Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer co...Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75 'C, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of 11.3%-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.展开更多
A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the ato...A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.展开更多
Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl...Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.展开更多
Controlled radical photopolymerization of n-butyl methacrylate(n-BMA) mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy(HTEMPO) was carried out in bulk at ambient temperature. It was found that obtained n...Controlled radical photopolymerization of n-butyl methacrylate(n-BMA) mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy(HTEMPO) was carried out in bulk at ambient temperature. It was found that obtained n-BMA homopolymers exhibited narrow polydispersities of around 1.4, which was characterized by GPC. Plots of number-average molecular weight vs. conversion and Ln([Mo]/[M]) vs. time were liner respectively, indicating that was a controlled photopolymerization.展开更多
The dynamics of a series of poly(n-alkyl methacrylates) is investigated by means of ^(13)C spin-lattice relaxation experiments. The results show that the dynamics has the polymer property dependence.
Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dos...Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dose and monomer concentration on grafting degree was determined. The grafted samples were verified by FTIR-ATR spectroscopy and swelling;thermal properties were analyzed by DSC and TGA. The stimuli-responsive behavior was studied by swelling and/or DSC. Thermo- and pH-sensitive films of (PP-g-DEAEMA)-g-NVCL presented a pH critical at 3.2 and LCST around 63.5℃.展开更多
The effects of oxygen on the chemical structure, morphology, hydrophilicity and drug release behavior of radio-frequency plasma poly n- butyl methacrylate (PPBMA) thin film were carded out for the first time. ATR-FT...The effects of oxygen on the chemical structure, morphology, hydrophilicity and drug release behavior of radio-frequency plasma poly n- butyl methacrylate (PPBMA) thin film were carded out for the first time. ATR-FTIR and XPS showed that oxygen had little influence on the chemical structure and composition of PPBMAs, which did not agree with the thought that the presence of oxygen gas would increase the oxidized carbon functionalities in the plasma polymer. SEM and static contact angle measurement indicated that in case of deposition with oxygen, the smoothness and hydrophilicity of PPBMA were dramatically improved. The drug release behavior showed that drug release from the PPBMA coating without oxygen was biphasic patterns, while from PPBMA coating with oxygen was Higuchi release. These results were helpful for the design and tailoring of the PPBMA polymer film and other of plasma polymers film, but could provide a new idea for the drug release controlled form.展开更多
A kind of novel copolymer hydrogel of poly(N, N-dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) (poly[DMAEMA/NIPAAm]) was synthesized by the initiation of K2S2O8, N, N'-methylene-bis(acrylamide) (Bis...A kind of novel copolymer hydrogel of poly(N, N-dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) (poly[DMAEMA/NIPAAm]) was synthesized by the initiation of K2S2O8, N, N'-methylene-bis(acrylamide) (Bis) was used as the crosslinker. The effects of monomer content, pH and temperature on swelling ratio of the hydrogel were investigated; the thermo-sensitivity in deionized water and in physiological saline was determined. It showed that the swelling ratio of the hydrogel could be changed by changing the temperature or pH alternately. Both swelling ratio and LCST (Lower Critical Solution Temperature) of the hydrogel decreased with the increase of NIPAAm in the co-polymer content.展开更多
Six different N-alkyl substituted acrylarnide nonionic hydrogels were prepared and their swelling characteristics were measured. Poly N-isopropyl acrylamide (PNIPA) and poly N-n-propyl-acrylamide (PNNPA) temperature s...Six different N-alkyl substituted acrylarnide nonionic hydrogels were prepared and their swelling characteristics were measured. Poly N-isopropyl acrylamide (PNIPA) and poly N-n-propyl-acrylamide (PNNPA) temperature sensitive hydrogels were chosen as the nonionic temperature sensitive hydrogels for concentration of very dilute aqueous protein solution. The separation properties of PNIPA and PNNPA hydr0gels with different network dimensions were studied and the modification of the hydrogels was surveyed in order to decrease their surface adsorption of protein molecules. The experimental results of the concentration of BSA (Bovin serum albumin) dilute aqueous solution by hydroxylpropyl methacrylate (HPMA) copolymerized PNIPA hydrogel were given. The value and the limitation of concentration of dilute aqueous protein solution by this method was evaluated.展开更多
Poly N-isopropyl acrylamide (abbreviated as PNIPA) as a kind of thermally sensitive hydrogel is utilized to concentrate Bovin Serum Albumin (BSA) solution. In order to decrease its surface adsorption to BSA in aqueous...Poly N-isopropyl acrylamide (abbreviated as PNIPA) as a kind of thermally sensitive hydrogel is utilized to concentrate Bovin Serum Albumin (BSA) solution. In order to decrease its surface adsorption to BSA in aqueous solution, surface layer grafting of the gels by radiation technology was carried out. The results showed that hydroxyl propyl methacrylate (HPMA) grained gel exhibited a low level of BSA adsorption and still kept the original thermally sensitive properties of PNIPA hydrogels.展开更多
Poly(N,N-dimethylaminoethyl methacrylate) (polyDMAEMA) hydrogels prepared by gamma-irradiation showed obvious temperature-sensitivity in a temperature range of 38-40degreesC and pH-sensitivity at pH=2.5. They also sho...Poly(N,N-dimethylaminoethyl methacrylate) (polyDMAEMA) hydrogels prepared by gamma-irradiation showed obvious temperature-sensitivity in a temperature range of 38-40degreesC and pH-sensitivity at pH=2.5. They also showed electric response behavior although it was not typical. The hydrogels were used in controlled release at different pH, temperature, and electric voltage. The release rates of methylene blue (MB) from the gels at 52degreesC and pH=1.24 were faster than those at 20degreesC and pH=10.56, respectively. In addition, the release rate at a field voltage of 5.0 was also faster than that without electric field.展开更多
基金The work was supported by the National Natural Science Foundation of China (Grant No. 20074033) and the High-TechResearch and Development Program of China (Grant no. 2002AA601230).
文摘Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75 'C, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of 11.3%-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.
文摘A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.
文摘Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.
基金Financially supports from the National Natural Science Foundation of China(No.20274023 and 20474036)Guangdong Province Natural Science Foundation(No.021241)are gratefully acknowledged.
文摘Controlled radical photopolymerization of n-butyl methacrylate(n-BMA) mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy(HTEMPO) was carried out in bulk at ambient temperature. It was found that obtained n-BMA homopolymers exhibited narrow polydispersities of around 1.4, which was characterized by GPC. Plots of number-average molecular weight vs. conversion and Ln([Mo]/[M]) vs. time were liner respectively, indicating that was a controlled photopolymerization.
基金Supported by The National Natural Science Foundation of China
文摘The dynamics of a series of poly(n-alkyl methacrylates) is investigated by means of ^(13)C spin-lattice relaxation experiments. The results show that the dynamics has the polymer property dependence.
文摘Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dose and monomer concentration on grafting degree was determined. The grafted samples were verified by FTIR-ATR spectroscopy and swelling;thermal properties were analyzed by DSC and TGA. The stimuli-responsive behavior was studied by swelling and/or DSC. Thermo- and pH-sensitive films of (PP-g-DEAEMA)-g-NVCL presented a pH critical at 3.2 and LCST around 63.5℃.
文摘The effects of oxygen on the chemical structure, morphology, hydrophilicity and drug release behavior of radio-frequency plasma poly n- butyl methacrylate (PPBMA) thin film were carded out for the first time. ATR-FTIR and XPS showed that oxygen had little influence on the chemical structure and composition of PPBMAs, which did not agree with the thought that the presence of oxygen gas would increase the oxidized carbon functionalities in the plasma polymer. SEM and static contact angle measurement indicated that in case of deposition with oxygen, the smoothness and hydrophilicity of PPBMA were dramatically improved. The drug release behavior showed that drug release from the PPBMA coating without oxygen was biphasic patterns, while from PPBMA coating with oxygen was Higuchi release. These results were helpful for the design and tailoring of the PPBMA polymer film and other of plasma polymers film, but could provide a new idea for the drug release controlled form.
文摘A kind of novel copolymer hydrogel of poly(N, N-dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) (poly[DMAEMA/NIPAAm]) was synthesized by the initiation of K2S2O8, N, N'-methylene-bis(acrylamide) (Bis) was used as the crosslinker. The effects of monomer content, pH and temperature on swelling ratio of the hydrogel were investigated; the thermo-sensitivity in deionized water and in physiological saline was determined. It showed that the swelling ratio of the hydrogel could be changed by changing the temperature or pH alternately. Both swelling ratio and LCST (Lower Critical Solution Temperature) of the hydrogel decreased with the increase of NIPAAm in the co-polymer content.
基金This project sponsored by the National Natural Science Foundation of China.
文摘Six different N-alkyl substituted acrylarnide nonionic hydrogels were prepared and their swelling characteristics were measured. Poly N-isopropyl acrylamide (PNIPA) and poly N-n-propyl-acrylamide (PNNPA) temperature sensitive hydrogels were chosen as the nonionic temperature sensitive hydrogels for concentration of very dilute aqueous protein solution. The separation properties of PNIPA and PNNPA hydr0gels with different network dimensions were studied and the modification of the hydrogels was surveyed in order to decrease their surface adsorption of protein molecules. The experimental results of the concentration of BSA (Bovin serum albumin) dilute aqueous solution by hydroxylpropyl methacrylate (HPMA) copolymerized PNIPA hydrogel were given. The value and the limitation of concentration of dilute aqueous protein solution by this method was evaluated.
基金This project is sponsored by the National Natural Science Foundation of China.
文摘Poly N-isopropyl acrylamide (abbreviated as PNIPA) as a kind of thermally sensitive hydrogel is utilized to concentrate Bovin Serum Albumin (BSA) solution. In order to decrease its surface adsorption to BSA in aqueous solution, surface layer grafting of the gels by radiation technology was carried out. The results showed that hydroxyl propyl methacrylate (HPMA) grained gel exhibited a low level of BSA adsorption and still kept the original thermally sensitive properties of PNIPA hydrogels.
基金This work was financially supported by the National Natural Science Foundation of China (No. 39870227) this paper was reported on International Symposium on Radiation Technology in Emerging Industry Application, held on Nov. 6-10, 2001 in Beijing, China
文摘Poly(N,N-dimethylaminoethyl methacrylate) (polyDMAEMA) hydrogels prepared by gamma-irradiation showed obvious temperature-sensitivity in a temperature range of 38-40degreesC and pH-sensitivity at pH=2.5. They also showed electric response behavior although it was not typical. The hydrogels were used in controlled release at different pH, temperature, and electric voltage. The release rates of methylene blue (MB) from the gels at 52degreesC and pH=1.24 were faster than those at 20degreesC and pH=10.56, respectively. In addition, the release rate at a field voltage of 5.0 was also faster than that without electric field.