【作者】 王琳；

【导师】 付志峰；

【作者基本信息】 北京化工大学 ， 高分子化学及物理， 2008， 博士

【摘要】 多卤化物是一种重要的原子转移自由基聚合（ATRP）引发剂,它们能够引发多种单体进行聚合,并可以经过一步或多步反应合成多种结构的聚合物,如嵌段、接枝、星型、超支化聚合物等。如果能够测出多卤化物引发聚合的官能度,将对分子结构设计有重要意义。另一方面,由于过渡金属及其络合物的高催化效率及较低的价格,它们经常被广泛用于原子转移自由基加成（ATRA）和聚合中,但产品后处理较困难。如果能将催化剂通过物理或化学方法负载在某种载体上将可能解决以上问题,使产品与催化剂很好的分离,且还能够达到回收和重复使用的目的。本论文进行了三部分研究工作,第一部分:通过多步反应对硅胶进行改性合成了一种多齿胺改性硅胶配体,合成过程如下:1)通过γ-氨丙基三甲氧基硅烷（γ-APS）与硅胶表面的硅羟基反应,使硅胶表面带有氨基;2)利用硅胶表面氨基与过量的三羟甲基丙烷三丙烯酸酯（TMPTA）发生Michael加成反应;3)利用二乙烯三胺（DETA）与TMPTA改性硅胶表面未反应的双键发生反应使硅胶表面氨基化;4)最后用丙烯酸正丁酯（BA）与DETA改性硅胶表面氨基充分反应成功合多齿胺改性硅胶配体。通过核磁C¹³NMR、红外光谱（FTIR）及元素分析（EA）分析表明以上各步反应产物的结构及含氮量。此多齿胺改性硅胶配体被分别多次重复用于四氯化碳与甲基丙烯酸甲酯（MMA）,三氯乙酸甲酯与苯乙烯（St）的ATRA反应中,通过气相色谱测定了原料的转化率随时间的变化,且通过核磁¹H NMR测定了产物的纯度,我们还进一步将此种多齿胺改性硅胶配体用于TCPP引发St的ATRP和MMTCB引发MMA的ATRP反应中,通过GPC测定所得聚合物的分子量。结果表明:成功合成了预期的多齿胺改性硅胶,此种配体的含氮量为2.5mmol/g。且此种多齿胺改性硅胶配体是ATRA反应很好的配体。在催化四氯化碳与MMA或三氯乙酸甲酯与St的ATRA反应中,此种配体至少可以重复使用7次,且第一次转化率在40h内可达到80%以上,第7次时仍可达到25%以上。但此种配体在用于ATRP反应时却不具有可控性。第二部分:通过多步反应合成了一种多齿胺改性磁性微球配体,合成过程如下:1)利用传统的共沉淀法合成纳米级的磁性四氧化三铁,并用油酸和十二烷基磺酸钠双层表面活性剂对其进行改性,制备稳定性好,能够很好的分散到极性溶剂中的磁流体。21以磁流体为种子,利用乳液聚合方法,以甲基丙烯酸甲酯和三羟甲基丙烷三丙烯酸酯为原料进行交联共聚而得到了表面带有双键的磁性高分子微球;3)利用二乙烯三胺（DETA）与磁性微球表面的双键发生Michael加成反应使硅胶表面氨基化;4)最后用丙烯酸正丁酯与DETA改性磁性微球表面氨基充分反应成功合成多齿胺改性磁性微球配体。通过表面元素分析（XPS）、红外光谱（FTIR）及元素分析（EA）分析表明以上各步反应产物的结构及含氮量。此多齿胺改性磁微球配体被分别多次重复用于四氯化碳与MMA和三氯乙酸甲酯与St的ATRA反应中,通过气相色谱测定了原料的转化率随时间变化。结果表明:成功合成了预期的多齿胺改性磁性微球,此种配体的含氮量约为1.0mmol/g。且此种多齿胺改性磁性微球是ATRA反应很好的配体。在催化四氯化碳与MMA和三氯乙酸甲酯与St的ATRA反应中,此种配体至少可以重复使用5次,且第一次转化率在40h内可达到80%以上,第5次时仍可达到35%以上。第三部分:以四氯化碳和三氯乙酸甲酯分别与苯乙烯（St）和甲基丙烯酸甲酯（MMA）发生原子转移自由基加成反应,合成了多官能卤化物1-苯基-1,3,3,3-四氯丙烷（TCPP）、2,2,4-三氯-4-苯基丁酸甲酯（MTCPB）、2,4,4,4-四氯-2-甲基丁酸甲酯（MMTCB）和2,2,4-三氯-4-甲基戊二酸二甲酯（DMTCMG）,然后分别以TCPP和MTCPB为引发剂、CuCl为催化剂、2,2′-联吡啶为配体,进行St的ATRP反应;以MMTCB和DMTCMG为引发剂、CuCl为催化剂、2,2′-联吡啶为配体,进行MMA的ATRP反应。采用¹HNRM和凝胶渗透色谱（GPC）对聚合物结构和分子量进行分析表征。结果表明:聚合物分子量与单体转化率之间存在较好的线性关系;TCPP和MTCPB都是St的ATRP双官能度引发剂;MMTCB是MMA的单官能度引发剂;DMTCMG引发MMA聚合时官能度为1.5。更多还原

【Abstract】 The polychloroalkanes is one kind of very important initiator of atom transfer radical polymerization （ATRP）. They can initiate many kinds of monomers to synthesize different kinds of architectures via single-step or multistep reaction, such as block, graft, star and hyperbranched Copolymers and so on. If the functionality of the polychloroalkanes in polymerization could be determined clearly, it woulde be important for the design of macromolecular structure. On the other hand, transition metal complex have been widely used because of their good catalytic efficiency for the atom transfer radical addition （ATRA） and ATRP, but the postpurification of the product is difficult. Supporting catalyst on insoluble particles is a possible solution to this problem. Catalysts immobilized on insoluble particles by physics or chemistry method can be easily separated from the reaction mixture and be recycled and reused.Three part of research works had been carried out in the dissertation. The first part: a kind of multidentate amine modified silica gel was synthesized through the following steps: （1） introduce the amino groups onto the surface of silica-gel by the treatment of surface silanol groups withγ-aminopropyl trimethoxy silane （γ-APS）; （2） michael addition of excess trihydroxymethyl propyl triacrylate （TMPTA） to amino groups on the silica gel surface; （3） amidation of the unreacted double bonds of TMPTA on the surface of TMPTA modified silica gel with diethylenetriamine （DETA）; （4） the multidentate amine modified silica gel was finally obtained by the reaction of amino groups on the surface of DETA modified silica gel with double bond of butyl acrylate （BA）. Their chemical structures were confirmed by C¹³ NMR, infrared spectrum （FTIR） and the nitrogen content in the particles was determined by elemental analysis （EA）. Then, the multidentate amine immobilized on silica gel was used as ligand for CuCl in ATRA of CCl₄ with MMA and methyl trichloroacetate with St repeatly. The conversion and purity of the product were determined through the gas chromatography and ¹H NMR respectively. Finally, the multidentate amine immobilized on silica gel was used as ligand for CuCl in ATRP of St initiated by TCPP and MMA initiated by MMTCB. The number average molecular weights of the polymers were determined through GPC. The results indicated that the multidentate amine modified silica gel ligand was synthesized successfully and the nitrogen content of this ligand is 2.5mmol/g. The multidentate amine modified silica gel is good catalytic ligand of ATRA reaction. This kind of ligand have been used seven times in the ATRA reaction of carbon tetrachloride with MMA and the methyl trichloroacetate with St, and the conversion for the first time reached above 80% in 40 hours, when the seventh time still exceeded 25%. But the multidentate amine modified silica gel ligand can not control ATRP reaction well. The second part: a kind of multidentate amine modified magnetic microspheres was synthesized through the following steps: （1） Fe₃O₄ magnetic nanoparticles were synthesized by the chemical co-precipitation and modified by oleic acid and sodium dodecyl sulfonate bilayer surfactants. The stability of the magnetic fluid is very good and can be dispersed well in polarity solvent. （2） The magnetic fluid was as seed and carried on the crossing linking copolymerization of methyl methacrylate（MMA） and trihydroxymethyl propyl triacrylate（TMPTA） through emulsion polymerition obtained the magnetic microspheres with the double bond on the surface. （3） amidation of the double bonds of magnetic microspheres on the surface with diethylenetriamine （DETA）; （4） the multidentate amine modified magnetic microspheres was finally obtained by the reaction of amino groups on the surface of DETA modified magnetic microspheres with double bond of butyl acrylate （BA）. Their chemical structures were confirmed by XPS, infrared spectrum （FTIR） and the nitrogen content in the particles was determined by elemental analysis （EA）. Then, the multidentate amine immobilized on magnetic microspheres was used as ligand for CuCl in ATRA of CCl₄ with MMA and methyl trichloroacetate with St repeatly. The conversion and purity of the product were determined through the gas chromatography respectively. The results indicated that the multidentate amine modified magnetic microspheres ligand was synthesized successfully and the nitrogen content of this ligand is 1.0mmol/g. The multidentate amine modified silica gel is good catalytic ligand of ATRA reaction. This kind of ligand have been used five times in the ATRA reaction of carbon tetrachloride with MMA and the methyl trichloroacetate with St, and the conversion for the first time reached above 80% in 40 hours, when the fifth time still exceeded 35%. The third part: 1,1,1,3-tetrachloro-3-phenylpropane（TCPP）, methyl 2,2,4-trichloro-4-phenylbutyrate（MTCPB）, methyl 2-methyl-2,4,4,4-tetrarchlorobutyrate（MMTCB） and dimethyl 2,2,4-trichloro-4- methyl -glutarate （DMTCMG） have been synthesized via ATRA from styrene （St） and methyl methacrylate （MMA） with carbon tetrachloride and methyl trichloroacetate respectively. When the TCPP and MTCPB were used as initiators for ATRP of St and the MMTCB and DMTCMG were used as initiators for ATRP of MMA in the presence of the cuprous chloride （CuCl）/ 2, 2’-bipyridine catalyst system respectively, a controlled polymerization process was achieved with the resulting polystyrene （PS） and polymethyl methacrylate （PMMA） having number average molecular weights which increased with monomer conversion and narrow molecular weight distributions. The number average molecular weights and structure of the PS and PMMA characterized by ¹H NMR and gel permeation chromatography （GPC） showed that TCPP and MTCPB both act as bifunctional initiators for the ATRP of St and the functionalities of MMTCB and DMTCMG for the ATRP of MMA were 1.0 and 1.5 respectively.更多还原