苯酚液化落叶松全树皮胶粘剂的制备

树皮是一种丰富的可再生天然高分子材料,随着石油资源的日趋短缺,研究并合理利用树皮制备高分子材料具有积极意义。首先在复合酸存在下采用高温苯酚液化法将落叶松全树皮进行液化处理,然后以此作为部分苯酚的替代物,制备耐水环保型树皮胶(即苯酚液化落叶松全树皮-甲醛胶粘剂)。重点研究了不同加碱次数对树皮胶主要性能的影响。结果表明:加碱次数对树皮胶的理化性能影响较大;采用2次加碱工艺制成的树皮胶具有相对最好的综合性能,其胶接性能及游离甲醛释放量均与纯酚醛树脂(PF)胶相当;苯酚液化落叶松全树皮对苯酚的替代量达到30%,但所得系列树皮胶的储存期较短。     

低游离甲醛含量酚醛树脂胶粘剂的合成

采用两次加碱一次回流法合成工艺代替一次法和两次碱法制备了酚醛树脂胶粘剂。对产物粘度,游离甲醛含量及固化物拉伸剪切强度测试,研究了酚醛比、催化剂加入量、反应温度、回流时间等对产物性能的影响。结果表明:苯酚与甲醛物质的量比1∶2,催化剂加入量为苯酚质量分数的25%,回流反应45 min可得到具有交联结构的酚醛树脂胶粘剂,产品分子质量及粘度适中,拉伸剪切强度可达到5 MPa以上,游离甲醛质量分数<0.03%,稳定性较好。     

核桃壳液化产物制备木材胶粘剂的研究

研究了核桃壳苯酚液化产物制备的酚醛树脂类木材胶粘剂及性能。结果表明,核桃壳经酸催化苯酚液化一段时间后,液化混合液的残渣率、游离苯酚和可被溴化物质量分数分别为22.11%、18.00%和33.10%,利用此液化混合液替代苯酚,所制备的酚醛树脂类胶粘剂能够满足混凝土模板用胶合板生产的要求。     

低摩尔比脲醛树脂胶粘剂研究进展

从脲醛树脂胶粘剂的游离甲醛含量及其胶接制品的甲醛释放量,低摩尔比脲醛树脂的合成及不同固化体系下低摩尔比脲醛树脂的固化特性等方面,综述了近几年来低摩尔比脲醛树脂作为木材胶粘剂的研究进展。     

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/竹材人造板用酚醛树脂胶粘剂制备技术

<正>本技术采用苯酚、甲醛在催化剂碱作用下两步加料法制备了高羟甲基含量的耐水性好的酚醛树脂胶粘剂,可用于室外木/竹材人造板制备,胶合强度按I类胶合板耐水性测试法测定达2.8～4.3 MPa,游离甲醛含量为0.07%～0.27%,游离苯酚含量为2%～5%,固含量≥50%,pH≥8.0,粘度≥100 mPa,即各项性能参数均达GB/T 14732-2006国家木材工业酚醛树脂胶粘剂标准。合作方式:技术转让     

苯酚处理液体木质素改性酚醛树脂胶粘剂的制备及性能表征

在碱性条件下,液体木质素先经苯酚处理后替代部分苯酚对酚醛树脂进行改性,制备得到液体木质素改性酚醛树脂(LPF)胶粘剂。考察了催化剂用量(苯酚处理木质素时氢氧化钠用量)、苯酚与甲醛(P/F)的物质的量之比、聚合温度、聚合时间对LPF胶粘剂性能的影响。研究结果表明:当催化剂用量3%、n(苯酚)∶n(甲醛)=1∶1.975、聚合温度90℃、聚合时间50 min时,所制备的LPF胶粘剂的干湿胶合强度分别为3.15、1.46 MPa,较未经改性的PF胶粘剂分别提高了17.5%、8.1%,游离苯酚的含量降低至0.62%;LPF胶粘剂的游离甲醛含量为0.22%,固体含量为52.8%,黏度为125 mPa·s。红外分析结果表明,苯酚处理后的木质素可以代替苯酚与甲醛发生反应生成新的物质,该物质有可能与PF胶粘剂发生接枝共聚产生新的醚键桥接,由此也说明在制备LPF胶粘剂过程中木质素发生了化学反应。     

改性的花旗松碱树皮胶粘剂制造法

专利摘要全树皮制备的碱树皮产品,用二羟甲基脲改性,制取一种热固性树脂,可用于胶合板胶粘剂。制备方法是将针叶树皮进行粉碎,然后在90—100℃NaOH溶液里蒸煮,直到预定的甲醛反应能力达到,生产出一种液体碱树皮。这种液体碱树皮包含全树皮的组成,并不分离成特选的部分,然后用二元酸的二羟甲基酰胺,如二羟甲基脲在60—75℃进行改性,生产出本发明的碱树皮产品,可用于胶合板胶粘剂,具有耐水性,能够直接代替胶粘剂配方中的酚醛树脂达65%,这种产品单独或者在胶合板中受到足够的热量能熔融和固化。     

苯酚/甘脲改性脲醛树脂胶黏剂的制备及性能研究

以尿素和甲醛为原料、苯酚/甘脲为甲醛捕收剂制备脲醛树脂(UF)。增加苯酚/甘脲用量,脲醛树脂中游离甲醛的质量分数降低,固化时间增加。增加缩聚时间,脲醛树脂的黏度增加,游离甲醛的质量分数降低。研究结果表明,当苯酚质量分数为0.5%、甘脲质量分数为0.5%、三聚氰胺质量分数为1%、缩聚时间为20 min时,采用一次性加入甲醛、分批次加入尿素和改性剂的碱-酸-碱合成工艺制备的UF中的游离甲醛的质量分数约为0.042 6%,远低于浙江DB33-T-494的E1级指标。     

四种原料生物油-酚醛树脂胶粘剂特性研究

利用生物质快速热解液化产物制备燃料或化工产品已成为国内外的研究热点。将四种生物质原料(落叶松、杨木、棉秸秆和玉米秸秆)快速热解液化产物作为苯酚替代物,由此制备出不同种类的热解生物油-PF(酚醛树脂)胶粘剂,并探讨了胶粘剂胶接强度与热解生物油组成的关系。结果表明:落叶松热解生物油-PF胶粘剂的胶接强度最大(1.277 MPa),玉米秸秆热解生物油-PF胶粘剂的胶接强度最小(1.021 MPa);胶粘剂的胶接强度主要与热解生物油中酚类物质含量有关。     

Preparation and characterization of wood polyalcohol‐based isocyanate adhesives

Sugi (Criptmeria Japonica) wood meal was liquefied at 150°C with a mixture of poly(ethylene glycol) 400 and glycerin in the presence of a sulfuric acid catalyst. The resulting liquefaction products were used directly to prepare isocyanate adhesives via mixing with polymeric diphenylmethane diisocyanate without the removal of the residue. The properties of the liquefaction products and the performances of bonded plywood were tested. The results showed that the residue content decreased and the hydroxyl value increased as the reaction time increased. The viscosity and weight‐average molecular weight significantly changed with the reaction time. All the dry test results of the shear strength met the Japanese Agricultural Standard (JAS) criteria for plywood. After a cyclic steaming treatment, however, only the plywood bonding with adhesives from the liquefied wood with a reaction time of 1.5 h satisfied the JAS criteria. The wood failure was very low. The emissions of formaldehyde and acetaldehyde were extremely low. Liquefied‐wood‐based isocyanate adhesives have the potential to become ideal wood adhesives because of their bond durability, safety, and recyclability.     

杉木苯酚液化物合成热固型酚醛树脂的研究

以杉木为研究树种,对比不同料液比(木材与苯酚质量比)液化物与甲醛在碱性环境中反应,进行热固酚醛树脂制备试验。考察不同甲醛与苯酚物质的量之比值(r_F/P)、氢氧化钠与苯酚物质的量之比值(r_NaOH/P)和树脂化温度对树脂理化性能的影响。结果表明,采用料液比为1:2的液化物,r_F/P1.8,r_NaOH/P0.7,树脂化温度 80℃ 条件下合成的杉木液化物树脂压制的杨木三层胶合板满足I类胶合板强度要求,各项物理力学性能与常规PF树脂压制的板材相当,板材的甲醛释放量为 0.1 mg/L,远低于GB/T 9846-2004《胶合板》中的E₀级要求。     

发泡性竹材苯酚液化物/多聚甲醛树脂的合成研究

在碱性条件下由竹材苯酚液化物和多聚甲醛制备出具有优良发泡性液化竹基酚醛树脂.考查了竹材液化物树脂化时间、温度、多聚甲醛与苯酚的物质的量比、氢氧化钠与苯酚物质的量比等因素对液化竹材酚醛树脂(BPE)黏度及其固含量的影响.结果表明,采用n(多聚甲醛)/n(苯酚)=1.2,树脂化时间为2 h,温度为70℃,n(氢氧化钠)/n...     

Phenolic resol resin adhesives prepared from alkali-catalyzed liquefied phenolated wood and used to bond hardwood

Wood-based resol resins were prepared from both water- and sodium hydroxide (NaOH)-catalyzed liquefied phenolated wood. The effects of various reaction parameters, e.g. the concentrations of phenol and formaldehyde, temperature, and time, on the extent of yield, free phenol content, molecular weight as well as the gluability of the resol resins have been evaluated. As far as the yield, free phenol content, and molecular weight are concerned, the optimum conditions of resol resin preparation were found to be a phenol : wood weight ratio of 4 : 6, a formaldehyde : phenol mole ratio of 1.5 : 1, a temperature of 82.5°C, and time 3 h. However, these optimum conditions changed when the performance of the adhesives was considered in terms of the adhesive bond strengths for plywood joints. The yield, molecular weights, polydispersity, and gluability of resol resins prepared from water-catalyzed liquefied wood were lower compared with those prepared from NaOH-catalyzed ones. In most cases, the dry-bond strengths of the experimental plywood joints exceeded the minimum Japan Agricultural Standard (JAS) values. On the other hand, except at a higher formaldehyde: phenol ratio (i.e. 2.0 : 1 mole ratio), the plywood joints of all samples delaminated during 'boil-dry-boil' cyclic treatments. However, both dry- and wet-bond strengths of the plywood joints could be improved to exceed standard values by using an additional crosslinking agent, e.g. poly(methylene (polyphenyl isocyanate)) (polymeric MDI). The adhesive perfomance of the wood-based resol resins was explained on the basis of the adhesion between wood veneers and resol resin adhesives.     

Evaluation of block shear properties of selected extreme‐pH structural adhesives by short‐term exposure test

Nine structural adhesives with varying pH were selected to examine the effect of adhesive pH on wood–adhesive bond quality. The adhesives evaluated included four highly alkaline phenol–formaldehyde, one intermediate pH phenol–resorcinol–formaldehyde, two acidic melamine–urea–formaldehyde, and two acidic melamine–formaldehyde resins. Block shear specimens were prepared using Douglas‐fir and black spruce wood. The adhesive performance was evaluated by measuring the shear properties (strength and wood failure) of the specimens tested at the dry and vacuum–pressure–redry (VPD) conditions. Adhesive pH, test condition, and wood species showed significant effects on shear properties. The different adhesives performed differently at the dry and VPD conditions. The high‐pH adhesives (phenol–formaldehyde and phenol–resorcinol–formaldehyde) showed similar high wood failures at both test conditions and performed better than the low‐pH adhesives (melamine–formaldehyde and melamine–urea–formaldehyde), especially after the VPD conditioning. The low‐pH adhesives showed high wood failure at the dry condition, but wood failure decreased significantly after VPD conditioning for both species, indicating that the low‐pH adhesives were less durable than the high‐pH adhesives. High‐pH adhesives did not have a negative impact on the strength of the bonded specimens. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of liquefied bark‐based resol resin and its application to particle board

Barks of Taiwan acacia (Acacia confusa) and China fir (Cunninghamia lanceolata) were liquefied in the presence of phenol with sulfuric acid (H₂SO₄) and hydrochloric acid (HCl) as catalyst. The properties of resins prepared from liquefied bark and the feasibility of liquefied bark‐based resol resins in particle board manufacturing were investigated. The viscosity and thermosetting property of liquefied bark‐based resol resins were affected by the kind of bark species and the catalyst used. Liquefied bark‐based resol resins using China fir bark as raw material had higher viscosity than the ones using Taiwan acacia bark. In the course of thermosetting, liquefied bark‐based resol resins using Taiwan acacia bark as raw material had a higher maximum temperature of exothermic peak and onset temperature as well as a larger quantity of exothermic heat than those using China fir bark. Resol resins prepared from bark liquefied with H₂SO₄ as catalyst had higher viscosity, while resins with HCl as catalyst had a higher maximum temperature and height of exothermic peak and a larger quantity of exothermic heat at thermosetting. Particle board made with A‐S adhesive that was prepared from liquefied Taiwan acacia bark with H₂SO₄ as catalyst had the best particle board properties than those made with other adhesives. For the particle board made with A‐S adhesive, its static bending strength and internal bonding strength would be increased as the hot‐pressing time extended. The particle board made with hot‐pressing temperature of 150°C and hot‐pressing time of 10 min had the maximum normal and wet static bending strength and internal bonding strength. Its normal static bending strength was 170.8 kgf/cm² and the particle board showed satisfactory wet static bending strength and internal bonding strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1837–1841, 2003     

Preparation of highly phenol substituted bio-oil–phenol–formaldehyde adhesives with enhanced bonding performance using furfural as crosslinking agent

Highly phenol substituted bio-oil–phenol–formaldehyde (BPF) adhesives were prepared via the phenolization-copolymerization method, in which furfural was used as a novel crosslinking agent to improve the bonding performance. The effects of bio-oil percentage, furfural content, curing temperature, and pressure on the performance of BPF adhesives have been studied in detail. A BPF adhesive with 75% bio-oil percentage and 15% furfural loading (named 75BPF_15) was synthesized, which was cured at 180 °C and 4 MPa. Compared to the conventional phenol–formaldehyde adhesive, the wet tensile strength of 75BPF_15 adhesive reached 2.84 MPa, which was significantly higher than the 1.54 MPa of PF. A possible mechanism of BPF adhesives crosslinked with furfural is proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46995.     

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