Study on the Preparation of Waterborne Polyurethane Adhesive

水性聚氨酯胶粘剂（WPU）除保留了溶剂型聚氨酯优异的粘接性能外，同时解决了传统胶粘剂使用有机溶剂造成的有机物挥发（VOC）、污染环境、危害健康等问题，越来越受到人们的重视，已广泛应用于汽车工业，食品软包装、制鞋工业等各个领域。但是国内对水性聚氨酯胶粘剂的应用研究水平不高，特别是对双组分水性聚氨酯胶粘剂的报道较少，研究不够详细。本文采用预聚体法分别制备了单组分及双组分的水性聚氨酯胶粘剂，重点研究了影响双组分水性聚氨酯性能的各种因素，以得到具有优异粘接性能的水性聚氨酯胶粘剂。具体工作内容如下： 1.以聚乙二醇（PEG）、甲苯二异氰酸酯（TDI）、2，2-二羟甲基丙酸（DMPA）、1，4-丁二醇（...In addition to retain the excellent bonding performance of solvent-based polyurethane, waterborne polyurethane (WPU) adhesives have solved the problems of organic solvent volatilization, environmental pollution, health hazards caused by the traditional solvent-based adhesive, and has got more and more attention. It has been widely used in the automotive industry, food packaging, footwear industry ...学位：理学硕士院系专业：材料学院_高分子化学与物理学号：2072010115011

Synthesis and Characterization of Two-component Waterborne Polyurethane Adhesive

以聚酯二元醇、甲苯二异氰酸酯(TdI)、二羟甲基丙酸(dMPA)、1,4-丁二醇(bdO)和三羟甲基丙烷(TMP)等为原料合成了双组分水性聚氨酯(WPu)的多元醇组分.考虑到溶解性、反应活性、工业成本等因素,本研究从小分子二元醇(如乙二醇、丙二醇、丁二醇、一缩乙二醇等),小分子三元醇(甘油),小分子四元醇(季戊四醇),聚乙二醇(相对分子质量200~2 000),聚丙二醇(相对分子质量300~2 000)等数十种醇类化合物中,反复试验,再三筛选,最后确定以聚乙二醇-800和六亚甲基二异氰酸酯(HdI)三聚体为原料合成了亲水性多异氰酸酯固化剂组分.将多元醇组分和固化剂组分混合配制,得到了双组分WPu胶黏剂.通过红外光谱(fT-Ir)、核磁共振(nMr)、黏度、吸水率、黏接强度、离心稳定性等性能测试,分别对多元醇组分和固化剂组分合成的关键步骤及影响产物性能的各种因素进行了探讨.结果表明,当dMPA、bdO、TMP的质量分数分别为6%、4%、3%时,多元醇组分的外观、稳定性、黏接强度等性能较好;选择聚乙二醇作为亲水组分对HdI三聚体进行改性,且当其添加的质量分数为11%及以上时,制备出的多异氰酸酯固化剂组分具有较好的水分散性.Polyol component of two-component waterborne polyurethane(WPU)was synthesized starting from polyeaster diol,tolyene diisocyanate(TDI),dimethylolbutanoic acid(DMPA),1,4-butanediol(BDO)and trimethylolpropane(TMP).Screening from numerous alcohol compounds such as glycols(e.g.,ethylene glycol,propylene glycol,butanediol,diethylene glycol,etc.),ternary alcohol(glycerin),quaternary alcohol(pentaerythritol),polyethylene glycol(PEG,molecular weight from 200 to 2 000),polypropylene glycol(molecular weight from 300 to 2 000)in respect of solubility,reactivity and industrial cost,PEG-800 and hexamethylene diisocyanate(HDI)trimer were selected as starting materials to synthesize hydrophilic isocyanate curing agent.Two-component WPU adhesive was prepared by mixing polyol component and curing agent.Characterized with FT-IR,1 H-NMR and determined with viscosity,water absorption,centrifugal stability and adhesive strength,various factors effecting the formation and properties of polyol component and curing agent were studied.Excellent appearance,stability and adhesive strength were shown for polyol components in the presence of 6% DMPA,4% BDO and 3% TMP.Using PEG-800 as the hydrophilic component with a content of 11%or more,the prepared polyisocyanate curing agent showed good water dispersibility

Reversible Addition-fragmentation Chain Transfer Polymerization of Styrene and Synthesis of Derived Block Copolymer

通信作者：ｙｓｚｏｕ＠ｘｍｕ．ｅｄｕ．ｃｎ[中文文摘]用三硫代碳酸双(α,α′-二甲基-α″-乙酸)酯作为可逆加成-断裂链转移(RAFT)聚合的链转移剂,制备了一系列具有不同相对分子质量,且相对分子质量分布较窄的聚苯乙烯均聚物.以得到的末端冠有链转移剂活性基团的聚苯乙烯作为大分子链转移剂,与丙烯酸乙酯(EA),丙烯酸丁酯(BA),甲基丙烯酸乙酯(EMA)和甲基丙烯酸丁酯(BMA)4种单体分别进行嵌段聚合反应;通过一步投料,合成了聚苯乙烯-聚(甲基)丙烯酸酯类的两亲性三嵌段共聚物.使用凝胶渗透色谱(GPC)、1 H-NMR对共聚物进行表征. [英文文摘]Ｐｏｌｙｓｔｙｒｅｎｅ　ｗａｓ　 ｐｏｌｙｍｅｒｉｚｅｄ　ｔｈｒｏｕｇｈ　ｕｓｉｎｇ　ｔｈｅ　Ｓ，Ｓ′－ｂｉｓ（Ｒ，Ｒ′－ｄｉｍｅｔｈｙｌａｃｅｔｉｃ　ａｃｉｄ）ｔｒｉｔｈｉｏｃａｒｂｏｎａｔｅ　 ａｓ　ｒｅｖｅｒｓｉｂｌｅ　ａｄｄｉｔｉｏｎｆｒａｇｍｅｎｔａｔｉｏｎ 　ｃｈａｉｎ　ｔｒａｎｓｆｅｒ（ＲＡＦＴ）ａｇｅｎｔｓ．Ｔｈｅ　ｓｙｎｔｈｅｓｉｚｅｄ　ｐｏｌｙｓｔｙｒｅｎｅ　ｈａｄ　ｖａｒｉｏｕｓ　ｃｏｎｔｒｏｌｌｅｄ　 ｍｏｌｅｃｕｌａｒ　ｗｅｉｇｈｔ　ａｎｄ　ｎａｒｒｏｗ　ｍｏｌｅｃｕｌａｒ 　ｗｅｉｇｈｔ　ｄｉｓｔｒｉｂｕｔｉｏｎ．Ａ　ｓｅｒｉｅｓ　ｏｆ　ｄｉｆｆｅｒｅｎｔ　ａｍｐｈｉｐｈｉｌｉｃ　ｔｒｉｂｌｏｃｋ　ｃｏｐｏｌｙｍｅｒｓ　ｗｅｒｅ　ｒｅｓｐｅｃｔｉｖｅｌｙ　ｓｙｎｔｈｅｓｉｚｅｄ　ｗｉｔｈ　ｔｈｅ　ａｄｄｉｔｉｏｎ　ｏｆ ｅｔｈｙｌ　ａｃｒｙｌａｔｅ，ｂｕｔｙｌ　ａｃｒｙｌａｔｅ，ｅｔｈｙｌ　ｍｅｔｈａｃｒｙｌａｔｅ　ａｎｄ　ｂｕｔｙｌ　ｍｅｔｈａｃｒｙｌａｔｅ．Ｄｕｒｉｎｇ　ｔｈｅ　ｓｙｎｔｈｅｓｉｓ　ｏｆ　ｔｒｉｂｌｏｃｋ　ｃｏｐｏｌｙｍｅｒｓ，ｔｈｅ　ａｂｏｖｅ　ｏｂｔａｉｎｅｄ　ｐｏｌｙｓｔｙｒｅｎｅ　ｗａｓ　ｕｓｅｄ　ａｓ　ｍａｃｒｏｍｏｌｅｃｕｌａｒ　ＲＡＦＴ　ａｇｅｎｔ．Ｔｈｅ　ｄｅｒｉｖｅｄ　ｐｏｌｙ（ｍｅｔｈｙ）ａｃｒｙｌａｔｅ　ｂｌｏｃｋ　ｐｏｌｙｓｔｙｒｅｎｅ　ｂｌｏｃｋ　ｐｏｌｙ（ｍｅｔｈｙ） ａｃｒｙｌａｔｅ　ｃｏｐｏｌｙｍｅｒｓ ｗｅｒｅ　ｃｈａｒａｃｔｅｒｉｚｅｄ　ｂｙ　ＧＰＣ　ａｎｄ　１　Ｈ－ＮＭＲ

The Effect of Cross-Linking Agent on the Preparation of the Thermally Expandable Microspheres

以丙烯腈为主要单体,以氢氧化镁为无机分散剂,采用常压聚合法,制备了膨胀倍率达到20-30倍的可膨胀小球。系统研究了二丙二醇二丙烯酸酯(dPgdA)、三缩丙二醇二丙烯酸酯(TPgdA)、新戊二醇二丙烯酸酯(nPgdA)、三羟甲基丙烷三丙烯酸酯(TMPTA)和二乙烯基苯(dVb)等5种交联单体对可膨胀小球制备的影响。通过扫描电子显微镜、热重分析、交联密度测定等手段研究了可膨胀小球的形貌、粒径、发泡剂的含量、交联密度、发泡倍率。确定dPgdA为最佳的交联剂种类,用量为1.7%。采用dPgdA作为交联剂的小球既具有较完好的球状形貌,又有较小的粒径,较高的发泡剂含量和较高的交联度,膨胀倍率可达30倍。The thermally expandable microspheres,using acrylonitrile as the main monomer and magnesium hydroxide as the inorganic dispersant,were prepared with atmospheric suspension polymerization.This study systematically researched the effect of cross-linking agent such as dipropylene glycol diacrylate(DPGDA),tripropylene glycol diacrylate(TPGDA),trimethylolpropane trimethacrylate(TMPTA), noe ponlyl glycol di acrylate(NPGDA)and divinylbenzene(DVB)on the preparation of the thermally expandable microspheres.By using scanning electron microscope,thermogravimetric analysis and determination of cross-linking density,the morphology,particle size,foaming agent content,cross-linking density and foaming ratio of thermally expandable microspheres were studied.As a result,DPGDA is found to be the most suitable cross-linking agent because the microspheres prepared with it have the perfect surface morphology,small particle size,high blowing agent content and high cross-linking degree and the dosage is 1.7%