Hydrolysable Chestnut Tannin Extract Chemical Complexity in Its Reactions for Non-Isocyanate Polyurethanes(NIPU)Foams

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.

Effect of Amine Type on Lignin Modification to Evaluate Its Reactivity in Polyol Construction for Non-Isocyanate Polyurethanes(NIPU)

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.

Soy Protein Isolate Non-Isocyanates Polyurethanes(NIPU)Wood Adhesives

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.

Polyurethanes from Kraft Lignin without Using Isocyanates

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.

Plant Oil-Based Waterborne Polyurethanes: A Brief Review

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.

Synthesis and Properties of Non-isocyanate Crystallizable Aliphatic Thermoplastic Polyurethanes

A simple non-isocyanate route synthesizing thermoplastic polyurethanes（TPUs） with good thermal and mechanical properties is described. Melt transurethane polycondensation of dimethyl 1,6-hexamethylene dicarbamate with 1,4-butanediol and 1,6-hexanediol was conducted at different molar ratios under the catalysis of tetrabutyl titanate. A series of crystallizable non-isocyanate TPUs with high molecular weight were prepared. The TPUs were characterized by gel permeation chromatography, FT-IR, 1 H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide angle X-ray diffraction, AFM, and tensile tests. The TPUs exhibited Mn ranging from 12 500 to 26 400 g/mol, Mw from 16 700 to 56 400 g/mol, Tm up to 151.4 °C, and initial decomposition temperature over 241.8 °C. Their tensile strength reached 42.99 MPa with a strain at break of 30.00%. TPUs constructed simply with butylene, hexylene, and urethane linkages were successfully synthesized through a non-isocyanate route.

Biodegradable and bioactive porous polyurethanes scaffolds for bone tissue engineering

Biodegradable porous polyurethanes scaffold have themselves opportunities in service, in-cluding controlled degradation rate, no-toxic degradation products. However, polyurethanes are lack of bioactive groups, which limits their application. This review gives the common modification methods, surface functionalization and blending modification. In finally, the review puts forward to the bulk modification as a new method to enhance the bioactivity of polyure-thanes.

STRUCTURAL EVOLUTION IN BIORENEWABLE SOY BASED POLYURETHANES

Spectroscopic studies have revealed that the amount of polyureas formed and the kinetics of their formation in soy based polyurethane systems are considerably different from traditional systems employing ethylene oxide-propylene oxide (EO-PO) based polyols.The aggregation of polyureas was characterized by the hydrogen bonds formed utilizing FTIR spectroscopy.This study offered the opportunity to assign the previously undefined infrared features.The structural transformation is reflected in the segmental rel...

GAS PERMEATION OF SEGMENTED POLYURETHANES AND THEIR BLENDS WITH PVC

Film specimens of four segmented polyurethanes with different soft segments, namely polycaprolactone, polytetramethylene adipate, polytetramethylene oxide and polypropylene oxide, and their blends with PVC of different compositions were obtained by solution cast. The permeability of these films to O_2, N_2 and H_2 and their density were measured by using gas chromatography and technique of density gradient column. The polyether polyurethanes were found to have higher permeability than the polyester ones due to their low glass transition temperature and /or the low density value. The blends of PVC and polyether polyurethanes, especially the PPO-based polyurethane, are incompatible, and their permeability coefficient-composition dependence has the typical S-shaped curves. PVC is well compatible with the soft segments in its blends with polyester polyurethanes. For these blends the composition dependence of permeability is characterized by a negative deviation from the semilogarithmic additivity rule, and it is possible to prepare blends having T_g 20℃ lower than that of PVC, but retaining its low permeability almost unchanged, results were discussed in according with the different approaches for the permeation behavior of compatible and incompatible blends.

STUDIES ON THE SPHERULITE FORMATION IN MELT CAST POLYCAPROLACTONE BASED POLYURETHANES

A series of PCL/MDI/BDO segmented polyurethanes have been synthesized by two-step method in solution.The hard segment content ranges from 10% to 48% by weight, and the molecular weight of PCL diols is 1500. Hard segment spherulites have been observed in compression molded specimens of all of the samples except the one of the lowest hard segment content. The difficulty in sphernlite formation was explained as only in a small temperature range,the microphase separation rate may be faster than the crystallization rate and all these processes are very slow due to the hydrogen bonding between hard and soft segments and the interactions between hard segments themselves. PCL soft segments of molecular weight 1500 is still crystallizable and may form different crystalline superstructures.

Design and Multicriteria Optimization of a Two-Stage Reactive Extrusion Process for the Synthesis of Thermoplastic Polyurethanes

This paper presents the implementation of two multicriteria optimization methods based on different approaches, namely, Rough Set Method (RSM) and Net Flow Method (NFM), to the manufacture by reactive extrusion of linear thermoplastic polyurethanes (TPUs), appropriate for medical applications. A preliminary study allowed determining the process operating conditions for which the polymerization time and the average residence time of the reactants in the extruder are of the same order of magnitude. Prior to the optimization, a neural network model able to predict with acceptable accuracy the effect of the operating conditions on the output process variables, was constructed and validated. This model was then used to determine, using Pareto’s concept, a set of non-dominated solutions constituting Pareto’s domain. These solutions were then ranked according to the preferences of a decision maker using NFM and RSM. This allowed providing the 10% highest ranked solutions of Pareto’s domain and proposing a set of optimal operating conditions for the production, with the lowest energy consumption, of TPUs with targeted properties and high purity. Experimental validation runs carried out under similar operating conditions gave rise to criteria values confirming the su- perior performance of NFM, without rejecting, at the same time, the values obtained using RSM.

Silane Terminated Prepolymers: An Alternative to Silicones and Polyurethanes

Silane terminated prepolymers for adhesives, sealants and coatings are of 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.

Impact of Natural Oil-Based Recycled Polyols on Properties of Cast Polyurethanes

In this study, castor oil, rapeseed oil and medium chain triglycerides of coconut oil, were transesterified bymeans of 2-ethyl-2-hydroxymethyl-1,3-propanediol (trimethylolpropane) and consequently used to convertpolycarbonate waste from end-of-life vehicles into liquid polyols. The prepared recycled polyols, composeduniquely of renewable and recycled components, had a hydroxyl number of ca. 250 mg KOH·g−1. They weresuccessfully applied as 100% replacement of a virgin polyol for preparation of solid crosslinked polyurethanes(PU) by solvent-free casting. The produced rigid cast PU exhibited the main transition temperature rangingfrom 44°C to 53°C, the hardness value from 46 to 61 Shore D and the beneficial low water absorption (0.4-0.5wt.%). The PU network structure was highly influenced by the presence of aromatic structures ofpolycarbonate-units and fatty acid compositions. A suitable selection of natural oil thus enabled to adjustthermo-mechanical properties and promote excellent optical transparency of the produced PU.

Synthesis and Wetting Behavior of Polyurethanes Containing Polyoxetane Soft Blocks with Semifluorinated and Bromomethyl Side Chains

Polyoxetanes bearing short fluorinated and/or bromomethyl pendant groups were prepared from 3,3-bis(2,2,2-trifluoroethoxymethyl)oxetane and/or 3,3-bisbromomethyloxetane by ring-opening polymerization.A series of novel polyurethanes(PUs)containing polyoxetanes as soft blocks was synthesized by the reaction of polyoxetanes,isophorone diisocyanate(IPDI),and 1,4-butanediol(BD).The thermal properties and wetting behavior of these novel polymers were evaluated using TGA,DSC and contact angle analysis.The cotton fabrics treated with PU3 showed good hydrophobic property,and its contact angle for water was 133°.

Preparation and Application of Anionic and Cationic Waterborne Polyurethanes and Graphene-Cellulose Nanocrystal as an Antistatic Agent for Cashmere

The main purpose of this research work is to improve anti-static properties of Cashmere fabric by introducing application comprising anti-static agent by foaming which was made with cationic waterborne polyurethane and graphene-CNC. Cashmere fabric was cut into 10 pieces of sample cloth of 5 cm * 5 cm size, washed with acetone solution, and then dried in an oven at 60℃. Three forms of waterborne polyurethanes such as two forms of Cationic waterborne polyurethane (CWPU) and a form of Anionic waterborne polyurethane (AWPU) were synthesized. Cellulose nanocrystalline (CNC)/graphite powder solution with the ratio of 0.5/1, 1/1, 2/1 was prepared by ultrasonic probe stripping method, and the concentration of graphite powder was ensured to be 1 mg/ml. The fabric was treated with anionic and cationic WPUs foaming solution until the weight gain reached 2.5 - 3.5 wt%. After drying, the elastic cloth was foamed with graphene solution until the graphite content of the cloth was close to 10%, 20%, 40%, 60% respectively, and then dried for reserving. Characterization properties of pure graphite powder, pure CNC and graphene solution with different proportions of three components were tested by Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), Thermalgravitimetric analysis (TGA) and scanning electron microscopy (SEM). Take the original cloth, only WPU treated cloth and four clothes with different graphite content for the fabric performance test.

A THEORETICAL APPROACH TO HYDROGEN BOND STRENGTH DISTRIBUTION IN POLYURETHANES

A new approach to the hydrogen bond strength distriubtion has been developed based on thehydrogen bond strength distribution model proposed by Coleman et al. By using the method ofequilibrium thermodynamics, a thermodynamic equation for describing the hydrogen bondstrength distribution has been derived for the first time. By means of the equation some IR thermalanalysis results can be explained theoretically. Furthermore, the formulas for calculating theenthalpy and entropy change of the hydrogen bond dissociation have been established.

MODULUS-COMPOSITION DEPENDENCE FOR BLENDS OF PVC WITH SEGMENTED POLYURETHANES OF DIFFERENT SOFT SEGMENTS

The dynamic mechanical modulus at 25℃ for blends of segmented polyurethanes with PVC was studied by using suitable mechanics models of multi-component systems. The analysis indicates that the blend morphology was mainly determined by soft segment structure of polyurethanes. The PPO-PU/PVC blends show typical two-phase morphology and their modulus-composition relations may be described by Halpin-Tsai model for domain-matrix two-phase systems.While the PCL-PU / PVC, PTMA-PU/PVC and PTMO-PU/PVC blends fit the Kerner's packed grain composite model. These results may imply that the modulus-composition relationship is sensitive to the interactions between the components and the mixture morphology of the blends.

TRANSMISSION ELECTRON MICROSCOPY OF SEGMENTED POLYURETHANES WITH RUTHENIUM TETROXIDE AS A STAINING AGENT

Microphase separation and lamellar structure of segmented polyether- and polyester-polyurethanes have been investigated by means of transmission electron microscopy with the ruthenium tetroxide staining technique. The results show that the RuO_4 staining technique is simpler and may give better image contrast than other staining methods for this polymer. Microphase separation and lamellar structure of segmented polyether-and polyester-polyurethanes were directly observed and discussed.

Visible Light-driven Self-healable Mechanochromic Polyurethanes

Polyurethanes incorporating spiropyran(SP)and diselenide(DiSe)in the main chain,which are confined in different hard segments are developed.Visible light-driven diselenide metathesis and mechanically induced ring opening of SP offer self-healing and mechanochromic properties of the polymers,respectively.Delicate selection of the polymer backbone is found essential to promote the dual functions.In particular for polyurethane with SP coupled into 4,4'-methylenebis(cyclohexyl isocyanate)and DiSe linked with isophorone diisocyanate,excellent mechanical,mechanochromic and self-healing properties are estimated.Moreover,combining self-healing and self-reporting moieties in one chain allows the discrimination of different healing mechanisms,including bond formation and chain entanglement,in a visualized way.

Bio-Based Rigid Polyurethane Foams for Cryogenic Insulation

Cryogenic insulation material rigid polyurethane(PU)foams were developed using bio-based and recycled feedstock.Polyols obtained from tall oil fatty acids produced as a side stream of wood biomass pulping and recycled polyethylene terephthalate were used to develop rigid PU foam formulations.The 4th generation physical blowing agents with low global warming potential and low ozone depletion potential were used to develop rigid PU foam cryogenic insulation with excellent mechanical and thermal properties.Obtained rigid PU foams had a thermal conductivity coefficient as low as 0.0171 W/m·K and an apparent density of 37-40 kg/m^(3).The developed rigid PU foams had anisotropic compression strength properties,which were higher parallel to the foaming direction.Moreover,the compression strength was also influenced by the type of applied bio-based polyol.The bio-based polyols with higher OH group functionality delivered higher crosslinking density of polymer matrix;thus,the mechanical properties were also higher.The mechanical strength of the foams increased when materials were tested at liquid nitrogen temperature due to the stiffening of the polymer matrix.The thermal properties of the developed materials were determined using differential scanning calorimetry,dynamic mechanical analysis,and thermogravimetric analysis methods.Lastly,the developed rigid PU foams had good adhesion to the aluminium substrate before and after applying cyroshock and an excellent safety coefficient of 4-5.Rigid PU foams developed using Solstice LBA delivered adhesion strength of~0.5 MPa and may be considered for application as cryogenic insulation in the aerospace industry.