基于Diels-Alder结构的光固化自修复聚氨酯制备及性能研究
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- 英文论文题名：Preparation and Properties of UV-curable Polyurethane Coatings Based on Diels-Alder Structure
- 论文作者：梁红波 ; 柯小雪
- 年：2016
- 作者机构：南昌航空大学材料科学与工程学院;
- 论文关键词：热可逆 ; UV固化 ; 聚氨酯 ; Diels-Alder
- 英文论文关键词：Thermal reversible ; Polyurethane ; UV curable ; Diels-Alder
- 会议召开时间：2016-09-07
- 会议录名称：2016第十七届中国辐射固化年会暨首届安庆市化工新材料产业高峰论坛论文报告集
- 语种：中文
- 分类号：TQ630.1
- 学会代码：GGXH
- 会议名称：2016第十七届中国辐射固化年会暨首届安庆市化工新材料产业高峰论坛
- 会议地点：中国安徽安庆
- 主办单位：中国感光学会辐射固化专业委员会、安庆市政府
- 学会名称：中国感光学会辐射固化专业委员会
- 页数：9
- 文件大小：906k
- 原文格式：O
- 会议级别：全国
摘要
本文合成了一系列基于Diels-Alder(DA)结构的新型聚氨酯丙烯酸酯树脂,其具有潜在的热可逆性和可光固化性能。该涂层体系可在35 s内经由紫外光辐照固化,最终丙烯酸酯双键的转化率均为80%以上,凝胶含量也均在80%以上,已形成了高度交联的大分子网络。光固化后的各涂层经测试显示出优良的物理性能:硬度2H以上,柔韧性0.5mm,附着力0级。升温/降温红外光谱、热分析等证实了涂层中DA结构的热可逆性具有良好的可重复能力。基于上述所有的特性,本文基于一把DA结构"钥匙"设计的可紫外光固化的聚氨酯涂层,其高度交联的大分子网络在热效应下可以不断地在交联-线性结构间切换,有望改善成为新型的可溶、可熔或可塑的光固化材料,从而拓展紫外光固化聚氨酯涂层的应用。
A series of polyurethane acrylate resins based on the thermal reversible DA structure were successfully synthesized,which could be UV cured and had a potential thermal reversibility.All the resin systems can be substantially cured into the coatings by UV irradiation within 35 s,the final conversion rates of acrylate C=C are above 80%,and the gel contents are above 80%,indicating the formation of highly crosslinked macromolecular networks.The UV cured coatings show excellent physical properties:hardness(>2H),flexibility(0.5 mm),and adhesion(0 level).FTIR with increasing/decreasing/constant temperature,differential scanning calorimetry(DSC)and dynamic mechanical analysis(DMA) were conducted to study the thermal reversible mechanism of UV cured polyurethane coatings,which results indicated the thermal reversibility of DA structure was well-repeatable.With all above features,the well-designed UV curable polyurethane coatings based on a "key" of DA structure with highly crosslinked macromolecular network,which can be constantly switched between crosslinked and linear state under the heating effect,are expected to be improved to novel soluble,fusible or plastic UV curing materials,thus expanding the application of UV curable polyurethane coating.
A series of polyurethane acrylate resins based on the thermal reversible DA structure were successfully synthesized,which could be UV cured and had a potential thermal reversibility.All the resin systems can be substantially cured into the coatings by UV irradiation within 35 s,the final conversion rates of acrylate C=C are above 80%,and the gel contents are above 80%,indicating the formation of highly crosslinked macromolecular networks.The UV cured coatings show excellent physical properties:hardness(>2H),flexibility(0.5 mm),and adhesion(0 level).FTIR with increasing/decreasing/constant temperature,differential scanning calorimetry(DSC)and dynamic mechanical analysis(DMA) were conducted to study the thermal reversible mechanism of UV cured polyurethane coatings,which results indicated the thermal reversibility of DA structure was well-repeatable.With all above features,the well-designed UV curable polyurethane coatings based on a "key" of DA structure with highly crosslinked macromolecular network,which can be constantly switched between crosslinked and linear state under the heating effect,are expected to be improved to novel soluble,fusible or plastic UV curing materials,thus expanding the application of UV curable polyurethane coating.
引文
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[12]邢锦娟,刘琳,钱建华等.N-(取代基)马来酰亚胺的合成及应用研究进展[J].化学试剂,2009,05:352-354.
[13]Gandini A.The furan/maleimide Diels-Alder reaction:A versatile click-unclick tool in macromolecular synthesis[.I].Progress in Polymer Science,2013,38(1):1-29.
[14]Lu X,Fei G,Xia H,et al.Ultrasound healable shape memory dynamic polymers[J].Journal of Materials Chemistry A,2014,2(38):16051-16060.
[15]Syrett J A,Mantovani G,Barton W R S,et al.Self-healing polymers prepared via living radical polymerisation[J].Polym Chem,2010,1(1):102-106.
[16]Heath W H,Pahnieri F,Adams J R,et al.Degradable Cross-Linkers and Strippable Imaging Materials for Step-and-Flash Imprint Lithography[J].Macromolecules,2007,41(3):719-726.
[17]Liao F,Zeng X,Li H,et al.Synthesis and properties of UV curable polyurethane acrylates based on two different hydroxyethyl acrylates[J].Journal of Central South University,2012,19:911-917.
[2]Xu H,Meng F,Zhong Z.Reversibly crosslinked temperature-responsive nano-sized polymersomes:synthesis and triggered drug release[J].Journal of Materials Chemistry,2009,19(24):4183-4190.
[3]Tesoro G C,Sastri V.Reversible crosslinking in epoxy resins.I.Feasibility studies[J].Journal of applied polymer science,1990,39(7):1425-1437.
[4]Canary S A,Stevens M P.Thermally reversible crosslinking of polystyrene via the furan-maleimide Diels-Alder reaction[J].Journal of Polymer Science Part A:Polymer Chemistry,1992,30(8):1755-1760.
[5]Philp D,Stoddart J F.Self-assembly in natural and unnatural systems[J].Angewandte Chemie International Edition in English,1996,35(11):1154-1196.
[6]Cerny J,Hobza P.Non-covalent interactions in biomacromolecules[J].Physical Chemistry Chemical Physics,2007,9(39):5291-5303.
[7]Rowan S J,Cantrill S J,Cousins G R L,et al.Dynamic covalent chemistry[J].Angewandte Chemie International Edition,2002,41(6):898-952.
[8]Maeda T,Otsuka H,Takahara A.Dynamic covalent polymers:reorganizable polymers with dynamic covalent bonds[J].Progress in Polymer Science,2009,34(7):581-604.
[9]Jackson A W,Fulton D A.Making polymeric nanoparticles stimuli-responsive with dynamic covalent bonds[J].Polymer Chemistry,2013,4(1):31-45.
[10]Yoon H J,Chun I S,Kim J P,et al.Ionic interactions of microspheres.Reversible coating of Prussian blue nanoparticles on the submicrospheres of platinum(II)complexes[J].Materials Letters,2008,62(17):2883-2886.
[11]Hou W,Wang Q.UV-driven reversible switching of a polystyrene/titania nanocomposite coating between superhydrophobicity and superhydrophilicity[J],Langmuir,2009,25(12):6875-6879.
[12]邢锦娟,刘琳,钱建华等.N-(取代基)马来酰亚胺的合成及应用研究进展[J].化学试剂,2009,05:352-354.
[13]Gandini A.The furan/maleimide Diels-Alder reaction:A versatile click-unclick tool in macromolecular synthesis[.I].Progress in Polymer Science,2013,38(1):1-29.
[14]Lu X,Fei G,Xia H,et al.Ultrasound healable shape memory dynamic polymers[J].Journal of Materials Chemistry A,2014,2(38):16051-16060.
[15]Syrett J A,Mantovani G,Barton W R S,et al.Self-healing polymers prepared via living radical polymerisation[J].Polym Chem,2010,1(1):102-106.
[16]Heath W H,Pahnieri F,Adams J R,et al.Degradable Cross-Linkers and Strippable Imaging Materials for Step-and-Flash Imprint Lithography[J].Macromolecules,2007,41(3):719-726.
[17]Liao F,Zeng X,Li H,et al.Synthesis and properties of UV curable polyurethane acrylates based on two different hydroxyethyl acrylates[J].Journal of Central South University,2012,19:911-917.