观结构、分子量分布无影响，但聚合物的立构规整度随Ａｌ／Ｌｉ的增加而增加，聚合速率随Ａｌ／Ｌｉ的增加而下降。求得了假一级表观增长速率常数与表观增长活化能。     

镍系催化十二烯聚合

我国镍系顺丁橡胶（ＢＲ）生产采用以加氢汽油为溶剂的Ｎｉ（ｎａｐｈ）２－Ａｌ（ｉ－Ｂｕ）３－ＢＦ３．ＯＥｔ２（简称Ｎｉ－Ａｌ－Ｂ）催化体系。聚合活性与Ａｌ／Ｂ（摩尔比）密切相关，Ａｌ／Ｂ值又是调节ＢＲ分子量的关键参数。催化活性中心上镍的价态分别为Ｎｉ（０）和Ｎｉ（Ｉ），聚合反应的表观活化能为Ｅａ［Ｎｉ（０）＜Ｅａ［Ｎｉ（Ｉ）］。ＡｌＲ２Ｆ也是组成活性中心配合物的结构单元。催化活性表现有低温聚合依时性     

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。     

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.     

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     

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。