o-Carborane-containing poly（hydroxy ethers）（P1, P2 and P3） were synthesized via ＂advancement reaction＂ of o-carborane-containing bisphenol（4） and diglycidyl ether of bisphenols（DGEBA and 1）. FTIR and 1^H^-,...o-Carborane-containing poly（hydroxy ethers）（P1, P2 and P3） were synthesized via ＂advancement reaction＂ of o-carborane-containing bisphenol（4） and diglycidyl ether of bisphenols（DGEBA and 1）. FTIR and 1^H^-, 13^C^-, and 11^ B-NMR were utilized to characterize the obtained polymers. TGA test was conducted under nitrogen and air. It is found that the shielding effect of carborane moiety on its adjacent aromatic structures contributes to high initial decomposition temperatures, while oxygen in air has an adverse effect on the initial decomposition temperature. The oxygen can combine with polymer chain to form peroxide and hydroperoxide groups, which are more reactive during the degradation process. Besides, o-carborane-containing poly（hydroxy ethers） have high char yield at elevated temperatures. The boron atom combines with oxygen from the polymer structure or/and from air, thus to form a three-dimensional network linked with B―O―B and B―C bonds, and retain the polymer weight to a large extent.展开更多
Two series of poly（imide-ester）s （PIEs） and poly（ether-imide-ester）s （PEIEs）, having benzoxazole or benzothiazole pendent groups, were conveniently prepared by the diphenylchlorophosphate-activated direct poly...Two series of poly（imide-ester）s （PIEs） and poly（ether-imide-ester）s （PEIEs）, having benzoxazole or benzothiazole pendent groups, were conveniently prepared by the diphenylchlorophosphate-activated direct polyesterification of two bis（imide-carboxylic acid）s （1）, such as 2-[3,5-bis（N-trimellitimidoyl）phenyl]benzoxazole （lo） and 2-[3,5-bis（N- trimellitimidoyl）phenyl]benzothiazole （Is） and two bis（imide-ether-carboxylic acid）s （2）, such as 2-[3,5-bis（4- trimellitimidophenoxy）-phenyl]benzoxazole （2o）, and 2-[3,5-bis（4-trimellitimidophenoxy）-phenyl]benzothiazole （2s） with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. The structures, solubilities and thermal properties of obtained polymers were investigated in detail. All of the resulting polymers were characterized by FTIR and IH-NMR spectroscopy and elemental analysis. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, tetrahydrofuran and m-cresol, as well as in polar organic solvents, such as N-methyl-2- pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and dimethyl sulfoxide. The modified polymers were obtained in quantitative yields with inherent viscosities between 0.47 and 0.67 dl·g^-1 Experimental results indicated that all the polymers had glass transition temperature between 198 ℃ and 262 ℃, the decomposition temperature at 10% weight loss between 398 ℃ and 531 ℃ under nitrogen.展开更多
Poly（butylene terephthalate）-poly（tetramethylene glycol） （PBT-PTMG） copolymer is prepared with terephthalic acid （PTA） rather than its dimethyl ester （DMT） as starting material by a two-step melt polycondens...Poly（butylene terephthalate）-poly（tetramethylene glycol） （PBT-PTMG） copolymer is prepared with terephthalic acid （PTA） rather than its dimethyl ester （DMT） as starting material by a two-step melt polycondensation. This process includes the synthesis of PBT prepolymer from PTA with 1,4-butanediol （BDO） in the first step, followed by the synthesis of PBT-PTMG copolymer from PBT prepolymer with PTMG in the second step. The molecular weight, composition as well as thermal and mechanical properties of the products from the two-step melt polycondensation are compared with the properties of the PBT-PTMG from the traditional one-step melt polycondensation. When the PTMG content is low, there is only slight difference in molecular weight, composition, thermal and mechanical properties among PBT-PTMG copolymers obtained from these two methods. However, when the PTMG content is high, only the two-step strategy is able to give high molecular weight products, and the products have comparable thermal and mechanical properties with those from traditional one-step strategy using DMT as starting material.展开更多
A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composit...A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.展开更多
From the self-assembly of the typical Salen-type Schiff-base ligand H2L and Zn（OAc）2.2H20 in the molar ratio of 1：1 or 1：2, the mononuclear [Zn（L）（H2O）] （1） or binuclear [Zn2（L）（OAc）2（H2O）] （2） are o...From the self-assembly of the typical Salen-type Schiff-base ligand H2L and Zn（OAc）2.2H20 in the molar ratio of 1：1 or 1：2, the mononuclear [Zn（L）（H2O）] （1） or binuclear [Zn2（L）（OAc）2（H2O）] （2） are obtained, respectively. For both complexes 1 and 2, the unsaturated five-coordinate coordination environment to the catalytic active centers （Zn2＋ ions） permits the monomer insertion for the effective solution copolymerization of cyclohexene oxide and maleic anhydride. All the solution copolymerizations afford poly（ester-co-ether）s, while lower catalyst and co-catalyst concentrations are helpful for the formation of alternating polyester. Of the three co-catalysts, 4-（dimethylamino）pyridine is found to be the most efficient, while an excess thereof is detrimental for chain growth of the copolymers.展开更多
A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA...A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA), 4, 4'-biphenyl-bis-[4-phthalazin-1(2H)-one], 4, 4- difluorodiphenylketone (DFK). The monomer and copolymer were characterized by FT-IR and 1H-NMR. DSC and TGA were used to the novel polymer.展开更多
基金financially supported by National Key R&D Program of China(No.2016YFB0302105)
文摘o-Carborane-containing poly（hydroxy ethers）（P1, P2 and P3） were synthesized via ＂advancement reaction＂ of o-carborane-containing bisphenol（4） and diglycidyl ether of bisphenols（DGEBA and 1）. FTIR and 1^H^-, 13^C^-, and 11^ B-NMR were utilized to characterize the obtained polymers. TGA test was conducted under nitrogen and air. It is found that the shielding effect of carborane moiety on its adjacent aromatic structures contributes to high initial decomposition temperatures, while oxygen in air has an adverse effect on the initial decomposition temperature. The oxygen can combine with polymer chain to form peroxide and hydroperoxide groups, which are more reactive during the degradation process. Besides, o-carborane-containing poly（hydroxy ethers） have high char yield at elevated temperatures. The boron atom combines with oxygen from the polymer structure or/and from air, thus to form a three-dimensional network linked with B―O―B and B―C bonds, and retain the polymer weight to a large extent.
文摘Two series of poly（imide-ester）s （PIEs） and poly（ether-imide-ester）s （PEIEs）, having benzoxazole or benzothiazole pendent groups, were conveniently prepared by the diphenylchlorophosphate-activated direct polyesterification of two bis（imide-carboxylic acid）s （1）, such as 2-[3,5-bis（N-trimellitimidoyl）phenyl]benzoxazole （lo） and 2-[3,5-bis（N- trimellitimidoyl）phenyl]benzothiazole （Is） and two bis（imide-ether-carboxylic acid）s （2）, such as 2-[3,5-bis（4- trimellitimidophenoxy）-phenyl]benzoxazole （2o）, and 2-[3,5-bis（4-trimellitimidophenoxy）-phenyl]benzothiazole （2s） with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. The structures, solubilities and thermal properties of obtained polymers were investigated in detail. All of the resulting polymers were characterized by FTIR and IH-NMR spectroscopy and elemental analysis. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, tetrahydrofuran and m-cresol, as well as in polar organic solvents, such as N-methyl-2- pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and dimethyl sulfoxide. The modified polymers were obtained in quantitative yields with inherent viscosities between 0.47 and 0.67 dl·g^-1 Experimental results indicated that all the polymers had glass transition temperature between 198 ℃ and 262 ℃, the decomposition temperature at 10% weight loss between 398 ℃ and 531 ℃ under nitrogen.
基金financially supported by the Key Research Program of the Chinese Academy of Sciences(No.KGZD-EW-606-16)Ningbo Key Lab of Polymer Materials(No.2010A22001)Ningbo Natural Science Foundation(Nos.2013A610025,2013A610023 and 2014A610135)
文摘Poly（butylene terephthalate）-poly（tetramethylene glycol） （PBT-PTMG） copolymer is prepared with terephthalic acid （PTA） rather than its dimethyl ester （DMT） as starting material by a two-step melt polycondensation. This process includes the synthesis of PBT prepolymer from PTA with 1,4-butanediol （BDO） in the first step, followed by the synthesis of PBT-PTMG copolymer from PBT prepolymer with PTMG in the second step. The molecular weight, composition as well as thermal and mechanical properties of the products from the two-step melt polycondensation are compared with the properties of the PBT-PTMG from the traditional one-step melt polycondensation. When the PTMG content is low, there is only slight difference in molecular weight, composition, thermal and mechanical properties among PBT-PTMG copolymers obtained from these two methods. However, when the PTMG content is high, only the two-step strategy is able to give high molecular weight products, and the products have comparable thermal and mechanical properties with those from traditional one-step strategy using DMT as starting material.
基金Funded by the National Natural Science Foundation of China(No.50873071)the Teaching and Research Award Program for Outstanding Young Professors in Higher Education Institute,MOE,China
文摘A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.
基金financially supported by the National Natural Science Foundation of China(Nos.91222201,21173165 and 20871098)the Program for New Century Excellent Talents in Universities from the Ministry of Education of China(No.NCET-10-0936)+4 种基金the State Key Laboratory of Structure Chemistry(20100014)the Provincial Natural Foundation(2011JQ2011) of Shaanxithe Education Committee Foundation of Shaanxi Province(11JK0588,12JK0577)Graduate Innovation and Creativity Fund(YZZ12038) of Northwest UniversityHong Kong Research Grants Council(HKBU 202407 and FRG/06-07/II-16)
文摘From the self-assembly of the typical Salen-type Schiff-base ligand H2L and Zn（OAc）2.2H20 in the molar ratio of 1：1 or 1：2, the mononuclear [Zn（L）（H2O）] （1） or binuclear [Zn2（L）（OAc）2（H2O）] （2） are obtained, respectively. For both complexes 1 and 2, the unsaturated five-coordinate coordination environment to the catalytic active centers （Zn2＋ ions） permits the monomer insertion for the effective solution copolymerization of cyclohexene oxide and maleic anhydride. All the solution copolymerizations afford poly（ester-co-ether）s, while lower catalyst and co-catalyst concentrations are helpful for the formation of alternating polyester. Of the three co-catalysts, 4-（dimethylamino）pyridine is found to be the most efficient, while an excess thereof is detrimental for chain growth of the copolymers.
基金This work is sponsored by the National Natural Science Foundation of China (No. 59473901).
文摘A new monomer of 4, 4-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenyl and phthalic anhydride, and a novel copoly(aryl ether ketone) (PPEK) was synthesized from 2, 2-bis(4-hydroxyphenyl)-propane (BPA), 4, 4'-biphenyl-bis-[4-phthalazin-1(2H)-one], 4, 4- difluorodiphenylketone (DFK). The monomer and copolymer were characterized by FT-IR and 1H-NMR. DSC and TGA were used to the novel polymer.
