新型嵌段共聚物的合成与性能研究
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摘要
本文以α-氯代丙酸乙酯(ECP)为引发剂,2,2′-联二吡啶(bpy)和N,N,N′,N″,N″-五甲基二亚乙基三胺(PMDETA)为配体,氯化亚铜(CuCl)为催化剂,在N,N′-二甲基甲酰胺(DMF)中使甲基丙烯酸叔丁酯(tBMA)进行原子转移自由基聚合(ATRP),考察了不同配体/催化剂条件下tBMA的ATRP反应过程。用凝胶渗透色谱(GPC)跟踪聚合物的相对分子质量变化,发现配体类型对tBMA的聚合反应速率有明显影响。通过改变引发剂与单体的物质的量之比(1:25～1:100),可将聚甲基丙烯酸叔丁酯(PtBMA-Cl)的相对分子质量控制在1.8×103～1×104范围内,并保持其相对分子质量分布≤1.30。同时用傅里叶红外光谱(FTIR)、核磁共振氢谱(1H-NMR)对产物的结构进行了表征,结果表明所得聚合物PtBMA-Cl的结构明确,为目标产物。
进而以5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环化合物(Me6[14]aneN4)为配体, CuCl为催化剂,由PtBMA-Cl引发4-乙烯基吡啶(4VP)进行溶液ATRP反应,合成得到了聚甲基丙烯酸叔丁酯-b-聚4-乙烯基吡啶(PtBMA-b-P4VP)嵌段共聚物。研究了溶剂、配体的种类对合成嵌段共聚物ATRP过程的影响,制得了分子量可控的PtBMA-b-P4VP。用FTIR、1H-NMR、GPC对产物的结构和分子量进行了表征,结果表明所得嵌段共聚物的结构明确,为目标产物。通过对嵌段共聚物PtBMA-b-P4VP的PtBMA链段进行定向水解,得到聚甲基丙烯酸-b-聚4-乙烯基吡啶(PMAA-b-P4VP)嵌段共聚物,初步研究其在不同pH条件下的胶束化行为。重点研究对P4VP链段进行了季铵化反应,得到了聚甲基丙烯酸-b-季铵化聚4-乙烯基吡啶(PMAA-b-QPVPB)亲水性嵌段共聚物。
以Me6[14]aneN4为配体,CuCl为催化剂,在异丙醇溶液中以对氯甲基苯乙烯(CMSt)为功能性引发剂引发4VP进行ATRP反应,以得到末端带有不饱和双键的大分子单体(St-P4VP),考察了不同配体对4VP的ATRP反应过程的影响。通过改变引发剂与单体的物质的量之比,可将St-P4VP的相对分子质量控制在2.0×103～1×104范围内。用FTIR、1H-NMR对产物的结构进行了表征,结果表明所得大分子单体St-P4VP的结构明确。使不同分子量的St-P4VP大分子单体进行均聚反应,由GPC测定结果显示,大分子单体的相对分子质量从2.90×103增加到2.88×104 ,从6.11×103增加到5.8×104,说明所制备的St-P4VP末端上的双键具有良好的聚合反应活性。由于该大分子单体端基α位上含有诱导共轭基团的氯原子,可以引发单体进行聚合,有望得到新的两嵌段大分子单体。
In this paper, a solusion atom transfer radical polymerization (ATRP) of tert-butylmethacrylate (tBMA) was first studied. Ethyl-2-chloro-propionate (ECP) was selected as initiator, 2,2’-bipyridyl (bpy) and N,N,N′,N″,N″-penta-methyldiethylenetriamine (PMDETA) as ligand, with CuCl as catalyst in DMF. It was found that ligand could clearly affect polymerization rate of tBMA monomer based on measurement of molecular weight of PtBMA-Cl by using gel permeation chromatography (GPC) under different ligand system. The polymerization regulations were compared for different systems. The number average molecular weight (Mn) of PtBMA-Cl could be controlled from 1.8×103 to 1×104 g/mol by varying the ratio of monomer to initiator in range of 1:25 to 1:100, and distribution of molecular weight (Mw/Mn) kept low than 1.30. The structure of the PtBMA-Cl was characterized by fourier transform infrared (FTIR) and nuclear magnetic resonance (1H-NMR). It was found that the obtained PtBMA-Cl had a specific structure.
A solution ATRP of 4-vinylpyridine (4VP) was then studied using resulting PtBMA-Cl as macroinitiator, CuCl as catalyst, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclote- tradecane (Me6[14]aneN4) as ligand to form block copolymer. It was found that different solvent and ligand could affect the polymerization of 4VP. PtBMA-b-P4VP was characterized by FTIR, 1H-NMR and GPC. Furthermore, the hydrolysis of the synthesized PtBMA-b-P4VP was finished under room temperature to form block copolymer PMAA-b-P4VP. The self-assembly of this block copolymer in selective solvents was also studied. The focus is that the quaternization of the synthesized PtBMA-b-P4VP was finished. The quaternizated diblock copolymer was then hydrolyzed under room temperature to form hydrophilic PMAA-b-QPVPB diblock copolymer.
Also, a solusion ATRP of 4VP was studied using CuCl as catalyst, p-chloromethylstyrene (CMSt) as functional initiator to synthesize macromonomer (St-P4VP) in the presence of bpy, PMDETA or Me6[14]aneN4 as ligand. Mn of St-P4VP could be controlled in a range from 2.0×103 to 1×104 g/mol by varying the ratio of monomer to initiator from 1:25 to 1:100. The structure was characterized by FTIR and 1H-NMR. In order to study the living character of C=C bond in St-P4VP end, a homopolymerization of St-P4VP is done. Mn was increased from 2.90×103 to 2.88×104, 6.11×103 to 5.8×104. It means that the C=C bond in end of St-P4VP has high reacting activity. The macromonomer with a halogen atom in end can initiate polymerization of new monomer which is expected to obtain diblock macromonomer.
进而以5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环化合物(Me6[14]aneN4)为配体, CuCl为催化剂,由PtBMA-Cl引发4-乙烯基吡啶(4VP)进行溶液ATRP反应,合成得到了聚甲基丙烯酸叔丁酯-b-聚4-乙烯基吡啶(PtBMA-b-P4VP)嵌段共聚物。研究了溶剂、配体的种类对合成嵌段共聚物ATRP过程的影响,制得了分子量可控的PtBMA-b-P4VP。用FTIR、1H-NMR、GPC对产物的结构和分子量进行了表征,结果表明所得嵌段共聚物的结构明确,为目标产物。通过对嵌段共聚物PtBMA-b-P4VP的PtBMA链段进行定向水解,得到聚甲基丙烯酸-b-聚4-乙烯基吡啶(PMAA-b-P4VP)嵌段共聚物,初步研究其在不同pH条件下的胶束化行为。重点研究对P4VP链段进行了季铵化反应,得到了聚甲基丙烯酸-b-季铵化聚4-乙烯基吡啶(PMAA-b-QPVPB)亲水性嵌段共聚物。
以Me6[14]aneN4为配体,CuCl为催化剂,在异丙醇溶液中以对氯甲基苯乙烯(CMSt)为功能性引发剂引发4VP进行ATRP反应,以得到末端带有不饱和双键的大分子单体(St-P4VP),考察了不同配体对4VP的ATRP反应过程的影响。通过改变引发剂与单体的物质的量之比,可将St-P4VP的相对分子质量控制在2.0×103～1×104范围内。用FTIR、1H-NMR对产物的结构进行了表征,结果表明所得大分子单体St-P4VP的结构明确。使不同分子量的St-P4VP大分子单体进行均聚反应,由GPC测定结果显示,大分子单体的相对分子质量从2.90×103增加到2.88×104 ,从6.11×103增加到5.8×104,说明所制备的St-P4VP末端上的双键具有良好的聚合反应活性。由于该大分子单体端基α位上含有诱导共轭基团的氯原子,可以引发单体进行聚合,有望得到新的两嵌段大分子单体。
In this paper, a solusion atom transfer radical polymerization (ATRP) of tert-butylmethacrylate (tBMA) was first studied. Ethyl-2-chloro-propionate (ECP) was selected as initiator, 2,2’-bipyridyl (bpy) and N,N,N′,N″,N″-penta-methyldiethylenetriamine (PMDETA) as ligand, with CuCl as catalyst in DMF. It was found that ligand could clearly affect polymerization rate of tBMA monomer based on measurement of molecular weight of PtBMA-Cl by using gel permeation chromatography (GPC) under different ligand system. The polymerization regulations were compared for different systems. The number average molecular weight (Mn) of PtBMA-Cl could be controlled from 1.8×103 to 1×104 g/mol by varying the ratio of monomer to initiator in range of 1:25 to 1:100, and distribution of molecular weight (Mw/Mn) kept low than 1.30. The structure of the PtBMA-Cl was characterized by fourier transform infrared (FTIR) and nuclear magnetic resonance (1H-NMR). It was found that the obtained PtBMA-Cl had a specific structure.
A solution ATRP of 4-vinylpyridine (4VP) was then studied using resulting PtBMA-Cl as macroinitiator, CuCl as catalyst, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclote- tradecane (Me6[14]aneN4) as ligand to form block copolymer. It was found that different solvent and ligand could affect the polymerization of 4VP. PtBMA-b-P4VP was characterized by FTIR, 1H-NMR and GPC. Furthermore, the hydrolysis of the synthesized PtBMA-b-P4VP was finished under room temperature to form block copolymer PMAA-b-P4VP. The self-assembly of this block copolymer in selective solvents was also studied. The focus is that the quaternization of the synthesized PtBMA-b-P4VP was finished. The quaternizated diblock copolymer was then hydrolyzed under room temperature to form hydrophilic PMAA-b-QPVPB diblock copolymer.
Also, a solusion ATRP of 4VP was studied using CuCl as catalyst, p-chloromethylstyrene (CMSt) as functional initiator to synthesize macromonomer (St-P4VP) in the presence of bpy, PMDETA or Me6[14]aneN4 as ligand. Mn of St-P4VP could be controlled in a range from 2.0×103 to 1×104 g/mol by varying the ratio of monomer to initiator from 1:25 to 1:100. The structure was characterized by FTIR and 1H-NMR. In order to study the living character of C=C bond in St-P4VP end, a homopolymerization of St-P4VP is done. Mn was increased from 2.90×103 to 2.88×104, 6.11×103 to 5.8×104. It means that the C=C bond in end of St-P4VP has high reacting activity. The macromonomer with a halogen atom in end can initiate polymerization of new monomer which is expected to obtain diblock macromonomer.
引文
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