交联改性大豆蛋白胶胶合板的工艺及湿剪切强度研究

为了确定应用交联改性大豆蛋白胶制造胶合板的工艺,采用正交试验,分析热压工艺参数和涂胶量对胶合板剪切强度的影响.在试验优化的工艺参数:热压温度160℃,压力1.5 MPa,时间2 min/rnm,双面涂胶量380 g/m2等条件下,胶合板的湿状剪切强度满足GB/T 9846-2004《胶合板》中Ⅰ类胶合板的要求,且不会随蒸煮时间的延长而出现明显下降,耐水性能稳定.     

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.     

改性大豆蛋白胶黏剂制造杨木胶合板热压工艺

利用单因素试验方法,研究了热压温度、热压时间、热压压力和施胶量对使用改性大豆蛋白胶黏剂制造的杨木胶合板胶合强度的影响规律.结果表明:在100～ 220℃热压温度范围内,随着热压温度的增加,胶合强度显著增大;在35～60 s/mm热压时间范围内,胶合强度随热压时间的增加呈上升趋势,当时间从60 s/mm升至85 s/mm,胶合强度几乎保持一致;热压压力在1.25 MPa时,胶合强度达到最大值;施胶量在130 ～430g/m2热压时间范围内,胶合强度随施胶量的增加呈上升趋势.由此得出最优工艺参数为:热压温度180℃,热压压力1.25 MPa,热压时间60 s/mm,施胶量为310g/m2.     

大豆蛋白-丙烯酸酯复合胶黏剂的研究

利用大豆蛋白大力发展绿色环保型胶黏剂,可以降低木材工业界的产品成本和对石化产业的依赖性。大豆基胶黏剂用于刨花板时表现出类似于或优于脲醛树脂胶黏剂的力学性能,这就表明,大豆基胶黏剂可以代替脲醛树脂胶黏剂用于室内建设和家具行业等领域中,从而避免了脲醛树脂胶黏剂中有毒气体的散发。笔者主要是研究配制出符合制造Ⅱ类胶合板用胶,满足其国标,从而达到保护环境、节省不可再生资源和降低成本的目的。通过实验得出2.5g大豆蛋白、10gPVA、36gMMA、0.32gAPS和200g水所制得的改性大豆蛋白胶胶合强度优异,且成本降低。通过正交实验确定出最佳的压板工艺条件:120℃、2MPa、5%固化剂所制得的胶合板为最优异。     

异氰酸酯改性竹材表面及其抗蚀性能研究

以异氰酸酯对竹材表面进行接枝改性,大幅提升了天然竹材的抗蚀性能。研究中分别以热水预处理竹材(H-bam)和碱预处理竹材(A-bam)为原料,采用二环己甲烷4,4′-二异氰酸酯(HMDI)为改性剂,得到改性竹材样品H-HMDI-bam和A-HMDI-bam。抗蚀机制研究表明:改性后竹材表面的羟基数量明显减少,羰基、酰胺官能团增加,HMDI成功接枝到纤维表面并成絮状包裹状,A-HMDI-bam和H-HMDI-bam的负载量分别为6.342和4.080 mmol/cm^2。改性样品疏水性明显增强,其中H-HMDI-bam表现优异,吸水率由原料的68.7%下降到35.5%,孔径和孔体积大幅下降到33.48 nm和0.039 0 cm^3/g。SEM观察表明H-HMDI-bam样品无明显被腐蚀的痕迹,腐蚀等级为0～1级,与工业传统炭化抗腐处理工艺水平相当。     

水性改性淀粉--多异氰酸酯胶粘剂的研究

对利用酯化玉米淀粉，制造水性高分子——异氰酸酯胶粘剂(API)的配方进行了系统的研究。将玉米淀粉的酯化产物处理成乳液，在一定酸碱度条件下，与无毒无公害的合成橡胶胶乳共聚制成API胶的主剂；将多异氰酸酯化合物的异氰酸酯基封闭处理后，作为API胶的固化剂，制成双组分无醛耐水的API胶。经生产性试验，用此API胶压制的三层实木复合地板、机拼细木工板、胶合板及集成材等胶合制品，其理化性能指标完全达到有关标准要求，并且制品无甲醛等有毒物质挥发。此种胶粘剂具有明显的生产可操作性，完全满足现有的工艺要求，其原料成本为同类进口胶粘剂的一半，具有明显的社会环境效益和经济效益。     

HN-PAE树脂对大豆蛋白胶黏剂的共交联改性研究

采用低成本、富含活性基团的无甲醛尿素-环氧树脂（代号为HN）为共交联改性剂,与交联剂聚酰胺多胺-环氧氯丙烷（PAE）树脂共混制备大豆蛋白胶。红外光谱（FTIR）表征与热重分析表明：HN树脂能与PAE树脂有效共交联,同时HN-PAE树脂能与大豆蛋白上的活性基团反应,提高大豆蛋白胶的热稳定性。通过胶合板性能测试对HN树脂用量和豆粉用量进行配方优化,将HN-PAE复合树脂溶液（HN树脂质量分数70%）稀释至质量分数为6%,豆粉相对用量为30%～35%时,制备的Ⅱ类胶合板的胶合强度满足GB/T 9846—2015《普通胶合板》的要求。     

改性大豆蛋白胶黏剂基料的制备及表征

以尿素为改性剂,亚硫酸氢钠、过硫酸铵(APS)为引发剂,将甲基丙烯酸缩水甘油酯(GMA)接枝到大豆分离蛋白(SPI)上制备改性大豆蛋白胶黏剂基料.研究了尿素浓度及处理时间、引发剂用量、反应温度、单体用量等因素对改性大豆蛋白胶黏剂基料的黏度和耐水性的影响,确定了最佳的工艺条件.最佳工艺条件为:尿素浓度3 mol/L,预处理时间30 min,反应温度50℃,NaHS03、APS和GMA分别占大豆蛋白的质量分数为5％、10％和84％.合成的基料黏度为59.68(mPa.s),胶膜水溶物含量为44.12％,对桦木的拉伸剪切强度为5.85 MPa,基本满足木材胶黏剂要求.红外光谱证明GMA和SPI发生了接枝反应.     

大豆蛋白功能性及改性技术研究进展1）

概述了大豆蛋白的溶解性,凝胶性,乳化性,吸水性、保水性,起泡性、成膜性等主要功能特性的产生机理、影响因素及改性方法,为大豆蛋白功能性的研究提供了理论参考,对大豆蛋白食品及新型蛋白食品的开发具有重要意义。     

用水性高分子异氰酸酯生产无醛胶合板生产工艺的研究

用低成本高分子异氰酸酯胶粘剂生产无醛胶合板，其生产工艺与常规脲醛树脂生产胶合板生产工艺相同，成本只有其它非甲醛系胶粘剂的50％，并彻底解决了游离甲醛释放问题。     

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     

三乙醇胺改性沙柳液化产物/异氰酸酯硬质泡沫材料研究

生物质多元醇液化产物与异氰酸酯等反应可制备硬质聚氨酯泡沫材料,而该类材料存在力学性能低、脆性大等缺点,使其应用领域受到限制.以沙柳多元醇液化产物为原料,与异氰酸酯(MDI)等共聚制备沙柳液化产物/异氰酸酯硬质泡沫材料(RPUF),研究添加不同质量分数交联剂三乙醇胺(TEOA)对RPUF物理力学、化学结构和热学特性的影响...     

大豆蛋白的碱处理研究

选用碱(NaOH)对豆粉进行降解处理,研究了加碱量、十二烷基苯磺酸钠量(SDBS)、固体含量、处理温度和处理时间对大豆蛋白水解度和降解液黏度的影响。研究结果表明,利用NaOH对豆粉进行降解处理的最佳条件为:NaOH加入量7%(占豆粉的质量分数),处理时间3 h,处理温度90℃,SDBS加入量1%,固体含量30%。此条件下制备的豆胶黏度1.5 Pa.s,水解度达45%。     

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     

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 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     

Modulus of elasticity in scarf-jointed wooden beams: a case study with polyvinyl acetate and isocyanate adhesives

In the present study, elastic properties of scarf-jointed oak (Quercus castaneifolia) timbers with the application of two different types of adhesives (polyvinyl acetate and isocyanate) were evaluated using free flexural vibration of free–free beam method in different flexural directions of vibration, i.e., tangential and redial directions. Samples were taken from trees of Hyrcanian forests in Iran with nominal dimensions of 20 × 20 × 360 mm³. Comparing the results of elastic properties of clear oak wood beams with scarf-jointed samples wood showed that scarf joints with the bonding angles of 70° and 75°, covered by polyvinyl acetate adhesive, did not demonstrate any significant effect on modules of elasticity. Scarf-jointed beams with smaller joint angles (60° and 65°) were considerably weaker or totally unreliable in their moduli of elasticity. It is also shown that the magnitude of effect gets worst by using isocyanate rather than polyvinyl acetate adhesive.     

Shear strength of furfurylated,N-methylol melamine and thermally modified wood bonded with three conventional adhesives

The shear strength of furfurylated, N-methylol melamine (NMM) and thermally modified wood bonded with emulsion polymer isocyanate, polyvinyl acetate (PVAc), and polyurethane (PU) adhesives was examined. Furfurylation and NMM modification of Scots pine had a significant negative effect on the bonding strength with all adhesives irrespective of the treatment intensity. The obtained low-shear strength values were related to the brittle nature of the wood after modifications rather to the failure of the bondline. PVAc showed a better bonding performance with both furfurylated and NMM modified wood while the combination of furfurylated wood and PU gave the highest reduction in bonding strength (47–51%). Shear strength also decreased significantly after thermal modification in both Scots pine (36–56%) and beech (34–48%) with all adhesives. With the exception of thermally modified beech samples bonded with PU, bondline was found to be the weakest link in thermally modified wood as it was revealed by the wood failure surfaces. Bondline thickness and effective penetration of adhesives did not relate to the shear strength of all modified wood materials. The lower shear strength of modified wood could be attributed to other factors, such as the reduced chemical bonding or mechanical interlocking of adhesives, and the reduced strength of brittle modified wood substrate.