The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution...The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4-diphenylmethane diisocyanate(MDI)with PECD that was derived from the copolymerization of carbon dioxide(CO_(2))and ethylene oxide(EO).The tensile strength,the elongation at break and 300%constant tensile strength of the PECD-PU were up to 66±2 MPa,880%±50%and 13 MPa,respectively,higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters.The PECD-PU with high CO_(2) carbonate content exhibited good solvent resistance and chemical stability.Of importance,the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO_(2),i.e.,the carbonate unit in PECD.This work provides comprehensive properties of PECD-derived PUs,indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.展开更多
In this study, a novel three functional chain extender （TATATRIOL） was synthesized from the reaction of 1,3,5- tri（prop-2-en-1-yl）-1,3,5-triazinane-2,4,6-trione （TATA） with 2-sulfanylethanol. Then new thermoplas...In this study, a novel three functional chain extender （TATATRIOL） was synthesized from the reaction of 1,3,5- tri（prop-2-en-1-yl）-1,3,5-triazinane-2,4,6-trione （TATA） with 2-sulfanylethanol. Then new thermoplastic polyurethanes （TPUs） were synthesized by a one-step bulk polymerization from the reaction of 1,1＇-methanediylbis（4- isocyanatocyclohexane） （H12MDI）, a poly（ethylene adipate） based polyester polyol and a chain extender. Butane-l,4-diol （BD） and the newly synthesized monomer, TATATRIOL, were used as chain extenders. The effects of TATATRIOL on the properties of the TPU were investigated and compared to those of the TPU prepared with BD. The TPUs which derived from the sulfur containing chain extender displayed lower modulus and high elongation at break values than the analogous TPUs derived from BD. Moreover sulfur containing TPUs exhibited higher thermal stability.展开更多
Background:The development of materials for cardiovascular surgery that would improve the effectiveness of surgical interventions remains an important task.Surgical intervention during the implantation of vascular pro...Background:The development of materials for cardiovascular surgery that would improve the effectiveness of surgical interventions remains an important task.Surgical intervention during the implantation of vascular prostheses and stents,and the body’s reaction to artificial materials,could lead to chronic inflammation,a local increase in the concentration of proinflammatory factors,and stimulation of unwanted tissue growth.The introduction of nonsteroidal anti-inflammatory drugs into implantable devices could be used to obtain vascular implants that do not induce inflammation and do not induce neointimal tissue outgrowth.Methods:The scaffolds were made by electrospinning from mixtures of polyurethane(PU)with diclofenac(DF).The kinetics of DF release from the scaffolds composed of 3%PU/10%HSA/3%DMSO/DF and 3%PU/DF were studied.The biocompatibility and anti-inflammatory effects of the obtained scaffolds on human gingival fibroblasts and umbilical vein endothelial cells were studied.Results:Both types of scaffolds are characterized by fast DF release.The viability of cells cultured on scaffolds is 2 times worse than that of cells cultured on plastic.The level of the proinflammatory cytokine IL-6 in the culture medium of cells cultured on DF-containing scaffolds was lower than that of cells cultured on scaffolds without DF.Conclusion:The introduction of DF into scaffolds minimizes the inflammation caused by cell reactions to an artificial material.展开更多
In ultraviolet cured-in-place-pipe(UV-CIPP)pipeline rehabilitation,resin performance critically determines repair effectiveness.Current UV-curable resins exhibit high volatile organic compound(VOC)emissions and inadeq...In ultraviolet cured-in-place-pipe(UV-CIPP)pipeline rehabilitation,resin performance critically determines repair effectiveness.Current UV-curable resins exhibit high volatile organic compound(VOC)emissions and inadequate post-cure toughness,which compromise fatigue resistance during service.To address these issues,we synthesized hydroxyl-terminated polyurethane acrylate prepolymers using diphenylmethane diisocyanate(MDI),polypropylene glycol(PPG),and hydroxyethyl methacrylate(HEMA).Fourier transform infrared spectroscopy(FTIR)confirmed successful prepolymer synthesis.We developed UV-curable resins by incorporating various crosslinking monomers and optimized the formulations through mechanical property analysis.Testing revealed that the polyurethane-acrylic UV-cured resin system combines polyurethane's mechanical excellence with acrylics'high UV-curing activity.The PPG200/MDI/HEMA formulation achieved superior performance,with a tensile strength of 55.31 MPa,an impact toughness of 22.7 kJ/m^(2),and a heat deflection temperature(HDT)of 132℃.The optimized system eliminates volatile components while maintaining high reactivity,addressing critical limitations in trenchless pipeline rehabilitation.The improved mechanical properties meet the operational demands of underground pipes,suggesting practical applicability in trenchless pipeline repair.展开更多
Polyurethanes consisting of tri-functional homopolymer of hexamethylene diisocyanate （tri-HDI） and polyethylene glycol （PEG） are synthesized, in which photo-reversible coumarin moieties act as pendant groups. Acco...Polyurethanes consisting of tri-functional homopolymer of hexamethylene diisocyanate （tri-HDI） and polyethylene glycol （PEG） are synthesized, in which photo-reversible coumarin moieties act as pendant groups. Accordingly, the polyurethanes can be repeatedly self-healed under UV lights at room temperature by taking advantages of the photodimerization and photocleavage habits of coumarin. Molecular weight of the soft segment, PEG, is found to be closely related to the healing performance of the polyurethanes. Lower molecular weight PEG that corresponds to higher initial coumarin concentration in the polymer is critical for obtaining higher healing efficiency in the case of the first healing action. Nevertheless, it does not guarantee high reversibility of the photo-remendability during the repeated healing events. In contrast, the polyurethane with moderate molecular weight PEG has achieved balanced performance. Reaction kinetics is less important for the healing effect.展开更多
To better investigate the degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering, a series of new waterborne biodegradable polyurethanes （PEGPUs） with low degree of crossli...To better investigate the degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering, a series of new waterborne biodegradable polyurethanes （PEGPUs） with low degree of crosslinking was synthesized using IPDI, BDO and L-lysine as hard segments, PCL and PEG as soft segment. The bulk structures and properties of the prepared polyurethanes were characterized by Fourier transform infrared spectroscopy （FTIR）, differential scanning calorimetry （DSC）, tensile mechanical tests and water contact angle （WCA） measurements. The degree of microphase separation was slightly improved because of the lowered crosslinking degree of these PEGPUs in comparison with the high cross-linking degree samples, leading to good mechanical properties, as indicated by DSC and stress-strain data. Moreover, biodegradability of the polyurethanes was evaluated in phosphate buffer solutions （PBS） under different pH values and enzymatic solution at pH 7.4 through weight loss monitoring. The results suggested that the degradation of these PEGPUs was closely related to their bulk and surface properties. And the degradation products didn＇t show apparent inhibition effect against fibroblasts in vitro. These studies demonstrated that the waterborne biodegradable polyurethanes could find potential use in soft tissue engineering and tissue regeneration.展开更多
Polyurethanes（PU） were prepared using toluene diisocyanate,polypropylene glycol,ethylene glycol, dimethylolpropionic acid and triethylamine,and a siloxane modified PU（PSU） was obtained through reaction of the PU p...Polyurethanes（PU） were prepared using toluene diisocyanate,polypropylene glycol,ethylene glycol, dimethylolpropionic acid and triethylamine,and a siloxane modified PU（PSU） was obtained through reaction of the PU prepolymers with bis（3-（1-methoxy-2-hydroxypropoxy）propyl） terminated polysiloxanes（PMTS） of different molecular weight,specifically designed for this purpose.Results showed that,with increases in molecular weight of PMTS and its content,viscosity of the final PSU latexes decreased;phase separation of the incorporated PMTS in PSU films increased;the average particle sizes of the latexes varied between 110 nm and 330 nm,and the surface tension in the final latexes was relatively constant regardless of PMTS amount and its molecular weight.It was likely that copolymerized polysiloxanes had trend to enrich on top of the film when PMTS molecular weight was around 2000 and its content above 5 wt%.In general, PMTS modified polyurethane films showed higher performance than those from unmodified waterborne polyurethane latexes.展开更多
Waterborne polyurethane composites containing silica nanoparticles are synthesized successfully via the in situ polymerization. The structure, thermal stability, surface hardness, tensile strength, UV-Vis absorbance, ...Waterborne polyurethane composites containing silica nanoparticles are synthesized successfully via the in situ polymerization. The structure, thermal stability, surface hardness, tensile strength, UV-Vis absorbance, dynamic mechanical properties and chemicals resistance of the resulting composites are investigated by FTIR, TEM, TGA, UV-Vis, DMA and chemicals soakage measurements. Results show that polyurethane molecules and silica nanoparticles are linked with covalent bonds. As a result, physical properties of polyurethane composites, such as thermal stability, surface hardness, weather and chemicals resistance are all improved when an appropriate concentration of silica nanoparticles are incorporated.展开更多
Soy-protein isolate(SPI)was used to prepare non-isocyanate polyurethane(NIPU)thermosetting adhesives for wood panels by reacting it with dimethyl carbonate(DMC)and hexamethylene diamine.Both linear as well as branched...Soy-protein isolate(SPI)was used to prepare non-isocyanate polyurethane(NIPU)thermosetting adhesives for wood panels by reacting it with dimethyl carbonate(DMC)and hexamethylene diamine.Both linear as well as branched oligomers were obtained and identified,indicating how such oligomer structures could further cross-link to form a hardened network.Unusual structures were observed,namely carbamic acid-derived urethane linkages coupled with lactam structures.The curing of the adhesive was followed by thermomechanical analysis(TMA).It appeared to follow a two stages process:First,at a lower temperature(maximum 130℃),the growth of linear oligomers occurred,finally forming a physically entangled network.This appeared to collapse and disentangle,causing a decrease of MOE,as the temperature increases.This appears to be due to the ever more marked Brownian movements of the linear oligomer chains with the increase of the temperature.Second,chemical cross-linking of the chains appeared to ensue,forming a hardened network.This was shown by the thermomechanical analysis(TMA)showing two distinct MOE maxima peaks,one around 130℃ and the other around 220℃,with a very marked MOE decrease between the two.Plywood panels were prepared and bonded with the SPI-NIPU wood adhesive and the results obtained are presented.The adhesive appeared to pass comfortably the requirements for dry strength of relevant standards,showing to be suitable for interior grade plywood panels.It did not pass the requirements for wet tests.However,addition of 15%of glycerol diglycidyl ether improved the wet tests results but still not enough to satisfy the standards requirements.展开更多
Thermoplastic poly(ether-ester-urethane)s were synthesized from poly(L-lactide) diols (PLLA diols), polytetrahydrofuran diol (PTMG diols), 4,4'-dicyclohexylmethane diisocyanate (HMDI), and 1,4-butanediol (BDO) by ...Thermoplastic poly(ether-ester-urethane)s were synthesized from poly(L-lactide) diols (PLLA diols), polytetrahydrofuran diol (PTMG diols), 4,4'-dicyclohexylmethane diisocyanate (HMDI), and 1,4-butanediol (BDO) by a two-step reaction, and the morphology and property of the resultant TPU could be adjusted by varying the PLLA contents. The soft segment was composed of PLLA and PTMG diols. By controlling the percentage of PLLA in the soft segment, the glass transition temperature and mechanical properties of the polyurethanes could be regulated. Based on the FTIR spectrum, we found that two kinds of hydrogen bonding existed individually in soft matrix and hard domain. The hydrogen bonding in soft matrix was unstable, which could be destroyed during elongation. With in situ stretching WAXS and SAXS experiments, we found that the PLLA crystal was destroyed and the PLLA domain oriented along the stretch direction. Finally, we proposed a schematic model to illustrate the microstructures of these elastomers before and after stretch.展开更多
Thermomechanical properties of polyurethanes（PUs） strongly depend on the molecular interactions and microphase structure. In this work, two chain extenders with different ratios, flexile 1,4-butanediol（BDO） and br...Thermomechanical properties of polyurethanes（PUs） strongly depend on the molecular interactions and microphase structure. In this work, two chain extenders with different ratios, flexile 1,4-butanediol（BDO） and branched trimethylolpropane mono allyl ether（TMPAE）, are used to tune the molecular interactions and microphase structures of a series of biodegradable thermoplastic polyurethanes（TPUs）. In TPUs, the biodegradable polycaprolactone（PCL, M_n of 2000） is used as soft segment while 1,6-diisocyanatohexane（HDI） and chain extenders are used as hard segment. Fourier transform infrared spectroscopy（FTIR）, proton nuclear magnetic resonance spectroscppy（~1 H-NMR）, gel permeation chromatography（GPC）, differential scanning calorimetry（DSC）, dynamic mechanical analysis（DMA） and mechanical tests were performed to characterize the bulk structure and properties of TPUs. Compared with BDO, the steric bulk of TMPAE is larger. The increment of TMPAE can help to increase the hydrogen bond content, microphase separation, and the elastic modulus ratio（R）, which would strongly affect the thermomechanical property of the TPUs. The results of this work verify the importance of the structure of chain extender on the properties of TPUs. It provides valuable information for further understanding the structure-property relationships of these polyurethanes.展开更多
A series of fluorinated phosphatidylcholine polyurethane macromolecular additives were synthesized by solution polymerization using methylenebis（phylene isocyanates） （MDI） and 1,4-butanediol （BDO） as hard segmen...A series of fluorinated phosphatidylcholine polyurethane macromolecular additives were synthesized by solution polymerization using methylenebis（phylene isocyanates） （MDI） and 1,4-butanediol （BDO） as hard segments, a new phoshporycholine, 2-（2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-10-（2-hydroxyethoxy）decyloxy） ethyl phosphorycholine （HDFOPC） as end-capper, and four polydiols, poly（tetramethylene glycol）s （PTMG）, polydimethylsiloxane （PDMS）, poly（1,6-hexyl-1,5-pentylcarbonate） （PHPC） and poly（propylene glycol） （PPG） as soft segments, respectively. The chemical structures of the synthesized polyurethanes were characterized by 1H-NMR and FTIR. DSC and DMA were employed to study the phase behavior of these novel polyurethanes due to their great influences on the surface properties, and hence their interactions with bio-systems. The results showed that phase separation of the fluorinated phosphatidylcholine end-capped polyurethanes was increased in comparison with that of normal polyurethanes. The effect of fluorinated phosphatidylcholine end-capped groups on the phase behavior was further demonstrated by analyzing the degree of hydrogen-bonding between hard and soft segments.展开更多
The reaction of a desulphurized kraft lignin with hexamethylene diamine and dimethyl carbonate has allowed the development of isocyanate-free polyurethane resins.The present research work is based on previous studies ...The reaction of a desulphurized kraft lignin with hexamethylene diamine and dimethyl carbonate has allowed the development of isocyanate-free polyurethane resins.The present research work is based on previous studies made with hydrolyzable and condensed tannins,but takes advantage of the higher number of hydroxyl groups present in lignin and their different aliphatic and aromatic character.The obtained materials were analyzed by Fourier transform infrared(FTIR)spectroscopy,matrix-assisted laser desorption ionization time-of-flight(MALDI-TOF)mass spectrometry and solid-state cross-polarization/magic angle spinning(CP MAS)13C nuclear magnetic resonance(NMR),which have revealed the presence of urethane functions.The interpretation of the results has shown a larger number of species than when tannins were used and has indicated the presence of two types of bonds in the new molecules formed:ionic and covalent bonds.展开更多
A series of random copolymers （PCLAs） were synthesized by ring-opening polymerization of D,L-lactide （LA） and ε-caprolactone （CL） with different molar ratios. PCLA based polyurethanes （PCLAUs） were obtained b...A series of random copolymers （PCLAs） were synthesized by ring-opening polymerization of D,L-lactide （LA） and ε-caprolactone （CL） with different molar ratios. PCLA based polyurethanes （PCLAUs） were obtained by chain-extending of PCLA and polytetramethylene ether （PTMEG） with hexamethylene diisocyanate （HDI）. All the PCLAUs exhibit good shape memory properties with high shape fixity ratios above 98% and shape recovery ratios above 82% in the first cycle and 91% in the second cycle. PCLAUs with less CL content show faster recovery speed and PCLAUs with more CL content show higher shape recovery ratio. The trigger temperature can be tuned or controlled around body temperature by adjusting the molar ratio of LA to CL. The PCLAUs have potential applications in implant biomedical devices, especially for minimally invasive deployable devices.展开更多
The increasing pressure from consumers and policy makers to reduce the use of synthetic polymers,whose production contributes to the depletion of non-renewable resources and are usually non-biodegradable,has prompted ...The increasing pressure from consumers and policy makers to reduce the use of synthetic polymers,whose production contributes to the depletion of non-renewable resources and are usually non-biodegradable,has prompted the efforts to find suitable bio-based sources for the production of polymers.Vegetable oils have been a frequently spotted in this search because they are versatile,highly available and a low cost liquid biosource,which can be used in the synthesis of a wide plethora of different polymers and reactive monomers.Following the same idea of reducing the environmental stress,the traditional polyurethanes that are soluble in organic solvents have been targeted for replacement,particularly in applications such as adhesives and coatings,in which the solvent is released to the atmosphere increasing the air pollution.Instead,waterborne polyurethanes(WBPU),which are polyurethane dispersions(PUD)prepared in aqueous media,release benign water to the atmosphere during use as supported or self-standing films for different applications.In this brief review,the contributions to the development of WBPUs based on vegetable oils are discussed,focusing mainly on the contributions of the last decade.The synthesis of ionic and nonionic PUDs,their characterization and the properties of the resulting dried materials,as well as derived composite materials are considered.展开更多
Non-isocyanate polyurethane(NIPU)foams from a commercial hydrolysable tannin extract,chestnut wood tannin extract,have been prepared to determine what chemical species and products are taking part in the reactions inv...Non-isocyanate polyurethane(NIPU)foams from a commercial hydrolysable tannin extract,chestnut wood tannin extract,have been prepared to determine what chemical species and products are taking part in the reactions involved.This method is based on two main steps:the reaction with dimethyl carbonate and the formation of urethane bonds by further reaction of the carbonated tannin with a diamine-like hexamethylene diamine.The hydroxyl groups on the tannin polyphenols and on the carbohydrates intimately linked with it and part of a hydrolysable tannin are the groups involved in these reactions.The carbohydrate skeleton of the hydrolysable tannin is also able to participate through its hydroxyl groups to the same two reactions rendering the whole molecular complex able to react to form NIPUs.The analysis by Matrix-Assisted Laser Desorption Ionization(MALDI-TOF)mass spectrometry and 13C Nuclear Magnetic Resonance(13C NMR)to further investigate the reaction mechanisms involved revealed the unsuspected complexity of chestnut hydrolysable tannin,with different fragments reacting in different manners forming a hardened network of considerable complexity.As the morphology and performance of these types of foams changes slightly with the change in the amount of glutaraldehyde and hexamine hardeners,the best performing foam formulation previously determined was scanned by SEM and analysed chemically for the structures formed.展开更多
1,2-Dioxetane is a well-known chemiluminescent mechanophore allowing real-time monitoring of polymer chain scission,but usually suffers from fluorescence quenching in polar environments.Herein,a series of mechanochemi...1,2-Dioxetane is a well-known chemiluminescent mechanophore allowing real-time monitoring of polymer chain scission,but usually suffers from fluorescence quenching in polar environments.Herein,a series of mechanochemiluminescent waterborne polyurethanes/carbon dots composites(WPU-CDs)have been synthesized by incorporating fluorescent CDs to promote the energy transfer process in different environments.The resulting bulk WPUs,and in particular,their swollen films filled with a large amount of polar solvents(water and ionic liquid)emit intense mechanochemiluminescence.Thus force-induced covalent bond scission and stress distribution within these different WPU-CDs films can be sensitively visualized.Furthermore,the ionic liquid containing films exhibited both electrical and luminescent signal changes under stretching,which offer a new kind of force sensor responsive at a broad detecting strain range and for multi-mode strain analysis.This study is expected to stimulate new research endeavors in mechanistic insight on waterborne polyurethanes and the corresponding stretchable sensing devices.展开更多
A series of fluorescent siloxane-polyurethanes（HPMS-PUs） containing an amino-functionalized,1 8-naphthalimide,fluorescent monomer（AABD） as a chain extender were synthesized.The properties of the HPMS-PUs were inve...A series of fluorescent siloxane-polyurethanes（HPMS-PUs） containing an amino-functionalized,1 8-naphthalimide,fluorescent monomer（AABD） as a chain extender were synthesized.The properties of the HPMS-PUs were investigated by UV–vis and fluorescence spectroscopies,thermogravimetric analysis and thermal migration behavior.The maximum absorption and emission wavelengths of HPMS-PUs showed a red shift of about 4 nm and a blue shift of about 9 nm,respectively,compared to those of AABD.The Stokes shifts of AABD and HPMS-PU2 were 3514 and 2931 cm 1,respectively.The quantum yield of HPMS-PU2 was 0.79,which was six times higher than that of AABD.Concentration self-quenching was observed in both AABD and HPMS-PUs.The fluorescence of HPMS-PUs was quite stable with respect to both temperature and fluorescence quencher effects.The thermal stability of HPMS-PUs increased with AABD content.The fluorophore units in the HPMS-PUs did not readily migrate.展开更多
Polyols are groups of organic compounds which contain carbon and are randomly linked to other atoms,especially carbon-carbon and carbon-hydrogen.These compounds are mainly used as reactants to make other polymers.Amon...Polyols are groups of organic compounds which contain carbon and are randomly linked to other atoms,especially carbon-carbon and carbon-hydrogen.These compounds are mainly used as reactants to make other polymers.Among biopolymers,lignin is regarded as the base of a new polymer in polyol construction.The present study aimed to investigate the effects of amine type(diethylenetriamine and ethylenediamine)on the modification of lignin-based polyols,so as to provide an alternative to petroleum polyols and,in turn,increase functional groups and reduce their harm to humans’health and the environment.To this aim,first,lignin was extracted from raw liquor.Next,the extracted lignin was reacted with diethylenetriamine(DETA)and ethylenediamine(EDA).Finally,the Mannich method was used for the reaction between amine lignin and propylene carbonate.The results of the Fourier Transform Infrared(FTIR)spectroscopy analysis showed that modification with DETA led to more structural change in lignin and peak 1100 indicates the presence of C–O bond related to urethane bonds in modified lignin.Moreover,adding propylene carbonate to aminated lignin did not result in much change in the results of the FTIR analysis.Additionally,urethane bonds can be seen in the results of GPC at 400℃–500℃.Furthermore,a slight decrease in thermal stability was observed in lignin modified with amine and propylene carbonate,compared to the raw lignin sample.展开更多
基金financially supported by the Maoming Science and Technology Bureau(No.2022DZXHT007)。
文摘The synthesis of polyurethanes(PUs)from the reaction of low molecular weight poly(ethylene carbonate)diol(PECD)is rarely investigated.This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4-diphenylmethane diisocyanate(MDI)with PECD that was derived from the copolymerization of carbon dioxide(CO_(2))and ethylene oxide(EO).The tensile strength,the elongation at break and 300%constant tensile strength of the PECD-PU were up to 66±2 MPa,880%±50%and 13 MPa,respectively,higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters.The PECD-PU with high CO_(2) carbonate content exhibited good solvent resistance and chemical stability.Of importance,the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO_(2),i.e.,the carbonate unit in PECD.This work provides comprehensive properties of PECD-derived PUs,indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.
基金financially supported by the Marmara University,Commission of Scientific Research Project(M.ü.BAPKO)(No.FENC-DRP-080410-0089)
文摘In this study, a novel three functional chain extender （TATATRIOL） was synthesized from the reaction of 1,3,5- tri（prop-2-en-1-yl）-1,3,5-triazinane-2,4,6-trione （TATA） with 2-sulfanylethanol. Then new thermoplastic polyurethanes （TPUs） were synthesized by a one-step bulk polymerization from the reaction of 1,1＇-methanediylbis（4- isocyanatocyclohexane） （H12MDI）, a poly（ethylene adipate） based polyester polyol and a chain extender. Butane-l,4-diol （BD） and the newly synthesized monomer, TATATRIOL, were used as chain extenders. The effects of TATATRIOL on the properties of the TPU were investigated and compared to those of the TPU prepared with BD. The TPUs which derived from the sulfur containing chain extender displayed lower modulus and high elongation at break values than the analogous TPUs derived from BD. Moreover sulfur containing TPUs exhibited higher thermal stability.
基金supported by the Russian state-funded project for ICBFM SB RAS(grant number 125012300656-5)。
文摘Background:The development of materials for cardiovascular surgery that would improve the effectiveness of surgical interventions remains an important task.Surgical intervention during the implantation of vascular prostheses and stents,and the body’s reaction to artificial materials,could lead to chronic inflammation,a local increase in the concentration of proinflammatory factors,and stimulation of unwanted tissue growth.The introduction of nonsteroidal anti-inflammatory drugs into implantable devices could be used to obtain vascular implants that do not induce inflammation and do not induce neointimal tissue outgrowth.Methods:The scaffolds were made by electrospinning from mixtures of polyurethane(PU)with diclofenac(DF).The kinetics of DF release from the scaffolds composed of 3%PU/10%HSA/3%DMSO/DF and 3%PU/DF were studied.The biocompatibility and anti-inflammatory effects of the obtained scaffolds on human gingival fibroblasts and umbilical vein endothelial cells were studied.Results:Both types of scaffolds are characterized by fast DF release.The viability of cells cultured on scaffolds is 2 times worse than that of cells cultured on plastic.The level of the proinflammatory cytokine IL-6 in the culture medium of cells cultured on DF-containing scaffolds was lower than that of cells cultured on scaffolds without DF.Conclusion:The introduction of DF into scaffolds minimizes the inflammation caused by cell reactions to an artificial material.
基金Funded by the National Natural Science Foundation of China(No.52473077)China Three Gorges Corporation(No.202403190)。
文摘In ultraviolet cured-in-place-pipe(UV-CIPP)pipeline rehabilitation,resin performance critically determines repair effectiveness.Current UV-curable resins exhibit high volatile organic compound(VOC)emissions and inadequate post-cure toughness,which compromise fatigue resistance during service.To address these issues,we synthesized hydroxyl-terminated polyurethane acrylate prepolymers using diphenylmethane diisocyanate(MDI),polypropylene glycol(PPG),and hydroxyethyl methacrylate(HEMA).Fourier transform infrared spectroscopy(FTIR)confirmed successful prepolymer synthesis.We developed UV-curable resins by incorporating various crosslinking monomers and optimized the formulations through mechanical property analysis.Testing revealed that the polyurethane-acrylic UV-cured resin system combines polyurethane's mechanical excellence with acrylics'high UV-curing activity.The PPG200/MDI/HEMA formulation achieved superior performance,with a tensile strength of 55.31 MPa,an impact toughness of 22.7 kJ/m^(2),and a heat deflection temperature(HDT)of 132℃.The optimized system eliminates volatile components while maintaining high reactivity,addressing critical limitations in trenchless pipeline rehabilitation.The improved mechanical properties meet the operational demands of underground pipes,suggesting practical applicability in trenchless pipeline repair.
基金financially supported by the National Natural Science Foundation of China(Nos.51333008,51273214 and 51073176)the project of key technological breakthrough for emerging industries of strategic importance(Nos.2011A091102001,and 2011A091102003)+2 种基金the Science and Technology Program of Guangdong Province(Nos.2010B010800021 and 2010A011300004)the Basic Scientific Research Foundation in Colleges and Universities of Ministry of Education of China(No.12lgjc08)the ST project of Hongyun Honghe Tobacco Group(No.HYHH2013YL06)
文摘Polyurethanes consisting of tri-functional homopolymer of hexamethylene diisocyanate （tri-HDI） and polyethylene glycol （PEG） are synthesized, in which photo-reversible coumarin moieties act as pendant groups. Accordingly, the polyurethanes can be repeatedly self-healed under UV lights at room temperature by taking advantages of the photodimerization and photocleavage habits of coumarin. Molecular weight of the soft segment, PEG, is found to be closely related to the healing performance of the polyurethanes. Lower molecular weight PEG that corresponds to higher initial coumarin concentration in the polymer is critical for obtaining higher healing efficiency in the case of the first healing action. Nevertheless, it does not guarantee high reversibility of the photo-remendability during the repeated healing events. In contrast, the polyurethane with moderate molecular weight PEG has achieved balanced performance. Reaction kinetics is less important for the healing effect.
基金supported by the National Natural Science Foundation of China(Nos.51073104 and 51173118)the Changjiang Scholars and Innovative Research Teams in Universities(No.IRT1163)the Sichuan Provincial Science Fund for Distinguished Young Scholars(No.09ZQ026-024)
文摘To better investigate the degradation and biocompatibility of waterborne biodegradable polyurethanes for tissue engineering, a series of new waterborne biodegradable polyurethanes （PEGPUs） with low degree of crosslinking was synthesized using IPDI, BDO and L-lysine as hard segments, PCL and PEG as soft segment. The bulk structures and properties of the prepared polyurethanes were characterized by Fourier transform infrared spectroscopy （FTIR）, differential scanning calorimetry （DSC）, tensile mechanical tests and water contact angle （WCA） measurements. The degree of microphase separation was slightly improved because of the lowered crosslinking degree of these PEGPUs in comparison with the high cross-linking degree samples, leading to good mechanical properties, as indicated by DSC and stress-strain data. Moreover, biodegradability of the polyurethanes was evaluated in phosphate buffer solutions （PBS） under different pH values and enzymatic solution at pH 7.4 through weight loss monitoring. The results suggested that the degradation of these PEGPUs was closely related to their bulk and surface properties. And the degradation products didn＇t show apparent inhibition effect against fibroblasts in vitro. These studies demonstrated that the waterborne biodegradable polyurethanes could find potential use in soft tissue engineering and tissue regeneration.
基金supported by the National Natural Science Foundation of China(No.20874040)Research Funds from University of Jinan(XKY0721)
文摘Polyurethanes（PU） were prepared using toluene diisocyanate,polypropylene glycol,ethylene glycol, dimethylolpropionic acid and triethylamine,and a siloxane modified PU（PSU） was obtained through reaction of the PU prepolymers with bis（3-（1-methoxy-2-hydroxypropoxy）propyl） terminated polysiloxanes（PMTS） of different molecular weight,specifically designed for this purpose.Results showed that,with increases in molecular weight of PMTS and its content,viscosity of the final PSU latexes decreased;phase separation of the incorporated PMTS in PSU films increased;the average particle sizes of the latexes varied between 110 nm and 330 nm,and the surface tension in the final latexes was relatively constant regardless of PMTS amount and its molecular weight.It was likely that copolymerized polysiloxanes had trend to enrich on top of the film when PMTS molecular weight was around 2000 and its content above 5 wt%.In general, PMTS modified polyurethane films showed higher performance than those from unmodified waterborne polyurethane latexes.
基金supported by the Open Fund of Key Laboratory of Road & Bridge and Underground Engineering of Gansu Province(No.Kfjj-10-05)"Qing Lan" Talent Engineering Funds by Lanzhou Jiaotong University(No.QL-08- 03A)
文摘Waterborne polyurethane composites containing silica nanoparticles are synthesized successfully via the in situ polymerization. The structure, thermal stability, surface hardness, tensile strength, UV-Vis absorbance, dynamic mechanical properties and chemicals resistance of the resulting composites are investigated by FTIR, TEM, TGA, UV-Vis, DMA and chemicals soakage measurements. Results show that polyurethane molecules and silica nanoparticles are linked with covalent bonds. As a result, physical properties of polyurethane composites, such as thermal stability, surface hardness, weather and chemicals resistance are all improved when an appropriate concentration of silica nanoparticles are incorporated.
文摘Soy-protein isolate(SPI)was used to prepare non-isocyanate polyurethane(NIPU)thermosetting adhesives for wood panels by reacting it with dimethyl carbonate(DMC)and hexamethylene diamine.Both linear as well as branched oligomers were obtained and identified,indicating how such oligomer structures could further cross-link to form a hardened network.Unusual structures were observed,namely carbamic acid-derived urethane linkages coupled with lactam structures.The curing of the adhesive was followed by thermomechanical analysis(TMA).It appeared to follow a two stages process:First,at a lower temperature(maximum 130℃),the growth of linear oligomers occurred,finally forming a physically entangled network.This appeared to collapse and disentangle,causing a decrease of MOE,as the temperature increases.This appears to be due to the ever more marked Brownian movements of the linear oligomer chains with the increase of the temperature.Second,chemical cross-linking of the chains appeared to ensue,forming a hardened network.This was shown by the thermomechanical analysis(TMA)showing two distinct MOE maxima peaks,one around 130℃ and the other around 220℃,with a very marked MOE decrease between the two.Plywood panels were prepared and bonded with the SPI-NIPU wood adhesive and the results obtained are presented.The adhesive appeared to pass comfortably the requirements for dry strength of relevant standards,showing to be suitable for interior grade plywood panels.It did not pass the requirements for wet tests.However,addition of 15%of glycerol diglycidyl ether improved the wet tests results but still not enough to satisfy the standards requirements.
基金financially supported by the National Key Research and Development Program of China (No. 2017YFB0309300)the National Natural Science Foundation of China (No. 51773218)+1 种基金Youth Innovation Promotion Association of CAS (No. 2018338)Ningbo Natural Science Foundation (No.2018A610109)
文摘Thermoplastic poly(ether-ester-urethane)s were synthesized from poly(L-lactide) diols (PLLA diols), polytetrahydrofuran diol (PTMG diols), 4,4'-dicyclohexylmethane diisocyanate (HMDI), and 1,4-butanediol (BDO) by a two-step reaction, and the morphology and property of the resultant TPU could be adjusted by varying the PLLA contents. The soft segment was composed of PLLA and PTMG diols. By controlling the percentage of PLLA in the soft segment, the glass transition temperature and mechanical properties of the polyurethanes could be regulated. Based on the FTIR spectrum, we found that two kinds of hydrogen bonding existed individually in soft matrix and hard domain. The hydrogen bonding in soft matrix was unstable, which could be destroyed during elongation. With in situ stretching WAXS and SAXS experiments, we found that the PLLA crystal was destroyed and the PLLA domain oriented along the stretch direction. Finally, we proposed a schematic model to illustrate the microstructures of these elastomers before and after stretch.
基金financially supported by the National Natural Science Foundation of China (No. 51573114)the National Science Fund for Distinguished Young Scholars of China (No. 51425305)the Project of State Key Laboratory of Polymer Materials Engineering (Sichuan University) (No. SKLPME 2016-2-04)
文摘Thermomechanical properties of polyurethanes（PUs） strongly depend on the molecular interactions and microphase structure. In this work, two chain extenders with different ratios, flexile 1,4-butanediol（BDO） and branched trimethylolpropane mono allyl ether（TMPAE）, are used to tune the molecular interactions and microphase structures of a series of biodegradable thermoplastic polyurethanes（TPUs）. In TPUs, the biodegradable polycaprolactone（PCL, M_n of 2000） is used as soft segment while 1,6-diisocyanatohexane（HDI） and chain extenders are used as hard segment. Fourier transform infrared spectroscopy（FTIR）, proton nuclear magnetic resonance spectroscppy（~1 H-NMR）, gel permeation chromatography（GPC）, differential scanning calorimetry（DSC）, dynamic mechanical analysis（DMA） and mechanical tests were performed to characterize the bulk structure and properties of TPUs. Compared with BDO, the steric bulk of TMPAE is larger. The increment of TMPAE can help to increase the hydrogen bond content, microphase separation, and the elastic modulus ratio（R）, which would strongly affect the thermomechanical property of the TPUs. The results of this work verify the importance of the structure of chain extender on the properties of TPUs. It provides valuable information for further understanding the structure-property relationships of these polyurethanes.
基金financially supported by the National Natural Science Foundation of China(No.50673063)Program for the New-Century Excellent Talents of Ministry of Education of China(NCET-08-0381)Sichuan Provincial Science Fund for Distinguished Young Scholars(09ZQ026-024)
文摘A series of fluorinated phosphatidylcholine polyurethane macromolecular additives were synthesized by solution polymerization using methylenebis（phylene isocyanates） （MDI） and 1,4-butanediol （BDO） as hard segments, a new phoshporycholine, 2-（2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-10-（2-hydroxyethoxy）decyloxy） ethyl phosphorycholine （HDFOPC） as end-capper, and four polydiols, poly（tetramethylene glycol）s （PTMG）, polydimethylsiloxane （PDMS）, poly（1,6-hexyl-1,5-pentylcarbonate） （PHPC） and poly（propylene glycol） （PPG） as soft segments, respectively. The chemical structures of the synthesized polyurethanes were characterized by 1H-NMR and FTIR. DSC and DMA were employed to study the phase behavior of these novel polyurethanes due to their great influences on the surface properties, and hence their interactions with bio-systems. The results showed that phase separation of the fluorinated phosphatidylcholine end-capped polyurethanes was increased in comparison with that of normal polyurethanes. The effect of fluorinated phosphatidylcholine end-capped groups on the phase behavior was further demonstrated by analyzing the degree of hydrogen-bonding between hard and soft segments.
文摘The reaction of a desulphurized kraft lignin with hexamethylene diamine and dimethyl carbonate has allowed the development of isocyanate-free polyurethane resins.The present research work is based on previous studies made with hydrolyzable and condensed tannins,but takes advantage of the higher number of hydroxyl groups present in lignin and their different aliphatic and aromatic character.The obtained materials were analyzed by Fourier transform infrared(FTIR)spectroscopy,matrix-assisted laser desorption ionization time-of-flight(MALDI-TOF)mass spectrometry and solid-state cross-polarization/magic angle spinning(CP MAS)13C nuclear magnetic resonance(NMR),which have revealed the presence of urethane functions.The interpretation of the results has shown a larger number of species than when tannins were used and has indicated the presence of two types of bonds in the new molecules formed:ionic and covalent bonds.
基金financially supported by the National Key Technology R&D Program(No.2012BAI17B05)
文摘A series of random copolymers （PCLAs） were synthesized by ring-opening polymerization of D,L-lactide （LA） and ε-caprolactone （CL） with different molar ratios. PCLA based polyurethanes （PCLAUs） were obtained by chain-extending of PCLA and polytetramethylene ether （PTMEG） with hexamethylene diisocyanate （HDI）. All the PCLAUs exhibit good shape memory properties with high shape fixity ratios above 98% and shape recovery ratios above 82% in the first cycle and 91% in the second cycle. PCLAUs with less CL content show faster recovery speed and PCLAUs with more CL content show higher shape recovery ratio. The trigger temperature can be tuned or controlled around body temperature by adjusting the molar ratio of LA to CL. The PCLAUs have potential applications in implant biomedical devices, especially for minimally invasive deployable devices.
基金the Consejo Nacional de Investigaciones Científicas y Técnicas(CONICET,Argentina)(PIP 20170100677)the Fondo para la Investigación Científica y Tecnológica(FONCYT)(PICT-2017-1318)the Universidad Nacional de Mar del Plata(UNMdP,15/G557,ING561/19)and to the Comisión de Investigaciones Científicas de la Provincia de Buenos Aires(CIC)and the Universidad Tecnológica Nacional(UTN)for their financial support.
文摘The increasing pressure from consumers and policy makers to reduce the use of synthetic polymers,whose production contributes to the depletion of non-renewable resources and are usually non-biodegradable,has prompted the efforts to find suitable bio-based sources for the production of polymers.Vegetable oils have been a frequently spotted in this search because they are versatile,highly available and a low cost liquid biosource,which can be used in the synthesis of a wide plethora of different polymers and reactive monomers.Following the same idea of reducing the environmental stress,the traditional polyurethanes that are soluble in organic solvents have been targeted for replacement,particularly in applications such as adhesives and coatings,in which the solvent is released to the atmosphere increasing the air pollution.Instead,waterborne polyurethanes(WBPU),which are polyurethane dispersions(PUD)prepared in aqueous media,release benign water to the atmosphere during use as supported or self-standing films for different applications.In this brief review,the contributions to the development of WBPUs based on vegetable oils are discussed,focusing mainly on the contributions of the last decade.The synthesis of ionic and nonionic PUDs,their characterization and the properties of the resulting dried materials,as well as derived composite materials are considered.
文摘Non-isocyanate polyurethane(NIPU)foams from a commercial hydrolysable tannin extract,chestnut wood tannin extract,have been prepared to determine what chemical species and products are taking part in the reactions involved.This method is based on two main steps:the reaction with dimethyl carbonate and the formation of urethane bonds by further reaction of the carbonated tannin with a diamine-like hexamethylene diamine.The hydroxyl groups on the tannin polyphenols and on the carbohydrates intimately linked with it and part of a hydrolysable tannin are the groups involved in these reactions.The carbohydrate skeleton of the hydrolysable tannin is also able to participate through its hydroxyl groups to the same two reactions rendering the whole molecular complex able to react to form NIPUs.The analysis by Matrix-Assisted Laser Desorption Ionization(MALDI-TOF)mass spectrometry and 13C Nuclear Magnetic Resonance(13C NMR)to further investigate the reaction mechanisms involved revealed the unsuspected complexity of chestnut hydrolysable tannin,with different fragments reacting in different manners forming a hardened network of considerable complexity.As the morphology and performance of these types of foams changes slightly with the change in the amount of glutaraldehyde and hexamine hardeners,the best performing foam formulation previously determined was scanned by SEM and analysed chemically for the structures formed.
基金financially supported by the National Natural Science Foundation of China(Nos.21905200,21975178 and 21734006)China Postdoctoral Science Foundation(No.2019M661006)。
文摘1,2-Dioxetane is a well-known chemiluminescent mechanophore allowing real-time monitoring of polymer chain scission,but usually suffers from fluorescence quenching in polar environments.Herein,a series of mechanochemiluminescent waterborne polyurethanes/carbon dots composites(WPU-CDs)have been synthesized by incorporating fluorescent CDs to promote the energy transfer process in different environments.The resulting bulk WPUs,and in particular,their swollen films filled with a large amount of polar solvents(water and ionic liquid)emit intense mechanochemiluminescence.Thus force-induced covalent bond scission and stress distribution within these different WPU-CDs films can be sensitively visualized.Furthermore,the ionic liquid containing films exhibited both electrical and luminescent signal changes under stretching,which offer a new kind of force sensor responsive at a broad detecting strain range and for multi-mode strain analysis.This study is expected to stimulate new research endeavors in mechanistic insight on waterborne polyurethanes and the corresponding stretchable sensing devices.
基金Financial support from the 863 program (No. 2011AA02A204)
文摘A series of fluorescent siloxane-polyurethanes（HPMS-PUs） containing an amino-functionalized,1 8-naphthalimide,fluorescent monomer（AABD） as a chain extender were synthesized.The properties of the HPMS-PUs were investigated by UV–vis and fluorescence spectroscopies,thermogravimetric analysis and thermal migration behavior.The maximum absorption and emission wavelengths of HPMS-PUs showed a red shift of about 4 nm and a blue shift of about 9 nm,respectively,compared to those of AABD.The Stokes shifts of AABD and HPMS-PU2 were 3514 and 2931 cm 1,respectively.The quantum yield of HPMS-PU2 was 0.79,which was six times higher than that of AABD.Concentration self-quenching was observed in both AABD and HPMS-PUs.The fluorescence of HPMS-PUs was quite stable with respect to both temperature and fluorescence quencher effects.The thermal stability of HPMS-PUs increased with AABD content.The fluorophore units in the HPMS-PUs did not readily migrate.
文摘Polyols are groups of organic compounds which contain carbon and are randomly linked to other atoms,especially carbon-carbon and carbon-hydrogen.These compounds are mainly used as reactants to make other polymers.Among biopolymers,lignin is regarded as the base of a new polymer in polyol construction.The present study aimed to investigate the effects of amine type(diethylenetriamine and ethylenediamine)on the modification of lignin-based polyols,so as to provide an alternative to petroleum polyols and,in turn,increase functional groups and reduce their harm to humans’health and the environment.To this aim,first,lignin was extracted from raw liquor.Next,the extracted lignin was reacted with diethylenetriamine(DETA)and ethylenediamine(EDA).Finally,the Mannich method was used for the reaction between amine lignin and propylene carbonate.The results of the Fourier Transform Infrared(FTIR)spectroscopy analysis showed that modification with DETA led to more structural change in lignin and peak 1100 indicates the presence of C–O bond related to urethane bonds in modified lignin.Moreover,adding propylene carbonate to aminated lignin did not result in much change in the results of the FTIR analysis.Additionally,urethane bonds can be seen in the results of GPC at 400℃–500℃.Furthermore,a slight decrease in thermal stability was observed in lignin modified with amine and propylene carbonate,compared to the raw lignin sample.
