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
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
A non-isocyanate-based polyurethane(NIPU)wood adhesive was produced from organosolv lignin,which is a bio-sourced raw material,available in large quantities and produced as a by-product of the paper industry.The formu...A non-isocyanate-based polyurethane(NIPU)wood adhesive was produced from organosolv lignin,which is a bio-sourced raw material,available in large quantities and produced as a by-product of the paper industry.The formulation of this new lignin-based NIPU adhesive,which is presented,was chemically characterised by Matrix-Assisted Laser Desorption Ionization Time of Flight(MALDI ToF)mass spectrometry and by Fourier Transform Infra-Red(FTIR)spectrometry analyses.The oligomers formed were determined and showed that the three species involved in the NIPU adhesive preparation were formed by the co-reaction of the three reagents used:lignin,dimethyl carbonate,and hexamethylene diamine.Linear and branched structures were both identi-fied.Mechanical properties of the adhesive were determined using the Automated Bonding Evaluation System(ABES)and internal bond(IB)strength test of the laboratory particleboard bonded with it.The adhesive has shown satisfactory mechanical properties after hot pressing at 230℃.Such a temperature is used industrially in the most modern particleboard factories,but since it is hardly feasible for more conventional wood bonding equipment,the reactivity of the NIPU adhesive was successfully increased with the addition of a small percentage of a silane coupling agent.With the addition of the silane,the proposed NIPU adhesive could also be used at a hot-pressing temperature lower than 200℃.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
ABSTRACT Non-isocyanate polyurethane(NIPU)foams using a hydrolysable tannin,also vulgarly called tannic acid,namely here commercial chestnut wood tannin extract was prepared.Compression strength did not appear to depe...ABSTRACT Non-isocyanate polyurethane(NIPU)foams using a hydrolysable tannin,also vulgarly called tannic acid,namely here commercial chestnut wood tannin extract was prepared.Compression strength did not appear to depend on the foam apparent density while the formulation composition of the NIPU foams has been shown to be more determinant.These NIPU foams appeared to be self-extinguishing once the high temperature flame is removed.The ignition time gave encouraging results but for improved fire resistance the foams may need some fire-retardant addition.FTIR spectrometry showed the formation of non-isocyanate urethane linkages.Thermogravimetric analysis indicated a good thermal resistance of these foams,with thermal degradation following four phases.First in the interval 25℃–120℃ range,mainly evaporation of water occurs with a maximal loss of 10%weight.In the 150℃–450℃ temperature range foams mass loss is of almost 70%.In particular in the 125℃–275℃ range occurs the degradation of some small molecular weight substances.In the 500℃–790℃ temperature range the foams do not present any further large degradation.展开更多
This review details the development of tannin-based biofoams for fire resistance and acoustic insulation and details the different varieties of these foams that have been developed,from tannin-furanic self-blowing foa...This review details the development of tannin-based biofoams for fire resistance and acoustic insulation and details the different varieties of these foams that have been developed,from tannin-furanic self-blowing foams to tannin-furanic polyurethanes and finally non-isocyanate tannin-basedcarbohydrates polyurethanes(NIPU).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
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.
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This research was financed by the ERA-CoBioTech project WooBAdh(Environmentally-friendly bioadhesives from renewable resources).The University of Ljubljana,Biotechnical Faculty was financed by the Slovenian Ministry of Education,Science and Sport and the Slovenian Research Agency within the framework of program P4-0015.The LERMAB was financed by the French Agence Nationale de la Recherche(ANR)as part of the laboratory of excellence(LABEX)ARBRE.
文摘A non-isocyanate-based polyurethane(NIPU)wood adhesive was produced from organosolv lignin,which is a bio-sourced raw material,available in large quantities and produced as a by-product of the paper industry.The formulation of this new lignin-based NIPU adhesive,which is presented,was chemically characterised by Matrix-Assisted Laser Desorption Ionization Time of Flight(MALDI ToF)mass spectrometry and by Fourier Transform Infra-Red(FTIR)spectrometry analyses.The oligomers formed were determined and showed that the three species involved in the NIPU adhesive preparation were formed by the co-reaction of the three reagents used:lignin,dimethyl carbonate,and hexamethylene diamine.Linear and branched structures were both identi-fied.Mechanical properties of the adhesive were determined using the Automated Bonding Evaluation System(ABES)and internal bond(IB)strength test of the laboratory particleboard bonded with it.The adhesive has shown satisfactory mechanical properties after hot pressing at 230℃.Such a temperature is used industrially in the most modern particleboard factories,but since it is hardly feasible for more conventional wood bonding equipment,the reactivity of the NIPU adhesive was successfully increased with the addition of a small percentage of a silane coupling agent.With the addition of the silane,the proposed NIPU adhesive could also be used at a hot-pressing temperature lower than 200℃.
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Supported bythe Research Award Programfor Outstanding Young Scientistsin Guizhou Province(2005-0514)Science Fundationfor Distinguished Overseas Chinese Scholars of MOP,(2003-50)Guizhou Governor's Foundationfor Outstanding Scientistsin Science,Technology and Education(2003-04)
文摘ABSTRACT Non-isocyanate polyurethane(NIPU)foams using a hydrolysable tannin,also vulgarly called tannic acid,namely here commercial chestnut wood tannin extract was prepared.Compression strength did not appear to depend on the foam apparent density while the formulation composition of the NIPU foams has been shown to be more determinant.These NIPU foams appeared to be self-extinguishing once the high temperature flame is removed.The ignition time gave encouraging results but for improved fire resistance the foams may need some fire-retardant addition.FTIR spectrometry showed the formation of non-isocyanate urethane linkages.Thermogravimetric analysis indicated a good thermal resistance of these foams,with thermal degradation following four phases.First in the interval 25℃–120℃ range,mainly evaporation of water occurs with a maximal loss of 10%weight.In the 150℃–450℃ temperature range foams mass loss is of almost 70%.In particular in the 125℃–275℃ range occurs the degradation of some small molecular weight substances.In the 500℃–790℃ temperature range the foams do not present any further large degradation.
文摘This review details the development of tannin-based biofoams for fire resistance and acoustic insulation and details the different varieties of these foams that have been developed,from tannin-furanic self-blowing foams to tannin-furanic polyurethanes and finally non-isocyanate tannin-basedcarbohydrates polyurethanes(NIPU).
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.
