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     

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 I: Thermal properties of isocyanate resin cured with water

The thermal properties of isocyanate (IC) resin cured with water were studied using dynamic mechanical analysis (DMA) and Fourier transform infrared spectroscopy. The thermal properties of cured phenol formaldehyde (PF) resin were also studied for comparison purposes. The DMA specimens were prepared using a unique technique. The relation between the mechanical and chemical changes of the resin during DMA was clarified. The cured PF resin had better thermal stability than the IC resin cured with water. The improvement of thermal stability in cured IC resin by heat treatment was considered to be less effective. The effect of the heating rate on the mechanical properties was also investigated. The apparent activation energy in the thermal degradation of cured IC resin was calculated based on the results obtained.Part of this paper was presented at the 47th Annual Meeting of the Japan Wood Research Society, Kochi, April 1997     

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     

脲醛树脂分子量分布与胶合性能关系的研究（续）：分次加尿素对脲醛树？…

主要探讨分次加尿素对脲醛树脂分子量分布及胶合性能的影响。研究结果表明：在脲醛树脂合成吕，分次加入尿素，不仅可起到降低胶中游离醛的作用，同时还可起到分子量的调解作用。尤其是加入第２次尿素时，对胶中大分子部分可起到降解重排、减少胶中醚键含量的作用，从而达到低毒的目的。加入第２次尿素时，可能会改变脲醛树脂的反应机理。     

稻草中密度纤维板用改性脲醛树脂的研究

对比三聚氰胺、二甲基硅油、硅树脂和偶联剂KH-550四种改性剂改性的脲醛(UF)树脂性能的差别及其对稻草中密度纤维板性能的影响,并进行经济评价,最终确定适用于稻草纤维板的改性UF树脂的工艺条件,同时借助于红外光谱(FT-IR)和差热扫描分析(DSC)研究最佳改性UF树脂的结构和固化特性.结果表明,三聚氰胺改性脲醛(MUF)树脂不论是对树脂性能、板性能改善还是从成本分析方面均为稻草纤维板最佳的胶黏剂,FT-IR显示出与未加三聚氰胺相比,加入三聚氰胺后树脂的羟甲基含量降低了10 %,DSC分析则表明其峰值温度有较大幅度的提高,但放出的热量较少.加入三聚氰胺改性的UF树脂其表面张力变小.     

基于UFC和葡萄糖改性脲醛树脂的合成与性能

在碱性条件下用尿素和甲醛合成脲醛预缩液(UFC),然后用UFC与尿素制备脲醛树脂(UFC/U),并添加葡萄糖对UFC/U改性得到G/UFC/U树脂,采用DSC和FT-IR等对树脂进行分析。结果表明:与普通脲醛树脂(UF)相比,UFC/U树脂胶合强度提高5.83%,游离甲醛含量降低3.70%,G/UFC/U树脂贮存期大于30 d,综合性能较好,G_1-25/UFC/U树脂游离甲醛含量降低44.44%,胶合板湿胶合强度为1.11 MPa,优于国家II类胶合板标准;DSC结果表明:UFC/U、G_1-25/UFC/U比UF树脂的固化特征温度高;FT-IR分析表明:G_1-25/UFC/U和UF树脂相比,羟基及亚甲基醚键的峰强度增强,改性树脂的羟甲基优先和葡萄糖分子C(6)的羟基发生反应生成亚甲基醚键。     

Development of new natural polymer-based wood adhesives I: dry bond strength and water resistance of konjac glucomannan,chitosan, and their composites

 Bonding properties of konjac glucomannan (KGM), chitosan, and their composites were investigated. After preparing three-ply plywood glued with these materials, the dry bond strength and the bond strength after water immersion treatment were measured. The bond strength of urea-formaldehyde resin adhesive, casein, and soybean glues was also studied for comparison. KGM developed relatively good dry bond strength in extremely small solid amounts, irrespective of alkaline treatment. However, the water resistance was extremely low for all of the conditions. Chitosan also developed good dry bond strength in small solid amounts and was better than conventional adhesives. Chitosan also exhibited excellent water resistance compared to casein and soybean glues. When KGM and chitosan were combined, the adhesiveness under the dry condition was enhanced, and the bonding properties were superior to those of casein and soybean glues. Therefore, it is expected that chitosan and chitosan–KGM composite can be used as environmentally friendly wood adhesives. Received: March 18, 2002 / Accepted: July 5, 2002 RID="*" ID="*" Part of this paper was presented at the 51th Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001     

Properties of wheat straw particleboards bonded with different types of resin

Wheat straw particleboard bonded with a urea–formaldehyde (UF) resin, usually employed in the manufacture of wood-based particleboards, or with a resin based on epoxidised oil was manufactured using a compression molding machine. The effects of resin type on internal bond strength, flexural modulus, and thickness swelling were examined. The properties of boards using UF resins were poor. Internal bond strength and thickness swelling, linked to adhesion quality, were especially low. The high compatibility between straw particles and oil-based resin was explained in terms of straw surface free energy. In straw, this parameter exhibits a much lower polar component than wood species and leads to higher compatibility with resins based on oil than with water-soluble systems like UF.     

腰果酚二醚曼尼希碱固化剂的合成及其相分离现象研究

腰果酚(CD)和1,3-二溴丙烷经Williamson醚化反应得到一种腰果酚二醚化合物(CDE),然后以CDE、多聚甲醛和二乙烯三胺为原料,经Mannich反应制备得到一种浅色的腰果酚二醚曼尼希碱固化剂(MBCDE)。通过傅里叶红外光谱(FT-IR)和核磁共振氢谱(~1H NMR)表征了产物的化学结构,并与氨乙基哌嗪(AEP)进行对比研究其相关性能。通过热重分析(TGA)、扫描电镜(SEM)和力学性能测试研究了两种固化剂与双酚A环氧树脂(DGEBA)固化材料的相关性能。结果表明:MBCDE/DGEBA的最大分解温度为351.6℃,具有良好的热稳定性。AEP/DGEBA环氧固化物的冲击强度为3.641 J/m,而添加80%的MBCDE后固化物的冲击强度则为5.155 J/m,提高了41.6%。SEM分析结果表明MBCDE固化材料中存在相分离。     

单板层积材的加速老化性能研究

本文对高频胶合的马尾松LVL和杨木LVL的老化性能进行了讨论,并比较了乳液酚醛树脂胶和酸固化酚醛树脂胶在BDB28和A1080加速老化后的胶合剪切强度的损失率。得出的结论如下:1)乳液酚醛树脂肢胶合的马尾松LVL,胶合剪切强度随老化时间的延长逐渐趋于稳定,最后稳定在老化前强度的70％左右;2)乳液酚醛树脂胶的老化性能比酸固化酚醛树脂胶好;3)对于乳液酚醛树脂胶马尾松LVL和酸固化酚醛树脂胶杨木LVL,可以用BDB28处理方法代替A1080加速老化方法快速测定其胶合剪切强度的损失率。     

水性异氰酸酯胶合板与细木工板的研究

以水性异氰酸酯胶粘剂试制胶合板和细木工板。研究结果表明,单板的材种和施胶量等对异氰酸酯胶合的板材性能有较大影响;采用异氰酸酯,胶合板用胶量较少,在施胶量为200g/m~2时,马尾松、杨木、荷木、枫木单板制成的胶合板胶合强度均能达到GB/T5849-1999的要求,枫木作中板的细木工板在施胶量为250g/m~2时胶合强度和横向静曲强度均达到国家标准;根据试验结果并结合生产实际的成本分析表明,胶合板成本增加了81～189元/m~3,细木工板的成本增加了120元/m~3和104元/m~3。     

Utilization of sweet sorghum bagasse and citric acid for manufacturing of particleboard II: influences of pressing temperature and time on particleboard properties

Development of environmentally friendly particleboard made from sweet sorghum bagasse and citric acid has recently attracted attention. In this study, we investigated the effects of pressing temperature and time on physical properties, such as dry bending (DB), internal bond strength (IB), and thickness swelling (TS) of particleboard. Wet bending (WB), screw-holding power (SH), biological durability, and formaldehyde emission of particleboard manufactured under effective pressing temperature and time were also evaluated. Particleboards bonded with phenol formaldehyde (PF) resin and polymeric 4,4′-methylenediphenyl isocyanate (pMDI) were manufactured as references. Effective pressing temperature and time were 200?°C and 10 min, respectively. It was clarified that DB, IB, and TS satisfied the type 18 requirements of the JIS A 5908 (2003), and were comparable to those of particleboard bonded with PF and pMDI. The WB and SH of particleboard did not satisfy type 18 of JIS. Particleboard manufactured under effective pressing conditions had good biological durability and low formaldehyde emission. Based on the results of infrared spectra measurement, the degree of ester linkages increased with increased pressing temperature and time.     

封闭异氰酸酯改性脲醛树脂制备胶合板

采用亚硫酸氢钠封闭异氰酸酯改性UF树脂制备胶合板,研究了制板用混合胶液的比例、热压时间、热压温度等热压工艺对胶合板性能的影响,结果表明,在UF/PAPI=100/10、热压温度为110℃、热压时间为4min时,所制备胶合板的甲醛释放量达到国家标准,并且具有较高的胶合性能.     

C NMR 定量分析

按酚醛(PF)树脂的制备工艺,采用CaO和NaOH为复合催化剂,在碱性条件下制备了95%～200%的系列尿素改性酚醛(PUF)树脂,贮存期达30 d以上。该系列PUF树脂压制的杨木三合板,胶合强度符合Ⅱ类胶合板要求,甲醛释放量<0.5 mg/L,符合E0级。其中选用尿素/苯酚(U/P)质量比为1.5∶1,甲醛与尿素-苯酚(F/(U+P))物质的量的比值为0.97的配方制胶,结合13C NMR分析手段,监控投料甲醛在反应过程中形成的亚甲基、羟甲基和亚甲基醚键的含量变化,以及最终PUF树脂的亚甲基(32.4%)、羟甲基(57%)和亚甲基醚键(10%)的结构比例。     

水性异氰酸酯交联剂的应用研究

采用不同链长的聚醚多元醇与多亚甲基多苯基多异氰酸酯（PAPI）反应,制备了两种不同结构的水性异氰酸酯（P-C、P-D）,联剂分别加入到氧化玉米淀粉胶黏剂和脲醛树脂胶黏剂中,以改善胶黏剂的胶接性能。通过粘接强度测试研究不同结构、不同用量的水性异氰酸酯对改性胶黏剂的胶接强度和耐水性的影响。实验结果表明：氧化玉米淀粉和脲醛树脂中加入水性异氰酸酯交联剂制备胶合板,胶接强度及耐水性均有显著提高。氧化玉米淀粉胶黏剂中加入10%的水性异氰酸酯P-D后,所制备胶合板的干态剪切强度可达2.64MPa。脲醛树脂胶黏剂中加入7.5%的P-D后,干态、湿态剪切强度分别为1.24MPa和1.23MPa,甲醛释放量为0.31mg/L,达到E0级标准。     

Phenol-formaldehyde resin curing and bonding under dynamic conditions

Summary To better understand the curing and bonding behavior of phenol-formaldehyde (PF) resin under dynamic conditions, flakeboards were manufactured either by conventional pressing at 7% or 12% mat moisture content or by steam injection pressing with 10 or 20 seconds steaming duration. Resin-impregnated glass-cloth samples and lap-shear tension specimens were embedded in the core of each flakeboard. After the flakeboards were pressed for various periods of times, the samples and specimens were quickly retrieved. The degree of resin cure was determined on the resin-impregnated glass-cloth samples by dynamic mechanical analysis. The bond strengths were measured from the lap-shear tension specimens on a mechanical testing machine. The results of resin curing and bonding were then correlated to the performance of the resin-bonded boards, which were evaluated by internal bond, modulus of rupture, modulus of elasticity, and thickness swelling. Resin curing and lap-shear bonding did not proceed simultaneously. In conventional pressing, the mat moisture content (MC) at 12% favored resin curing, but slightly retarded lap-shear bonding, as compared to 7%MC. In steam injection pressing, the rates of resin curing and lap-shear bond strength development were much faster for 20 seconds than for 10 seconds of steaming duration. Longer press times were needed to obtain boards with maximum strength in the 12%MC conventional pressing and the 20-s steam duration steam injection pressing than in those conditions where moisture content was lower or steam time was less. The need for longer press times must be attributed to higher internal vapor pressures and/or lower wood and resin component strengths, rather than to incomplete cure or bonding.This material is based on work supported by the Ministry of International Affairs, Quebec Government, the Natural Sciences and Engineering Research Council of Canada, and Laval University (Quebec City). The work was also supported by the U.S. Department of Agriculture under research joint venture agreement FP-92-1835     

The Degradation of Particleboard Strength

AlthoughPFresinsaregeneralIyrecognizedtobemuchdurablcthanUFresins,thcreisnotaclcardifferencebetwCcnparticlebordsbondedwiththesetwoadriesives.Infact,anumberofresearchcrshavefoundUFresinbondedparticleboardsandPFresinbondedparticleboardstodisplaythesimilarsh…     

Effect of postcure conditions on the dynamic mechanical behavior of water-based polymer-isocyanate adhesive for wood

To study the effect of postcure conditions on the viscoelastic behavior of water-based polymer isocyanate adhesives for wood (API adhesive), dynamic mechanical analysis (DMA) was performed for a simplified model of API adhesives under various postcure conditions. These conditions were achieved by storing the samples at room temperature or by heating them in an oven. Fourier transform infrared (FT-IR) spectroscopy was performed to test for residual isocyanate groups (NCO) and isocyanate derivatives to elucidate the reaction mechanism under the postcure conditions. DMA revealed that the postcure conditions led to wide variations in the viscoelastic behaviors of API films. FT-IR analysis confirmed the decrease of residual isocyanate during postcure treatments. However, the complete consumption of isocyanate could not be achieved under the postcure conditions. A good correlation was found between the DMA result and the chemical changes in the API samples heated above 140°C. However, no correlation was observed in the case of the samples heated at temperatures less than 140°C. This implies that postcure conditions led to a difference in the reaction chemistry of API. Part of this article was presented at the 55th Annual Meeting of the Japan Wood Research Society, Kyoto, March 2005     

Effects of sealed press on improving the properties of particleboard

To improve the properties of particleboard, boards were produced using a sealed press. With the sealed press, boards were processed under high-temperature and high-pressure steam. This increased the saturation temperature, causing a dramatic rise in temperature inside the board, faster curing of the binder, and a shorter pressing time. The boards were bonded with urea formaldehyde resin, melamine urea formaldehyde resin, or poly(methylene diphenyl diisocyanate) (PMDI). The sealed press improved the internal bond strength and thickness swelling of boards regardless of the binder used during the reduced pressing time. The increased bonding strength improved the board properties, allowing PMDI with a lower resin content to be used for bonding the boards.