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
Ternary polyamide(tPA) copolymer is susceptible to degradation when it is irradiated by electron beam(e-beam), and effective methods to avoid degradation and increase gel content are highly desirable for crosslinking....Ternary polyamide(tPA) copolymer is susceptible to degradation when it is irradiated by electron beam(e-beam), and effective methods to avoid degradation and increase gel content are highly desirable for crosslinking.Carboxylated multiwall carbon nanotube(MWCNT) is modified by hydroxyethyl acrylate(HEA) in this paper and used as a co-agent for the e-beam irradiation crosslinking of tPA copolymer. HEA modified MWCNT can function as an effective co-agent for the e-beam irradiation crosslinking of tPA copolymer to increase the gel content and improve the mechanical properties of tPA copolymer. Under an irradiation of 160 kGy, addition of 2 parts per hundred(phr) HEA modified MWCNT into tPA copolymer can increase the gel content of tPA copolymer from about 20% to 40%(mass ratio) and increase the tensile strength from 45 to 59 MPa. The irradiation also affects the glass transition temperature of tPA copolymer by increasing the gel content. The results show that HEA modified MWCNT can act as a nucleating agent to increase the crystallization temperature, melting temperature and crystallinity of tPA copolymer.展开更多
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.
基金the National Natural Science Foundation of China(No.51273109)
文摘Ternary polyamide(tPA) copolymer is susceptible to degradation when it is irradiated by electron beam(e-beam), and effective methods to avoid degradation and increase gel content are highly desirable for crosslinking.Carboxylated multiwall carbon nanotube(MWCNT) is modified by hydroxyethyl acrylate(HEA) in this paper and used as a co-agent for the e-beam irradiation crosslinking of tPA copolymer. HEA modified MWCNT can function as an effective co-agent for the e-beam irradiation crosslinking of tPA copolymer to increase the gel content and improve the mechanical properties of tPA copolymer. Under an irradiation of 160 kGy, addition of 2 parts per hundred(phr) HEA modified MWCNT into tPA copolymer can increase the gel content of tPA copolymer from about 20% to 40%(mass ratio) and increase the tensile strength from 45 to 59 MPa. The irradiation also affects the glass transition temperature of tPA copolymer by increasing the gel content. The results show that HEA modified MWCNT can act as a nucleating agent to increase the crystallization temperature, melting temperature and crystallinity of tPA copolymer.
