Here,we report the synthesis and the chain-lengthdependent self-assembling behaviors of discrete di-,tetra-,and hexaketones terminally functionalized with hydrogen-bonding carboxyl(C1,C2,and C3)and 3-acylaminopyridine...Here,we report the synthesis and the chain-lengthdependent self-assembling behaviors of discrete di-,tetra-,and hexaketones terminally functionalized with hydrogen-bonding carboxyl(C1,C2,and C3)and 3-acylaminopyridine groups(P1,P2,and P3).These polyketones were prepared by the coupling reactions of silylated analogues of 3,3-dimethylpentane-2,4-dione and t-butyl 2,2-dimethyl-3-oxobutanoate and the subsequent hydrolysis or amidation with 3-aminopyridine.Single-crystal Xray diffraction analysis revealed that C1 and C2 form helical assemblies in which the components are connected by the dimerization of terminal carboxyl groups,whereas the longer C3 showed infinite hydrogen-bonded chains mediated by 1,4-dioxane used as a crystallization solvent.Pyridine-terminated P1 exhibited a three-dimensional hydrogen-bonded network owing to multiple NH…N(pyridine)hydrogen bonds in the solid state.P2 generated a double-helix-like fiber structure in the crystalline state.Among the pyridine-terminated polyketones P1−P3,only P2 showed gelation behavior in chloroform(100 mM concentration)at 25℃.The scanning electron microscopy measurement of xerogel P2 revealed the formation of rod-like structures with a thickness of approximately 0.5−3.5μm.These results demonstrate that the precise control of the polyketone chain length can significantly alter hydrogen-bonded self-assembly in the solid state and in solution even with the same terminal structures.展开更多
Polyketone resins have been prepared by the Friedel-Crafts polymerization of dithiophenylidenecyclopentanone (I), dithiophenylidenecyclohexanone (II) and dithiophenylideneacetone (III) with adipoyl, sebacoyl and...Polyketone resins have been prepared by the Friedel-Crafts polymerization of dithiophenylidenecyclopentanone (I), dithiophenylidenecyclohexanone (II) and dithiophenylideneacetone (III) with adipoyl, sebacoyl and terephthaloyl dichlorides using boron trifluoride as catalyst and carbon disulphide as solvent. Polymers were characterized with IR, 1H- NMR, and the results showed the presence of carbonyl of ketonic groups in the main chain. The polyketones have inherent viscosities of 0.40-0.70 dL/g. All the polymers are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in aprotic solvents. The temperatures of 50% weight loss are as high as 185℃ to 280℃ in air, indicating that these aromatic polyketones have excellent thermal stability. All the polyketones were tested for their antimicrobial activity against bacteria and fungi.展开更多
The crosslinked polyacrylonitrile (PAN) wassynthesized by suspension polymerization using acrylonitrile(ANT) and divinylbenzene (DVB). Effects of a varietyof conditions on the polymerization of PAN particle sizeand st...The crosslinked polyacrylonitrile (PAN) wassynthesized by suspension polymerization using acrylonitrile(ANT) and divinylbenzene (DVB). Effects of a varietyof conditions on the polymerization of PAN particle sizeand stiffness were investigated. Polyketone was preparedby the copolymerization of carbon monoxide (CO) andstyrene (ST) catalyzed by PAN resin-supported palladiumacetate. The resin-supported catalyst and the copolymerizationproduct were characterized by infrared spectroscopy(IR) and Scanning Electron Microscopy (SEM). Effects ofthe components of a catalytic system and reaction time onthe catalytic activity were studied. The reusability of theresin-supported catalyst was also investigated.Results indicatedthat the resin-supported catalyst has excellent catalyticproperty. The yield of polyketone was 6.2348 g whenusing 1 g of resin and 22.4 mg of palladium acetate.展开更多
Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with c...Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with carbonmonoxide, in which the ligand was a bidentate phosphorus chelating ligand. The experimental results showed that this kindof Cu catalyst system exhibited high activity. When DPPP (1, 3-bis(diphenylphosphine)propane) and CH_3COOH were usedas ligand and acid, the corresponding catalyst system had the best activity of 108.1 g copolymer/(gCu·h). The novel Cu catalyst system had the advantages of high stability and low cost.展开更多
A novel coordinated complex [(5-nitrophen)Pd(CF3CO2)2] (5-nitrophen = 5-nitro-1,10-phenanthroline) was first synthesized. By using XPS, IR, and 1H-NMR, its coordination unit was studied in comparison with those of com...A novel coordinated complex [(5-nitrophen)Pd(CF3CO2)2] (5-nitrophen = 5-nitro-1,10-phenanthroline) was first synthesized. By using XPS, IR, and 1H-NMR, its coordination unit was studied in comparison with those of complexes [(N-N)Pd(CH3CO2)2] and [(N-N)Pd(CF3CO2)2]. The H2,9 proton signals of 1H-NMR spectra of the complexes are excellent probes to monitor the evolution of the environment of the palladium atom. The state of anionic coordination was confirmed by the presence of IR absorption peaks of COO in complexes ([(N — N)Pd(CH3CO2)2] and [(N — N)Pd(CF3CO2)2]). Bonding energies of N1s and Pd3d5 obtained from XPS data testified to the strength of the N-Pd coordinating bond. The conclusion can be drawn by analyzing these data from IR, XPS and 1H-NMR that it is the unsymmetrical substitution of the 1,10-phenanthroline (phen) that makes the [(5-nitrophen)Pd(CF3CO2)2] more active. Experimental results showed that [(5-nitrophen)Pd(CF3CO2)2] exhibits much higher activity than [(bipy)Pd(CF3CO2)2] (1,1'- bipyridine = bipy) and [(phen)Pd(CF3CO2)2] under the same conditions.展开更多
The CO-ethene copolymerization has been efficiently carried out in the water/CH2Cl2 emulsion by using water insolvable Pd(II) complexes. By using the surfactant SDS very high molecular weight copolymers have been obta...The CO-ethene copolymerization has been efficiently carried out in the water/CH2Cl2 emulsion by using water insolvable Pd(II) complexes. By using the surfactant SDS very high molecular weight copolymers have been obtained with high productivity (ca. 13,000 g/(gPd.h)).展开更多
The introduction of carbonyl group with a high density in polyethylene backbone corresponds to polyketone materials,which features excellent mechanical strength,crystallinity,photodegradability,hydrophilicity,surface ...The introduction of carbonyl group with a high density in polyethylene backbone corresponds to polyketone materials,which features excellent mechanical strength,crystallinity,photodegradability,hydrophilicity,surface and barrier properties.Due to the extremely high binding affinity of carbon monoxide(CO)and kinetic preference for its subsequent insertion,the formation of nonalternating structure with extra ethylene insertion is exceptionally challenging,however,this nonalternating strategy is of significant importance for polymer modification in term of processing and solubility.Here,we have communicated our study on cationic palladium coordinated diphosphazane monoxide(PNPO)for the nonalternating copolymerization of ethylene with CO,the systematical investigation on the amine and phosphine oxide moieties in PNPO platform in term of electronic and steric modulation has been performed.It is discovered that the installation of aliphatic structure on amine moiety favors the improvement of catalyst activity and longevity,while the amino groups on phosphine oxide moiety promotes the nonalternating copolymerization.In particular,we have computationally investigated herein the aspects of the nonalternating degree by comparing with PNPO platform and 1,3-bis(diphenylphosphanyl)propane ligands based palladium catalysts.These mechanistic studies can help to understand the catalyst structure and polyketone property relationships and shed light on future design of high-performance copolymerization catalysts.展开更多
Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone (PK). The effect of the additive structure and their feed ratios on the melting temperature, crystalliza...Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone (PK). The effect of the additive structure and their feed ratios on the melting temperature, crystallization temperature, and crystallization rate of PK were studied. We found that the crystallization temperature could be reduced significantly by introducing a small quantity of organic additive, in particular, an anhydride. On addition of 1 phr of anhydride, the crystallization temperature was reduced by 10.7 ℃. Therefore, the non-isothermal crystallization kinetics of aliphatic PKJanhydride blends with various feed ratios was investigated using DSC. The results were analyzed by various theoretical models, such as Avrami, Ozawa and combined Avrami-Ozawa models.展开更多
In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature (Tg) was determined, and ...In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature (Tg) was determined, and the composition dependence of Tg for these blends was well described by the Kwei equation. The strong intermolecular interaction between the two polymer components was confirmed by melting-point depression. The isothermal-crystallization kinetics were analyzed on the basis of the Avrami approach. A linear increase in the radii of the spherulites with time was observed for all compositions. All the spherulites continued to grow at nearly identical growth rates. With increasing polyamide-6 content, the size of the spherulites in the polyketone/polyamide-6 blends gradually decreased, and the number of spherulites in the blends increased.展开更多
In this study, we attempt to prepare a new blending system of poly(vinylidene fluoride) (PVDF) and aliphatic polyketone (POK) by melt compounding, The latter is a promising engineering plastic with comprehensive...In this study, we attempt to prepare a new blending system of poly(vinylidene fluoride) (PVDF) and aliphatic polyketone (POK) by melt compounding, The latter is a promising engineering plastic with comprehensive mechanical performances. When POK acted as minor phase to homogeneously disperse in and intimately contact with PVDF matrix, the brittle tensile behavior of neat PVDF transferred into a remarkably flexible manner (the elongation at break increased for 20 times), and more interestingly, the room- temperature durability of β-form PVDF in the uniaxially drawn blend film was obviously better than that in the neat PVDF film. Fourier transform infrared spectroscopy revealed that specific dipole interaction existed between CF2 group of PVDF and C=O group of POK. The intermolecular dipolar interaction induced good compatibility in the PVDF/POK blends, as evidently proved by fine two-phase morphology and decreased melting points of POK crystals. Therefore, the good compatibility and interracial enhancement are responsible for the improvement of the stretch ductility and β-form room-temperature durability of the PVDF/POK blends.展开更多
Density functional theory has been employed to study the homogeneous catalytic copolymerization of styrene with carbon monoxide. The copolymerization reaction is catalyzed by Pd(II) coordinated with 2,2'-bipyridine...Density functional theory has been employed to study the homogeneous catalytic copolymerization of styrene with carbon monoxide. The copolymerization reaction is catalyzed by Pd(II) coordinated with 2,2'-bipyridine, a conventional nitrogen-containing bidentate ligand with achiral C2v symmetry. The chain propagation mechanism for the alternating copolymerization as well as the side reactions, including multiple insertions of CO and homopolymerization of styrene, has been investigated. This study focused exclusively on regioisomerism and stereoisomerism. We have demonstrated that the strictly alternating copolymerization is kinetically and thermodynamically favored over the side reactions (i.e., multiple insertions of CO and homopolymerization of styrene). The regiochemistry study indicates the 2,1 type. Furthermore, the stereochemistry study shows that the syndiotactic conformation is preferred over the isotactic or atactic conformations.展开更多
基金a JSPS Grant-in-Aid for Challenging Research(Exploratory)(No.20K21214)Scientific Research(B)(No.22H02058)+3 种基金JST FOREST Program(No.JPMJFR211H)Nagase Science and Technology Foundation of which Y.Inokuma is the principal investigatorThe Institute for Chemical Reaction Design and Discovery(ICReDD)was established by the World Premier International Research Initiative(WPI),MEXT,Japan.Y.Ide is grateful for a Grant-in-Aid for Early-Career Scientists grant(No.21K14597)and Scientific Research on Innovative Areas“Soft Crystals”.Y.M.would like to acknowledge the Grant-in-Aid for JSPS Research Fellow(No.21J11228)。
文摘Here,we report the synthesis and the chain-lengthdependent self-assembling behaviors of discrete di-,tetra-,and hexaketones terminally functionalized with hydrogen-bonding carboxyl(C1,C2,and C3)and 3-acylaminopyridine groups(P1,P2,and P3).These polyketones were prepared by the coupling reactions of silylated analogues of 3,3-dimethylpentane-2,4-dione and t-butyl 2,2-dimethyl-3-oxobutanoate and the subsequent hydrolysis or amidation with 3-aminopyridine.Single-crystal Xray diffraction analysis revealed that C1 and C2 form helical assemblies in which the components are connected by the dimerization of terminal carboxyl groups,whereas the longer C3 showed infinite hydrogen-bonded chains mediated by 1,4-dioxane used as a crystallization solvent.Pyridine-terminated P1 exhibited a three-dimensional hydrogen-bonded network owing to multiple NH…N(pyridine)hydrogen bonds in the solid state.P2 generated a double-helix-like fiber structure in the crystalline state.Among the pyridine-terminated polyketones P1−P3,only P2 showed gelation behavior in chloroform(100 mM concentration)at 25℃.The scanning electron microscopy measurement of xerogel P2 revealed the formation of rod-like structures with a thickness of approximately 0.5−3.5μm.These results demonstrate that the precise control of the polyketone chain length can significantly alter hydrogen-bonded self-assembly in the solid state and in solution even with the same terminal structures.
文摘Polyketone resins have been prepared by the Friedel-Crafts polymerization of dithiophenylidenecyclopentanone (I), dithiophenylidenecyclohexanone (II) and dithiophenylideneacetone (III) with adipoyl, sebacoyl and terephthaloyl dichlorides using boron trifluoride as catalyst and carbon disulphide as solvent. Polymers were characterized with IR, 1H- NMR, and the results showed the presence of carbonyl of ketonic groups in the main chain. The polyketones have inherent viscosities of 0.40-0.70 dL/g. All the polymers are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in aprotic solvents. The temperatures of 50% weight loss are as high as 185℃ to 280℃ in air, indicating that these aromatic polyketones have excellent thermal stability. All the polyketones were tested for their antimicrobial activity against bacteria and fungi.
基金the National Natural Science Foundation of China(Grant No.20476080).
文摘The crosslinked polyacrylonitrile (PAN) wassynthesized by suspension polymerization using acrylonitrile(ANT) and divinylbenzene (DVB). Effects of a varietyof conditions on the polymerization of PAN particle sizeand stiffness were investigated. Polyketone was preparedby the copolymerization of carbon monoxide (CO) andstyrene (ST) catalyzed by PAN resin-supported palladiumacetate. The resin-supported catalyst and the copolymerizationproduct were characterized by infrared spectroscopy(IR) and Scanning Electron Microscopy (SEM). Effects ofthe components of a catalytic system and reaction time onthe catalytic activity were studied. The reusability of theresin-supported catalyst was also investigated.Results indicatedthat the resin-supported catalyst has excellent catalyticproperty. The yield of polyketone was 6.2348 g whenusing 1 g of resin and 22.4 mg of palladium acetate.
文摘Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with carbonmonoxide, in which the ligand was a bidentate phosphorus chelating ligand. The experimental results showed that this kindof Cu catalyst system exhibited high activity. When DPPP (1, 3-bis(diphenylphosphine)propane) and CH_3COOH were usedas ligand and acid, the corresponding catalyst system had the best activity of 108.1 g copolymer/(gCu·h). The novel Cu catalyst system had the advantages of high stability and low cost.
基金This project was supported by the National Natural Science Foundation of China (Grant No. 20244001).
文摘A novel coordinated complex [(5-nitrophen)Pd(CF3CO2)2] (5-nitrophen = 5-nitro-1,10-phenanthroline) was first synthesized. By using XPS, IR, and 1H-NMR, its coordination unit was studied in comparison with those of complexes [(N-N)Pd(CH3CO2)2] and [(N-N)Pd(CF3CO2)2]. The H2,9 proton signals of 1H-NMR spectra of the complexes are excellent probes to monitor the evolution of the environment of the palladium atom. The state of anionic coordination was confirmed by the presence of IR absorption peaks of COO in complexes ([(N — N)Pd(CH3CO2)2] and [(N — N)Pd(CF3CO2)2]). Bonding energies of N1s and Pd3d5 obtained from XPS data testified to the strength of the N-Pd coordinating bond. The conclusion can be drawn by analyzing these data from IR, XPS and 1H-NMR that it is the unsymmetrical substitution of the 1,10-phenanthroline (phen) that makes the [(5-nitrophen)Pd(CF3CO2)2] more active. Experimental results showed that [(5-nitrophen)Pd(CF3CO2)2] exhibits much higher activity than [(bipy)Pd(CF3CO2)2] (1,1'- bipyridine = bipy) and [(phen)Pd(CF3CO2)2] under the same conditions.
文摘The CO-ethene copolymerization has been efficiently carried out in the water/CH2Cl2 emulsion by using water insolvable Pd(II) complexes. By using the surfactant SDS very high molecular weight copolymers have been obtained with high productivity (ca. 13,000 g/(gPd.h)).
基金This work is supported by the National Natural Science Foundation of China(NSFC,Grant 22071016)the Program for Changjiang Scholars(Q2018046)+1 种基金from the Ministry of Education of the People's Republic of China,the Young Top Talents Project of Liaoning Province(No.XLYC2007059)the Fundamental Research Funds for the Central Universities(DUT22LAB609).
文摘The introduction of carbonyl group with a high density in polyethylene backbone corresponds to polyketone materials,which features excellent mechanical strength,crystallinity,photodegradability,hydrophilicity,surface and barrier properties.Due to the extremely high binding affinity of carbon monoxide(CO)and kinetic preference for its subsequent insertion,the formation of nonalternating structure with extra ethylene insertion is exceptionally challenging,however,this nonalternating strategy is of significant importance for polymer modification in term of processing and solubility.Here,we have communicated our study on cationic palladium coordinated diphosphazane monoxide(PNPO)for the nonalternating copolymerization of ethylene with CO,the systematical investigation on the amine and phosphine oxide moieties in PNPO platform in term of electronic and steric modulation has been performed.It is discovered that the installation of aliphatic structure on amine moiety favors the improvement of catalyst activity and longevity,while the amino groups on phosphine oxide moiety promotes the nonalternating copolymerization.In particular,we have computationally investigated herein the aspects of the nonalternating degree by comparing with PNPO platform and 1,3-bis(diphenylphosphanyl)propane ligands based palladium catalysts.These mechanistic studies can help to understand the catalyst structure and polyketone property relationships and shed light on future design of high-performance copolymerization catalysts.
文摘Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone (PK). The effect of the additive structure and their feed ratios on the melting temperature, crystallization temperature, and crystallization rate of PK were studied. We found that the crystallization temperature could be reduced significantly by introducing a small quantity of organic additive, in particular, an anhydride. On addition of 1 phr of anhydride, the crystallization temperature was reduced by 10.7 ℃. Therefore, the non-isothermal crystallization kinetics of aliphatic PKJanhydride blends with various feed ratios was investigated using DSC. The results were analyzed by various theoretical models, such as Avrami, Ozawa and combined Avrami-Ozawa models.
文摘In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature (Tg) was determined, and the composition dependence of Tg for these blends was well described by the Kwei equation. The strong intermolecular interaction between the two polymer components was confirmed by melting-point depression. The isothermal-crystallization kinetics were analyzed on the basis of the Avrami approach. A linear increase in the radii of the spherulites with time was observed for all compositions. All the spherulites continued to grow at nearly identical growth rates. With increasing polyamide-6 content, the size of the spherulites in the polyketone/polyamide-6 blends gradually decreased, and the number of spherulites in the blends increased.
基金supported by the National Natural Science Foundation of China (Nos. 51373108 and 21574088)
文摘In this study, we attempt to prepare a new blending system of poly(vinylidene fluoride) (PVDF) and aliphatic polyketone (POK) by melt compounding, The latter is a promising engineering plastic with comprehensive mechanical performances. When POK acted as minor phase to homogeneously disperse in and intimately contact with PVDF matrix, the brittle tensile behavior of neat PVDF transferred into a remarkably flexible manner (the elongation at break increased for 20 times), and more interestingly, the room- temperature durability of β-form PVDF in the uniaxially drawn blend film was obviously better than that in the neat PVDF film. Fourier transform infrared spectroscopy revealed that specific dipole interaction existed between CF2 group of PVDF and C=O group of POK. The intermolecular dipolar interaction induced good compatibility in the PVDF/POK blends, as evidently proved by fine two-phase morphology and decreased melting points of POK crystals. Therefore, the good compatibility and interracial enhancement are responsible for the improvement of the stretch ductility and β-form room-temperature durability of the PVDF/POK blends.
基金financially supported by the NSFC(Nos.91127046 and 20974078)KPCME(No.109043)+1 种基金SRFDP (No.200800561006)High Performance Computing Center of Tianjin University,China and National Supercomputer Center in Tianjin,China
文摘Density functional theory has been employed to study the homogeneous catalytic copolymerization of styrene with carbon monoxide. The copolymerization reaction is catalyzed by Pd(II) coordinated with 2,2'-bipyridine, a conventional nitrogen-containing bidentate ligand with achiral C2v symmetry. The chain propagation mechanism for the alternating copolymerization as well as the side reactions, including multiple insertions of CO and homopolymerization of styrene, has been investigated. This study focused exclusively on regioisomerism and stereoisomerism. We have demonstrated that the strictly alternating copolymerization is kinetically and thermodynamically favored over the side reactions (i.e., multiple insertions of CO and homopolymerization of styrene). The regiochemistry study indicates the 2,1 type. Furthermore, the stereochemistry study shows that the syndiotactic conformation is preferred over the isotactic or atactic conformations.