聚己内酯型聚氨酯丙烯酸酯的合成及应用

以不同结构的三元醇为骨架,合成了一系列高性能的聚氨酯丙烯酸树脂（PUA）,探讨了合成线路对PUA固化膜性能的影响.研究表明,以聚己内酯三元醇作骨架,采用预封端法合成的PUA,具有黏度低,相对固化速度快,拉伸性能高、硬度高等特点.     

Synthesis of poly(lactic acid)‐based polyurethanes

Poly(lactic acid) (PLA) is a biodegradable aliphatic polyester, but its brittleness makes it unsuitable for many packaging and appliance applications. The goal of the work reported was to create novel poly(ester urethane)s that incorporate biodegradable poly(lactic acid) diols (PLA‐OHs) and good mechanical properties of increased molecular weight via crosslinked network formation for engineering plastics applications. Three kinds of polyols (PLA‐OHs, PLA‐OHs/poly(tetramethylene ether) glycol or PLA‐OHs/poly(butylene adipate) glycol (PBA)) and two kinds of diisocyanates (4,4‐diphenylmethane diisocyanate (MDI) or toluene 2,4‐diisocyanate (TDI)) were chosen for the soft and hard segments to compare their mechanical properties. In addition, 1,4‐butanediol and trimethylolpropane were each used as chain extender agents. Results showed the PLA/PBA‐polyurethanes (PLA/PBA‐PUs) of the MDI series and the PLA/PBA‐PUs of the TDI series had improved thermal stability and enhanced mechanical properties. Degradation behavior showed the PLA‐based polyurethanes could be degraded in phosphate‐buffered saline solution and enzyme solution. © 2012 Society of Chemical Industry     

Thermal stability of chemically crosslinked moisture‐cured polyurethane coatings

Polyurethane prepolymers are widely used in reactive hot melt adhesives and moisture‐cured coatings. The segmented moisture‐cured formulations, based on polytetramethylene glycol (PTMG‐1000)/trimethylol propane (TMP)/isophorone diisocyanate (IPDI) and PTMG/TMP/toluene diisocyanate (TDI), were prepared with NCO/OH ratio of 1.6 : 1.0. The excess isocyanate groups of the prepolymers were chain extended in the ratio of 2 : 1 (NCO/OH) with different aliphatic diols and 4 : 1 with different aromatic diamines. The surplus isocyanate groups of the formulations were completely reacted with atmospheric moisture, and the thermal stability of the postcured materials obtained as cast films were evaluated by thermogravimetric (TG) analysis. It was observed that initial degradation temperatures were above 270°C, with two‐ or three‐step degradation profiles. The degradation parameters were evaluated using the Broido and Coats–Redfern methods. The thermal resistance of moisture‐cured formulations using diisocyanates with the cycloaliphatic structures (IPDI) and the aromatic TDI, at the same NCO/OH ratio (1.6), and TMP content were compared from the isothermal TG experiments at different temperatures and dynamic TG experiments at different heating rates in nitrogen and oxygen environments. The observation suggests that polyurethane‐containing sulfone groups and straight‐chain diol chain extenders were more stable. It was also observed that at lower temperature polyurethane, prepared from aliphatic diisocyanates (IPDI), was more stable than the aromatic diisocyanate (TDI) containing polyurethanes. At high temperature, the stability order follows the reverse trend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1509–1518, 2005     

Synthesis and thermal dissociation of phenol- and naphthol-blocked diisocyanates

Phenol-, 2-naphthol-, and 1-nitroso-2-naphthol-blocked toluene diisocyanate (TDI) and isophorone diisocyanate (IPDI) adducts and their polymers with PPG-1000 were prepared and characterized by nitrogen estimation, IR, and ¹H-NMR spectroscopy. The absence of an IR absorption band at 2270 cm^?1 confirmed the completion of the reaction between the isocyanate and the blocking agents, whereas the presence of a band at 1075–1150 cm^?1 confirmed the formation of poly(ether urethanes). The deblocking temperatures were determined by the use of DSC and by the carbon dioxide evolution methods. The thermal stabilities of the 2-naphthol-blocked diisocyanates were less than the phenol-blocked diisocyanates. Dissociation temperature was also reduced by the nitroso group in the blocking agent. Mass spectral data confirmed the product analysis. The solubility of the adducts were determined in the different polyols. Adducts based on IPDI showed better solubility than did those based on TDI. © 1994 John Wiley & Sons, Inc.     

Preparation and properties of UV‐curable waterborne polyurethane–acrylate emulsion

Polyurethane–acrylate oligomer terminated with multiple unsaturated bonds was prepared using isophorone diisocyanate, (IPDI), methylene diphenyl diisocyanate, and polyols as monomers, using 2,2‐dimethylol propionic acid as hydrophilic chain extender, together with pentaerythritol triacrylate (PETA) as end‐capper. The UV‐curable waterborne polyurethane–acrylate (UV‐WPUA) composite emulsion was obtained by mixing the PUA oligomer with certain content of reactive diluents and then dispersing the mixture in water. The molecular structure of the polyurethane prepolymer, PUA oligomer, and UV‐cured polymer was investigated by Fourier transform infrared spectroscopy. The influence of the composition and content of the diluents and end‐capper on UV‐WPUA properties, including the emulsion stability, thermal property, water resistance, adhesion, hardness, glossiness of polymer film were studied. The results show that the WPUA emulsion has excellent stability, and the UV‐cured film features good hardness and remarkable water resistance when PETA is used as end‐capper and the end‐capping ratio of the polyurethane prepolymer is 70% and dipentaerythritol hexaacylate/dipropylene glycol diacrylate (mass ratio 1:1) is used as diluent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45208.     

Effect of diisocyanate on pyridine containing shape memory polyurethanes based on N,N‐bis(2‐hydroxylethyl)isonicotinamide

This article demonstrates a comparative investigation about the effect of diisocyanate on pyridine containing shape memory polyurethanes (Py‐SMPUs), which are synthesized with N,N‐bis(2‐hydroxylethyl)isonicotinamide (BINA) and four different diisocyanates: 1,6‐hexanediisocyante (HDI), isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI), and tolylene diisocyanate (TDI). Results show that all BINA–SMPU systems have amorphous reversible phase. Comparatively, the MDI–BINA and TDI–BINA systems show higher T_g; and the HDI–BINA and IPDI–BINA systems show better thermal stability. In addition, the HDI–BINA and the IPDI–BINA systems exhibit good thermal‐induced shape memory effect and good moisture‐sensitive shape memory effect due to their better moisture absorption properties. Particularly, the HDI–BINA system has better response speed and better shape recovery. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40721.     

Poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) with 2,4‐toluene diisocyanate and m‐xylene diisocyanate. I. Compatibility and impact strength of copolymers

In this study, slightly crosslinked poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) (PDMS urethane‐co‐PMMA) graft copolymers based on two diisocyanates, 2,4‐toluene diisocyanate (2,4‐TDI) and m‐xylene diisocyanate (m‐XDI), were successfully synthesized. Glass‐transition behaviors of the copolymers were investigated. Results confirm that PDMS–urethane and PMMA are miscible in the 2,4‐TDI system, but are only partially miscible in the m‐XDI system. The methylene groups adjoining the isocyanate in the m‐XDI system show increased phase‐separation behavior over the 2,4‐TDI system, in which the benzene ring adjoins the isocyanate. The functional group of PDMS–urethane improves the impact strength of the copolymers. The toughness depends on the compatibility of PDMS–urethane and PMMA segments in the copolymers. In the m‐XDI system, the impact strength of the copolymer containing 3.75 phr macromonomer achieves a maximum value (from 13.02 to 22.21 J/m). The fracture behavior and impact strength of the copolymers in the 2,4‐TDI system are similar to that of PMMA homopolymer, although they are independent of the macromonomer content in the copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1875–1885, 2002     

Effect of acrylic acid on the physical properties of UV-cured poly(urethane acrylate-co-acrylic acid) films for metal coating

UV-cured poly(urethane acrylate-co-acrylic acid) (PU-co-AA) films with five different compositions were prepared by reacting isophorone diisocyanate (IPDI), polycaprolactone triol (PCLT), 2-hydroxyethyl acrylate (HEA), and different weight ratios of trimethylolpropane triacrylate (TMPTA) and acrylic acid (AA) as diluents. Their synthesis and physical properties including gel content, adhesion properties, morphological structure, thermal properties, and mechanical hardness were investigated as a function of the AA content. It was found that the physical properties of the PU-co-AA films are strongly dependent upon the AA content. Crosscut tests showed that PU-co-AA films with lower AA content showed 0% adhesion (0B), and the adhesion of films increased dramatically as the AA content increased to 40–50%. The pull-off measurements showed that the adhesion force of the PU-co-AA films to stainless steel substrates varied from 6 to 31 kg_f/cm² and increased linearly with increasing AA content. PU-co-AA films with higher AA content can be good candidates for UV-curable coating of metal substrates such as stainless steel. However, the thermal stabilities and mechanical hardness decreased with increasing AA content, which results from the relatively linear and flexible structure of AA.     

Effect of the diisocyanate structure and the molecular weight of diols on bio‐based polyurethanes

Bio‐based polyurethanes (PU) containing poly(ε‐caprolactone) diol (PCL) and hydroxyl telechelic natural rubber (HTNR) were synthesized. The effect of the diisocyanate structure and the molecular weights of diols on the mechanical properties of PU were investigated. Three different molecular structures of diisocyanate were employed: an aliphatic diisocyanate (hexamethylene diisocyanate, HDI), an aromatic diisocyanate (toluene‐2,4‐diisocyanate, TDI) and a cycloalkane diisocyanate (isophorone diisocyanate, IPDI). Two molecular weights of each diol were selected. When HDI was employed, a crystalline PU was generated while asymmetrical structures of TDI and IPDI provided an amorphous PU. The presence of crystalline domains was responsible of a change in tensile behavior and physical properties. PU containing TDI and IPDI showed a rubber‐like behavior: low Young's modulus and high elongation at break. The crystalline domains in PU containing HDI acted as physical crosslinks, enhancing the Young's modulus and reducing the elongation at break, and they are responsible of the plastic yielding. The crystallinity increased the tear strength, the hardness and the thermal stability of PU. There was no significant difference between the TDI and IPDI on the mechanical properties and the physical characteristics. Higher molecular weight of PCL diol changed tensile behavior from the rubber‐like materials to the plastic yielding. Thermal and dynamic mechanical properties were determined by using DSC, TGA and DMTA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Properties of UV-curable polyurethane acrylates using nonyellowing polyisocyanate for floor coating

UV-curable polyurethane acrylates for poly(vinyl chloride) (PVC) floor coating were prepared using nonyellowing polyisocyanates. The effects of the chemical structure of the polyisocyanates and hydroxyacrylates, and the compositions of the prepolymer/diluent on the properties of the UV-curable polyurethane acrylates were investigated. Several different urethane acrylate prepolymers from four different polyisocyanates, isophorone diisocyanate (IPDI) adduct, hexamethylene diisocyanate (HDI) adduct, HDI biuret, and HDI isocyanurate, and two different hydroxyacrylates, hydroxyapropyl acrylate (HPA), polycaprolactone modified hydroxyethylhexylacrylate (PCMHEA). UV-curable coating materials were formulated from the prepolymers and 1-hydroxycyclohexylphenyl ketone as a photoinitiator with polyethylene glycol diacrylate (PEGDA) as a diluent. The polyurethane acrylates prepared with HDI isocyanurate and the equimolar mixture of HPA and PCMHEA showed balanced coating properties such as tensile properties, hardness, weatherability, and good adhesion. The dynamic mechanical studies showed the properties of those polyurethane acrylates were well correlated with their glass transition temperature behaviors. It was also found that the adhesion was best as a PVC floor coating with the appropriate viscosity (below 150 P at 25°C) when 35% PEGDA as a diluent was used. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of diethylene glycol monobutyl ether—Blocked diisocyanate crosslinkers

Typically blocked isocyanate systems are used to obtain the performance of two component polyurethane (PU) system in a one-component mixture. In this study four types of isocyanates namely, hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and toluene diisocyanate (TDI) were blocked with diethylene glycol monobutyl ether (DEGMBE). Elimination of the isocyanate groups and the formation of urethane bonds were studied by FTIR spectroscopy and titration methods. Thermal dissociation of blocked diisocyanates was analyzed by DSC and TGA techniques.Deblocking temperature obtained by DSC and TGA techniques was compared. Based on DSC data, it was found that deblocking of blocked MDI and TDI starts at lower temperatures compared to that of the aliphatic one (HDI). Reactivity of the blocked IPDI is between blocked MDI and blocked TDI.In general, TGA results show the same trend as DSC except for IPDI which shows the lowest deblocking temperature. Deblocking temperature values obtained by TGA technique were lower than DSC values.     

Synthesis and characterization of diethylene glycol monobutyl ether—Blocked diisocyanate crosslinkers

Typically blocked isocyanate systems are used to obtain the performance of two component polyurethane (PU) system in a one-component mixture. In this study four types of isocyanates namely, hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and toluene diisocyanate (TDI) were blocked with diethylene glycol monobutyl ether (DEGMBE). Elimination of the isocyanate groups and the formation of urethane bonds were studied by FTIR spectroscopy and titration methods. Thermal dissociation of blocked diisocyanates was analyzed by DSC and TGA techniques.     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Hydroxyl‐terminated poly(urethane acrylate) as a soft liner in dental applications: Synthesis and characterization

Hydroxyl‐terminated poly(urethane acrylate)s were synthesized for use in biomedical applications. Acrylate end capping via an interesterification reaction was successfully achieved with methacryloyl chloride addition to the hydroxyl ends of the polyurethane at low temperatures. 2,4‐Toluene diisocyanate, 1,6‐hexane diisocyanate, and methylene diphenyl diisocyanate were used as diisocyanates for urethane synthesis, and they were end‐capped with methyl methacrylate and hydroxyethyl methacrylate. The nature of the monomers that we used had an effect on the thermal and morphological properties that were interpreted in terms of the level of hydrogen bonding and the degree of phase separation. The synthesized polymers were characterized by NMR, Fourier transform infrared/attenuated total reflectance spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The number‐average molecular weights of the poly(urethane acrylate)s were 2500–6000 g/mol. To use the polymer as a soft‐liner material in denture applications, the residual isocyanate should not exist. In this study, we showed that a prepolymer without residual isocyanate could be synthesized. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermoplastic urethane elastomers. III. Effects of variations in isocyanate structure

The dynamic mechanical properties of thermoplastic urethane elastomers have been compared for materials based on different diisocyanate structures, either 4,4′-diphenylmethane diisocyanate (MDI) or an isomeric ratio of tolylene diisocyanate (TDI). Two comparable series of polymers were prepared with a polycaprolactone diol as the soft segment and varying concentrations of hard segments based on the respective diisocyanates and 1,4-butanediol. Over the composition range studied, the polymer glass transition temperatures increased for the TDI-based polyurethanes, but remained relatively constant for the series containing MDI. Differences in the degree of macroscopic order within the hard segments, due to variations in the symmetry of the diisocyanate structures, are suggested as an explanation of these dynamic mechanical properties.     

Preparation of novel CNSL‐based urethane polyol via nonisocyanate route: Curing with melamine‐formaldehyde resin and structure–property relationship

In this study, we report preparation of a novel cashew nut shell liquid (CNSL)‐based polyol bearing urethane groups. The urethane group in the polyol was induced via isocyanate free route from the reaction of cyclic carbonate with primary amine. The polyol was characterized by determination of hydroxyl number, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and so forth. The polyol was then used as coating component and cured with hexamethoxy methylene melamine (HMMM). Another CNSL‐based polyol without urethane moiety from our earlier reported work was used for preparation of coating for comparative study to determine the effect of urethane group on the coating properties. The coating formulations based on these two polyols were cured with variable amounts of HMMM hardener to optimize coating properties. All the coatings were evaluated for mechanical properties such as adhesion, flexibility, pencil and scratch hardness, impact resistance, pull‐off, and adhesion. The optimized coatings were also evaluated for chemical and thermal properties. It was observed that the urethane containing polyol resulted in better adhesion to the metal substrate at higher quantity of HMMM hardener compared to the other polyol providing significant improvement in various coating properties. The final coating properties were also compared with the acrylic polyurethane coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41391.     

Synthesis,characterization and thermal dissociation of 2‐butoxyethanol‐blocked diisocyanates and their use in the synthesis of isocyanate‐terminated prepolymers

A series of blocked diisocyanates has been synthesized from toluene diisocyante (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′‐diphenylmethane diisocyanate (MDI) and 2‐butoxyethanol. The synthesis of blocked diisocyanate adducts was confirmed by Fourier transform infrared, ¹H NMR, electron impact mass spectrometry and nitrogen analysis. Differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and carbon dioxide evolution were used to determine the minimum de‐blocking temperatures. De‐blocking temperatures determined by these three techniques were found to be in the order DSC > TGA > CO₂ evolution. The effect of different metal catalysts on thermal de‐blocking reaction of the blocked diisocyanates was studied, using the carbon dioxide evolution method. It was found that iron(III) oxide has the maximum catalytic activity on de‐blocking. The solubility of the blocked diisocyanate adducts was determined in different solvents. The study revealed that at 30 °C blocked IPDI and HDI adducts show better solubility than adducts based on TDI and MDI. Isocyanate‐terminated prepolymers of blocked diisocyanates and hydroxyl‐terminated polybutadiene (HTPB) were prepared. The storage stability and gelation times of the prepolymers were studied. Results showed that all the diisocyanate‐HTPB compositions are stable at 50 °C for more than three months. However, aliphatic diisocyanate‐HTPB compositions require greater gelation time than aromatic diisocyanate‐HTPB compositions at their respective de‐blocking temperatures. Copyright © 2007 Society of Chemical Industry     

Biobased chain extended polyurethane and its composites with silk fiber

The biobased chain extended polyurethane (PU) was synthesized by reacting castor oil based polyol with different diisocyanates [toluene‐2,4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI)] and chain extender such as glutaric acid. Biocomposites have been fabricated by incorporating the silk fiber into both TDI‐ and HMDI‐based PUs. The effect of incorporation of silk fiber into TDI‐ and HMDI‐based neat PU on the physicomechanical properties such as density, surface hardness, tensile strength, and percentage elongation have been investigated. The dynamic mechanical properties and the thermal stability of neat PUs and the silk fiber incorporated PU composites have been evaluated. The TDI‐based neat PU has showed higher mechanical properties compared to HMDI‐based PU. The incorporation of 10% silk fiber into TDI‐ and HMDI‐based PU resulted in an enhancement of tensile strength by 1.8 and 2.2 folds, respectively. The incorporation of silk fiber into biobased chain extended PU increased the glass transition temperature (T_g) of the resultant biocomposites. The morphology of tensile fractured neat PUs and their biocomposites with silk fiber was studied using scanning electron microscope (SEM). POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Influence of Diisocyanate Structure on the Synthesis and Properties of Ionic Polyurethane Dispersions

A number of aqueous polyurethane dispersions based on polytetramethylene glycol (PTMG), 1,4-butanediol (1,4-BDO), dimethylol propionic acid (DMPA) and diisocyanates of differing structures such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H₁₂MDI) were prepared. IR Spectroscopy was used to check the end of polymerization reaction and also the polymer characterization. The effects of diisocyanate structure on the particle size, contact angle, mechanical and thermal properties of the emulsion-cast films were studied. Average particle size of prepared polyurethane emulsions change by different diisocyanate based polyurethane. TDI based PU shows higher average particle size and contact angle than the others. Tensile strength, hardness, and elongation at break were higher in the case of MDI based polyurethane. Thermal property and thermal stability is also affected by variation of diisocyanate molecular structure.     

Improvement of thermal stability of new heteroaromatic poly(azomethine urethane)s

New poly(azomethine urethane)s were synthesized in the conventional literature manner by reacting a new bisphenol‐containing azomethine group, N,N′‐bis(4‐hydroxyl‐3‐methoxy benzylidine)‐2,6‐diaminopyridine (I) with various diisocyanates, such as hexamethylene diisocyanate (HDI) (a), methylene‐4,4′‐diphenyl diisocyanate (MDI) (b), and toluene‐2,4‐diisocyanate (TDI) (c). The resulting polymers I(a–c) were confirmed by ¹H‐NMR, FTIR, UV, and CHN analyses. Thermogravimetric analysis (TGA) revealed that the polymers have high thermal stability. A semicrystalline behavior was noticed for polymers by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1198–1204, 2006