Kinetics of the hydroxymethylation of phenol II: values of rate parameters and results of simulation experiments

The reaction course of the sodium hydroxidecatalyzed hydroxymethylation of phenol was analyzed by use of high-performance liquid chromatography (HPLC), and the rate constants for the seven reactions taking place consecutively and competitively were evaluated by means of a computer simulation technique. Calibration was done at the quantification of the six phenolic monomers from the peak areas in the HPLC chromatogram, taking the differences in molar ultraviolet absorption intensities of the six compounds into account. The values of the energies of activation for the seven reactions obtained differed greatly from those reported by Eapen and Yeddanapalli. Simulation experiments carried out by use of the newly obtained rate parameters showed that the amounts of phenol left unreacted and 2,4,6-trihydroxymethylphenol in the final reaction product increased as the reaction temperature was increased and the alkali/phenol molar ratio decreased. These phenomena can be attributed to the differences in the energies of activation for the seven reactions and differences in the acid strengths of the six phenolic monomers.Part of this paper was presented at the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998 and at the 1998 annual meeting of the Forest Products Society, Merida, Mexico, June 1998     

Factors affecting the resinification of liquefied phenolated wood

Wood of Chinese fir and poplar were liquefied in phenol at 150℃ and atmospheric pressure. The liquefied wood were reacted with formaldehyde to synthesize the liquefied wood-based resin. The factors affecting the resinification and the properties of new resin were investigated. The results show that the formaldehyde/liquefied wood molar ratio, reaction temperature, reaction time and sodium hydroxide/liquefied wood molar ratio have important influence on the resin characteristics. With the increase of formaldehyde/liquefied wood molar ratio, the yield of resin increases, and the flee phenol content of resins decreases, showing that the resinification of liquefied wood is more complete at higher formaldehyde/liquefied wood molar ratios. The reaction temperature on the viscosity of the liquefied resin has considerable effect; the viscosity of resin increased with increasing reaction temperature, and the amount of liquefied poplar resin increased more quickly than that of liquefied Chinese fir resin. The resinification time also has obvious influence on the viscosity of resin; the viscosity of liquefied poplar resin is more sensitive to resinification time compared with that of liquefied Chinese fir. The amount of sodium hydroxide can improve the water miscibility of liquefied wood resin. The optimum sodium hydroxide/liquefied wood molar ratio for preparation of liquefied wood-based resins exceeds 0.4.     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate II: Hydroxymethylation and subsequent sulfonation of phenolized lignin model compounds

Highly condensed lignin can be transformed by three reactions — phenolation, hydroxymethylation, and neutral sulfonation — to water-soluble lignosulfonate. To elucidate reactivities and products in the latter two reactions, simple compounds were selected as lignin model compounds. With hydroxymethylation of creosol at 60°C, the yield of a condensed-type product with the diarylmethane structure was less than 10%. Hydroxymethylation of 1-guaiacyl-1-p-hydroxy-phenylethane (compound VI) as a phenolized guaiacyl lignin model compound gave four compounds. The initial reaction introduced the hydroxymethyl group mainly in the guaiacyl nucleus, and the additional reaction created two hydroxymethyl groups in the p-hydroxyphenyl nucleus. Contrary to our estimation, treatment of the models with ¹³C-labeled formaldehyde (H¹³CIIO) did not form any diarylmethane structure. Neutral sulfite treatment of hydroxymethylated products gave corresponding sulfonates in high yields. Phenolized guaiacylglycerol--aryl ether (compound XVI) showed a reactivity similar to that of compound VI.This paper was presented at the 45th and 46th annual meetings of the Japan Wood Research Society at Tokyo and Kumamoto, April 1995 and April 1996, respectively     

竹材加工剩余物液化及液化产物制备发泡树脂的工艺研究

采用苯酚和聚乙二醇-400复合液化试剂,对竹材加工剩余物进行液化和液化产物的树脂化试验。采用单因素法,探讨主要工艺因素对液化效果及对树脂性能的影响,得到竹材酚醇复合液化工艺及树脂化工艺的优化参数。利用液化产物制备的树脂,可用于制造建筑用发泡材料,提高竹材加工剩余物的附加值。     

油茶饼粕苯酚液化物的树脂化研究

以油茶饼粕苯酚液化物为原料制备酚醛树脂,测定树脂的理化性能,评价树脂的胶合性能.考察了甲醛与苯酚的摩尔比(F/P)、氢氧化钠与苯酚的摩尔比(NaOH/P)和树脂化时间对树脂理化性能和胶合性能的影响.结果显示,在F/P 1.8、NaOH/P 0.6、树脂化时间70 min的条件下合成的酚醛树脂压制的胶合板能满足Ⅰ类胶合板强度要求.FTIR分析显示液化物树脂具有常规酚醛树脂典型的官能团特征,树脂中含有较多的羟甲基等活性官能团.     

PMUF树脂胶黏剂的制备与性能

以尿素和三聚氰胺作为酚醛树脂改性单体制备苯酚-三聚氰胺-尿素-甲醛(PMUF)树脂胶黏剂,研究甲醛、苯酚、尿素、三聚氰胺及氢氧化钠用量对PMUF树脂胶黏剂性能的影响,并采用DSC和13C-NMR对其进行表征.结果表明:PMUF树脂游离甲醛含量低,能满足耐水、耐候性能要求较高的人造板产品的生产.当甲醛、苯酚、尿素、三聚氰胺、NaOH的摩尔比为3.1∶1∶0.7∶0.3∶0.5时胶黏剂性能最佳,其最佳固化温度为135.5℃.     

核桃壳苯酚液化及其产物树脂化制备木材胶黏剂的研究

采用硫酸催化剂,考察了苯酚与核桃壳质量比等条件对核桃壳液化的影响。结果表明相同液化条件下,随着苯酚与核桃壳质量比从2∶1升至5∶1,残渣率从26.49%降至6.60%;随着浓硫酸加入量从2%增至4%、反应时间从5 min延至120 min、反应温度从100℃增至150℃,残渣率则分别从20.79%降至10.48%、48.84%降至15.62%、28.86%降至9.39%,游离酚含量分别从17.32%降至12.67%、41.71%降至10.25%、21.94%降至14.33%。同时,液化产物重均相对分子质量(MW)可降至706~1 030、分散度可降至1.04~1.25;液化产物中高相对分子质量部分随着苯酚与核桃壳质量比的增加有所降低,但随着浓硫酸加入量、液化反应时间和温度的增加而有所增加;核桃壳液化产物/苯酚/甲醛共缩聚树脂胶黏剂(WPF)与传统酚醛树脂胶黏剂(PF)的对比表明,WPF的胶接强度可达1.33 MPa,可作为胶合板用胶黏剂。     

The receptivity of powdered beech wood (Fagus crenata) to cyanuric chloride

Summary The chemical modification of powdered beech wood by reaction with cyanuric chloride (2,4,6-trichloro-s-triazine) is discussed in terms of the reaction time and temperature, as well as the concentration of the aqueous sodium hydroxide solutions used in the preparation of alkali-treated wood powders. The influence of the surface structure of wood on the receptivity of alkali-treated wood powders to this reagent is also discussed. The amount of cyanuric chloride taken up by the wood powder treated with the highest concentration of aqueous sodium hydroxide (18% NaOH) is about 0.8 mmol/g. This exceeds the theoretical amount of cyanuric chloride which can be reacted with the primary surface in the void model previously proposed. the extent of cross-linking at longer reaction times is minimal in case of the treatment of wood with 0.8% sodium hydroxide. On the other hand, the hydrolysis of C–Cl bonds of the second and third chlorine on the s-triazine ring and/or the internal cross-linking reactions are accelerated by increases in the concentration of sodium hydroxide. However, these reactions (the hydrolysis of C–Cl bonds and the internal cross-linking) are independent of the change in the structure of wood caused by the mercerizing alkalinity.The authors are thankful to K. Sakurai of the Forestry and Forest Products Research Institute for his elemental analyses for nitrogen and chlorine     

思茅松的苯酚液化及树脂化研究

研究了硫酸催化条件下，将恩茅松在苯酚中液化用于制备酚醛树脂的技术工艺，分析了各工艺参数对思茅松液化效率的影响，测定了由液化产物制备的液化木基酚醛树脂的物理化学性质和胶合强度。结论如下：1）．液比、反应温度、时间和木粉目数是影响液化反应效率的重要因素，液化产物的残渣率均随上述工艺参数值的升高而降低。2）．残渣含量对树脂物化性质和胶合强度均有影响，残渣含量降低，树脂粘度减小，聚合时间缩短，游离酚含量降低，胶合强度升高。3）．甲醛／苯酚摩尔比对树脂的物化性质和胶合强度也有影响，甲醛／苯酚摩尔比增加，树脂粘度增加，聚合时间减少，游离酚含量减低，胶合强度升高。     

Predicting the hydroxymethylation rate of phenols with formaldehyde by molecular orbital calculation

The rates (k) of hydroxymethylation of phenol, resorcinol, phloroglucinol, and several methylphenols in diluted 10% dimethylformamide aqueous alkaline solution were calculated based on the consumption of phenols and formaldehyde. Thek values of phloroglucinol and resorcinol relative to that of phenol were about 62000 and 1200 times, respectively. The phenols that have methyl or hydroxyl groups at the C-3 or C-5 position (or both) have larger rate constants than phenols with substituents at other positions. Several kinds of atomic charge of the carbons on the aromatic ring of phenols were calculated using the semiempirical orab initio method. The correlations between the averagek (Ave.k) and average electrostatic charges (Ave.q) at the carbons were fairly good. Highest occupied molecular orbitals (HOMO) were observed. The best correlation between Ave.k and Ave.q was obtained when diphenols and triphenols were assumed to exist in solution as their respective di-anion.     

酚醛树脂原料配比对麻毡板性能的影响

研究了酚醛树脂的不同原料配比对麻毡板性能的影响。结果表明：1)麻毡板的内结合强度随着F／P摩尔比的增加而增加，随尿素用量的增加而降低；在一定范围内，碱用量、甲基葡萄糖甙(TD)的用量对其影响不大。2)麻毡板的吸水厚度膨胀率随着F／P摩尔比的增加而减少，随着碱、尿素、甲基葡萄糖甙用量的增加而增加。适宜的原料配比为：尿素量在树脂总量的4％，F／P摩尔比为2．0，NaOH／P摩尔比为0．06，甲基葡萄糖甙在树脂总量的4％。     

结构集成材用胶粘剂的研究

本文探讨了络合剂的种类与加入量对树脂性能的影响和初摩尔比与终摩尔比对树脂的工作时间、凝胶时间、贮存期及胶合性能的影响。结果表明:(1)合成时需加入20％的丙酮与烷基间苯二酚络合能抑制烷基间苯二酚的活性;(2)初摩尔比为0.3～0.5时均可合成胶合性能优良的树脂胶;(3)终摩尔比为1.3～1.6。     

Comparative analysis of a wood: adhesive bondline

The wood–adhesive interface was analyzed using five methods with the objective of quantitatively assessing penetration of adhesive into the porous wood network. Methods included fluorescence microscopy, scanning electron microscopy, backscatter electron imaging, wavelength dispersive spectroscopy, and X-ray microtomography (XMT). Each method provided a visual inspection, and all of the analysis methods were applied to the same field of view. XMT was the primary technique of interest. Rubidium hydroxide was used in place of sodium hydroxide in the formulation of phenol–formaldehyde adhesive. Rubidium was found to increase the X-ray attenuation of the adhesive. However, rubidium migrated beyond the adhesive interphase during specimen preparation, thus reducing its effectiveness for image contrast enhancement. The wood species studied included red oak (Quercus rubra), Douglas-fir (Pseudotsuga menziesii), and hybrid poplar (Populus deltoides × Populus trichocarpa). All techniques used for this study were useful, but each presented some limitations for bondline analysis. Despite the problem with rubidium migration, XMT for this application was promising.     

Dynamic wettability and curing characteristics of liquefied bark-modified phenol formaldehyde resin (BPF) on rice straw surfaces

Larch bark was liquefied in the presence of phenol and the obtained liquefied resultant was reacted with formaldehyde to prepare the liquefied bark-modified phenol formaldehyde resin (BPF) in an attempt to apply for preparing straw boards. The dynamic wettability of the BPF resin was evaluated on the surfaces of rice straw; either on the alkali solution treated or untreated rice straw surfaces. A new wetting model was employed to quantify the resins’ penetration performances using the spreading–penetration parameters (K value) as a constant to characterize penetration rate. The bigger the K value was, the stronger the penetration and spreading capacity was. Moreover, the curing kinetics of the BPF resin was also investigated with dynamic differential scanning calorimetry. The results showed that the K value of BPF resin was the highest, followed by those of BPF mixed with polymethylene diphenyl diisocyanate PMDI resin and conventional phenol formaldehyde (PF) resin, indicating that the BPF resin had the best wettability. The activation energy of BPF was close to that reported for wood/phenol/formaldehyde resins, but was higher than that of PF resin. The curing reaction was almost complete at 40 % conversion.     

光催化提高黑荆树单宁与甲醛反应能力研究

为提高黑荆树单宁与甲醛反应能力,以纳米TiO 2为催化剂对黑荆树单宁进行紫外光催化降解。以降解物的甲醛结合量为指标,分析催化剂用量对黑荆树单宁降解产物甲醛反应能力的影响。采用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)测定黑荆树单宁和具有最大甲醛结合量黑荆树单宁降解产物的分子量和聚合度。采用傅里叶转换红外光谱(FT-IR)对黑荆树单宁及具有最大甲醛结合量黑荆树单宁降解产物的官能团进行表征。结果表明,催化剂用量对降解物甲醛结合量的影响较大,当紫外光功率为400 W、溶液初始质量浓度为60 g/L、反应温度为(35±5)℃、纳米TiO 2添加量为4%(质量分数,以黑荆树单宁质量计)、降解时间为10 h时,降解物的甲醛结合量达到最大值(1.13 g/g),超过了苯酚和间苯二酚的甲醛结合量(0.89 g/g和0.94 g/g),有替代苯酚和间苯二酚与甲醛反应制备木材用胶黏剂的潜能。MALDI-TOF MS分析表明,黑荆树单宁的聚合度和分子量均有明显地下降趋势,降解物分子量分布集中于低分子量部分。FT-IR分析表明,单宁结构中连接棓酰基的醚键、棓儿茶素的苯环骨架、芳醚键、单元间C—C连接键均被破坏。以上结果表明,可通过紫外光催化降解调控黑荆树单宁的化学组成并降低其聚合度和分子量,获得的降解物具有良好的甲醛反应能力。     

Preparation of sulfuric acid-catalyzed phenolated wood resin

Summary Birch wood meal was phenolated in the presence of sulfuric acid used as a catalyst by changing several reaction conditions, such as, phenol-to-wood ratio, temperature, time, and catalyst concentration to make novolak-type resin. A phenol-to-wood ratio of 2–5, reaction temperature of 60–150 °C, time of 60–120 min, and acid concentration of 1–3% were found to be usable values for obtaining good enough amounts of combined phenol and less amounts of unreacted wood residue. The flow properties (flow temperature and apparent melt-viscosity) of the phenolated wood obtained increased with the increase in the amount of combined phenol, however, decreased with the increase in the moisture content and free phenol in the phenolated wood. Furthermore, it was found that the solubility of the phenolated wood in the organic solvents depended, greatly, on the hydrogen bonding strength of the solvents.     

Determination of reaction rate parameters for the acid copper chromate fixation reactions on oak (Quercus castaneifolia C. A. Mey) sapwood

Acid copper chromate fixation reactions on oak (Quercus castaneifolia C. A. Mey) sapwood were characterized by at least two distinguished reaction periods which differ in their kinetic behavior, particularly reaction rate. In this research, chemical rate equation parameters were studied in detail as a function of chromium fixation time. Theoretically, the kinetic data were distinguished between the adsorption and reduction reactions and consequently, the rate parameters were determined for each stage distinctly. The obtained results showed that at the investigated thermal range (25–33°C), almost for every 3°C increase in temperature the reaction duration has decreased 20.4?min for the first reaction period and 78?min for the second reaction period. Besides that, in all sample replications, up to 58.3% of hydrogen ions function at the reduction reactions of the initial period, demonstrating that acidity (H⁺ ions) has a major effect on reaction rate constant. Accordingly, adsorption reactions of the hexavalent chromium at the starting point follow a pseudo-first-order kinetic reaction. Different to the adsorption reaction the Cr^VI reduction reaction is exothermic with a measured exothermal energy of 48.2?kJ/mol.     

The formation of LC and other aromatic end-group structures in <Emphasis Type="Italic">O</Emphasis>-alkyl-substituted cellulose during kraft pulping conditions

Ultraviolet resonance Raman spectroscopy (UVRRS) was used to study the formation of aromatic and/or lignin-carbohydrate (LC) structures at the reducing end groups of O-alkyl-substituted cellulose under conditions simulating the initial phase of kraft pulping. The derivatives studied were methyl cellulose (MC) with degree of substitution (DS) of 1.64–1.95, carboxymethyl cellulose (CMC) with DS ∼0.6, and a lignin model compound, creosol. The total alkali concentrations in the treatments were 0.1 M and 0.5 M and the sulfidities were 1%, 10%, and 30%. HS⁻ ions and creosol are both strong nucleophiles and they compete for the hot-alkali-generated unsaturated electrophilic reaction sites in the reducing end groups of the polysaccharides. The results indicated that conditions similar to those in the initial phase of conventional kraft cooking (high OH⁻ and low HS⁻ ion concentrations) increased the aromatic nature of the end groups and conditions similar to those in the initial phase of super batch cooking (low OH⁻ and high HS⁻ ion concentrations) partly inhibited the formation of aromatic and LC end groups.     

Condensation reactions of phenolic resins III: self-condensations of 2,4-dihydroxymethylphenol and 2,4,6-trihydroxymethylphenol (1)

This study reexamined the kinetics of the condensation reactions of hydroxymethylphenols with the purpose of elucidating the reaction mechanisms. This report discusses experimental results on the self-condensations of 2,4-dihydroxymethylphenols (2,4-DHMP) and 2,4,6-trihydroxymethylphenol (THMP), focusing on the order of reaction. The relations between the initial rates of reaction and the initial concentrations of reactants were investigated. Results quite different from those of previous reports were obtained. The order of reaction of the selfcondensation of 2,4-DHMP was found to be 1.1, which did not change with the alkali/2,4-DHMP molar ratio. The order of reaction of the self-condensation of THMP was found to vary with both the concentration of THMP and the alkali/THMP molar ratio. In the region of THMP concentrations above 1.5mol/l, the order of reaction was confirmed to be 2.0, which did not change with the alkali/THMP molar ratio. In the region of THMP concentrations below 1.0mol/l, the order of reaction varied with the alkali/THMP molar ratio, showing fractional numbers of 1.2–1.6. These results indicate that unimolecular reaction(s) and bimolecular reaction(s) take place simultaneously as the ratedetermining step in the condensation reactions of 2,4-DHMP and THMP and that the reaction mechanism changes with the species of reactant and, in some cases, with the reaction conditions.Part of this study was presented at the Wood Adhesives 2000 symposium, South Lake Tahoe, Nevada, USA, June 2000     

Curing kinetics study of melamine–urea–formaldehyde resin/liquefied wood

The objective of this research was to investigate the effect of liquefied wood (LW) on the cure kinetics and network properties of melamine–urea–formaldehyde (MUF) resins by differential scanning calorimetry. The MUF/LW compounds exhibited two distinct cross-linking processes. It can be assumed that there did not appear to be a coreaction of the MUF with the LW. The overall apparent activation energies (E _a) of the curing reactions were calculated using the Kissinger equation. An nth-order kinetic model was used to describe the cross-linking of MUF/LW compounds, of various compositions, cured at different heating rates. The E _a values for the cross-linking process of the MUF/LW compounds predominantly tended to be approximately 80 and 71 kJ mol^?1 for MUF and LW, respectively. The apparent reaction orders of the MUF cross-linking process of the MUF/LW compounds were in the range 1–2, whereas the n values of the LW were approximately unity or less, which hints to there being a more complex mechanism of this process.