Technologies of liquefaction of bamboo and preparation of adhesive

The technology of liquefying processed-waste bamboo with phenol is investigated by single factor trials and an orthogonal design. We studied the preparation technology and properties of adhesives from this phenol-liquefied bamboo with formaldehyde (BPF). The results show that temperature has a significant effect on liquefaction. The effect of the mass ratio of phenol to bamboo comes second and the catalyst dosage within the range of 2%–4% is the least effective. The optimum conditions of liquefaction are as follows: a mass ratio of phenol to bamboo 3.5, a catalyst dosage of 4%, liquefying temperature 145°C and liquefying time 60 min. The liquefaction rate of bamboo reached 99.1%. For the preparation of the adhesive, a mass ratio of liquefied bamboo products to formaldehyde (37%) is 100 to 164.8–199.5, while the ratio 100 to 108.2 is the best. This adhesive has a lower curing temperature than that of normal PF resin. At a hot-press temperature of 130 or 140°C, this new adhesive provides excellent bonding strength of plywood. The most favorable temperature for hot-pressing is 140°C. __________ Translated from Chemistry and Industry of Forest Products, 2007, 27(6): 65–70 [译自: 林产化学与工业]     

HDI交联聚乙烯醇木材胶黏剂的研究

以聚乙烯醇溶液为基质,采用正交试验法探究表面活性剂OP-10、催化剂、交联剂HDI的加入量,搅拌时间,反应温度和聚乙烯醇的相对体积质量分数对改性聚乙烯醇木材胶黏剂性能的影响。结果表明:HDI以及催化剂的加入能较大幅度地提高胶黏剂的稳定性和粘结性能,从而达到改性聚乙烯醇胶黏剂的目的。试验可得到乳白色的稳定产品,可用于建筑行业作木材胶黏剂,且更为环保。     

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.     

聚酰胺多胺环氧氯丙烷树脂大豆胶黏剂制备及性能研究

采用己二酸(AA)、二乙烯三胺、环氧氯丙烷(ECH)合成聚酰胺多胺环氧氯丙烷树脂(PAE),将其与大豆蛋白按比例混合制备PAE大豆胶黏剂。在合成预聚体(PA)后,通过单因素试验,探究AA与ECH摩尔比、大豆蛋白添加量对胶合板胶合强度的影响,研究了PAE对大豆蛋白的改性作用及胶接机理。结果表明:在胶黏剂合成过程中AA与ECH摩尔比为1:1.0,大豆蛋白添加量为30%,热压温度为120℃、压力1.0 MPa、热压时间6 min条件下,PAE大豆蛋白胶黏剂胶合强度可达1.02 MPa,满足GB/T 9846-2015Ι类板指标要求。     

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。     

新型酚醛树脂改性大豆蛋白基胶黏剂的研究

以脱脂大豆粉为原料制备大豆蛋白基胶黏剂(豆胶,S),以普通甲醛制备的酚醛树脂(PF_1)和高浓度甲醛制备的酚醛树脂(PF_2)为交联剂,使用前将两者直接混合得酚醛树脂改性豆胶(PF_1/S、PF_2/S)。利用差示扫描量热(DSC)、红外光谱(FT-IR)、动态热机械性能(DMA)和核磁共振碳谱(~(13) C NMR)分析对产品性能进行了测试与表征。结果表明:等物质的量之比条件下,高浓度甲醛较之普通甲醛制备的酚醛树脂改性豆胶胶合板干、湿剪切强度分别提高4.3%和11.6%,并且强度稳定性好;动态DSC分析表明,PF_2可以降低豆胶体系的固化温度和活化能,与豆胶的交联反应较容易;~(13) C NMR分析表明,PF_2体系羟甲基达88.73%,明显高于PF_1的80.91%;FT-IR分析证实酚醛树脂与豆胶中的氨基发生反应,并且PF_2反应效率更高;DMA分析表明,PF_2/S能够改善胶合产品的力学性能和热稳定性,降低豆胶的固化反应起始温度,提高固化反应速率。     

生物乙醇木质素-PAE改性大豆蛋白胶黏剂合成工艺研究

将生物乙醇木质素与自合成的聚酰胺多胺环氧氯丙烷(PAE)树脂进行接枝共聚改性大豆蛋白,制备环保型胶合板用胶黏剂,并通过单因素试验确定了木质素种类、木质素与PAE质量比、木质素与PAE树脂反应时间、大豆蛋白添加量等工艺条件对大豆蛋白胶黏剂胶合强度的影响。结果表明:当选用生物乙醇木质素与PAE进行接枝共聚、木质素与PAE质量配比为1∶4、反应时间为30 min、大豆蛋白添加量为50%(以木质素-PAE总质量而言)时,制得的三层胶合板湿胶合强度(1.03 MPa)可达到GB/T 9846—2015Ι类杨木胶合板的指标要求。     

乙酸酐对大豆基木材胶粘剂的改性研究

用乙酸酐改性大豆基木材胶粘剂,研究了乙酸酐为不同浓度时,双因素(pH值和温度)对耐水胶合强度的影响。试验结果得到4个不同浓度下pH值和温度的最佳组合值为:乙酸酐体积分数为1.2%、1.8%、2.4%、3.0%时对应的pH值/温度是8/55℃、8/55℃、7/70℃、7/70℃,最佳耐水胶合强度可提高到0.72 MPa。以乙酸酐体积分数为1.8%为例,采用茚三酮法测得大豆蛋白质的酰化程度,分析不同温度下pH值对酰化程度的影响,结果显示:耐水胶合强度与酰化程度不成正相关。由红外光谱分析可知,乙酸酐与大豆蛋白的游离氨基发生了交联反应,从而提高了大豆基木材胶粘剂的耐水胶合强度。     

玉米酒精粕基木材胶黏剂的制备及其性能

以玉米酒精粕(DDGS)为原料、聚酰胺环氧氯丙烷树脂(PAE)为交联剂、水溶性豆粕(SM)为增强剂制备玉米酒精粕基木材胶黏剂,对比了DDGS与SM蛋白质含量及其氨基酸种类与含量,测试了胶黏剂黏度与制备胶合板的胶合强度,表征了固化胶黏剂功能性基团、热稳定性、断面形态,解析了DDGS基胶黏剂组分对性能的影响规律与增强作用机...     

Gluability of thermally modified beech (Fagus silvatica L.) and birch (Betula pubescens Ehrh.) wood

Abstract

One of the main disadvantages of wood is hygroscopicity resulting from its polar character. The sorption–desorption of water causes unwanted swelling and shrinkage in wood. Thermal modification substantially reduces this inconvenient feature. Unfortunately, the same chemical changes that reduce water sorption alter the polar character of the material and result in poorer wetting of thermally treated wood by waterborne adhesives. Gluability of thermally modified beech (Fagus silvatica L.) and birch (Betula pubescens Ehrh.) wood with two commercial amino resins, melamine–urea–formaldehyde (MUF) and melamine–formaldehyde (MF), and a two-component polyurethane (PUR) adhesive was investigated. Both wood species were modified according to two temperature regimes: 160°C and 190°C. Shear strengths of the joints were then determined according to EN 205:2003 standard. The results showed that thermally modified beech and birch wood can be effectively glued not only with commercially available PUR adhesives, but also with aqueous MF and MUF resins. The resultant shear strengths of the joints were limited by the strength of the thermally modified substrate.     

多胺基聚合物改性室温固化型MUF树脂胶黏剂

为解决三聚氰胺-尿素-甲醛(MUF)树脂作为室外级结构集成材胶黏剂时存在的脆性大、易开裂的问题,得到韧性优秀且综合性能满足室外级结构集成材标准的室温固化型MUF树脂胶黏剂,本研究在MUF树脂合成中使用两种改性剂尿素-乙二胺(UE)、尿素-三(2-氨基乙基)胺(UD)分别替代部分三聚氰胺合成了MUF-UE、MUF-UD树脂胶黏剂。通过制备树脂拉伸试样以及胶合木考察改性后的MUF树脂的物理力学性能,借助DSC、DMA分析改性前后树脂的热性能,使用FT-IR、ESI-MS分析改性前后树脂的结构变化。试验结果表明:相较于未改性MUF树脂,MUF-UE树脂拉伸强度和断裂伸长率分别提高51.5%和30.8%,所制备胶合木剪切强度高达8.00 MPa,冷、沸水二次循环剥离率均为0%;MUF-UD树脂拉伸强度相比改性前会有所下降,但断裂伸长率以及胶合木剪切强度对比改性前有一定提高。结构分析表明,UE和UD能够参与MUF树脂合成反应并形成共缩聚产物,且不改变树脂体系中主要官能团结构。     

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。     

豆基胶黏剂的改性与应用研究进展

在总结国外大豆基胶黏剂改性和应用研究的基础上,指出化学改性可使蛋白质结构发生变化,从而显著提高豆胶的粘接强度和耐水性,并可应用于秸秆人造板的制造,是一种大有希望的环保型胶黏剂.     

两种常温固化木材胶粘剂胶接强度分析

对两种木材用常温固化胶粘剂--单宁-甲醛胶粘剂和聚氨酯胶粘剂胶接的速生杨木的静态剪切强度进行了测试与分析.研究结果表明,以速生杨I-72为被胶接对象,自制的双组分型单宁胶压缩剪切强度范围为8.08～8.92MPa,但木破率较低,要满足日本集成材JAS标准中用胶规定,需进一步研究改进.相比较而言,聚氨酯胶粘剂的胶接强度较高,其压缩剪切强度值均在9.8MPa以上,木破率在75%以上,能够满足日本集成材JAS标准中用胶的规定.     

API胶接硬木的耐水耐热性能研究

对水性高分子-异氰酸酯胶黏剂(API)主剂进行改性,以提高API的耐水、耐热及胶接硬木的性能。首先对比了不同聚乙烯醇及增塑剂对API性能的影响。然后在API主剂中引入耐水、耐热树脂或外交联剂(三聚氰胺甲醛树脂、酚醛树脂、N-羟甲基丙烯酰胺),讨论了它们对API胶接性能的影响。通过试验得出三聚氰胺甲醛树脂改性API的效果最好,并用正交试验设计优化了主剂的配方,最终合成了适合高档硬木胶接用的水性高分子异氰酸酯胶黏剂。在试验过程中采用日本JIS K6806-2003标准,并用柞木代替桦木提高了胶接难度。     

A feasibility study of using two-component polyurethane adhesive in constructing wooden structures

This investigation was conducted to determine the feasibility of using a two-component polyurethane （PUR） adhesive, with special waterproof properties, in constructing wooden structures. We designed and conducted tests to compare the shear strength and adhesion performance of PUR with polyvinyl acetate （PVAc） adhesive on block-shear specimens constructed of oriental beech （Fagus orientalis L.）, fir （Abies alba Mill.）, poplar （Populus deltoides Bartr.）, white oak （Quercus alba L.）, sycamore （Platanus orientalis L.） and white walnut （Juglans cinerea L.）. The values of the percentage of wood failure were also determined in specimens constructed with each adhesive. The highest shear strength values of both adhesives were obtained in specimens constructed of beech, while the lowest shear strength values were obtained in fir and poplar specimens. Average shear strength of the PUR adhesive was 16.5% higher than that of the PVAc adhesive. Specimens constructed of fir, poplar and sycamore were characterised by the highest percentages of wood failure, whereas the lowest average percentages of wood failure were obtained in beech and oak specimens. With the exception of oak specimens, there was no statistically significant difference between percentage of wood failure among the PUR and PVAc adhesives. Generally, the PUR adhesive showed an acceptable adhesion performance on wood materials used in our study.     

[Rh(COD)Cl]_2催化剂的制备及催化松节油加氢反应

采用恒温搅拌回流的方式制备了[Rh(COD)Cl]_2,并通过正交试验对制备条件进行了优化,得出催化剂适宜制备条件:n(COD)∶n(RhCl_3·3H_2O)为3.5∶1,回流温度80℃,回流时间3 h。将制备的[Rh(COD)Cl]_2作为催化剂用于松节油的氢化反应,通过单因素试验和正交试验考察了反应压力、反应温度、催化剂用量及反应时间对反应的影响,优选出适宜反应条件,即4 g松节油,催化剂用量为松节油质量的2.5%,反应压力2.5 MPa,反应时间4 h,反应温度45℃。在此反应条件下,α-蒎烯转化率为98.21%,产物顺式蒎烷对映选择性为97.46%,收率为95.72%。     

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     

Application of cure-accelerated phenol-formaldehyde (PF) adhesives for three-layer medium density fiberboard (MDF) manufacture

 This study was conducted to optimize hot pressing time and adhesive content for the manufacture of three-layer medium density fiberboard (MDF) through the cure acceleration of phenol-formaldehyde (PF) adhesives by adding three carbonates (propylene carbonate, sodium carbonate, and potassium carbonate) in the core layer. Carbonate type, carbonate level, PF resin content, and hot pressing time were evaluated on the basis of the performance of MDF panels prepared. The application of cure-accelerated PF adhesives by the addition of propylene carbonate reduced both PF resin content and total hot pressing time by 38% and 29%, respectively, for the manufacture of quality three-layer MDF panels (19.1 mm thickness) under the hot-pressing temperature of 205 °C. The optimum concentration of propylene carbonate for cure acceleration of PF resin was found to be 3 wt% by weight based on the resin solids. Bending properties, on one hand, were independent of carbonate type and level, and complied with the minimum requirements by ANSI. Internal bond (IB) strength, on the other hand, was closely related with carbonate types and level used. Received 13 March 1999     

改性豆粕胶压制长白山臭松包装箱板的研究

以豆粕为原料制备环保型胶黏剂。采用甲苯二异氰酸酯对豆粕胶进行改性,用制成的豆粕-甲苯二异氰酸酯胶黏剂压制长白山臭松包装箱板,并对板的胶合强度进行分析。结果表明:理想的工艺参数为150g水、25g改性剂、5g盐酸。胶合强度能满足GB/T9846—2015标准要求。