Effect of polyol on thermo-oxidative degradation of isocyanate resin for wood adhesives

The thermo-oxidative degradation of various polyol-added isocyanate resins for wood adhesives was studied using differential scanning calorimetry and thermogravimetry. The degradation of the resin cured with water began at 150°C. When a certain polyol was added to the resin at an NCO/OH ratio of 25 in addition to water, the cured resin began to degrade at 200°C. To clarify the cause of the good thermal stability in polyol-added resins, the effect of various polyols on the reactivity of isocyanate was investigated. It was found that the reactivity of isocyanate was enhanced by the addition of a dipropylene glycol and glycerin-type polyols. In addition, the effect of the NCO/ polyol-OH ratio was investigated using dipropylene glycoltype polyol. The reactivity of isocyanate increased with increasing polyol content. The thermal stability of the resin was improved to a certain degree by addition of a small amount of the polyol but deteriorated when a large amount of the polyol was added.Part of this paper was presented at the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998     

Durability of isocyanate resin adhesives for wood IV: degradation under constant steam heating

The durability of isocyanate resins consisting of emulsion-type polymeric diphenylmethane diisocyanate (EMDI) was investigated under constant steam heating. Two kinds of resin, water only-added resin and polyol/water-added resin, were used in this study. The degradation of the resins under steam heating was observed using Fourier transform infrared spectroscopy (FT-IR), weight changes, and thermogravimetric analysis (TGA). FT-IR analysis showed that the degradation reaction of the resins scarcely proceeded for a few hours and then increased significantly. The weights of the resins decreased linearly during steam heating. The thermal stability of steam-treated resins was made clear by TGA. The bond strength reductions of the specimens bonded with the resins were also observed. The best fitting regression function for the behavior of bond strength reduction was determined statistically. The apparent activation energy of each resin was calculated from the regression function, for the half-life period. Considering the calculated values, the adhesion durability of using polyol-added resin was superior to that of using water only-added resin. It was clarified that the durability of the isocyanate resins under steam heating was markedly inferior to that under dry heating.Part of this paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, 2000     

Durability of isocyanate resin adhesives for wood III: degradation under constant dry heating

The durability of isocyanate resins consisting of emulsion-type polymeric diphenylmethane diisocyanate (EMDI) was investigated under constant dry heating. Two kinds of resin, water only-added resin and polyol/wateradded resin, were used in this study. The kinetic studies based on the weight losses of the resins were carried out by isothermal thermogravimetry (TG) at temperatures ranging from 260° to 320°C. The apparent activation energies of the resins were calculated for weight losses of 5%, 10%, and 15%. The values of apparent activation energy of the resins increased with increasing weight loss. The bond-strength reductions of the specimens bonded with the resins were observed at various temperatures from 120° to 180°C. The best-fitting regression function for the behavior of bond-strength reduction was determined statistically. The apparent activation energy of each resin was calculated from the regression function for the half-life period. According to the calculated values, the adhesion durability of polyol/wateradded resin was superior to that of water only-added resin. To speculate on the changes in weight loss and the chemical structure of the resins in the glue lines under dry heating, changes in the cured resins were also observed.Part of this paper was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, 1999     

新型酚醛树脂改性大豆蛋白基胶黏剂的研究

以脱脂大豆粉为原料制备大豆蛋白基胶黏剂(豆胶,S),以普通甲醛制备的酚醛树脂(PF_1)和高浓度甲醛制备的酚醛树脂(PF_2)为交联剂,使用前将两者直接混合得酚醛树脂改性豆胶(PF_1/S、PF_2/S)。利用差示扫描量热(DSC)、红外光谱(FT-IR)、动态热机械性能(DMA)和核磁共振碳谱(~(13) C NMR)分析对产品性能进行了测试与表征。结果表明:等物质的量之比条件下,高浓度甲醛较之普通甲醛制备的酚醛树脂改性豆胶胶合板干、湿剪切强度分别提高4.3%和11.6%,并且强度稳定性好;动态DSC分析表明,PF_2可以降低豆胶体系的固化温度和活化能,与豆胶的交联反应较容易;~(13) C NMR分析表明,PF_2体系羟甲基达88.73%,明显高于PF_1的80.91%;FT-IR分析证实酚醛树脂与豆胶中的氨基发生反应,并且PF_2反应效率更高;DMA分析表明,PF_2/S能够改善胶合产品的力学性能和热稳定性,降低豆胶的固化反应起始温度,提高固化反应速率。     

氢化萜烯马来酸酐与环氧树脂固化物的性能研究

研究了氢化萜烯马来酸酐(HTMA)与环氧树脂固化物的机械强度、热稳定性及电气绝缘等性能及其主要影响因素.实验结果表明,采用氢化萜烯马来酸酐固化后的环氧树脂具有较好的机械强度、热稳定性及电气绝缘性能.氢化萜烯马来酸酐的化学结构与固化物的机械强度及热稳定性密切相关.不同化学结构脂环酸酐固化后的环氧树脂电气绝缘性能相近.     

Phenol–formaldehyde impregnation of densified wood for improved dimensional stability

To produce a highly stable wood-based product with increased mechanical properties, phenol formaldehyde (PF) resin impregnation was combined with the viscoelastic thermal compression (VTC) process. Dimensional stability and bending stiffness were evaluated. Two PF resins with weight average molecular weights of 172 and 780 were studied at three different concentrations, 5, 10 and 20%. After 24-h room temperature water soak and 2-h boil, both PF treatments at all concentration levels showed high levels of dimensional stability compared to non-impregnated VTC processed controls. The higher molecular weight PF provided greater stability with an average thickness swell value of 12% compared to 20 and 37% for the lower molecular weight PF resin treatment and control, respectively. High anti-swelling efficiency values were recorded for both low and high molecular weight resins, implying these modifications were effective at reducing the volumetric swelling which occurred in the unmodified control. PF treatments were also extremely effective at reducing irreversible swelling. The low and high molecular weight resin treatments had 1/5th and 1/7th the irreversible swelling than the unmodified VTC processed controls, respectively. All dimensional stability values improved as resin concentrations increased. Both resin types at all concentration levels reduced Young’s modulus.     

茶油皂脚脂肪酸甲酯制备的水溶性改性胺固化物性能研究

以茶油皂脚脂肪酸甲酯制备的水溶性改性胺(CA-921)与水性环氧树脂固化,通过热重分析、差示扫描量热法(DSC)、机械性能测试及扫描电镜分析,研究了环氧树脂分散相粒子的粒径和黏度、环氧基与胺氢物质的量之比及固化温度对固化物性能的影响.研究结果表明,黏度及粒径均较小的水性环氧乳液AB-EP-20与固化剂CA-921复配所...     

Durability of isocyanate resin adhesives for wood V: changes of color and chemical structure in photodegradation

The effect of ultraviolet (UV) light irradiation on the color and chemical structure of water-cured polymeric diphenylmethane diisocyanate (PMDI) was investigated using a UV long-life fade meter. Control treatment was performed without UV light irradiation using a thermohygrostat for comparison. Two kinds of resin were used in this study: that to which only water had been added, and resin to which a small amount of polyol and water had been added. In addition, lauan (Shorea spp.) wood was used as a reference. The photodegradation of the resins over a period of up to 300 h was observed using a colorimeter and Fourier transform infrared (FT-IR) spectroscopy. When the resins were treated with UV light, the color difference (ΔE ^* ab) of the resins increased signifi cantly in a short time, and then reached a near-constant value. For lightness, L ^* decreased rapidly for a few hours and then decreased gradually. The color darkened compared with that of the wood used. When treatment was performed without UV light irradiation, ΔE ^* ab and ΔL ^* of the resins showed negligible change. Based on the results of FT-IR analysis, severe degradation such as cleavage of the main chemical bond was hardly observed under UV light irradiation irrespective of the type of resin. Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, Japan, and at the 6th International Wood Science Symposium, Bali, Indonesia     

Comparison of protein-based adhesive resins for wood composites

The search for new value-added uses for oilseed and animal proteins led us to develop protein-based wood adhesives. Low-fat soy and peanut flours and blood meal were hydrolyzed in an alkaline state, and PF-cross-linked protein resins were formulated by reacting the protein hydrolyzates with phenol-formaldehyde (PF) in solid-tosolid ratios ranging from 70% to 50% hydrolyzates and 30% to 50% PF. Physical properties of medium density fiberboard (MDF) bonded with protein-based phenolic resins were compared to those of boards bonded with ureaformaldehyde (UF) and PF resins, and flakeboard bonded with soy protein-based phenolic resin was compared to PF-bonded board. As MDF binders, adhesive properties of protein-based phenolic resins depended upon protein content of proteinacious materials. MDF board bonded with blood-based phenolic resin was comparable to PF-bonded board and met the requirements for exterior MDF. Boards bonded with soy-protein-based phenolic resin met requirements for interior MDF, while peanut-based phenolic failed to meet some of the requirements. Flakeboard bonded with soy-protein-based phenolic resins was inferior to PF-bonded board but outperformed PF-bonded board in accelerated aging tests. Although they exhibit a slow curing rate, the cost effectiveness and superior dimensional stability of protein-based phenolic resins may make them attractive for some uses.     

Manufacture of oriented board using mild steam treatment of plant fiber bundles

This study investigated the effects of mild steam treatment (0.1 MPa for 2 h) of natural bio-based fibers and orientation (0° and 90°) of those fibers in various fiberboards. Ramie bast, pineapple leaf, and sansevieria fiber bundles were used as materials. The composite fiberboards were prepared using phenol-formaldehyde (PF) resin. To investigate the effect of mild steam treatment on wettability, contact angles of PF resin to the fiber were measured. The mechanical properties of the boards were examined as well as their dimensional stability. The contact angle data showed that mild steam treatment was effective in improving the wettability of fibers. Unioriented steam-treated boards showed better performance of internal bond (IB), moduli of rupture (MOR) and elasticity (MOE), thickness swelling (TS), and water absorption (WA) than other boards. Unioriented steam-treated sansevieria board with longitudinal fiber direction showed higher average values of MOR (403 MPa), MOE (39.2 GPa), and IB (1.33 MPa) and lower values of TS (5.15%) and WA (8.68%) than other boards. The differences in the mechanical properties and dimensional stability of boards were found mainly due to the differences in the ratios of fiber fraction of the boards to the density of the fiber bundles.     

Strength,decay and termite resistance of oriented kenaf fiberboards

The development of oriented fiberboards made from kenaf (Hibiscus cannabinus L.) and their suitability as a construction material has been investigated. Three different types of boards consisting of five layers with individual orientations were prepared using a combination of low molecular weight and high molecular weight phenol-formaldehyde (PF) resin for impregnation and adhesion purposes. Additional boards with the same structure were prepared using high molecular weight PF resin only. The mechanical properties of the boards have been examined as well as their resistance against fungal decay and termite attack. All kenaf fiberboards showed elevated mechanical properties compared with medium-density fiberboard made from wood fibers, and showed increased decay and termite resistance. Differences in the decay and termite resistance between the board types were caused by the presence of the low molecular weight PF resin for the impregnation of the fibers. No significant difference was found for the mechanical properties. The effect of the PF resin for impregnation was much clearer in fungal decay resistance than for termite resistance; however, fiber orientation had no effect on both decay and termite resistance of the specimens.     

Veneer strand flanged I-beam with MDF or particleboard as web material II: effect of resin type,application rate,strand dimension,and pressing time on the basic properties

Optimization of the manufacturing conditions of the veneer strand flanged I-beam invented in the previous study was investigated using different combinations of strand dimensions, resin types between web and flange, different pressing times, and different wood–resin moisture contents under conventional hot pressing conditions. The main results revealed that the strand dimensions have no effect on the bending properties of the flange part and the dimensional stability of the I-beam. Increasing the resin application rate between strands was found to improve the dimensional stability of the I-beams. The use of isocyanate (MDI) resin between web and flange significantly improved the bond strength between web and flange, the modulus of rupture of the I-beam, and the modulus of rupture of the flange part. Dimensional stability was also improved. Shortening the pressing time from 20 to 12min was found to be feasible. Using low wood-resin moisture content was found to interfere with the curing of the phenol–formaldehyde (PF) resin at the flange part resulting in poor quality beams. Of the three moisture content levels tested, 12% was found to be the optimal level for producing I-beams with balanced mechanical properties and dimensional stability.Part of this work was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, March 2003     

Performance of Sugi lamina impregnated with low-molecular weight phenolic resin

This study was conducted to evaluate the performance of Sugi lamina impregnated with low-molecular weight phenolic (LMWP) resin using the full cell process followed by curing at high temperature. In this study, penetration of LMWP resin into finger-jointed lamina was examined. Physical and mechanical properties, such as surface hardness, dimensional stability, bending and shear strength of LMWP-resin-treated and untreated lamina were investigated. In addition, the bonding quality and nail-withdrawal resistance of 3-ply assembly specimen made from LMWP-resin-treated and untreated lamina bonded using resorcinol–phenol formaldehyde resin adhesive were also investigated. The main results were as follows: LMWP resin was found to have penetrated sufficiently into finger-jointed lamina. The physical properties of LMWP-resin-treated lamina were found to have improved significantly in comparison with untreated lamina. However, no significant difference was found between LMWP-resin-treated and untreated lamina in terms of their mechanical properties. There was an improvement in bonding quality of the assembly made from LMWP-resin-treated lamina when compared with that made from untreated lamina. In the assembly made from untreated lamina, a significant decrease in nail-withdrawal resistance was observed between dry conditions test and after humidity conditioning test. However, the same tendency was not found in the assembly made from LMWP-resin-treated lamina.     

Curing kinetics of phenol formaldehyde resin and wood-resin interactions in the presence of wood substrates

The curing kinetics of resol PF resin and resin–wood interactions in the presence of wood substrates have been studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The activation energy of cure of PF resin generally increases when PF resin is mixed with wood, mainly due to the decrease of the pH values resulting from the presence of wood. However, wood decreases the curing enthalpy of PF resin through diffusion and the change in the phase of the curing system, which suggests that the curing reactions reached a lower final degree of conversion for the mixtures of PF resin with wood than for the PF resin alone. Moreover, DSC curves and the variation of activation energy with conversion indicate that wood accelerates the addition reactions and retards condensation ones during the curing process of PF resin with wood. The study also revealed that almost no chemical reactions occur between PF resin and wood, but the secondary force interactions of hydroxyl groups between PF resin and wood have been detected. These most significant secondary forces can catalyze the self-condensation reactions of PF resin, although their effect is not vital on the curing kinetics of PF resin.     

Optimum preparation technology for Chinese fir wood/Ca-montmorillonite （Ca-MMT） composite board

For this study, an intercalation compounding method was used to prepare Chinese fir wood/Ca-montmorillonite （Ca-MMT） composite board to improve its properties such as surface mechanical properties, flame retardance and dimensional stability. By virtue of water-soluble phenolic resin （PF）, Chinese fir wood and Ca-MMT were mixed by pressure and vacuum impregnation. The optimum impregnation technology of Chinese fir wood/Ca-MMT composite board was obtained by using an orthogonal design and a single factor design of pressure and vacuum impregnation, using weight percent gain （WPG） as the basic index. The results are as follows： 1） On the basis of the orthogonal design and an actual experiment, the optimum preparation technology of Chinese fir wood/Ca-MMT composite board is 20% PF resin dispersion concentration （wt%）, 1.0 CEC amount of organic intercalation agent, 0.098 MPa vacuum degree, 5% concentration of Ca-MMT and 1.0 MPa pressure. 2） The WPG of the composite board samples of 450 mm length was much larger than that of the samples of 600, 750 and 900 mm length. Warm water extraction contributed little to WPG     

杨木材性对酚醛树脂浸渍改性材的影响

采用低分子量酚醛树脂对速生杨木进行浸渍处理、干燥定型,使树脂固化制得改性材。试验表明：低分子量酚醛树脂对杨木具有较好的浸注性,改性材的密度和力学强度均有明显的提高,两组试件改性后浸注性和密度相差不大,但前期经过热水处理的试件改性后密度相对均匀,力学强度略好于直接浸渍的试件。杨木自身材性对改性后物理力学性能的影响各不相同,在实际生产中要根据指标的重要性程度选取最佳方案。     

Pyrolysis of medium density fiberboard impregnated with phenol-formaldehyde resin

Woodceramics (WCS) are new porous carbon materials that have been shown to possess many excellent properties, but the chemical mechanism during pyrolysis has not been reported yet. In order to investigate this process, pyrolysis of medium density fiberboard (MDF) was analyzed by thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) in this study. The results showed that the pyrolysis consisted of three stages up to 700°C. The first stage of the pyrolysis occurred below 240.0°C and was mainly due to moisture evaporation. The second stage between 240.0° and 390.2°C accompanied the main mass loss. The maximum pyrolysis speed (mass loss) was about 3.79% per minute at 313.2°C. This was believed to coincide with the cleavage of ether bridges between the wood material and phenol-formaldehyde (PF) resin, and pyrolysis of carbohydrate. At higher temperature, the pyrolysis of PF resin and lignin was the main reason for the mass loss in the third stage. The microcosmic environments of both the MDF and PF resin in the MDF treated with PF resin were different from the untreated MDF and PF resin, so that the temperatures at which their pyrolysis occurred and the quantities of evolved gases were different. During the process of WCS preparation, the rate of temperature increase should be very slow before it reaches 700°C, especially at around 313.2°C, at which point violent pyrolysis occurs. Such temperature control should allow uniform sintering of the sample and should reduce flaws in the product.     

Investigation of the effects of bark fiber as core material and its resin content on three-layer MDF performance by response surface methodology

The effects of using 100% black spruce (Picea mariana) bark fibers as core layer material accounting for up to 70% of the board and its resin content (between 6 and 10%) on the properties of three-layer medium-density fiberboard (MDF) were investigated using a full factorial experimental design with two independent variables and three levels. Five response variables, namely internal bond strength, modulus of rupture, modulus of elasticity, thickness swelling and water absorption were statistically analyzed using a response surface methodology and two-way analysis of variance. The effects of the proportion of core layer (bark fibers) and its resin content on panel properties were significant. All properties studied were positively affected by increasing core layer resin content. The effects of the proportion of core layer (bark fibers) on mechanical properties and water absorption were negative, but positive on thickness swelling. Simultaneous optimization of panel properties indicated that at a density of 850 kg/m³, a three-layer MDF with a core layer resin content of 6.5%, a face resin content of 12 and 60% of core layer proportion (spruce bark fibers) would satisfy the minimum requirements of ANSI standard for 130-grade MDF. Overall, black spruce bark, a major residue source in the Eastern Canada, should be considered as a supplemental furnish for the core layer materials of a three-layer MDF.     

竹木复合单板层积材制备工艺

以浸渍酚醛树脂的杨木单板和竹帘为原料制备竹木复合单板层积材, 探讨制造工艺对复合材料性能的影响.结果表明,竹木复合材料的MOE及MOR均达到或超过了日本JAS标准的相关规定,尺寸稳定性良好; 单板厚度、树脂浓度、压缩率对MOE和MOR有显著影响;组坏方式对MOR影响显著;而吸水厚度膨胀率的影响作用比较复杂.     

地板用高密度纤维板的研制

研究了以酚醛树脂为胶粘剂制造地板用高密度纤维板的工艺条件,探讨了热压时间、热压温度、施胶量对高密度纤维板物理力学性能和防潮性能的影响。采用优选工艺制得的产品各项指标均达到或优于欧洲地板用高密度纤维板标准。