We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols.Four poly(dithioacetal)s(P1-P4)were prepared via the base-catalyzed thiol-yne"...We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols.Four poly(dithioacetal)s(P1-P4)were prepared via the base-catalyzed thiol-yne"click"polyaddition of two dithiols(1,4-butanedithiol(4S)and 1,5-pentanedithiol(5S))and two alkynones(3-butyn-2-one(Y1)and 1-phenyl-2-propyn-1-one(Y2))at high concentrations.We systematically investigated the base-catalyzed polymerization of 4S and Y1(for polymer PI)under different conditions,and found that this polymerization was a highly concentration-dependent dynamic system:polymer PI was formed at high concentration,while seven-membered dithioacetal,1-(1,3-dithiepan-2-yl)propan-2-one(C1),was obtained at low concentration.The polymerization of 4S and Y2(for polymer P4)displayed similar polymerization behavior,generating 2-(1,3-dithiepan-2-yl)-1-phenylethanone(C4)at low concentration.On the contrary,polymer P2(from Y1 and 5S)was exclusively obtained with no formation of eight-membered dithioacetal.The polymerizations of Y1 with 1,2-ethanedithiol(2S)and 1,3-dimercaptopropane(3S)only afforded corresponding five-and six-membered dithioacetals,1-(1,3-dithiolan-2-yl)propan-2-one(C2)and 1-(1,3-dithian-2-yl)propan-2-one(C3).This dynamic behavior of PI and P4 was attributed to the concentration-dependent retro-Michael addition reaction between a thiol and a β-sulfido-α,β-unsaturated carbonyl compound catalyzed by bases.Furthermore,polymers P1 and P4 could be depolymerized into Cl and C4 in yields of 58% and 95%,respectively.The ring-opening polymerization of Cl at high concentration could successfully regenerate polymer PI.Thus,a new type of closed-loop recyclable poly(dithioacetal)s was developed.展开更多
A stable epoxy emulsion was prepared with epoxy resin （EP） as raw material, 2-acrylamido-2- methyl-l-propanesulfonic acid （AMPS） as modifier and benzoyl peroxide as initiator. By criterion of yield of the copolyme...A stable epoxy emulsion was prepared with epoxy resin （EP） as raw material, 2-acrylamido-2- methyl-l-propanesulfonic acid （AMPS） as modifier and benzoyl peroxide as initiator. By criterion of yield of the copolymer AMPS-EP, water-solubility, change of the acid value and intrinsic viscosity [η] along with reaction time, the copolymerization course was deduced. It is found that during the process, AMPS takes part in both the grafting copolymerization with epoxy principal chain and the ring-opening polyaddition with epoxy group. It is also discovered that the yield of AMPS-EP and water dispersing varies with reaction time. When it reaches 1.5 h, AMPS-EP can obtain good water-solubility; but the water-solubility will go bad gradually if it exceeds 3.5 h.. R spectrum analysis indicates that partial epoxy group partially remains and the others create sulfonic ester.展开更多
In recent years, sugar-derived polymer materials have been actively investigated. In research of polyurethane (PU), sugar has been used as a raw material because it has properties similar to polyol. However, the elast...In recent years, sugar-derived polymer materials have been actively investigated. In research of polyurethane (PU), sugar has been used as a raw material because it has properties similar to polyol. However, the elastic property of the obtained PU is substantially lost. Hence, the introduction of a sugar unit to PU while maintaining the elastic property remains a challenge in polymer chemistry. Here, we report the synthesis of a polyurethane elastomer (PUE) with a trehalose unit using raw materials such as an aromatic diisocyanate (4,4’-diphenylmethane diisocyanate), polyols including a polyether polyol (polytetramethylene glycol), two polyester polyols (polycaprolactone and polycarbonate diol), and trehalose. Novel PUEs with trehalose units are synthesized by a one-shot method. Trehalose, which has non-reducing properties, is used as sugar. The use of trehalose, which has been scarcely applied to PUE, is essential to obtain the desired PUEs with sugar units.展开更多
By using diphenyliodonium salts with different counterions as photo acid generators (PAGs), the effect of acidity on ring-opening polymerization of epoxy monomers and polycondensation of polyol with hexamethoxymethyl ...By using diphenyliodonium salts with different counterions as photo acid generators (PAGs), the effect of acidity on ring-opening polymerization of epoxy monomers and polycondensation of polyol with hexamethoxymethyl melamine (HMMM) was studied. The result shows that the rate of ring-opening polymerization is evidently dependent on the acidity of the acid and strong photo-generated acid is required. However, there is a leveling effect in the polycondensation system; if the photo-generated acid is stronger than protonated HMMM, the acidity does not obviously affect the polycondensation rate.展开更多
As anyone who has taught polymer chemistry to undergraduate students might already appreciate, we are faced with inherent difficulties in clearly communicating the subject matter due its interdisciplinary character. T...As anyone who has taught polymer chemistry to undergraduate students might already appreciate, we are faced with inherent difficulties in clearly communicating the subject matter due its interdisciplinary character. This paper is thus aimed at proposing a new educational plan to teach this fundamental course in order to overcome some inherent obstacles. It is especially devoted to professors in charge of teaching a first course in polymer chemistry. We intend to emphasize polymerization by beginning with the simplest chemical pathway, namely the living anionic polymerization. In addition, some pedagogical difficulties are outlined all along this paper. This novel and distinct way to teach polymer chemistry makes the students with a background in organic chemistry more equipped to face difficulties arising from the introduction of new concepts.展开更多
Polyaddition using isocyanate and polyol forms polyurethane elastomer (PUE). However, this method has rarely been applied to the construction of PUEs containing sucrose. Hence, the introduction of sucrose (disaccharid...Polyaddition using isocyanate and polyol forms polyurethane elastomer (PUE). However, this method has rarely been applied to the construction of PUEs containing sucrose. Hence, the introduction of sucrose (disaccharide) as a cross-linker via polyaddition remains a challenging subject in polymer chemistry. Here, we report the synthesis of PUEs using an aromatic isocyanate (4,4’-diphenylmethane diisocyanate), polyols including a polyether polyol (polytetramethylene glycol) and two polyester polyols (polycaprolactone and polycarbonate diols), and sucrose as a crosslinker by a one-shot method. The PUEs containing sucrose were successfully produced. The use of sucrose was essential to obtain the desired PUEs containing sucrose units in the main chain.展开更多
基金This work was financially supported by the National Key Research and Development Program of China(No.2016YFA0201400)the National Natural Science Foundation of China(Nos.21971005 and 21534001).
文摘We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols.Four poly(dithioacetal)s(P1-P4)were prepared via the base-catalyzed thiol-yne"click"polyaddition of two dithiols(1,4-butanedithiol(4S)and 1,5-pentanedithiol(5S))and two alkynones(3-butyn-2-one(Y1)and 1-phenyl-2-propyn-1-one(Y2))at high concentrations.We systematically investigated the base-catalyzed polymerization of 4S and Y1(for polymer PI)under different conditions,and found that this polymerization was a highly concentration-dependent dynamic system:polymer PI was formed at high concentration,while seven-membered dithioacetal,1-(1,3-dithiepan-2-yl)propan-2-one(C1),was obtained at low concentration.The polymerization of 4S and Y2(for polymer P4)displayed similar polymerization behavior,generating 2-(1,3-dithiepan-2-yl)-1-phenylethanone(C4)at low concentration.On the contrary,polymer P2(from Y1 and 5S)was exclusively obtained with no formation of eight-membered dithioacetal.The polymerizations of Y1 with 1,2-ethanedithiol(2S)and 1,3-dimercaptopropane(3S)only afforded corresponding five-and six-membered dithioacetals,1-(1,3-dithiolan-2-yl)propan-2-one(C2)and 1-(1,3-dithian-2-yl)propan-2-one(C3).This dynamic behavior of PI and P4 was attributed to the concentration-dependent retro-Michael addition reaction between a thiol and a β-sulfido-α,β-unsaturated carbonyl compound catalyzed by bases.Furthermore,polymers P1 and P4 could be depolymerized into Cl and C4 in yields of 58% and 95%,respectively.The ring-opening polymerization of Cl at high concentration could successfully regenerate polymer PI.Thus,a new type of closed-loop recyclable poly(dithioacetal)s was developed.
文摘A stable epoxy emulsion was prepared with epoxy resin （EP） as raw material, 2-acrylamido-2- methyl-l-propanesulfonic acid （AMPS） as modifier and benzoyl peroxide as initiator. By criterion of yield of the copolymer AMPS-EP, water-solubility, change of the acid value and intrinsic viscosity [η] along with reaction time, the copolymerization course was deduced. It is found that during the process, AMPS takes part in both the grafting copolymerization with epoxy principal chain and the ring-opening polyaddition with epoxy group. It is also discovered that the yield of AMPS-EP and water dispersing varies with reaction time. When it reaches 1.5 h, AMPS-EP can obtain good water-solubility; but the water-solubility will go bad gradually if it exceeds 3.5 h.. R spectrum analysis indicates that partial epoxy group partially remains and the others create sulfonic ester.
文摘In recent years, sugar-derived polymer materials have been actively investigated. In research of polyurethane (PU), sugar has been used as a raw material because it has properties similar to polyol. However, the elastic property of the obtained PU is substantially lost. Hence, the introduction of a sugar unit to PU while maintaining the elastic property remains a challenge in polymer chemistry. Here, we report the synthesis of a polyurethane elastomer (PUE) with a trehalose unit using raw materials such as an aromatic diisocyanate (4,4’-diphenylmethane diisocyanate), polyols including a polyether polyol (polytetramethylene glycol), two polyester polyols (polycaprolactone and polycarbonate diol), and trehalose. Novel PUEs with trehalose units are synthesized by a one-shot method. Trehalose, which has non-reducing properties, is used as sugar. The use of trehalose, which has been scarcely applied to PUE, is essential to obtain the desired PUEs with sugar units.
基金This project was supported by the National Natural Science Foundation of China(59633110 and 59773007)
文摘By using diphenyliodonium salts with different counterions as photo acid generators (PAGs), the effect of acidity on ring-opening polymerization of epoxy monomers and polycondensation of polyol with hexamethoxymethyl melamine (HMMM) was studied. The result shows that the rate of ring-opening polymerization is evidently dependent on the acidity of the acid and strong photo-generated acid is required. However, there is a leveling effect in the polycondensation system; if the photo-generated acid is stronger than protonated HMMM, the acidity does not obviously affect the polycondensation rate.
文摘As anyone who has taught polymer chemistry to undergraduate students might already appreciate, we are faced with inherent difficulties in clearly communicating the subject matter due its interdisciplinary character. This paper is thus aimed at proposing a new educational plan to teach this fundamental course in order to overcome some inherent obstacles. It is especially devoted to professors in charge of teaching a first course in polymer chemistry. We intend to emphasize polymerization by beginning with the simplest chemical pathway, namely the living anionic polymerization. In addition, some pedagogical difficulties are outlined all along this paper. This novel and distinct way to teach polymer chemistry makes the students with a background in organic chemistry more equipped to face difficulties arising from the introduction of new concepts.
文摘Polyaddition using isocyanate and polyol forms polyurethane elastomer (PUE). However, this method has rarely been applied to the construction of PUEs containing sucrose. Hence, the introduction of sucrose (disaccharide) as a cross-linker via polyaddition remains a challenging subject in polymer chemistry. Here, we report the synthesis of PUEs using an aromatic isocyanate (4,4’-diphenylmethane diisocyanate), polyols including a polyether polyol (polytetramethylene glycol) and two polyester polyols (polycaprolactone and polycarbonate diols), and sucrose as a crosslinker by a one-shot method. The PUEs containing sucrose were successfully produced. The use of sucrose was essential to obtain the desired PUEs containing sucrose units in the main chain.
