Properties of Polyurethane Elastomers with Different Hard/Soft Segment Ratio

Three polyurethane elastomers (PU) containing different hard/soft (h/s) segment ratios were prepared. The PUs were characterized using Gel Permeation Chromatography (GPC), DSC, Wide Angle X-ray Diffraction (WAXD). Dynamic Mechanical Thermal Analysis (DMTA), and Stress-controlled rheometry. The surface properties were evaluated from contact angle measurements. The PUs were used as raw materials for solvent-based adhesives, whose adhesion properties were measured from T-peel tests of solvent-wiped polyvinyl chloride (PVC)/polyurethane adhesive joints. The increase in the amount of h/s segment ratio affected the structure and morphology of the PUs, reducing the degree of phase separation and the extent of the secondary interactions between polymer chains. The h/s segment ratio determined the thermal, mechanical, rheological and adhesion properties of the PUs.     

Influence of the length of the chain extender on the properties of thermoplastic polyurethanes

Three polyurethane elastomers (PUs) were prepared using MDI (diphenylmethane-4,4'-diisocyanate), polyadipate of 1,4-butanediol, and three linear chain extenders with different lengths (ethylene glycol, 1,4-butanediol, and 1,6-hexanediol). The prepolymer procedure was used to prepare the PUs. The PUs were characterized using gel permeation chromatography, differential scanning calorimetry, wide angle X-ray diffraction, dynamic mechanical thermal analysis, and stress-controlled rheometry. The surface properties were evaluated from contact angle measurements. The PUs were used as raw materials for solvent-based adhesives, the adhesion properties of which were assessed from T-peel tests of solvent-wiped poly(vinyl chloride) (PVC)/polyurethane adhesive joints. The use of a short-chain extender produced phase separation, high crystallinity, and adequate rheological properties in the PUs. The length of the chain extender used in this study did not affect the surface properties of the PUs nor the T-peel strength of PVC/polyurethane adhesive joints but a change in the locus of failure was obtained: the decrease in the length of the chain extender, i.e. the improved crystallinity and the high degree of phase separation in the PUs, favoured the interfacial failure.     

高固含量水性聚氨酯分散体的合成

引　言水性聚氨酯是水溶型、水分散型和水乳化型聚氨酯的统称 .水性聚氨酯与溶剂型相比较 ,具有生产、运输和使用安全 ,不污染环境的优点 ,在涂料、黏合剂和皮革涂饰剂等方面的应用备受重视[1] ,成为近 10年来全世界的研究热点 .水性聚氨酯的弱点是其制成的涂料和涂饰剂的机械性能、耐水性不如溶剂型聚氨酯 .克服这些弱点 ,是近年来各国研究者努力的方向[2 ] .在改善水性聚氨酯性能方面有大量研究报道 ,诸如降低亲水基团含量 ,增大乳液粒径 ,采用强力机械分散增加乳液贮存稳定性 ,改善乳液对涂膜基材表面的润湿性、黏附力等等[3] .但很少见…     

Structure–protein adsorption relationships of polyurethanes

A series of hydroxyl‐terminated polybutadiene (HTPB) and 4,4′‐dicyclohexylmethane diisocyanate (H₁₂MDI)‐based polyurethanes (PUs) with different molecular weight, hard‐segment content, or 4‐vinyl pyridine content (4‐VP content) were synthesized by solution polymerization. Protein adsorption ratio of fibrinogen to albumin (F/A molar ratio), which was adopted as the indicator of blood compatibility, was measured. The F/A molar ratio on the film's surface was affected by surface composition. The surface composition was quantified by carbonyl group to butadiene group (C=O/C=C) adsorption ratio on FTIR‐ATR spectra and oxygen to carbon atom (O/C) ratio, which was determined by ESCA. PUs with more hard‐segment content on the surface (i.e., high C=O/C=C ratio) possess more fibrinogen adsorption and less albumin deposition (i.e., high F/A molar ratio). The C=O/C=C ratio, hydrogen‐bonding index (HBI value), frequency shift and difference (Δν), glass transition temperature of soft segment (T_gs) as a measure of homogeneity, average strength of interpolymer hydrogen bonds, and interpenetrating networks (IPNs) were utilized to study the surface composition, intermolecular attraction, and IPN formation of the prepared PUs. The effect of hard‐segment content, molecular weight or 4‐VP content on the F/A molar ratio were investigated. The results of FTIR and ESCA explain well the surface composition, and hence, the F/A molar ratio as well. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 297–305, 1999     

Block architecture influence on the structure and mechanical performance of drawn polyurethane elastomers

Some natural biopolymers such as spider silk exhibit superb mechanical properties, characterised by their great toughness. Synthetic polyurethane (PU) copolymers also endow great toughness but lack silk's stiffness and strength. The aim of this work was to elucidate the role of segment block architectural features that influence PU stiffness and strength after cold drawing. For this purpose PUs with varied soft segment character, crystalline versus rubbery, as well as with different hard segment chemistries, 4,4′‐diphenylmethane diisocyanate/1,4‐butanediol versus 1,6‐hexamethylene diisocyanate/1,4‐butanediol, were synthesised by a two‐step polymerisation method. We found that the architecture of both block segments has a dramatic influence on drawn PU mechanical performance, in which PUs with crystallisable soft segments and crystalline hard segments are shown to have a greater impact on developing stiffer and stronger materials. © 2013 Society of Chemical Industry     

Waterborne polyurethane dispersions obtained with polycarbonate of hexanediol intended for use as coatings

Three waterborne polyurethane dispersions derived from polycarbonate of hexanediol (PCD) with molecular weight of 1000 Da were synthesized by the acetone method and used as coatings for stainless steel plates. Different hard segments content in the polyurethanes were obtained by varying the isocyanate/macroglycol (NCO/OH) molar ratio. A decrease in the NCO/OH ratio produced an increase in the mean particle size as well as a decrease in the Brookfield viscosity of the dispersions. Furthermore, the greater the NCO/OH ratio the higher the urea and urethane hard segment content, the higher the glass transition temperature value and the higher the elastic modulus of the polyurethane was. On the other hand, the NCO/OH ratio affected the adhesion of the polyurethanes. The adhesion was evaluated by using three different procedures: T-peel strength tests of flexible PVC/waterborne polyurethane dispersion/flexible PVC joints; single lap-shear tests of aluminium/waterborne polyurethane dispersion/aluminium joints and cross-cutter adhesion test of polyurethane coatings on stainless steel pieces. Finally, several properties of the polyurethane coatings on stainless steel pieces were tested including Persoz hardness, gloss, chemical resistance and yellowness index.     

Morphology of polyurethanes at various length scale: The influence of chain structure

Micro‐structural investigation of polyurethanes (PUs) with different chain structure has been reported. Polarized optical microscopic studies of aliphatic polyurethanes demonstrate the development of micro clusters with increasing hard segment content (HSC) and crystallization. DSC and XRD results support the crystalline and amorphous nature of aliphatic and aromatic PUs, respectively. Self‐assembled biphasic morphology is discernible in aliphatic polyurethane while nanometer size domains are observed in aromatic PUs. The dimension of micro‐domain has been measured by using AFM and established its size as independent of hard segment content. The self‐assembly is greater for higher HSC aliphatic PUs leading to the formation of bigger domain while the meager hydrogen bond formation restricts the domain size of aromatic polyurethanes. Segmented morphology of surface as well as in bulk of aliphatic polyurethanes is evident from SEM and TEM images and grows with increasing HSC. In contrast, homogeneous and amorphous nature has been observed for aromatic PUs. In situ segregation of phases in aliphatic PUs have been captured through light transmittance and optical images which is categorically absent in aromatic polyurethane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterisation of polyurethanes derived from waste black liquor lignin

Waste black liquor lignin, obtained from bagasse from the small-scale paper industry, can be utilized for the synthesis of polyurethanes (PUs). Several polyurethane samples were prepared from laboratory black liquor (LBL) by reacting varying amounts of lignin ranging from 5 to 70% (w/v) in poly(ethylene glycol) (PEG) (having molecular weights of 200, 600, 1000, 1500 and 4000) with tolylene 2,4-diisocyanate (TDI). The effects of lignin concentration and molecular weight of PEG on mechanical and thermal properties of PUs obtained were investigated. The polyurethanes synthesised were characterized for different properties such as shear strength, adhesion and thermal stability. The shear strength of PU joints with aluminum was found to decrease with increase in both lignin concentration and molecular weight of PEG. Maximum shear strength, i.e. 3.6 N/mm², was shown by 50% (w/v) lignin in PEG of molecular weight 200.     

Synthesis and characterization of chlorine‐containing flame‐retardant polyurethane nanocomposites via in situ polymerization

We have developed flame‐retardant polyurethanes (FRPUs) and polyurethane (PU) nanocomposites via in situ polymerization. Three series of thermoplastic elastomeric PUs were synthesized to investigate the effect of incorporating 3‐chloro‐1,2‐propanediol (CPD) and nanoclay on mechanical, thermal properties, and also resistance to burning. PU soft segments were based on poly(propylene glycol). Hard segments were based on either CPD or 1,4‐buthane diol (BDO) in combination with methyl phenyl di‐isocyanate named PU or FRPU, respectively. In the third series, CPD was used as chain extender also nanoclay (1% wt) and incorporated and named as flame‐retardant polyurethane nanocomposites (FRPUN). Mechanical properties and LOI of PUs and nanocomposites have been evaluated. Results showed that increasing the hard segment (chlorine content) leads to the increase in flame retardancy and burning time. Addition of nanoclay to CPD‐containing PUs leads to obtain self‐extinguish PUs using lower CPD contents, higher Young's modulus, and strength without any noticeable decrease in elongation at break. Investigation of the TGA results showed that copresence of nanoclay and chlorine structure in the PU backbone can change thermal degradation pattern and improve nanocomposite thermal stability. X‐ray diffraction and transmission electron microscopy studies confirmed that exfoliation and intercalation have been well done. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Role of isophorone diisocyanate in the optimization of adhesion tendency of polyurethane pressure sensitive adhesives

The present work describes the role of accurate selection of diisocyanate on the adhesion strength of polyurethanes (PUs). The concentration of diisocyanate induces the hard segment (HS) in the main architecture of PUs which decides the viscoelastic properties of the polymers. A balanced ratio of viscoelastic properties ultimately determines the adhesion strength. The composition of the polymers consists of a blend of macrodiol of hydroxyl-terminated polybutadiene and polypropylene glycol with different molecular weights. Isophorone diisocyanate (IPDI) is used to develop the urethane linkages by maintaining its contribution from 28 to 67% as HS contents. It determines the adhesion strength of the final product. The adhesion strength is evaluated by texture analyzer and 180° peel test. The probe tack analysis shows maximum adhesion energy of 156.2 J cm⁻² and 180° peel test shows 18.80 N/25 mm peel force. The glass-transition (T _g) values obtained through differential scanning calorimetry are in good agreement with theoretically calculated Flory–Fox temperature. The proportion of the loss tangent to the storage modulus (tan δ/E′) shows the optimum value of 2.80 MPa⁻¹. The ideal concentration of IPDI results to achieve better adhesion properties of PU pressure sensitive adhesives. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47124.     

Diffusion and sorption of benzene vapor through polybutadiene‐, polybutadiene/styrene‐, and polybutadiene/acrylonitrile‐based polyurethanes

A series of polyurethane (PU) films made from toluene diisocyanate (TDI), 1,4‐butanediol (BDO), and hydroxyl‐terminated polybutadiene (HTPB), hydroxyl terminated polybutadiene/styrene (HTBS), or hydroxyl terminated polybutadiene/acrylonitrile (HTBN) was synthesized by solution polymerization. The absorption of benzene vapor was found mainly in the soft phase. The equilibrium adsorption (M_∞) was reduced with increasing hard segment content for all the PUs. The values of M_∞ were in the sequence of HTBN‐PUs > HTBS‐PUs > HTPB‐PUs, which could be explained by the different interaction parameters between soft segments and benzene. The HTBN‐PU film showed the lowest degree of phase segregation and had more hard segments intermixed in the soft phase, restricting the movement of soft segments, and therefore resulted to non‐Fickian behavior, while the HTPB‐PU is antithetical. FTIR and atomic force microscopy were utilized to identify the hydrogen bonding behavior and morphology change of the PU films before and after the absorption of benzene vapor. The tensile strength of the HTBN‐PUs showed a greater decrease than that of HTBS‐PUs and HTPB‐PUs after absorbing benzene vapor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2984–2991, 2004     

The compatibility of the blends of PUs with PVC and the adhesion behavior of PU to PVC

Three series of polyurethane adhesives—polyethyleneadipateurethane (PEAU), polybuthyleneadipateurethane (PBAU), and polyhexyleneadipateurethane (PHAU)—with the same MW and hard/soft segment ratio, based on the three polyesters polyethyleneadipate (PEA), polybuthyleneadipate (PBA), polyhexyleneadipate (PHA), with 4,4′-diphnylmethane diisocyanate (MDI), and butendiol were synthesized by solution polymerization. The crystallinity of these polyesters and polyurethanes (PUs) and the compatibility of blends of PUs with PVC were studied by means of wide-angle x-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic thermomechanical analysis (DMA), testing of solubility, and phase contrast microscopy. The results indicated that PBAU/PVC and PHAU/PVC were compatible systems, but PEAU/PVC was incompatible. The adhesive strengths of the three adhesives were quite different from one another, in the order of PBAU ≥ PHAU ? PEAU. The influences of crystallinity and compatibility on adhesion were discussed, and the Diffusion Theory for PU-PVC systems was recommended. © 1995 John Wiley & Sons, Inc.     

Characterization of thermoplastic polyurethane adhesives with different hard/soft segment ratios containing rosin as an internal tackifier

Three thermoplastic polyurethanes (TPUs) containing different hard/soft (h/s) segment ratios (1.05-1.4) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′diisocyanate) and polyadipate of 1,4-butanediol (M _w = 2440) were allowed to react to produce the prepolymer. To provide the polyurethanes with high immediate adhesion to different substrates, a rosin + 1,4-butanediol mixture (1 : 1 equivalent%) was used as chain extender (TPU-Rs). These TPU-Rs had two types of hard segments: (i) Urethane hard segments, produced by reaction of the isocyanate and the 1,4-butanediol, and (ii) Urethan-amide hard segments, produced by reaction of the isocyanate and the carboxylic acid functionality of the rosin. The TPUs and TPU-Rs were characterized using FTIR spectroscopy, gel permeation chromatography, differential scanning calorimetry, stress-controlled plate-plate rheology, stress-strain measurements, and Brookfield viscosity. The TPUs and TPU-Rs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC joints. The addition of rosin as an internal tackifier increased the average molecular weight, more markedly in the TPU-Rs containing higher hard/soft segment ratios, but the elastic and viscous moduli decreased. An increase in the hard/soft segment ratio of the TPU-Rs retarded the kinetics of crystallization (which was determined by the soft segment content in the polyurethane), and increased the immediate T-peel strength in PVC/polyurethane adhesive/PVC joints (which was determined by the urethan-amide hard segments). Furthermore, addition of rosin to the polyurethanes decreased the final adhesion, although always reasonably high peel strength values were obtained.     

Polyurethanes having shape memory effects

Segmented polyurethanes (PUs) were prepared from polycaprolactone diols (PCLs), 4,4′-diphenylmethane diisocyanate, and 1,4-butanediol, and tested for shape memory effects. Effects of soft segment molecular weight (M_n = 2000, 4000 and 8000), soft segment content (50–90%), and maximum strain (_m = 100, 200, and 600%) on the cyclic tensile properties as well as the dynamic mechanical, and mechanical properties below (25°C) and above (65°C) the shape recovery temperatures were studied. With increasing soft segment contents: i) glassy state modulus increased and rubbery state modulus decreased; ii) hardness increased at room temperature, and decreased at 65°C; iii) recovery strain decreased with PCL 2000, and increased with PCL 8000 based PUs. On the other hand, the increase in soft segment length resulted in: i) increased rubbery state modulus as well as glass state modulus; ii) increased hardness at room and high temperatures; iii) increased recovery strain at high soft segment content. Tensile yielding became clear with increasing soft segment length and content. Strain upon cooling and unloading (_u) and residual strain (_p) increased, and recovery strain (_r) decreased with cycling. Among these, residual strain was most sensitive to the cycling. Most of the cycling effects were confined during the first one or two cycles. These results were interpreted in terms of soft segment-hard segment phase separation and soft segment crystallization.     

Effect of glycols on the properties of polyester polyols and of room‐temperature‐curable casting polyurethanes

A series of liquid polyester polyols (PEs) from adipic acid (AA), phthalic anhydride (PA) and trihydroxymethylpropane (TMP), and such glycols as ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), butanediol (BD) and hexanediol (HD), were prepared. Polyurethanes (PUs) were obtained from the PEs and polyaryl polymethylene isocyanate (PAPI) at room temperature. The effects of the structures of the glycols on viscosity, glass transition temperature and crystallinity of the PEs, and the mechanical, thermal and boiling‐water‐resistant properties of PUs were studied. The experiments showed that the viscosities and glass transition temperatures of the PEs decreased as the length of the glycol chains increased. The polyester based on HD lost flowability because of crystallization. The tensile strength and hardness of the PUs obtained decreased with increasing the length of the glycol chains, while the resistance to thermal deformation and boiling water increased. Thermogravimetric analysis demonstrated that thermal degradation of the polyurethane based on DEG proceeded in one step and for the others in two steps. The initial degradation temperature of the polyurethane based on EG was the lowest and that of the polyurethane based on BD was the highest. The residue of the former at 450 °C was the greatest, while that of the latter was the lowest. Copyright © 2004 Society of Chemical Industry     

Polyurethane membrane prepared via a dry/wet phase inversion method for protein adsorption

Hydroxyl‐terminated polybutadiene (HTPB)‐ and 4,4′‐dicyclohexyl‐methane (H₁₂MDI)‐based polyurethanes (PUs) were synthesized by solution polymerization. PU membranes were prepared by a dry/wet phase inversion method. Protein adsorption ratio of fibrinogen to albumin (F/A molar ratio) was measured. Low F/A molar ratio was found on these PUs. It was found that surface composition of these PUs has a subtle effect on F/A adsorption molar ratio. The F/A molar ratio was increased as the increase of hard segment content distributed on the surface. The variation of surface composition of these membranes and the effect on the F/A molar ratio were investigated by the difference in surface energy between nonpolar HTPB soft segment and polar hard segment, concentration, and temperature of coagulation medium, polymer content, and alcohol type. The CO/CC ratio, frequency shift, and difference (Δν) as a measure of polymer homogeneity and the average strength of interpolymer hydrogen bonds were utilized to study the surface composition. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1334–1340, 1999     

Synthesis and characterization of waterborne polyurethane adhesive from MDI and HDI

A series of waterborne polyurethane adhesives (WPUAs) were prepared from diphenylmethane‐4,4′‐diisocyanate (MDI), 1,6‐hexamethylene diisocyanate (HDI), poly(1,4‐butanediol adipate) diol (PBA), 1,4‐butanediol (BDO), and internal‐emulsifying agents by the prepolymer mixing method. The viscosity, mechanical properties, thermal properties, and adhesion strength of the samples were measured. The structure–property relationship was discussed primarily. The results indicated that the MDI/HDI and PBA/BDO molar ratio influenced these properties. The WPUA exhibited excellent T‐peel strength and mechanical properties at a suitable MDI/HDI (or PBA/BDO) molar ratio. Moreover, higher MDI/HDI (or PBA/BDO) molar ratio resulted in higher thermal stability. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

复合薄膜用水性聚氨酯-丙烯酸酯胶粘剂的合成

以聚醚二元醇、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)等为原料合成了聚氨酯预聚体,用丙烯酸羟丙酯(HPA)将其部分封端,制得一种水性聚氨酯丙烯酸酯分散体,再加入乙烯基单体进行自由基引发聚合,制备出水性聚氨酯-丙烯酸酯(PUA)复合乳液。用红外光谱仪(FTIR)、差示量热扫描仪(DSC)、热重分析(TG)、马尔文粒度分析等测试手段,对合成产物进行了结构和性能表征。研究了软硬段质量比、亲水基团含量、丙烯酸酯单体的加入对PUA乳液性能的影响。结果表明,m(软段)∶m(硬段)=2∶1,m(PU)∶m(PA)=4∶1,—COOH质量分数为2.8%,以该乳液配制的胶粘剂应用于包装用CPP/CPP薄膜、OPP/VMOPP薄膜的剥离强度分别达31.9N/m和28.1 N/m。     

Effect of the hard segment on the properties of UV curable waterborne blocked polyurethanes

Two types of UV curable waterborne blocked polyurethanes (PUs) were obtained from 2,4-tolylene diisocyanate(TDI) and isophorone diisocyanate (IPDI), which had the same soft segments and different hard segments. The PUs contained both the UV curable C=C bond and the blocked NCO groups which could be de-blocked when heated. Effect of the hard segment on the properties of the two types of PUs was investigated. The FTIR spectra method was employed to confirm the structure of the PUs. The photo-DSC was used to study the photo-polymerization rate of the PUs under UV irradiation in the presence of a photo-initiator and the C=C conversion behaviors. Heating-up IR analysis was used to track the de-blocking process and the heat curing process. The thermal degradation analysis (TGA) was employed to investigate the thermal stability of the UV cured films before and after heat curing process. Dynamic mechanical properties of the UV and heat cured films were investigated by the dynamic mechanical thermal analysis (DMTA).     

Preparation and properties of polyurethane coatings based on acrylic polyols and trimer of isophorone diisocyanate

This paper presents a study on the effect of NCO/OH ratio and an increase in hydroxyl content of acrylic polyols on the properties of polyurethane (PU) coatings. Coating properties studied are gloss, scratch resistance, flexibility and adhesion, mechanical properties include tensile strength, modulus, percent elongation and Shore hardness, while physicochemical properties include chemical resistance and solvent absorption of coated PU samples. A series of acrylic polyols (copolymers) based on butyl acrylate (BA), methyl methacrylate (MMA), styrene and 2-hydroxy ethylacrylate (HEA) were prepared by selecting different percentage of hydroxyl content. Trimer of isophorone diisocyanate (IPDI) was also synthesized in the laboratory. This trimer has trifunctionality. Isocyanurate ring of trimer increases thermal properties of PU. Polyurethanes from these acrylic polyols (containing different percent hydroxyl) and trimer of IPDI were prepared with two different NCO/OH ratios viz, 1.1:1 and 1.2:1. Polyurethanes were coated on substrates for measuring coating properties. Mechanical properties were measured on cast films of the PUs. The experimental results revealed that all polyurethane coatings based on acrylic polyols and IPDI trimer showed good gloss, scratch resistance and excellent adhesion. Thermal stability of these PU samples was found to be better. Physicochemical properties reflected that these PU have excellent chemical and solvent resistance.