中国科学院成都有机化学研究所 硕士学位论文
（可交联）高分子表面活性剂的合成及其乳液聚合的动力学研究
摘要
本文 通 过 无皂乳液聚合制备了碱溶性无规共聚物P( MMA/EA/MAA)，用红外光谱(IR )、示差量热扫描〔DSC ),凝胶渗透色谱(GPC)等分析手段对无规共聚物的结构进行了表征;并考察了单体配比、共聚物浓度、分子量、pH值等因素对无规共聚物表面活性的影响。
以碱 溶 性 无规共聚物P( MMA/E A/ MAA)为高分子表面活性剂进行(甲基)丙烯酸酷的乳液聚合，TEM和粒径分析表明所制备的丙烯酸醋乳液粒径范围在40-100nm之间，乳胶粒子呈较明显的核/壳结构。研究了该乳液聚合的动力学，并考察了反应温度，引发剂浓度，表面活性剂浓度等因素对反应速率(Rp)的影响。并根据实验结果提出了以碱溶性无规共聚物P( MMA/EA / MAA)为高分子表面活性剂进行乳液聚合的成核机理合成 了 带 活性拨基的碱溶性无规共聚物P( MMA/EA/MAA/DAAM) ，表征了其结构，并以之为高分子表面活性剂进行(甲基)丙烯酸酷的乳液聚合，制备的乳液呈较明显的核/壳结构。分别 以 P( MMA/E A/ MAA)和P( MMA/EA/MAA/DAAM)为高分子表面活性剂进行丙烯酸酷的乳液聚合或丙烯酸醋与双丙酮丙烯酞胺(DAAM)的乳液共聚，在含活性拨基的乳液中加入交联剂己二酸二酞脐(ADH)制备了核/壳、核(交联)/壳、核/壳(交联)和核(交联)/壳(交联)四种乳液。通过交联度测定和溶胀度实验考察了不同类型乳液及交联剂含量对乳胶膜性能的影响。
关键词:碱溶性无规共聚物聚丙烯酸酷乳液聚合核/壳结构交联
Synthesis of (crosslinkable) polymeric surfactant and study of kinetics of emulsion polymerization of using it as surfactant Liujin(Polymer Chemistry and Physics) Directed by Prof.X iaobinD ING Int h is d i ssertation,an a lkali-solublera ndomt erpolymer(P MMA/EA/MAA)w as synthesized by soap-free emulsion polymerization. The efects of terpolymer concentration, the amount of MAA and DDM and the value of pH on surface activity ofth ete rpolymerso lutionw erein vestigated.IF ,D SCa ndG PCw ereu sedto a nalyze the structure of the alkali-soluble random terpolymer.
Alk al i-so luble random terpolymerw asu sed asa polymeric surfactanti nemulsionp olymerizationo fac rylate.T hela texw as studiedb yt ransmissione lectron micrographa ndl aserli ghtsc attering,th er esultsin dicateth atth em orphologyo fth e latex particles was core/shell and the size of the latex was about 40-80mn. And the reaction mechanism of the emulsion polymerization with alkali-soluble random 1s. he terpolymerus eda sp olymericsu rfactantw aspu tfo rwardw ithth ee xperimentre su The kinetics of the emulsion polymerization was
initiator, and pol studied. The efects of concentration of polymerization rate Al ka li- so lu ble
emulsifier, ymerization temperature on (Rp)w erei nvestigatedin d etail. random copolymer P (MMA/EA/MAA/DAAM )was synthesized.T hes tructureo fth era ndomc opolymerw asst udiedb yIR . Fou r k in dso fc ore/shella crylatee mulsionsw erep reparedb y emulsion polymerization of acrylate or acrylate and diacetone-acrylamide using alkali-soluble randomc opolymerP ( MMA/EA/MAA/DAAM)or P ( MMA/EA/MAA)as po lymeric surfactant.O ne-componentcr osslinkablec ore/shellac rylatee mulsionw as obtainedb y additiono fcr osslinkinga gent(A DH)to th ee mulsionsco ntainingk etoneg roups.The effect of crosslinking reaction on latex films was investigated by crosslinking degre and swelling degree.
Keywords:A lkali-solublera ndomc opolymer,Po lyacrylate,Em ulsionp olymerization,Core/shell structure, Crosslinking
（可交联）高分子表面活性剂的合成及其乳液聚合的动力学研究
摘要
本文 通 过 无皂乳液聚合制备了碱溶性无规共聚物P( MMA/EA/MAA)，用红外光谱(IR )、示差量热扫描〔DSC ),凝胶渗透色谱(GPC)等分析手段对无规共聚物的结构进行了表征;并考察了单体配比、共聚物浓度、分子量、pH值等因素对无规共聚物表面活性的影响。
以碱 溶 性 无规共聚物P( MMA/E A/ MAA)为高分子表面活性剂进行(甲基)丙烯酸酷的乳液聚合，TEM和粒径分析表明所制备的丙烯酸醋乳液粒径范围在40-100nm之间，乳胶粒子呈较明显的核/壳结构。研究了该乳液聚合的动力学，并考察了反应温度，引发剂浓度，表面活性剂浓度等因素对反应速率(Rp)的影响。并根据实验结果提出了以碱溶性无规共聚物P( MMA/EA / MAA)为高分子表面活性剂进行乳液聚合的成核机理合成 了 带 活性拨基的碱溶性无规共聚物P( MMA/EA/MAA/DAAM) ，表征了其结构，并以之为高分子表面活性剂进行(甲基)丙烯酸酷的乳液聚合，制备的乳液呈较明显的核/壳结构。分别 以 P( MMA/E A/ MAA)和P( MMA/EA/MAA/DAAM)为高分子表面活性剂进行丙烯酸酷的乳液聚合或丙烯酸醋与双丙酮丙烯酞胺(DAAM)的乳液共聚，在含活性拨基的乳液中加入交联剂己二酸二酞脐(ADH)制备了核/壳、核(交联)/壳、核/壳(交联)和核(交联)/壳(交联)四种乳液。通过交联度测定和溶胀度实验考察了不同类型乳液及交联剂含量对乳胶膜性能的影响。
关键词:碱溶性无规共聚物聚丙烯酸酷乳液聚合核/壳结构交联
Synthesis of (crosslinkable) polymeric surfactant and study of kinetics of emulsion polymerization of using it as surfactant Liujin(Polymer Chemistry and Physics) Directed by Prof.X iaobinD ING Int h is d i ssertation,an a lkali-solublera ndomt erpolymer(P MMA/EA/MAA)w as synthesized by soap-free emulsion polymerization. The efects of terpolymer concentration, the amount of MAA and DDM and the value of pH on surface activity ofth ete rpolymerso lutionw erein vestigated.IF ,D SCa ndG PCw ereu sedto a nalyze the structure of the alkali-soluble random terpolymer.
Alk al i-so luble random terpolymerw asu sed asa polymeric surfactanti nemulsionp olymerizationo fac rylate.T hela texw as studiedb yt ransmissione lectron micrographa ndl aserli ghtsc attering,th er esultsin dicateth atth em orphologyo fth e latex particles was core/shell and the size of the latex was about 40-80mn. And the reaction mechanism of the emulsion polymerization with alkali-soluble random 1s. he terpolymerus eda sp olymericsu rfactantw aspu tfo rwardw ithth ee xperimentre su The kinetics of the emulsion polymerization was
initiator, and pol studied. The efects of concentration of polymerization rate Al ka li- so lu ble
emulsifier, ymerization temperature on (Rp)w erei nvestigatedin d etail. random copolymer P (MMA/EA/MAA/DAAM )was synthesized.T hes tructureo fth era ndomc opolymerw asst udiedb yIR . Fou r k in dso fc ore/shella crylatee mulsionsw erep reparedb y emulsion polymerization of acrylate or acrylate and diacetone-acrylamide using alkali-soluble randomc opolymerP ( MMA/EA/MAA/DAAM)or P ( MMA/EA/MAA)as po lymeric surfactant.O ne-componentcr osslinkablec ore/shellac rylatee mulsionw as obtainedb y additiono fcr osslinkinga gent(A DH)to th ee mulsionsco ntainingk etoneg roups.The effect of crosslinking reaction on latex films was investigated by crosslinking degre and swelling degree.
Keywords:A lkali-solublera ndomc opolymer,Po lyacrylate,Em ulsionp olymerization,Core/shell structure, Crosslinking