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
Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast...Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.展开更多
Self-healable polyacrylamide-based hydrogels were prepared at room temperature via a one-step emulsion copolymerization of acrylamide（AM）,dodecyl 2-methacryIate（DM）,and 5-acetylaminopentyl acrylate（AAPA） using s...Self-healable polyacrylamide-based hydrogels were prepared at room temperature via a one-step emulsion copolymerization of acrylamide（AM）,dodecyl 2-methacryIate（DM）,and 5-acetylaminopentyl acrylate（AAPA） using sodium dodecyl sulfonate（SDS） as the emulsifier and ammonium persulfate（APS）as the initiator.The produced linear multi-block copolymer chains are composed of randomly-linked hydrophilic polyacrylamide segments（PAM） and hydrophobic segments constituted by DM and AAPA units（P（DM-co-AAPA））.The P（DM-co-AAPA） segments will self-aggregate into hydrophobic microdomains during the polymerization process driven by the hydrophobic interactions,and finally separate from water phase,acting as the crosslinks and leading to the formation of strong hydrogels with a storage modulus as high as 400 Pa.These hydrophobic microdomains will be dissolved in water when the temperature increases to 70℃,resulting in a temperature-responsive reversible sol-gel transition of the prepared hydrogels.Furthermore,the prepared hydrogels have excellent self-healing ability.The broken hydrogels can be automatically healed into a body with a same strength within 2-min＇s contact.This work provides a new simple way to prepare reversible physical crosslinked hydrogel with high strength and self-healing efficiency.展开更多
The effect of oleates as emulsifiers on graft copolymerization of starch with acrylamide (AM) and acrylic acid (AA) in the inverse emulsion system is studied in this paper .The effect of the kinds of emulsifiers, the ...The effect of oleates as emulsifiers on graft copolymerization of starch with acrylamide (AM) and acrylic acid (AA) in the inverse emulsion system is studied in this paper .The effect of the kinds of emulsifiers, the proportion of mixed emulsifiers, the dosage of emulsifiers as well as the preparation methods of water-in-oil emulsion on monomer conversion, grafting ratio, and specific viscidity is discussed. The result indicates that calcium oleate or magnesium oleate as the emulsifier is better than sodium oleate or potassium oleate, and the mixture of oleic acid and its salt is better than any single compound.It is also concluded that monomer conversion reaches 99.7% and grafting ratio reaches 98.4% when m(oleic acid)/m(oleate sodium) is 60/40,m(starch)/m(monomers) is 1/1(among the monomers m(AM)/m(AA) is 4/1),v(oil phase)/v(water phase) is 1.2/1, initiator concentration is 2.4×10 -4mol·L -1,reaction temperature is 45～50℃,and reaction time is 6 hours.When mixed emulsifers concentration is 6%, the intrinsic viscidity reaches 1100ml·g -1.展开更多
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 supported by the National Natural Science Foundation of China (No. 21674059)
文摘Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.
基金supported by the Petro China Innovation Foundation(No.2014D-5006-0201)the National Natural Science Foundation of China(Nos.51473152 and 51573174)the Fundamental Research Funds for the Central Universities(Nos.WK2060200012,WK3450000001)
文摘Self-healable polyacrylamide-based hydrogels were prepared at room temperature via a one-step emulsion copolymerization of acrylamide（AM）,dodecyl 2-methacryIate（DM）,and 5-acetylaminopentyl acrylate（AAPA） using sodium dodecyl sulfonate（SDS） as the emulsifier and ammonium persulfate（APS）as the initiator.The produced linear multi-block copolymer chains are composed of randomly-linked hydrophilic polyacrylamide segments（PAM） and hydrophobic segments constituted by DM and AAPA units（P（DM-co-AAPA））.The P（DM-co-AAPA） segments will self-aggregate into hydrophobic microdomains during the polymerization process driven by the hydrophobic interactions,and finally separate from water phase,acting as the crosslinks and leading to the formation of strong hydrogels with a storage modulus as high as 400 Pa.These hydrophobic microdomains will be dissolved in water when the temperature increases to 70℃,resulting in a temperature-responsive reversible sol-gel transition of the prepared hydrogels.Furthermore,the prepared hydrogels have excellent self-healing ability.The broken hydrogels can be automatically healed into a body with a same strength within 2-min＇s contact.This work provides a new simple way to prepare reversible physical crosslinked hydrogel with high strength and self-healing efficiency.
文摘The effect of oleates as emulsifiers on graft copolymerization of starch with acrylamide (AM) and acrylic acid (AA) in the inverse emulsion system is studied in this paper .The effect of the kinds of emulsifiers, the proportion of mixed emulsifiers, the dosage of emulsifiers as well as the preparation methods of water-in-oil emulsion on monomer conversion, grafting ratio, and specific viscidity is discussed. The result indicates that calcium oleate or magnesium oleate as the emulsifier is better than sodium oleate or potassium oleate, and the mixture of oleic acid and its salt is better than any single compound.It is also concluded that monomer conversion reaches 99.7% and grafting ratio reaches 98.4% when m(oleic acid)/m(oleate sodium) is 60/40,m(starch)/m(monomers) is 1/1(among the monomers m(AM)/m(AA) is 4/1),v(oil phase)/v(water phase) is 1.2/1, initiator concentration is 2.4×10 -4mol·L -1,reaction temperature is 45～50℃,and reaction time is 6 hours.When mixed emulsifers concentration is 6%, the intrinsic viscidity reaches 1100ml·g -1.
