Effect of Poly(dimethylsiloxane) Content on the Properties of Water-Borne Poly(urethane-urea)s Containing MDI

Low photo- and water-resistance is often cited as the problem of MDI-based WBPU. This study addressed this problem. Water-borne poly(urethane-urea)s (WBPUs) were synthesized using a pre-polymer mixing process from 4,4'-methylenebis(phenyl isocyanate)(MDI)/4,4-dicyclohexylmethyl diisocyanate (H₁₂MDI) (15/85 mole %)/dimethylol propionic acid (DMPA)/ethylene diamine (EDA)/triethylamine (TEA) with different poly(propylene glycol) (PPG, M _n = 2000)/hydroxyl terminated poly(dimethylsiloxane) (PDMS, M _n = ～550) molar ratios. This study highlights the effect of PDMS content on the inherent viscosity, hydrogen-bonding, storage modulus, tan δ peak intensity, tensile modulus/strength, elongation (%) at break, water swelling (%), contact angle, and the yellowness index of WBPUs containing MDI. The mechanical properties (strength/modulus), water-resistance and photo-resistance of WBPUs containing MDI increased significantly in proportion to the PDMS content. These results indicate the potential for using multi-performance WBPU with PDPS for WBPU coatings.     

Synthesis and properties of waterborne poly(urethane urea)s containing polydimethylsiloxane

To obtain flexible waterborne poly(urethane urea) (WBPU) coatings with functionalities such as shape recovery and water resistance, we synthesized a series of WBPUs by a prepolymer mixing process from hexamethylene diisocyanate, polyol, 2,2‐bis(hydroxymethyl) propionic acid, ethylenediamine, and triethylamine with polyol blends [hydroxyl‐terminated polydimethylsiloxane (PDMS) with a number‐average molecular weight of ≈ 550 and poly(tetramethylene oxide) glycol (PTMG) with a number‐average molecular weight of 650] of different molar ratios. The effects of the PDMS content in PDMS/PTMG on the dynamic thermal and mechanical properties, hardness, tensile properties, water resistance (water absorption, contact angle, and surface energy), and shape‐memory properties of WBPU films were investigated. As the molar percentage of PDMS in WBPUs increased, the storage modulus, tensile strength and modulus, elongation at break, hardness, and shape‐retention rate (30–15%) decreased; however, the water resistance and shape‐recovery rate (80–90%) increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of polyurethane‐urea‐based liquid bandage materials

To obtain ideal liquid bandage polymer materials, a series of polyurethane‐urea dispersions were synthesized from 4,4′‐diisocyanato dicyclohexylmethane (H₁₂MDI) and ethylene diamine with different molar ratio of polyol blend [polyethylene glycol (PEG, M_n = 2000 g/mol)/hydroxy terminated poly(dimethylsiloxane) (PDMS, M_n = ～ 550 g/mol)] and acetone/ethanol as a solvent. The effect of PDMS content in PEG/PDMS on the viscosity, mechanical properties, water contact angle/surface energy, insolubility in water (%), water absorption (%), equilibrium water content (%), and water vapor transmission rate (g m^?2 day^?1) of polyurethane‐urea films was investigated. As PDMS content increased, the water contact angle, insolubility in water, and tensile strength/elastic recovery of film sample increased; however, the surface energy, water absorption (%), equilibrium water content (%), and water vapor transmission rate (g m^?2 day^?1) of film sample decreased. By a wound‐healing evaluation using a full‐thickness rat model experiment, it was found that a wound covered with a typical polyurethane‐urea liquid bandage film (PD2 sample) was filled with new epithelium without any significant adverse reactions. These results suggest that the polyurethane‐urea‐based liquid bandages (samples: PD2 and PD3) prepared in this study may have high potential as new wound dressing materials, which provide and maintain the adequate wet environment required to prevent scab formation and dehydration of the wound bed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Properties of waterborne polyurethane‐fluorinated marine coatings: The effect of different types of diisocyanates and tetrafluorobutanediol chain extender content

Three series of waterborne polyurethane‐ (WBPU) fluorinated coatings were prepared with single aliphatic (4,4′‐dicyclohexylmethane diisocyanate, H₁₂MDI), aromatic (4,4′‐diphenylmethane, MDI) and a mixture of aliphatic and aromatic diisocyanates (1 : 1). Different contents of 2,2,3,3‐tetrafluoro1,4‐butanediol (TFBD) as a chain extender were used in the WBPU coatings. The fluoro‐enriched surface of the WBPU coatings was obtained with a combination of a high TFBD content (8.77 mol %) as well as the aliphatic or mixed diisocyanates. The tensile strength, Young's modulus, elongation at break (%) and adhesive strength were characterized with respect to the TFBD contents. The mechanical strength and adhesive strength increased with increasing TFBD content in the three series. In artificial salt water, the maximum adhesive strength of WBPU was observed for this coating, which was achieved by TFBD bonded H₁₂MDI of mixed diisocyanates with a higher TFBD content (8.77 mol %). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39905.     

Polyols from epoxidized soybean oil and alpha hydroxyl acids and their adhesion properties from UV polymerization

Two types of biobased polyols, ESOGA and ESOLA, were synthesized from epoxidized soybean oil (ESO) with glycolic acid (GA) and lactic acid (LA), respectively, using a solvent-free/catalyst-free method. An ESO epoxy conversion rate of over 93% was achieved for both polyols. ESOGA has a weight-/number-average molecular weight (M_w/M_n) of 27,700/3900 g/mol and average hydroxyl functionality (f_OH) of 12.9, and ESOLA has M_w/M_n of 8800/3000 g/mol and f_OH of 11.7. The structures of the polyols were further characterized with Fourier transform infrared spectroscopy and ¹H-nuclear magnetic resonance. Rheology and thermal properties were studied with a rheometer and a differential scanning calorimeter. The polyols were polymerized with ESO to adhesive polymers using UV light in the presence of cationic photoinitiator. The curing rate decreased as the amount of polyol increased for resins based on ESOGA and ESOLA (EGA and ELA). With the same amount of polyol, ELA resins cured faster than EGA resins. The peel strength and tack of EGA and ELA adhesives increased significantly as the ratio of polyol in the resin increased. ELA exhibited obviously higher peel strength and tack than EGA with the same amount of polyol. All resin tapes exhibited high static shear values (20,000+min). Overall, both ESOGA and ESOLA exhibited great potential as polyols for pressure-sensitive adhesive applications.     

Effect of copolymerizing fluorine‐bearing monomers on the relationship among internal structure,gas permeability,and transparency in copolymer networks composed of methacrylates and siloxane macromers

To clarify the effect of the type of acrylic monomer and the molecular weight (M_n) of polydimethylsiloxane (PDMS) on the relationship among the internal structure, oxygen permeability coefficient [P(O₂)] and transparency, crosslinked copolymers were prepared with two different acrylic monomers : methyl methacrylate (MMA) and trifluoroethyl methacrylate (TFEMA). PDMS macromers with M_n of 1700, 3300, 4700, and 7800 g/mol were used. DSC measurements suggested that all constituent phases were insoluble with each other. The M_n of PDMS affected both the light transmittance and P(O₂). The relationship between the M_n and P(O₂) over the low M_n range (1700 and 3300 g/mol), and the calculated PDMS domain size ratio, were found to support the [M_n]^2/3 rule into the crosslinked copolymer. Furthermore, a 3300 g/mol M_n copolymer became transparent when the amount of PDMS was greater than PMMA. In addition, copolymerization with TFEMA drastically affected those properties, and this effect was much greater than the effect of the PDMS M_n. To clarify the mechanism of P(O₂) improvement induced by TFEMA copolymerization, calculations on the relationship among the P(O₂), PDMS volume fraction, and morphology model were performed, and some properties such as solubility parameters should play important roles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of MDI/H12MDI‐based water‐borne poly(urethane‐urea)s—Effects of MDI content and radiant exposure

Water‐borne poly(urethane‐urea)s (WBPUs) were prepared by a prepolymer mixing process using aromatic diisocyanate (MDI, 4,4′‐diphenylmethane diisocyanate)/aliphatic diisocyanate (H₁₂MDI, 4,4′‐methylenebis cyclohexyl isocyanate), polypropylene glycol (PPG, M_n = 1000), dimethylol propionic acid, and ethylene diamine as a chain extender, and triethylamine as a neutralizing agent. The effect of MDI on the molecular weight, chemical structure, dynamic thermo, and tensile properties of WBPUs was investigated. The yellowness index (YI, photo‐oxidation behavior) change of WBPUs under accelerated weathering exposure was also investigated. The WBPUs containing higher MDI content showed lower molecular weight, which verified the participation of some high reactive isocyanate groups of MDI into side reaction instead of chain growing reaction. As the MDI content increased, the storage modulus and tensile modulus/strength of WBPUs film increased, and their glass transitions of soft segments (T_gs) and hard segments (T_gh) were shifted to higher temperature. The intensity of tan δ peak of all three samples increased with increasing radiant exposure. The YI of H₁₂MDI‐based WBPU sample (WBPU‐0) was not occurred. The YI of WBPUs containing MDI increased with increasing MDI content and radiant exposure. However, the YI of sample WBPU‐25 containing 25 mol % of MDI at 11.3 MJ/m² (radiant exposure) was 6.6 which is a permissible level for exterior applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mesomorphic polyblends of poly(p-phenylene terephthalamide) and poly(4,4′-terephthanilide adipamide)

A simultaneous dissolution of two lyotropic polyamides, poly(p-phenylene terephthalamide) (PPTA) and poly(4,4′-terephthanilidc adipamide) (PTAd), in a concentrated H₂SO₄ (1 to 1.5% wt) produced an isotropic single phase solution. The crystallinity of PPTA/PTAd blends confirmed formation of a mesomorphic polyblend to the molecular level. With increasing concentration, solutions of these PPTA/PTAd blends in 100% H₂SO₄ showed a sequential phase change typical of a single lyotropic polymer. Further, the ternary solution exhibited a wider biphase range than both binary solutions of PPTA/100% H₂SO₄ and PTAd/100% H₂SO₄. Dry-jet wet spinning of anisetropic solution of this ternary composition with a PTAd weight fraction less than 0.5 enabled us to obtain PPTA/PTAd blend fibers. Including a PTAd weight fraction of 0.1-0.15 reduced both the orientation angle and fibrillation. The particular blend fiber with a PTAd weight fraction of 0.15 exhibited a synergistic effect on the mechanical properties.     

Effect of polyisocyanate hardener on adhesive force of waterborne polyurethane adhesives

A series of waterborne polyurethane (WBPU)/hardener adhesives were obtained from mixing of WBPU containing different types of polyol as a soft segment with aliphatic and aromatic polyisocyanates hardeners. By characterization of allophanate and biuret bonds formed from the reaction of hardener NCO with urethane/urea groups of WBPU using ¹HNMR spectroscopy. It was found that the optimum number ratio (molar ratio) of NCO group of hardener to urethane/urea group of WBPU that shows the highest adhesion force was depended on the type of hardener (aliphatic/aromatic polyisocyanate) and dimethylol propionic acid (DMPA) content (total content of urethane/urea groups); however independent of the type of soft segment (polyol) of WBPU. The optimum number ratio (molar ratio) of NCO group of aromatic polyisocyanate hardener to urethane/urea was higher than that of aliphatic hardener to achieve the highest adhesion force of WBPU. The adhesive force increased with increasing hardener content up to the optimum point and then decreased. Poly(tetramethylene adipate glycol) (PTAd) based WBPUs with aliphatic hardener show higher adhesive force than Poly(tetramethylene oxide glycol) (PTMG) and aliphatic hardener‐based WBPUs at the optimum number ratio (molar ratio) of NCO group of hardener to urethane/urea group of WBPU. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3663–3669, 2007     

Synthesis and characterization of waterborne polyurethane adhesives containing different amount of ionic groups (I)

A series of waterborne polyurethanes (WBPU) containing different amount of 2,2‐bis(hydroxymethyl) propionic acid (DMPA) were synthesized using prepolymer mixing process. Relationships between the DMPA content and physical, mechanical, and thermal properties as well as adhesive behavior at different condition were investigated. Stable aqueous dispersions of WBPU were obtained when the DMPA content was more than 10 mol %. At higher DMPA content, the particle size of the WBPU dispersion was lower but the viscosity of the dispersion was higher. Water swelling and tensile strength of the films increased with increasing of DMPA content. The optimum adhesive strength of WBPU adhesives was found to be depended on the DMPA content, pressing temperature, and pressure on adhesion process. The adhesive strength of WBPU adhesives increased with increasing DMPA content. The optimum pressing temperature decreased with increasing DMPA content. The adhesive strength of WBPU adhesives increased with increasing pressure up to 15 kg f/cm² and then leveled off. The optimum pressing temperature of WBPU adhesives samples containing 24.02, 22.05, and 17.05 mol % DMPA was about 100, 120, and 140°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5684–5691, 2006     

Nitroxide‐mediated synthesis of styrenic‐based segmented and tapered block copolymers using poly(lactide)‐functionalized TEMPO macromediators

Poly(styrene)‐poly(lactide) (PS‐PLA), poly (tert‐butyl styrene)‐poly(lactide) (PtBuS‐PLA) diblocks, and poly(tert‐butyl styrene)‐poly(styrene)‐poly(lactide) (PtBuS‐PS‐PLA) segmented and tapered triblocks of controlled segment lengths were synthesized using nitroxide‐mediated controlled radical polymerization. Well‐defined PLA‐functionalized macromediators derived from hydroxyl terminated TEMPO (PLA_T) of various molecular weights mediated polymerizations of the styrenic monomers in bulk and in dimethylformamide (DMF) solution at 120–130°C. PS‐PLA and PtBuS‐PLA diblocks were characterized by narrow molecular weight distributions (polydispersity index (M_w/M_n) < 1.3) when using the PLA_T mediator with the lowest number average molecular weight M_n= 6.1 kg/mol while broader molecular weight distributions were exhibited (M_w/M_n = 1.47‐1.65) when using higher molecular weight mediators (M_n = 7.4 kg/mol and 11.3 kg/mol). Segmented PtBuS‐PS‐PLA triblocks were initiated cleanly from PtBuS‐PLA diblocks although polymerizations were very rapid with PS segments ～ 5–10 kg/mol added within 3–10 min of polymerization at 130°C in 50 wt % DMF solution. Tapering from the PtBuS to the PS segment in semibatch mode at a lower temperature of 120°C and in 50 wt % DMF solution was effective in incorporating a short random segment of PtBuS‐ran‐PS while maintaining a relatively narrow monomodal molecular weight distribution (M_w/M_n ≈ 1.5). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Transmission electron microscopic observations of the multilevel microstructure of crosslinked copolymers with methacrylates and siloxane macromers by a radically polymerizable tuning approach

We investigated by Transmission Electron Microscopy (TEM) the morphologies of crosslinked copolymers from methacrylate monomers from methylmethacrylate (MMA) and trifluoroethylmethacrylate (TFEMA), polydimethylsiloxane (PDMS) macromers with molecular weight (Mn) of 1,700 and 4,700 g/mol, and crosslinker. Depending on the PDMS content, we observed, spherical PMMA islands in which small PDMS domains were dispersed, PMMA continuous phase, closely packed PTFEMA islands, and homogeneously dispersed PDMS domains were observed with low or middle magnification. Fine observation at 100,000‐fold magnification revealed the “fundamental” common size domain, which was determined by the M_n value of the PDMS macromer. Thus we found two microstructure types: (1) a “fundamental domain” due to the M_n of the PDMS macromer, and (2) an aggregated domain. The former was constant under all conditions, but the latter was affected by the comonomer and its ratio. The present results are essential in understanding the chemical and physical characteristics of crosslinked copolymers from PDMS macromers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Properties of Waterborne Polyurethane Adhesives: Effect of Chain Extender and Polyol Content

A series of waterborne polyurethane (WBPU) adhesives were prepared with various ratios of polyol, poly(tetramethylene oxide glycol) (PTMG), and chain extender, ethylene diamine (EDA), at a fixed content of diisocyanate, 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI) and hydrophilic agent, 2,2-dimethylol propionic acid (DMPA). WBPU adhesives were characterized by IR and ¹H-NMR spectroscopies, X-ray diffraction (XRD) and gel permeation chromatography (GPC). It was found that the extent of hydrogen bonds between hard–hard segment (i.e., hydrogen bonds between the NH and carbonyl groups) increased with increasing chain extender content (decreasing polyol content). Moreover, the disordered hydrogen bond of carbonyl group (hydrogen bond of urethane groups in the interfacial region) increased with increasing chain extender content (decreasing polyol content). The cyclic urea and allophanate group, which are attributed to the side reaction and cross-linking reaction, respectively, were found above a molar ratio 0.17 of chain extender to diisocyanate. The adhesive strength was maximum with 0.95 wt% and 63.10 wt% chain extender and soft segment (PTMG), respectively (H2 sample) at room temperature for the WBPU adhesive. However, with increasing application temperature the adhesive strength decreased for all samples.     

Contribution of soft segment entanglement on the tensile properties of silicone–urea copolymers with low hard segment contents

Novel, segmented thermoplastic silicone–urea (TPSU) copolymers based on rather high molecular weight aminopropyl terminated polydimethylsiloxane (PDMS) soft segments (<M_n> 10,800 and 31,500 g/mol), a cycloaliphatic diisocyanate (HMDI) and various diamine chain extenders were synthesized. Copolymers with very low urea hard segment contents of 1.43–14.4% by weight were prepared. In spite of very low hard segment contents, solution cast films showed very good microphase separation and displayed reasonable mechanical properties. Tensile strengths of TPSU copolymers showed a linear dependence on their urea hard segment contents, regardless of the structure of the diamine chain extender used. The modulus of silicone–urea copolymers is dependent on the urea concentration, but not on the extender type or PDMS molecular weight. When silicone–urea copolymers with identical urea hard segment contents were compared, copolymers based on PDMS-31,500 showed higher elongation at break values and ultimate tensile strengths than those based on PDMS-10,800. Since the critical entanglement molecular weight (M_e) of PDMS is about 24,500 g/mol, these results suggest there is a significant contribution from soft segment chain entanglement effects in the PDMS-31,500 system regarding the tensile properties and failure mechanisms of the silicone–urea copolymers.     

UV-shielding by a polyurethane/f-Oil fly ash-CeO2 protective coating

A waste material called oil fly ash (OFA) was acid-functionalized, yielding f-OFA-COOH, which was then reacted with cerium oxide (CeO₂) to make CeO₂-functionalized OFA, or f-OFA-CeO₂. Pristine OFA and f-OFA-CeO₂ were used to make waterborne polyurethane (WBPU) dispersions, referred to as WBPU/OFA and WBPU/f-OFA-CeO₂, respectively, with defined OFA and f-OFA-CeO₂ content. All the dispersions were applied to mild steel as organic coatings to evaluate their protective properties, such as their hydrophobicity, adhesive strength and UV-shielding resistance. These protective properties varied based on the OFA and f-OFA-CeO₂ content. The highest water contact angle, minimum water swelling and maximum adhesive strength were found using WBPU/f-OFA-CeO₂-20 coating (using 2.00 wt% f-OFA-CeO₂), which also showed the maximum ultraviolet (UV) absorption via UV–vis spectroscopy analysis. This UV shielding result also matched field test results, as that coating was found to exhibit the lowest UV degradation near a marine atmosphere, as shown by X-ray photoelectron spectroscopy (XPS) analysis. The least affected hydrophobicity was also recorded for the sample with the WBPU/f-OFA-CeO₂-20 coating.     

Effect of trifunctional cross-linker triallyl isocyanurate (TAIC) on the surface morphology and viscoelasticity of the acrylic emulsion pressure-sensitive adhesives

Acrylic pressure sensitive adhesive (PSA) latexes were synthesized via a starved monomer-seeded semi-continuous emulsion polymerization process with butyl acrylate (BA), methyl methacrylate, acrylic acid (AA), 2-hydroxyethyl acrylate and trifunctional cross-linker, triallyl isocyanurate (TAIC). Influences of TAIC on the resultant latex and PSA properties were comprehensively investigated. The results indicated that latex particle size was independent of the amount of TAIC in the pre-emulsion feed, while the viscosity of the latex increased remarkably with TAIC content increased. Thermal gravimetric analysis result showed that the thermal stability of the polymers was improved significantly with the addition of TAIC. Besides, with the increase in TAIC content, gel content of the polymer increased significantly, while molecular weight between cross link points (M_c) and sol molecular weight (M_w, M_n) of the polymer decreased remarkably. Moreover, for the cross-linked adhesive film, the shear strength was improved greatly while at the sacrifice of loop tack and peel strength, when compared with the uncrosslinked counterparts. Finally, dynamic mechanical analysis and atomic force microscopy were also used to evaluate the viscoelastic properties and surface morphology of the acrylic emulsion PSA film, respectively.     

Synthesis of block copolymers from PDMS macroinitiators

The synthesis of polystyrene‐b‐polydimethylsiloxane‐b‐polystyrene (PSt‐b‐PDMS‐b‐PSt) copolymers is described. Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide resulting in the PDMS macroinitiators. The terminal alkyl bromide groups were then used as initiators for atom transfer radical polymerization (ATRP) to produce block copolymers. Using this technique, triblock copolymers consisting of a PDMS centre block and polystyrene terminal blocks were synthesized. ATRP of St from those macroinitiators showed linear increases in M_n with conversion, demonstrating the effectiveness of ATRP to synthesize a variety of inorganic/organic polymer hybrids. Copyright © 2004 Society of Chemical Industry     

Synthesis and properties of waterborne polyurethane adhesives: effect of chain extender of ethylene diamine,butanediol, and fluoro-butanediol

Waterborne polyurethane (WBPU) adhesives were prepared using poly(tetramethylene oxide glycol), 4,4’-dicyclohexylmethane diisocyanate (H₁₂MDI), hydrophilic agent dimethylol propionic acid and chain extender of 2,2,3,3-tetrafluoro-1,4-butanediol (TFBD), ethylene diamine (EDA), and 1,4-butanediol. All three chain extenders have been used as single and mixed (different ratio) content during synthesis, and the effect of chain extender and their content to the properties of tensile strength, Young’s modulus, water swelling (%), and adhesive strength was investigated. The adhesive strength value was higher using EDA as a single-chain extender; however, the potentiality of adhesive strength under water was improved using mixed-chain extenders of EDA and TFBD in WBPU adhesives. The maxima potentiality was observed with 6.31 mole% TFBD and 2.10 mole% EDA in WBPU adhesives.     

Synthesis and properties of crystalline dicarboxylated poly(L‐lactic acid) prepolymers

Crystalline dicarboxylated poly(L ‐lactic acid)s (dcPLLAs) with number‐average molecular weights (M_n's) of 10³ to 10⁴ g/mol were synthesized via the melt polycondensation of L ‐lactic acid (LLA) in the presence of succinic anhydride (SAD), with tin(II) chloride and toluene‐4‐sulfonic acid as binary catalysts. They were characterized by end‐group titration, ¹H‐NMR, differential scanning calorimetry, and wide‐angle X‐ray diffraction. The terminal COOH percentage reached over 98%, and the molecular weight could be controlled by the molar ratio of LLA to SAD. The thermal behaviors depended on the molecular weight. The poly(L ‐lactic acid)s (PLLAs) crystallized slowly for M_n ≤ 2000 but quickly for M_n ≥ 4000. The crystallinity increased from 27 to 40% when M_n grew from 4000 to 10,000. With comparison to ordinary PLLA, the dcPLLA had the same crystallization structure but a slightly lower crystallizability. The glass‐transition temperature was clearly higher than that of amorphous dcPLLAs. With a controllable molecular weight, high COOH percentage, and crystallinity, the dcPLLA with M_n ≥ 4000 appeared to be a suitable prepolymer for the preparation of high‐molecular‐weight crystalline PLLA via chain extension. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Glycolyzed poly(ethylene terephthalate) waste and castor oil-based polyols for waterborne polyurethane adhesives containing hexamethoxymethyl melamine

Glycolysis of poly(ethylene terephthalate) (PET) waste using different molar ratio of poly(ethylene glycol) (PEG400), was used to produce saturated hydroxyl-functional polyester polyols with castor oil (CO) by transesterification process. The waterborne polyurethane (WBPU) adhesives were synthesized from these saturated polyester polyols, isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA), and hexamethoxymethyl melamine (HMMM) as cross-linking agent by a conventional prepolymer process. The glycolyzed polyols and polyester polyos formations were characterized using Fourier transform infrared spectroscopy (FTIR) and the molecular weights were determined using gel permeation chromatography (GPC). The cross-linking reaction between WBPU and HMMM was verified using FTIR and ¹H NMR analysis. Thermal properties were investigated by thermogravimetric analysis (TG). Thermal stability of cross-linked WBPU significantly increased with decreasing castor oil content in the process of transesterification to obtain polyester polyol as a soft segment. The T_15% and T_50% (the temperature where 15 and 50% weight loss occurred) of WBPU increased with the decreasing of castor oil content in the obtained polyester polyols, caused by the steric hindrance of polyester polyol with higher castor oil content, in the process of cross-linking reactions with HMMM. The physico-mechanical properties of WBPU, such as hardness, adhesion test, and gloss of the dried films were also determined considering the effect of participation of HMMM in cross-linking reactions with polyurethane, on coating properties.