Development of room-temperature curing aqueous emulsion-type acrylic adhesive I: effect of monomer composition on the initial adhesive strength

For the purpose of developing a new aqueous emulsion-type adhesive for wood or paper use that does not release formaldehyde or volatile organic solvents, a honeymoon-type acrylic adhesive was examined. An adhesive system consisting of acrylic monomers copolymerized with functional monomers and a cross-linking agent was selected for the purposes of increasing initial adhesive strength and ensuring room-temperature curing. The initial adhesive strength increased by the use of cross-linkers such as dihydrazides and also polymeric methylene diphenyl diisocyanate (pMDI). Thus an adhesive with reasonable to good initial adhesive strength and room-temperature curing was obtained. The effect of pMDI on the initial adhesive strength was not significant and decreased when the amount of acrylamide in a copolymer was high.     

Preliminary study of the effects of EVA coupling agents on properties of wood-plastic composites

As a hot-melt adhesive, ethylene-vinyl-acetate (EVA) has been used in many industrial applications. But studies of the application of EVA in wood-plastic composites (WPC) are relatively few, so we have investigated the proposition of whether EVA is a suitable coupling agent for WPC or not. The results show that EVA with 8% VA is not a suitable coupling agent, because it reduces the mechanical properties of WPC without any significant effect on its physical properties. With an increase in the amount of wood powder, the mechanical properties of WPC decrease and the ability of water absorption of WPC increases.     

高含水率单板胶接工艺的研究

研究了单组分湿固化异氰酸酯胶粘剂胶接高含水率单板的工艺条件,详细讨论了含水率、涂胶量、加压压力、加 压时间和养生时间对胶合性能的影响。结果表明:单板含水率、涂胶量是重要的影响因子,单组分湿固化异氰酸酯胶粘 剂可胶接含水率高达100％的单板,在保证胶接强度的前提下,涂胶量仅为传统胶粘剂的1／2-1／3。     

Characterisation of the curing of liquefied wood by rheometry, DEA and DSC

Liquefied wood is a naturally based product which has the potential to be used as an adhesive. The bonding of wood with liquefied wood requires a high enough temperature to cure the liquid polymers and achieve bond strength. Dielectric analysis, rheometry and differential scanning calorimetry were used to analyse the curing process of low solvent liquefied wood. For the liquefaction, ethylene glycol was used as a solvent and sulphuric acid was used as a catalyst. The dielectric analysis was used for in situ measurements of the curing of liquefied wood during the bonding of wood. It was found that curing started after a temperature of 100 °C had been reached in the bond. This is correlated with the water evaporation and the diffusion of water and ethylene glycol from the liquefied wood into the wood substrate. Rheological measurements proved the influence of the substrate on the curing of the liquefied wood during bonding. Differential scanning calorimetry showed that the curing of liquefied wood occurs in two parts: first, the initial elimination of water and ethylene glycol from the liquefied wood, and then the chemical reaction of the liquefied wood at higher temperatures.     

Development of a novel polyvinyl acetate type emulsion curing agent for urea formaldehyde resin

High formaldehyde emission and poor water resistance are two main disadvantages of urea formaldehyde (UF) resin. For that reason, a novel polyvinyl acetate (PVAc) type emulsion curing agent was developed in this paper. PVAc type emulsions, including PVAc, the co-polymer of PVAc and N-hydroxymethyl acrylamide (PVAc–NMA), and the ternary co-polymer of PVAc, NMA, and urea (PVAc–NMA–urea), were the main components. Water, aluminum chloride, ammonium dihydrogen phosphate, polypropylene glycol, silicone oil, and urea were the other components. Under heating, aluminum chloride and ammonium dihydrogen phosphate often underwent thermal decomposition and hydrolysis in solution, produce free acid to cure UF resin, so the curing agent could enhance the curing rate, and then shorten the curing time. In this curing agent, ammonium dihydrogen phosphate and urea worked as formaldehyde removers and reacted with free formaldehyde in UF resin, thus the formaldehyde emission exuded from the plywood could be effectively limited and reduced. The bonding strength of plywood was not improved very much, especially the dry bonding strength, but the wet bonding strength was little enhanced for the active hydroxymethyl group contained in PVAc–NMA and PVAc–NMA–urea underwent a self-cross-linking reaction to improve the bonding strength and adhesion force to the bonded substrate. More importantly, the results from the industrial production experiments were shown to be very good.     

Development of room-temperature curing aqueous emulsion-type acrylic adhesive II: effect of monomer composition on the final adhesive strength

In a series of studies, development of a new aqueous emulsion-type adhesive for use with wood or paper, which does not release formaldehyde or volatile organic solvents, was attempted. For the purpose of increasing both initial and final adhesive strengths, we selected a system consisting of acrylic monomers copolymerized with functional monomers such as diacetone acrylamide and some cross-linking agents such as dihydrazide or polymeric methylene diphenyl diisocyanate (pMDI). It was found that dihydrazide cross-linker was effective for both the initial and final adhesive strengths, suggesting contribution of hydrazone bonds to the bonding strengths. Cross-linking with pMDI might be slow and was not important in the initial bonding. However, its cross-linking effect might develop gradually, because the adhesive showed good final strengths using pMDI as a cross-linker.     

Liquefaction of bamboo, preparation of liquefied bamboo adhesives, and properties of the adhesives

This study investigated the liquefaction of bamboo in phenol, which involved the effects of weight ratios of phenol to bamboo, amount of catalyst, temperature, etc. The study showed that liquefaction could be accomplished with a phenol to bamboo weight ratio of 2–1: 1, a 5% catalyst of HCl or BF₃, and a temperature of 115°C. Liquefied bamboo formaldehyde (BLF) resin adhesive for exterior use could be obtained with a phenol to formaldehyde molar ratio of 1:1.6–2.0. The curing behavior of BLF resin adhesive, studied by TG-DSC and IR analyses, showed that BLF resin adhesives had a lower curing temperature than PF adhesives but had the same characteristic trough in IR spectra as PF adhesives. __________ Translated from Chemistry and Industry of Forest Products, 2004, 24(3) [译自: 林产化学与工业, 2004, 24(3)]     

秸秆板贴面用异氰酸酯胶的改性

通过对异氰酸酯(API)主剂进行改性,从而减少交联剂的用量,降低API胶黏剂的生产成本。将改性API胶黏剂用于秸秆板薄木贴面的试验表明,当主剂、交联剂、填料之比为100∶4∶30,热压温度为60~110℃时,秸秆板的贴面效果达到相关国标要求。     

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。     

单宁和纳米SiO2改性大豆基胶黏剂的制备及其性能

为制备无甲醛的环保型生物基木材胶黏剂,以单宁和纳米SiO₂改性脱脂豆粉制备大豆基胶黏剂（DSF）,并分析了改性大豆基胶黏剂的性能。研究结果显示：单宁和纳米SiO₂二元复合改性大豆基胶黏剂（DSF-T-SiO₂）在固化过程中能够形成稳定的交联结构;TG分析表明单宁和SiO₂改性显著提高了胶黏剂的热稳定性;单宁改性大豆基胶黏剂（DSF-T）可提高干态和湿态胶合性能,纳米SiO₂改性大豆基胶黏剂（DSF-SiO₂）的干态胶合性能略有提高,但湿态胶合性能无明显改善。经分析以25 g脱脂豆粉、 5 g单宁、 0.1 g纳米SiO₂和70 g去离子水混合均匀搅拌得到的改性胶黏剂DSF-T-SiO₂-2的起始黏度比未改性的DSF降低了79.58%;DSF-T-SiO₂-2的固化胶层水溶解率为（27.5±0.05）%,比对照组DSF下降了28.4个百分点。此外,DSF-T-SiO₂-2...     

浸渍杨木用间苯二酚树脂剪切强度的研究

主要研究了间苯二酚树脂胶黏剂的制备,用其冷压氨基类树脂改性浸渍杨木,用于木结构房屋建筑。通过正交试验研究了甲醛与间苯二酚物质的量比、胶黏剂与固化剂质量比、冷压时间等条件对间苯二酚树脂胶黏剂性能湿剪切强度结果的影响。采用红外光谱、电镜分析与热重分析仪等分析,表征了间苯二酚树脂的结构与性能,且对树脂与试件断面处进行断面微观形貌分析。研究结果表明:当甲醛n(F)∶间苯二酚n(R)=0.8∶1,胶黏剂∶固化剂=10∶3,冷压60 min时,其检测结果为湿剪切强度6.12 MPa,煮沸剥离满足2个周期,满足GB/T 26899—2011《结构用集成材》标准要求。     

偶氮二甲酰胺发泡剂对脲醛树脂性能的影响

采用单因素试验方法,将偶氮二甲酰胺发泡剂与脲醛树脂复配制备发泡型胶黏剂,测试胶黏剂的基本性能及拉伸剪切强度,利用热重分析仪(TG)和同步热分析仪(TG-DSC)对胶黏剂的热稳定性和固化特性进行表征。结果表明:偶氮二甲酰胺发泡剂的加入有利于提升树脂体系的流动性,降低树脂的初期固化速度,提高树脂的热稳定性,且对树脂的固体含量及黏度无明显影响;较优的发泡剂添加量为6%;拉伸剪切强度为2.45 MPa。开发的偶氮二甲酰胺/脲醛树脂发泡胶黏剂在轻质人造板领域具有较大的应用潜力。     

Adhesive application method in MDI-UF particleboard manufacture

Chinese wood-based composite manufacturers are plagued with serious formaldehyde emission (F-emission) problems. In this study, we investigated the use of an emulsifiable diphenylmethane-4, 4′-diisocyanate (MDI) — urea formaldehyde (UF) mixture adhesive in particleboard manufacture, in order to decrease F-emission to below 9 mg per 100 g board. We paid close attention to the effect of NH₄Cl on MDI-UF curing and the method of adhesive application by differential scanning calorimetric (DSC) analysis and compared mechanical properties. Both results showed that the acidic agent NH₄Cl did hinder EMDI-UF curing and it also affected the adhesive application method. We are of the opinion that when EMDI and UF are mixed first, without adding NH₄Cl and then sprayed onto particles, mechanical properties will be improved and F-emissions will meet E1 grade requirements. __________ Translated from Scientia Silvae Sinicae, 2005, 41(2) [译自: 林业科学, 2005, 41(2)]     

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     

三聚氰胺改性低毒脲醛树脂耐水性研究

不同摩尔比的两类低毒脲醛树脂(JQ21未改性,JQ22与5%三聚氰胺共聚),分别与不同质量比的三聚氰胺树脂混合,并在不同的固化体系中固化,用于胶合板的压制.对胶合板的胶合性能及甲醛释放量进行了研究.实验结果表明:固化体系不同,胶接强度也不相同;随着摩尔比的增加,胶接强度提高,甲醛释放量亦相应提高;同时采用共聚和共混两种方法进行改性的脲醛树脂,其胶接强度和甲醛释放量均优于单一的采用共混改性的脲醛树脂;并且混合胶液中三聚氰胺的比例越低,胶接性能越筹,甲醛释放量变化逐渐趋于平稳.     

木质废料/无机胶黏剂刨花板的制备及其阻燃性能研究

以废旧建筑模板和家具为原料,使用环保型无机胶黏剂制备刨花板。利用扫描电子显微镜(SEM)观察刨花板的微观形貌,同时利用量热仪、氧指数测定仪、同步热分析仪等评价板材的阻燃性及热稳定性。结果表明:当板材密度为0.95g/cm^3时,除24h吸水厚度膨胀率外,其余物理力学性能均符合国标中的P3型刨花板要求;SEM观察到无机胶黏剂包覆刨花,填充板材孔隙,使板材物理力学强度大幅提高;选择氯化镁为固化剂,当表层/芯层刨花的固化剂用量为4.5%/5.0%时,压制的密度为0.95g/cm^3的刨花板,其氧指数为31%,具有较好阻燃性能。     

Measuring interfacial stiffness of adhesively bonded wood

Adhesive bond line stiffness is an important property that plays a significant role in the properties of wood composites, but is typically ignored by methods used for characterizing adhesive quality. This paper proposes a new test method that can measure effective bond line stiffness. The experiments measured the global stiffness of double-lap shear specimens and then calculated an adhesive stiffness property using shear-lag analysis of each specimen’s specific geometry and layer properties. Experiments were done for phenol formaldehyde (PF) and polyvinyl acetate (PVA) bonding wood strands of hybrid poplar and densified hybrid poplar. The stiffness of PF bond lines was an order of magnitude higher than PVA bond lines, and both were affected by the amount of adhesive coverage. The bond line stiffness with densified wood was similar to, or higher than undensified wood despite the lack of penetration of resin into the densified strands.     

阻燃型无甲醛双组分水性聚氨酯木材胶黏剂的研究

聚乙烯醇(PVA)通过KMnO4氧化为氧化聚乙烯醇(O-PVA),然后与亚磷酸二乙酯发生加成反应生成含磷聚乙烯醇(P-PVA),通过红外光谱和核磁共振确定了其结构。将P-PVA作为双组分水性聚氨酯主剂,多亚甲基多苯基异氰酸酯(PAPI)作为固化剂,考察了所制备的胶黏剂在木材刨花板中的阻燃性能。当施胶量为18%时,刨花板的极限氧指数(LOI)为27.9。热重分析表明,添加了以P-PVA为主剂的聚氨酯胶(P-PU)后,与普通聚氨酯胶(PU)相比,木材刨花板初始分解温度提前,延长了低温脱水炭化阶段,同时提高了在高温下的残炭量。     

指接材专用粘合剂的研制与开发

根据指接材用粘合剂的特点,分析了国产普通醋酸乙烯酯均聚乳液存在的主要问题,应用交联技术,引入少量活性官能单体－甲基丙烯酸羟丙酯（HPMA）,并加入各种助剂,最终研制出专用于指接材的粘合剂,因其考虑了原料来源、成本、工序可操作性等多种综合因素,故具有广泛的应用前景。     

基于面料熨烫胶接的木质家具饰面翻新研究

为实现木质旧家具在居家条件下的翻新改造,采用熨烫固化胶接方法用面料对桦木板表面进行饰面翻新,通过探究胶黏剂种类、熨烫温度和熨烫时间对面料翻新木材的胶合强度及耐水性的影响,得出理想的烫熨胶接工艺并将之用于木质旧家具的饰面翻新。结果表明:使用电熨斗的熨烫固化代替热压机的热压固化可实现居家条件下对木质家具的面料饰面翻新,胶黏剂种类、熨烫温度和熨烫时间对饰面翻新木材的胶合强度及耐水性有着重要影响;适当提高熨烫温度和延长熨烫时间可促进胶黏剂的固化进而确保胶合性能;在3种胶黏剂中最适于居家饰面翻新木质家具的胶黏剂为API胶黏剂。通过手工熨烫方法可实现对旧家具的个性化翻新,在避免家居审美疲劳的同时实现旧家具的再利用。