Aqueous polyurethane dispersions derived from polycarbonatediols

Aqueous polyurethane dispersions derived from polycarbonatediols, isophorone diisocyanate, and carboxylic diols including dimethylol propionic acid and dimethylol butyric acid were prepared. The effect of dispersing procedure is investigated by FT IR, GPC, and the tensile film properties. The polyurethane dispersions prepared by a standard procedure exhibit lower molecular weights due to the overhydrolysis of the NCO groups. The polyurethane dispersions prepared by a modified procedure exhibit significantly higher molecular weights due to more effective chain extension, and their cast films exhibit higher tensile strength. The particle size, tensile properties, thermal properties, and dynamic mechanical properties are investigated. The chemical structure of the polycarbonatediols seems to affect the tensile strength. The glass transition temperature of the soft segments, T_g(S), of the polyurethane dispersions can be seem from the DSC and DMA data. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1723–1729, 2004     

Polyurethane dispersions derived from polycarbonatediols and m‐di(2‐isocyanatopropyl)benzene

Aqueous polyurethane dispersions derived from various polycarbonatediols, m‐di(2‐isocyanatopropyl)benzene(TMXDI), and various carboxylic diols including dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), and a carboxylic polycaprolactonediol (Placcel 205BA) were prepared by a method in which the dispersing procedure was modified to enhance the molecular weight. The NH₂/NCO ratio during chain extension affected the molecular weight of the polyurethanes, significantly, and an optimum ratio of 0.67:1.0 was used. The molecular weight, particle size, tensile properties, and thermal properties of the polyurethane dispersions were investigated. The effect chemical structure of the polycarbonatediols on the properties shows no obvious trend, but the polyurethane dispersions derived from the carboxylic polycaprolactonediol exhibit smaller particle size and softer tensile properties when compared with those derived from DMPA and DMBA. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Aqueous polyurethane dispersions derived from polycarbonatediols and Di(4‐isocyanatocyclohexyl)methane

Aqueous polyurethane dispersions derived from various polycarbonatediols, di(4‐isocyanatocyclohexyl)methane (HMDI), and various carboxylic diols, including dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), and a carboxylic polycaprolactonediol, were prepared by a method in which the dispersing procedure was modified to enhance the molecular weight. The molecular weight, particle size, tensile properties, thermal properties, and dynamic mechanical properties of the polyurethane dispersions were investigated. The dynamic mechanical property data indicate that these polyurethane dispersions can exhibit higher temperature resistance when compared with those derived from isophorone diisocyanate (IPDI). POLYM. ENG. SCI. 46:588–593, 2006. © 2006 Society of Plastics Engineers     

Clear polyurethane dispersions of nanometer size derived from carboxylic polycaprolactonediols

Aqueous polyurethanes dispersions of nanometer size derived from various carboxylic polycaprolactonediols of different molecular weights, carboxylic diols, including 2,2‐di(hydroxymethyl)propanoic acid (DMPA), 2,2‐di(hydroxymethyl)butanoic acid (DMBA), and di(4‐isocyanatocyclohexyl)methane (HMDI) were prepared by a method in which the dispersing procedure was modified to enhance the molecular weight. The molecular weight, particle size, and UV–vis spectra of the polyurethane dispersions were investigated. The tensile properties of the cast films were determined. The modified dispersing procedure gave polyurethane dispersions with higher molecular weight and better tensile strength. As the molecular weight of the carboxylic polycaprolactonediol decreases, the content of the ionic groups increases, the particle size decreases accordingly. As the molecular weight of the carboxylic polycaprolactonediol used is 1000 g/mol or below, the polyurethanes dispersions become completely clear. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Anionic waterborne polyurethane dispersions based on hydroxyl‐terminated polybutadiene and poly(propylene glycol): Synthesis and characterization

Nonpolluting systems based on anionic polyurethane aqueous dispersions were obtained. The prepolymer based on hydroxyl‐terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), and dimethylolpropionic acid (DMPA) were synthesized in bulk. After neutralization with triethylamine (TEA), the anionomer prepolymer was dispersed in water, followed by a chain‐extension reaction with ethylenediamine (EDA). The prepolymers were characterized by Fourier transform infrared spectrometry (FTIR) and the average particle size of the aqueous dispersions was determined by laser light scattering (LLS). The mechanical behavior of polyurethane‐cast films and the adhesive properties of the aqueous dispersions as coatings for wood were evaluated. It was observed that an increase in the HTPB content provoked an increase in the viscosity and in the particle size of the dispersions. The tensile strength and the modulus values of the films and the adhesiveness of the coatings in wood were also increased by increasing the HTPB content. On the other hand, the elongation of the polyurethane‐cast films and the tackness of the surface coatings decreased as the HTPB was increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 566–572, 2001     

Effects of TDI and FA‐703 on physico‐mechanical properties of polyurethane dispersion

A series of water dispersion polyurethanes dispersions (PUDs) were prepared by polyaddition reaction using isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), poly(oxytetramethylene) glycol (PTMG), dimethylol propionic acid (DMPA), and triol (trade name FA‐703). Various formulations were designed to investigate the effects of process variables such as TDI and FA‐703 on the physico‐mechanical properties of PUD. IR spectroscopy was used to check the end of polymerization reaction and characterization of polymer. Evolution of the particle size distribution, contact angle, T_g, molecular weight, viscosity, and mechanical properties of the emulsion‐cast films were significantly affected by variable content of TDI and FA‐703. Average particle size of the prepared polyurethane emulsions and contact angle decrease with increase of content of FA‐703 and TDI. Molecular weight, T_g, tensile strength, tear strength, hardness, viscosity and elongation at break increase with increase of content of FA‐703 and TDI. The increase of molecular weight, tensile strength, tear strength and elongation at break properties are interpreted in terms of increasing hard segments, chain flexibility, and phase separation in high content of FA‐703 and TDI‐based polyurethane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

乙二胺扩链剂对水性聚氨酯性能的影响

以聚醚220、异佛尔酮二异氰酸酯(IPDI)为主要原料,二羟甲基丙酸(DMPA)为亲水性扩链剂,丁二醇(BD)和乙二胺(EA)为小分子扩链剂,按不同配比合成了系列水性聚氨酯分散体。主要考察了乙二胺扩链剂用量对水性聚氨酯乳液的稳定性、乳液粒径、粘度以及膜吸水性和力学性能的影响。结果表明,随乙二胺扩链剂用量的增加,乳液粒径增大、分散稳定性变差、粘度减小、胶膜的拉伸强度增加、断裂伸长率减小、耐溶剂性增加、吸水率变化不明显、硬段相Tg升高,软硬段相分离程度增加。胶膜的ATR红外表现为PPG类聚醚型聚氨酯典型的红外光谱。     

Modification of aqueous polyurethane dispersions via tetraphenylethane iniferters

Aqueous polyurethane (PU) dispersions containing tetraphenylethane iniferter groups were prepared from 4,4′‐diphenylmethane diisocyanate, poly(propylene oxide)glycols, dimethylol propionic acid, and 1,1,2,2‐tetraphenylethane‐1,2‐diol. To improve the water resistance of the dispersions, methyl methacrylate monomers were added into these dispersions and block‐copolymerized onto the main PU chain. The viscosity and particle size of the dispersions were determined. Dispersion‐cast films were characterized in terms of the contact angle, the swell in water, and the mechanical properties. Contact‐angle and water‐swell measurements showed that the hydrophilicity of the films was decreased significantly when methyl methacrylate was polymerized in the presence of tetraphenylethane containing aqueous PU dispersions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2993–3000, 1999     

The effects of the molecular weight and structure of polycarbonatediols on the properties of waterborne polyurethanes

A series of waterborne polyurethanes (WPUs) were synthesized by a pre-polymer process from isophorone diisocyanate, 1,6-hexamethylene diisocyanate and polycarbonatediol with varying molecular weight (1000–2000 Da) and molecular structure (copolycarbonate and homopolycarbonate). The effect of polycarbonatediols on the performance of the emulsion was studied by means of apparent viscosity, particle size distribution and Zeta potential analysis. Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, X-ray diffraction, dynamic mechanical analysis, physical and mechanical measurements and water droplet contact angle tests were employed to characterize the thermal stability, crystallinity, low temperature flexibility, physical and mechanical properties and wettability of the films derived from the emulsions. The results indicated that WPU dispersions with mean particle size in the range of 50–70 nm and Zeta potential value about −50 mV displayed excellent storage stability. It was found that the mean particle size, thermal stability, crystallinity, low temperature flexibility, mechanical properties and hydrophobicity increased and the particle distribution decreased with the increase of molecular weight of the polycarbonatediols. Moreover, copolycarbonate-based WPUs showed higher crystallinity of hard segments, thermal stability and wettability than the homopolycarbonate-based ones.     

Characterization of polydimethylsiloxane–polyurethanes synthesized by graft or block copolymerizations

We synthesized polydimethylsiloxane–polyurethane dispersions modified with graft copolymerization (PDMS-G-PUDs) and polydimethylsiloxane–polyurethane dispersions modified with block copolymerization (PDMS-B-PUDs). We systematically investigated the effects of PDMS’s structure, content, and molecular weight on properties of copolymer including viscosity, particle size, and stability of dispersions as well as the properties of the film formed by dispersions including gloss, contact angle, water resistance, oil resistance, and mechanical properties. The results demonstrated that the viscosity, particle size, water resistance increased but gloss decreased with the increase of PDMS content and molecular weight. In addition, we compared the properties of PDMS-B-PUD films and PDMS-G-PUD films with the same amount of PDMS and similar molecular weight. PDMS-G-PUD films showed higher water and oil resistance, but lower gloss and poorer mechanical properties. Scanning electron microscopy–energy dispersive spectroscopy analysis (SEM–EDS) indicated that the films of PDMS-G-PUD had better microphase separation and PDMS surface enrichment.     

Anionomeric waterborne poly(urethane semicarbazide) dispersions and their adhesive properties

Aqueous polyurethane dispersions were prepared from isocyanate‐terminated ionic polyurethane prepolymers by chain extension with dihydrazides. These water‐borne dispersions had excellent adhesive properties and were used to bond leather and canvas. The base polymers were varied with respect to (1) the ionic content with the same chain extender and (2) the nature of the chain extender with the ionic content kept constant. Studies on the particle size and viscosity revealed that the ionic content had an influence on the aforementioned properties: the particle size decreased and the viscosity increased with increasing ionic content. The polarity of the films cast from the dispersions were determined with contact‐angle measurements: hydrophilic character was exhibited by all the compositions. X‐ray studies revealed that the increase in the ionic content led to increasing intensities of the diffraction peaks due to increased secondary forces of bonding. The tensile strength measurements showed that the films were highly elastomeric and had good mechanical strength, which varied with the composition. A shear strength and peel strength analysis of specimens obtained through the bonding of leather to leather, leather to canvas, and canvas to canvas revealed that the waterborne dispersions were excellent adhesives for bonding leather surfaces. Thus, a very efficient, ecofriendly waterborne dispersion of polyurethane that could find applications in bonding leather in the footwear industry was prepared successfully. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

Preparation and characterization of thermoplastic water‐borne polycarbonate‐based polyurethane dispersions and cast films

Stable water‐borne polyurethane dispersions (PUDs) were prepared from bifunctional aliphatic polycarbonate‐based macrodiol, 2,2‐bis(hydroxymethyl)propionic acid (DMPA), 1,6‐diisocyanatohexane, 1,4‐butanediol (BD), and triethylamine. Water‐borne dispersion particles are thus solely formed from self‐assembled linear PU chains. Both PUDs and PUD‐based films were characterized with regards to the concentration of DMPA (ionic species content) and BD (hard‐segment content). Average particle size of PUDs decreased and their long‐term stability increased with increasing DMPA and decreasing BD concentration. Functional properties of cast films made from PUDs are substantially influenced by the character of the original colloidal particle dispersions. The swelling behavior of the films, their surface morphology, and mechanical properties are more influenced by DMPA than BD contents. At DMPA concentrations higher than 0.2 mmol g^?1 of the solid mass of polyurethane, distinct self‐organization of individual nanoparticles into fibril‐like structures was detected by atomic force microscopy and scanning electron microscopy. PU films made from PUD containing high BD as well as high DMPA concentrations have the best utility properties namely sufficient tensile properties and a very low swelling ability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42672.     

Preparation and Properties of Water-borne Polyurethanes

Following a prepolymer mixing process, polyurethane (PU) anionomer dispersions were prepared from polyethylene adipate glycol (PEA), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and dimethylol propionic acid (DMPA) as a potential ionic centre. Effects of prepolymer molecular weight, PEA molecular weight, hard segment content, DMPA content, degree of neutralization and mixed diisocyanates have been studied in terms of particle size and viscosity of emulsion, and surface, mechanical and dynamic mechanical properties of the emulsion-cast films. Particle size decreased and emulsion viscosity increased with increase in prepolymer molecular weight and PEA molecular weight, DMPA content, the degree of neutralization and IPDI content in mixed isocyanate systems. The decrease in particle size was due to increased chain flexibility and/or hydrophilicity of the PU. The mechanical and dynamic mechanical properties of the PU ionomer dispersions were interpreted in terms of soft segment–hard segment phase separations, hard segment content, chain flexibility and coulombic forces. © of SCI.     

Aqueous poly(urethane–urea) dispersions and cast films based on m‐TMXDL. 1. Structure–property relationships

Aqueous poly(urethane–urea) dispersions were prepared from polycaprolactone diol, α,α,α′,α′‐tetramethyl‐1,3‐xylylene diisocyanate (m‐TMXDI) and α,α‐dimethylol propionic acid (DMPA) using a prepolymer mixing process. In the process, polyurethane prepolymers were neutralised with triethylamine and the chains extended in water with either hydrazine, 1,2‐ethylene diamine or 1,2‐propylene diamine. For comparison, some samples were prepared from a more commonly used diisocyanate, isophorone diisocyanate (IPDI). Dispersion characteristics and basic structure–property relationships of the cast films were determined. m‐TMXDI provided some advantages over IPDI in the preparations since its use gave lower prepolymer viscosities and better resistance to elevated temperatures. Films prepared from m‐TMXDI dispersions exhibited considerably lower values of Young's modulus and hardness and higher elongations at break than those prepared from IPDI‐based dispersions for analogous compositions, whereas differences in the average particle sizes or viscosities of the dispersions were only small. When the DMA content was varied, the dispersions and cast films of m‐TMXDI‐based systems showed similar changes as are known to occur in IPDI‐based systems: as the DMPA content was increased, the average particle size of the dispersions decreased and the viscosity increased, and for the cast films, the Young's modulus and tensile strength increased and the maximum elongation at break decreased. Changing the chain‐extension agent from hydrazine to 1,2‐ethylene diamine, to 1,2‐propylene diamine and had little effect on the particle size of the dispersions, but increased the Young's modulus and hardness of the respective cast films. Molar masses of the chain‐extended polymers were unexpectedly low. DSC analysis of cast films indicated that the degree of crystallisation of the soft or hard domains was low. © 2002 Society of Chemical Industry     

Polyurethane ionomer dispersions from a blocked aromatic‐diisocyanate prepolymer

Aqueous anionic blocked aromatic polyurethane prepolymers were synthesized by a prepolymer mixing process and their dispersions were obtained by adding water to the blocked prepolymer solutions. A series of prepolymers were prepared by using toluene 2,4‐diisocyanate, 4,4′‐diphenylmethane diisocyanate, polytetramethylene glycol, dimethylol propionic acid, methyl ethyl ketoxime and ε‐caprolactam. The aqueous dispersions were characterized by Fourier‐transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The particle sizes, viscosities, pH and storage stabilities of the dispersions were studied and compared. Some mechanical properties of the cast films obtained from the aqueous dispersions and the adhesive properties of the dispersions were also evaluated. Copyright © 2004 Society of Chemical Industry     

水性聚氨酯分散液的制备与性能研究

以含有磺酸盐基团的聚酯二元醇和异佛二酮二异氰酸酯（IPDI）为主要原料,以二羟甲基丙酸（DMPA）为亲水单体,制备了一组不同组成的水性聚氨酯分散液,经力学性能测定和差示扫描量热法（DSC）分析,研究了亲水单体含量、软段相对分子质量及磺酸盐基团含量对分散液及其胶膜性能的影响。结果表明：软段中磺酸盐基团含量及软段相对分子质量对分散液胶膜的热力学性能和胶黏剂的初粘强度都有影响。     

Effect of dicarboxylic acids on the performance properties of polyurethane dispersions

A series of low molecular weight linear polyester polyols were synthesized by using various diacids, neopentyl glycol, as a diol, and a trimethylol propane, as a branching monomer. Polyurethane dispersions were prepared primarily from isophorone diisocyanate, polyester polyol, and dimethylol propionic acid, as potential ionic center for water dispersibility, and were subsequently chain extended with ethylene diamine. The effect of polyester polyols based on variable diacids, on the physico‐chemical and thermal properties of polyurethane dispersions were evaluated by hardness, flexibility, impact resistance, solvent resistance, thermogravimetric analysis, and differential scanning calorimetry. Particle size was evaluated by particle size analyzer. It was observed that the number of alkylene groups present in the polyester polyol soft segment in addition to its molecular weight had a pronounced effect on the particle size, physico‐chemical, and thermal properties. With a proper selection of the soft segment, it is possible to fine‐tune properties of aqueous polyurethane dispersion coatings with respect to the final application. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation,mechanical properties of waterborne polyurethane and crosslinked polyurethane‐acrylate composite

The waterborne polyurethane (PU) prepolymer was first prepared based on isophorone diisocyanate, polyether polyol (NJ‐210), dimethylol propionic acid (DMPA), and hydroxyethyl methyl acrylate via in situ method. The crosslinked waterborne polyurethane‐acrylate (PUA) dispersions were prepared with the different functional crosslinkers. The chemical structures, optical transparency, and thermal properties of PU and PUA were confirmed by Fourier transform infrared spectrometry, ultraviolet–visible spectrophotometry, and differential scanning calorimetry. Some physical properties of the aqueous dispersions such as viscosity, particle size, and surface tension were measured. Some mechanical performances and solvent resistance of PUA films were systemically investigated. The experimental results showed that the particle sizes of the crosslinked PUA aqueous dispersions were larger than the PU and increased from 57.3 to 254.4 nm. When the ratios of BA/St, BA/TPGDA, and BA/TMPTA were 70/30, PUA films exhibited excellent comprehensive mechanical properties. The tensile strength and elongation at break of the film were 2.17 MPa and 197.19%. When the ratio of BA/St was 30/70, the film had excellent water resistance and was only 6.47%. The obtained PUA composites have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings, and wood finishes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of the hard-to-soft segment ratio on the adhesion of water-borne polyurethane adhesive

Three water-borne polyurethane dispersions were synthesised by the pre-polymer mixing process. Different hard segment contents in the polyurethanes were obtained by varying the diisocyanate/macroglycol (NCO/OH) molar ratio. A decrease in the NCO/OH ratio produced an increase in the mean particle size and in the pre-polymer viscosity, as well as a decrease in the molecular weight of the polyurethane. On the other hand, the lower the NCO/OH ratio, the more crystalline the polyurethane and the lower the resistance to flow at high temperature. Lower NCO/OH ratios improved the thermal degradation stability of the polyurethane. Finally, a high initial adhesion to PVC was obtained in all joints produced with the aqueous polyurethane dispersions and the final adhesion increased as the NCO/OH ratio in the water-borne polyurethane adhesive decreased.