氯化富勒烯在负离子聚合中的偶联作用

以氯化富勒烯(C60Cln)为偶联剂，用n—BuLi引发苯乙烯负离子聚合。紫外光谱分析表明，产物中含有C60Cln检测显示，试样的相对分子质量分布比母体聚合物要宽，在高相对分子质量部分出现了含％的新峰，证明发生了偶联反应。平均每个C60上接有2条聚苯乙烯链。     

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。     

不对称醚存在下丁二烯负离子聚合动力学

研究了以丁基锂为引发剂，4种新型不对称醚为调节剂，环己烷为溶剂的丁二烯负离子均聚。结果表明，4种新型不对称醚（GBSE，GBIE，GBCE，GBPE）均未发现有失活现象存在，且它们对丁二烯聚合速率的影响由大到小依次为：GBIE，GBSE，GBCE，GBPE。     

氧对正丁基锂引发的丁二烯负离子聚合的影响

分别研究了两种溶剂对氧的吸附和脱附作用;氧对正丁基锂的反应历程以及对由正丁基锂引发的丁二烯负离子聚合过程的影响。     

负离子聚合法合成丁二烯-异戊二烯无规共聚物的序列结构

以正丁基锂(n-BuLi)为引发剂、十二烷基苯磺酸钠(SDBS)为调节剂,在环己烷中对丁二烯(Bd)和异戊二烯(Ip)进行负离子聚合制得Bd-Ip共聚物,考察了反应温度、单体配比及调节体系对Ip共聚活性及共聚物序列分布的影响。结果表明,提高反应温度或增加Ip单体含量、SDBS/n-BuLi(摩尔比)由0/1.0增大到0.5/1.0,均可提高Ip共聚活性;共聚物序列分布服从一级Markov统计模型,在70℃、Ip/Bd(质量比)5/5、SDBS/n-BuLi(摩尔比)0.5/1.0、单体质量浓度0.12 g/mL的条件下,在共聚物中Ip、Bd 2种单元的同等长度单元组浓度趋于一致,所得共聚物的无规化程度高。     

乙二醇二乙氨基乙基丁基醚存在下的丁二烯负离子聚合

研究了以乙二醇二乙氨基乙基丁基醚(GABE)为调节剂,正丁基锂为引发剂的丁二烯负离子聚合的聚合动力学及聚合物的微观结构。结果表明,随着GABE用量的增加,丁二烯的聚合速率增加,聚丁二烯中1,2-结构质量分数增加,聚合温度升高,聚合速率增加,但聚丁二烯中1,2-结构质量分数有所降低。     

以邻甲基苯酚钾为助引发剂的丁二烯负离子调节聚合

以邻甲基苯酚钾(o—ROK)为助引发剂,正丁基锂(n—BuLi)为引发剂,2G为极性添加剂,二甲苯为溶剂兼链转移剂的丁二烯负离子调节聚合,考察了o—ROK在不同溶剂和不同温度下的溶解性,研究了o—ROK对丁二烯调节聚合能力和聚合物微观结构的影响规律。     

混甲基苯酚钾作助引发剂的丁二烯负离子调节聚合

采用对环境友好,价格便宜的氢氧化钾和混甲基苯酚合成混甲基苯酚钾(ROK),并研究了以其作助引发剂,正丁基锂(n—BuLi)为引发剂,二乙二醇二甲醚(2G)为极性添加剂,二甲苯为溶剂兼链转移剂的丁二烯负离子调节聚合,考察了ROK在不同有机溶剂中的溶解性和ROK用量对调聚的影响规律。结果表明,ROK在溶剂中的溶解度从大到小的顺序依次为2G,THF,乙醚,甲苯;随ROK用量的增加,聚丁二烯相对分子质量呈指数下降,链转移数超过50,说明ROK具有较好的调聚效果.     

异戊二烯在二氧六环中的负离子聚合动力学

研究了以正丁基锂为引发剂 ,异戊二烯在二氧六环溶剂中负离子聚合的动力学。结果表明 ,增长反应对单体浓度和引发剂浓度皆为一级反应 ,活化能为45.22kJ/mol,频率因子为4.832×108L/(mol·min) ,并求出了生成1,4 -结构、1,2 -结构和3,4 -结构产物的速率常数分别为2.77×1012exp( -74760/RT) ,9.82×106exp( -39190/RT) ,8.02×107exp( -41180/RT)。     

用环氧化液体聚丁二烯作丁二烯负离子聚合偶联剂

采用负离子聚合法制备了1,2-结构质量分数为17%、数均相对分子质量为2 800、多分散指数为1.19的液体聚丁二烯;以甲酸、过氧化氢为环氧化剂,甲苯为溶剂进行环氧化反应,得到环氧化液体聚丁二烯(ELPB);以丁二烯为单体、正丁基锂为引发剂、四氢呋喃为极性添加剂、环己烷为溶剂、ELPB为偶联剂合成星形聚丁二烯.结果表明,随着偶联剂用量的增加,偶联效率增大,相对臂数减少,平均臂数增加,多分散指数减小;随着极性添加剂的增加,偶联效率逐渐降低.     

碳笼烯钕系催化异戊二烯聚合的动力学行为

测定了Ｎｄ（ｎａｐｈ）３－碳笼烯衍生物（Ｃ６０Ｘｎ）－Ａｌ（ｉ－Ｂｕ）３催化体系引发异戊二烯溶液聚合的动力学行为。在低转化率条件下,体系呈现稳态聚合特征,测量聚合反应速率方程为Ｒｐ＝Ｋｐ［Ｎｄ］＾１．８［Ｍ］０,表观活化能为２７．７ｋＪ／ｍｏｌ。体系具有聚合活性的高温稳定性和准活性聚合的特征。     

Separation of fullerenes C60 and C70 using a crystallization‐based process

A crystallization‐based process that separates pure fullerenes C₆₀ and C₇₀ from their mixture using o‐xylene as the solvent has been developed. Isothermal solid–liquid equilibrium phase diagrams of the C₆₀‐C₇₀‐o‐xylene ternary system for a number of temperatures were first determined at 1 atm. Taking advantage of the shift in solvent‐free composition of the C₆₀‐C₇₀ double saturation point with temperature and based on the solid solution‐forming phase behavior between C₆₀ and C₇₀, the flowsheet of a general crystallization process was then synthesized. It involved the fractionation of a C₆₀‐C₇₀ fullerene mixture into C₆₀‐rich and C₇₀‐rich solid solutions using temperature‐swing crystallization, followed by purification of the solid solutions with multistage crystallization into pure C₆₀ and C₇₀ solids. To demonstrate process feasibility, bench‐scale batch experiments were performed using a commercially available fullerene mixture that was pretreated by adsorption to remove higher fullerenes. C₆₀ and C₇₀ solids of purity higher than 99 wt % were obtained. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Coupling effect of fullerene chloride in anionic polymerization

以氯化富勒烯(C60 Cln)为偶联剂,用n-BuLi引发苯乙烯负离子聚合.紫外光谱分析表明,产物中含有C60.GPC检测显示,试样的相对分子质量分布比母体聚合物要宽,在高相对分子质量部分出现了含C60的新峰,证明发生了偶联反应.平均每个C60上接有2条聚苯乙烯链.     

Preparation of C60 bonded Poly(N-vinylcarbazole) with C60Cln/CuCl/Bpy catalyst system

Summary C₆₀ bonded poly(N-vinylcarbazole) has been synthesized by C₆₀Cln (the average value of n is 20)/CuCl/2,2'-bipyridine (Bpy) catalyst system and its structure was analyzed by UV-Vis and proton NMR. The polymerization mechanism was proposed proceeding via an atom transfer radical polymerization (ATRP). The photoconducting properties of C₆₀ bonded poly(N-vinylcarbazole) was better than poly(N-vinylcarbazole) initiated by AIBN. Received: 16 October 2001 /Revised version: 8 February 2002/ Accepted: 19 February 2002     

Kinetic study of anionic polymerization of butadiene in a polar solvent

The kinetics of the propagation reaction for the polymerization of butadiene initiated by cumyl potassium in tetrahydrofuran solution at several temperatures have been studied. Kinetic data and electrolytic behaviour indicate that polybutadienyl free ions assume the whole of the propagation reaction. At 0°C, the respective rate constants for ion-pairs and free ions are 1 l mol^?1 s^?1 and 4.8 × 10⁴ l mol^?1 s^?1 respectively. The ionic dissociation constant is 7.8 × 10^?9 mol/l. The activation energy of the propagation reaction for free ions is 6.5 kcal/mol.     

Synthesis of functionalized fullerene‐C60 by the living anionic polymerization technique

The synthesis of functionalized fullerene‐C₆₀ (C₆₀) was performed using living anionic polymerization. The metalation of the benzylic hydrogen atom on toluene or p‐substituted toluene was conducted with the alkyllithium/amine system, and examined by living anionic polymerization of 1,3‐cyclohexadiene. The number of carbanions bonded onto C₆₀ was estimated by the grafting reaction of living polymer onto C₆₀. The tert‐butyllithium/N,N,N′,N′‐tetramethylethylenediamine system was an effective metalation reagent, and toluene‐, p‐xylene‐, 4‐methyltriphenylamine‐functionalized C₆₀s having good solubility were successfully synthesized. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Styrene/isoprene/butadiene integrated rubber prepared by anionic bulk polymerization in a twin‐screw extruder

Styrene/isoprene/butadiene integrated rubber (SIBR) was synthesized using anionic bulk polymerization in a corotating intermeshing twin‐screw extruder. In order to study the relationship between microstructure and physical properties, three SIBRs were synthesized using different initiator complexes: n‐BuLi (N‐butyl lithium), n‐BuLi/THF (tetrahydrofuran), and n‐BuLi/TMEDA (tetramethylethylenediamine). The microstructure of the rubber products was analyzed by gel permeation chromatography and H nuclear magnetic resonance. SIBR prepared with pure n‐BuLi exhibited a multiblock microstructure. With the addition of THF or TMEDA, the vinyl content of the alkadiene increased; and the microstructure of SIBRs was randomized, indicated by the presence of a high weight content of styrene microblocks. Transmission electron microscopy demonstrated similar morphology in both the SIBRs and SSBR2003 (an industrial product). Dynamic mechanical analysis of the vulcanized SIBRs showed that the randomized SIBRs were quite suitable for the preparation of high‐performance tires. Tensile and tear test results of SIBRs were equivalent to those of SSBR2003. The low manufacturing cost of reactive extrusion technology will allow the large‐scale industrialization of SIBRs. POLYM. ENG. SCI., 55:1163–1169, 2015. © 2014 Society of Plastics Engineers     

超声波对丁二烯／苯乙烯共聚的影响

研究了超声波辐照对n-BuLi／2G／加氢汽油／丁二烯阴离子聚合的影响。实验表明,与无超声波辐照相比,较低温度下转化率降低,1H-NMR谱图表明,2G提高产物1,2含量的作用有所降低,共聚物接合苯乙烯,1,2PB含量降低,在2G／Li+=0．8时,cis／trans比例发生逆转,由顺式含量较高变为反式含量较高。