超支化低聚物的合成及在UV喷墨油墨中的应用
摘要
光活性低聚物是光固化产品中比例较大的组分之一，它和活性稀释剂一起占到整个配方质量的90％以上，是光固化体系的基体树脂，构成固化产品的基本骨架，即固化后产品的基本性能(包括硬度、柔韧性、附着力、光学性能、耐老化等)主要由光活性低聚物决定。
本文采用两种办法合成了低粘度光活性超支化低聚物。其一，以乙二胺(EDA)与乙氧化三羟甲基丙烷三丙烯酸酯(EO-TMPTA)为原料，采用“准一步法”合成了超支化低聚物P1。研究了反应物配比、反应温度、反应时间及溶剂用量对目标产物的影响。结果表明，P1的较佳合成条件为n(EO-TMPTA)：n(EDA)=5：1，反应温度25-30℃，反应时间6-8 h，溶剂甲醇的用量为总体系的20％左右。其二，以丙烯酸、PP50及己二酸为原料，采用“一步法”合成了超支化低聚物P2。研究了反应温度、反应时间、催化剂用量和溶剂用量对产物及产率的影响。结果表明，P2的较佳制备工艺为反应温度80-90℃，反应时间10 h，催化剂用量1.5％，溶剂用量20％。
考察了P1和P2的理化性能及油墨适用性。分别对其粘度、光固化时间、体积收缩率、固化膜柔韧性、铅笔硬度及附着力等理化性能进行了测试，并与国外同类商品Viajet100，CN3100，CN3105及CN132作了详细比较。分别以P1，P2和Viajet100为主体树脂配制了光固化喷墨油墨A、油墨B和油墨C。对比研究了其粘度、光固化时间、体积收缩率、固化膜柔韧性、铅笔硬度及附着力等性能。
重点以P1为主体树脂制备了黄色UV喷墨油墨，研究了黄色UV喷墨油墨分散稳定性的影响因素及固化后涂膜的理化性能。通过对黄色颜料H4G进行研磨处理，讨论了研磨时间对颜料粒度的影响，考察了不同湿润分散剂及其用量对H4G油墨体系分散性的影响。将经过研磨处理的颜料配制成UV喷墨油墨，通过SEM研究了颜料的粒径及分布，并对油墨固化时间、涂膜性能、耐化学性进行了测试。
The UV curable oligomer, which determined the properties of film ( hardness, flexility, adhesion, optical performance and aging resistance), was one of the most important raw materials in UV curing coating materials. The oligomer and monomer were more than 90%wt in the coating formulation.
The UV curable hyperbranched oligomers were synthesized in two different ways. Firstly, a hyperbranched oligomer with eight double bonds (P1) was synthesized by Michael addition reaction of ethylene diamine (EDA) and ethyoxyl trimethylolpropane triacrylate (EO-TMPTA) under mild conditions. That was, the mole ratio of EO-TMPTA and EDA was 5.0: 1.0, reaction time was 6-8 h, reaction temperature was 25-30℃, and the dosage of methanol as the catalyst and solvent was about 20%. Secondly, the other UV curable oligomer with six double bonds (P2) was synthesized by acrylic acid, PP50 and hexanedioic acid. The best conditions of synthesis was, the reaction temperature was 80-90℃, reaction time was 10 h, the dosages of catalyst was 1.5% and solvent was 20%.
The physical and chemical properties of P1 and P2 using in inks were analyzed by testing the hardness, flexility and adhesion of the coatings capability. And these properties were close to commercial products such as Viajet100, CN3100, CN3105 and CN132. The jet inks A, B and C was prepared by P1, P2 and Viajet 100 separately. The performances of them were analyzed and compared by studying the viscosity, curing time, shrinkage ratio, flexility, hardness and adhesion.
Furthermore, the yellow UV curable jet ink was preparation with PL The dispersing stability, physical and chemical performances of yellow UV curable jet ink were studied. Good pigment-dispersing stability is necessary for pigment-based ink-jet inks. In this study, the pigment with grinding medium is grinded into color paste which is then used in UV curable jet inks. The correlation of the grinding time and granularity of the pigments is investigated. The applicable dispersant and the best content used in H4G based UV curable jet inks are also discussed. The improvement of pigment dispersability of H4G-based UV curable ink jet inks with grinded yellow pigment is confirmed by SEM. Moreover, the curing time, hardiness, flexility and several chemical resistant of the coating which was cured by UV curable jet inks are measured.
本文采用两种办法合成了低粘度光活性超支化低聚物。其一，以乙二胺(EDA)与乙氧化三羟甲基丙烷三丙烯酸酯(EO-TMPTA)为原料，采用“准一步法”合成了超支化低聚物P1。研究了反应物配比、反应温度、反应时间及溶剂用量对目标产物的影响。结果表明，P1的较佳合成条件为n(EO-TMPTA)：n(EDA)=5：1，反应温度25-30℃，反应时间6-8 h，溶剂甲醇的用量为总体系的20％左右。其二，以丙烯酸、PP50及己二酸为原料，采用“一步法”合成了超支化低聚物P2。研究了反应温度、反应时间、催化剂用量和溶剂用量对产物及产率的影响。结果表明，P2的较佳制备工艺为反应温度80-90℃，反应时间10 h，催化剂用量1.5％，溶剂用量20％。
考察了P1和P2的理化性能及油墨适用性。分别对其粘度、光固化时间、体积收缩率、固化膜柔韧性、铅笔硬度及附着力等理化性能进行了测试，并与国外同类商品Viajet100，CN3100，CN3105及CN132作了详细比较。分别以P1，P2和Viajet100为主体树脂配制了光固化喷墨油墨A、油墨B和油墨C。对比研究了其粘度、光固化时间、体积收缩率、固化膜柔韧性、铅笔硬度及附着力等性能。
重点以P1为主体树脂制备了黄色UV喷墨油墨，研究了黄色UV喷墨油墨分散稳定性的影响因素及固化后涂膜的理化性能。通过对黄色颜料H4G进行研磨处理，讨论了研磨时间对颜料粒度的影响，考察了不同湿润分散剂及其用量对H4G油墨体系分散性的影响。将经过研磨处理的颜料配制成UV喷墨油墨，通过SEM研究了颜料的粒径及分布，并对油墨固化时间、涂膜性能、耐化学性进行了测试。
The UV curable oligomer, which determined the properties of film ( hardness, flexility, adhesion, optical performance and aging resistance), was one of the most important raw materials in UV curing coating materials. The oligomer and monomer were more than 90%wt in the coating formulation.
The UV curable hyperbranched oligomers were synthesized in two different ways. Firstly, a hyperbranched oligomer with eight double bonds (P1) was synthesized by Michael addition reaction of ethylene diamine (EDA) and ethyoxyl trimethylolpropane triacrylate (EO-TMPTA) under mild conditions. That was, the mole ratio of EO-TMPTA and EDA was 5.0: 1.0, reaction time was 6-8 h, reaction temperature was 25-30℃, and the dosage of methanol as the catalyst and solvent was about 20%. Secondly, the other UV curable oligomer with six double bonds (P2) was synthesized by acrylic acid, PP50 and hexanedioic acid. The best conditions of synthesis was, the reaction temperature was 80-90℃, reaction time was 10 h, the dosages of catalyst was 1.5% and solvent was 20%.
The physical and chemical properties of P1 and P2 using in inks were analyzed by testing the hardness, flexility and adhesion of the coatings capability. And these properties were close to commercial products such as Viajet100, CN3100, CN3105 and CN132. The jet inks A, B and C was prepared by P1, P2 and Viajet 100 separately. The performances of them were analyzed and compared by studying the viscosity, curing time, shrinkage ratio, flexility, hardness and adhesion.
Furthermore, the yellow UV curable jet ink was preparation with PL The dispersing stability, physical and chemical performances of yellow UV curable jet ink were studied. Good pigment-dispersing stability is necessary for pigment-based ink-jet inks. In this study, the pigment with grinding medium is grinded into color paste which is then used in UV curable jet inks. The correlation of the grinding time and granularity of the pigments is investigated. The applicable dispersant and the best content used in H4G based UV curable jet inks are also discussed. The improvement of pigment dispersability of H4G-based UV curable ink jet inks with grinded yellow pigment is confirmed by SEM. Moreover, the curing time, hardiness, flexility and several chemical resistant of the coating which was cured by UV curable jet inks are measured.
引文
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[4] 焦红军，黄毓礼，牛爱杰，等．溶剂型喷墨墨水连接料的合成及性能研究[J]．北京化工大学学报(自然科学版)，2005，32(5)：68-70
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[7] Myung-Eon Song, Ju-Young Kim, Kyung-Do Suh. Coatings Technol., 1986,68 (862):43-50
[8] Wolfgang Fischer, Jan Weikard, 谢建达．新型低粘度聚氨脂丙烯酸酯，Rad. Tech. Asia'2005 Conference Proceedings, Shanghai, China, 2005: 151-159
[9] 王丽，张育川，曾宪玉，等．喷墨CTP版UV墨水用超低黏度聚氨酯丙烯酸酯的合成及性能[J]，北京化工大学学报(自然科学版)，2006，Vol33，No．2：59-63
[10] 任飙，文应军，可紫外固化多官能团丙烯酸酯聚酯树脂的合成和性能，丙烯酸化工与应用[J]，2002，Vol．15，No．3：17-20
[11] 国外简讯[J]，涂料工业，2002，12：54
[12] 陈文，杨双民，彭学军，等．UV固化皮革上光油的研制[J]，包装工程，2005，Vol．26，No．3：40-41
[13] Frechet J.M.J. Functional polymers and dendfimers:reactivity, molecular architecture, and interracial energy[J], Science, 1994, 263:1710-1715
[14] Jikei M., Kakimoto M-A. Hyperbrached polymers: a promising new class of materials[J], Prog. Poly. Sci., 2001, 26:1233-1285
[15] Flory P.J.J.Molecular size distribution in three dimensional polymers. Ⅳ. Branched polymers containing A-R-B_(f-l) type units[J], Am. Chem. Soc., 1952, 75:2718
[16] Buhleier E., Wehner W.,Vogtle F. Synthesis[J], 1978:155-158
[17] 王国建，颜德岳．高支化聚合物的合成与表征[J]，高分子通讯，1999，2：1-10
[18] Tomalia D.A., Hall M., Hedstrand D.M. Starburt Dendrimers 3. The Importance of Branch Junction Symmetry in the Development of Topological Shell Molecules[J], J. Am. Chem. Soc., 1987, 109:1601
[19] Uchida H., Kabe Y., Yoshino K., Kawamata T., Masamune S. General Strategy for the Systematic Synthesis of Oligosiloxanes Silicone Dendrmers[J], J.Am.Chem.Soc., 1990, 112:7077
[20] 施文芳，黄宏．超支化聚合物研究进展[J]，高等学校化学学报，1997，18：1398-1405
[21] 魏焕郁，施文芳．超支化聚合物的结构特征、合成及其应用[J]，高等学校化学学报，2001．22：338-344
[22] Owen A. Matthews, Andrew N.Shipway, J.Fraser Stoddart. Dendrimers-branching out from curiosities into new thechnologies[J], Prog. Poly. Sci.,1998, 23, 1-56
[23] (a)谭惠民，罗运军．树枝形聚合物[M]，化学工业出版社，2002：23-25 (b) Hawker C.J., Frechet J.M.J. Preparation of polymers with controlled molecular architecture a new convergent approach to dendritic macromolecules[J],J.Am.Chem.Soc., 1990, 112:7638-7647
[24] Mourey T.H., Turner S.R., Rubinstein M., Wooley K.L., Frechet J.M.J., Hawker C.J., Unique behavior of bendritic macromolecules:intrinsic viscosity of polyether dendrimers, Macromolecules, 1992, 25, 2401-2408
[25] (a)谭惠民，罗运军．树枝形聚合物[M]，化学工业出版社，2002：16-19 (b) Wooley K.L., Frechet J.M.J. Influnce of shape on thereactivity and properties of dendritic, hyperbranched, and linear aromatic polyesters, Polymer[J], 1994, 35:4489-4495
[26] Malmstroem E., Johansson M., Hult A. Hyperbranched aliphatic polyeaster, Macromolecules[J], 1995, 28:1698-1703
[27] Kim Y.H., Webster O.W. Water-soluble hyperbranched polyphenylene: "aunimolecular micelle"[J], J. Am. Chem. Soc., 1990, 12:4592
[28] Kim Y.H., Webster O.W. Hyperbranched polyphenlenes[J], Macromolecules, 1992, 25:5561-5572
[29] Diudea M V, Parv B. Molecular topology 25 hyper-wiener index of dendrimers[J]. J Chem Inf Comput Sci. 1995, 35:1015-1018
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