有机硅改性聚丙烯酸酯涂料印花粘合剂的制备及性能研究
|
摘要
涂料印花因其具有工艺简单、色谱齐全、印花后无需水洗、节能、减排等优点，而被纺织行业列为推行清洁生产的工艺之一。但当前，在我国广泛应用的聚丙烯酸酯类涂料印花粘合剂普遍存在胶膜耐水性差、“热黏冷脆”、不耐沾污以及涂料印花色牢度与手感矛盾等缺陷，限制了涂料印花的普及和发展。为此，课题拟通过制备一种双端丙烯酰氧基聚醚硅油，对聚丙烯酸酯改性，合成一种有机硅改性聚丙烯酸酯涂料印花粘合剂，在提高印花织物耐摩擦色牢度的同时，改善印花织物的手感，以实现二者的统一。论文主要分为三部分：
第一部分为双端丙烯酰氧基聚醚硅油（DTAPS）的制备及表征。本部分以丙烯酸和双端羟基封端聚醚硅油为原料，通过酯化反应制备双端丙烯酰氧基聚醚硅油（DTAPS）,实验研究了催化剂用量、反应温度和时间、甲苯溶剂用量、阻聚剂用量等因素对酯化率的影响，并用红外光谱仪和核磁共振波谱仪对产物的结构进行了表征。结果表明：酯化反应的最佳条件为催化剂和甲苯溶剂用量分别为反应物总质量的5%、70%，阻聚剂用量为丙烯酸质量的0.75%，反应温度为110℃，反应时间为4h；红外光谱和核磁谱图显示产物结构为丙烯酰氧基聚醚硅油。
第二部分为有机硅改性聚丙烯酸酯涂料印花粘合剂的制备及性能。本部分在前人实验的基础上，固定软硬单体比为2.5:1，交联单体N-羟甲基丙烯酰胺用量为2%，丙烯酸用量为3%，研究了双端丙烯酰氧基聚醚硅油（DTAPS）加入方式、阴/非乳化体系、双端丙烯酰氧基聚醚硅油（DTAPS）分子中聚硅氧烷链段分子量、双端丙烯酰氧基聚醚硅油（DTAPS）用量等因素对乳液性能、乳胶膜性能及涂料印花性能的影响，并用扫描电镜(SEM)、水接触角分析仪、红外光谱仪、透射电镜（TEM）、粒径分析仪、热重分析仪（TG）等仪器对胶乳及胶膜的结构和性能进行了分析。结果表明：双端丙烯酰氧基聚醚硅油（DTAPS）与丙烯酸酯类单体混合乳化聚合，可以有效提高乳液的聚合稳定性；当阴/非乳化剂配比为2:1，用量为5%时，乳液聚合具有较高的单体转化率和较低的凝聚率，胶乳各项稳定性良好；双端丙烯酰氧基聚醚硅油（DTAPS）分子中聚硅氧烷链段分子量越大，通过共聚接枝到聚丙烯酸酯分子链上的量越少，胶膜焙烘过程中相分离现象和未聚合双端丙烯酰氧基聚醚硅油（DTAPS）富集团聚形成的大颗粒越多，涂料印花性能越差；聚硅氧烷链段分子量约为1600的有机硅单体用量为6%-8%时，乳液聚合稳定性较好，改性胶膜耐水性能及力学性能较高，印花织物干、湿摩可达4级，手感柔软；红外谱图显示聚丙烯酸酯大分子中含有聚硅氧烷链段成分；透射电镜（TEM）和粒径分析仪显示乳胶粒呈规则的圆球状，粒径大小为85nm,粒径分布较窄；胶膜表面水接触角和热重分析显示，经有机硅改性后，胶膜表面疏水性变大，耐热稳定性变好。
第三部分为有机硅改性聚丙烯酸酯涂料印花粘合剂的应用研究。本部分主要探讨了自制硅丙共聚涂料印花粘合剂用量、焙烘温度、焙烘时间等因素对棉织物涂料印花性能的影响，并与市场上使用的商品粘合剂的性能进行了比较。结果表明：自制硅丙共聚涂料印花粘合剂用量为16%，焙烘温度为160℃，焙烘时间4min时,印花织物干、湿摩均可达4级，手感柔软，均好于市场上目前所用的涂料印花粘合剂。
论文研究表明采用无APEO阴/非乳化剂、自制双端丙烯酰氧基聚醚硅油（DTAPS）、丙烯酸酯类单体，通过混合乳化滴加法制备的硅丙共聚涂料印花粘合剂应用于涂料印花后，印花织物具有较好的手感，耐干、湿摩擦色牢度可达4级，基本实现了涂料印花色牢度和织物手感二者的统一，即具有良好的色牢度和柔软顺滑的手感。
Pigment printing was regarded as one of clean production process by textile industrybecause of its many advantages, such as simple process, complete color chromatography,needless washing after fixation, energy saving, emission reduction. However, the polyacrylatelatex as binder for pigment printing which was used widely in our country generally existedmany defects, such as poor property of waterproof and stain resistance of latex film and hotsticky-cool brittle performance of the film, and there are contradiction between handle and colorfastness of printed fabric, which limited the popularity and development of pigment printing. Inview of the above, a double terminated acryloyl-polyether silicon oil was synthesized andapplied in the preparation of silicon-modified polyacrylate latex for pigment printing, in order toimprove the color fastness and the handle of printed fabric. There are3parts in this research.
Part1: Synthesis and characterization of double terminated acryloyl-polyether silicon oil
In this part, a double terminated acryloyl-polyether silicon oil (DTAPS) was prepared byesterification reaction with acrylic acid and polyether silicon oil terminated by double hydroxylas raw materials. The influences of reaction factors such as amount of catalyst, reactiontemperature and time, dosage of solvent and inhibitor on the esterification rate were investigated,and the structure of product was characterized by FTIR and1H-NMR. The results showed thatthe optimal esterification condition was that the amounts of catalyst and solvent were5%and70%of total reactant mass respectively, the dosage of inhibitor were0.75%of the amounts ofacrylic acid, reaction temperature was110℃and reaction time was4h. FTIR and1H-NMRanalysis indicated that the structure of product was acryloyl-polyether silicon oil.
Part2: Preparation and properties of silicon-modified polyacrylate latex for pigmentprinting
On the basis of previous experiments, fixed the mole ratio soft monomer and hardmonomer is2.5:1, the amounts of cross-linking monomers(NMA) is2%, the dosage of acrylic is3%, the effects of addition methods of DTAPS, emulsification system, molecular weight ofpolysiloxane in the DTAPS, the amounts of DTAPS on the properties of organic silicon modified polyacrylate latex, latex film and pigment printing were studied, the structure and propertieswere analyzed by SEM, FTIR, TEM, particle size analyzer, water contact angle analyzer, and thethermo-gravimetric analyzer. The results showed that the method of which DTAPS and acrylicmonomers polymerized after blinding, could effectively increase the stability of the emulsionpolymerization. When the mass ratio of anionic emulsifier to nonionic emulsifier was2:1and theamount of compound emulsifier was5%, the emulsion polymerization exhibited highermonomer conversion and lower polymerization coagulation rate, the latex had good stability. Thehigher molecular weight of polysiloxane was, the less content of organic silicon monomer whichgrafted to the polyacrylate molecular chain by copolymerization was, the larger particle whichwas formed by enrichment and agglomeration of the organic silicon was, the poorer properties ofpigment printing was. The amount of organic silicon monomer with1600molecular weight was6%-8%, the stability of emulsion polymerization was good, water resistance and mechanicalproperties were good, the dry and wet rubbing fastness of pigment printing fabric reached4grades, and the printed fabric’s handle became softer. FTIR analysis indicated that organicsilicon monomer had grafted to polyacrylate molecular chain, TEM and particle size analysisdisplayed latex particle showed a regular ball shape, the average diameter was85nm anddistribution was narrow, water contact angle analysis and TG analysis indicated thathydrophobicity and heat-resistant stability of the modified film improved obviously.
Part3: Research on the application of organic silicone modified polyacrylate binder in thepigment printing
In this part, the influences of the amounts of organic silicone modified polyacrylate latexbinder, curing temperature and curing time on properties of pigment printing for cotton fabricwere studied, and the organic silicone modified polyacrylate binder was compared with otherpigment printing binder. It was found that when the binder was16%, curing temperature was160℃, curing time was4min, the printed fabric had good handle, and dry rubbing fastness and wetrubbing fastness can reach grade4. Compared with other pigment printing binder, the fabricprinted with silicone modified polyacrylate binder had better handle and color fastness.
The research showed that after the silicone modified polyacrylate latex as binder forpigment printing which being synthesized with non-APEO emulsifier, double terminatedacryloyl-polyether silicon oil and acrylate monomers was applied in pigment printing, the printed fabric had better handle, and the dry and wet rubbing fastness of the printed fabric reached4grades, basically achieved the unification of handle and colorfastness.
第一部分为双端丙烯酰氧基聚醚硅油（DTAPS）的制备及表征。本部分以丙烯酸和双端羟基封端聚醚硅油为原料，通过酯化反应制备双端丙烯酰氧基聚醚硅油（DTAPS）,实验研究了催化剂用量、反应温度和时间、甲苯溶剂用量、阻聚剂用量等因素对酯化率的影响，并用红外光谱仪和核磁共振波谱仪对产物的结构进行了表征。结果表明：酯化反应的最佳条件为催化剂和甲苯溶剂用量分别为反应物总质量的5%、70%，阻聚剂用量为丙烯酸质量的0.75%，反应温度为110℃，反应时间为4h；红外光谱和核磁谱图显示产物结构为丙烯酰氧基聚醚硅油。
第二部分为有机硅改性聚丙烯酸酯涂料印花粘合剂的制备及性能。本部分在前人实验的基础上，固定软硬单体比为2.5:1，交联单体N-羟甲基丙烯酰胺用量为2%，丙烯酸用量为3%，研究了双端丙烯酰氧基聚醚硅油（DTAPS）加入方式、阴/非乳化体系、双端丙烯酰氧基聚醚硅油（DTAPS）分子中聚硅氧烷链段分子量、双端丙烯酰氧基聚醚硅油（DTAPS）用量等因素对乳液性能、乳胶膜性能及涂料印花性能的影响，并用扫描电镜(SEM)、水接触角分析仪、红外光谱仪、透射电镜（TEM）、粒径分析仪、热重分析仪（TG）等仪器对胶乳及胶膜的结构和性能进行了分析。结果表明：双端丙烯酰氧基聚醚硅油（DTAPS）与丙烯酸酯类单体混合乳化聚合，可以有效提高乳液的聚合稳定性；当阴/非乳化剂配比为2:1，用量为5%时，乳液聚合具有较高的单体转化率和较低的凝聚率，胶乳各项稳定性良好；双端丙烯酰氧基聚醚硅油（DTAPS）分子中聚硅氧烷链段分子量越大，通过共聚接枝到聚丙烯酸酯分子链上的量越少，胶膜焙烘过程中相分离现象和未聚合双端丙烯酰氧基聚醚硅油（DTAPS）富集团聚形成的大颗粒越多，涂料印花性能越差；聚硅氧烷链段分子量约为1600的有机硅单体用量为6%-8%时，乳液聚合稳定性较好，改性胶膜耐水性能及力学性能较高，印花织物干、湿摩可达4级，手感柔软；红外谱图显示聚丙烯酸酯大分子中含有聚硅氧烷链段成分；透射电镜（TEM）和粒径分析仪显示乳胶粒呈规则的圆球状，粒径大小为85nm,粒径分布较窄；胶膜表面水接触角和热重分析显示，经有机硅改性后，胶膜表面疏水性变大，耐热稳定性变好。
第三部分为有机硅改性聚丙烯酸酯涂料印花粘合剂的应用研究。本部分主要探讨了自制硅丙共聚涂料印花粘合剂用量、焙烘温度、焙烘时间等因素对棉织物涂料印花性能的影响，并与市场上使用的商品粘合剂的性能进行了比较。结果表明：自制硅丙共聚涂料印花粘合剂用量为16%，焙烘温度为160℃，焙烘时间4min时,印花织物干、湿摩均可达4级，手感柔软，均好于市场上目前所用的涂料印花粘合剂。
论文研究表明采用无APEO阴/非乳化剂、自制双端丙烯酰氧基聚醚硅油（DTAPS）、丙烯酸酯类单体，通过混合乳化滴加法制备的硅丙共聚涂料印花粘合剂应用于涂料印花后，印花织物具有较好的手感，耐干、湿摩擦色牢度可达4级，基本实现了涂料印花色牢度和织物手感二者的统一，即具有良好的色牢度和柔软顺滑的手感。
Pigment printing was regarded as one of clean production process by textile industrybecause of its many advantages, such as simple process, complete color chromatography,needless washing after fixation, energy saving, emission reduction. However, the polyacrylatelatex as binder for pigment printing which was used widely in our country generally existedmany defects, such as poor property of waterproof and stain resistance of latex film and hotsticky-cool brittle performance of the film, and there are contradiction between handle and colorfastness of printed fabric, which limited the popularity and development of pigment printing. Inview of the above, a double terminated acryloyl-polyether silicon oil was synthesized andapplied in the preparation of silicon-modified polyacrylate latex for pigment printing, in order toimprove the color fastness and the handle of printed fabric. There are3parts in this research.
Part1: Synthesis and characterization of double terminated acryloyl-polyether silicon oil
In this part, a double terminated acryloyl-polyether silicon oil (DTAPS) was prepared byesterification reaction with acrylic acid and polyether silicon oil terminated by double hydroxylas raw materials. The influences of reaction factors such as amount of catalyst, reactiontemperature and time, dosage of solvent and inhibitor on the esterification rate were investigated,and the structure of product was characterized by FTIR and1H-NMR. The results showed thatthe optimal esterification condition was that the amounts of catalyst and solvent were5%and70%of total reactant mass respectively, the dosage of inhibitor were0.75%of the amounts ofacrylic acid, reaction temperature was110℃and reaction time was4h. FTIR and1H-NMRanalysis indicated that the structure of product was acryloyl-polyether silicon oil.
Part2: Preparation and properties of silicon-modified polyacrylate latex for pigmentprinting
On the basis of previous experiments, fixed the mole ratio soft monomer and hardmonomer is2.5:1, the amounts of cross-linking monomers(NMA) is2%, the dosage of acrylic is3%, the effects of addition methods of DTAPS, emulsification system, molecular weight ofpolysiloxane in the DTAPS, the amounts of DTAPS on the properties of organic silicon modified polyacrylate latex, latex film and pigment printing were studied, the structure and propertieswere analyzed by SEM, FTIR, TEM, particle size analyzer, water contact angle analyzer, and thethermo-gravimetric analyzer. The results showed that the method of which DTAPS and acrylicmonomers polymerized after blinding, could effectively increase the stability of the emulsionpolymerization. When the mass ratio of anionic emulsifier to nonionic emulsifier was2:1and theamount of compound emulsifier was5%, the emulsion polymerization exhibited highermonomer conversion and lower polymerization coagulation rate, the latex had good stability. Thehigher molecular weight of polysiloxane was, the less content of organic silicon monomer whichgrafted to the polyacrylate molecular chain by copolymerization was, the larger particle whichwas formed by enrichment and agglomeration of the organic silicon was, the poorer properties ofpigment printing was. The amount of organic silicon monomer with1600molecular weight was6%-8%, the stability of emulsion polymerization was good, water resistance and mechanicalproperties were good, the dry and wet rubbing fastness of pigment printing fabric reached4grades, and the printed fabric’s handle became softer. FTIR analysis indicated that organicsilicon monomer had grafted to polyacrylate molecular chain, TEM and particle size analysisdisplayed latex particle showed a regular ball shape, the average diameter was85nm anddistribution was narrow, water contact angle analysis and TG analysis indicated thathydrophobicity and heat-resistant stability of the modified film improved obviously.
Part3: Research on the application of organic silicone modified polyacrylate binder in thepigment printing
In this part, the influences of the amounts of organic silicone modified polyacrylate latexbinder, curing temperature and curing time on properties of pigment printing for cotton fabricwere studied, and the organic silicone modified polyacrylate binder was compared with otherpigment printing binder. It was found that when the binder was16%, curing temperature was160℃, curing time was4min, the printed fabric had good handle, and dry rubbing fastness and wetrubbing fastness can reach grade4. Compared with other pigment printing binder, the fabricprinted with silicone modified polyacrylate binder had better handle and color fastness.
The research showed that after the silicone modified polyacrylate latex as binder forpigment printing which being synthesized with non-APEO emulsifier, double terminatedacryloyl-polyether silicon oil and acrylate monomers was applied in pigment printing, the printed fabric had better handle, and the dry and wet rubbing fastness of the printed fabric reached4grades, basically achieved the unification of handle and colorfastness.
引文
[1]Tatiana Scbymizek.Progressive range for Pigment Printing[J].International dyer，1997(9):P17,20,23.
[2]M Elmolla, R Schneider.Development of ecofriendly binders for pigment printing of all typesof textile fabrics [J]. Dyes and Pigments,2006,71:130-137.
[3]Yokoi Tomomi,Kon Shigeto,Yoshida.Yutaka. Binder for pigment printing:JP Patent,2007270632[P].2007-10-18.
[4]Oren Levy. A pigment system to replace dyestufs[J].The international Dyer Textile PrinterBleacher&Finisher.2002,(10):29-32．
[5]余一鳄.高档纺织品涂料印染研究进展，印染，2000，(2): p46-48.
[6]刘永强,周煜,孙雅清.从生态环境看涂料印花的发展[J].国外纺织技术,2000,(5):1-3.
[7]Frank J. Maile, Gerhard Pfaff, Peter Reynders. Effect pigments—past, present and future[J].Progress in Organic Coatings.2005(54):150–163.
[8]胡平藩.印花[M],北京:中国纺织出版社,2006,4:213-214.
[9]Galgali M R.Development of ecofriendly product for pigment printing [J]. Colourage,1998,45(7):20-22.
[10] Seddon R.Acrylic polymers in the printing industry [J]. Book Pap1990Int Conf Exhib,1990:279-286．
[11]李宾雄,周国梁.涂料印花[M],北京:纺织工业出版社,1989.
[12]王菊生，宋心远.染整工艺原理-第四册（第六章），北京:纺织工业出版社，1987，P123-155.
[13]赵涛.染整工艺原理-第二册,北京:纺织工业出版社，2007.
[14]IyerN.D.Pigment printing[J].Colourage,1991,38(4):23-24.
[15]Luiken,A.H.,Marsman,M.P.W.,Holwe,R.B.M.Radiation-curable coatings and Pigmentbinders for textile substratess[J].Coated Faber,1992,21(4)：68-80.
[16]V.GiesenandR.Eisenlohr，Review of Progress in Coloration and Related Topics[J].PigmentPrinting,1994,24:26-32.
[17]AehwalW.B. Optimization of pigment printing from quality and ecological consideration[J].Colourage,1995,42(1).
[18]Hammonds A.G.Choosing the right binder for pigment[J]. America Textiles International,1996,25(3).
[19]Sehneider R:Halder U.New development in pigment printing[J].Melliand International,1996,2.
[20]PatelD.C.Synthetic binders for pigment printing[J]. Textile Printing,1997,24.
[21]沈翠惠，杨成龙，朱广林，等.环保型低温涂料印花粘合剂的研制[J].中国胶黏剂，2008,17(3)：18-22.
[22]朱晓丽，王海艳，孔祥正，等.室温自交联聚丙烯酸酯乳液的制备与表征[J].高分子学报，2009,5:471-476.
[23]徐琦.聚丙烯酸酯核壳结构涂料印花粘合剂的合成研究[D].安徽理工大学，2007.
[24]孙中新，李继航，李毅.有机硅改性丙烯酸酯乳液的结构表征及性能研究[J].化学建材，2002(1):34-39.
[25]Zhu Fang, Zhang Gaoyong, Wang Zengzhang. Research on self crosslinkable γ-metha-cryloxypropyltrimethoxysilane modified acrylic latex by miniemulsion polymerization[J].Polymeric Materials Science and Engineering.2007,23(4):82-85.
[26]Xuejun Cui, Shuangling Zhong, Hongyan Wang a, Organic–inorganic hybrid proton exchan-ge membranes based on silicon-containing polyacrylate nanoparticles with phosphotungstic acid[J].Journal of Power Sources.2007(73):28–35.
[27]Jian-Zhong Ma,Jing Hu,Zhi-Jie Zhang.Polyacrylate/silica nanocomposite materials preparedby solgelprocess[J]. European Polymer Journal,2007(43):4169-4177.
[28]Dezheng Liu. Preparation of polysiloxane-acrylic composite latex with core-shell structure [J].Modern Chemical Industry,2002,86(3):34-36.
[29]C Peinado, A Alonso, F Catalina. Using linear and branchedpolysilanes for the photoinitiatedpolymerization of a commercial silicone-acrylate resin. a real time FTIR study [J]. Journal ofPhotochemistry and Photobiology A: Chemistry,2001,141:85-91.
[30]刘玉阳.功能化硅丙乳液的应用基础研究[D].浙江:浙江大学,2003.
[31] KONG Xiang-zheng,KAN Cheng-you,LUO Dong,et al.Synthetic methods of acrylate pol-ymer latexes modified with organosilicons and their film properties[J].1995,16(11):1810-1813.
[32]杨宏伟，许立新.有机硅改性聚丙烯酸酯微乳液的研究进展及应用[J].北京联合大学学报，2006,65(3)：80-83.
[33]陈红梅，马承银，王松，等.有机硅改性聚丙烯酸酯聚合物的方法[J].江苏化工，2000,30(5)：23-26.
[34]Ping Yan, Liying Qiu, Preparation and characterization of polysiloxane-acrylate latexes withMPS-PDMS oligomer as macromonomer [J]. Journal of Applied Polymer Science,2009,114(2):760-768.
[35]谭文丽，王树根，田秀枝.核壳型有机硅改性丙烯酸酯涂料印花粘合剂的研制[J].印染，2008,12:5-8.
[36]罗英武，许画君，李宝芳.细乳液聚合制备有机硅丙烯酸酯乳液及其性能[J].化工学报，2006,57（12）:2981-2985.
[37]Jian-Zhong Ma,Jing Hu,Zhi-Jie Zhang.Polyacrylate/silica nanocomposite materials preparedby solgel process[J]. European Polymer Journal,2007(43):4169–4177.
[38]Xuejun Cui,Shuangling Zhong,Hongyan Wang.Emulsifier-free coreeshell polyacrylate latexnanoparticles containing fluorine and silicon in shell[J].Polymer,2007(48):7241-7248.
[39]黄世强,黄鹤,李盛彪.含氢聚甲基硅氧烷/聚丙烯酸酯复合乳液研究[J].高分子材料科学与工程,1998,14(6):44~46.
[40]郭明，孙建中，周其云.聚硅氧烷/聚丙烯酸酯共聚乳液的合成与表征[J].高等化学工程学报，2002,16（2）：180-184.
[41]吴福迪,周智峰.聚硅氧烷-g-聚丙烯酸酯乳液接枝共聚的研究[J].高分子材料科学与工程,1999,15(3):61~63.
[42]Ping Yan, Liying Qiu, Preparation and characterization of polysiloxane-acrylate latexes withMPS-PDMS oligomer as macromonomer [J]. Journal of Applied Polymer Science,2009,114(2):760-768.
[43]Chen, M. J，Osterholtz, D. F. Silcone in high solids and waterbone coatings Jounral of Coatin-g Technology,1997,69(870):43
[44]Hamid Javaherian Naghash，Shadpour Mallakpour, Nader Mokhtarian. Synthesis and charac-terization of silicone-modified vinyl acetate-acrylic emulsion copolymers. Progress in Organi C-oating，2006,55:375-381.
[45]韩朝阳，龚兴宇，范晓东，等.有机硅改性聚丙烯酸酯无皂乳液的合成及性能[J].高分子材料科学与工程，2004,20(5)：81-84.
[46]Yan Ping, Qiu Liying. Synthesis and characterization of PDMS-Acrylate latexes with MPS-PDMS oligomer as macromonomer and Gemini Surfactant as coemulsifier [J]. Polymer Bulletin,2007,59:351-362.
[47]Dezheng Liu. Preparation of polysiloxane-acrylic composite latex with core-shell structure [J].Modern Chemical Industry,2002,86(3):34-36.
[48]彭鹤验，续通，蔡再生.有机硅改性丙烯酸酯微乳液的合成与表征[J].有机硅材料，2010,24(1):27-31.
[49]杜现礼，刘长利，吴碧茹，等.光敏性有机硅丙烯酸酯的合成及其改性紫外光固化材料研究[J].化工新型材料，2009，37(3):66-68.
[50]胡生祥，张军营.紫外光固化有机硅丙烯酸酯的合成研究[J].化工新型材料，2008,36(3):54-56.
[51]范青华，黄英，刘香莺.有机硅改性胶乳膜性能的研究[J].有机硅材料及应用,1995,1:24.
[1]彭鹤验，蔡再生，续通.乙烯基有机硅微乳液的合成及表征[J].有机硅材料，2009，23（6）：367-371.
[2]董建朋，吴明华.反应性聚硅氧烷微乳液的合成研究[J].应用化工，2009,38（12）：1738-1742.
[3]张超灿，韦丽莉，廖海军，等.甲基丙烯酰氧丙基（三甲基硅氧基）硅烷的制备[J].武汉理工大学学报，2003，,25（9）：5-8.
[4]刘长利，吴文健，张学骜等.紫外光固化有机硅预聚物研究进展[J].有机硅材料，2005，19(5):26-32.
[5]黄月文，刘伟区.UV固化丙烯酸酯化有机硅及杂化材料的研究与应用[J].广州化学，2008,33（4）：48-54.
[6]刘长利，吴文健，张学骜，等.光敏性有机硅丙烯酸酯的合成及表征[J].化工新型材料，2006,34（6）：42-44.
[7]胡生祥.紫外光固化有机硅丙烯酸酯预聚物合成与固化性能研究[D].北京化工大学，材料学系，2008.
[8]吴明艳，冯圣玉，田胜军.含羟烃基聚硅氧烷的研究及应用[J].有机硅材料，2002,16（5）：26-29.
[9]乔宏琴,周建成.丁大伟，等.聚醚多元醇的酯化优化[J].化工进展,2009,28:161-163.
[10]雷海琴，曹惠庆，朱新宝.甲基丙烯酸聚氧乙烯酯合成的研究进展[J].江苏化工，2008，36（1）：9-12.
[11]王景慧，王德松，罗青枝，等.Span80与甲基丙烯酸酯化反应制备反应性乳化剂[J].化学世界，2008,2:109-112.
[12]蓝文坚，李丽，崔崇.甲氧基聚乙二醇丙烯酸酯大单体的制备[J].烟台大学学报，2010,23（2）：148-153.
[13]罗策，张小伟，李春新，等.溶剂酯化法制备甲基丙烯酸聚乙二醇单甲醚-750酯[J].西北师范大学学报，2008,44(1):64-68.
[14]郭睿，赵艳艳，来肖.聚乙二醇单甲醚丙烯酸酯的制备与表征[J].陕西科技大学学报，2010,28（6）：31-34.
[15]王素娟，严云，胡志华.甲基丙烯酸聚乙二醇（400）单酯的合成[J].材料科学与工程学报，2009,27(2):250-254.
[16]张志贤，张瑞镐.有机官能团定量分析[M].北京，化学工业出版社，1993.
[1]黄芳.有机硅改性涂料印花粘合剂的研制[D].南京林业大学，2005.
[2]施强，李辉，耿兵.乙烯基硅油改性聚丙烯酸酯乳液的合成与性能[J].济南大学学报，2010,24（3）：258-261.
[3]郭明，孙建中，周其云.聚硅氧烷/聚丙烯酸酯共聚乳液的合成与表征[J].高校化学工程学报，2002,16（2）：180-184.
[4]黄文润.硅油及二次加工品[M].化学工业出版社，2004.
[5]黄英，刘春銮，师彤.硅氧烷乳液聚合过程中大颗粒形成机理研究[J].应用化学，1994，11（2）：44-47.
[6]林子云.有机硅改性涂料印花粘合剂的研制[J].胶体与聚合物，2004,22（2）：4-6.
[7] A M Goni, D C Sherrington. Reactive surfactants in heterophase polymerisation XXIII.Synthesis and characterisation of novel dialkyl maleate cationic surfmers[J]. Polymer,1999(40):1067-1079.
[8] H Robert, J Edward. Polymerizable surfactant: US Patent,5162475[P].1992-11-1.
[9]李晓洁，赵如松.有机硅-丙烯酸酯符合乳液性能[J].石油化工高等学校学报，2006,19（2）：47-50.
[10]徐彦.有机硅丙烯酸酯共聚乳液的合成与性能研究[D].苏州大学，2008.
[11]张莉.有机硅/丙烯酸酯复合共聚乳液的制备工艺研究[D].贵州大学，2008.
[12]陈静.有机硅-丙烯酸酯乳液的制备与研究[D].华中科技大学，2005.
[13]佘广为，徐瑞芬.乳化剂对有机硅改性丙烯酸酯乳液性能的研究[J].有机硅材料，2004,18（4）：1-4.
[14] Yoo Youngjae, Hong Geunhye. Preparation of acrylic copolymers and crosslinking agentsand properties as a film[J]. Journal of Applied Polymer Science,2009,12(3):1587-1594.
[15]范青华，黄英，刘春銮.聚硅氧烷改性苯乙烯-丙烯酸丁酯共聚乳液膜性能的研究[J].合成橡胶工业，1995,18（5）：276-278.
[16]范青华，黄英，刘春銮.有机硅改性胶乳膜的性能研究[J].有机硅材料及应用，1995,2：24-25.
[17]邓惠萍，侯有军，曾幸荣.乙烯基有机硅也的合成研究[J].化学与黏合，2006,28（3）：149-152.
[18]张庆轩，杨普江，高颖,等.高固含量有机硅改性丙烯酸酯微胶乳的合成及性能[J].合成橡胶工业,2006,29(6):414-419.
[19]范青华，黄英，刘春銮.聚硅氧烷改性苯丙乳液—共聚改性[J].有机硅材料及应用，1995,4：1-3.
[20]黄伟，黄英，余云照.双乙烯基封端聚二甲基硅氧烷的合成及其与苯乙烯的共聚物.高技术通讯，2000,12.
[1]吕晶.低温水性聚丙烯酸醋胶乳的研制及其在纺织上的应用[D].上海:东华大学,2003.
[2]萧继华.无甲醛涂料印花粘合剂的合成、聚合动力学及应用性能研究[D].上海:东华大学,2001.
[3]胥正安,陆建辉,严向军,等.互穿网络型涂料印花粘合剂的应用[J].纺织导报,2008,8:95-97.
[2]M Elmolla, R Schneider.Development of ecofriendly binders for pigment printing of all typesof textile fabrics [J]. Dyes and Pigments,2006,71:130-137.
[3]Yokoi Tomomi,Kon Shigeto,Yoshida.Yutaka. Binder for pigment printing:JP Patent,2007270632[P].2007-10-18.
[4]Oren Levy. A pigment system to replace dyestufs[J].The international Dyer Textile PrinterBleacher&Finisher.2002,(10):29-32．
[5]余一鳄.高档纺织品涂料印染研究进展，印染，2000，(2): p46-48.
[6]刘永强,周煜,孙雅清.从生态环境看涂料印花的发展[J].国外纺织技术,2000,(5):1-3.
[7]Frank J. Maile, Gerhard Pfaff, Peter Reynders. Effect pigments—past, present and future[J].Progress in Organic Coatings.2005(54):150–163.
[8]胡平藩.印花[M],北京:中国纺织出版社,2006,4:213-214.
[9]Galgali M R.Development of ecofriendly product for pigment printing [J]. Colourage,1998,45(7):20-22.
[10] Seddon R.Acrylic polymers in the printing industry [J]. Book Pap1990Int Conf Exhib,1990:279-286．
[11]李宾雄,周国梁.涂料印花[M],北京:纺织工业出版社,1989.
[12]王菊生，宋心远.染整工艺原理-第四册（第六章），北京:纺织工业出版社，1987，P123-155.
[13]赵涛.染整工艺原理-第二册,北京:纺织工业出版社，2007.
[14]IyerN.D.Pigment printing[J].Colourage,1991,38(4):23-24.
[15]Luiken,A.H.,Marsman,M.P.W.,Holwe,R.B.M.Radiation-curable coatings and Pigmentbinders for textile substratess[J].Coated Faber,1992,21(4)：68-80.
[16]V.GiesenandR.Eisenlohr，Review of Progress in Coloration and Related Topics[J].PigmentPrinting,1994,24:26-32.
[17]AehwalW.B. Optimization of pigment printing from quality and ecological consideration[J].Colourage,1995,42(1).
[18]Hammonds A.G.Choosing the right binder for pigment[J]. America Textiles International,1996,25(3).
[19]Sehneider R:Halder U.New development in pigment printing[J].Melliand International,1996,2.
[20]PatelD.C.Synthetic binders for pigment printing[J]. Textile Printing,1997,24.
[21]沈翠惠，杨成龙，朱广林，等.环保型低温涂料印花粘合剂的研制[J].中国胶黏剂，2008,17(3)：18-22.
[22]朱晓丽，王海艳，孔祥正，等.室温自交联聚丙烯酸酯乳液的制备与表征[J].高分子学报，2009,5:471-476.
[23]徐琦.聚丙烯酸酯核壳结构涂料印花粘合剂的合成研究[D].安徽理工大学，2007.
[24]孙中新，李继航，李毅.有机硅改性丙烯酸酯乳液的结构表征及性能研究[J].化学建材，2002(1):34-39.
[25]Zhu Fang, Zhang Gaoyong, Wang Zengzhang. Research on self crosslinkable γ-metha-cryloxypropyltrimethoxysilane modified acrylic latex by miniemulsion polymerization[J].Polymeric Materials Science and Engineering.2007,23(4):82-85.
[26]Xuejun Cui, Shuangling Zhong, Hongyan Wang a, Organic–inorganic hybrid proton exchan-ge membranes based on silicon-containing polyacrylate nanoparticles with phosphotungstic acid[J].Journal of Power Sources.2007(73):28–35.
[27]Jian-Zhong Ma,Jing Hu,Zhi-Jie Zhang.Polyacrylate/silica nanocomposite materials preparedby solgelprocess[J]. European Polymer Journal,2007(43):4169-4177.
[28]Dezheng Liu. Preparation of polysiloxane-acrylic composite latex with core-shell structure [J].Modern Chemical Industry,2002,86(3):34-36.
[29]C Peinado, A Alonso, F Catalina. Using linear and branchedpolysilanes for the photoinitiatedpolymerization of a commercial silicone-acrylate resin. a real time FTIR study [J]. Journal ofPhotochemistry and Photobiology A: Chemistry,2001,141:85-91.
[30]刘玉阳.功能化硅丙乳液的应用基础研究[D].浙江:浙江大学,2003.
[31] KONG Xiang-zheng,KAN Cheng-you,LUO Dong,et al.Synthetic methods of acrylate pol-ymer latexes modified with organosilicons and their film properties[J].1995,16(11):1810-1813.
[32]杨宏伟，许立新.有机硅改性聚丙烯酸酯微乳液的研究进展及应用[J].北京联合大学学报，2006,65(3)：80-83.
[33]陈红梅，马承银，王松，等.有机硅改性聚丙烯酸酯聚合物的方法[J].江苏化工，2000,30(5)：23-26.
[34]Ping Yan, Liying Qiu, Preparation and characterization of polysiloxane-acrylate latexes withMPS-PDMS oligomer as macromonomer [J]. Journal of Applied Polymer Science,2009,114(2):760-768.
[35]谭文丽，王树根，田秀枝.核壳型有机硅改性丙烯酸酯涂料印花粘合剂的研制[J].印染，2008,12:5-8.
[36]罗英武，许画君，李宝芳.细乳液聚合制备有机硅丙烯酸酯乳液及其性能[J].化工学报，2006,57（12）:2981-2985.
[37]Jian-Zhong Ma,Jing Hu,Zhi-Jie Zhang.Polyacrylate/silica nanocomposite materials preparedby solgel process[J]. European Polymer Journal,2007(43):4169–4177.
[38]Xuejun Cui,Shuangling Zhong,Hongyan Wang.Emulsifier-free coreeshell polyacrylate latexnanoparticles containing fluorine and silicon in shell[J].Polymer,2007(48):7241-7248.
[39]黄世强,黄鹤,李盛彪.含氢聚甲基硅氧烷/聚丙烯酸酯复合乳液研究[J].高分子材料科学与工程,1998,14(6):44~46.
[40]郭明，孙建中，周其云.聚硅氧烷/聚丙烯酸酯共聚乳液的合成与表征[J].高等化学工程学报，2002,16（2）：180-184.
[41]吴福迪,周智峰.聚硅氧烷-g-聚丙烯酸酯乳液接枝共聚的研究[J].高分子材料科学与工程,1999,15(3):61~63.
[42]Ping Yan, Liying Qiu, Preparation and characterization of polysiloxane-acrylate latexes withMPS-PDMS oligomer as macromonomer [J]. Journal of Applied Polymer Science,2009,114(2):760-768.
[43]Chen, M. J，Osterholtz, D. F. Silcone in high solids and waterbone coatings Jounral of Coatin-g Technology,1997,69(870):43
[44]Hamid Javaherian Naghash，Shadpour Mallakpour, Nader Mokhtarian. Synthesis and charac-terization of silicone-modified vinyl acetate-acrylic emulsion copolymers. Progress in Organi C-oating，2006,55:375-381.
[45]韩朝阳，龚兴宇，范晓东，等.有机硅改性聚丙烯酸酯无皂乳液的合成及性能[J].高分子材料科学与工程，2004,20(5)：81-84.
[46]Yan Ping, Qiu Liying. Synthesis and characterization of PDMS-Acrylate latexes with MPS-PDMS oligomer as macromonomer and Gemini Surfactant as coemulsifier [J]. Polymer Bulletin,2007,59:351-362.
[47]Dezheng Liu. Preparation of polysiloxane-acrylic composite latex with core-shell structure [J].Modern Chemical Industry,2002,86(3):34-36.
[48]彭鹤验，续通，蔡再生.有机硅改性丙烯酸酯微乳液的合成与表征[J].有机硅材料，2010,24(1):27-31.
[49]杜现礼，刘长利，吴碧茹，等.光敏性有机硅丙烯酸酯的合成及其改性紫外光固化材料研究[J].化工新型材料，2009，37(3):66-68.
[50]胡生祥，张军营.紫外光固化有机硅丙烯酸酯的合成研究[J].化工新型材料，2008,36(3):54-56.
[51]范青华，黄英，刘香莺.有机硅改性胶乳膜性能的研究[J].有机硅材料及应用,1995,1:24.
[1]彭鹤验，蔡再生，续通.乙烯基有机硅微乳液的合成及表征[J].有机硅材料，2009，23（6）：367-371.
[2]董建朋，吴明华.反应性聚硅氧烷微乳液的合成研究[J].应用化工，2009,38（12）：1738-1742.
[3]张超灿，韦丽莉，廖海军，等.甲基丙烯酰氧丙基（三甲基硅氧基）硅烷的制备[J].武汉理工大学学报，2003，,25（9）：5-8.
[4]刘长利，吴文健，张学骜等.紫外光固化有机硅预聚物研究进展[J].有机硅材料，2005，19(5):26-32.
[5]黄月文，刘伟区.UV固化丙烯酸酯化有机硅及杂化材料的研究与应用[J].广州化学，2008,33（4）：48-54.
[6]刘长利，吴文健，张学骜，等.光敏性有机硅丙烯酸酯的合成及表征[J].化工新型材料，2006,34（6）：42-44.
[7]胡生祥.紫外光固化有机硅丙烯酸酯预聚物合成与固化性能研究[D].北京化工大学，材料学系，2008.
[8]吴明艳，冯圣玉，田胜军.含羟烃基聚硅氧烷的研究及应用[J].有机硅材料，2002,16（5）：26-29.
[9]乔宏琴,周建成.丁大伟，等.聚醚多元醇的酯化优化[J].化工进展,2009,28:161-163.
[10]雷海琴，曹惠庆，朱新宝.甲基丙烯酸聚氧乙烯酯合成的研究进展[J].江苏化工，2008，36（1）：9-12.
[11]王景慧，王德松，罗青枝，等.Span80与甲基丙烯酸酯化反应制备反应性乳化剂[J].化学世界，2008,2:109-112.
[12]蓝文坚，李丽，崔崇.甲氧基聚乙二醇丙烯酸酯大单体的制备[J].烟台大学学报，2010,23（2）：148-153.
[13]罗策，张小伟，李春新，等.溶剂酯化法制备甲基丙烯酸聚乙二醇单甲醚-750酯[J].西北师范大学学报，2008,44(1):64-68.
[14]郭睿，赵艳艳，来肖.聚乙二醇单甲醚丙烯酸酯的制备与表征[J].陕西科技大学学报，2010,28（6）：31-34.
[15]王素娟，严云，胡志华.甲基丙烯酸聚乙二醇（400）单酯的合成[J].材料科学与工程学报，2009,27(2):250-254.
[16]张志贤，张瑞镐.有机官能团定量分析[M].北京，化学工业出版社，1993.
[1]黄芳.有机硅改性涂料印花粘合剂的研制[D].南京林业大学，2005.
[2]施强，李辉，耿兵.乙烯基硅油改性聚丙烯酸酯乳液的合成与性能[J].济南大学学报，2010,24（3）：258-261.
[3]郭明，孙建中，周其云.聚硅氧烷/聚丙烯酸酯共聚乳液的合成与表征[J].高校化学工程学报，2002,16（2）：180-184.
[4]黄文润.硅油及二次加工品[M].化学工业出版社，2004.
[5]黄英，刘春銮，师彤.硅氧烷乳液聚合过程中大颗粒形成机理研究[J].应用化学，1994，11（2）：44-47.
[6]林子云.有机硅改性涂料印花粘合剂的研制[J].胶体与聚合物，2004,22（2）：4-6.
[7] A M Goni, D C Sherrington. Reactive surfactants in heterophase polymerisation XXIII.Synthesis and characterisation of novel dialkyl maleate cationic surfmers[J]. Polymer,1999(40):1067-1079.
[8] H Robert, J Edward. Polymerizable surfactant: US Patent,5162475[P].1992-11-1.
[9]李晓洁，赵如松.有机硅-丙烯酸酯符合乳液性能[J].石油化工高等学校学报，2006,19（2）：47-50.
[10]徐彦.有机硅丙烯酸酯共聚乳液的合成与性能研究[D].苏州大学，2008.
[11]张莉.有机硅/丙烯酸酯复合共聚乳液的制备工艺研究[D].贵州大学，2008.
[12]陈静.有机硅-丙烯酸酯乳液的制备与研究[D].华中科技大学，2005.
[13]佘广为，徐瑞芬.乳化剂对有机硅改性丙烯酸酯乳液性能的研究[J].有机硅材料，2004,18（4）：1-4.
[14] Yoo Youngjae, Hong Geunhye. Preparation of acrylic copolymers and crosslinking agentsand properties as a film[J]. Journal of Applied Polymer Science,2009,12(3):1587-1594.
[15]范青华，黄英，刘春銮.聚硅氧烷改性苯乙烯-丙烯酸丁酯共聚乳液膜性能的研究[J].合成橡胶工业，1995,18（5）：276-278.
[16]范青华，黄英，刘春銮.有机硅改性胶乳膜的性能研究[J].有机硅材料及应用，1995,2：24-25.
[17]邓惠萍，侯有军，曾幸荣.乙烯基有机硅也的合成研究[J].化学与黏合，2006,28（3）：149-152.
[18]张庆轩，杨普江，高颖,等.高固含量有机硅改性丙烯酸酯微胶乳的合成及性能[J].合成橡胶工业,2006,29(6):414-419.
[19]范青华，黄英，刘春銮.聚硅氧烷改性苯丙乳液—共聚改性[J].有机硅材料及应用，1995,4：1-3.
[20]黄伟，黄英，余云照.双乙烯基封端聚二甲基硅氧烷的合成及其与苯乙烯的共聚物.高技术通讯，2000,12.
[1]吕晶.低温水性聚丙烯酸醋胶乳的研制及其在纺织上的应用[D].上海:东华大学,2003.
[2]萧继华.无甲醛涂料印花粘合剂的合成、聚合动力学及应用性能研究[D].上海:东华大学,2001.
[3]胥正安,陆建辉,严向军,等.互穿网络型涂料印花粘合剂的应用[J].纺织导报,2008,8:95-97.