Synthesis Of DMAEMA/ BMA Block Copolymer

ATRP is one of the widely used Radical Polymerization in recent years.Our group has reported the molecular weight distribution of the resulting polymer which polymerized in the presence of oxidized transition-metal complex by normal ATRP was rather narrow and the system showed good controllability.The polymerization and copolymerization of BMA and DMAEMA had been investigated in the presence of oxidized transition-metal complex by normal ATRP.1. Synthesis and Characterization of MA5-DETAMA5-DETA was synthesis by a known method,we characterised it by 1H-NMR and elemental analysis. MA5-DETA was proved to be synthesized successfully.2. ATRP of BMA use MA5-DETA as a ligandMA5-DETA and PMDETA were using as ligands in ATRP of BMA.The result showed the polymerization rate of BMA was slower, and the molecular weight distribution of the resulting polymer was wider which use MA5-DETA as ligand. And compare with ligand MA5-DETA in this system, the ATRP of BMA can be well polymerized by using the [EbiB]/[CuCl]/[CuCl2·2H2O]/ [PMDETA] system.We investigated the effect of different initiators in ATRP of BMA using MA5-DETA as ligand. The result showed the rate of polymerization was the slowest and the molecular weight distribution of the resulting polymer was wide by using DCT as initiator.The conversion of reaction reached a high level in only 3 hours and the molecular weight distribution of the resulting polymer was rather narrow with MBP as initiator.However when with EbiB as initiator,the rate of polymerization was slower than which with MBP as initiator, but a higher conversion. And PDIMBP <PDIEbiB< PDIDCT .3. Synthesis of DMAEMA/ BMA Block Copolymer in ATRPSynthesis the copolymer of 2-(N,N-dimethylamino)ethyl methacrylate(DMAEMA)by conventional polymerization has been reported for a long time. However, their utility is limited because the control of molecular weight, polydispersities, and copolymer topology is difficult in conventional radical polymerization. Nagasaki first synthesis homopolymer of DMAEMA in oxyanion– initiated polymerization. However the polymerization condition of oxyanion– initiated polymerization is limited and nearly impossible to put in practice out of lab. Since the appearance of controlled/living radical polymerization, especially ATRP, the block polymer of DMAEMA and other monomer with a total aggregate rapid development. But most of them use macroinitiators method, the excellence is the purity of its polymers is high, the disadvantage is everytime one monomer was polymerized,we should deposited and separated, then dissolved it to polymerize the second monomer. The process is cockamamie.2-(N,N-dimethylamino)ethyl methacrylate(DMAEMA) and n-butyl methacrylate (BMA) block copolymer was synthesized by atom transfer radical polymerization (ATRP) in this study. In addition to the traditional macroinitiator method, this paper focuses on continuous feeding method which was more convenient. A series of different block ratio of PBMA-b-PDMAEMA were characterized by GPC and 1H-NMR, the results showed the structure of different block ratio of PBMA-b-PDMAEMA obtained by two methods was almost same. This prove simple continuous feeding method is feasible. A new ATRP behaviour of DMAEMA was found : the initiation efficiency of polymerization of DMAEMA was greater than 1, whether DMAEMA was as the first monomer or the second monomer. The investigate of kinetic indicated that during the polymerization process, the number of active centers have a rising trend. The polymerization of DMAEMA is not typical ATRP.