A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The su...A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.展开更多
A series of hydrophobically associating polyacrylamides modified by small amounts （〈 3 mol%） of a self- associative cationic monomer 4-（2-（acryloyloxy） ethoxy） benzyl tri-ethyl ammonium bromide （AEBA） as hydr...A series of hydrophobically associating polyacrylamides modified by small amounts （〈 3 mol%） of a self- associative cationic monomer 4-（2-（acryloyloxy） ethoxy） benzyl tri-ethyl ammonium bromide （AEBA） as hydrophobe were synthesized by radical copolymerization in aqueous solutions without external surfactants. The resulting eopolymers containing a multiblock structure exhibited a high tendency for hydrophobic association and a high thickening capacity. Solution properties and aggregation structures were investigated by viscometry and fluorescence technique. The high viscosity enhancement was found as the polymer concentration beyond a critical value c＊ and strongly depended on the copolymer microstructures. The number and length of hydrophobic microblocks within the copolymer backbones could be controlled by changing the AEBA concentration in copolymerization system. Addition of salt induced more hydrophobic association and viscosity enhancement. The synthesis method used was simple and environmentally friendly without any external surfactant contamination in comparison with the conventional micellar copolymerization.展开更多
A novel dualfunctional monomer, 2-（2＇,2＇,6＇,6＇-tetramethyl-piperidinyl-1＇-oxy）methylbenzene-1,4-dioyl chloride hydrochloride, with two acid chloride groups for step-growth polymerization and a nitroxide group f...A novel dualfunctional monomer, 2-（2＇,2＇,6＇,6＇-tetramethyl-piperidinyl-1＇-oxy）methylbenzene-1,4-dioyl chloride hydrochloride, with two acid chloride groups for step-growth polymerization and a nitroxide group for the mediation of living radical polymerization was synthesized. It was first copolymerized with terephthaloyl chloride and p- phenylenediamine at a feed molar ratio of 1：3：4 in N-methyl-2-pyrrolidone containing 10 wt% calcium chloride at -10℃ to yield a poly（p-phenylene terephthalamide） based macroinitiator, which initiated radical polymerization of styrene at 125℃ to obtain a series of poly（p-phenylene terephthalamide）-g-polystyrenes. A combinatory analysis of proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, elementary analysis, thermogravimetry and gel permeation chromatography indicated that the macroinitiator induced the radical polymerization of styrene to proceed in a well- controlled way. The molecular weight of side-chains increased with an increase of monomer conversion, and the molecular weight distribution index remained lower than 1.5. The graft copolymers showed a remarkably improved solubility in N- methyl-2-pyrrolidone and much depressed crystallinity in bulk.展开更多
This study examines the issues in development of pharmacokinetic single compartment model for systems that obey free radical copolymerization kinetics. Copolymer composition as a function of reactivity ratios of comon...This study examines the issues in development of pharmacokinetic single compartment model for systems that obey free radical copolymerization kinetics. Copolymer composition as a function of reactivity ratios of comonomers for well mixed case was derived. For some cases, such as DEF-AN, diethyl fumarate and acrylonitrile system multiplicity in composition were found. The analysis is extended to n monomers. State space model expressions are used and the QSSA assumption is stated in state space equation form. Conditions when damped oscillations can be expected are noted. In addition to multiplicity in product composition, an account of reactivity ratios and other instances of multi- plicity were found during the pharmacodynamics of the free radical polymerization reactions. A careful study of initiated case, thermal case, 1 CSTR and 2 CSTRS was undertaken and results were presented. Numerical integration techniques were employed on the desktop computer. Steady state and transient state conversion for initiated case and thermal case for 1 CSTR and 2 CSTRs were calculated and plotted in Figures 7-9 and 12. No multiplicity was found in the thermal case for 1 CSTR in the dynamics of transient monomer conversion. Multiplicity was found in the initiated case for 1 CSTR in the dynamics of transient conversion of monomer. The multiplicity was found in the second CSTR for the case of 2 CSTRs in series. No multiplicity was found in the case of initiator decay.展开更多
Polystyrene macromonomers with different molecular weight were prepared by radical polymerization of styrene(St) in benzene using β-methacryloxylethyl 2-N,N-diethyldithiocarbamylacetate (MAEDCA) as a monomer-iniferte...Polystyrene macromonomers with different molecular weight were prepared by radical polymerization of styrene(St) in benzene using β-methacryloxylethyl 2-N,N-diethyldithiocarbamylacetate (MAEDCA) as a monomer-iniferter.Characterization of the macromonomer by ~1H-NMR showed that the end groups were α-methacrylyoxylethyloxycarbonyl-methyl and ω-(N,N-diethyldithiocarbamyl). The macromonomer was difficult to homopolymerize, but it was easilycopolymerized with methyl methacrylate (MMA) initiated by AIBN to form graft copolymers (PMMA-g-PSt) with PStbranches randomly distributed along the PMMA backbone. Copolymerization reaction and the structure of the graft copolymers were strongly affected by M_n and concentration of the macromonomer. The composition and M_n of the purified graft copolymer were determined by ~1H-NMR and GPC analysis.展开更多
合成了含氢聚甲基硅氧烷/聚丙烯酸酯共聚乳液.研究了聚合工艺、配方组成及操作方式对聚合稳定性、动力学、乳液的粒径分布和产物性能的影响.采用部分预乳化单体滴加法(工艺A)和部分纯单体滴加法(工艺B)两种工艺,聚硅氧烷采用高速预乳化...合成了含氢聚甲基硅氧烷/聚丙烯酸酯共聚乳液.研究了聚合工艺、配方组成及操作方式对聚合稳定性、动力学、乳液的粒径分布和产物性能的影响.采用部分预乳化单体滴加法(工艺A)和部分纯单体滴加法(工艺B)两种工艺,聚硅氧烷采用高速预乳化滴加进料方式.用COULTER LS 粒径仪和Nicolet 傅立叶变换红外光谱仪分别测定共聚乳液的粒径分布和产物的结构.研究结果表明,采用A、B两种工艺均能得到平均粒径为0.101~0.103(m的单峰窄分布共聚乳液,并能有效地将含氢聚硅氧烷引入到共聚物大分子中.含氢聚硅氧烷的引入量为3%(质量)时,共聚物涂膜具有柔软、滑爽和强度高等优点.展开更多
基金This work was partly supported by the National Natural Science Foundation of China (No. 50273008)Qingdao Municipal Science and Technology Commission.
文摘A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.
文摘A series of hydrophobically associating polyacrylamides modified by small amounts （〈 3 mol%） of a self- associative cationic monomer 4-（2-（acryloyloxy） ethoxy） benzyl tri-ethyl ammonium bromide （AEBA） as hydrophobe were synthesized by radical copolymerization in aqueous solutions without external surfactants. The resulting eopolymers containing a multiblock structure exhibited a high tendency for hydrophobic association and a high thickening capacity. Solution properties and aggregation structures were investigated by viscometry and fluorescence technique. The high viscosity enhancement was found as the polymer concentration beyond a critical value c＊ and strongly depended on the copolymer microstructures. The number and length of hydrophobic microblocks within the copolymer backbones could be controlled by changing the AEBA concentration in copolymerization system. Addition of salt induced more hydrophobic association and viscosity enhancement. The synthesis method used was simple and environmentally friendly without any external surfactant contamination in comparison with the conventional micellar copolymerization.
基金supported by the National Natural Science Foundation of China(No.20774001)the National Science Fund for Distinguished Young Scholars(No.20325415)
文摘A novel dualfunctional monomer, 2-（2＇,2＇,6＇,6＇-tetramethyl-piperidinyl-1＇-oxy）methylbenzene-1,4-dioyl chloride hydrochloride, with two acid chloride groups for step-growth polymerization and a nitroxide group for the mediation of living radical polymerization was synthesized. It was first copolymerized with terephthaloyl chloride and p- phenylenediamine at a feed molar ratio of 1：3：4 in N-methyl-2-pyrrolidone containing 10 wt% calcium chloride at -10℃ to yield a poly（p-phenylene terephthalamide） based macroinitiator, which initiated radical polymerization of styrene at 125℃ to obtain a series of poly（p-phenylene terephthalamide）-g-polystyrenes. A combinatory analysis of proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, elementary analysis, thermogravimetry and gel permeation chromatography indicated that the macroinitiator induced the radical polymerization of styrene to proceed in a well- controlled way. The molecular weight of side-chains increased with an increase of monomer conversion, and the molecular weight distribution index remained lower than 1.5. The graft copolymers showed a remarkably improved solubility in N- methyl-2-pyrrolidone and much depressed crystallinity in bulk.
文摘This study examines the issues in development of pharmacokinetic single compartment model for systems that obey free radical copolymerization kinetics. Copolymer composition as a function of reactivity ratios of comonomers for well mixed case was derived. For some cases, such as DEF-AN, diethyl fumarate and acrylonitrile system multiplicity in composition were found. The analysis is extended to n monomers. State space model expressions are used and the QSSA assumption is stated in state space equation form. Conditions when damped oscillations can be expected are noted. In addition to multiplicity in product composition, an account of reactivity ratios and other instances of multi- plicity were found during the pharmacodynamics of the free radical polymerization reactions. A careful study of initiated case, thermal case, 1 CSTR and 2 CSTRS was undertaken and results were presented. Numerical integration techniques were employed on the desktop computer. Steady state and transient state conversion for initiated case and thermal case for 1 CSTR and 2 CSTRs were calculated and plotted in Figures 7-9 and 12. No multiplicity was found in the thermal case for 1 CSTR in the dynamics of transient monomer conversion. Multiplicity was found in the initiated case for 1 CSTR in the dynamics of transient conversion of monomer. The multiplicity was found in the second CSTR for the case of 2 CSTRs in series. No multiplicity was found in the case of initiator decay.
文摘Polystyrene macromonomers with different molecular weight were prepared by radical polymerization of styrene(St) in benzene using β-methacryloxylethyl 2-N,N-diethyldithiocarbamylacetate (MAEDCA) as a monomer-iniferter.Characterization of the macromonomer by ~1H-NMR showed that the end groups were α-methacrylyoxylethyloxycarbonyl-methyl and ω-(N,N-diethyldithiocarbamyl). The macromonomer was difficult to homopolymerize, but it was easilycopolymerized with methyl methacrylate (MMA) initiated by AIBN to form graft copolymers (PMMA-g-PSt) with PStbranches randomly distributed along the PMMA backbone. Copolymerization reaction and the structure of the graft copolymers were strongly affected by M_n and concentration of the macromonomer. The composition and M_n of the purified graft copolymer were determined by ~1H-NMR and GPC analysis.
文摘合成了含氢聚甲基硅氧烷/聚丙烯酸酯共聚乳液.研究了聚合工艺、配方组成及操作方式对聚合稳定性、动力学、乳液的粒径分布和产物性能的影响.采用部分预乳化单体滴加法(工艺A)和部分纯单体滴加法(工艺B)两种工艺,聚硅氧烷采用高速预乳化滴加进料方式.用COULTER LS 粒径仪和Nicolet 傅立叶变换红外光谱仪分别测定共聚乳液的粒径分布和产物的结构.研究结果表明,采用A、B两种工艺均能得到平均粒径为0.101~0.103(m的单峰窄分布共聚乳液,并能有效地将含氢聚硅氧烷引入到共聚物大分子中.含氢聚硅氧烷的引入量为3%(质量)时,共聚物涂膜具有柔软、滑爽和强度高等优点.
