甲醚化三聚氰胺甲醛树脂的合成与表征
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摘要
以四羟甲基三聚氰胺、甲醇为原料,单因素法优化甲醚化三聚氰胺甲醛树脂合成条件,并对树脂结构进行了~1H-NMR、FT-IR、GPC分析表征。结果表明,树脂制备较优工艺如下:四羟甲基三聚氰胺与甲醇物质的量比为1.0∶6.5,醚化温度45℃,pH 4.0,醚化保温时间50~60 min,醚化后70℃下减压蒸馏45 min脱醇脱水,得到的树脂游离甲醛质量分数≤0.5%,粘度4 000~6 000 m Pa·s,pH 8.50~9.50时,贮存时间>180 d,树脂水溶性好。树脂含羟甲基、亚氨基、甲氧基等特征官能团,平均分子质量380左右。
The methyl etherified melamine formaldehyde resin was synthesized by using tetrahydroxymethyl melamine and methanol as raw materials and the etherification reaction conditions were optimized by single factor method. The structure of the product resin was characterized by~1 H-NMR,FT-IR and GPC. The resin optimized synthetic conditions were as followed :molar ratio of tetrahydroxymethyl melamine to methanol 1. 0 ∶ 6. 5,ether reaction temperature 45 ℃,pH value 4. 0,ether reaction time 50-60 min. After etherification the alcohol and water were removed by distillation at 70 ℃ for 45 min under reduced pressure. The obtained resin had a free formaldehyde content less than 0. 5 %,and a viscosity of 4 000 to6 000 m Pa ·s. The resin could be stored at pH of 8. 50 to 9. 50 for 180 d or more. The resin had good water solubility. The resin contained the characteristic functional groups such as methylol group,imino group and methoxy group,and had an average molecular weight of about 380.
The methyl etherified melamine formaldehyde resin was synthesized by using tetrahydroxymethyl melamine and methanol as raw materials and the etherification reaction conditions were optimized by single factor method. The structure of the product resin was characterized by~1 H-NMR,FT-IR and GPC. The resin optimized synthetic conditions were as followed :molar ratio of tetrahydroxymethyl melamine to methanol 1. 0 ∶ 6. 5,ether reaction temperature 45 ℃,pH value 4. 0,ether reaction time 50-60 min. After etherification the alcohol and water were removed by distillation at 70 ℃ for 45 min under reduced pressure. The obtained resin had a free formaldehyde content less than 0. 5 %,and a viscosity of 4 000 to6 000 m Pa ·s. The resin could be stored at pH of 8. 50 to 9. 50 for 180 d or more. The resin had good water solubility. The resin contained the characteristic functional groups such as methylol group,imino group and methoxy group,and had an average molecular weight of about 380.
引文
[1]魏雨.甲醚化三聚氰胺树脂交联剂的合成与应用研究[D].郑州:郑州大学,2006.
[2]吴兆强,曾繁森,刘春英,等.磺化三聚氰胺甲醛树脂的合成与水溶性稳定性研究[J].高分子材料科学与工程,1998,14(4):103-106.
[3]孙立水,李少香,史新研,等.涂料用高醚三聚氰胺甲醛树脂的合成[J].中国涂料,2006,21(2):19-21.
[4]杨惊,李小瑞.高固含量醚化蜜胺甲醛树脂制备及其稳定性[J].热固性树脂,2005,20(1):12-14,21.
[5]张友恭,杨秀芳,李运涛.高稳定性多羟甲基三聚氰胺初缩体的合成[J].精细化工,1996,13(5):32-34.
[6]Tsvetkov V E,Zueva Yu M.Synthesis and properties of modified melamine formaldehyde impregnating oligomers[J].Polymer Science,Series D,Glues and Sealing Materials,2011,4(3):164-166.
[7]Martin Kohlmayr,Gerhard Zuckersttter,Andreas Kandelbauer.Modification of melamine-formaldehyde resins by substances from renewable resources[J].Journal of Applied Polymer Science,2012,124(6):4416-4423.
[8]孙巧路.高甲醚化三聚氰胺甲醛树脂的合成与表征[D].杭州:浙江大学,2015
[9]Ludwigshsfen BASF Aktiengesellschaft.Continuous Method for Producing Highly Methylolated Melamine and Etherified Melamine Formaldehyde Resins:US2010/0113693A1[P].1984-01-10.
[10]江苏国立化工科技有限公司.提高六甲氧基甲基三聚氰胺树脂醚化度方法:CN101696258A[P].2010-04-21.
[11]陈聪.三聚氰胺甲醛树脂合成工艺优化及改性应用研究[D].郑州:郑州大学,2012.
[12]刘泽,赵科,孙培勤.干法制备高醚化三聚氰胺树脂[J].精细化工,2015,32(1):78-81.
[13]刘平飞.环保型醚化蜜胺树脂的制备[J].精细石油化工进展,2012,13(2):40-43.
[14]Lukowsky D.Influence of the formaldehyde content of waterbased melamine formaldehyde resins on physical properties of Scots pine impregnated therewith.European Journal of Wood and Wood Products,2002,60(5):349-355.
[2]吴兆强,曾繁森,刘春英,等.磺化三聚氰胺甲醛树脂的合成与水溶性稳定性研究[J].高分子材料科学与工程,1998,14(4):103-106.
[3]孙立水,李少香,史新研,等.涂料用高醚三聚氰胺甲醛树脂的合成[J].中国涂料,2006,21(2):19-21.
[4]杨惊,李小瑞.高固含量醚化蜜胺甲醛树脂制备及其稳定性[J].热固性树脂,2005,20(1):12-14,21.
[5]张友恭,杨秀芳,李运涛.高稳定性多羟甲基三聚氰胺初缩体的合成[J].精细化工,1996,13(5):32-34.
[6]Tsvetkov V E,Zueva Yu M.Synthesis and properties of modified melamine formaldehyde impregnating oligomers[J].Polymer Science,Series D,Glues and Sealing Materials,2011,4(3):164-166.
[7]Martin Kohlmayr,Gerhard Zuckersttter,Andreas Kandelbauer.Modification of melamine-formaldehyde resins by substances from renewable resources[J].Journal of Applied Polymer Science,2012,124(6):4416-4423.
[8]孙巧路.高甲醚化三聚氰胺甲醛树脂的合成与表征[D].杭州:浙江大学,2015
[9]Ludwigshsfen BASF Aktiengesellschaft.Continuous Method for Producing Highly Methylolated Melamine and Etherified Melamine Formaldehyde Resins:US2010/0113693A1[P].1984-01-10.
[10]江苏国立化工科技有限公司.提高六甲氧基甲基三聚氰胺树脂醚化度方法:CN101696258A[P].2010-04-21.
[11]陈聪.三聚氰胺甲醛树脂合成工艺优化及改性应用研究[D].郑州:郑州大学,2012.
[12]刘泽,赵科,孙培勤.干法制备高醚化三聚氰胺树脂[J].精细化工,2015,32(1):78-81.
[13]刘平飞.环保型醚化蜜胺树脂的制备[J].精细石油化工进展,2012,13(2):40-43.
[14]Lukowsky D.Influence of the formaldehyde content of waterbased melamine formaldehyde resins on physical properties of Scots pine impregnated therewith.European Journal of Wood and Wood Products,2002,60(5):349-355.