聚甲基丙烯酰亚胺树脂的分子结构研究
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摘要
以聚甲基丙烯酰亚胺(PMI)泡沫分子结构为研究对象,通过对其原位加热的傅里叶变换红外(FR-IR)分析,发现样品Cascell IH型PMI泡沫预聚物在160℃/2 h处理条件下,-COOH与-CN基团就开始发生亚胺化反应;200℃/2 h处理后,-NH伸缩振动的峰型和峰面积不再发生改变,-C=N伸缩振动峰出现;通过碳核磁谱图分析发现,Cascell IH泡沫预聚物不存在相邻的-COOH;结果说明Cascell IH泡沫预聚物经过高温处理后只会发生成环的亚胺化反应和形成梯形的环化反应。通过激光光散射(LLS)和凝胶渗透色谱仪(GPC)测定Cascell IH分子量与分布,结果显示都出现双峰,表明Cascell IH泡沫预聚物的分子量较大且分布较宽,符合自由基共聚合的特点。
In this paper,the molecular structure of polymethacrylimide(PMI) was studied.Based on the Fourier transform infrared(FR-IR) analysis in situ heating,it was found that the Casecell IH PMI foam prepolymer began the reaction of-COOH and-CN groups turning hexahydric imide ring in the condition of 160 ℃/2 h.The-NH stretching vibration peak type and area were no longer changed,and-C = N stretching vibration peak appeared after treatment at 200℃/2 h.The results of13 C NMR showed that the adjacent-COOH groups were not included in Casecell IH PMI prepolymer.PMI foam prepolymer only underwent ring formation of the imidization reaction and trapezoidal reaction at high temperature.The molecular weight and distribution of Casecell IH were measured by laser light scattering(LLS) and gel permeation chromatography(GPC).The results showed that the weight average molecular weight appeared double peaks,indicating that the molecular weight of Casecell IH perpolymer was larger and the distribution wide,consistent with the characteristics of free radical copolymerization.
In this paper,the molecular structure of polymethacrylimide(PMI) was studied.Based on the Fourier transform infrared(FR-IR) analysis in situ heating,it was found that the Casecell IH PMI foam prepolymer began the reaction of-COOH and-CN groups turning hexahydric imide ring in the condition of 160 ℃/2 h.The-NH stretching vibration peak type and area were no longer changed,and-C = N stretching vibration peak appeared after treatment at 200℃/2 h.The results of13 C NMR showed that the adjacent-COOH groups were not included in Casecell IH PMI prepolymer.PMI foam prepolymer only underwent ring formation of the imidization reaction and trapezoidal reaction at high temperature.The molecular weight and distribution of Casecell IH were measured by laser light scattering(LLS) and gel permeation chromatography(GPC).The results showed that the weight average molecular weight appeared double peaks,indicating that the molecular weight of Casecell IH perpolymer was larger and the distribution wide,consistent with the characteristics of free radical copolymerization.
引文
[1]杨士勇,胡爱军,王志媛,等.一种聚丙烯酰亚胺类泡沫材料及其制备方法:CN101328243[P/OL].2008-12-24.http://zgzl.infoeach.com/item-744600.html.
[2]胡爱军,王志媛,金诤,等.泡沫夹芯型吸波隐身结构复合材料的发展趋势[J].宇航材料工艺,2009,39(1):1-4.
[3]杨士勇,胡爱军,陶志强,等.阻燃性聚甲基丙烯酰亚胺泡沫材料及其制备方法与应用:CN101463107[P/OL].2009-06-24.http://zgzl.infoeach.com/goods-776715.html.
[4]陈一民,何斌.聚甲基丙烯酰亚胺(PMI)泡沫制备及结构表征[J].化工新型材料,2007,35(2):32-34.
[5]Seibert H F.PMI Rigid Foam Plastics[J].KUNSTOFFE,1999,89(4):32-33.
[6]胡培.PMI泡沫:夹层结构的芯材[J].玻璃钢,2003(2):9-17.
[7]佘烨.作芯材用的硬聚甲基丙烯酰亚胺泡沫材料[J].国外机车车辆工艺,2000(5):46-49.
[8]陈挺,张广成,刘铁民,等.丙烯腈/甲基丙烯酸共聚物泡沫塑料的制备与表征[J].中国塑料,2006,20(3):72-75.
[9]曹明法,胡培.船用玻璃钢/复合材料阶层结构中的泡沫芯材[J].江苏船舶,2004,21(2):3-6.
[10]Seibert H.F.PMI Foam Cores Find Further Applications[J].Reinforced Plastics,2000,44(1):36-38.
[11]屈晓玲.新型PMI泡沫[J].黑龙江科技信息,2003(10):104.
[12]余烨译.作芯材用的硬聚甲基丙烯酰亚胺泡沫塑料[J].国外机车车辆工艺,2000(3):46-49.
[13]朱诚身.聚合物结构分析[M].北京:科学出版社,2005:40.
[14]周子南,孝延文,高新风,等.聚甲基丙烯酸乙酯链结构核磁共振(NMR)研究[J].高分子学报,1992(3):321-327.
[15]Sabine S.,Werner G.,Norbert R.,et al.Method for Producing Block-shaped Polymethacryl imide Foamed Materials:US6670405[P/OL].2003-12-30.http://www.freepatentsonline.com/6670405.pdf.
[2]胡爱军,王志媛,金诤,等.泡沫夹芯型吸波隐身结构复合材料的发展趋势[J].宇航材料工艺,2009,39(1):1-4.
[3]杨士勇,胡爱军,陶志强,等.阻燃性聚甲基丙烯酰亚胺泡沫材料及其制备方法与应用:CN101463107[P/OL].2009-06-24.http://zgzl.infoeach.com/goods-776715.html.
[4]陈一民,何斌.聚甲基丙烯酰亚胺(PMI)泡沫制备及结构表征[J].化工新型材料,2007,35(2):32-34.
[5]Seibert H F.PMI Rigid Foam Plastics[J].KUNSTOFFE,1999,89(4):32-33.
[6]胡培.PMI泡沫:夹层结构的芯材[J].玻璃钢,2003(2):9-17.
[7]佘烨.作芯材用的硬聚甲基丙烯酰亚胺泡沫材料[J].国外机车车辆工艺,2000(5):46-49.
[8]陈挺,张广成,刘铁民,等.丙烯腈/甲基丙烯酸共聚物泡沫塑料的制备与表征[J].中国塑料,2006,20(3):72-75.
[9]曹明法,胡培.船用玻璃钢/复合材料阶层结构中的泡沫芯材[J].江苏船舶,2004,21(2):3-6.
[10]Seibert H.F.PMI Foam Cores Find Further Applications[J].Reinforced Plastics,2000,44(1):36-38.
[11]屈晓玲.新型PMI泡沫[J].黑龙江科技信息,2003(10):104.
[12]余烨译.作芯材用的硬聚甲基丙烯酰亚胺泡沫塑料[J].国外机车车辆工艺,2000(3):46-49.
[13]朱诚身.聚合物结构分析[M].北京:科学出版社,2005:40.
[14]周子南,孝延文,高新风,等.聚甲基丙烯酸乙酯链结构核磁共振(NMR)研究[J].高分子学报,1992(3):321-327.
[15]Sabine S.,Werner G.,Norbert R.,et al.Method for Producing Block-shaped Polymethacryl imide Foamed Materials:US6670405[P/OL].2003-12-30.http://www.freepatentsonline.com/6670405.pdf.