The Synthesis of Block Copolymers with Reversible Addition-Fragmentation Chain Transfer Polymerization

利用RAFT聚合技术可以在温和条件下合成结构可控的聚合物，如嵌段，接枝，星型，树枝状，支化及超支化等结构的聚合物。其中两亲性嵌段结构的共聚物以其独特结构在油墨润湿剂，涂料分散剂等工业领域有着较广泛的应用，并且其在一定条件下形成的球形，棒状，囊泡等不同形态和结构的聚集体也使之在材料制备、纳米技术、药物输运等高新技术领域具有良好的应用前景。RAFT聚合技术近年来已成为制备两亲性嵌段共聚物的重要技术。 国内外一些研究者已作了类似的研究，但他们重点研究了嵌段共聚物的自组装行为和其在实际中如药物缓释等的应用。本论文重点研究RAFT聚合对相对分子质量大小的控制性，目的在于合成预设相对分子质量的聚合物，...Polymers of controllable structure can be synthesized under mild conditions by using RAFT polymerization technology, such as polymers, grafting polymers, star polymers, dentrites polymers, branched polymers and hyperbranched polymers, etc. Amphiphilic block copolymers with its unique structure have the widespread application in the printing ink wetting agents area and coating dispersant industrial...学位：理学硕士院系专业：材料学院材料科学与工程系_高分子化学与物理学号：2072009115006

Study on One Part Blocked Polyurethane-Ag Conductive Adhesive

通讯作者: [email protected][中文文摘]以封闭型聚氨酯为基体、三羟甲基丙烷(TMP)为固化剂,制备了单组份银粉导电胶,并研究其性能.该聚氨酯基体由2,4-甲苯二异氰酸酯(TDI)、TMP和少量聚乙二醇进行缩聚,并与己内酰胺反应而得.在基体中添加TMP固化剂、银粉和二氧化硅并充分搅拌后制得单组份导电胶.通过红外光谱、剪切强度和电阻率的测定对产物进行了表征,结果表明,70℃下TMP、TDI的加成反应需要时间为4~4.5 h,与己内酰胺的封闭反应时间为3~4 h;银粉的质量分数为75%时产物性能最好;加入少量二氧化硅能够提高导电胶的剪切强度,但电阻率会随之升高.[英文文摘]The preparation and properties of one-component Ag powder conductive adhesive which consisted of TMP-TDI adduct as matrix and TMP as hardener were studied.TMP-TDI adduct was synthesized by TMP,TDI and PEG.Then the prepolymer was blocked by caprolactam to get blocked polyurethane.Hardener,Ag powder and fumed silica were added to the polyurethane to prepare one-component conductive adhesive through agitating well.The products were characterized by FTIR,moreover,their shear strength and electrical resistivity were measured respectively. The results demonstrated that the addition reaction of TMP and TDI needed 4~4.5 h, while the blocked reaction needed 3~ 4 h. The optimum mass fraction of Ag powder was 75%. Employing fumed silica to the conductive adhesive reinforced the shear strength and elect rical resistivity

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%