Characterization of canola oil based polyurethane wood adhesives

A novel bio-based poly (ether ester) polyol containing both primary and secondary functional groups was synthesized from canola oil using a low cost and efficient procedure. In this work, use of the new canola oil derived polyol for the production of polyurethane (PU) adhesives was demonstrated. The canola oil based PU adhesives had similar or better adhesive properties in terms of lap shear strength than three commercial PU adhesives. The effect of NCO/OH ratio and temperature on adhesive characteristics on wood bonding was also evaluated by lap shear tests. It was found that the use of an elevated curing temperature (i.e. 100 °C), as well as optimized NCO/OH molar ratio (higher than 1.5/1.0), improved the wood adhesive properties. The overall chemical resistance of bio-based PU adhesives to cold water, acid and alkali was comparable to that of commercial PU adhesives whilst its resistance to hot water was superior.     

Synthesis of Polyurethane Acrylate and Application to Ultraviolet-Curable Pressure-Sensitive Adhesive

Synthesis of polyurethane acrylates (PUA) using dimer acid-based polyester diol and hydrogenated castor oil (HCO) and preparations of the UV-curable pressure-sensitive adhesive (PSA) were reported. The effect of hydroxyl from dimer acid polyester diol/hydroxyl from HCO ratio (OH_Diol/OH_HCO), hydroxyl from both HCO and DAPD/2-hydroxyethyl acrylate ratio (OH_Polyol/_HEA), and tackifying resin/PUA ratio on the dynamic viscoelastic properties and performance of UV-cured PSA were investigated. The study revealed that, with OH_Diol/OH_HCO and OH_Polyol/_HEA increased, the storage modulus (G′), the loss modulus (G″), and complex viscosity (Eta?) of UV-cured PSA increased, and so did the corresponding holding power (HP). Peeling strength, however, decreased. As increasing the tackifying resin/PUA ratio, G′, G″ and Eta? decreased, and so did HP, whereas the peeling strength increased. Catalysts affected the dynamic properties and the performance of PSA. In contrast with PSA corresponding to dibutyltin dilaurate (DBTDL), the PSA corresponding to organic bismuth (OB) had higher dynamic modulus, complex viscosity, and holding power, but lower peeling strength.     

Synthesis of polyurethane acrylates by hydrogenated castor oil and dimer‐based polyester diol and study on pressure‐sensitive adhesive

Synthesis of polyurethane acrylate (PUA) and preparation of the UV‐cured pressure‐sensitive adhesives (PSA) are reported. Molecular weight (M_w) (by gel permeation chromatography) and viscosity (η*) of PUA were measured. Characterization of PUA and PSA before and after UV‐curing was made by FTIR. Increase of the hydroxyls from hydrogenated castor oil/hydroxyls from dimer‐based polyester diol (OH_HCO/OH_Diol) ratio decreased the M_w and η* value of PUA. Dynamic viscoelastic properties (by dynamic rheological spectrometer) and performance of the UV‐cured PSA were also studied. Increase of the OH_HCO/OH_Diol ratio increased the storage modulus (G′), the loss modulus (G″), and complex viscosity (Eta*) of the UV‐cured PSA, which, in turn, enhanced holding power and shear adhesion failure temperature (SAFT) and yet decreased peeling strength. Substitution of OB for DBTDL depressed the M_w and η* value of PUA, while the G″ and Eta* values of the UV‐cured PSA were elevated, which, in turn, increased the holding power and SAFT and yet depressed the peeling strength. Elevation of the tackifying resin content depressed the G′, G″, and Eta* values of the cured PSA and yet increased glass transition temperatures (T_g) of PSA, measured by differential scanning calorimetry. Peeling strength of PSA elevated as increasing the tackifying resin, while the holding power and SAFT fell. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1814–1821, 2005     

Effects of NCO:OH ratio on the mechanical properties and chemical structure of Kraft lignin–based polyurethane adhesive

ABSTRACT

This work aimed to evaluate the influence of the aliphatic and aromatic hydroxyl level on the polyurethane adhesive property and chemical structure. This adhesive was obtained through the reaction of technical Kraft lignin (TKL) as polyol with diphenylmethane diisocyanate (MDI). Thus, lignopolyurethane adhesives were obtained with NCO:OH ratios of 0.8:1.0, 0.9:1.0, 1.0:1.0, 1.1:1.0, and 1.2:1.0. Initially only the TKL aliphatic hydroxyl level was taken into consideration in the stoichiometry in order to define the mass ratio between MDI and polyol. Subsequently, lignopolyurethane adhesive was obtained using the same NCO:OH ratios considering TKL total hydroxyls’ level, and aromatic and aliphatic hydroxyls. The chemical structures of the synthesized adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹³C NMR). The mechanical property of the adhesively bonded joints, comprising wood substrates and synthesized adhesives, was measured using single lap shear tests. Results illustrated that by increasing the NCO:OH ratio, there is an increase in the free isocyanate content leading to higher shear strength values. Higher free isocyanate content leads to MDI dimer formation in the lignopolyurethane structure.     

Durability of green polyurethane adhesive bonded aluminum alloy in dry and hydrothermal ageing conditions

Polyurethane (PU) adhesives were prepared from the reaction of polycaprolactone (PCL) polyols based on palm kernel oil based polyesteramide (PPKO) with an aromatic and cycloaliphatic diisocyanate. Four different formulations of PU adhesives were prepared by varying the NCO : OH ratio, in order to investigate the effects of NCO : OH ratios on adhesion strength. The adhesive strength of metal–metal bonding both in dry and hydrothermal ageing—was determined by single lap shear joint testing. The resistance to hydrolysis of the PU adhesives was determined by performing water absorption tests. The water absorption test samples suggested that the durability of the adhesives correlated to lower water absorption due to higher NCO content. The correlation between the crosslinking of the PU network and adhesive strength was also studied by performing swelling tests. The higher NCO content showed that, the higher crosslink density of PUs led to higher cohesion and adhesion strengths. PU1.7 showed optimal properties in terms of durability and resistance to hydrolysis, whereas PU2.0 revealed deterioration in durability and resistance to hydrolysis due to the presence of greater micro‐voids content in the PU2.0 matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41151.     

Preparation of polyurethane wood adhesives by polyols formulated with polyester polyols based on castor oil

The aim of this work was the synthesis of polyester polyols from renewable sources as one of the important compounds of polymeric polyurethane (PU) adhesives. The polyester polyols were synthesized by condensation polymerization of different dicarboxylic acids with castor oil and the reaction conditions were in agreement with green chemistry principles. The preparation of PU wood adhesives was carried out by the reaction of each obtained polyester polyol with 4, 4′-diphenylmethane diisocyanate (MDI). The adhesive performance was improved by mixing the obtained polyester polyols with polypropylene glycol (PPG 400) and butanediol (BD). Different NCO/OH ratios were used to obtain adhesives with appropriate properties. The structures of the synthesized polyesters and adhesives were characterized by FTIR, thermogravimetric analysis (TGA) and lap shear strength values were also determined in various conditions such as cold water, hot water, acid and alkali solutions.     

Synthesis and characterization of lignin-polyurethane based wood adhesive

The present work aims to evaluate the influence of addition of kraft lignin in moisture curing polyurethane (PU) based wood adhesives. The mechanical, thermal properties and chemical structure of the adhesive were studied. The lignin-PU adhesives were obtained by replacing 1%, 3% and 5% of polypropylene glycol (PPG) by Kraft lignin and further reacted with monomeric diphenylmethanediisocyanate (MDI). The aliphatic hydroxyl level of lignin was not taken into consideration in the stoichiometry, in order to find out effect on % free NCO of the final product. The chemical structure of the synthesized lignin-PU adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR). The lap shear strength of the adhesives was tested by bonding canarium wood substrates. The results illustrated that by increasing the weight % of lignin in such lignin-PU adhesives, a decrease in the free isocyanate content, leading to slower setting time but higher shear strength values, were observed. Similarly, the thermal properties of lignin-PU adhesive were also studied, showing an increase in glass transition temperature (Tg) with increase in lignin content.     

Eco-economical polyurethane wood adhesives from cellulosic waste: Synthesis, characterization and adhesion study

This study reports the preparation of polyurethane adhesives using polyols obtained from cellulosic waste and detailed study on its adhesive strength in wood joints. Keeping in view the environmental hazards related to the huge paper-waste generation across the world, low-viscosity polyols have been prepared using magazine paper waste and vegetable oils with different physicochemical properties and were used to prepare two-component polyurethane adhesives for wood bonding. Polyurethane was analyzed by FTIR spectroscopy and TGA was used for the analysis of thermal properties. The adhesive strength was measured and compared with commercially available adhesives under different environmental conditions. The synthesized adhesive with NCO/OH ratio of 1.2 and curing time of 5 days was found to be superior to the commercial adhesives Fevicol™ and Araldite™ when compared simultaneously for the single-lap shear strength in different environmental conditions.     

Experimental and numerical analysis of single lap bonded joints: Epoxy and castor oil PU-glass fibre composites

ABSTRACT

Currently, there is a growing concern for the environment. Several studies of new materials to reduce environmental impact have been carried out by different research groups, and many companies have replaced parts made of fossil sources by renewable materials. The use of polyurethane (PU) derived from castor oil as a matrix for composite materials and adhesives is one example. Hence, the present work aims to compare the numerical and experimental analyses of castor oil PU and epoxy resin not only as a matrix of composite materials, but also as an adhesive of bonded joints. The joint coupons were manufactured by using castor oil PU-glass fibre and epoxy-glass fibre as adherents, which were bonded by epoxy or castor oil PU. Thus, four combinations of adherents and adhesives were investigated. Specimens with identical geometry were used in all tests, which were based on guidelines for single lap bonded joints. Computational simulations via Finite Element Method were performed for predictions of the adhesive layer stresses and strength. In addition, a material model is proposed to predict the failure of the adhesive layer. The experimental and numerical results showed that PU derived from castor oil has good mechanical performance, making this material a feasible alternative for bonded joints, mostly nowadays when environment is a major concern.     

Synthesis and properties of polyurethane wood adhesives derived from crude glycerol-based polyols

Crude glycerol, a waste stream of the biodiesel production process, is low-cost renewable feedstock for the production of chemicals and polymers. In this study, polyurethane (PU) adhesives were synthesized from crude glycerol-based polyols (CG-based polyols) for wood bonding applications. Effects of different variables, including hydroxyl values of CG-based polyols, chain extenders, and the molar ratio of NCO/OH on the properties of PU adhesives were investigated. The chemical structures of PU adhesives were characterized, and their thermal, mechanical, and chemical resistance properties were evaluated. The experimental results indicated that an increase of the NCO/OH molar ratio (1.3) substantially improved bonding strength by up to 38 MPa. Higher thermal stability and stronger chemical resistance to hot and cold water and to alkali and acid solutions were observed comparing to vegetable oil-based adhesives. However, the effect of the hydroxyl value of polyols on bonding strength was not significant. Additionally, bond strength of crude glycerol-based PU adhesives was comparable to that of some commercial PU wood adhesives. All these properties demonstrated the potential of CG for PU wood adhesive applications, particularly for fast-curing uses.     

Rubber solution adhesives for wood-to-wood bonding

Rubber solutions were prepared and used for bonding wood pieces. The effect of the variation of chlorinated natural rubber (CNR) and phenolformaldehyde (PF) resin in the adhesive solutions on lap shear strength was determined. Natural rubber and neoprene-based adhesive solutions were compared for their lap shear strength. The storage stability of the adhesive prepared was determined. The change in lap shear strength before and after being placed in cold water, hot water, acid, and alkali was tested. The bonding character of these adhesives was compared with different commercially available solution adhesives. The room-temperature aging resistance of wood joints was also determined. In all the studies, the adhesive prepared in the laboratory was found to be superior compared to the commercial adhesives. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1185–1189, 1998     

Polyurethane wood adhesive from palm oil-based polyester polyol

Polyurethane (PU) adhesives for wood bonding were prepared from palm oil-based polyester polyol in a solventless condition that reduces the risk of volatile organic compounds to human health and the environment. The polyester polyol was synthesized from epoxidized palm olein prior to reacting with polymeric 4,4′-methylene diphenyl diisocyanate (pMDI) and toluene 2,4-diisocyanate (TDI) to produce wood-bonding PU adhesives. The effect of glycerol cross-linker, dibutyltin dilaurate catalyst and NCO/OH ratio on lap shear strength and pot life of the PU adhesives were studied. The green strength of the PU adhesives was achieved on day 4 for TDI-based adhesives and day 5 for pMDI-based adhesives. The newly formulated PU adhesives have superior chemical resistance in cold water, hot water, acidic medium and alkaline medium by only showing light deterioration (2–8%) in lap shear strength. The PU adhesives prepared from pMDI exhibited higher lap shear strength and thermal stability as compared to adhesives prepared from TDI adduct. Both adhesives have improved mechanical performance (two folds higher in lap shear strength) as compared to commercial wood bonding adhesives.     

Synthesis and characterization of polyesteramide based hot melt adhesive obtained with dimer acid,castor oil and ethylenediamine

Polyesteramide based hot melt adhesives were synthesized from high purity dimer acid (composition: ~1% trimer acid, ~98% dimer acid and ~1% linoleic acid), ethylenediamine and castor oil. The effect of castor oil content on the properties of the hot melts, such as thermal properties: glass transition temperature (T_g), melting temperature (T_m), enthalpy of melting (H_m), crystallization temperature (T_c), enthalpy of crystallization (H_c) and softening point (T_s); mechanical properties: tensile strength, elongation at break and Shore D hardness; adhesion properties: lap shear strength (LSS) and T-Peel strength (TPS); and rheological properties were investigated. Ethylenediamine was replaced by 5%, 10% and 15% (molar basis) of castor oil. It was found that T_g, T_m, H_m, T_c, H_c, T_s, LSS, TPS, tensile strength, Shore D hardness and viscosity, all decreased with increased concentration of castor oil. This is due to the decrease in the crystallinity of the polyesteramide caused by conversion of amide linkages by ester linkages and increased distance between two ester linkages (due to the bulky nature of castor oil).     

Effect of phenolic resin structure on the bonding properties of nitrile rubber-based adhesives

Three phenolic resins were used to study the effect of resin structure and its percentage content on the bonding properties of nitrile rubber-based adhesives. The phenolic resins studied are derived from phenol, resorcinol and para-t-butyl phenol, and are of novalac type. These resins were characterized by infra-red and thermal studies. Several formulations were prepared by varying the phenolic resin/nitrile rubber ratio and these formulations were tested for viscosity and bonding properties. At a given resin-to-rubber ratio, the viscosity for resorcinol-formaldehyde resin was higher than phenol-formaldehyde resin followed by para-t-butyl phenol-formaldehyde resin. The peel strength of nitrile rubber-based adhesive prepared from resorcinol-formaldehyde resin was higher than adhesives that from para-t-butyl phenol-formaldehyde resin followed by phenol-formaldehyde resin. The lap shear strength of nitrile rubber-based adhesive containing para-t-butyl phenol-formaldehyde resin was higher than of adhesives containing the other two resins. The trend observed in peel strength could be explained on the basis of hydrogen bonding between hydroxyl groups of phenolic resin (adhesive) and hydroxyl groups of the starch-coated canvas cloth (adherend), whereas the trend observed in lap shear strength could be explained on the basis of extent of linearity in the resin structure.     

Effects of adding nano-clay (montmorillonite) on performance of polyvinyl acetate (PVAc) and urea-formaldehyde (UF) adhesives in Carapa guianensis,a tropical species

The aim of this study was to improve the bond strength resistance of polyvinyl acetate (PVAc) and urea-formaldehyde (UF) adhesives modified with nano-clay (montmorillonite) with a tropical species of wood known to exhibit adhesion related problems. These adhesives were evaluated with 1.0 and 1.5 wt% nano-clay concentrations with lap shear strength (SS), and the percentage of wood failure (PWF) in dry and wet conditions being evaluated. An additional aim of this study was to observe the presence of nano-clay within both adhesive types using Atomic Force Microscopy (AFM) and the Transmission Electron Microscopy (TEM). Color, viscosity and the thermostability of these adhesives with nano-clay were also evaluated. First, AFM and TEM studies showed adequate dispersion and impregnation of nano-clay. The viscosity of PVAc adhesive was not affected by the incorporation of nano-clay, whereas the UF adhesive was. With both PVAc and UF adhesives, the presence of nano-clay increased the L^⁎ and b^⁎ color parameters, especially when 1.5 wt% nano-clay was used. The incorporation of the nano-clay improved thermostability, as determined by thermogravimetric analysis (TGA). Finally, it was shown that the nano-clay incorporation improved SS and PWF. The highest values of SS were obtained when nano-clay was added at 1.5 wt% concentration in the PVAc adhesive under dry conditions. SS was not affected by nano-clay addition in the UF adhesive under dry conditions. However, under wet conditions, both 1.0 and 1.5 wt% loadings of nano-clay increased SS with both adhesive types. The addition of nano-clay in both proportions increased PWF by approximately 15% and between 20–30% in dry and wet conditions, respectively, for the PVAc adhesive. For the UF adhesive, PWF increased by approximately 10% under dry conditions and 25–50% in wet conditions.     

Synthesis and Properties of Polyurethane Elastomers with Castor Oil as Crosslinker

Castor oil–polyurethane elastomers were prepared by reacting poly (1,4-butane diol) (Terathane 1400) with aliphatic 1,6-hexamethylene diisocyanate. The prepolymers were chain-extended with bifunctional precursor chains and/or with castor oil as a trifunctional crosslinker at stoichiometric ratios. These resulted in a series of crosslinked polyurethane elastomers with different structures of the hard segment. The properties of the material were measured by differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, as well as tensile properties measurements. The effect of stoichiometric balance (i.e., OH/NCO molar ratio) on the final properties was evaluated. The formation of hydrogen bonds was observed by Fourier transform infrared.spectroscopy The measured properties were found to be strongly influenced by the molar ratio of chain extenders to the diisocyanate component. The glass transition temperatures (T _g) for the polyurethanes with OH_polyol/NCO/OH_{chain extender} having molar ratios of 1:2:1 and 1:4:3 were found to be −70 and −57 °C, respectively. The polyurethanes networks with a OH/NCO molar ratio of 1:2:1 had excellent mechanical properties, indicating that this is the optimum ratio to be used in castor oil polyurethane elastomer formulations. The objective of this work was to study the effect of the castor oil crosslinker on the morphology of the resulting crosslinked polyurethanes and to correlate the morphology with the properties of these bio-based crosslinked polyurethanes.     

Properties of isocyanate‐reactive waterborne polyurethane adhesives: Effect of cure reaction with various polyol and chain extender content

Three series of isocyanate‐reactive waterborne polyurethane adhesives were prepared with various contents of chain extender (4.25/8.25/12.50 mol %) and polyol (20.75/16.75/12.50 mol %). Each series had a fixed amount of excess (residual) NCO group (0.50–2.00 mol %). FTIR and ¹H‐NMR spectroscopy identified the formation of urea crosslink structure mainly above 80°C of various cure temperatures (20–120°C) with excess diisocyanate. The molecular weight, tensile strength, Young's modulus, and adhesive strength depend on excess NCO content and cure temperature and also varied with polyol and chain extender content. The optimum cure temperature was 100°C for all the samples. The tensile strength, Young's modulus, and adhesive strength increased with increasing cure temperature above 60°C up to the optimum temperature) (100°C) and then almost leveled off. Among all the samples, the maximum values of tensile strength, Young's modulus, and adhesive strength were found with 63.22 wt % polyol, 0.93 wt % chain extender, and 1.50 mol % excess (residual) NCO content at 100°C optimum cure temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and performance of urethane-modified polytriazole adhesives

Polytriazole adhesives are a new type of adhesives with excellent heat resistance, but the lap shear strength at room temperature is not ideal, which is about 15 MPa. In order to improve its adhesion performance at room temperature, a series of urethane-modified polytriazole (UPTA) adhesives were successfully synthesized via 1, 3-dipolar cycloaddition reaction between azides, and alkynes. Firstly, an alkynyl-terminated urethane monomer di(but-3-yn-1-yl) (1,3-phenylenebis(methylene)) dicarbamate (DBPMD) was synthesized and characterized. Then DBPMD was reacted with biphenyl dibenzyl azide (BPDBA) and N′,N′,N′,N′-tetrapropargyl-p,p′-diaminodiphenyl methane (TPDDM) to prepare UPTA adhesives. Curing behavior, thermal properties, bonding performance, and resistance to damp heat aging of UPTA adhesives were studied. The results show that the introduction of urethane group has almost no effect on the curing behavior. The glass transition temperature (T_g) and the 5% thermal weight loss temperature (T_d5) gradually decreased with the increased proportion of DBPMD added. T_g of UPTA adhesives ranged from 185 to 215°C and T_d5 of UPTA adhesives were all above 300°C, which indicated its outstanding thermal stability. The lap shear strength at room temperature of UPTA adhesives increased first and then decreased with the increasing amount of DBPMD, which ranged from 13.9 to 19.9 MPa. The highest lap shear strength of UPTA adhesives can reach 19.9 MPa, which was 31.8% higher than PTA adhesive. The lap shear strength retention rate of UPTA adhesives at 180°C was all over 75%. Lap shear strength retention rate of UPTA adhesives under 168 h damp heat aging time was all over 80%. UPTA adhesives have good bonding performance, heat resistance, and damp heat aging resistance, which can meet many complex construction requirements.     

The effect of curing temperature on thermal,physical and mechanical characteristics of two types of adhesives for aerospace structures

The effects of cure temperatures on the thermal, physical and mechanical characteristics of two types of thermosetting structural epoxy film adhesives were determined in detail. The aim of this paper is to assess the effect of cure temperatures (82–121 °C) on the degree of cure of the two adhesives and the relevant void formations that need to be addressed in bonded part production and repair. Two thermal parameters were used to characterize the advancement of the reaction, such as degree of cure and glass transition temperature. The joint properties with respect to the cure temperatures were characterized by void content and bond-line thickness measurements and lap shear strength tests. Experimental results presented that all lap shear strengths were well within minimum shear strength (29 MPa) required by the specification of the film-type adhesive. However, the lap shear strength testing after aging at 82 °C and 95%R.H for 1000 h showed that the improved durability when the adhesive is cured at 121 °C did not occur for the 82 °C cure. Low curing conversion (75–77% degree of cure) combined with high voids (over 2 areal%) has a catastrophic effect on the bonding qualities at the metal-adhesive interface and due to lack of cohesion in the adhesive. The changes in the interface caused by the low temperature curing may contribute to an increased susceptibility of the bonded joint to moisture and consequent bond-line degradation.     

A bio-based adhesive composed of polyelectrolyte complexes of lignosulfonate and cationic polyelectrolytes

Abstract

Polyelectrolyte complexes composed of lignosulfonate and cationic polyelectrolytes were used as bio-based adhesives. Sodium lignosulfonate (L-SO₃Na), a wood-derived anionic polyelectrolyte, was combined with three different cationic polyelectrolytes and the adhesive strength of the resulting complexes was evaluated on various substrates. Higher adhesive strength was observed with polar substrates (stainless steel, aluminum, and wood) compared to a nonpolar substrate (polypropylene). Complexes L-SO₃Na/poly(allylamine) and L-SO₃Na/ε-poly-l-lysine exhibited higher adhesive strength than the other polyelectrolyte complexes on aluminum and a commercial polyvinyl acetate adhesive on wood. In addition, our adhesives do not require any additional chemical reagents, such as organic solvents, crosslinkers, or condensation agents. The L-SO₃Na/ε-poly-l-lysine complex is a strong and completely biodegradable adhesive. This study demonstrates the use of lignosulfonate in the development of low-toxicity, sustainable, and biodegradable adhesives with excellent adhesive strength.