超细颜料水性体系用高分子分散剂的合成与应用
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摘要
通过自由基溶液聚合法，以甲基丙烯酸甲酯、马来酸酐为单体，合成了超细颜料水性体系用高分子分散剂。并且运用红外光谱法、核磁共振(~1H NMR)及凝胶色谱法对共聚物的结构进行了表征，运用分光光度计法、扫描电镜(SEM)、粒径测定和Zeta电位测定等方法对其应用性能进行了研究。
实验结果表明，高分子分散剂MMH是甲基丙烯酸甲酯-马来酸酐共聚物的部分水解物；聚合物中甲基丙烯酸甲酯与马来酸酐的摩尔比为3：1；分子量为45,103，具有较窄的分子量分布。
应用实验表明，实验合成的MMH高分子分散剂应用于超细颜料在水性体系中的分散，具有良好的分散效果。共聚物中马来酸酐含量在25.5左右时，分散效果较好，此时单体比例为甲基丙烯酸甲酯/马来酸酐为1.5：1。分散剂的用量增加，分散体系的稳定性先增加后减小。与传统的分散剂相比较，MMH在对颜料的分散中，具有较好的分散稳定性性能。颜料分散液的扫描电镜图表明，加入MMH后颜料在水性体系中的分散更加均匀，颜料颗粒变小。高分子分散剂MMH对颜料进行分散时，空间阻碍与静电斥力同时存在，马来酸酐溶剂化链提供了足够的亲水性，聚甲基丙烯酸甲酯锚固基团提供了足够的与颜料间的结合力，有效地阻止了颜料粒子的重新聚集。
Copolymer of methyl methacrylate and maleic anhydride (MM) was prepared by free radical solution polymerization methods. The structure of copolymer was characterized by techniques of Fourier-Transform Infrared spectroscopy and 1H Nuclear Magnetic Resonance spectroscopy and Gel Permeation Chromatography. The application was studied by techniques of spectrophotometry and particle sizer and zeta meter and Scanning Electron Microscope (SEM).
The experimental results showed that the water soluble polymeric dispersant was a partly hydrolyzed MM and the Mol ratio of methyl methacrylate and maleic anhydride in the copolymer was 3:1. Mn was 45,103, and the polydispersity was 1.65.
The polymer MMH was a good dispersant for super-fine organic pigment in water. It was found that the best dispersity was achieved when the maleic anhydride was 25 percent in the dispersant and the monomer ratio of maleic anhydride to methyl methacrylate was 1:1.5. The stability increased and then decreased as the dosage of the MMH increased. The dispersity of polymeric dispersant MMH and the traditional dispersants were compared in this paper. It was indicated that the polymeric dispersant had better dispersity than the traditional ones. The SEM of dispersions indicated that the polymeric dispersant made the pigment microparticles smaller and well-distributed. In the dispersion spacial steric hindrance played the effective role besides static repulsion. The polymeric dispersant contained two parts in its molecular structure. One part was solvatable chain, the maleic anhydride, which stretched in the water and formed an adsorption layer with adequate thickness on the pigment surface. Another part was anchorin
g group, poly(the methyl methacrylate), which could be
tightly absorbed on the surface of pigment, and this effectively prevented the reconglomeration of pigment particles.
实验结果表明，高分子分散剂MMH是甲基丙烯酸甲酯-马来酸酐共聚物的部分水解物；聚合物中甲基丙烯酸甲酯与马来酸酐的摩尔比为3：1；分子量为45,103，具有较窄的分子量分布。
应用实验表明，实验合成的MMH高分子分散剂应用于超细颜料在水性体系中的分散，具有良好的分散效果。共聚物中马来酸酐含量在25.5左右时，分散效果较好，此时单体比例为甲基丙烯酸甲酯/马来酸酐为1.5：1。分散剂的用量增加，分散体系的稳定性先增加后减小。与传统的分散剂相比较，MMH在对颜料的分散中，具有较好的分散稳定性性能。颜料分散液的扫描电镜图表明，加入MMH后颜料在水性体系中的分散更加均匀，颜料颗粒变小。高分子分散剂MMH对颜料进行分散时，空间阻碍与静电斥力同时存在，马来酸酐溶剂化链提供了足够的亲水性，聚甲基丙烯酸甲酯锚固基团提供了足够的与颜料间的结合力，有效地阻止了颜料粒子的重新聚集。
Copolymer of methyl methacrylate and maleic anhydride (MM) was prepared by free radical solution polymerization methods. The structure of copolymer was characterized by techniques of Fourier-Transform Infrared spectroscopy and 1H Nuclear Magnetic Resonance spectroscopy and Gel Permeation Chromatography. The application was studied by techniques of spectrophotometry and particle sizer and zeta meter and Scanning Electron Microscope (SEM).
The experimental results showed that the water soluble polymeric dispersant was a partly hydrolyzed MM and the Mol ratio of methyl methacrylate and maleic anhydride in the copolymer was 3:1. Mn was 45,103, and the polydispersity was 1.65.
The polymer MMH was a good dispersant for super-fine organic pigment in water. It was found that the best dispersity was achieved when the maleic anhydride was 25 percent in the dispersant and the monomer ratio of maleic anhydride to methyl methacrylate was 1:1.5. The stability increased and then decreased as the dosage of the MMH increased. The dispersity of polymeric dispersant MMH and the traditional dispersants were compared in this paper. It was indicated that the polymeric dispersant had better dispersity than the traditional ones. The SEM of dispersions indicated that the polymeric dispersant made the pigment microparticles smaller and well-distributed. In the dispersion spacial steric hindrance played the effective role besides static repulsion. The polymeric dispersant contained two parts in its molecular structure. One part was solvatable chain, the maleic anhydride, which stretched in the water and formed an adsorption layer with adequate thickness on the pigment surface. Another part was anchorin
g group, poly(the methyl methacrylate), which could be
tightly absorbed on the surface of pigment, and this effectively prevented the reconglomeration of pigment particles.
引文
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[2]王利军，梁兴国等．水性涂料中有机颜料的分散．染料工业．1997(5)：1-8
[3]Tsubokawk N. Prog Polym Sci, 1992, 17: 417
[4]王利军等．化工进展，1997，93(6)：27
[5]Korayashi T. Prog Org Coat,1996,28:79
[6]Korayashi T, et al. J Coat Techal, 1992,64(890):41
[7]吴煜，王利军，刘志华，梁兴国，张友兰．水性涂料／油墨用聚合物型分散剂．涂料工业．1999(1)：31-34
[8]李子勇，李自法，梁华．水溶性涂料的发展．涂料工业，1991(4)：29～32
[9]周春隆．超分散剂及其在颜料中的应用．染料工业．1991(3)：41-47
[10]俞鸿安．高分子颜料分散剂的制备和应用．化工物资．1993(6)：14-19
[11]陈红，刘凌云．颜料分散及超分散剂的应用．印染．1998(8)：50-53
[12]Dr. A. Bouvy, Polym. Paint Color J. 1994, V184, No.4360: 540-543
[13]吴煜，吴自强．水体系中颜料分散过程的研究．涂料工业．1998(9)：35-37
[14]魏彤，范壮军．水性体系中有机颜料分散的影响因素．化学推进剂与高分子材料．1999(3)：17～20
[15]张清岑，黄苏萍．水性体系分散剂应用新进展．中国粉体技术．2000(8)：32-34
[16]伊月燕，王利军，张友兰等．水性体系用颜料分散剂的分子量剂分子量分布的控制．涂料工业．1999(10)：17-21
[17]朱骥良，吴申年．颜料工艺学．北京化工出版社：190-213
[18]周春隆．有机颜料润湿、分散及分散稳定性．化工进展．1998(4)：12-19
[19]周春隆．有机颜料物理化学特性及其未来发展趋势．染料工业2000(6)：1-3
[20]Franklux. A versatile hyperdispersant system for controlling the size of conducting polymer particles. Poly(2-hydroxyethylmethacrylate-co-styrene-4-sulfonic acid, sodium salt).Synthetic Metals102(1999)1190～1193
[21]J.Hampton etal. Organic pigment and printing inks. Amer. Ink Makers. 1985(1): 16-22
[22]E.E. Jaffe. Journal of Coating Techology. 1995(66): 21
[23]王世荣，陈启凡，周春隆．新型表面活性剂．化工商品科技情报1995(3)：51-55
[24]S chofield.J.D, hyperdispersant. JOCCA, 1991(6):204
[25]Clowley A C D, Improving dispersion of pigments with hyperdispersants. JOCCA, 1987, (8), 207
[26]Stanislaw Chibowski, J. Colloid Interface Sci. 1990, 140(2), 444-449
[27]周春隆，穆振义编著．有机颜料化学及工艺学．中国石油化工出版社：1997
[28]D.H.Napper and A. Netschey, J. Colloid Interface Sci., 1971,37,528
[29]Napper D.H., J. Colloid Interface Sci., 1980, 75(2): 525-54
[30]张卫红，龙复．水性涂料用聚合物分散剂新进展．涂料工业．1997(2)：37-39
[31]J.D.Jchofield J.O.C.C.A, 1991(6204)
[32]王平，黄毓礼．化工进展．1989(5)：20-26
[33]F.J.Carrion etal. J.Colloid Interface Sci., 1980,74,301-302
[34]Grezzo Page, Loretta Ann; Pearlstine, Kathryn Amy. Ink set and process for alleviating bleed between adjacent inks in multicolor printed elements. EP753551(1997)
[35]Fryd, Michael; Visscher, Karyn B. Dispersions having improved stability using polymer dispersant for encapsulating pigment. WO2000200520(2000)
[36] Grezzo Page, Loretta Ann; Bendnarek, Milan Bohuslav. Graft copolymers contai ning sulfonate and phosphonate groups having particular utility as pigmented ink dispersant. USP5708095(1996)
[37] Jorg S chmitz,Harald Frommelius, Heinz-Guither Schulte, A new concept for dispersing agents in aqueous coatings. Progess in organic coatings. 1999(35) : 191-196
[38] F.Haselmeyer, J. Water Borne, Coat.1984(2)
[39] H.van den Haak,Waterborne, Higher Solids and Powder Symp.,New Orlean,1997
[40] John F.Bishop.Rochester; David Alan Czekai, Honneoye Fall. Ink Jet Inks Containing Nanoparticles Of Organic Pigment. USP 5679138(1997)
[41] Cowleg A. et al. Polymers Paint Colour Journal, 1991 (181) :736-738
[42] A.W.M.delaat,H.F.M.S, J.Colloid Interface Sci, 1998, 200,228-234
[43] A.W.M.delaat,H.F.M.S, J.Colloid Interface Sci, 1997, 191,416-423
[44] Jakubauskas, Henry L, Acrylic polymer dispersant for aqueous acrylic coating compositions. USP3980602
[45] Beach, Bradley Leonard; Pearson, Anna Marie; Feeman, James Frederic, Sun, Jing Xiao, Aqueous ink composition for ink jet printing, Ep722994 (1995)
[46]Grezzo Page, Loretta Ann; Pearlstine, Kathryn Amy. Ink set and process for alleviating bleed between adjacent inks in multicolor printed elements. EP753551
[47]Farrar, David; Hawe, Malcolm. Water soluble polymers and dispersions containing them. EP129329 A2
[48]Yanagi, Hideki; Ishii, Masuki. Storage-stable aqueous pigment-containing inks. JP181722
[49]Jakubauskas, Henry L, Acrylic polymer dispersant for aqueous acrylic coating compositions. USP3980602(1976)
[50]Suzuki, Atsushi; Yui, Toshiki; Aqueous Ink-jet recording ink with good discharge responsibility and discharge stability, JP11228891-(1998)
[51]Simms, J.A. New graft polymer pigment dispersant synthesis. Progress in Organic Coatings. Vol.35, No.1-4, 1999.205-214
[52]张天胜．表面活性剂应用技术．北京．化学工业出版社2001：448-453
[53]Jenardhan R.Kanman M V K. Studies on the squential adsorption of allkyed resin on anarase TiO_2 and iron powder. Journal of Coating Technology, 1990, 62(788): 69
[54]王世荣，陈启凡，周春隆．新型表面活性剂．化工商品科技情报1995(3)：51-55
[55]R.D.Arthey, Modern Paint and Coatings, 1984(2)31-34
[56]陈荣圻．有机颜料表面改性处理．印染．2000(2)，38-40；2000(3)43-44；2000(4)44-46
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