聚氨酯预聚体改性酚醛泡沫的研究进展
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摘要
酚醛泡沫是近几年发展起来的一类新型泡沫塑料,具有阻燃、低烟、自熄等独特性能,传统酚醛泡沫是由酚醛树脂在固化剂、发泡剂、表面活性剂及其他助剂存在条件下,同时发泡、固化制成。固化后的酚醛树脂因自身结构的缺陷,从而使得制备的酚醛泡沫存在延伸率低、硬度大、耐冲击性差、粉碎率高等问题,限制了其产品应用及快速发展。因此对酚醛树脂及其泡沫进行改性研究以降低其脆性,提高其韧性,具有一定理论和现实意义。文中阐述了酚醛泡沫的增韧方法,着重介绍了直接混合法、NCO链端预聚体法以及OH链端预聚体法等3种聚氨酯预聚体增韧酚醛泡沫的方法,并分析了聚氨酯预聚体增韧酚醛泡沫的增韧机理。最后总结了聚氨酯预聚体改性酚醛泡沫存在的问题。
Phenolic foams(PFs),made from the chemical foaming of phenolic resins after the addition of additives(e.g. hardening agent,foam stabilizer and foaming agent),are polymeric materials with many advantages such as extremely high flame retardancy,low smoke quantity,and self-extinguishing. However,the application of PFs is severely limited by their brittleness and high pulverizability due to their unique molecular structure. To further exploit the desirable properties of PFs,it's necessary to improve the toughness of PFs and reduce the brittleness and pulverizability. This paper reviewed the main toughening methods of PFs,PFs toughened with polyurethane prepolymer(PUP)(PFs toughened by direct mixing method,PFs toughened with NCO-terminated PUP and OH-terminated PUP) as well as the toughening mechanism was introduced. In addition,the problems of PFs toughened with PUP were summarized.
Phenolic foams(PFs),made from the chemical foaming of phenolic resins after the addition of additives(e.g. hardening agent,foam stabilizer and foaming agent),are polymeric materials with many advantages such as extremely high flame retardancy,low smoke quantity,and self-extinguishing. However,the application of PFs is severely limited by their brittleness and high pulverizability due to their unique molecular structure. To further exploit the desirable properties of PFs,it's necessary to improve the toughness of PFs and reduce the brittleness and pulverizability. This paper reviewed the main toughening methods of PFs,PFs toughened with polyurethane prepolymer(PUP)(PFs toughened by direct mixing method,PFs toughened with NCO-terminated PUP and OH-terminated PUP) as well as the toughening mechanism was introduced. In addition,the problems of PFs toughened with PUP were summarized.
引文
[1]Li Q,Chen L,Li X,et al.Effect of multi-walled carbon nanotubes on mechanical,thermal and electrical properties of phenolic foam via in-situ polymerization[J].Composites Part A,2016,82:214-225.
[2]Zhou J,Yao Z,Chen Y,et al.Fabrication and mechanical properties of phenolic foam reinforced with graphene oxide[J].Polym.Compos.,2014,35:581-586.
[3]Rangari V K,Hassan T A,Zhou Y,et al.Cloisite clay-infused phenolic foam nanocomposites[J].J.Appl.Polym.Sci.,2007,103:308-314.
[4]Gao M,Wu W,Wang Y,et al.Phenolic foam modified with dicyandiamide as toughening agent[J].J.Therm.Anal.Calorim.,2016,124:189-195.
[5]Kaynak C,Cagatay O.Rubber toughening of phenolic resin by using nitrile rubber and amino silane[J].Polym.Test.,2006,25:296-305.
[6]Hu X M,Wang D M,Cheng W M,et al.Effect of polyethylene glycol on the mechanical property,microstructure,thermal stability,and flame resistance of phenol-urea-formaldehyde foams[J].J.Mater.Sci.,2014,49:1556-1565.
[7]Yang H,Wang X,Yuan H,et al.Fire performance and mechanical properties of phenolic foams modified by phosphorus-containing polyethers[J].J.Polym.Res.,2012,19:9831.
[8]Choe J,Kim M,Kim J.A microwave foaming method for fabricating glass fiber reinforced phenolic foam[J].Compos.Struct.,2016,152:239-246.
[9]Desai A,Nutt S R,Alonso M V.Modeling of fiber-reinforced phenolic foam[J].J.Cell.Plast.,2008,44:391-413.
[10]Liang B,Li X,Hu L,et al.Foaming resol resin modified with polyhydroxylated cardanol and its application to phenolic foams[J].Ind.Crops Prod.,2016,80:194-196.
[11]Del Saz-Orozco B,Oliet M,Alonso M V,et al.Formulation optimization of unreinforced and lignin nanoparticle-reinforced phenolic foams using an analysis of variance approach[J].Compos.Sci.Technol.,2012,72:667-674.
[12]Gong R,Xu Q,Chu Y,et al.A simple preparation method and characterization of epoxy reinforced microporous phenolic open-cell sound absorbent foam[J].RSC Adv.,2015,5:68003-68013.
[13]Auad M L,Zhao L,Shen H,et al.Flammability properties and mechanical performance of epoxy modified phenolic foams[J].J.Appl.Polym.Sci.,2007,104:1399-1407.
[14]钱瑞莉,陈凤福.聚氨酯改性酚醛泡沫塑料[J].辽宁化工,1994(6):18-20.Qian R L,Chen F F.Polyurethane modified phenolic foam[J].Liaoning Chemical Industry,1994(6):18-20.
[15]殷锦捷,戴英华,赵志超,等.复合增韧酚醛泡沫塑料及其热稳定性能的研究[J].应用化工,2010,39(11):1693-1695.Yin J J,Dai Y H,Zhao Z C,et al.Study on composite toughing and thermal stability of phenolic foam[J].Applied Chemical Industry,2010,39(11):1693-1695.
[16]梁明莉,金关泰,祝军,等.聚氨酯改性酚醛泡沫塑料[J].北京化工大学学报(自然科学版),2002,29(1):47-50.Liang M L.Jin G T,Zhu J,et al.Polyurethane modified phenolic foam[J].Journal of Beijing University of Chemical Technology(Natural Science Edition),2002,29(1):47-50.
[17]程珏,梁明莉,金关泰.聚氨酯预聚物改性酚醛泡沫塑料脆性的研究[J].塑料工业,2004,32(1):7-9.Cheng J,Liang M L,Jin G T.Study of brittleness of phenolic foam modified by urethane oligomer[J].China Plastics Industry,2004,32(1):7-9.
[18]吴崇珍,高书亚,张丽.聚氨酯预聚体增韧改性酚醛泡沫塑料[J].化工进展,2016,35(4):1144-1148.Wu C Z,Gao S Y,Zhang L.Phenolic foam modified with polyurethane prepolymer[J].Chemical Industry and Engineering Progress,2016,35(4):1144-1148.
[19]薄采颖,胡立红,周静,等.蓖麻油基聚氨酯预聚体改性酚醛泡沫的制备及表征[J].林产化学与工业,2015,35(4):8-14.Bo C Y,Hu L H,Zhou J,et al.Preparation and characterization of phenolic foams modified by castor oil-based polyurethane prepolymer[J].Chemistry and Industry of Forest Products,2015,35(4):8-14.
[20]刘娟,陈日清,王春鹏,等.端异氰酸根聚氨酯预聚体增韧改性酚醛泡沫塑料性能研究[J].化工新型材料,2016,44(1):149-152.Liu J,Chen R Q,Wang C P,et al.study on property of isocyanate polyurethane prepolymer modified phenolic foam[J].New Chemical Materials,2016,44(1):149-152.
[21]李侗,张丽,姜合民,等.聚氨酯改性酚醛泡沫塑料的研究[C].武汉:第十三届全国包装工程学术会议,2010:277-281.
[22]刘朝晖,杨洁,赵伟,等.TDI型聚氨酯半预聚体增韧酚醛发泡材料的研究[J].聚氨酯工业,2010,25(4):17-19.Liu C H,Yang J,Zhao W,et al.Study on phenolic foam modified by quasi-prepolymer of TDI-based polyurethane[J].Polyurethane Industry,2010,25(4):17-19.
[23]路国忠,代德伟,吕懿训,等.聚氨酯预聚体增韧酚醛泡沫保温板的性能研究[J].墙材革新与建筑节能,2014(8):52-55.Lu G Z,Dai D W,LüY X,et al.Study of properties of phenolic foam modified by urethane oligomer[J].Wall Materials Innovation&Energy Saving in Buildings,2014(8):52-55.
[24]Yang H,Wang X,Yu B,et al.A novel polyurethane prepolymer as toughening agent:preparation,characterization,and its influence on mechanical and flame retardant properties of phenolic foam[J].J.Appl.Polym.Sci.,2013,128:2720-2728.
[25]Yuan H,Xing W,Yang H,et al.Mechanical and thermal properties of phenolic/glass fiber foam modified with phosphoruscontaining polyurethane prepolymer[J].Polym.Int.,2013,62:273-279.
[26]Ding H,Wang J,Liu J,et al.Preparation and properties of a novel flame retardant polyurethane quasi-prepolymer for toughening phenolic foam[J].J.Appl.Polym.Sci.,2015,132:DOI:10.1002/app.42424.
[27]Bo C,Wei S,Hu L,et al.Synthesis of a cardanol-based phosphorus-containing polyurethane prepolymer and its application in phenolic foams[J].RSC Adv.,2016,6:62999-63005.
[28]刘朝晖,杨洁,赵伟,等.端羟基PU半预聚体改性酚醛发泡材料的研究[J].塑料工业,2010,38(1):36-38.Liu C H,Yang J,Zhao W,et al.Study on phenolic foam modified by hydroxyl-ended quasi-prepolymer of PU[J].China Plastics Industry,2010,38(1):36-38.
[29]刘义红,刘胜平,张玉军.酚醛树脂/聚氨酯复合体系的研究[J].哈尔滨理工大学学报,2002,7(5):90-93.Liu Y H,Liu S P,Zhang Y J.A study on composite system of phenolic resin/polyurethane[J].Journal of Harbin University of Science and Technology,2002,7(5):90-93.
[30]许亮,文振广,程珏.聚氨酯/酚醛树脂双组份体系泡沫体的制备[J].北京化工大学学报(自然科学版),2010,37(3):73-77.Xu L,Wen Z G,Cheng J.Preparation of a polyurethane/phenolic foam from a polyurethane prepolymer[J].Journal of Beijing University of Chemical Technology(Natural Science Edition),2010,37(3):73-77.
[31]杨彦峰,何继敏.酚醛树脂的增韧方法及增韧机理分析[J].塑料科技,2013,41(5):108-113.Yang Y F,He J M.Analysis on toughening methods and mechanism of phenolic resins[J].Plastics Science and Technology,2013,41(5):108-113.
[2]Zhou J,Yao Z,Chen Y,et al.Fabrication and mechanical properties of phenolic foam reinforced with graphene oxide[J].Polym.Compos.,2014,35:581-586.
[3]Rangari V K,Hassan T A,Zhou Y,et al.Cloisite clay-infused phenolic foam nanocomposites[J].J.Appl.Polym.Sci.,2007,103:308-314.
[4]Gao M,Wu W,Wang Y,et al.Phenolic foam modified with dicyandiamide as toughening agent[J].J.Therm.Anal.Calorim.,2016,124:189-195.
[5]Kaynak C,Cagatay O.Rubber toughening of phenolic resin by using nitrile rubber and amino silane[J].Polym.Test.,2006,25:296-305.
[6]Hu X M,Wang D M,Cheng W M,et al.Effect of polyethylene glycol on the mechanical property,microstructure,thermal stability,and flame resistance of phenol-urea-formaldehyde foams[J].J.Mater.Sci.,2014,49:1556-1565.
[7]Yang H,Wang X,Yuan H,et al.Fire performance and mechanical properties of phenolic foams modified by phosphorus-containing polyethers[J].J.Polym.Res.,2012,19:9831.
[8]Choe J,Kim M,Kim J.A microwave foaming method for fabricating glass fiber reinforced phenolic foam[J].Compos.Struct.,2016,152:239-246.
[9]Desai A,Nutt S R,Alonso M V.Modeling of fiber-reinforced phenolic foam[J].J.Cell.Plast.,2008,44:391-413.
[10]Liang B,Li X,Hu L,et al.Foaming resol resin modified with polyhydroxylated cardanol and its application to phenolic foams[J].Ind.Crops Prod.,2016,80:194-196.
[11]Del Saz-Orozco B,Oliet M,Alonso M V,et al.Formulation optimization of unreinforced and lignin nanoparticle-reinforced phenolic foams using an analysis of variance approach[J].Compos.Sci.Technol.,2012,72:667-674.
[12]Gong R,Xu Q,Chu Y,et al.A simple preparation method and characterization of epoxy reinforced microporous phenolic open-cell sound absorbent foam[J].RSC Adv.,2015,5:68003-68013.
[13]Auad M L,Zhao L,Shen H,et al.Flammability properties and mechanical performance of epoxy modified phenolic foams[J].J.Appl.Polym.Sci.,2007,104:1399-1407.
[14]钱瑞莉,陈凤福.聚氨酯改性酚醛泡沫塑料[J].辽宁化工,1994(6):18-20.Qian R L,Chen F F.Polyurethane modified phenolic foam[J].Liaoning Chemical Industry,1994(6):18-20.
[15]殷锦捷,戴英华,赵志超,等.复合增韧酚醛泡沫塑料及其热稳定性能的研究[J].应用化工,2010,39(11):1693-1695.Yin J J,Dai Y H,Zhao Z C,et al.Study on composite toughing and thermal stability of phenolic foam[J].Applied Chemical Industry,2010,39(11):1693-1695.
[16]梁明莉,金关泰,祝军,等.聚氨酯改性酚醛泡沫塑料[J].北京化工大学学报(自然科学版),2002,29(1):47-50.Liang M L.Jin G T,Zhu J,et al.Polyurethane modified phenolic foam[J].Journal of Beijing University of Chemical Technology(Natural Science Edition),2002,29(1):47-50.
[17]程珏,梁明莉,金关泰.聚氨酯预聚物改性酚醛泡沫塑料脆性的研究[J].塑料工业,2004,32(1):7-9.Cheng J,Liang M L,Jin G T.Study of brittleness of phenolic foam modified by urethane oligomer[J].China Plastics Industry,2004,32(1):7-9.
[18]吴崇珍,高书亚,张丽.聚氨酯预聚体增韧改性酚醛泡沫塑料[J].化工进展,2016,35(4):1144-1148.Wu C Z,Gao S Y,Zhang L.Phenolic foam modified with polyurethane prepolymer[J].Chemical Industry and Engineering Progress,2016,35(4):1144-1148.
[19]薄采颖,胡立红,周静,等.蓖麻油基聚氨酯预聚体改性酚醛泡沫的制备及表征[J].林产化学与工业,2015,35(4):8-14.Bo C Y,Hu L H,Zhou J,et al.Preparation and characterization of phenolic foams modified by castor oil-based polyurethane prepolymer[J].Chemistry and Industry of Forest Products,2015,35(4):8-14.
[20]刘娟,陈日清,王春鹏,等.端异氰酸根聚氨酯预聚体增韧改性酚醛泡沫塑料性能研究[J].化工新型材料,2016,44(1):149-152.Liu J,Chen R Q,Wang C P,et al.study on property of isocyanate polyurethane prepolymer modified phenolic foam[J].New Chemical Materials,2016,44(1):149-152.
[21]李侗,张丽,姜合民,等.聚氨酯改性酚醛泡沫塑料的研究[C].武汉:第十三届全国包装工程学术会议,2010:277-281.
[22]刘朝晖,杨洁,赵伟,等.TDI型聚氨酯半预聚体增韧酚醛发泡材料的研究[J].聚氨酯工业,2010,25(4):17-19.Liu C H,Yang J,Zhao W,et al.Study on phenolic foam modified by quasi-prepolymer of TDI-based polyurethane[J].Polyurethane Industry,2010,25(4):17-19.
[23]路国忠,代德伟,吕懿训,等.聚氨酯预聚体增韧酚醛泡沫保温板的性能研究[J].墙材革新与建筑节能,2014(8):52-55.Lu G Z,Dai D W,LüY X,et al.Study of properties of phenolic foam modified by urethane oligomer[J].Wall Materials Innovation&Energy Saving in Buildings,2014(8):52-55.
[24]Yang H,Wang X,Yu B,et al.A novel polyurethane prepolymer as toughening agent:preparation,characterization,and its influence on mechanical and flame retardant properties of phenolic foam[J].J.Appl.Polym.Sci.,2013,128:2720-2728.
[25]Yuan H,Xing W,Yang H,et al.Mechanical and thermal properties of phenolic/glass fiber foam modified with phosphoruscontaining polyurethane prepolymer[J].Polym.Int.,2013,62:273-279.
[26]Ding H,Wang J,Liu J,et al.Preparation and properties of a novel flame retardant polyurethane quasi-prepolymer for toughening phenolic foam[J].J.Appl.Polym.Sci.,2015,132:DOI:10.1002/app.42424.
[27]Bo C,Wei S,Hu L,et al.Synthesis of a cardanol-based phosphorus-containing polyurethane prepolymer and its application in phenolic foams[J].RSC Adv.,2016,6:62999-63005.
[28]刘朝晖,杨洁,赵伟,等.端羟基PU半预聚体改性酚醛发泡材料的研究[J].塑料工业,2010,38(1):36-38.Liu C H,Yang J,Zhao W,et al.Study on phenolic foam modified by hydroxyl-ended quasi-prepolymer of PU[J].China Plastics Industry,2010,38(1):36-38.
[29]刘义红,刘胜平,张玉军.酚醛树脂/聚氨酯复合体系的研究[J].哈尔滨理工大学学报,2002,7(5):90-93.Liu Y H,Liu S P,Zhang Y J.A study on composite system of phenolic resin/polyurethane[J].Journal of Harbin University of Science and Technology,2002,7(5):90-93.
[30]许亮,文振广,程珏.聚氨酯/酚醛树脂双组份体系泡沫体的制备[J].北京化工大学学报(自然科学版),2010,37(3):73-77.Xu L,Wen Z G,Cheng J.Preparation of a polyurethane/phenolic foam from a polyurethane prepolymer[J].Journal of Beijing University of Chemical Technology(Natural Science Edition),2010,37(3):73-77.
[31]杨彦峰,何继敏.酚醛树脂的增韧方法及增韧机理分析[J].塑料科技,2013,41(5):108-113.Yang Y F,He J M.Analysis on toughening methods and mechanism of phenolic resins[J].Plastics Science and Technology,2013,41(5):108-113.