Hyperbranched polyethers with different structures and molecular weights（MW） were synthesized using the A2＋B3 approach by varying monomer ratio, A2 structure, and reaction time. Effects of backbone structure and MW...Hyperbranched polyethers with different structures and molecular weights（MW） were synthesized using the A2＋B3 approach by varying monomer ratio, A2 structure, and reaction time. Effects of backbone structure and MW on melt rheological behaviors were investigated by both small amplitude oscillatory shear and steady shear measurements. Master curves were constructed using the time-temperature superposition principle and compared. In the reduced frequency range covered, lg G″-lg（ω·aT） always show a slope of 1.0, suggesting a terminal zone behavior; in contrast, unexpected step changes or plateaus are observed on lg G′ master curves. Effects of backbone structure and MW on master curves were discussed. The Cox-Merz rule was tested at different temperatures and was found to be applicable when flow instability was absent.展开更多
The toughening of the diglycidyl ether of bisphenol A epoxy resin with isocyanateterminated polyethers （ITPE） was investigated. The progress of the reaction and the structural changes during modification process wer...The toughening of the diglycidyl ether of bisphenol A epoxy resin with isocyanateterminated polyethers （ITPE） was investigated. The progress of the reaction and the structural changes during modification process were studied using FTIR spectroscopy. The studies support the proposition that TDI （tolylene diisocyanate） acts as a coupling agent between the epoxy and polyethers, forming a urethane linkage with the former and the latter, respectively. Me THPA-cured ER/ITPs blends were characterized using dynamic mechanical analysis （DMA） and thermogravimetric analysis （TGA）. It is indicated the glass transition temperature （T） of systems was lower than the T of pure epoxy resin and overfull ITPE separated from the modified epoxy resin and formed another phase at an ITPE-content of more than 10wt%. The thermal stability was decreased by the introduction of ITPE. The impact strength and the flexural strength of the cured modifiedepoxy increased with increasing the ITPE content and a maximum plateau value of about 24.03 kJ/m^2 and 130.56 MPa was measured in 10wt% ITPE. From scanning electron microscopy （SEM） studies of the fractrue surfaces of ER/ITPE systems, the nature of the micromechanisms responsible for the increases in toughness of the systems was identified.展开更多
A high performance thermosetting epoxy resin crosslinkable at room temperature was obtained via directly moulding diglycidyl ether of bisphenol A（DGEBA） and flexibleα,ω-bisamino（n-alkylene）phenyl terminated poly...A high performance thermosetting epoxy resin crosslinkable at room temperature was obtained via directly moulding diglycidyl ether of bisphenol A（DGEBA） and flexibleα,ω-bisamino（n-alkylene）phenyl terminated poly（ethylene glycol）.The influences of the n-alkylene inserted in aminophenyl of flexible amino-terminated polythers（ATPE） on the mechanical properties,fractographs and curing kinetics of the ATPE-DGEBA cured products were studied.The results show that the insertion of n-alkylene group into the aminophenyl group of the ATPE,on one hand,can significantly increase the strain relaxation rate and decrease glass transition temperature of the ATPE-DGEBA cured products,resulting in slight decrease of the Young’s modulus and tensile strength,and significant increase of the toughness and elongation of the ATPE-DGEBA cured products.On the other hand,it can remarkably enhance the reactivity of amine with epoxy,much accelerating the curing rate of the ATPE-DGEBA systems.The activation energy of DGEBA cured by BAPTPE,BAMPTPE and BAEPTPE was 53.1,28.5 and 25.4 kJ·mol;,respectively.The as-obtained ATPE-DGEBA cured products are homogeneous, transparent,and show excellent mechanical properties including tensile strength and toughness.Thus they are promising to have important applications in structure adhesives,casting bulk materials,functional coatings,cryogenic engineering, damping and sound absorbing materials.展开更多
The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.
Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potass...Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potassium hydroxide(KOH), and characterized with infrared spectrum(FTIR) and nuclear magnetism resonance(NMR). The effects of catalyst concentration, reaction temperature, charging rate and EO/PO mixture ratio on the polymerization reaction were investigated. It was revealed that the optimal reaction condition is the ratio of 2.5∶1 000(KOH mass vs. product mass), at 114.6℃ and pressure below 0.4 MPa. The residual KOH was neutralized by phosphoric acid(H 3PO 4). Then the crude copolyether was refined with adsorbents, and the refined copolyether, which contains less than 0.7 μg/ml K+, was obtained as colorless, viscous liquid.展开更多
Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymeriza...Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.展开更多
Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemica...Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemical intermediate generation for new material innovation [1].For instance,PO's downstream derivatives,such as polyether polyols,carbonic esters,and polyurethanes,are widely utilized in wind power generation,battery electrolytes,solar cells,and CO_(2)-based degradable polymers,contributing to sustainable decarbonization in industry [2].展开更多
Covalent organic skeletons(COFs)have been widely used in gas separation due to their excellent pore structure,high crystallinity,and high specific surface area.In this work,Dha Tab-COF was synthesized by solvothermal ...Covalent organic skeletons(COFs)have been widely used in gas separation due to their excellent pore structure,high crystallinity,and high specific surface area.In this work,Dha Tab-COF was synthesized by solvothermal method and filled in polyether block polyamide(PEBAX)to form mixed matrix membranes(MMMs).Various characterization methods such as Fourier transform infrared spectroscopy(FT-IR),Xray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM)and X-ray diffractometry(XRD)were used to characterize the structure of Dha Tab-COF as well as the MMMs.The effects of operating pressure,operating temperature and the content of Dha Tab-COF particles on the CO_(2)/CH_(4)separation performance of the membranes were investigated.The best separation performance with a CO_(2)permeability of 295.8 barrer(1 barrer=7.52×10^(-18)m^(3)·(STP)·m^(-2)·m·s^(-1)·Pa^(-1))and a CO_(2)/CH_(4)selectivity of 21.6 was achieved when the Dha Tab-COF content is 2%(mass),which were 45.7%and 108.1%higher than that of the pure PEBAX membrane,respectively.展开更多
The bioinert nature of polyether ether ketone(PEEK)material limits the widespread clinical application of PEEK implants.Although the porous structure is considered to improve osseointegration of PEEK implants,it is ha...The bioinert nature of polyether ether ketone(PEEK)material limits the widespread clinical application of PEEK implants.Although the porous structure is considered to improve osseointegration of PEEK implants,it is hardly used due to its mechanical properties.This study investigated the combined influence of the porous structure and in vivo mechanical stimulation on implantation safety and bone growth based on finite element analysis of the biomechanical behavior of the implantation system.The combined control of pore size and screw preloads allows the porous PEEK implant to achieve good osseointegration while maintaining a relatively high safety level.A pore size of 600μm and a preload of 0.05 N·m are the optimal combination for the long-term stability of the implant,with which the safety factor of the implant is>2,and the predicted percentage of effective bone growth area of the bone-implant interface reaches 97%.For further clinical application,PEEK implants were fabricated with fused filament fabrication(FFF)three-dimensional(3D)printing,and clinical outcomes demonstrated better bone repair efficacy and long-term stability of porous PEEK implants compared to solid PEEK implants.Moreover,good osteointegration performance of 3D-printed porous PEEK implants was observed,with an average bone volume fraction>40%three months after implantation.In conclusion,3D-printed porous PEEK implants have great potential for clinical application,with validated implantation safety and good osseointegration.展开更多
Over the last half-century,polyether ether ketone(PEEK)has emerged as a widely adopted thermoplastic polymer,primarily due to its lower density,exceptional mechanical properties,high-temperature and chemical resistanc...Over the last half-century,polyether ether ketone(PEEK)has emerged as a widely adopted thermoplastic polymer,primarily due to its lower density,exceptional mechanical properties,high-temperature and chemical resistance,and biocompatibility.PEEK and its composites have found extensive applications across various fields,including machinery,aerospace,military equipment,electronics,and biomedicine,positioning themselves as promising substitutes for traditional metal structures.Nevertheless,achieving optimal performance and functional molding of PEEK and its composites presents a formidable challenge,given their inherent characteristics,such as semi-crystallinity,high melting temperature,heightened viscosity,low dielectric coefficient,and hydrophobic properties.In this paper,we present a comprehensive review of the molding methods and processes of PEEK and its composites,including extrusion molding,hot compression molding,injection molding,and 3D printing.We also introduce typical innovative applications within the fields of mechanics,electricity,and biomedicine while elucidating methodologies that leverage the distinctive advantages of PEEK and its composites.Additionally,we summarize research findings related to manipulating the properties of PEEK and its composites through the optimization of machine parameters,process variables,and material structural adjustments.Finally,we contemplate the prevailing development trends and outline prospective avenues for further research in the advancement and molding of PEEK and its composites.展开更多
Nuclear magnetic resonance(NMR)is an advanced technique for the molecular weight(MW)determination of polymers at quantitative conditions.In this study,we investigate the effect of liquid^(1)H-NMR instrumental setting ...Nuclear magnetic resonance(NMR)is an advanced technique for the molecular weight(MW)determination of polymers at quantitative conditions.In this study,we investigate the effect of liquid^(1)H-NMR instrumental setting parameters on the MW determination of polyether diols,namely poly(ethylene glycol)(PEG)and poly(tetramethylene oxide)(PTMO)diols,using hydroxymethylene groups as chain-ends.Our results show that the protons in chain-ends have larger spin-lattice relaxation time(T_(1))than those in main chains.To let most of the excited protons relax to the equilibrium state,the delay time(d_(1))should be much larger than T_(1)of end-groups.When^(13)C decoupling is inactive,the relative errors can be greater than 60%,due to the^(13)C-coupled proton satellite peaks,which can overlap with chain-end groups or be misassigned as chainends.The optimal quantitative NMR conditions for the MW estimation of polyethers are revealed below:standard pulse with inverted gated^(13)C decoupling pulse sequence,32 scans,2.0 s acquisition time in 90 degree of flip angle and 30 s d_(1).The MWs determined from^(1)H quantitative NMR are all smaller than those from SEC which are relative to polystyrene(PS)standards,since the size of polyether chains is larger than that of PS with the same MW.In addition,the MW obtained from SEC for PTMOs shows larger overestimation than PEGs,suggesting PEG chains are more flexible than PTMO’s.展开更多
Polyester and polyether are two key oxygenated polymers, and completely alternative sequence of poly(ester-alt-ether) could efficiently combine the advantages(including flexibility, degradability, etc.) of both segmen...Polyester and polyether are two key oxygenated polymers, and completely alternative sequence of poly(ester-alt-ether) could efficiently combine the advantages(including flexibility, degradability, etc.) of both segments. Currently, despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides, perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs. Moving forward, synthesizing poly(ester-alt-ether) from commercially available and largescale monomers would be a significant advance. For example, successfully commercialized poly(glycolic acid)(PGA), which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle, would encounter a new paradigm if engineered into poly(ester-altether). In this work, starting from the design of monomer with hybrid structures, we successfully synthesized a series of 1,4-dioxan-2-one containing different substituents based on glycolide(GA) and epoxides using commercially available Salen-Cr(III) and PPNCl catalytic systems.The new monomers underwent ring-opening polymerization(ROP) to form a series of poly(ester-alt-ether) with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base. The poly(ester-alt-ether) have significantly lower glass-transition temperature than PGA. Additionally, the poly(ester-alt-ether) can be chemically recovered to monomer using Sn(Oct)2 or 1,8-diazabicyclo[5.4.0]undecane-7-ene(DBU) as a catalyst in solution, thus establishing a closed-loop life cycle. From monomers derived from GA and epoxides, this work furnishes a novel strategy for the synthesis of poly(ester-alt-ether) with chemical recyclability.展开更多
[Objectives] This study was conducted to establish an LC-MS/MS method for the determination of three kinds of polyether residues in eggs with QuEChERS dSPE EMR-Lipid as a pretreatment method, which was established acc...[Objectives] This study was conducted to establish an LC-MS/MS method for the determination of three kinds of polyether residues in eggs with QuEChERS dSPE EMR-Lipid as a pretreatment method, which was established according to Agilent Bond Elut enhanced lipid removal EMR-Lipid technology. [ Methods] Egg was extracted by acidified acetonitrile, purified by Bond Elut EMR-Lipid QuEChERS, and detected by HPLC-MS/MS. [ Results] The three kinds of polyether residues had good linear relationships in the range of 2.0 - 100 μg/L with peak areas, r 〉 0. 999. The recoveries ranged from 84.6% to 107.0%. [ Conclusions ] The method is convenient and accurate, and the quantitative results are accurate and reproducible. It is suitable for the determination of the three kinds of polyether residues in eggs.展开更多
Amino-terminated polyethers and amino-terminated polyurethane were used as curing agent to cure the epoxy resin together and get a series of cured products. The damping properties of the composites were studied by DMA...Amino-terminated polyethers and amino-terminated polyurethane were used as curing agent to cure the epoxy resin together and get a series of cured products. The damping properties of the composites were studied by DMA test at different measurement frequencies. Damping mechanical tests show that the flexible epoxy resin has higher loss factor than common epoxy. The highest loss factor reaches 1.57. Also the height and position of loss factor peak of the flexible epoxy resin varies by changing the content of amino-terminated polyethers. Results shows that the flexible epoxy resin can be used as damping polymer materials at room temperature or in common frequency range.展开更多
Highly active calcium chloride（CaCl2） doped Zn-Co^Ⅲdouble metal-cyanide（Ca-DMC） catalysts were firstly reported.Ca-DMCs presented a very higher polymer yield（54 kg polymer/g catalyst） at relative low temperatur...Highly active calcium chloride（CaCl2） doped Zn-Co^Ⅲdouble metal-cyanide（Ca-DMC） catalysts were firstly reported.Ca-DMCs presented a very higher polymer yield（54 kg polymer/g catalyst） at relative low temperature（80-115℃） toward ringopening polymerization（ROP） of propylene oxide（PO） than did DMC catalysts without modification.展开更多
The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/M...The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.展开更多
Silane terminated prepolymers for adhesives, sealants and coatings are of <span style="font-family:"">great industrial importance. They are very important because of their low toxicity over polyur...Silane terminated prepolymers for adhesives, sealants and coatings are of <span style="font-family:"">great industrial importance. They are very important because of their low toxicity over polyurethanes, silicones, and solvent-based products. Hence, many pieces of literature which deal with the synthesis, properties and applications of this Silane terminated polymers hybrid system exist. Silylated polyether (MS polymers) and Silylated Polyurethane Polymers (SPUR) are the bases for numerous sealants, adhesives and coatings used worldwide. A hybrid system mixed with organic-polyurethane proportion and inorganic-alkoxysilane proportion combines the benefits of conventional polyurethane and silicone-based products. This article reviews the chemistry of MS polymers and SPUR and their advantages and disadvantages in silyl terminated prepolymer-based adhesives, sealants and coatings as well as provides information on different end applications.展开更多
waterborne polyurethane (WPU) dispersions have gained attention towards environm entally-friendly synthesis. In this article, a series of waterborne polyurethane em ulsions was successfully synthesized and extensively...waterborne polyurethane (WPU) dispersions have gained attention towards environm entally-friendly synthesis. In this article, a series of waterborne polyurethane em ulsions was successfully synthesized and extensively characterized in terms of thermal, mechanical properties, hydrophilic behavior and morphology. Snowwas chosen as dispersant instead of comm only used water. Preparation param eters such as intrinsic properties and molecular weight of polyols were discussed systematically. A chain structure was confirmed by Fourier transform infrared (FT-IR) spectroscopy. when com paring the nature of the polyols (PPG, PEG and PNA, 2000g/mol) of this study, as-synthesized polyether waterborne polyurethane provided higher solid content, viscosity and water-resistance. However, polyester waterborne polyurethane perform ed differently and it exhibited higher therm al stability and crystallinity. When com paring the samples (WPU-N210, WPU-N220, WPU-N230 and WPU-N240) with different molecular weight of the same polyol (PPG) used as soft segment, the emulsion WPU-N220 with molecular weight of 2000g/mol PPG provided the highest solid content and lowest viscosity. It was observed th at particle size was uniform and highly dispersed for all sam ples from TEM images. Therm ogravim etric, differential scanning calorim etry (DSC) and X-ray diffraction results dem onstrated that the emulsion WPU-N230 with m olecular weight of 3000 g/mol PPG possessed higher therm al stability and crystallinity than the other samples. The reason was that the Tg and thermal stability were increased with increasing molecular weight. when molecular weight increased, the arrangem ent of soft segm ent became more regular and so did the regularity of the molecular chains. This work demonstrated that different polyols as soft segment applied could lead to great differences in the structure and property of the resulting WPU.展开更多
A novel liquid hyperbranched polyether epoxy （HBPEE） based on commercially available hydroquinone （HQ） and 1,1,1-trihydroxymethylpropane triglycidyl ether （TMPGE） was synthesized through an A2 ＋ B3 one-step pro...A novel liquid hyperbranched polyether epoxy （HBPEE） based on commercially available hydroquinone （HQ） and 1,1,1-trihydroxymethylpropane triglycidyl ether （TMPGE） was synthesized through an A2 ＋ B3 one-step proton transfer polymerization. In order to improve the toughness, the synthesized HBPEE was mixed with diglycidyl ether of bisphenol A （DGEBA） in different ratios to form hybrids and cured with triethylenetetramine （TETA）. Thermal and mechanical properties of the cured hybrids were evaluated. Results show that addition of HBPEE can improve the toughness of cured hybrids remarkably at 〈 20 wt% loading, without compromising the tensile strength. However, the glass transition temperature （Tg） of the cured hybrids decreases with increasing HBPEE content. Fracture surface images from scanning electron microscope show oriented fibrils in hybrids containing HBPEE. The formation and orientation of the fibrils can absorb energy under impact and lead to an improvement of toughness. Furthermore, based on the morphology of fractured surfaces and the single Tg in each hybrid, no sign of phase separation was found in the cured hybrid systems. As a result, the toughening mechanism could be explained by in situ homogeneous toughening mechanism rather than phase separation mechanism.展开更多
Six groups of segmented polyurethanes with amorphous soft segment domains based on mixed hydrophobic polyester and hydrophilic polyether soft monomers were prepared from 4, 4′ diphenylmethane diisocyanate （MDI）, po...Six groups of segmented polyurethanes with amorphous soft segment domains based on mixed hydrophobic polyester and hydrophilic polyether soft monomers were prepared from 4, 4′ diphenylmethane diisocyanate （MDI）, polybutylene adipate glycol 2000 （PBA2000）, polytetramethylene glycol 1000 （PTMG1000） and polyethylene glycol 1000 （PEG1000） with 1,4-butanediol （BDO） as the chain extender. Furthermore, the representative properties of the hydrophilic polyurethanes, moisture permeability and water resistance, were investigated. The results show that the chemical structure, molecular weight and concentration of soft monomers have remarkable effects on the main application properties of hydrophilic polyurethane. The important factors in diffusion are the content of hydrophilic ether bond and the mobility of hydrophilic chain in the soft phase, which is represented with a good approximation by the average mean molecular weight of soft segment. On the contrary, the functional properties of the hydrophilic polyurethane are almost not affected by its hard segment.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51173012)"The Fundamental Research Funds for the Central Universities"at Beijing University of Chemical Technology
文摘Hyperbranched polyethers with different structures and molecular weights（MW） were synthesized using the A2＋B3 approach by varying monomer ratio, A2 structure, and reaction time. Effects of backbone structure and MW on melt rheological behaviors were investigated by both small amplitude oscillatory shear and steady shear measurements. Master curves were constructed using the time-temperature superposition principle and compared. In the reduced frequency range covered, lg G″-lg（ω·aT） always show a slope of 1.0, suggesting a terminal zone behavior; in contrast, unexpected step changes or plateaus are observed on lg G′ master curves. Effects of backbone structure and MW on master curves were discussed. The Cox-Merz rule was tested at different temperatures and was found to be applicable when flow instability was absent.
基金the Natural Science Foundation of Hubei Province (No.2006ABA321)
文摘The toughening of the diglycidyl ether of bisphenol A epoxy resin with isocyanateterminated polyethers （ITPE） was investigated. The progress of the reaction and the structural changes during modification process were studied using FTIR spectroscopy. The studies support the proposition that TDI （tolylene diisocyanate） acts as a coupling agent between the epoxy and polyethers, forming a urethane linkage with the former and the latter, respectively. Me THPA-cured ER/ITPs blends were characterized using dynamic mechanical analysis （DMA） and thermogravimetric analysis （TGA）. It is indicated the glass transition temperature （T） of systems was lower than the T of pure epoxy resin and overfull ITPE separated from the modified epoxy resin and formed another phase at an ITPE-content of more than 10wt%. The thermal stability was decreased by the introduction of ITPE. The impact strength and the flexural strength of the cured modifiedepoxy increased with increasing the ITPE content and a maximum plateau value of about 24.03 kJ/m^2 and 130.56 MPa was measured in 10wt% ITPE. From scanning electron microscopy （SEM） studies of the fractrue surfaces of ER/ITPE systems, the nature of the micromechanisms responsible for the increases in toughness of the systems was identified.
基金supported by the National 863 Plan(No.2006AA03A209)New Century Excellent Talent Plan (No.NECT-05-0660) from Ministry of EducationDefense Basic Research Item(No.D1420061057)
文摘A high performance thermosetting epoxy resin crosslinkable at room temperature was obtained via directly moulding diglycidyl ether of bisphenol A（DGEBA） and flexibleα,ω-bisamino（n-alkylene）phenyl terminated poly（ethylene glycol）.The influences of the n-alkylene inserted in aminophenyl of flexible amino-terminated polythers（ATPE） on the mechanical properties,fractographs and curing kinetics of the ATPE-DGEBA cured products were studied.The results show that the insertion of n-alkylene group into the aminophenyl group of the ATPE,on one hand,can significantly increase the strain relaxation rate and decrease glass transition temperature of the ATPE-DGEBA cured products,resulting in slight decrease of the Young’s modulus and tensile strength,and significant increase of the toughness and elongation of the ATPE-DGEBA cured products.On the other hand,it can remarkably enhance the reactivity of amine with epoxy,much accelerating the curing rate of the ATPE-DGEBA systems.The activation energy of DGEBA cured by BAPTPE,BAMPTPE and BAEPTPE was 53.1,28.5 and 25.4 kJ·mol;,respectively.The as-obtained ATPE-DGEBA cured products are homogeneous, transparent,and show excellent mechanical properties including tensile strength and toughness.Thus they are promising to have important applications in structure adhesives,casting bulk materials,functional coatings,cryogenic engineering, damping and sound absorbing materials.
文摘The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.
文摘Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potassium hydroxide(KOH), and characterized with infrared spectrum(FTIR) and nuclear magnetism resonance(NMR). The effects of catalyst concentration, reaction temperature, charging rate and EO/PO mixture ratio on the polymerization reaction were investigated. It was revealed that the optimal reaction condition is the ratio of 2.5∶1 000(KOH mass vs. product mass), at 114.6℃ and pressure below 0.4 MPa. The residual KOH was neutralized by phosphoric acid(H 3PO 4). Then the crude copolyether was refined with adsorbents, and the refined copolyether, which contains less than 0.7 μg/ml K+, was obtained as colorless, viscous liquid.
基金financially supported by the National Key R&D Program of China(No.2022YFC2805103)the National Natural Science Foundation of China(Nos.52022031 and 52263001)the Foundation from Qinghai Science and Technology Department(No.2022-ZJ-944Q)。
文摘Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.
基金supported by the National Natural Science Foundation of China (29792072, 22278441, 22478452)National Key Research and Development Program of China (937) (2006CB202508)the SINOPEC Project (419019-2, 413108)。
文摘Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemical intermediate generation for new material innovation [1].For instance,PO's downstream derivatives,such as polyether polyols,carbonic esters,and polyurethanes,are widely utilized in wind power generation,battery electrolytes,solar cells,and CO_(2)-based degradable polymers,contributing to sustainable decarbonization in industry [2].
基金supported by the National Natural Science Foundation of China(No.22271022,No 22378327).
文摘Covalent organic skeletons(COFs)have been widely used in gas separation due to their excellent pore structure,high crystallinity,and high specific surface area.In this work,Dha Tab-COF was synthesized by solvothermal method and filled in polyether block polyamide(PEBAX)to form mixed matrix membranes(MMMs).Various characterization methods such as Fourier transform infrared spectroscopy(FT-IR),Xray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM)and X-ray diffractometry(XRD)were used to characterize the structure of Dha Tab-COF as well as the MMMs.The effects of operating pressure,operating temperature and the content of Dha Tab-COF particles on the CO_(2)/CH_(4)separation performance of the membranes were investigated.The best separation performance with a CO_(2)permeability of 295.8 barrer(1 barrer=7.52×10^(-18)m^(3)·(STP)·m^(-2)·m·s^(-1)·Pa^(-1))and a CO_(2)/CH_(4)selectivity of 21.6 was achieved when the Dha Tab-COF content is 2%(mass),which were 45.7%and 108.1%higher than that of the pure PEBAX membrane,respectively.
基金supported by the National Key R&D Program of China(No.2023YFB4603500)the Program for Innovation Team of Shaanxi Province(No.2023-CX-TD-17)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Shaanxi Province Qinchuangyuan“Scientist+Engineer”Team Construction Project(No.2022KXJ-106).
文摘The bioinert nature of polyether ether ketone(PEEK)material limits the widespread clinical application of PEEK implants.Although the porous structure is considered to improve osseointegration of PEEK implants,it is hardly used due to its mechanical properties.This study investigated the combined influence of the porous structure and in vivo mechanical stimulation on implantation safety and bone growth based on finite element analysis of the biomechanical behavior of the implantation system.The combined control of pore size and screw preloads allows the porous PEEK implant to achieve good osseointegration while maintaining a relatively high safety level.A pore size of 600μm and a preload of 0.05 N·m are the optimal combination for the long-term stability of the implant,with which the safety factor of the implant is>2,and the predicted percentage of effective bone growth area of the bone-implant interface reaches 97%.For further clinical application,PEEK implants were fabricated with fused filament fabrication(FFF)three-dimensional(3D)printing,and clinical outcomes demonstrated better bone repair efficacy and long-term stability of porous PEEK implants compared to solid PEEK implants.Moreover,good osteointegration performance of 3D-printed porous PEEK implants was observed,with an average bone volume fraction>40%three months after implantation.In conclusion,3D-printed porous PEEK implants have great potential for clinical application,with validated implantation safety and good osseointegration.
基金supported by the National Key R&D Program of China(No.2022YFC2401903)the“Pioneer”and the“Leading Goose”R&D Program of Zhejiang Province(No.2023C01170)+1 种基金the National Natural Science Foundation of China(No.52205424)the Key Project of Science and Technology Innovation 2025 of Ningbo(No.2023Z029),China.
文摘Over the last half-century,polyether ether ketone(PEEK)has emerged as a widely adopted thermoplastic polymer,primarily due to its lower density,exceptional mechanical properties,high-temperature and chemical resistance,and biocompatibility.PEEK and its composites have found extensive applications across various fields,including machinery,aerospace,military equipment,electronics,and biomedicine,positioning themselves as promising substitutes for traditional metal structures.Nevertheless,achieving optimal performance and functional molding of PEEK and its composites presents a formidable challenge,given their inherent characteristics,such as semi-crystallinity,high melting temperature,heightened viscosity,low dielectric coefficient,and hydrophobic properties.In this paper,we present a comprehensive review of the molding methods and processes of PEEK and its composites,including extrusion molding,hot compression molding,injection molding,and 3D printing.We also introduce typical innovative applications within the fields of mechanics,electricity,and biomedicine while elucidating methodologies that leverage the distinctive advantages of PEEK and its composites.Additionally,we summarize research findings related to manipulating the properties of PEEK and its composites through the optimization of machine parameters,process variables,and material structural adjustments.Finally,we contemplate the prevailing development trends and outline prospective avenues for further research in the advancement and molding of PEEK and its composites.
基金financially supported by the National Natural Science Foundation of China(Nos.22231008 and 22071167)the Natural Science Foundation of Jiangsu Higher Education Institutions of China(No.22KJA150005)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Nuclear magnetic resonance(NMR)is an advanced technique for the molecular weight(MW)determination of polymers at quantitative conditions.In this study,we investigate the effect of liquid^(1)H-NMR instrumental setting parameters on the MW determination of polyether diols,namely poly(ethylene glycol)(PEG)and poly(tetramethylene oxide)(PTMO)diols,using hydroxymethylene groups as chain-ends.Our results show that the protons in chain-ends have larger spin-lattice relaxation time(T_(1))than those in main chains.To let most of the excited protons relax to the equilibrium state,the delay time(d_(1))should be much larger than T_(1)of end-groups.When^(13)C decoupling is inactive,the relative errors can be greater than 60%,due to the^(13)C-coupled proton satellite peaks,which can overlap with chain-end groups or be misassigned as chainends.The optimal quantitative NMR conditions for the MW estimation of polyethers are revealed below:standard pulse with inverted gated^(13)C decoupling pulse sequence,32 scans,2.0 s acquisition time in 90 degree of flip angle and 30 s d_(1).The MWs determined from^(1)H quantitative NMR are all smaller than those from SEC which are relative to polystyrene(PS)standards,since the size of polyether chains is larger than that of PS with the same MW.In addition,the MW obtained from SEC for PTMOs shows larger overestimation than PEGs,suggesting PEG chains are more flexible than PTMO’s.
基金financially supported by the National Key R&D Program of China (No. 2021YFA1501700)the Science and Technology Development Plan of Jilin Province (Nos.20230101042JC and 20210201059GX)+2 种基金the National Natural Science Foundation of ChinaBasic Science Center Program (No.51988102)the National Natural Science Foundation of China (Nos. 52203017 and 52073272)。
文摘Polyester and polyether are two key oxygenated polymers, and completely alternative sequence of poly(ester-alt-ether) could efficiently combine the advantages(including flexibility, degradability, etc.) of both segments. Currently, despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides, perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs. Moving forward, synthesizing poly(ester-alt-ether) from commercially available and largescale monomers would be a significant advance. For example, successfully commercialized poly(glycolic acid)(PGA), which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle, would encounter a new paradigm if engineered into poly(ester-altether). In this work, starting from the design of monomer with hybrid structures, we successfully synthesized a series of 1,4-dioxan-2-one containing different substituents based on glycolide(GA) and epoxides using commercially available Salen-Cr(III) and PPNCl catalytic systems.The new monomers underwent ring-opening polymerization(ROP) to form a series of poly(ester-alt-ether) with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base. The poly(ester-alt-ether) have significantly lower glass-transition temperature than PGA. Additionally, the poly(ester-alt-ether) can be chemically recovered to monomer using Sn(Oct)2 or 1,8-diazabicyclo[5.4.0]undecane-7-ene(DBU) as a catalyst in solution, thus establishing a closed-loop life cycle. From monomers derived from GA and epoxides, this work furnishes a novel strategy for the synthesis of poly(ester-alt-ether) with chemical recyclability.
基金Supported by Science and Technology Planning Project of Huizhou City(20161117141959)
文摘[Objectives] This study was conducted to establish an LC-MS/MS method for the determination of three kinds of polyether residues in eggs with QuEChERS dSPE EMR-Lipid as a pretreatment method, which was established according to Agilent Bond Elut enhanced lipid removal EMR-Lipid technology. [ Methods] Egg was extracted by acidified acetonitrile, purified by Bond Elut EMR-Lipid QuEChERS, and detected by HPLC-MS/MS. [ Results] The three kinds of polyether residues had good linear relationships in the range of 2.0 - 100 μg/L with peak areas, r 〉 0. 999. The recoveries ranged from 84.6% to 107.0%. [ Conclusions ] The method is convenient and accurate, and the quantitative results are accurate and reproducible. It is suitable for the determination of the three kinds of polyether residues in eggs.
基金Funded by the National Natural Science Foundation of China(No.50502027)
文摘Amino-terminated polyethers and amino-terminated polyurethane were used as curing agent to cure the epoxy resin together and get a series of cured products. The damping properties of the composites were studied by DMA test at different measurement frequencies. Damping mechanical tests show that the flexible epoxy resin has higher loss factor than common epoxy. The highest loss factor reaches 1.57. Also the height and position of loss factor peak of the flexible epoxy resin varies by changing the content of amino-terminated polyethers. Results shows that the flexible epoxy resin can be used as damping polymer materials at room temperature or in common frequency range.
基金the financial supports of the National Science Foundation of the People's Republic of China(No.20704034)Provincial Natural Science Foundation of Zhejiang(No.Y4090047)
文摘Highly active calcium chloride（CaCl2） doped Zn-Co^Ⅲdouble metal-cyanide（Ca-DMC） catalysts were firstly reported.Ca-DMCs presented a very higher polymer yield（54 kg polymer/g catalyst） at relative low temperature（80-115℃） toward ringopening polymerization（ROP） of propylene oxide（PO） than did DMC catalysts without modification.
文摘The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.
文摘Silane terminated prepolymers for adhesives, sealants and coatings are of <span style="font-family:"">great industrial importance. They are very important because of their low toxicity over polyurethanes, silicones, and solvent-based products. Hence, many pieces of literature which deal with the synthesis, properties and applications of this Silane terminated polymers hybrid system exist. Silylated polyether (MS polymers) and Silylated Polyurethane Polymers (SPUR) are the bases for numerous sealants, adhesives and coatings used worldwide. A hybrid system mixed with organic-polyurethane proportion and inorganic-alkoxysilane proportion combines the benefits of conventional polyurethane and silicone-based products. This article reviews the chemistry of MS polymers and SPUR and their advantages and disadvantages in silyl terminated prepolymer-based adhesives, sealants and coatings as well as provides information on different end applications.
基金supported by the National Natural Science Foundation of China (Grant No. 51772243)PhD Research Startup Foundation of Xi’an University of Technology (Grant No. 108256081703)+4 种基金Beijing Laboratory for Food Quality and Safety, Beijing Technology and Business University (Grant No. FQS-201709)the Innovative Team Support Program (2017KCT-17)Key Laboratory of Processing and Quality Evaluation Technology of Green Plastics of China National Light Industry Council, Beijing Technology and Business University (Grant No. BS201702)the China Postdoctoral Science Foundation Funded Project (Grant No. 2016M592824)the Science and Technology Plan of Yulin City (Grant No. 2016-16-7), and the Science and Technology Plan of Beilin District (Grant No. GX1710)
文摘waterborne polyurethane (WPU) dispersions have gained attention towards environm entally-friendly synthesis. In this article, a series of waterborne polyurethane em ulsions was successfully synthesized and extensively characterized in terms of thermal, mechanical properties, hydrophilic behavior and morphology. Snowwas chosen as dispersant instead of comm only used water. Preparation param eters such as intrinsic properties and molecular weight of polyols were discussed systematically. A chain structure was confirmed by Fourier transform infrared (FT-IR) spectroscopy. when com paring the nature of the polyols (PPG, PEG and PNA, 2000g/mol) of this study, as-synthesized polyether waterborne polyurethane provided higher solid content, viscosity and water-resistance. However, polyester waterborne polyurethane perform ed differently and it exhibited higher therm al stability and crystallinity. When com paring the samples (WPU-N210, WPU-N220, WPU-N230 and WPU-N240) with different molecular weight of the same polyol (PPG) used as soft segment, the emulsion WPU-N220 with molecular weight of 2000g/mol PPG provided the highest solid content and lowest viscosity. It was observed th at particle size was uniform and highly dispersed for all sam ples from TEM images. Therm ogravim etric, differential scanning calorim etry (DSC) and X-ray diffraction results dem onstrated that the emulsion WPU-N230 with m olecular weight of 3000 g/mol PPG possessed higher therm al stability and crystallinity than the other samples. The reason was that the Tg and thermal stability were increased with increasing molecular weight. when molecular weight increased, the arrangem ent of soft segm ent became more regular and so did the regularity of the molecular chains. This work demonstrated that different polyols as soft segment applied could lead to great differences in the structure and property of the resulting WPU.
基金supported by the Natural Science Foundation of Beijing(No.2092023)National Natural Science Foundation of China(No.51173012)the Fundamental Research Funds for the Central Universities(No.ZZ0912)
文摘A novel liquid hyperbranched polyether epoxy （HBPEE） based on commercially available hydroquinone （HQ） and 1,1,1-trihydroxymethylpropane triglycidyl ether （TMPGE） was synthesized through an A2 ＋ B3 one-step proton transfer polymerization. In order to improve the toughness, the synthesized HBPEE was mixed with diglycidyl ether of bisphenol A （DGEBA） in different ratios to form hybrids and cured with triethylenetetramine （TETA）. Thermal and mechanical properties of the cured hybrids were evaluated. Results show that addition of HBPEE can improve the toughness of cured hybrids remarkably at 〈 20 wt% loading, without compromising the tensile strength. However, the glass transition temperature （Tg） of the cured hybrids decreases with increasing HBPEE content. Fracture surface images from scanning electron microscope show oriented fibrils in hybrids containing HBPEE. The formation and orientation of the fibrils can absorb energy under impact and lead to an improvement of toughness. Furthermore, based on the morphology of fractured surfaces and the single Tg in each hybrid, no sign of phase separation was found in the cured hybrid systems. As a result, the toughening mechanism could be explained by in situ homogeneous toughening mechanism rather than phase separation mechanism.
基金Funded by the Key Natural Science Foundation of Shaanxi Province Education Department (No.04JK-181)the Direction Program of China Textile Industry Association (No.2007-049)
文摘Six groups of segmented polyurethanes with amorphous soft segment domains based on mixed hydrophobic polyester and hydrophilic polyether soft monomers were prepared from 4, 4′ diphenylmethane diisocyanate （MDI）, polybutylene adipate glycol 2000 （PBA2000）, polytetramethylene glycol 1000 （PTMG1000） and polyethylene glycol 1000 （PEG1000） with 1,4-butanediol （BDO） as the chain extender. Furthermore, the representative properties of the hydrophilic polyurethanes, moisture permeability and water resistance, were investigated. The results show that the chemical structure, molecular weight and concentration of soft monomers have remarkable effects on the main application properties of hydrophilic polyurethane. The important factors in diffusion are the content of hydrophilic ether bond and the mobility of hydrophilic chain in the soft phase, which is represented with a good approximation by the average mean molecular weight of soft segment. On the contrary, the functional properties of the hydrophilic polyurethane are almost not affected by its hard segment.
