自催化型萜烯基环氧树脂多元醇水分散体的制备与表征
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摘要
利用N-苄基乙醇胺(BEA)或二乙醇胺(DEA)改性萜烯-马来酐缩水甘油酯型环氧树脂(TME),制备了分子结构中含有叔胺基团的自催化型萜烯基环氧树脂多元醇(TBP或TDP)。通过分析合成反应的影响因素,确定了制备环氧树脂基多元醇TBP和TDP的最佳反应条件:反应温度80℃,反应时间1 h,溶剂乙醇用量为反应物总质量的10%。采用傅里叶红外(FT-IR)光谱、核磁共振(NMR)光谱及凝胶渗透色谱(GPC)表征了环氧树脂基多元醇及其水分散体(WTBP或WTDP)的化学结构和相对分子质量分布,以激光粒径仪考察了中和度对多元醇水分散体粒径分布的影响。当中和度为90%时,多元醇水分散体(WTBP和WTDP)粒径为多峰分布,分散体稳定性较差;当中和度为100%时,水分散体粒径为单峰分布,达到纳米级分散。
Self-catalyzing polyol dispersions with tertiary amine groups(TBP or TDP) were prepared by reaction of terpinene-maleic ester based epoxy resin(TME) with N-benzylethanolamine(BEA) or diethanolamine(DEA). The tertiary amine groups in the polyol structure could catalyze the crosslinking reaction between hydroxyl group and isocyanate group in the crosslinking reaction of polyol dispersions and polyisocyanate to form two-component waterborne polyurethane. Suitable synthesis conditions were obtained by studying the effect factors of synthesis reaction. The optimum reaction conditions of the preparation of TME based polyols TBP or TDP were reaction at 80 ℃ for 1 h with using ethanol as solvent and the amount of ethanol was about 10% of the total quality of reactants. The chemical structures of the polyols were characterized by FT-IR and NMR and the average molecular weight of the polyoys was determined by GPC. The effect of neutralization degree on the particle size distribution of polyol dispersions was investigated by laser particle sizer. When the neutralization degree was 90%, the particle size distribution of polyol dispersions was multimodal and the stability of the dispersions was poor. However, when the neutralization degree was 100%, the particle size distribution of the dispersions was unimodal and achieved nanoscale dispersion.
Self-catalyzing polyol dispersions with tertiary amine groups(TBP or TDP) were prepared by reaction of terpinene-maleic ester based epoxy resin(TME) with N-benzylethanolamine(BEA) or diethanolamine(DEA). The tertiary amine groups in the polyol structure could catalyze the crosslinking reaction between hydroxyl group and isocyanate group in the crosslinking reaction of polyol dispersions and polyisocyanate to form two-component waterborne polyurethane. Suitable synthesis conditions were obtained by studying the effect factors of synthesis reaction. The optimum reaction conditions of the preparation of TME based polyols TBP or TDP were reaction at 80 ℃ for 1 h with using ethanol as solvent and the amount of ethanol was about 10% of the total quality of reactants. The chemical structures of the polyols were characterized by FT-IR and NMR and the average molecular weight of the polyoys was determined by GPC. The effect of neutralization degree on the particle size distribution of polyol dispersions was investigated by laser particle sizer. When the neutralization degree was 90%, the particle size distribution of polyol dispersions was multimodal and the stability of the dispersions was poor. However, when the neutralization degree was 100%, the particle size distribution of the dispersions was unimodal and achieved nanoscale dispersion.
引文
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[2]WANG L,XU F,LI H X,et al. Preparation and stability of aqueous acrylic polyol dispersions for two-component waterborne polyurethane[J]. Journal of Coatings Technology and Research,2017,14(1):215-223.
[3]WU G M,LIU G F,CHEN J,et al. Preparation and properties of thermoset composite films from two-component waterborne polyurethane with low loading level nanofibrillated cellulose[J]. Progress in Organic Coatings,2017,106:170-176.
[4]WICKS Z,WICKS D,ROSTHAUSER J. Two package waterborne urethane systems[J]. Progress in Organic Coatings,2002,44(2):161-183.
[5]巫辉,夏亚敏,明三军. 双组分水性聚氨酯的成膜过程[J]. 聚氨酯工业,2005,20(1):10-12. WU H,XIA Y M,MING S J. Film formation of two-component waterborne polyurethanes[J]. Polyurethane Industry,2005,20(1):10-12.
[6]任娜娜,余喜红,宇研,等. 催化剂对水性双组分聚氨酯涂料的成膜及性能的影响[J]. 涂料工业,2010,40(3):27-31. REN N N,YU X H,YU Y,et al. Influences of catalysts on the film formation and performance of 2K waterborne polyurethane[J]. Paint & Coatings Industry,2010,40(3):27-31.
[7]HE Z A,BLANK W J,PICCI M E. A selective catalyst for two-component waterborne polyurethane coatings[J]. Journal of Coatings Technology,2002,74(930):31-36.
[8]王庭慰,陈存友,狄超,等. 水性聚氨酯涂料催化剂研究进展[J]. 电镀与涂饰,2010,41(8):58-61. WANG T W,CHEN C Y,DI C,et al. Research progress on catalysts of waterborne polyurethane coating[J]. Electroplating & Finishing,2010,41(8):58-61.
[9]WERNER J. Advances in catalysis for organic coatings[J]. Chimia International Journal for Chemistry,2002,56(5):191-196.
[10]VAN MARIS R. Polyurethane catalysis by tertiary amines[J]. Journal of Cellular Plastics,2005,41:305-322.
[11]JANG J K. Amines as occupational hazards for visual disturbance[J]. Industrial Health,2016,54(2):101-115.
[12]FOLEY G D,TUCKER S P,COOPER C V. Analysis of air for tertiary amine catalysts used in the polyurethane foam industry[J]. American Industrial Hygiene Association Journal,1991,52(12):664-665.
[13]吴国民,孔振武,储富祥.氢化萜烯马来酸酐合成环氧树脂的研究[J].林产化学与工业,2007,27(3):57-62. WU G M,KONG Z W,CHU F X. Synthesis of epoxy resin from hydrogenated terpinene-maleic anhydride[J]. Chemistry and Industry of Forest Products,2007,27(3):57-62.
[14]孙曼灵. 环氧树脂应用原理与技术[M]. 北京:机械工业出版社,2002. SUN M L. Application Principle and Technology of Epoxy Resin[M]. Beijing:China Machine Press,2002.