The process of producing high viscosity polyester by transesterification polycondensation needs to adjust the operating conditions and equipment structure of pre-polycondensation kettle and final polycondensation kett...The process of producing high viscosity polyester by transesterification polycondensation needs to adjust the operating conditions and equipment structure of pre-polycondensation kettle and final polycondensation kettle to realize process intensification.In view of this,the fluid volume function method of computational fluid dynamics numerical simulation was used to investigate the film formation and surface renewal characteristics of horizontal polycondensation kettle under different operating conditions,including viscosity,rotating speed and liquid height.The results show that the viscosity and rotating speed were positively correlated with the film area and surface renewal in the pre-polycondensation stage.However,increasing the viscosity by several orders of magnitude in the final polycondensation kettle,the larger the film area and film thickness,but the overall surface renewal of the disk decreased.Therefore,a hexagonal hole disk is designed.By comparison,it is found that the film is more uniform,the surface update frequency is higher,and the power consumption can be reduced by more than 20%.展开更多
A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation proc...A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.展开更多
The increase in the residue content resulting from polycondensation would be adverse to the utilization of lignocellulose and to the quality of products obtained from liquefied lignocellulosic material.The yield of th...The increase in the residue content resulting from polycondensation would be adverse to the utilization of lignocellulose and to the quality of products obtained from liquefied lignocellulosic material.The yield of the residue formed from liquefaction and the mechanism of polycondensation were reported mainly by Lin,Yamada and Kobayashi.The major products of cellulosic liquefaction are levulinic acid and hydroxymethylfurfural（HMF） derivatives under polyhydric alcohols and phenolated compounds under phenols.The cleavage of the β-O-4 bonds is the major reaction pathway of lignin liquefaction under various liquefying reagents regardless of whether they contain acid catalysts or not.The break up compounds by decomposition are polymerized to substances with high molecular weight by polycondensation in lignocellulosic liquefaction.The molecular weight of condensed residues increases almost linearly as a function of liquefaction time at the later stage of lignocellulosic liquefaction.The longer the time required,the greater the content of new residue generated by polycondensation during the entire process of liquefaction.We conclude that the condensed residues may stem from the interaction of degraded lignin and cellulose components in wood or from the products of two major components reacting with liquefying reagents.展开更多
A non-aqueous suspension polycondensation method was proposed to proceed the reaction ofp-phenylenediamine and terephthaloyl chloride for the preparation of poly（p-phenylene terephthalamide） （PPTA）. The system was...A non-aqueous suspension polycondensation method was proposed to proceed the reaction ofp-phenylenediamine and terephthaloyl chloride for the preparation of poly（p-phenylene terephthalamide） （PPTA）. The system was operated with NMP-CaCI2 solution as the dispersed phase and inert liquid paraffin as the continuous phase. Each of NMP-CaCl2 solution microdroplet suspended in paraffin served as a microreactor where the polycondensation took place. According to the results of TGA, XRD, IR, SEM and EA, PPTA with good quality was obtained through this novel method, and a number of main factors influencing this process were investigated to determine the optimum condition for the preparation of PPTA. Besides, this two-phase polycondensation system brings many unique advantages compared to the conventional solution polycondensation method, including a sealed reaction environment keeping the reactants away from oxygen and water, easy removal of HCI to promote the reaction, well-controlled temperature and low viscosity which means less energy cost.展开更多
A highly efficient and eco-friendly protocol for the synthesis of an alternating copolymer poly(7,7'-diazaisoindigo-alt-(E)-1,2- bis(3,4-difluorothien-2-yl)ethene)(PAIID-4FTVT) via direct arylation polycondensatio...A highly efficient and eco-friendly protocol for the synthesis of an alternating copolymer poly(7,7'-diazaisoindigo-alt-(E)-1,2- bis(3,4-difluorothien-2-yl)ethene)(PAIID-4FTVT) via direct arylation polycondensation (DArP) is presented. Through detailed study, we found that the inhibitory effect of 7,7'-diazaisoindigo on DArP stemmed from the coordination of N atom with catalyst can be overcome by using dimethylacetamide (DMAc) as the co-solvent. Thus, PAIID-4FTVT with number-average molecular weight (Mn)>100kDa was synthesized via DArP by optimizing the content of DMAc. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy revealed that PAIID-4FTVT was defect-free. Top gate and bottom contact (TG/BC) organic thin-film transistors (OTFTs) were fabricated to characterize the semiconducting properties of the polymers. PAIID-4FTVT displayed unipolar n-type characteristics with the electron mobility (μe) strongly dependent on Mn. The highest μe up to 0.25 cm^2·V^-1 s^-1 was achieved with the high molecular weight sample.展开更多
The concentration of acetaldehyde(AA) is the main quality index of poly(ethylene terephthalate)(PET) used in food and drink packaging.A new method for AA removal has been developed by using supercritical carbon dioxid...The concentration of acetaldehyde(AA) is the main quality index of poly(ethylene terephthalate)(PET) used in food and drink packaging.A new method for AA removal has been developed by using supercritical carbon dioxide(sc CO2) during the solid-state polycondensation of PET.The influence factors of AA removal including the temperature,pressure,reaction time and the size of pre-polymer particles are systematically studied in this work.The results indicate that it is a highly efficient way to obtain high molecular weight PET with relative low concentration of AA.Correspondingly,the polymerization degree of PET could increase from 27.9 to 85.6 while the concentration of AA reduces from 0.229 × 10^(-6) to 0.055 × 10^(-6) under the optimal operation conditions of 230 °C,8 MPa and size of 0.30–0.45 mm.Thermodynamic performance tests show the increasing extent of PET crystallinity due to the fact that the plasticization of sc CO_2 is not obvious with extended reaction time,therefore the increasing crystallinity has no significant influence on AA removal.SEM observations reveal that the effects of sc CO_(2-) induced plasticization and swelling on PET increase significantly with the decrease of prepolymer size,and the surface of PET becomes more loose and porous in favor of the AA removal.展开更多
Poly(silphenylene-siloxane)s had been synthesized through dehydrocarbon polycondensation of 1,4- bis(dimethylsilyl)benzene(BDSB)and dialkoxysilane.The polymer composition and structure was characterized by ^(29)Si-NMR...Poly(silphenylene-siloxane)s had been synthesized through dehydrocarbon polycondensation of 1,4- bis(dimethylsilyl)benzene(BDSB)and dialkoxysilane.The polymer composition and structure was characterized by ^(29)Si-NMR.The influence of temperature,B(C_6F_5)_3 concentration and monomer structure on the composition and the microstructure of the copolymers were investigated.It shows that elevating reaction temperature or using substrate (R O)_2R_2R_1Si with bulk organic group of R_1 or R_2 augments the run numb...展开更多
In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO）...In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO） and nano-SiO2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly（butylene terepbthalate-co-lactate） （PBTL）, and the abundant hydroxyl groups on the surface of nano-SiO2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO2 particles were chemically wrapped with PBTL to form PBTL/nano- SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO2 particles with the copolyester matrix, the tensile strength and the Young＇s modulus increased from 5.4 and 5.6 MPa for neat PBTL to 16 and 390 MPa for PBTL/nano-SiO2 hybrids with 5 wt.% nano-SiO2, respectively. The mechanical properties of PBTL/nano-SiO2 hybrids were substantially improved.展开更多
A theoretical approach to polycondensation reaction of Aa-Bb type Involving intramolecular cycllzatlon has been proposed by Tang Au-chin et al.. In this paper, the theoretical sol-gel distribution is tested by polycon...A theoretical approach to polycondensation reaction of Aa-Bb type Involving intramolecular cycllzatlon has been proposed by Tang Au-chin et al.. In this paper, the theoretical sol-gel distribution is tested by polycondensation of adipic acid with trimethylol propane in a sto-ichiometric ratio of 0. 8, and the effect of intramolecular cyclization is discussed in detail.展开更多
The fundamental experiments were performed to establish the operational conditions required to prepare the microcapsules containing paraffin wax as a phase change material (PCM) and SiC powder with the interfacial pol...The fundamental experiments were performed to establish the operational conditions required to prepare the microcapsules containing paraffin wax as a phase change material (PCM) and SiC powder with the interfacial polycondensation reaction. It was investigated how SiC powder affected a few characteristics of microcapsules such as the diameters of microcapsules, latent heat storage density, thermal responsibility and supercooling. In the experiment, the concentration of oil soluble surfactant, the revolution speed of impeller for preparing the (O/W) emulsion and the added weight of SiC powder were changed stepwise. The microcapsules containing PCM in which SiC powder was dispersed could be prepared well and characterized. The diameters of microcapsules increased by containing SiC powder and the content of SiC powder could be increased by performing surface modification of SiC powder. Latent heat storage density decreased with the content of SiC powder. Supercooling of PCM and thermal responsibility could be improved to some degree by containing SiC powder.展开更多
Four thiophene derivatives were prepared by replacing the 3,4 positions of thiophene by―OCH3, ―CH3―COOCH3 and ―CN, respectively. The polycondensations via direct arylation took place between the four thiophene der...Four thiophene derivatives were prepared by replacing the 3,4 positions of thiophene by―OCH3, ―CH3―COOCH3 and ―CN, respectively. The polycondensations via direct arylation took place between the four thiophene derivatives and 2,7-dibromo-9,9-dioctylfluorene under six various catalytic conditions to investigate the substituent effects. The substituent can affect the electron cloud density of the active C―H bond, which can be monitored by the NMR chemical shift. The experimental results show that the reactivity decreases with increasing the chemical shift of active C―H bonds in the four thiophene derivatives, and thus can promote the direct arylation polycondensation. This phenomenon is explained by the electrophilic aromatic substitution（SEAr） mechanism. UV-Visible absorption and photoluminescence were studied to investigate the substituent effect on optical properties of the four copolymers. The results show that these alternating fluorene-thiophene copolymers with different substituents are good fluorescent materials and promising in PLED applications.展开更多
The solubility of a direct arylation polycondensation(DArP)synthesized conjugated polymer,i.e.,poly(3,6-bis(furan-2-yl)-2,5-bis(4-tetradecyloctadecyl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-1,2-bis(3,4-d ifl uorot...The solubility of a direct arylation polycondensation(DArP)synthesized conjugated polymer,i.e.,poly(3,6-bis(furan-2-yl)-2,5-bis(4-tetradecyloctadecyl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-1,2-bis(3,4-d ifl uorothien-2-yl)ethene)(PFuD PP-4FTVT),in variou s organic solvents was studied.The polymer is soluble in 3-methylcyclohexanone(3-MC),a green solvent from peppermint oil,besides other solvents such as anisole,cyclopentyl methyl ether(CPME)and o-dichlorobenzene(o-DCB),etc.Based on the Hansen solu bility parameters(HSP)analysis,3-MC is identified as a"marginal solvent"of PFuDPP-4FTVT.The morphology of the spin-coated films with 3-MC as the solvent strongly correlated with the solution preparation conditions.With a 3-MC solution aged for 3 h at 70℃,n-channel organic thin-film transistors(OTFTs)with electron mobility(μe)above 1 cm^(2)·V^(-1)·s^(-1) and current on/off ratio(Ion/Ioff)higher than 105 were fabricated by spin-coating.This is the first report on high mobility conjugated polymers for OTFTs processible with natu rally occurred green solvent.展开更多
Introducing covalently crosslinked network to polymer matrix can merge the advantages in reprocessing and durability of polymers.In this contribution,a series of high-performance vitrimeric elastomers were achieved vi...Introducing covalently crosslinked network to polymer matrix can merge the advantages in reprocessing and durability of polymers.In this contribution,a series of high-performance vitrimeric elastomers were achieved via polycondensation.The topological structures of polymers were tuned by varying the feeding ratios of bisacetoacetate,hex–substituted bisacetoacetate,bisamine and tris(2-aminoethyl)amine.With these structural manipulations,the vitrimeric elastomers presented great elastic recovery properties(strain recovery value up to 80%)benefiting from the introduction of long chain branch.Furthermore,the elastomers exhibited excellent reprocessing property,water vapor/oxygen barrier and adhesive properties.Specially,the elastomers could be degraded into monomer under acid conditions which enabled the elastomer synthesis again in closed loop recycling system.The ease of the polycondensation in this work to prepare highly elastic and recyclable vitrimeric elastomers demonstrated exciting opportunities for the synthesis of sustainable polymers.展开更多
The kinetic data of solid state polycondensation of PET and its copolymers are determined.It is shown that the reaction rate of copolycondensation is higher than that of PET polyconden-sation, and increases with the c...The kinetic data of solid state polycondensation of PET and its copolymers are determined.It is shown that the reaction rate of copolycondensation is higher than that of PET polyconden-sation, and increases with the comonomers content. But the reaction rate of copolycondensationin melt state of this kind of copolymers is lower than that of PET. It is considered that the chemi-cal reactivity of comonomer is the main factor which affect the polycondensation in melt state,whereas the aggregative structure of the polymer is the main factor in solid state. The crystallinity and crystallite size of the copolymers have been measured by X-ray method.展开更多
The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB2 polycondensation with substitution effect were derived by the kinetic mec...The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB2 polycondensation with substitution effect were derived by the kinetic mechanism. The reactivity difference between the 13 group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained. The concentration of terminal units has a maximum with the increase of the conversion of A groups （x）. The higher the reactivity ratio （r） of linear B group to branched one is, the later the maximum appears and the larger it is. The degree of branching of the hyperbranched polymers obtained is controllable by adjusting the parameters of r and x, which increases with increasing both x and r.展开更多
Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild con...Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild conditions. The electron-rich hydroxyl groups of bisphenols favoured the polycondensation reaction and the order of relative reactivities of bisphenols is as follow:bisphenoI-A> hydroquinone ～ bisphenol-S> chlorohydroquinone. The mesomorphic properties of copolyesters were examined by birefringence under polarizing microscope, melt transparency. DSC and X-ray diffraction. The minimum molar fraction of mesogenic units needed for the appearance of liquid crystallinity is not higher than 0. 1 despite of the different varieties and lengths of the spacers studied.展开更多
A new method of surface chemical modification of nano-SiO2 is proposed in this paper. In the presence of catalyst, the active hydroxyl groups on the surface of nano-SiO2 reacted with AB2-type monomer （N, N-dihydroxye...A new method of surface chemical modification of nano-SiO2 is proposed in this paper. In the presence of catalyst, the active hydroxyl groups on the surface of nano-SiO2 reacted with AB2-type monomer （N, N-dihydroxyethyl-3-amino methyl propionate） by one-step polycondensation. And the product＇s Fourer transform infrared （FTIR） graphs and transmission electron microscopy（TEM） images proved that hyperbranched poly （amine-ester） was grafted on nano-SiO2 surface successfully. Results show that the modified nano-SiO2 exhibits excellent dispersion and stability in some solvents such as alcohol and chloroform.展开更多
Cross-linked polyamides(c PAs)were prepared through direct bulk Michael addition and subsequent polycondensation.Several mixed hexanediamine multi-esters(HDAMEs)were generated through the Michael addition of 1,6-hexan...Cross-linked polyamides(c PAs)were prepared through direct bulk Michael addition and subsequent polycondensation.Several mixed hexanediamine multi-esters(HDAMEs)were generated through the Michael addition of 1,6-hexanediamine(HDA)and methyl acrylate(MA)at50℃ with different HDA/MA molar ratios.Melt polycondensation of HDAMEs then proceeded at 150 or 170℃ in flasks to obtain viscous fluids,and curing was continued in tetrafluoroethylene molds to obtain c PA films.The Michael addition was monitored on the basis of FTIR and ESI-MS spectra.The c PA films were characterized by DSC,TGA,dynamic mechanical analysis,and tensile test.These directly prepared c PAs exhibited Tg of 1–39℃,tensile strength of up to 45 MPa,and strain at break from 18%to 40%.The c PAs with high tensile strength and good toughness were successfully synthesized through the direct bulk Michael addition from HDA and MA followed with polycondensation.展开更多
Amorphous poly (L-2-hydroxy-3-phenylpropanoic acid) (PLHPPA) was synthesized by the microwave-assisted polycondensation of L-2-hydroxy-3-phenylpropanoic acid (LHPPA). The weight average molar mass (Mw) of PLHPPA range...Amorphous poly (L-2-hydroxy-3-phenylpropanoic acid) (PLHPPA) was synthesized by the microwave-assisted polycondensation of L-2-hydroxy-3-phenylpropanoic acid (LHPPA). The weight average molar mass (Mw) of PLHPPA ranged from 3600 to 5300 and polydispersity index (Mw/Mn) from 1.0 to 1.4 when the reaction mixture was irradiated by microwave at 255, 340 and 510 w for 1 to 10 h, respectively.展开更多
基金the financial support of the National Key Research and Development Program of China(2020YFA0710202,2018YFC0808805)。
文摘The process of producing high viscosity polyester by transesterification polycondensation needs to adjust the operating conditions and equipment structure of pre-polycondensation kettle and final polycondensation kettle to realize process intensification.In view of this,the fluid volume function method of computational fluid dynamics numerical simulation was used to investigate the film formation and surface renewal characteristics of horizontal polycondensation kettle under different operating conditions,including viscosity,rotating speed and liquid height.The results show that the viscosity and rotating speed were positively correlated with the film area and surface renewal in the pre-polycondensation stage.However,increasing the viscosity by several orders of magnitude in the final polycondensation kettle,the larger the film area and film thickness,but the overall surface renewal of the disk decreased.Therefore,a hexagonal hole disk is designed.By comparison,it is found that the film is more uniform,the surface update frequency is higher,and the power consumption can be reduced by more than 20%.
基金supported by the National Key Projects for Fundamental Research and Development of China(2016YFB0600903)the National Natural Science Foundation of China(91434107,21506226,21476245)the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDY-SSW-JSC011)~~
文摘A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.
基金supported by the Forestry Public Special Scientific Research (No. 201004057)
文摘The increase in the residue content resulting from polycondensation would be adverse to the utilization of lignocellulose and to the quality of products obtained from liquefied lignocellulosic material.The yield of the residue formed from liquefaction and the mechanism of polycondensation were reported mainly by Lin,Yamada and Kobayashi.The major products of cellulosic liquefaction are levulinic acid and hydroxymethylfurfural（HMF） derivatives under polyhydric alcohols and phenolated compounds under phenols.The cleavage of the β-O-4 bonds is the major reaction pathway of lignin liquefaction under various liquefying reagents regardless of whether they contain acid catalysts or not.The break up compounds by decomposition are polymerized to substances with high molecular weight by polycondensation in lignocellulosic liquefaction.The molecular weight of condensed residues increases almost linearly as a function of liquefaction time at the later stage of lignocellulosic liquefaction.The longer the time required,the greater the content of new residue generated by polycondensation during the entire process of liquefaction.We conclude that the condensed residues may stem from the interaction of degraded lignin and cellulose components in wood or from the products of two major components reacting with liquefying reagents.
基金financially supported by the National Natural Science Foundation of China(Nos.U1463208 and 91334201)
文摘A non-aqueous suspension polycondensation method was proposed to proceed the reaction ofp-phenylenediamine and terephthaloyl chloride for the preparation of poly（p-phenylene terephthalamide） （PPTA）. The system was operated with NMP-CaCI2 solution as the dispersed phase and inert liquid paraffin as the continuous phase. Each of NMP-CaCl2 solution microdroplet suspended in paraffin served as a microreactor where the polycondensation took place. According to the results of TGA, XRD, IR, SEM and EA, PPTA with good quality was obtained through this novel method, and a number of main factors influencing this process were investigated to determine the optimum condition for the preparation of PPTA. Besides, this two-phase polycondensation system brings many unique advantages compared to the conventional solution polycondensation method, including a sealed reaction environment keeping the reactants away from oxygen and water, easy removal of HCI to promote the reaction, well-controlled temperature and low viscosity which means less energy cost.
基金financially supported by the National Key R&D Program of “Strategic Advanced Electronic Materials” (No. 2016YFB0401101) of the Chinese Ministry of Science and Technologythe National Natural Science Foundation of China (No. 51333006)
文摘A highly efficient and eco-friendly protocol for the synthesis of an alternating copolymer poly(7,7'-diazaisoindigo-alt-(E)-1,2- bis(3,4-difluorothien-2-yl)ethene)(PAIID-4FTVT) via direct arylation polycondensation (DArP) is presented. Through detailed study, we found that the inhibitory effect of 7,7'-diazaisoindigo on DArP stemmed from the coordination of N atom with catalyst can be overcome by using dimethylacetamide (DMAc) as the co-solvent. Thus, PAIID-4FTVT with number-average molecular weight (Mn)>100kDa was synthesized via DArP by optimizing the content of DMAc. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy revealed that PAIID-4FTVT was defect-free. Top gate and bottom contact (TG/BC) organic thin-film transistors (OTFTs) were fabricated to characterize the semiconducting properties of the polymers. PAIID-4FTVT displayed unipolar n-type characteristics with the electron mobility (μe) strongly dependent on Mn. The highest μe up to 0.25 cm^2·V^-1 s^-1 was achieved with the high molecular weight sample.
基金Supported by the National Key Research and Development Program of China(2016YFB0302702)the National Natural Science Foundation of China(21676083)+1 种基金the Shanghai Rising-Star Program(16QB140130)the 111 Project(B08021)
文摘The concentration of acetaldehyde(AA) is the main quality index of poly(ethylene terephthalate)(PET) used in food and drink packaging.A new method for AA removal has been developed by using supercritical carbon dioxide(sc CO2) during the solid-state polycondensation of PET.The influence factors of AA removal including the temperature,pressure,reaction time and the size of pre-polymer particles are systematically studied in this work.The results indicate that it is a highly efficient way to obtain high molecular weight PET with relative low concentration of AA.Correspondingly,the polymerization degree of PET could increase from 27.9 to 85.6 while the concentration of AA reduces from 0.229 × 10^(-6) to 0.055 × 10^(-6) under the optimal operation conditions of 230 °C,8 MPa and size of 0.30–0.45 mm.Thermodynamic performance tests show the increasing extent of PET crystallinity due to the fact that the plasticization of sc CO_2 is not obvious with extended reaction time,therefore the increasing crystallinity has no significant influence on AA removal.SEM observations reveal that the effects of sc CO_(2-) induced plasticization and swelling on PET increase significantly with the decrease of prepolymer size,and the surface of PET becomes more loose and porous in favor of the AA removal.
文摘Poly(silphenylene-siloxane)s had been synthesized through dehydrocarbon polycondensation of 1,4- bis(dimethylsilyl)benzene(BDSB)and dialkoxysilane.The polymer composition and structure was characterized by ^(29)Si-NMR.The influence of temperature,B(C_6F_5)_3 concentration and monomer structure on the composition and the microstructure of the copolymers were investigated.It shows that elevating reaction temperature or using substrate (R O)_2R_2R_1Si with bulk organic group of R_1 or R_2 augments the run numb...
基金support from the Natural Science Foundation of Ningbo(No.2007A610030)Science and Technology Department of Zhejiang Province(No.2008C11092-2)
文摘In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO） and nano-SiO2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly（butylene terepbthalate-co-lactate） （PBTL）, and the abundant hydroxyl groups on the surface of nano-SiO2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO2 particles were chemically wrapped with PBTL to form PBTL/nano- SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO2 particles with the copolyester matrix, the tensile strength and the Young＇s modulus increased from 5.4 and 5.6 MPa for neat PBTL to 16 and 390 MPa for PBTL/nano-SiO2 hybrids with 5 wt.% nano-SiO2, respectively. The mechanical properties of PBTL/nano-SiO2 hybrids were substantially improved.
文摘A theoretical approach to polycondensation reaction of Aa-Bb type Involving intramolecular cycllzatlon has been proposed by Tang Au-chin et al.. In this paper, the theoretical sol-gel distribution is tested by polycondensation of adipic acid with trimethylol propane in a sto-ichiometric ratio of 0. 8, and the effect of intramolecular cyclization is discussed in detail.
文摘The fundamental experiments were performed to establish the operational conditions required to prepare the microcapsules containing paraffin wax as a phase change material (PCM) and SiC powder with the interfacial polycondensation reaction. It was investigated how SiC powder affected a few characteristics of microcapsules such as the diameters of microcapsules, latent heat storage density, thermal responsibility and supercooling. In the experiment, the concentration of oil soluble surfactant, the revolution speed of impeller for preparing the (O/W) emulsion and the added weight of SiC powder were changed stepwise. The microcapsules containing PCM in which SiC powder was dispersed could be prepared well and characterized. The diameters of microcapsules increased by containing SiC powder and the content of SiC powder could be increased by performing surface modification of SiC powder. Latent heat storage density decreased with the content of SiC powder. Supercooling of PCM and thermal responsibility could be improved to some degree by containing SiC powder.
基金financially supported by the National Natural Science Foundation of China(Nos.60976019 and 61250016)Education Department Program(No.JA12069)and Program for Innovative Research Team in Science and Technology in Fujian Province
文摘Four thiophene derivatives were prepared by replacing the 3,4 positions of thiophene by―OCH3, ―CH3―COOCH3 and ―CN, respectively. The polycondensations via direct arylation took place between the four thiophene derivatives and 2,7-dibromo-9,9-dioctylfluorene under six various catalytic conditions to investigate the substituent effects. The substituent can affect the electron cloud density of the active C―H bond, which can be monitored by the NMR chemical shift. The experimental results show that the reactivity decreases with increasing the chemical shift of active C―H bonds in the four thiophene derivatives, and thus can promote the direct arylation polycondensation. This phenomenon is explained by the electrophilic aromatic substitution（SEAr） mechanism. UV-Visible absorption and photoluminescence were studied to investigate the substituent effect on optical properties of the four copolymers. The results show that these alternating fluorene-thiophene copolymers with different substituents are good fluorescent materials and promising in PLED applications.
基金financially supported by the National Natural Science Foundation of China(Nos.51933008 and 52121002)the Fundamental Research Funds for the Central Universities。
文摘The solubility of a direct arylation polycondensation(DArP)synthesized conjugated polymer,i.e.,poly(3,6-bis(furan-2-yl)-2,5-bis(4-tetradecyloctadecyl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-1,2-bis(3,4-d ifl uorothien-2-yl)ethene)(PFuD PP-4FTVT),in variou s organic solvents was studied.The polymer is soluble in 3-methylcyclohexanone(3-MC),a green solvent from peppermint oil,besides other solvents such as anisole,cyclopentyl methyl ether(CPME)and o-dichlorobenzene(o-DCB),etc.Based on the Hansen solu bility parameters(HSP)analysis,3-MC is identified as a"marginal solvent"of PFuDPP-4FTVT.The morphology of the spin-coated films with 3-MC as the solvent strongly correlated with the solution preparation conditions.With a 3-MC solution aged for 3 h at 70℃,n-channel organic thin-film transistors(OTFTs)with electron mobility(μe)above 1 cm^(2)·V^(-1)·s^(-1) and current on/off ratio(Ion/Ioff)higher than 105 were fabricated by spin-coating.This is the first report on high mobility conjugated polymers for OTFTs processible with natu rally occurred green solvent.
基金supported by National Natural Science Foundation of China(NSFC,Nos.21971230,U19B6001,22201003)Excellent Research and Innovation Team Project of Anhui Province(No.2022AH010001)Anhui Province Key Laboratory of Environment-friendly Polymer Materials。
文摘Introducing covalently crosslinked network to polymer matrix can merge the advantages in reprocessing and durability of polymers.In this contribution,a series of high-performance vitrimeric elastomers were achieved via polycondensation.The topological structures of polymers were tuned by varying the feeding ratios of bisacetoacetate,hex–substituted bisacetoacetate,bisamine and tris(2-aminoethyl)amine.With these structural manipulations,the vitrimeric elastomers presented great elastic recovery properties(strain recovery value up to 80%)benefiting from the introduction of long chain branch.Furthermore,the elastomers exhibited excellent reprocessing property,water vapor/oxygen barrier and adhesive properties.Specially,the elastomers could be degraded into monomer under acid conditions which enabled the elastomer synthesis again in closed loop recycling system.The ease of the polycondensation in this work to prepare highly elastic and recyclable vitrimeric elastomers demonstrated exciting opportunities for the synthesis of sustainable polymers.
文摘The kinetic data of solid state polycondensation of PET and its copolymers are determined.It is shown that the reaction rate of copolycondensation is higher than that of PET polyconden-sation, and increases with the comonomers content. But the reaction rate of copolycondensationin melt state of this kind of copolymers is lower than that of PET. It is considered that the chemi-cal reactivity of comonomer is the main factor which affect the polycondensation in melt state,whereas the aggregative structure of the polymer is the main factor in solid state. The crystallinity and crystallite size of the copolymers have been measured by X-ray method.
基金financially supported by the National Natural Science Foundation of China(Nos.20774038,21044003)the fund of the State Key Laboratory of Metal Matrix Composites
文摘The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB2 polycondensation with substitution effect were derived by the kinetic mechanism. The reactivity difference between the 13 group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained. The concentration of terminal units has a maximum with the increase of the conversion of A groups （x）. The higher the reactivity ratio （r） of linear B group to branched one is, the later the maximum appears and the larger it is. The degree of branching of the hyperbranched polymers obtained is controllable by adjusting the parameters of r and x, which increases with increasing both x and r.
文摘Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild conditions. The electron-rich hydroxyl groups of bisphenols favoured the polycondensation reaction and the order of relative reactivities of bisphenols is as follow:bisphenoI-A> hydroquinone ～ bisphenol-S> chlorohydroquinone. The mesomorphic properties of copolyesters were examined by birefringence under polarizing microscope, melt transparency. DSC and X-ray diffraction. The minimum molar fraction of mesogenic units needed for the appearance of liquid crystallinity is not higher than 0. 1 despite of the different varieties and lengths of the spacers studied.
基金Sponsored by the Ministerial Level Advanced Research Foundation (120701BQ0126)
文摘A new method of surface chemical modification of nano-SiO2 is proposed in this paper. In the presence of catalyst, the active hydroxyl groups on the surface of nano-SiO2 reacted with AB2-type monomer （N, N-dihydroxyethyl-3-amino methyl propionate） by one-step polycondensation. And the product＇s Fourer transform infrared （FTIR） graphs and transmission electron microscopy（TEM） images proved that hyperbranched poly （amine-ester） was grafted on nano-SiO2 surface successfully. Results show that the modified nano-SiO2 exhibits excellent dispersion and stability in some solvents such as alcohol and chloroform.
基金financially supported by the Beijing Natural Science Foundation (No. 2182056)the National Natural Science Foundation of China (No. 21244006)
文摘Cross-linked polyamides(c PAs)were prepared through direct bulk Michael addition and subsequent polycondensation.Several mixed hexanediamine multi-esters(HDAMEs)were generated through the Michael addition of 1,6-hexanediamine(HDA)and methyl acrylate(MA)at50℃ with different HDA/MA molar ratios.Melt polycondensation of HDAMEs then proceeded at 150 or 170℃ in flasks to obtain viscous fluids,and curing was continued in tetrafluoroethylene molds to obtain c PA films.The Michael addition was monitored on the basis of FTIR and ESI-MS spectra.The c PA films were characterized by DSC,TGA,dynamic mechanical analysis,and tensile test.These directly prepared c PAs exhibited Tg of 1–39℃,tensile strength of up to 45 MPa,and strain at break from 18%to 40%.The c PAs with high tensile strength and good toughness were successfully synthesized through the direct bulk Michael addition from HDA and MA followed with polycondensation.
基金The study is financially supported by the Research foundation of State Education Department of China and National 973 Project of China.
文摘Amorphous poly (L-2-hydroxy-3-phenylpropanoic acid) (PLHPPA) was synthesized by the microwave-assisted polycondensation of L-2-hydroxy-3-phenylpropanoic acid (LHPPA). The weight average molar mass (Mw) of PLHPPA ranged from 3600 to 5300 and polydispersity index (Mw/Mn) from 1.0 to 1.4 when the reaction mixture was irradiated by microwave at 255, 340 and 510 w for 1 to 10 h, respectively.
