紫外光固化环氧肉桂酸酯树脂的合成与表征
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摘要
采用邻甲酚醛环氧树脂与肉桂酸反应合成了一种新型的紫外光固化环氧肉桂酸酯树脂(ECA),利用羧基打开环氧引入部分双键,然后加入四氢邻苯二甲酸酐(THPA)与第1步反应生成的羟基反应,引入另一种不饱和键和一定量的羧基。由于肉桂酸中的双键只对紫外光敏感,所以第1步酯化反应不需要添加阻聚剂。采用核磁共振氢谱、红外光谱和紫外可见分光光度计对产物的结构和性能进行了表征,并采用实时红外光谱法研究了ECA的光聚合动力学,随着光强和光引发剂用量的增加,双键转化率逐渐增大,最佳条件分别是25.0 mW/cm~2的光强和4%的引发剂用量,而随着肉桂酸含量的增加,双键转化率逐渐降低。相应的光固化膜表现出良好的附着力、较高的光泽度,在光泽度要求较高的阻焊油墨和光敏涂料方面有较好的应用前景。
A novel UV-curable epoxy cinnamic resin(ECA) was synthesized via firstly reacting O-cresolformaldehyde epoxy resin(EOCN) with cinnamic acid, the carboxyl groups opened epoxy groups, and then partial double bonds were introduced. After that, tetrahydrophthalic anhydride(THPA) was added to the system to react with hydroxyl groups produced in the first step, so another kind of unsaturated bonds and certain amount carboxyl groups were introduced. Since the double bond in cinnamic acid is only sensitive to ultraviolet light, the first esterification reaction does not require the addition of a polymerization inhibitor. The structure and properties of the product were characterized by ~1H-NMR, FT-IR and UV-Vis. The photopolymerization kinetics of ECA was studied by real-time infrared spectroscopy. As the intensity of light and the amount of photoinitiator increase, the double bond conversion rate gradually increases, and the optimum dosage is 25.0 mW/cm~2 and 4%, respectively. And as the cinnamic acid content increases, the double bond conversion rate gradually decreases. The results show that the cured film of the ECA system possesses an excellent adhesive force and high glossiness, and this kind of novel ECA resin has potential application in industry, especially in solder resist ink and photosensitive coating with the requirements of high glossiness.
A novel UV-curable epoxy cinnamic resin(ECA) was synthesized via firstly reacting O-cresolformaldehyde epoxy resin(EOCN) with cinnamic acid, the carboxyl groups opened epoxy groups, and then partial double bonds were introduced. After that, tetrahydrophthalic anhydride(THPA) was added to the system to react with hydroxyl groups produced in the first step, so another kind of unsaturated bonds and certain amount carboxyl groups were introduced. Since the double bond in cinnamic acid is only sensitive to ultraviolet light, the first esterification reaction does not require the addition of a polymerization inhibitor. The structure and properties of the product were characterized by ~1H-NMR, FT-IR and UV-Vis. The photopolymerization kinetics of ECA was studied by real-time infrared spectroscopy. As the intensity of light and the amount of photoinitiator increase, the double bond conversion rate gradually increases, and the optimum dosage is 25.0 mW/cm~2 and 4%, respectively. And as the cinnamic acid content increases, the double bond conversion rate gradually decreases. The results show that the cured film of the ECA system possesses an excellent adhesive force and high glossiness, and this kind of novel ECA resin has potential application in industry, especially in solder resist ink and photosensitive coating with the requirements of high glossiness.
引文
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[2] Shen L,Li Y,Zheng J,et al.Modified epoxy acrylate resin for photocurable temporary protective coatings[J].Prog.Org.Coat.,2015,89:17-25.
[3] Liu R,Zhang X P,Zhu J J,et al.UV-curable coatings from multiarmed cardanol-based acrylate oligomers[J].ACS Sustain.Chem.Eng.,2015,3:1313-1320.
[4] 刘敬成,贾秀丽,张胜文,等.聚氨酯丙烯酸酯改性环氧树脂的结构与性能[J].高分子材料科学与工程,2011,27(8):87-90.Liu J C,Jia X L,Zhang S W,et al.Structure and properties of epoxy resins modified by polyurethane acrylate[J].Polymer Materials Science & Engineering,2011,27(8):87-90.
[5] Sinsermsuksakul R,Bualek S.Spectroscopic studies of photocrosslinking of polysiloxane containing cinnamic esters[J].J.Mol.Struct.,1995,348:175-178.
[6] Gao Q Z,Li H Q,Zeng X R.Preparation and characterization of UV-curable hyperbranched polyurethane acrylate[J].J.Coat.Technol.Res.,2011,8:61-66.
[7] Sung S J,Cho K Y,Yoo J H,et al.Dimerization behavior of cinnamate group attached to flexible polymer backbone and its effect on the molecular orientation[J].Chem.Phys.Lett.,2004,394:238-243.
[8] Sung S J,Cho K Y,Hah H,et al.Two different reaction mechanisms of cinnamate side groups attached to the various polymer backbones[J].Polymer,2006,47:2314-2321.
[9] Zhang X H,Wang H,Wang L,et al.A photosensitive copolymer for the gate insulator of organic thin-film transistors[J].Appl.Phys.,A,2010,99:85-91.
[10] Lecamp L,Youssef B,Bunel C,et al.Photoinitiated polymerization of a dimethacrylate oligomer:1.Influence of photoinitiator concentration,temperature and light intensity[J].Polymer,1997,38:6089-6096.
[11] Sun F,Jiang S L,Liu J.Study on cationic photopolymerization reaction of epoxy polysiloxane[J].Nucl.Instrum.Meth.,B,2007,264:318-322.
[12] Nagata M,Hizakae S.Synthesis and characterization of photocrosslinkable biodegradable polymers derived from 4-hydroxycinnamic acid[J].Macromol.Biosci.,2003,3:412-419.