凝胶渗透色谱用聚甲基丙烯酸标样的制备方法
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摘要
由于非体积效应的存在,以单分散非聚电解质为标样建立的凝胶渗透色谱测定聚电解质的分子量及分布的方法存在误差,为了解决这一问题,本文通过一系列方法制备了凝胶渗透色谱用聚甲基丙烯酸标样,研究工作具体包括以下几点：
(1)提出了一种酯类水解的方法,结果表明,将聚甲基丙烯酸甲酯(PMMA)标样配成10%的1,4-二氧六环溶液,在氮气氛保护下,加入KOH甲醇溶液回流水解24小时,蒸干溶剂后继续在1mol/L NaOH水溶液中回流水解24小时,其水解率接近99%。
(2)以甲苯为良溶剂,石油醚为沉淀剂,通过等温沉淀分级将PMMA粗产品分级成6个窄分布的标样,所得PMMA标样分子量分布均匀,分级效率较好。将自制PMMA标样逐个水解为聚甲基丙烯酸(PMAA)标样,GPC分析显示自制PMAA标样峰形对称,分散系数小,分子量分布均匀,适用于PMAA及其衍生物类分子量的测定。
(3)以甲醇为良溶剂,乙醚为沉淀剂,通过等温沉淀分级将PMAA粗产品分级成5个窄分布的标样,随后利用二氯亚砜先酰氯化再醇解的方法,将自制窄分布PMAA酯化为PMMA,由PMMA标样分子量计算自制]PMAA标样分子量及分布,用乌氏粘度计对粘均分子量的计算值进行检验,两者的相对误差不超过10%。GPC分析显示自制PMAA及PMMA标样峰形对称,峰窄,且分子量分布均匀。
(4)研究发现,聚丙烯酸(PAA)与PMAA测定四种不同类型聚羧酸减水剂的分子量及分布的结果误差基本小于20%,但非电解质标样聚乙二醇(PEG)与PMAA标样的测定结果却相差甚远,表明了非聚电解质标样在测定聚电解质的分子量及分布时会带来很大的误差。光散射的测定值与以自制PMAA为标样的GPC测定结果误差不超过20%,再次证明了本文建立的通过自制聚电解质标样测定聚羧酸减水剂分子量及分布的方法是可靠的。
Due to the presenced of non-volume effect, when used monodisperse non-polyelectrolyte as standards, the method of determination of molecular weight and distribution of the polyelectrolyte by GPC presenced errors. To solve this problem, we prepared polymethylacrylic acid standard samples for GPC calibration through series of methods. The research including the following:
(1) Proposed an method of ester hydrolysis, the results showed that dubbed poly (methyl methacrylate)(PMMA) standard samples in10%dioxane solution, reflux hydrolyzed24hours in KOH methanol solution under the protection of nitrogen atmosphere, evaporated solvent and continued to reflux hydrolysis24hours in1mol/L NaOH aqueous solution, the degree of hydrolysis could be reached99%.
(2) Uesed toluene as good solvent, petroleum ether as the precipitant, through isothermal precipitation grading, PMMA crude products were graded into six narrow distribution standard samples with molecular weight in3.1X103～4.3X104. The obtained PMMA standard samples molecular weight distributed evenly and had good grade efficiency. Individually hydrolyzed self-made PMMA standard samples to PMAA samples, GPC analysis showed the self-made PMAA sample peak shape and symmetry, the dispersion coefficients were small, they could be applied to determinate the molecular weight and distribution of PMAA and its derivatives.
(3) Used methanol as good solvent, ethyl ether as precipitating agent, the PMAA crude products were graded into five narrow distribution standards by isothermal precipitation grading.With self-made narrow distribution PMAA as raw materials for esterification, using thionyl chlorided and alcohol decomposed to get narrow distribution of PMMA. The molecular weight of obtained PMMA samples were in the range of2.97x103-3.63x104, molecular weight distribution coefficient were less than2, GPC analysis showed the peak of self-made PMAA and PMMA standard samples were symmetrical and narrow, molecular weight distribution were evenly. The viscosity average molecular weight values by calculating were tested by Ubbelohde viscometer,the relative error did not exceed10%, proved that the method preparing PMAA samples in this paper was feasible, and the molecular weight values were accurate and reliable.
(4) The study found that,when used polyacrylic acid (PAA) and PMAA respectively to determinate molecular weight and distribution of four different types of polycarboxylate superplasticizers, the error were less than20%, but the determination results of non-electrolyte standard polyethylene glycol (PEG) and PMAA samples falls far short, which indicating non-polyelectrolyte standards will bring significant errors in the determination of molecular weight and distribution of the polyelectrolyte. The error between the determination results by light scattering and GPC measurements results by self-made PMAA as standards were less than20%, proved that determination of molecular weight and distribution of polycarboxylate superplasticizer by self-made polyelectrolyte standards was reliable.
(1)提出了一种酯类水解的方法,结果表明,将聚甲基丙烯酸甲酯(PMMA)标样配成10%的1,4-二氧六环溶液,在氮气氛保护下,加入KOH甲醇溶液回流水解24小时,蒸干溶剂后继续在1mol/L NaOH水溶液中回流水解24小时,其水解率接近99%。
(2)以甲苯为良溶剂,石油醚为沉淀剂,通过等温沉淀分级将PMMA粗产品分级成6个窄分布的标样,所得PMMA标样分子量分布均匀,分级效率较好。将自制PMMA标样逐个水解为聚甲基丙烯酸(PMAA)标样,GPC分析显示自制PMAA标样峰形对称,分散系数小,分子量分布均匀,适用于PMAA及其衍生物类分子量的测定。
(3)以甲醇为良溶剂,乙醚为沉淀剂,通过等温沉淀分级将PMAA粗产品分级成5个窄分布的标样,随后利用二氯亚砜先酰氯化再醇解的方法,将自制窄分布PMAA酯化为PMMA,由PMMA标样分子量计算自制]PMAA标样分子量及分布,用乌氏粘度计对粘均分子量的计算值进行检验,两者的相对误差不超过10%。GPC分析显示自制PMAA及PMMA标样峰形对称,峰窄,且分子量分布均匀。
(4)研究发现,聚丙烯酸(PAA)与PMAA测定四种不同类型聚羧酸减水剂的分子量及分布的结果误差基本小于20%,但非电解质标样聚乙二醇(PEG)与PMAA标样的测定结果却相差甚远,表明了非聚电解质标样在测定聚电解质的分子量及分布时会带来很大的误差。光散射的测定值与以自制PMAA为标样的GPC测定结果误差不超过20%,再次证明了本文建立的通过自制聚电解质标样测定聚羧酸减水剂分子量及分布的方法是可靠的。
Due to the presenced of non-volume effect, when used monodisperse non-polyelectrolyte as standards, the method of determination of molecular weight and distribution of the polyelectrolyte by GPC presenced errors. To solve this problem, we prepared polymethylacrylic acid standard samples for GPC calibration through series of methods. The research including the following:
(1) Proposed an method of ester hydrolysis, the results showed that dubbed poly (methyl methacrylate)(PMMA) standard samples in10%dioxane solution, reflux hydrolyzed24hours in KOH methanol solution under the protection of nitrogen atmosphere, evaporated solvent and continued to reflux hydrolysis24hours in1mol/L NaOH aqueous solution, the degree of hydrolysis could be reached99%.
(2) Uesed toluene as good solvent, petroleum ether as the precipitant, through isothermal precipitation grading, PMMA crude products were graded into six narrow distribution standard samples with molecular weight in3.1X103～4.3X104. The obtained PMMA standard samples molecular weight distributed evenly and had good grade efficiency. Individually hydrolyzed self-made PMMA standard samples to PMAA samples, GPC analysis showed the self-made PMAA sample peak shape and symmetry, the dispersion coefficients were small, they could be applied to determinate the molecular weight and distribution of PMAA and its derivatives.
(3) Used methanol as good solvent, ethyl ether as precipitating agent, the PMAA crude products were graded into five narrow distribution standards by isothermal precipitation grading.With self-made narrow distribution PMAA as raw materials for esterification, using thionyl chlorided and alcohol decomposed to get narrow distribution of PMMA. The molecular weight of obtained PMMA samples were in the range of2.97x103-3.63x104, molecular weight distribution coefficient were less than2, GPC analysis showed the peak of self-made PMAA and PMMA standard samples were symmetrical and narrow, molecular weight distribution were evenly. The viscosity average molecular weight values by calculating were tested by Ubbelohde viscometer,the relative error did not exceed10%, proved that the method preparing PMAA samples in this paper was feasible, and the molecular weight values were accurate and reliable.
(4) The study found that,when used polyacrylic acid (PAA) and PMAA respectively to determinate molecular weight and distribution of four different types of polycarboxylate superplasticizers, the error were less than20%, but the determination results of non-electrolyte standard polyethylene glycol (PEG) and PMAA samples falls far short, which indicating non-polyelectrolyte standards will bring significant errors in the determination of molecular weight and distribution of the polyelectrolyte. The error between the determination results by light scattering and GPC measurements results by self-made PMAA as standards were less than20%, proved that determination of molecular weight and distribution of polycarboxylate superplasticizer by self-made polyelectrolyte standards was reliable.
引文
[1]于立娟.聚电解质研究进展[J].上海塑料.2011(1)：5-8.
[2]周剑平,上官勇刚,吴强,等.聚电解质材料—(Ⅱ)工程应用研究进展[J].高分子材料科学与工程.2008,24(9)：10-13.
[3]张黎明.具有反聚电解质溶液行为的两性聚合物[J].高分子通报.1998(4)：80-85.
[4]杨晓峰,李晓东,沈家骢.胶束增强型聚电解质微胶囊的制备[J].高等学校化学学报.2007,28(5)：974-977.
[5]Zhang X, Chen H, Zhang H. Layer-by-layer assembly: from conventional to unconventional methods[J]. Chem. Commun.2006(14):1395-1405.
[6]Razali M, Ahmad Z, Ahmad M, et al. Treatment of pulp and paper mill wastewater with various molecular weight of polyDADMAC induced flocculation[J]. Chemical Engineering Journal.2011, 166(2):529-535.
[7]Ucbeyiay Sahinkaya H, Ozkan A. Investigation of shear flocculation behaviors of colemanite with some anionic surfactants and inorganic salts[J]. Separation and purification technology.2011,80(1): 131-139.
[8]Ramachandran V S. Concrete admixtures handbook: properties, science, and technology[M]. William Andrew,1995.
[9]Andreas K, Zehbe R, Kazubek M, et al. Biodegradable insulin-loaded PLGA microspheres fabricated by three different emulsification techniques:Investigation for cartilage tissue engineering[J]. Acta Biomaterialia.2011,7(4):1485-1495.
[10]王文燕,郑昌仁.水溶性功能高聚物的分子量对阻垢性能的影响[J].工业水处理.1992,1(003)：3-6.
[11]Jones L W. Development of a mineral scale inhibitor[J]. Corrosion (1961) 17, 110. 1961,114.
[12]虞志光.高聚物分子量及其分布的测定[M].上海科学技术出版社,1984.
[13]周如真,张修健.小角激光散射仪及其在多糖类高分子药物参数测定中的应用[J].国外医学：药学分册.1994,21(003)：164-167.
[14]王明君,姚善泾.小角激光光散射法测定纤维素硫酸钠的分子量[J].过程工程学报.2009,9(6)：1159-1163.
[15]Chen M H, Bergman C J. Method for determining the amylose content, molecular weights, and weight-and molar-based distributions of degree of polymerization of amylose and fine-structure of amylopectin[J]. Carbohydrate polymers.2007, 69(3):562-578.
[16]仲宣惟,黄清泉,奚廷斐.多角度激光光散射检测器和示差折光检测器联用测定壳聚糖分子量及分子量分布[J].药物分析杂志.2006,26(009)：1258-1260.
[17]黄志萍.激光光散射仪及应用[J].现代仪器.2007,12(6)：49-53.
[18]Hirsch E, Altgelt K H. Integrated structural analysis. Method for the determination of average structural parameters of petroleum heavy ends[J]. Analytical Chemistry.1970,42(12): 1330-1339.
[19]Carmichael J B. Theory of gel filtration separation of biopolymers assuming a Gaussian distribution of pore sizes[J]. Biopolymers.1968,6(10): 1497-1499.
[20]Yau W W, Malone C P. An approach to diffusion theory of gel permeation chromatographic separation[J]. Journal of Polymer Science Part B:Polymer Letters.1967,5(8):663-669.
[21]Steere R L, Ackers G K. Restricted-diffusion chromatography through calibrated columns of granulated agar gel; a simple method for particle-size determination[J]. Nature.1962,3:475-476.
[22]Dimarzio E A, Guttman C M. Separation by flow[J]. Journal of Polymer Science Part B:Polymer Letters.1969,7(4):267-272.
[23]Verhoff F H, Sylvester N D. Hydrodynamic fractionation of macromolecules. I. A simple theory[J]. Journal of Macromolecular Science—Chemistry.1970,4(4):979-1001.
[24]韩冬,叶美玲,施良和.水溶性凝胶色谱中的非体积排除效应[J].色谱.1995,13(6)：432-436.
[25]Snyder L R, Dolan J W, Cox G B. Preparative high-performance liquid chromatography based on reversed-phase gradient elution::Optimum experimental conditions for heavily overloaded separation[J]. Journal of Chromatography A. 1991,540:21-40.
[26]Crone H D. Ion-exclusion chromatography of compounds of biological interest[J]. Journal of Chromatography A.1975,107(1):25-33.
[27]Stenlund B. Polyelectrolyte effects in gel chromatography.[J]. Advances in chromatography. 1976, 14:38.
[28]Sinibaldi M, Lederer M. Adsorption of inorganic anions on Sephadex gels[J]. Journal of Chromatography A.1975,107(1):210-212.
[29]Pellinen J, Salkinoja-Salonen M. Aqueous size exclusion chomatography of industrial lignins[J]. Journal of Chromatography A.1985,322:129-138.
[30]戴军,尹鸿萍,陈尚卫,等.杜氏盐藻多糖的高效体积排阻色谱的保留特性及其分析方法的研究[J].色谱.2006,6(24)：560-565.
[31]李静,左雄军.麦草碱木素及其热化学降解产物相对分子质量分布的测定[J].分析测试学报.2002,21(002)：67-69.
[32]Awan M A, Dimonie V L, El Aasser M S. Anionic dispersion polymerization of styrene. I. Investigation of parameters for preparation of uniform micron - size polystyrene particles with narrow molecular weight distribution[J]. Journal of Polymer Science Part A: Polymer Chemistry.1996,34(13): 2633-2649.
[33]高艳梅,陈永平.甲基丙烯酸甲酯的原子转移自由基沉淀聚合[J].化学工程师.2010,176(005)：63-65.
[34]薛英楠,王艳辉,刘枫,等.短链支化聚乙烯的合成与表征[J].高等学校化学学报.2009,30(009)：1870-1875.
[35]俞国星,范晓东,张翔宇,等.窄分子量分布聚四氢呋喃的合成[J].合成化学.2006,14(005)：450-453.
[36]Szwarc M. Living'polymers[J]. Nature. 1956,178:1168-1169.
[37]Szwarc M, Levy M, Milkovich R. POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERSI[J]. Journal of the American Chemical Society.1956,78(11):2656-2657.
[38]张洪敏,侯元雪.活性聚合[M].中国石化出版社,1998.
[39]潘祖仁.高分子化学(Polymer Chemistry)[Z]北京：化学工业出版社(Beijing: Chemical Industry Press),1997.
[40]Anderson B C, Andrews G D, Arthur Jr P, et al. Anionic polymerization of methacrylates. Novel functional polymers and copolymers[J]. Macromolecules. 1981,14(5):1599-1601.
[41]曹俊奎,沈家聪.窄分布聚甲基丙烯酸甲酯的合成与表征[J].高分子学报.1990(05)：613-617.
[42]Kawaguchi S, Tomootakahashi, Tajima H. Preparation, Characterization, and Dissociation Properties of Poly(acrylic acid) and Poly(methacrylic acid) with Narrow Molecular Weight Distribution[J]. Polymer Journal.1996,9(28):735-741.
[43]Wang J S, Matyjaszewski K. 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.
[44]Webster O W, Hertler W R, Sogah D Y, et al. Group-transfer polymerization. 1. A new concept for addition polymerization with organosilicon initiators[J]. Journal of the American Chemical Society. 1983,105(17):5706-5708.
[45]Doherty M A, Muller A H E. Kinetics of group transfer polymerization of tert - butyl methacrylate in tetrahydrofuran[J]. Die Makromolekulare Chemie.1989, 190(3):527-539.
[46]郑昌仁.高聚物分子量及其分布[M].化学工业出版社,1986.
[47]Sihtola H, Kaila E, Virkola N. Fractionation of high polymers by lowering the temperature of the solution[J]. Die Makromolekulare Chemie.1953,11(1):70-78.
[48]Baker C A. Slide block connection for reciprocating flush-cutting tool[Z]. US Patent 2,736,351, 1956.
[49]Sayre E V. The distribution of polymer fractions[J]. Journal of Polymer Science.1953,10(2): 175-183.
[50]Vollmert B. Polymer chemistry[M]. Springer-Verlag New York, 1973.
[51]Zhang H, Ishikawa H, Ohata M, et al. Anionic polymerization of alkyl methacrylates and molecular weight distributions of the resulting polymers[J]. Polymer. 1992,33(4):828-833.
[52]Mori H, Miiller A H E. New polymeric architectures with (meth) acrylic acid segments[J]. Progress in polymer science.2003,28(10):1403-1439.
[53]Mykytiuk J, Armes S P, Billingham N C. Group-transfer polymerization of benzyl methacrylate: A convenient method for synthesis of near-monodisperse poly (methacrylic acid) s[J]. Polymer Bulletin.1992,29(1):139-145.
[54]Erhardt R, Zhang M, Boker A, et al. Amphiphilic Janus micelles with polystyrene and poly (methacrylic acid) hemispheres[J]. Journal of the American Chemical Society.2003,125(11): 3260-3267.
[55]郭丽萍,陈莉,杜小弟,等.凝胶渗透色谱用聚丙烯酸标样的制备[J].应用化学.2011,28(4)：443-447.
[56]Wiederhorn N M, Brown A R. Viscosity - molecular weight relation for polymethacrylic acid in methanol[J]. Journal of Polymer Science. 1952,8(6):651-656.
[57]颜德岳,吴邦瑗,裘祖文,等.甲基丙烯酸甲酯的阴离子聚合反应--(1)产物的核磁共振波谱[J].同济大学学报(自然科学版).1980,4(4)：34-43.
[58]邹友思,夏海平,潘容华.甲基丙烯酸甲酯的基团转移聚合[J].高分子学报.1990,4(4)：481-484.
[59]黄俊,柳青,吴壁耀.甲基丙烯酸甲酯的原子转移自由基聚合[J].武汉工程大学学报.2009, 31(007)：62-63.
[60]郭丽萍,陈莉,杜小弟,等.凝胶渗透色谱用聚丙烯酸标样的制备[J].应用化学.2011,28(04)：443-447.
[61]Brandrup J, Immergut E H, Grulke E A. Polymer handbook[J]. New York. 1975:12-13.
[62]杜小弟,张安富,雷家珩,等.聚丙烯酸的凝胶渗透色谱分离及相对分子质量测定[J].分析测试学报.2011,30(002)：167-170.
[63]王尚弟,沈晓清.甲基丙烯酸甲酯(MMA)生产中水解和酯化反应特性的研究[J].化学反应工程与工艺.1994,10(3)：217-226.
[64]喻名强,刘广义,尹兴荣,等.酰氯的合成方法及其应用新进展[J].精细化工中间体.2011,41(4)：1-7.
[65]蔡宝国,龚钢明.双硬脂酸曲酸酯的制备及应用[J].化学世界.2003,44(001)：38-40.
[66]程永浩,邹小毛,任雪玲,等.对苯二甲酰氯合成[J].化学试剂.2003,25(2)：118.
[67]赵东欣,卢奎,薛永亮.乙酰阿魏酰丙氨酸甲酯的液相合成[J].中国化学会第十二届全国应用化学年会论文集.2011.
[68]Chidambaram S, Gundiah S. Conformational transition in poly (methacrylic acid)[J]. Die Makromolekulare Chemie.1985,186(1):123-129.
[69]Okada E, Sakagami K. Process for preparation of AE concrete or AE mortar[P].4325736.
[70]Puertas F, Santos H, Palacios M, et al. Polycarboxylate superplasticiser admixtures: effect on hydration, microstructure and rheological behaviour in cement pastes[C]. Institution of Civil Engineers (ICE), 2005.
[71]Aramendia M A, Benitez J A, Borau V, et al. Colloids and Surfaces A: Physicochem[J]. Eng. Aspects.2000,168:27.
[2]周剑平,上官勇刚,吴强,等.聚电解质材料—(Ⅱ)工程应用研究进展[J].高分子材料科学与工程.2008,24(9)：10-13.
[3]张黎明.具有反聚电解质溶液行为的两性聚合物[J].高分子通报.1998(4)：80-85.
[4]杨晓峰,李晓东,沈家骢.胶束增强型聚电解质微胶囊的制备[J].高等学校化学学报.2007,28(5)：974-977.
[5]Zhang X, Chen H, Zhang H. Layer-by-layer assembly: from conventional to unconventional methods[J]. Chem. Commun.2006(14):1395-1405.
[6]Razali M, Ahmad Z, Ahmad M, et al. Treatment of pulp and paper mill wastewater with various molecular weight of polyDADMAC induced flocculation[J]. Chemical Engineering Journal.2011, 166(2):529-535.
[7]Ucbeyiay Sahinkaya H, Ozkan A. Investigation of shear flocculation behaviors of colemanite with some anionic surfactants and inorganic salts[J]. Separation and purification technology.2011,80(1): 131-139.
[8]Ramachandran V S. Concrete admixtures handbook: properties, science, and technology[M]. William Andrew,1995.
[9]Andreas K, Zehbe R, Kazubek M, et al. Biodegradable insulin-loaded PLGA microspheres fabricated by three different emulsification techniques:Investigation for cartilage tissue engineering[J]. Acta Biomaterialia.2011,7(4):1485-1495.
[10]王文燕,郑昌仁.水溶性功能高聚物的分子量对阻垢性能的影响[J].工业水处理.1992,1(003)：3-6.
[11]Jones L W. Development of a mineral scale inhibitor[J]. Corrosion (1961) 17, 110. 1961,114.
[12]虞志光.高聚物分子量及其分布的测定[M].上海科学技术出版社,1984.
[13]周如真,张修健.小角激光散射仪及其在多糖类高分子药物参数测定中的应用[J].国外医学：药学分册.1994,21(003)：164-167.
[14]王明君,姚善泾.小角激光光散射法测定纤维素硫酸钠的分子量[J].过程工程学报.2009,9(6)：1159-1163.
[15]Chen M H, Bergman C J. Method for determining the amylose content, molecular weights, and weight-and molar-based distributions of degree of polymerization of amylose and fine-structure of amylopectin[J]. Carbohydrate polymers.2007, 69(3):562-578.
[16]仲宣惟,黄清泉,奚廷斐.多角度激光光散射检测器和示差折光检测器联用测定壳聚糖分子量及分子量分布[J].药物分析杂志.2006,26(009)：1258-1260.
[17]黄志萍.激光光散射仪及应用[J].现代仪器.2007,12(6)：49-53.
[18]Hirsch E, Altgelt K H. Integrated structural analysis. Method for the determination of average structural parameters of petroleum heavy ends[J]. Analytical Chemistry.1970,42(12): 1330-1339.
[19]Carmichael J B. Theory of gel filtration separation of biopolymers assuming a Gaussian distribution of pore sizes[J]. Biopolymers.1968,6(10): 1497-1499.
[20]Yau W W, Malone C P. An approach to diffusion theory of gel permeation chromatographic separation[J]. Journal of Polymer Science Part B:Polymer Letters.1967,5(8):663-669.
[21]Steere R L, Ackers G K. Restricted-diffusion chromatography through calibrated columns of granulated agar gel; a simple method for particle-size determination[J]. Nature.1962,3:475-476.
[22]Dimarzio E A, Guttman C M. Separation by flow[J]. Journal of Polymer Science Part B:Polymer Letters.1969,7(4):267-272.
[23]Verhoff F H, Sylvester N D. Hydrodynamic fractionation of macromolecules. I. A simple theory[J]. Journal of Macromolecular Science—Chemistry.1970,4(4):979-1001.
[24]韩冬,叶美玲,施良和.水溶性凝胶色谱中的非体积排除效应[J].色谱.1995,13(6)：432-436.
[25]Snyder L R, Dolan J W, Cox G B. Preparative high-performance liquid chromatography based on reversed-phase gradient elution::Optimum experimental conditions for heavily overloaded separation[J]. Journal of Chromatography A. 1991,540:21-40.
[26]Crone H D. Ion-exclusion chromatography of compounds of biological interest[J]. Journal of Chromatography A.1975,107(1):25-33.
[27]Stenlund B. Polyelectrolyte effects in gel chromatography.[J]. Advances in chromatography. 1976, 14:38.
[28]Sinibaldi M, Lederer M. Adsorption of inorganic anions on Sephadex gels[J]. Journal of Chromatography A.1975,107(1):210-212.
[29]Pellinen J, Salkinoja-Salonen M. Aqueous size exclusion chomatography of industrial lignins[J]. Journal of Chromatography A.1985,322:129-138.
[30]戴军,尹鸿萍,陈尚卫,等.杜氏盐藻多糖的高效体积排阻色谱的保留特性及其分析方法的研究[J].色谱.2006,6(24)：560-565.
[31]李静,左雄军.麦草碱木素及其热化学降解产物相对分子质量分布的测定[J].分析测试学报.2002,21(002)：67-69.
[32]Awan M A, Dimonie V L, El Aasser M S. Anionic dispersion polymerization of styrene. I. Investigation of parameters for preparation of uniform micron - size polystyrene particles with narrow molecular weight distribution[J]. Journal of Polymer Science Part A: Polymer Chemistry.1996,34(13): 2633-2649.
[33]高艳梅,陈永平.甲基丙烯酸甲酯的原子转移自由基沉淀聚合[J].化学工程师.2010,176(005)：63-65.
[34]薛英楠,王艳辉,刘枫,等.短链支化聚乙烯的合成与表征[J].高等学校化学学报.2009,30(009)：1870-1875.
[35]俞国星,范晓东,张翔宇,等.窄分子量分布聚四氢呋喃的合成[J].合成化学.2006,14(005)：450-453.
[36]Szwarc M. Living'polymers[J]. Nature. 1956,178:1168-1169.
[37]Szwarc M, Levy M, Milkovich R. POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERSI[J]. Journal of the American Chemical Society.1956,78(11):2656-2657.
[38]张洪敏,侯元雪.活性聚合[M].中国石化出版社,1998.
[39]潘祖仁.高分子化学(Polymer Chemistry)[Z]北京：化学工业出版社(Beijing: Chemical Industry Press),1997.
[40]Anderson B C, Andrews G D, Arthur Jr P, et al. Anionic polymerization of methacrylates. Novel functional polymers and copolymers[J]. Macromolecules. 1981,14(5):1599-1601.
[41]曹俊奎,沈家聪.窄分布聚甲基丙烯酸甲酯的合成与表征[J].高分子学报.1990(05)：613-617.
[42]Kawaguchi S, Tomootakahashi, Tajima H. Preparation, Characterization, and Dissociation Properties of Poly(acrylic acid) and Poly(methacrylic acid) with Narrow Molecular Weight Distribution[J]. Polymer Journal.1996,9(28):735-741.
[43]Wang J S, Matyjaszewski K. 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.
[44]Webster O W, Hertler W R, Sogah D Y, et al. Group-transfer polymerization. 1. A new concept for addition polymerization with organosilicon initiators[J]. Journal of the American Chemical Society. 1983,105(17):5706-5708.
[45]Doherty M A, Muller A H E. Kinetics of group transfer polymerization of tert - butyl methacrylate in tetrahydrofuran[J]. Die Makromolekulare Chemie.1989, 190(3):527-539.
[46]郑昌仁.高聚物分子量及其分布[M].化学工业出版社,1986.
[47]Sihtola H, Kaila E, Virkola N. Fractionation of high polymers by lowering the temperature of the solution[J]. Die Makromolekulare Chemie.1953,11(1):70-78.
[48]Baker C A. Slide block connection for reciprocating flush-cutting tool[Z]. US Patent 2,736,351, 1956.
[49]Sayre E V. The distribution of polymer fractions[J]. Journal of Polymer Science.1953,10(2): 175-183.
[50]Vollmert B. Polymer chemistry[M]. Springer-Verlag New York, 1973.
[51]Zhang H, Ishikawa H, Ohata M, et al. Anionic polymerization of alkyl methacrylates and molecular weight distributions of the resulting polymers[J]. Polymer. 1992,33(4):828-833.
[52]Mori H, Miiller A H E. New polymeric architectures with (meth) acrylic acid segments[J]. Progress in polymer science.2003,28(10):1403-1439.
[53]Mykytiuk J, Armes S P, Billingham N C. Group-transfer polymerization of benzyl methacrylate: A convenient method for synthesis of near-monodisperse poly (methacrylic acid) s[J]. Polymer Bulletin.1992,29(1):139-145.
[54]Erhardt R, Zhang M, Boker A, et al. Amphiphilic Janus micelles with polystyrene and poly (methacrylic acid) hemispheres[J]. Journal of the American Chemical Society.2003,125(11): 3260-3267.
[55]郭丽萍,陈莉,杜小弟,等.凝胶渗透色谱用聚丙烯酸标样的制备[J].应用化学.2011,28(4)：443-447.
[56]Wiederhorn N M, Brown A R. Viscosity - molecular weight relation for polymethacrylic acid in methanol[J]. Journal of Polymer Science. 1952,8(6):651-656.
[57]颜德岳,吴邦瑗,裘祖文,等.甲基丙烯酸甲酯的阴离子聚合反应--(1)产物的核磁共振波谱[J].同济大学学报(自然科学版).1980,4(4)：34-43.
[58]邹友思,夏海平,潘容华.甲基丙烯酸甲酯的基团转移聚合[J].高分子学报.1990,4(4)：481-484.
[59]黄俊,柳青,吴壁耀.甲基丙烯酸甲酯的原子转移自由基聚合[J].武汉工程大学学报.2009, 31(007)：62-63.
[60]郭丽萍,陈莉,杜小弟,等.凝胶渗透色谱用聚丙烯酸标样的制备[J].应用化学.2011,28(04)：443-447.
[61]Brandrup J, Immergut E H, Grulke E A. Polymer handbook[J]. New York. 1975:12-13.
[62]杜小弟,张安富,雷家珩,等.聚丙烯酸的凝胶渗透色谱分离及相对分子质量测定[J].分析测试学报.2011,30(002)：167-170.
[63]王尚弟,沈晓清.甲基丙烯酸甲酯(MMA)生产中水解和酯化反应特性的研究[J].化学反应工程与工艺.1994,10(3)：217-226.
[64]喻名强,刘广义,尹兴荣,等.酰氯的合成方法及其应用新进展[J].精细化工中间体.2011,41(4)：1-7.
[65]蔡宝国,龚钢明.双硬脂酸曲酸酯的制备及应用[J].化学世界.2003,44(001)：38-40.
[66]程永浩,邹小毛,任雪玲,等.对苯二甲酰氯合成[J].化学试剂.2003,25(2)：118.
[67]赵东欣,卢奎,薛永亮.乙酰阿魏酰丙氨酸甲酯的液相合成[J].中国化学会第十二届全国应用化学年会论文集.2011.
[68]Chidambaram S, Gundiah S. Conformational transition in poly (methacrylic acid)[J]. Die Makromolekulare Chemie.1985,186(1):123-129.
[69]Okada E, Sakagami K. Process for preparation of AE concrete or AE mortar[P].4325736.
[70]Puertas F, Santos H, Palacios M, et al. Polycarboxylate superplasticiser admixtures: effect on hydration, microstructure and rheological behaviour in cement pastes[C]. Institution of Civil Engineers (ICE), 2005.
[71]Aramendia M A, Benitez J A, Borau V, et al. Colloids and Surfaces A: Physicochem[J]. Eng. Aspects.2000,168:27.