界面模板乳液聚合制备间规窄分布UHMWPS的研究
|
摘要
本论文将长碳链烷基胺聚氧乙烯醚应用于苯乙烯聚合反应中,通过GPC表征所制备的聚苯乙烯(polystyrene, PS)呈双峰或三峰分布。通过研究证实,低分子量部分由过氧化二苯甲酰(BPO)/烷基胺聚氧乙烯醚、BPO/连二亚硫酸钠(Na2S204)组成的两种氧化还原体系引发聚合而得。高分子量端的数均分子量最高达1.25×106,属于超高分子量聚苯乙烯(Ultra-high molecular weight polystyrene, UHMWPS),是由体系中BPO氧化烷基胺聚氧乙烯醚所得氧化胺引发聚合而得。
基于此研究发现,本论文主要是通过开发新型反应型表面活性剂——长碳链烷基胺聚氧乙烯醚氧化物(氧化胺),在不添加其他任何引发剂、链转移剂、电解质等的条件下,将未经任何提纯操作的工业级氧化胺进行苯乙烯乳液聚合,制备出具有一定间规度的窄分子量分布的超高分子量聚苯乙烯。本论文主要包括以下几个方面：
通过H202氧化反应在高转化率下制备长碳链烷基胺聚氧乙烯醚氧化物,通过AP-ES及表面张力测试,对氧化胺的结构和表面活性进行表征,结果表明制备的氧化胺具有较好的表面活性。
系统的考察了烷基胺聚氧乙烯醚氧化物聚合体系中聚合反应时间、水与苯乙烯的用量比、氧化胺用量及烷基胺聚氧乙烯醚对聚合反应动力学、聚苯乙烯的微观结构、分子量及其分布、玻璃化转变温度及结晶性能的影响,并采用GPC、1H-NMR,13C-NMR, DSC, FT-IR对聚合所得UHMWPS进行表征。
研究表明,该体系制备的UHMWPS分子量随聚合反应转化率逐渐增加,分子量分布保持较窄分布,具有“活性”聚合特征。UHMWPS的数均分子量M。最高达2.53×106,分子量分布指数最小为1.10。烷基氧胺作为聚合模板,可控制UHMWPS的微观结构。由'H-NMR及溶解提取法计算得UHMWPS为富间规结构,sPS含量大于84%。通过DSC测试,UHMWPS在220-290℃之间有较宽的结晶熔融吸热峰。
这种新型的具有稳定自由基特征的界面反应型表面活性剂价格低廉,易于制备,通过简单的乳液聚合反应,制备出具有一定立构规整性的窄分子量分布的UHMWPS,为UHMWPS及富间规聚苯乙烯的合成提供了新的研究方向。
In this paper, long chain ethoxylated fatty amines were used as surfactant of styrene emulsion polymerization. Unlike other types of styrene polymerization, Polystyrene (PS) obtained from this polymerization system showed double or trimodal distribution characterized by GPC. Through studying, the low part molecular weight was obtained from BPO/ethoxylated fatty amines initiator system, meanwhile, the lower part was from BPO/Na2S2O4initiator system. The number averaged molecular weight of the high part molecular weight had reached1.25X10, which was in Ultra-high molecular weight polystyrene's (UHMWPS) range. The UHMWPS was obtained from the ethoxylated fatty amine oxides prepared from BPO's oxidation.
Based on the study, this paper had developed novel reactive surfactants long chain ethoxylated fatty amine oxides (AO) of industrial grade for styrene emulsion polystyrene, without adding any other initiator, chain transfer agent and electrolyte and purification process, and had got UHMWPS with narrow molecular weight distribution and rich syndiotacticity. The main contents are listed as follows:
Long chain ethoxylated fatty amine oxides were synthesized from H2O2oxidation reaction with high conversion. The chemical structure and surface properties were tested by API-ES and surface tension-meter. Those amine oxides showed good surfactivity and low CMC concentration.
The AO initiator systems were studied systematically. The effects of reaction time, H2O/styrene ratio, amount of amine oxides and corresponding amine addition on the rate of emulsion polymerization, polystyrene's microstructure, molecular weight and its distribution, glass transition temperature and crystalline properties were investigated. Synthetic UHMWPS was characterized with GC、1H-NMR、13C-NMR, DS、FT-IR.
The results showed that the number averaged molecular weights of the obtained UHMWPS increased with monomer conversion, presented certain "living" characteristics. The number averaged molecular weights gave a highest value of2.53X106and molecular weight distributions (MWD) were unimodal throughout the reaction and the minimum MWD was l.10. As polymerization matrix, long chain ethoxylated fatty amine oxides could control polymer's microstructure. The microstructure confirmed by NMR, DSC and solvent extraction method showed that UHMWPS was rich in syndiotactic structure (rr%>84%) and had wide crystal melting temperature from220oC to290oC.
This novel interface matrix polymerization initiator with stable free radicals characteris-tics and emulsifying property could be prepared easily and cheap in price, meanwhile, provide a new method for UHMWPS and rich syndiotactic polystyene's research.
基于此研究发现,本论文主要是通过开发新型反应型表面活性剂——长碳链烷基胺聚氧乙烯醚氧化物(氧化胺),在不添加其他任何引发剂、链转移剂、电解质等的条件下,将未经任何提纯操作的工业级氧化胺进行苯乙烯乳液聚合,制备出具有一定间规度的窄分子量分布的超高分子量聚苯乙烯。本论文主要包括以下几个方面：
通过H202氧化反应在高转化率下制备长碳链烷基胺聚氧乙烯醚氧化物,通过AP-ES及表面张力测试,对氧化胺的结构和表面活性进行表征,结果表明制备的氧化胺具有较好的表面活性。
系统的考察了烷基胺聚氧乙烯醚氧化物聚合体系中聚合反应时间、水与苯乙烯的用量比、氧化胺用量及烷基胺聚氧乙烯醚对聚合反应动力学、聚苯乙烯的微观结构、分子量及其分布、玻璃化转变温度及结晶性能的影响,并采用GPC、1H-NMR,13C-NMR, DSC, FT-IR对聚合所得UHMWPS进行表征。
研究表明,该体系制备的UHMWPS分子量随聚合反应转化率逐渐增加,分子量分布保持较窄分布,具有“活性”聚合特征。UHMWPS的数均分子量M。最高达2.53×106,分子量分布指数最小为1.10。烷基氧胺作为聚合模板,可控制UHMWPS的微观结构。由'H-NMR及溶解提取法计算得UHMWPS为富间规结构,sPS含量大于84%。通过DSC测试,UHMWPS在220-290℃之间有较宽的结晶熔融吸热峰。
这种新型的具有稳定自由基特征的界面反应型表面活性剂价格低廉,易于制备,通过简单的乳液聚合反应,制备出具有一定立构规整性的窄分子量分布的UHMWPS,为UHMWPS及富间规聚苯乙烯的合成提供了新的研究方向。
In this paper, long chain ethoxylated fatty amines were used as surfactant of styrene emulsion polymerization. Unlike other types of styrene polymerization, Polystyrene (PS) obtained from this polymerization system showed double or trimodal distribution characterized by GPC. Through studying, the low part molecular weight was obtained from BPO/ethoxylated fatty amines initiator system, meanwhile, the lower part was from BPO/Na2S2O4initiator system. The number averaged molecular weight of the high part molecular weight had reached1.25X10, which was in Ultra-high molecular weight polystyrene's (UHMWPS) range. The UHMWPS was obtained from the ethoxylated fatty amine oxides prepared from BPO's oxidation.
Based on the study, this paper had developed novel reactive surfactants long chain ethoxylated fatty amine oxides (AO) of industrial grade for styrene emulsion polystyrene, without adding any other initiator, chain transfer agent and electrolyte and purification process, and had got UHMWPS with narrow molecular weight distribution and rich syndiotacticity. The main contents are listed as follows:
Long chain ethoxylated fatty amine oxides were synthesized from H2O2oxidation reaction with high conversion. The chemical structure and surface properties were tested by API-ES and surface tension-meter. Those amine oxides showed good surfactivity and low CMC concentration.
The AO initiator systems were studied systematically. The effects of reaction time, H2O/styrene ratio, amount of amine oxides and corresponding amine addition on the rate of emulsion polymerization, polystyrene's microstructure, molecular weight and its distribution, glass transition temperature and crystalline properties were investigated. Synthetic UHMWPS was characterized with GC、1H-NMR、13C-NMR, DS、FT-IR.
The results showed that the number averaged molecular weights of the obtained UHMWPS increased with monomer conversion, presented certain "living" characteristics. The number averaged molecular weights gave a highest value of2.53X106and molecular weight distributions (MWD) were unimodal throughout the reaction and the minimum MWD was l.10. As polymerization matrix, long chain ethoxylated fatty amine oxides could control polymer's microstructure. The microstructure confirmed by NMR, DSC and solvent extraction method showed that UHMWPS was rich in syndiotactic structure (rr%>84%) and had wide crystal melting temperature from220oC to290oC.
This novel interface matrix polymerization initiator with stable free radicals characteris-tics and emulsifying property could be prepared easily and cheap in price, meanwhile, provide a new method for UHMWPS and rich syndiotactic polystyene's research.
引文
[1]聂建,张一烽,沈之荃等.超高分子量聚苯乙烯的合成和聚合反应动力学[J].高分子学报,2002,2：203-207.
[2]彭朝荣,陈浩,汪秀英等.辐射法合成超高分子量聚苯乙烯及其表征[J].辐射研究与辐射工艺学报,2007,25(6)：355-358.
[3]BANK D, BRENTIN Robert. New metallocene engineering thermoplastic turns up the heat [J]. Plastics Technology,1997,43(6):52-56.
[4]杨第伦,金璟,齐陈泽等.超高分子量聚苯乙烯的性能测定[J].高等学校化学学报,1993,14(11)：1627-1628.
[5]郭秀春.国外聚苯乙烯的现状与发展动向[J].塑料工业,1990,4：3-6.
[6]吴林波.稀土催化苯乙烯聚合及超高分子量聚苯乙烯[D].杭州：浙江大学,2001.
[7]杜娟,周永丰,颜德岳.氧负离子聚合在超支化聚合物合成中得应用[J].高分子学报,2010,3：255-267.
[8]SZWARC M, LEVY M, MILKOVICH R. Polymerization initiated by electron transfer to monomer. A new method of foumation of block polymers [J]. Journal of American Chemical Society,1956,78(11):2656-2657.
[9]SZWARC M. 'Living' polymers[J]. Nature,1956,178:1168-1169.
[10]薛联宝,金关泰.阴离子聚合的理论与应用[M].北京：机械工业出版社,1990.
[11]潘祖仁.高分子化学[M].北京：化学工业出版社,2003.
[12]HAIEH H L, QUICK R P. Anionic polymerization:principles and practical applications [J]. New York:Marcel Dekker, INC.,1996.
[13]BASKARAN D, MULLER AHE. Anionic vinyl Polymerization-50 Years after Michael Szwarc [J]. Progress in Polymer Science,2007,32:173-219.
[14]许德成,吕在民,林晶华.一种超高分子量窄分布聚苯乙烯的研制和表征.石油化工,1995,24(7)：468-472.
[15]DRIDDY D B, PRIC M, MEISTER B J. Development of continuous anionic styrene polymerization technology [J]. Polymer Reaction Engineering,1993,1 (2): 343-356.
[16]杨英,贾刚治.高相对分子质量聚苯乙烯树脂合成技术[J].上海塑料,2006,2：14-19.
[17]MOORE E R, DALKE B D, MALAGA M, et al. Anionic polymerization of purified monovinyldene aromatic monomer feed stock [P]:US, US4883846.1989-11-28.
[18]WUENSCH J, TUTTELBERG L, HEINRICH F, et al. Polymerization of styrene to give filterable polystyrene disperisions [P]. Ger offen, DE1950777.1996-09-12.
[19]余学海,徐军,程镕时等.常压法系列窄分布聚苯乙烯样品的制备[J].石油化工,1991,20(11)：760-764.
[20]TUNG L H.合成聚合物的分级原理和应用[M].上海：上海科学技术出版社,1984.
[21]欧阳均.稀土催化剂与聚合[M].长春：吉林科学技术出版社,1991.
[22]乔三阳.稀土催化丁二烯的本体聚合[J].合成橡胶工业,1993,16(1)：11-15.
[23]赵姜维,吴懿弦,王静等.用一稀土催化剂合成高分子量聚苯乙烯[J].高分子学报,2007,3：240-245.
[24]LIMING JIANG, ZHTQUAN SHEN, YUHUI YANG, et al. Synthesis of ultra-high molecular weight polystyrene with rare earth-magnesium alkyl catalyst system:general features of bulk polymerization [J]. Polymer International,2001,50:63-66.
[25]杨第伦,金璟,马振田等.本体溶液法合成超高分子量聚苯乙烯[J].高等学校化学学报,1995,16(2)：312-314.
[26]MIKULASOVA D, CHRASTOVA V, CITOVICKY P. Polymerization of styrene initiated by heterogeneous Macromolecules initiator [J]. European Polymer Journal,1974,10: 551-556.
[27]SUYAMA SHUJI, Taura Katsuki. Bifunctional peroxyester [P]. JPN. JP02-131463, 1990-05-21.
[28]UENO SHOJI, NINOMIYA TAKAO. Preparation of polymer having ultrahigh molecular weight [P]. JPN. JP82-117505,1982-07-22.
[29]KISHIDA K, HASEGAWA A, YANAGASE A. Production of monodispersible supermol-ecular weight polymer [P]. JPN. JP82-042703,1982-03-10.
[30]MEILUN GAO, WEI WANG, HAO WANG, et al. A study on synthesizing UHMWPS with emulsion polymerization. In:Edited by Hou Xianglin, Proc Int Conf Pec Refin & Petroehem Proce-ssing [C]. Beijing:Int. Acad. Publ.1991,3:1198-1203.
[31]STIGTER L A, Auke G, et al. Imido perestesas polymerization initiators for manufacture of styrene polymers with high moleeular weight and curing agents for rubber and unsaturated polyesters [P]. W097/03962,1997-02-06.
[32]OKUMARA R, Izumida Kiichi. Catalysts for polymerization of styreneic monomer [P]. EPS 01288,1992-09-02.
[33]SUYAMA S, TAURA K. Di(tertiary-amylperoxy)hexa-hydrophthalate as polymeriza-tion initiator [P]. JPN. JP01242567.1989-09-27.
[34]邱桂花,夏和生,王琪.超声辐照乳液聚合研究进展[J].高分子材料科学与工程,2003,19 (2)： 39-42.
[35]何玉晖,曹亚.用可聚合表面活性剂在超声辐照下乳液聚合制备聚苯乙烯纳米粒子[J].高分子材料科学与工程,2004,20(6)：72-75.
[36]张静志,曹亚.高分子表面活性剂存在下超声辐照引发苯乙烯乳液聚合的研究[J].精细化工,2003,20(11)：663-667.
[37]张静志,曹亚.高分子表面活性剂对超声辐照下苯乙烯乳液聚合的研究[J].高分子材料科学与工程,2003,19(3)：112-115.
[38]汤建萍,曾宪标.低分散度高分子量聚苯乙烯的合成及其表征[J].湖南师范大学自然科学学报,2003,26(2)：66-69.
[39]薛祖源.聚苯乙烯生产与发展综述[J].化工设计,2006,16(6)：6-16.
[40]浦鸿汀,沈志刚,周文乐等.间规聚苯乙烯结晶性能的研究进展[J].高分子材料科学与工程,2002,18(6)：5-10.
[41]范荣.均相茂金属体系催化苯乙烯间规聚合过程的研究[D].杭州：浙江大学,2001.
[42]史丰田.等规聚苯乙烯的高真空阴离子合成及其在一体化橡胶中的应用[D].北京：北京化工大学,2011.
[43]ISHIHARA N, SEMIOYA T, COIN V. Crystalline syndiotactic polystyrene. Macromolecules,1986,19:2464-2469.
[44]王进,林尚安.合成间规聚苯乙烯用茂金属催化剂的研究进展[J].高分子材料科学与工程,2001,17(3)：1-5.
[45]ISHIHARA N, KURAMOTO M, UOI M. Stereospecific polymerization of styrene giving the syndiotactic polymer [J]. Macromolecules,1988,21(12):3356-3360.
[46]ZAMBELLI A, PELLECCHIA C, OLIVA L, et al. Catalyst for syndio tactic-specific polymerization of styrene:Atentative interpreta tion of some experimental data [J]. Macromolecular Chemistry and Physics,1991,192:223-231.
[47]ISHIHARA N, KURAMOTO M. Catalyst Design for Tailor-Made Polyolefins [J]. Kodansha (Tokyo)-Elsevier,1994,89:339.
[48]GREEN M L H, ISHIHARA N. New ansa-metallocene of the Group 4 transition metals as homogeneous catalysts for the polymerization of propene and styrene [J]. Journal of the Chemical Society,1994:657-665.
[49]阎卫东,陈金晖,周鼐等.间规聚苯乙烯的技术进展[J].石油化工,1999,28(10)：716-721.
[50]LONGO P, GRASSI A, PROTO A, et al. Syndiotactic polymerization of styrene:mode of addition to the double bond [J]. Macromolecules,1988,21:24-25.
[51]ZAMBELLI A, LONGO P, PELLECCHIA C, et al. β-Hydrogen abstraction and reg-iospecif ic insertion in syndiotactic polymerization of styrene. Macromolecules, 1987,20:2035-2037.
[52]ZAMBELLI A, AMMENDOLA P, Stereospecific polymerization of α-olef ins:End groups, polymer structure and reaction mechanism [J]. Progress in Polymer Science,1991, 16:203-218.
[53]CHIEN J C W, SALAJKA Z. Syndiospecific polymerization of styrene II. monocyclopentadiemyl-tributoxy titanium/methylaluminoxane catalyst [J]. Journal of Polymer Science. Part A, Polymer Chemistry,1991,29:1253-1263.
[54]KAMINSKY W, LENK S, SCHOZ V, et al. Fluorinated half-sandwich complexes as catalysts in syndiospecific styrene polymerization. Macromolecules,1997,30 (25):7647-7650.
[55]YUNJIE L, BALDAMUS J, ZHAOMIN H. Scandium half-metallocene-catalyzed syndio-specif ic styrene polymerizationand styrene-ethylene copolymerization:unprece-dented incorporation of syndiotactic styrene-styrene sequences in styrene-ethylene copolymers [J]. Journal of American Chemical Society,2004,126: 13910-13911.
[56]PATRICK F, CHIEN J C W, RAUSCH M D. Highly stable catalysts for the stereospecif ic polymerization of styrene [J]. Organometallics,1996,15 (9):2404-2409.
[57]WALTER K, YOUNGWHAN P. Syndiospecific polymerization of styrene with arene titanium(II) complexes as catalyst precursors [J]. Macromolecules Rapid Communications,1995,16 (5):343-346.
[58]ALFONSO G, CHIARA L, ADOLFO Z, et al. Syndiospecific Styrene Polymerization Promoted by Half-Titanocene Catalysts:! A Kinetic Investigation Providing a Closer Insight to the Active Species [J]. Macromolecules,1997,30 (7): 1884-1889.
[59]YOUNGJO K, YOUNGKYU D. Syndiotactic polystyrene with very high molecular weight produced by sterically and electronically modified catalyst [J]. Journal of Organometallic Chemistry,2002,665:186-191.
[60]CIMINO S, MARTUSCELLI E, et al. Syndiotatic polystyrene:crystallization and melting behavior [J]. Polymer,1991,32 (6):1080-1083.
[61]陈德铨,胡炳镛.间规聚苯乙烯的特性及应用前景[J].合成树脂及塑料,1997,14(2)：58-61.
[62]MARTON A, Polymerization of styrene with Alfin catalysts [J]. Industrial & Engineering Chemistry,1950,42:1488-1492.
[63]ZIEGLER K, MONTECATINI H. Catalysts of α-olefins polymerization [P]. Belgium Pat.543259,1955.
[64]NATTAG, PINO P, CORRADINI P, et al. Crystalline high polymers of a-olefins [J]. Journal of American Chemical Society,1955,77:1708-1710.
[65]MONTECATINI A P. Isotactic polystyrene [P]. Italy,1965.
[66]周新华,赵振河,林尚安等.含稀土钛系催化剂的苯乙烯高活性定向聚合研究[J].高分子学报,1987,4：265-270.
[67]SOGA K, YANAGIHARA H. Synthesis of highly isotactic polystyrene by using Solvay-type titanium trichloride in combination with dicyclopenta diethyldimethyltitanium [J]. Macromolecular Chemistry and Physics,1988,9: 23-25.
[68]ANAND C L, KAPUR L S. Polymerization of styrene with VOCl3-aluminium alkyls [J]. Journal of Polymer Science. Part A, Polymer Chemistry,1967,5:2079-2089.
[69]王国成.等规聚苯乙烯和乙烯-苯乙烯共聚物的合成、表征及结晶性能研究[D].杭州：浙江大学,2005.
[70]许光学,卢泽俭,林尚安.等规聚苯乙烯结构与性能研究进展[J].高分子通报,1994,2： 65-70.
[71]辛燕.等规聚苯乙烯单链、寡链和多链聚集体的结晶、结构和形态[D].上海：复旦大学,2005.
[72]JOHN C, EZIO R, SAN H, et al. Living free-radical polymerization by reversible addition-fragmentation chain transfer:The RAFT Process[J]. Macromolecules, 1998,31 (16):5559-5562.
[73]WANG J, KRZYSZTOF M. Controlled/" living" radical polymerization atom transfer radical polymerization in the presence of transition-metal complexes [J]. Journal of the American Chemical Society,1995,117 (20):5614-5615.
[74]MICHAEL K G, RICHARD P, KAZMAIER M, et al. Narrow molecular weight resins by a free-radical polymerization process [J]. Macromolecules,1993,26 (11): 2987-2988.
[75]FISCHER A, BREMBILLA, LOCHON P. Nitroxide-Mediated radical polymerization of 4-vinylpridine:study of the pseudo-living character of the reaction and influence of temperature and nitroxide concentration [J]. Macromolecules,1999, 32 (19):6069-6072.
[76]ATSUSHI G, TAKESHI F. Kinetic study on nitroxide-mediated free radical polymerization of tert-butyl acrulate [J]. Macromolecules,1999,32 (3): 618-623.
[77]赵康,徐文健,朱秀林等.氮氧自由基调控下苯乙烯的活性自由基聚合[J].化学研究与应用,2005,17(3)：310-312.
[78]唐雅娟,李成海,张海明.反应型表面活性剂对乳液聚合的影响[J].中国胶黏剂,2006,15(7)：35-38.
[79]龚涛,鲁德平,管蓉.可聚合乳化剂[J].胶体与聚合物,2003,2(3)：27-30.
[80]熊娉婷,鲁德平,黄宏志.可聚合表面活性剂的研究进展[J].高分子通报,2006,8：14-20.
[81]HAROLD H F, PHILIP M, MEDALIA A I. Polysoaps. II. The preparation of vinyl soaps [J]. Journal of Organic Chemisty,1958,23 (1):76-82.
[82]PHILIPPE R, KRISTINA M, KLAUS M, et al. Polymerizable and nonpoly merizable isophthalic acid derivatives as surfactants in emulsion polymerization [J]. Macromolecules,2000,33 (21):7718-7723.
[83]刘书秀.氧化胺的制备、性质及应用[J].河北化工,2004,4：21-22.
[84]ALLISON M, SIGISMUND J, NIEGOWSKI M. Preparation of tertiary amine oxides by ozonization [J]. Ozone Chemisty and Technology,1959,31:202-204.
[85]朱学文,顾维康,赵立勤.长链脂肪族氧化胺对合成纤维的抗静电作用[J].合成纤维工业,1991,14(5)：16-19.
[86]COPE A C, LEBEL N A. Amine oxides. Ⅶ. The thermal decomposition of the N-oxides of N-methylazacyloalkane s[J]. Journal of the American Chemical Society,1960, 82 (17):4656-4662.
[87]孙云.新型驱油用表面活性剂的研制[D].江苏：江南大学,2009.
[88]陆用海.氧化胺(I)[J].日用化学工业,1996,6：23-27.
[89]舒红英,肖薇薇,丁教.十二烷基二甲基氧化胺含量的化学法测定[J].江西化工,2000,3：21-23.
[90]尹东霞,马沛生,夏淑倩.液体表面张力测定方法的研究进展[J].科技通报,2007,23(3)：424-430.
[91]钟振声,周衷蕙,穆筱梅等.十二烷基二甲基氧化叔胺合成方法的探索[J].精细化工,2002,14：45-47.
[2]彭朝荣,陈浩,汪秀英等.辐射法合成超高分子量聚苯乙烯及其表征[J].辐射研究与辐射工艺学报,2007,25(6)：355-358.
[3]BANK D, BRENTIN Robert. New metallocene engineering thermoplastic turns up the heat [J]. Plastics Technology,1997,43(6):52-56.
[4]杨第伦,金璟,齐陈泽等.超高分子量聚苯乙烯的性能测定[J].高等学校化学学报,1993,14(11)：1627-1628.
[5]郭秀春.国外聚苯乙烯的现状与发展动向[J].塑料工业,1990,4：3-6.
[6]吴林波.稀土催化苯乙烯聚合及超高分子量聚苯乙烯[D].杭州：浙江大学,2001.
[7]杜娟,周永丰,颜德岳.氧负离子聚合在超支化聚合物合成中得应用[J].高分子学报,2010,3：255-267.
[8]SZWARC M, LEVY M, MILKOVICH R. Polymerization initiated by electron transfer to monomer. A new method of foumation of block polymers [J]. Journal of American Chemical Society,1956,78(11):2656-2657.
[9]SZWARC M. 'Living' polymers[J]. Nature,1956,178:1168-1169.
[10]薛联宝,金关泰.阴离子聚合的理论与应用[M].北京：机械工业出版社,1990.
[11]潘祖仁.高分子化学[M].北京：化学工业出版社,2003.
[12]HAIEH H L, QUICK R P. Anionic polymerization:principles and practical applications [J]. New York:Marcel Dekker, INC.,1996.
[13]BASKARAN D, MULLER AHE. Anionic vinyl Polymerization-50 Years after Michael Szwarc [J]. Progress in Polymer Science,2007,32:173-219.
[14]许德成,吕在民,林晶华.一种超高分子量窄分布聚苯乙烯的研制和表征.石油化工,1995,24(7)：468-472.
[15]DRIDDY D B, PRIC M, MEISTER B J. Development of continuous anionic styrene polymerization technology [J]. Polymer Reaction Engineering,1993,1 (2): 343-356.
[16]杨英,贾刚治.高相对分子质量聚苯乙烯树脂合成技术[J].上海塑料,2006,2：14-19.
[17]MOORE E R, DALKE B D, MALAGA M, et al. Anionic polymerization of purified monovinyldene aromatic monomer feed stock [P]:US, US4883846.1989-11-28.
[18]WUENSCH J, TUTTELBERG L, HEINRICH F, et al. Polymerization of styrene to give filterable polystyrene disperisions [P]. Ger offen, DE1950777.1996-09-12.
[19]余学海,徐军,程镕时等.常压法系列窄分布聚苯乙烯样品的制备[J].石油化工,1991,20(11)：760-764.
[20]TUNG L H.合成聚合物的分级原理和应用[M].上海：上海科学技术出版社,1984.
[21]欧阳均.稀土催化剂与聚合[M].长春：吉林科学技术出版社,1991.
[22]乔三阳.稀土催化丁二烯的本体聚合[J].合成橡胶工业,1993,16(1)：11-15.
[23]赵姜维,吴懿弦,王静等.用一稀土催化剂合成高分子量聚苯乙烯[J].高分子学报,2007,3：240-245.
[24]LIMING JIANG, ZHTQUAN SHEN, YUHUI YANG, et al. Synthesis of ultra-high molecular weight polystyrene with rare earth-magnesium alkyl catalyst system:general features of bulk polymerization [J]. Polymer International,2001,50:63-66.
[25]杨第伦,金璟,马振田等.本体溶液法合成超高分子量聚苯乙烯[J].高等学校化学学报,1995,16(2)：312-314.
[26]MIKULASOVA D, CHRASTOVA V, CITOVICKY P. Polymerization of styrene initiated by heterogeneous Macromolecules initiator [J]. European Polymer Journal,1974,10: 551-556.
[27]SUYAMA SHUJI, Taura Katsuki. Bifunctional peroxyester [P]. JPN. JP02-131463, 1990-05-21.
[28]UENO SHOJI, NINOMIYA TAKAO. Preparation of polymer having ultrahigh molecular weight [P]. JPN. JP82-117505,1982-07-22.
[29]KISHIDA K, HASEGAWA A, YANAGASE A. Production of monodispersible supermol-ecular weight polymer [P]. JPN. JP82-042703,1982-03-10.
[30]MEILUN GAO, WEI WANG, HAO WANG, et al. A study on synthesizing UHMWPS with emulsion polymerization. In:Edited by Hou Xianglin, Proc Int Conf Pec Refin & Petroehem Proce-ssing [C]. Beijing:Int. Acad. Publ.1991,3:1198-1203.
[31]STIGTER L A, Auke G, et al. Imido perestesas polymerization initiators for manufacture of styrene polymers with high moleeular weight and curing agents for rubber and unsaturated polyesters [P]. W097/03962,1997-02-06.
[32]OKUMARA R, Izumida Kiichi. Catalysts for polymerization of styreneic monomer [P]. EPS 01288,1992-09-02.
[33]SUYAMA S, TAURA K. Di(tertiary-amylperoxy)hexa-hydrophthalate as polymeriza-tion initiator [P]. JPN. JP01242567.1989-09-27.
[34]邱桂花,夏和生,王琪.超声辐照乳液聚合研究进展[J].高分子材料科学与工程,2003,19 (2)： 39-42.
[35]何玉晖,曹亚.用可聚合表面活性剂在超声辐照下乳液聚合制备聚苯乙烯纳米粒子[J].高分子材料科学与工程,2004,20(6)：72-75.
[36]张静志,曹亚.高分子表面活性剂存在下超声辐照引发苯乙烯乳液聚合的研究[J].精细化工,2003,20(11)：663-667.
[37]张静志,曹亚.高分子表面活性剂对超声辐照下苯乙烯乳液聚合的研究[J].高分子材料科学与工程,2003,19(3)：112-115.
[38]汤建萍,曾宪标.低分散度高分子量聚苯乙烯的合成及其表征[J].湖南师范大学自然科学学报,2003,26(2)：66-69.
[39]薛祖源.聚苯乙烯生产与发展综述[J].化工设计,2006,16(6)：6-16.
[40]浦鸿汀,沈志刚,周文乐等.间规聚苯乙烯结晶性能的研究进展[J].高分子材料科学与工程,2002,18(6)：5-10.
[41]范荣.均相茂金属体系催化苯乙烯间规聚合过程的研究[D].杭州：浙江大学,2001.
[42]史丰田.等规聚苯乙烯的高真空阴离子合成及其在一体化橡胶中的应用[D].北京：北京化工大学,2011.
[43]ISHIHARA N, SEMIOYA T, COIN V. Crystalline syndiotactic polystyrene. Macromolecules,1986,19:2464-2469.
[44]王进,林尚安.合成间规聚苯乙烯用茂金属催化剂的研究进展[J].高分子材料科学与工程,2001,17(3)：1-5.
[45]ISHIHARA N, KURAMOTO M, UOI M. Stereospecific polymerization of styrene giving the syndiotactic polymer [J]. Macromolecules,1988,21(12):3356-3360.
[46]ZAMBELLI A, PELLECCHIA C, OLIVA L, et al. Catalyst for syndio tactic-specific polymerization of styrene:Atentative interpreta tion of some experimental data [J]. Macromolecular Chemistry and Physics,1991,192:223-231.
[47]ISHIHARA N, KURAMOTO M. Catalyst Design for Tailor-Made Polyolefins [J]. Kodansha (Tokyo)-Elsevier,1994,89:339.
[48]GREEN M L H, ISHIHARA N. New ansa-metallocene of the Group 4 transition metals as homogeneous catalysts for the polymerization of propene and styrene [J]. Journal of the Chemical Society,1994:657-665.
[49]阎卫东,陈金晖,周鼐等.间规聚苯乙烯的技术进展[J].石油化工,1999,28(10)：716-721.
[50]LONGO P, GRASSI A, PROTO A, et al. Syndiotactic polymerization of styrene:mode of addition to the double bond [J]. Macromolecules,1988,21:24-25.
[51]ZAMBELLI A, LONGO P, PELLECCHIA C, et al. β-Hydrogen abstraction and reg-iospecif ic insertion in syndiotactic polymerization of styrene. Macromolecules, 1987,20:2035-2037.
[52]ZAMBELLI A, AMMENDOLA P, Stereospecific polymerization of α-olef ins:End groups, polymer structure and reaction mechanism [J]. Progress in Polymer Science,1991, 16:203-218.
[53]CHIEN J C W, SALAJKA Z. Syndiospecific polymerization of styrene II. monocyclopentadiemyl-tributoxy titanium/methylaluminoxane catalyst [J]. Journal of Polymer Science. Part A, Polymer Chemistry,1991,29:1253-1263.
[54]KAMINSKY W, LENK S, SCHOZ V, et al. Fluorinated half-sandwich complexes as catalysts in syndiospecific styrene polymerization. Macromolecules,1997,30 (25):7647-7650.
[55]YUNJIE L, BALDAMUS J, ZHAOMIN H. Scandium half-metallocene-catalyzed syndio-specif ic styrene polymerizationand styrene-ethylene copolymerization:unprece-dented incorporation of syndiotactic styrene-styrene sequences in styrene-ethylene copolymers [J]. Journal of American Chemical Society,2004,126: 13910-13911.
[56]PATRICK F, CHIEN J C W, RAUSCH M D. Highly stable catalysts for the stereospecif ic polymerization of styrene [J]. Organometallics,1996,15 (9):2404-2409.
[57]WALTER K, YOUNGWHAN P. Syndiospecific polymerization of styrene with arene titanium(II) complexes as catalyst precursors [J]. Macromolecules Rapid Communications,1995,16 (5):343-346.
[58]ALFONSO G, CHIARA L, ADOLFO Z, et al. Syndiospecific Styrene Polymerization Promoted by Half-Titanocene Catalysts:! A Kinetic Investigation Providing a Closer Insight to the Active Species [J]. Macromolecules,1997,30 (7): 1884-1889.
[59]YOUNGJO K, YOUNGKYU D. Syndiotactic polystyrene with very high molecular weight produced by sterically and electronically modified catalyst [J]. Journal of Organometallic Chemistry,2002,665:186-191.
[60]CIMINO S, MARTUSCELLI E, et al. Syndiotatic polystyrene:crystallization and melting behavior [J]. Polymer,1991,32 (6):1080-1083.
[61]陈德铨,胡炳镛.间规聚苯乙烯的特性及应用前景[J].合成树脂及塑料,1997,14(2)：58-61.
[62]MARTON A, Polymerization of styrene with Alfin catalysts [J]. Industrial & Engineering Chemistry,1950,42:1488-1492.
[63]ZIEGLER K, MONTECATINI H. Catalysts of α-olefins polymerization [P]. Belgium Pat.543259,1955.
[64]NATTAG, PINO P, CORRADINI P, et al. Crystalline high polymers of a-olefins [J]. Journal of American Chemical Society,1955,77:1708-1710.
[65]MONTECATINI A P. Isotactic polystyrene [P]. Italy,1965.
[66]周新华,赵振河,林尚安等.含稀土钛系催化剂的苯乙烯高活性定向聚合研究[J].高分子学报,1987,4：265-270.
[67]SOGA K, YANAGIHARA H. Synthesis of highly isotactic polystyrene by using Solvay-type titanium trichloride in combination with dicyclopenta diethyldimethyltitanium [J]. Macromolecular Chemistry and Physics,1988,9: 23-25.
[68]ANAND C L, KAPUR L S. Polymerization of styrene with VOCl3-aluminium alkyls [J]. Journal of Polymer Science. Part A, Polymer Chemistry,1967,5:2079-2089.
[69]王国成.等规聚苯乙烯和乙烯-苯乙烯共聚物的合成、表征及结晶性能研究[D].杭州：浙江大学,2005.
[70]许光学,卢泽俭,林尚安.等规聚苯乙烯结构与性能研究进展[J].高分子通报,1994,2： 65-70.
[71]辛燕.等规聚苯乙烯单链、寡链和多链聚集体的结晶、结构和形态[D].上海：复旦大学,2005.
[72]JOHN C, EZIO R, SAN H, et al. Living free-radical polymerization by reversible addition-fragmentation chain transfer:The RAFT Process[J]. Macromolecules, 1998,31 (16):5559-5562.
[73]WANG J, KRZYSZTOF M. Controlled/" living" radical polymerization atom transfer radical polymerization in the presence of transition-metal complexes [J]. Journal of the American Chemical Society,1995,117 (20):5614-5615.
[74]MICHAEL K G, RICHARD P, KAZMAIER M, et al. Narrow molecular weight resins by a free-radical polymerization process [J]. Macromolecules,1993,26 (11): 2987-2988.
[75]FISCHER A, BREMBILLA, LOCHON P. Nitroxide-Mediated radical polymerization of 4-vinylpridine:study of the pseudo-living character of the reaction and influence of temperature and nitroxide concentration [J]. Macromolecules,1999, 32 (19):6069-6072.
[76]ATSUSHI G, TAKESHI F. Kinetic study on nitroxide-mediated free radical polymerization of tert-butyl acrulate [J]. Macromolecules,1999,32 (3): 618-623.
[77]赵康,徐文健,朱秀林等.氮氧自由基调控下苯乙烯的活性自由基聚合[J].化学研究与应用,2005,17(3)：310-312.
[78]唐雅娟,李成海,张海明.反应型表面活性剂对乳液聚合的影响[J].中国胶黏剂,2006,15(7)：35-38.
[79]龚涛,鲁德平,管蓉.可聚合乳化剂[J].胶体与聚合物,2003,2(3)：27-30.
[80]熊娉婷,鲁德平,黄宏志.可聚合表面活性剂的研究进展[J].高分子通报,2006,8：14-20.
[81]HAROLD H F, PHILIP M, MEDALIA A I. Polysoaps. II. The preparation of vinyl soaps [J]. Journal of Organic Chemisty,1958,23 (1):76-82.
[82]PHILIPPE R, KRISTINA M, KLAUS M, et al. Polymerizable and nonpoly merizable isophthalic acid derivatives as surfactants in emulsion polymerization [J]. Macromolecules,2000,33 (21):7718-7723.
[83]刘书秀.氧化胺的制备、性质及应用[J].河北化工,2004,4：21-22.
[84]ALLISON M, SIGISMUND J, NIEGOWSKI M. Preparation of tertiary amine oxides by ozonization [J]. Ozone Chemisty and Technology,1959,31:202-204.
[85]朱学文,顾维康,赵立勤.长链脂肪族氧化胺对合成纤维的抗静电作用[J].合成纤维工业,1991,14(5)：16-19.
[86]COPE A C, LEBEL N A. Amine oxides. Ⅶ. The thermal decomposition of the N-oxides of N-methylazacyloalkane s[J]. Journal of the American Chemical Society,1960, 82 (17):4656-4662.
[87]孙云.新型驱油用表面活性剂的研制[D].江苏：江南大学,2009.
[88]陆用海.氧化胺(I)[J].日用化学工业,1996,6：23-27.
[89]舒红英,肖薇薇,丁教.十二烷基二甲基氧化胺含量的化学法测定[J].江西化工,2000,3：21-23.
[90]尹东霞,马沛生,夏淑倩.液体表面张力测定方法的研究进展[J].科技通报,2007,23(3)：424-430.
[91]钟振声,周衷蕙,穆筱梅等.十二烷基二甲基氧化叔胺合成方法的探索[J].精细化工,2002,14：45-47.