Kinetics of wood phenolysis in the presence of HCL as catalyst

Monarch birch wood (Betula maximowiczina Regel) wastes were phenolated in the presence of HCl as a catalyst at 60–150°C for various reaction times. Typical kinetic parameters along with percent reacted wood and phenol were determined by using kinetic models. In addition, according to the transition‐state theory the activation parameters of wood phenolysis was determined. The percent reacted wood wastes depicted that about 90% of the wood could be liquefied into phenol at a temperature of 150°C. However, about 30% of phenol was found to react with wood components. The kinetic studies showed that wood phenolysis with HCl catalyst at 60–150°C obviously followed a bimolecular type of second‐order reaction. Activation energy was found to be 13.438 kJ mol^?1 from an Arrhenius plot. Furthermore, the findings related with activation enthalpy showed that the wood phenolysis had dominantly endothermic reaction nature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1098–1103, 2002     

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     

Synthesis and properties of polyurethane resins based on liquefied wood

Three polyurethane resins were synthesized from liquefied wood and three diisocyanates, i.e., TDI, IPDI, and HDI. The liquefied wood was obtained by the liquefaction of benzylated wood wastes using Dibasic esters (DBE) as solvent with hydrochloric acid as catalyst for 3 h, at 80°C. The thermal stability and microphase morphology of polyurethane films were investigated by TG, DSC, WAXD, and SEM methods. The experimental results indicated that polyurethane resins from liquefied wood had higher thermal stability than traditional ones, and the special structure and the difference of chemical structure of diisocyanates resulted in the crytallinity and microphase separation of obtained polyurethanes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 351–356, 2004     

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     

杉木液化产物用于胶粘剂制备的研究

研究用少量的苯酚液化木材及其产物用于胶粘剂制备的方法,在硫酸催化剂作用下,用苯酚液化杉木木粉,得到木材液化产物.在液化产物中加入适量的甲醛和氢氧化钠溶液制备热固性酚醛树脂.压板测试结果表明,由木材液化产物所得树脂的干状胶合强度令人满意,但经蒸汽循环试验后,湿状胶合强度尚达不到JAS标准的要求,在下阶段工作中,需进一步研究木材液化产物胶粘剂的改性以提高其胶合耐久性.     

木材加工用耐水性苯酚液化树皮-甲醛胶粘剂的研制

树皮是一种来源丰富可再生的天然高分子材料。本文采用高温苯酚液化的方法,在复合酸存在下将落叶松全树皮液化成为木材胶粘剂的原料。研究了树皮液化产物制备木材胶粘剂的合成工艺,特别是碱用量对苯酚液化落叶松全树皮一甲醛胶粘剂各主要性能的影响。结果表明,增加碱用量会缩短树皮胶的贮存期,但可降低胶中的游离甲醛;通过降低树皮胶合成时的终点黏度,并在合成末期用水稀释,可有效提高树皮胶的适用期,并可确保树皮胶具有很好的胶接强度和耐水性、较快的固化速率以及很低的游离甲醛释放量。     

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     

Characterization of liquefied wood residues from different liquefaction conditions

The amount of wood residue is used as a measurement of the extent of wood liquefaction. Characterization of the residue from wood liquefaction provides a new approach to understand some fundamental aspects of the liquefaction reaction. Residues were characterized by wet chemical analyses, Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), and scanning electron microscopy (SEM). The Klason lignin content of the residues decreased, while the holocellulose and α‐cellulose contents increased as the phenol to wood ratio (P/W) increased. A peak at 1735 cm^?1, which was attributed to the ester carbonyl group in xylan, disappeared in the FTIR spectra of the residues from liquefied wood under a sealed reaction system, indicating significantly different effects of atmospheric versus sealed liquefaction. The crystallinity index of the residues was higher than that of the untreated wood particles and slightly increased with an increase in the P/W ratio. The SEM images of the residues showed that the fiber bundles were reduced to small‐sized bundles or even single fibers as the P/W ratio increased from 1/1 to 3/1, which indicated that the lignin in the middle lamella had been dissolved prior to the cellulose during liquefaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

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     

Molecular weight distributions in novolac type phenol-formaldehyde polymerizations

In the acid-catalysed condensation polymerization of phenol and formaldehyde, the ortho and para positions of the phenol ring are known to exhibit different reactivities^1,2. Along with this on polymer molecules, the internal sites have lower reactivity due to molecular shielding. To model the novolac formation, five reactive sites have been proposed³ and their reactivities are assumed to be completely determined by the site involved. To find the molecular weight distribution (MWD) of the polymer from this information, a given polymer chain has been assumed to consist of these sites in the same relative ratio as in the reaction mass. A mass balance, on polymer molecules of given size, has been made and solved numerically as a function of time. The sensitivity analysis has been carried out to show that the MWD is little affected by the variation of reactivities of the internal sites. The reactivity of para external positions and the ratio of phenol and formaldehyde, however, play a major role in determining the MWD.     

Molecular weights and molecular weight distributions of irradiated cellulose fibers by gel permeation chromatography

Radiation degradation of cellulose fibers was investigated by gel permeation chromatography (GPC). Scoured cotton of Mexican variety (cellulose I), Polynosic rayon (cellulose II), and their microcrystalline celluloses obtained by hydrolysis of the original fibers were irradiated by Co-60 γ-rays under vacuum or humid conditions. The irradiated samples were then nitrated under nondegradative conditions. The molecular weights and molecular weight distributions were measured by GPC using tetrahydrofran as solvent. The relationship between molecular weight and elution count was obtained with cellulose trinitrate standards fractionated by preparative GPC. The degree of polymerization of the fibers decreased with increasing irradiation dose, but their microcystalline celluloses were only slightly degraded by irradiation, especially in microcrystalline cellulose from cellulose I. Degradation of the fibers irradiated under humid conditions was less than that irradiated under vacuum. It was found that the G-values for main-chain scission for the irradiated cellulose I, cellulose II, microcrystalline cellulose I, and microcrystalline cellulose II were 2.8, 2.9, less than 1, and 2.9, respectively, but the G-value for main-chain scission for the irradiated cellulose II was increased to 11.2 at irradiation doses above 3 Mrad. Consequently, it is inferred that cellulose molecules in the amorphous regions are degraded more readily, and the well-aligned molecules in crystalline regions are not as easily degraded by irradiation.     

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.     

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     

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.     

Properties of liquefied wood modified melamine-formaldehyde (MF) resin adhesive and its application for bonding particleboards

In this study, we modified melamine-formaldehyde (MF) resin adhesive with liquefied wood (LW) and determined the properties of MF–LW adhesive mixtures. Furthermore, we produced particleboards using prepared MF–LW mixtures and evaluated their mechanical and physical properties. Results showed that with increasing content of LW in the adhesive mixture gel time and peak temperature increased while reaction enthalpy decreased. With increasing substitution of MF resin adhesive with LW the thermal stability of adhesive mixture reduced, namely thermal degradation started at lower temperature and weight loss increased. Properties of particleboards improved with increasing amount of LW in the adhesive mixture up to 20% and then deteriorated. Nevertheless, the properties of particleboard with 30% LW in the adhesive mixture were comparable to the properties of particleboard without LW while they worsen at greater portion of LW. Consequently, MF resin adhesive with 30% LW substitution could be used to produce particleboards with suitable mechanical properties and reduced formaldehyde release content.     

液化石油气杂质含量的气相色谱法测定

通过恒温水浴完全气化样品,建立了用毛细管气相色谱法测定液化石油气中二甲醚、甲醇及甲缩醛含量的方法。采用PLOT/Q(30 m×0.53 mm×40μm)毛细管柱、热导池检测器,以面积校正归一化法计算杂质含量。结果表明:该方法操作简单,实用性强,重复性好,可以用于液化石油气中杂质含量的快速分析。     

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     

采用液化天然气冷量的空分系统新流程

从多个角度分析了空分装置中应用液化天然气(LNG)冷量的优势,针对不同的场合提出了2种引进LNG冷量的液体空分流程新方案。方案1适用于投资建设新设备的场合,方案2适用于现有流程的改造生产液体的场合,2种方案有一个共同点即使用LNG冷量冷却循环氮气制冷。采用Aspen P lus软件对2个方案进行了模拟计算,结果表明:引进LNG冷量之后,所需循环氮气量明显减少,系统最高运行压力降低由传统流程的4.2—5.0 MPa降低到2.1—2.6 MPa,液态产品的单位能耗从约0.5 kW.h/kg降低到0.327—0.338 kW.h/kg,节能效果明显。LNG气化过程中换热压力的提高对冷量回收影响较小,而采用液泵加压节省能耗,将气化过程安排在升压过程之后有利于能源的合理利用。     

Structure and gas permeation properties of asymmetric polyimide membranes made by dry–wet phase inversion: Influence of the polyimide molecular weight

In this article, we report the influence of the polyimide molecular weight (1.2 × 10⁵, 2.6 × 10⁵, and 4.1 × 10⁵) on the structure and the gas permeation properties of asymmetric polyimide membranes made by the dry–wet phase‐inversion process. The apparent skin layer thickness of the asymmetric membrane increased with increasing molecular weight, and the thicknesses of the membranes prepared from the three polyimides with a casting polymer solution containing 8.0 wt % butanol were 132, 350, and 739 nm, respectively. That is, the gas permeance in the asymmetric membranes increased with decreasing molecular weight. In contrast, the gas selectivity of the asymmetric membranes did not depend on the skin layer thickness. The solvent evaporation in the dry phase‐inversion process and the nonsolvent diffusion in the dry process were important factors that determined the formation of the asymmetric membrane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010