Synthesis and cure kinetics of liquefied wood/phenol/formaldehyde resins

Wood liquefaction was conducted at a 2/1 phenol/wood ratio in two different reactors: (1) an atmospheric three‐necked flask reactor and (2) a sealed Parr reactor. The liquefied wood mixture (liquefied wood, unreacted phenol, and wood residue) was further condensed with formaldehyde under acidic conditions to synthesize two novolac‐type liquefied wood/phenol/formaldehyde (LWPF) resins: LWPF1 (the atmospheric reactor) and LWPF2 (the sealed reactor). The LWPF1 resin had a higher solid content and higher molecular weight than the LWPF2 resin. The cure kinetic mechanisms of the LWPF resins were investigated with dynamic and isothermal differential scanning calorimetry (DSC). The isothermal DSC data indicated that the cure reactions of both resins followed an autocatalytic mechanism. The activation energies of the liquefied wood resins were close to that of a reported lignin–phenol–formaldehyde resin but were higher than that of a typical phenol formaldehyde resin. The two liquefied wood resins followed similar cure kinetics; however, the LWPF1 resin had a higher activation energy for rate constant k₁ and a lower activation energy for rate constant k₂ than LWPF2. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of wood species on the properties of biopolyurethane prepared from liquefied wood with residue

Biopolyurethane prepared from liquefied wood with the residue of the liquefied wood product was investigated in this article. Previous results indicated that the residue of the liquefaction product was composed mostly of compounds originated from lignin. The chemical structures of lignin in softwood and hardwood are different. The influence of soft‐ and hardwood species on the chemical structure and mechanical properties of biopolyurethane prepared from liquefied wood with residue was investigated by tensile testing and Fourier transform infrared spectroscopy. The experimental results showed that the liquefaction of softwood occurs within a shorter time than that of hardwood and the biopolyurethane prepared from softwood was harder than that prepared from hardwood, which suggests that the properties of the liquefaction product and biopolyurethane are influenced by the chemical structure of the lignin. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation of liquefied wood residues based on cellulose,hemicellulose, and lignin

Chinese eucalyptus was subjected to a liquefaction process using glycerol/ethylene glycol (EG) as liquefaction solvent. The effects of various liquefaction conditions, including reaction time, liquefaction temperature, acid concentration, and liquor ratio on the chemical composition of liquefied wood residues were studied. The results showed that the whole liquefaction process took place in two stages, the liquefaction yield of wood depended on the reaction temperature, acid concentration and liquor ratio. With increased acid concentration the liquefaction yield, acid‐insoluble lignin, and hemicellulose content of the residues were increased, and the relative content of cellulose was decreased. Fourier transform infrared (FT‐IR) analyses of the residues showed that hemicellulose and lignin were almost decomposed at the initial stages of reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of epoxy resins from alcohol‐liquefied wood and the mechanical properties of the cured resins

New wood‐based epoxy resins were synthesized from alcohol‐liquefied wood. Wood was first liquefied by the reaction with polyethylene glycol and glycerin. The alcohol‐liquefied wood with plenty of hydroxyl groups were precursors for synthesizing the wood‐based epoxy resins. Namely, the alcoholic OH groups of the liquefied wood reacted with epichlorohydrin under alkali condition with a phase transfer catalyst, so that the epoxy groups were put in the liquefied wood. The wood‐based epoxy resins and the alcohol‐based epoxy resins as reference materials were cured with polyamide amine. The glass transition temperature (Tg), the tensile strength, and the modulus of elasticity of the wood‐based epoxy resin were higher than those of the alcohol‐based epoxy resin. Also, the shear adhesive strength of the wood‐based epoxy resin to steel plates was higher than those of the alcohol‐based epoxy resins, which was equivalent to the level of petroleum‐based bisphenol‐A type epoxy resins. The higher Tg of the wood‐based epoxy resin than that of the alcohol‐based epoxy resin is one of the evidences that the wood‐derived molecules were chemically incorporated into the network structures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

固化剂用量对苯甲基化木材制得的聚氨酯树脂微相分离的影响

以二价酸酯与乙酸丁酯混合溶剂为液化试剂,将苯甲基化木材溶液化,得到的木材溶液与三羟甲基丙烷与甲苯二异氰酸酯的预聚物反应制备聚氨酯树脂。利用FTIR、SEM、DTA、TG及DSC等测试手段,研究了固化剂用量对聚氨酯树脂的微观结构和热性能的影响。结果表明,由于木材结构的特殊性和复杂性,使木材溶液得到的聚氨酯树脂较传统的聚氨酯热稳定性提高,表现在其软段、硬段的初始分解温度比传统的聚氨酯分别提高了 4℃和 99℃;随着w(固化剂)由 23. 8%增大到 69 .9%,树脂的玻璃化转变温度提高,微相分离程度增大,并出现相转变;且相转变完成后,即w(固化剂) =69. 9%时,涂膜各项性能指标发生明显的改善,其铅笔硬度可达 4H,附着力≥1级。     

Properties and microstructure of polyurethane resins from liquefied wood

In this article, polyurethane resins were synthesized from liquefied benzylated wood and toluene diisocyanate (TDI)–trihydromethylene propane (TMP) prepolymer (as curing agent). The relations of their segmented structure and properties of were investigated. Results indicated that polyurethane resins made from benzylated wood solution have good mechanical and thermal properties. With the increase of curing agent amount from 23.8 to 53.5%, the degree of phase segregation increased, and under experimental conditions in this article, phase transition was detected with a curing agent amount of 69.9%. After this transition, the mechanical properties of polyurethane resins were improved. Thermal history treatment can also influence microstructure and thermal stabilities of polyurethane samples. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1175–1180, 2005     

Physicomechanical and thermal properties of moldings made from liquefied wood‐based novolak PF resins under various hot‐pressing conditions

The wood powder of Cryptomeria japonica (Japanese cedar) was liquefied in phenol, with H₂SO₄ and HCl as a catalyst. The liquefied wood was used to prepare the liquefied wood‐based novolak phenol formaldehyde (PF) resins by reacting with formalin. Furthermore, novolak PF resins were mixed with wood flour, hexamethylenetetramine, zinc stearate as filler, curing agent, and lubricating agent, respectively, and hot‐pressed under 180 or 200°C for 5 or 10 min to manufacture moldings. The results showed that physicomechanical properties of moldings were influenced by the hot‐pressing condition. The molding made with hot‐pressing temperature of 200°C for 10 min had a higher curing degree, dimensional stability, and internal bonding strength. The thermal analysis indicated that using a hot‐pressing temperature of 180°C was not sufficient for the liquefied wood‐based novolak PF resins to completely cure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of compression‐molded plates made from wood powders impregnated with liquefied wood‐based novolak‐type phenol‐formaldehyde resins

Novolak‐type phenol‐formaldehyde (PF) resins with solution form were prepared by reacting phenol‐liquefied Cryptomeria japonica (Japanese cedar) wood with formalin in the presence of methanol. Wood powders of Albizzia falcate (Malacca albizzia) impregnated with these resins were air dried followed by an oven‐dried at 60°C. DSC analysis showed the PF resin existing in wood powders could be melted, and could be cured if hexamine was mixed and heated at high temperature. Compression‐molded plates made with PF resin impregnated woods had a high degree of curing reaction. However, compression‐molded plates hot‐pressed at 180°C for 8 min or 200°C for 5 min had better internal bonding strength and dimensional stability than others. Premixing hexamine with PF resin and impregnating into wood powders simultaneously could enhance the reactivity of PF resin, but it was not useful for improving the properties of compression‐molded plates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Variations in the microstructure of carbon fibers prepared from liquefied wood during carbonization

After spinning by adding hexamethylenetetramine and the curing treatment, carbon fibers from liquefied wood (LWCFs) were prepared by direct carbonization. Microstructure change of LWCFs during carbonization is studied by X‐ray, Raman spectroscopy, and FTIR. Raman spectroscopy shows both the D peak at 1360 cm^?1 and the G peak at 1595 cm^?1 exist after 600°C, and a significant decrease is found in I_D/I_G during carbonization. X‐ray diffraction shows the crystallite size (L_c(002) and L_a(100)) of LWCFs firstly decreases before 800°C and then increases with heat treatment temperature (HTT) increasing, whereas the interlayer spacing (d₀₀₂) gradually decreases during carbonization. It is also found that the crystallite shape (L_a/L_c) and the degree of graphitization (G) all increase with increasing HTT. It is also found that structure of the precursor fibers from liquefied wood has been completely changed after carbonization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Physical properties of moldings from liquefied wood resins

The liquefied wood resins obtained by liquefying wood in the presence of phenol using phosphoric acid as a catalyst were applied to prepare the moldings by using hexamine as a hardener. The effects of the molding conditions and the moldings' compositions on flexural properties and water-sorption kinetics of the moldings were investigated. It was found that the liquefied wood resins had satisfactory and almost uniform curing reactivity, although they were composed of different kinds of wood components. The flexural properties of the liquefied wood moldings were enhanced with an increase in the amount of combined phenol within the liquefied wood and became comparable to those of the commercial novolak when the amounts of combined phenol were larger than 75%. Furthermore, it was also found that with an increase in the content of wood fillers the flexural properties of the liquefied wood moldings were enhanced more effectively than were the cases of the commercial novolak moldings, exhibiting that the liquefied wood resins could gain a greater reinforced effect from compounding with the wood fillers than did the commercial novolak resins, and the greater the amount of combined phenol, the higher the reinforcing performance of wood fillers. In addition, water-sorption measurements and the SEM observations of the moldings indicated that the liquefied wood resins had much greater hydrophilicity than that of the novolak and revealed a greater compatibility with wood fillers. © 1995 John Wiley & Sons, Inc.     

Microscopic analysis of the wood bond line using liquefied wood as adhesive

The bonding of beech (Fagus sylvatica L.) with liquefied wood (LW) causes deterioration of the wood surface, resulting in a high percentage of wood failure at a relatively low bond shear strength. Light microscopy, scanning electron microscopy, FT-IR micro-spectroscopy and elemental carbon, nitrogen and sulphur (CNS) analysis techniques were used to investigate the formation of such bonds. It was assumed that the degradation of lignin, hemicelluloses and parts of the cellulose occurred in the cells of the wood surface where the LW had been applied. At the elevated temperatures occurring during the bonding process, the deteriorated cells were carbonised to some extent. The weak boundary layer of the bond was determined to be a layer of delignified cells located between the zone of partly carbonised cells on the one side and the cells of the undamaged wood of the adherend on the other side. The bonds which formed during the bonding of wood with LW were found to be very untypical compared to bonds formed by synthetic wood adhesives. No adhesive film was formed, the adhesive-adherend interface was not clear and the cells of the adherend subsurface were damaged.     

Molecular weights and molecular weight distributions of liquefied wood obtained by acid-catalyzed phenolysis

By means of gel permeation chromatography analysis, the molecular weights and molecular weight distributions of liquefied wood obtained under various liquefaction conditions and species of catalysts were investigated in order to trace the change in the structural characteristics of the liquefied wood. The results indicated that during the liquefaction reaction, wood components were subjected to decomposition, phenolation, and recondensation. The intensities of these reactions depended greatly on the reaction conditions and the species of catalysts, and their competing result determined the structural characteristics of the resulting liquefied wood. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 351–357, 1997     

Studies on the reactivity of epoxy/polyol/isocyanate blend resins and the properties of epoxy/polyurethane composites

Epoxy resin (ER) is one of the most widely used synthetic resins, and the improvement of its toughness is an important issue. In this study, Epon 828 is used as ER resin, polytetramethylene ether glycol (PTMG) and liquefied wood (LW) are used as polyol, and IPDI, H₁₂-MDI, Desmodur N, and Desmodur L are used as isocyanate. The influence of polyurethane resin (PU) composition on the reactivity of ER/polyol/isocyanate blended resin and the properties of ER/PU composite are investigated. The results show that the mixture of ER/PTMG/IPDI has greater reactivity, followed by ER/PTMG/Desmodur N, while ER/PTMG/Desmodur L has lower reactivity. In the structure of ER/PU blended resin composites, ER and PU resins not only form a physical interpenetrating structure, but also undergo a copolymerization crosslinking reaction. The modulus of elasticity of ER/PU composites prepared with trifunctional Desmodur L and Desmodur N is greater than that of bifunctional IPDI and H₁₂-MDI, while those with LW as polyol is greater than that of PTMG as the raw material.     

稻壳液化产物用于聚氨酯胶黏剂的制备与性能

将稻壳在多元醇中液化制备具有反应活性的稻壳基多元醇,然后以所制备的稻壳基多元醇、低聚物多元醇、二苯基甲烷二异氰酸酯(MDI)和小分子交联剂等为主要原料合成聚氨酯(PU)乳液。分别从预聚反应温度、稻壳基多元醇的添加量、低聚物多元醇种类、R值(-NCO与-OH的摩尔比)以及小分子交联剂种类5个方面进行研究。通过对所制备的聚氨酯乳液进行红外光谱、黏度、稳定性和力学性能等分析测试,结果表明:在预聚反应温度为70℃、聚己二酸丁二醇酯1000(PBA1000)为原料、稻壳基多元醇添加量为10%、R值为1.2、三羟甲基丙烷(TMP)为交联剂的条件下,合成的PU胶黏剂效果最佳。     

Structure and properties of polyurethane acrylate prepolymers based on hydroxy‐terminated polybutadiene

Precursors of polyurethane acrylate based on hydroxy‐terminated polybutadiene (HTPB) soft segments, different diisocyanate and hydroxy ethyl acrylate (HEA) as hard units, were synthesized in bulk or in solution in methyl methacrylate. During precursor synthesis (in bulk), microphase separation was observed by small‐angle X‐ray scattering (SAXS). Diffusing particles are around 50 Å in size and are assumed to be assembling of hard segments. From these morphologies, it can be deduced that some isocyanate groups were trapped/or buried in hard domains. At a larger scale, around millimeters, hard segment crystallites were observed. Properties such as molar masses, melting and glass‐transition temperatures, and viscosities were correlated with precursor structure and morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 225–233, 2002     

Synthesis and properties of copolymer epoxy resins prepared from copolymerization of bisphenol A,epichlorohydrin, and liquefied Dendrocalamus latiflorus

Dendrocalamus latiflorus Munro (ma bamboo) was liquefied in phenol and polyhydric alcohol (polyethylene glycol/glycerol cosolvent) with H₂SO₄ as catalyst. Liquefied bamboos reacted with bisphenol A and epichlorohydrin were then employed to prepare copolymer epoxy resins. The curing property and thermal property of copolymer epoxy resins were investigated. The results showed that copolymer epoxy resins could cure at room temperature after the hardener was added, and its curing process was an exothermic reaction. Comparison showed that copolymer epoxy resins prepared with phenol‐liquefied bamboo as raw material had higher heat released than those prepared with polyhydric alcohol‐liquefied bamboo during curing. The DSC analysis showed that heat treatment could enhance the crosslinking of copolymer epoxy resins cured at room temperature. However, resins prepared with polyhydric alcohol‐liquefied bamboo had a lower glass transition temperature. The TGA analysis showed that resins prepared with phenol‐liquefied bamboo had better thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of pressing parameters on the shear strength of beech specimens bonded with low solvent liquefied wood

Liquefied wood (LW) is a naturally based product which has the potential to be used as an adhesive. It can be used as a part of a polymer formulation, as a part of an adhesive mixture with commercial adhesives, or as an independent material for wood bonding. In this study, wood was liquefied at 180?°C using ethylene glycol as the solvent and sulphuric acid as a catalyst. In the first part of research, LW with different pH values was used for the bonding of solid wood at 200?°C for 15?min. In the second part, LW with an optimal pH value was used for bonding at different press temperatures for 15?min. In the third part, the minimum pressing time at the optimal pH value and at the optimal press temperature was determined. Unmodified LW with a negative pH value, a press temperature of 180?°C, and a pressing time of 12?min was determined to be optimal (based on highest shear strength) for the bonding of 5?mm thick wood lamellas with the LW used in this study. At these conditions bonds exhibited shear strength of around 7?N/mm² which was too low to attain standard requirements. Despite this, high wood failure (100%) was observed as a consequence of low pH value and high press temperature which caused damage of the part of beech lamellas where LW was applied.     

Liquefaction of wood,synthesis and characterization of liquefied wood polyester derivatives

Liquefaction of Central‐European softwoods meal was performed using a mixture of diethylene glycol and glycerol and a minor addition of p‐toluenesulfonic acid as a catalyst. The liquefied wood was used as a replacement of a certain amount of the polyhydroxy alcohol in the polyester synthesis, enabled by the large number of hydroxyl groups that were available in the liquefied wood. Three different polyesters were synthesized by using adipic acid and phthalic acid anhydride as reagents. The products were characterized using FTIR, GPC/SEC, and viscosity measurements. The polyesters have hydroxyl values that were reduced due to esterification, from 1043 mg KOH/g of the liquefied wood to 400–800 mg KOH/g. Polyhydroxyl alcohols (22–23%) in the polyester formulations were replaced by wood derivatives. Such saturated polyesters are suitable for further use in polyurethane foam production. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Bamboo tar‐based polyurethane wood coatings

Bamboo tar is a natural resource of aromatic polyol obtained from a residue of by setting or distilling crude bamboo vinegar. In this study, the two‐packed polyurethane (PU) coatings were prepared by blending bamboo tar and castor oil varying with different weight ratios and polymeric toluene diisocyanate (PTDI) was used as a hardener at the NCO/OH molar ratio of 1.0. Six kinds of PU coatings were formulated and the viscosity, pot‐life, drying time, mechanical properties (hardness, tensile strength, impact resistance, adhesion, and abrasion resistance), gel content, durability, lightfastness, FTIR, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA) were characterized. The results indicated that the bamboo tar containing PU film appearance is semitransparent yellow‐brown color and the wood texture could be kept after finishing. All PU films possessed excellent adhesion as well as durability. The increase in bamboo tar content led to shorten drying time of coatings and to increase in hardness, tensile strength, lightfastness, and thermal stability of films. From these results and due to a light smell flavor, it is suggested that the bamboo tar‐based PU coatings is suitable to be used as an exterior wood coatings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Resol‐type phenolic resin from liquefied phenolated wood and its application to phenolic foam

A liquefied wood‐based resol resin was prepared with excellent yield by a reaction of liquefied wood and formaldehyde under alkaline conditions. The effects of various reaction parameters on the extent of the yield of the resol resin, unreacted phenol content, and viscosity were investigated. Milder resol resinification conditions were required as compared to those used in conventional methods. The liquefied wood‐based resol resin was successfully applied to produce phenolic foam using appropriate combinations of foaming agents. Diisopropyl ether with a relatively higher boiling temperature was suitable for the foaming of liquefied wood‐based resol resin. Hydrochloric acid and poly(ethylene ether) of sorbitan monopalmitate were used as a catalyst and a surfactant, respectively. The obtained foams showed satisfactory densities and compressive properties, comparable to those of foams obtained from conventional resol resin. Foams with low density were obtained by the blending of liquefied wood‐based resol resin and conventional resol resin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 468–472, 2002; DOI 10.1002/app.10018