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.     

Impregnation and mechanical properties of three softwoods treated with a new fire retardant chemical

Three softwoods, Sugi (Cryptomeria japonica), Korean Pine (Pinus koraiensis) and Hinoki (Chamaecyparis obtusa), were vacuum–pressure impregnated with a fire retardant chemical consisting of ammonium phosphate polymer (APP), guanyl urea phosphate (GUP), phosphonic acid and a minor amount of additives. The variation in impregnation between and within wood species was investigated. A significant relationship and similar trends were found between fire retardant chemical (FR) uptake and specific gravity (SG), as well as void volume filled (VVF) and SG. Moreover, the effects of fire retardant treatment on mechanical properties, including modulus of rupture (MOR), static modulus of elasticity (MOE) and dynamic modulus of elasticity (DMOE), were evaluated. The results indicated that the trend of impregnation and regression function varied between species and positions within the same species. However, the relationship of SG and chemical uptake and that of VVF and chemical uptake could be represented by a positive linear regression, and the trends were similar between wood species. Both of SG and VVF increased with increasing FR uptake. After fire retardant treatment, the MOR and static MOE were reduced compared with before treatment. Conversely, the DMOE increased after treatment.     

The fire-retardant properties of the melamine-modified urea–formaldehyde resins mixed with ammonium polyphosphate

Fire retardancy of melamine-modified urea–formaldehyde resin (MUF) containing intumescent fire-retardant ammonium polyphosphate (APP) (MUF/APP) was conducted by cone calorimeter with surface treatment of medium density fiberboard (MDF). The results showed that the six MUF resins synthesized with different F/(M + U) and M/U molar ratios containing APP significantly improved the fire retardancy of the MDF by prolonging ignition time, reducing heat release rate and total heat release, and decreasing mass loss rate. The fire-retardant properties of the six synthesized MUF/APP acted differently even though each MUF resin containing the same mass ratio of APP. The melamine content in the MUF should not be too high, otherwise it would decrease the fire-retardant properties of MUF/APP. Based on this study, the higher the APP amounts, the better the fire-retardant performance of the resin was. The fire retardancy of MUF/APP increased with the increase in the amount of glue that spread on the material surface. However, only the amount of glue spread exceeded 250 g/m², whereas the ability of MUF/APP in inhibiting heat release did not increase significantly any longer.     

广宁县竹香骨下脚料制备竹碎料刨花板及其复合改性研究

采用竹香骨下脚料为原料,以脲醛树脂和三聚氰胺改性脲醛树脂胶粘剂制备竹碎料刨花板,并与木纤维复合改性,检测并分析了内结合强度、静曲强度、弹性模量和吸水性。结果表明,在热压温度为160℃时,竹碎料板和竹木复合碎料板的物理力学性能均满足国标规定在干燥状态下使用的普通用板要求。当木纤维与竹碎料复合后,复合板材的静曲强度和弹性模量有一定程度提高,但内结合强度降低。     

Chemical mechanism of fire retardance of boric acid on wood

It is commonly accepted that the fire retardant mechanism of boric acid is a physical mechanism achieved by the formation of a coating or protective layer on the wood surface at high temperature. Although a char-forming catalytic mechanism has been proposed by some researchers, little direct experimental support has been provided for such a chemical mechanism. In this paper, new experimental results using thermal analysis, cone calorimetry (CONE), and gas chromatography–Fourier transform infrared spectroscopy (GC–FTIR) analysis are presented and the fire retardant mechanism of boric acid on wood is discussed. Basswood was treated with boric acid, guanylurea phosphate (GUP), and GUP–boric acid. Treated wood was then analyzed by thermogravimetry (TG/DTG), differential thermal analysis (DTA), CONE, and GC–FTIR analysis. Thermogravimetry showed that the weight loss of basswood treated with boric acid was about three times that of untreated or GUP-treated wood at 165°C, a temperature at which GUP is stable. The DTA curve showed that boric acid treated basswood has an exothermal peak at 420°C, indicating the exothermal polymerization reaction of charring. CONE results showed that boric acid and GUP had a considerable synergistic fire retardant effect on wood. The GC–FTIR spectra indicated that compounds generated by boric acid treated wood are different than those generated by untreated wood. We conclude that boric acid catalyzes the dehydration and other oxygen-eliminating reactions of wood at a relatively low temperature (approximately 100–300°C) and may catalyze the isomerization of the newly formed polymeric materials by forming aromatic structures. This contributes partly to the effects of boric acid on promoting the charring and fire retardation of wood. The mechanism of the strong fire retardant synergism between boric acid and GUP is due to the different fire retardant mechanisms of boric acid and GUP and the different activation temperatures of these two chemicals.The Forest Products Laboratory is maintained in cooperation with the University of Wisconsin. This article was written and prepared by U.S. Government employees on official time, and it is therefore in the public domain and not subject to copyright. The use of trade or firm names in this publication is for reader information and does not imply endorsement by the U.S. Department of Agriculture of any product or service.     

阻燃杉木胶合层积材的制造工艺

利用质轻、松软、强度低、径极小的杉木间伐材，经阻燃液浸渍处理、干燥后，生产阻燃杉木胶合层积材。制出的胶合层积材物理力学性能满足日本农林集成材标准，同时又具有一定的阻燃效果，可供作室内装饰和家具等用材。     

Tensile strength of softwood butt end joints. Part 2: Improvement of bond strength by a hydroxymethylated resorcinol primer

Abstract

In a previous study it was shown that the mechanical stability of an end-grain joint bonded with a one-component polyurethane adhesive (PUR) was insufficient compared with melamine–urea–formaldehyde and phenol–resorcinol–formaldehyde bonding. Based on this, the aim of this study was to improve the mechanical stability of the end-grain joint by means of a hydroxymethylated resorcinol (HMR) primer and by increasing the spreading quantity. To study the effect of HMR and the increased spreading quantity on the adhesive bond strength of end-grain to end-grain-bonded wood samples, three-part Norway spruce wood specimens were tested in tension. Before bonding, each end-grain surface was treated with an aqueous solution of HMR. The two axially orientated outer parts of the specimens were jointed with the middle part using a PUR adhesive. Compared with untreated, i.e. non-primed samples, the tensile strength of HMR-treated specimens was more than doubled. Furthermore, a positive effect of increased adhesive spread was shown for untreated PUR-bonded samples. An increase in adhesive spread by a factor of 1.6 led to an improvement in tensile strength by a factor of about 2.6.     

磷酸三聚氰胺复配硼酸锌阻燃中密度纤维板的燃烧性能

选用磷酸三聚氰胺与硼酸锌复配,制备阻燃中密度纤维板(MDF),并采用锥形量热仪测试其燃烧性能,分析复配阻燃剂对板材燃烧性能的影响.结果表明:复配阻燃剂可有效提高MDF试材的阻燃抑烟性能,降低其热释放速率、总热释放量、产烟速率、总产烟量、CO及CO2生成速率,以磷酸三聚氰胺和硼酸锌等质量复配时,MDF试材的阻燃效果最优.     

稻壳形态对稻壳--木材复合材料性能的影响

测试了稻壳形态对稻壳-木材复合材料物理力学性能的影响。试验结果表明，以20网日、30网日和40网目的稻壳为补充材料制备的密度为0．80g／cm^3的板的物理力学性能均达到国标二级品的要求。确立20网目的稻壳适宜于稻壳-木材复合材料。     

阻燃刨花板阻燃剂的研制

以氨基树脂为载体,磷-氮系阻燃液与固体无机耐火剂所构成的刨花板用阻燃体系,采用阻燃剂与刨花直接混合的添加工艺,不会造成阻燃剂的浪费,不污染环境。所生产的阻燃刨花板主要物理力学性能达到国家标准。阻燃性能:氧指数40%～50%.1000℃火焰穿透时间15～25分钟,发烟等级为一级。对人低毒。     

PMUF树脂胶黏剂的制备与性能

以尿素和三聚氰胺作为酚醛树脂改性单体制备苯酚-三聚氰胺-尿素-甲醛(PMUF)树脂胶黏剂,研究甲醛、苯酚、尿素、三聚氰胺及氢氧化钠用量对PMUF树脂胶黏剂性能的影响,并采用DSC和13C-NMR对其进行表征.结果表明:PMUF树脂游离甲醛含量低,能满足耐水、耐候性能要求较高的人造板产品的生产.当甲醛、苯酚、尿素、三聚氰胺、NaOH的摩尔比为3.1∶1∶0.7∶0.3∶0.5时胶黏剂性能最佳,其最佳固化温度为135.5℃.     

Preparation of composite board using foil-laminated and plastic-laminated liquid packaging paperboard as raw materials

We investigated the properties of composite board formed using base sheets of aluminum foil-laminated and polyethylene (PE) plastic-laminated liquid packaging paperboard (LP) as an alternative to recycling these items in wastepaper stream. Boards of different specific gravities ranging from 0.55 to 0.75 were made by pressing shredded LP blended with urea resin having resin content of 6%–10% at 180°C. Subsequently, we also prepared mixed particleboard [wood (WD) particles and LP mixed], three-layered particleboard (LP as the middle layer, WD in the upper and lower layers), and wood particleboard all having resin content of 10% and various specific gravities. Static bending and internal bonding strengths and thickness swelling of the specimens were determined to examine their properties. At the same specific gravity, the properties of LP particleboards were affected by their resin content. The modulus of rupture (MOR), modulus of elasticity (MOE), and internal bond strength of the LP particleboards increased with increasing specific gravity of the boards at the same resin content, but thickness swelling of the LP particleboards showed the reverse trend. The average MOR of the LP particleboards approximated that of the mixed particleboards and was greater than those of the three-layered particleboards and wood particleboards. Internal bond strength and thickness swelling of the LP particleboards were smaller than those of the other particleboards. Based on the above observations, we deemed that LP can be made into composite boards with adequate properties either alone or mixed with wood particles.     

竹模板湿变形特性的初步研究

本文研究了在使用竹模板浇成的混凝土结构产生严重变形的原因，是由于竹模板吸收了现浇混凝土的水分所造成。进一步测定了竹模板的相对吸水率对其静曲强度和弹性模量的显著影响，并给出了计算公式，供在竹模板的间距支撑设计和使用时参考。     

酸碱处理对制备再生桉木颗粒板的影响

废弃人造板中的胶黏剂影响人造板的回收利用。笔者利用化学法对废弃桉木颗粒板中的胶黏剂进行处理,分别探究不同浓度的硫酸、甲酸、硝酸、氢氧化钾分解废弃木颗粒板中脲醛树脂的最佳条件。结果表明,在90℃,水浴处理2 h条件下,甲酸浓度大于60%,硫酸浓度大于25%,或硝酸浓度大于25%可完全分解固化后的脲醛胶黏剂;对酸处理后的木颗粒的颜色、形貌、化学性质进行分析,甲酸对木颗粒的形态、颜色影响较小。用酸处理后制得的再生木颗粒板,力学性能相对于未经处理的再生木颗粒板得到显著提高。     

Influence of the melamine content in melamine-urea-formaldehyde resins on formaldehyde emission and cured resin structure

The effect of melamine content in melamine-urea-formaldehyde (MUF) resins on the formaldehyde emission and resin structure was investigated using six MUF resins synthesized with different F/(M + U) and M/U molar ratios. The formaldehyde emission from the plywood decreased as the F/(M + U) molar ratio decreased and the M/ U molar ratio increased. In addition, the bond performance was enhanced as the M/U molar ratio increased in the MUF resins with a fixed F/(M + U) molar ratio. Quantitative solution¹³C-NMR spectra of MUF resins revealed that the MUF resins with a high melamine content consisted of more highly branched crosslinkage structure and free melamine compared to the resins with low melamine contents. Furthermore, solid-state¹³C CP-MAS NMR spectra of cured MUF resins proved that more methylol groups, dimethylene ether, and branched methylene structures were present in the MUF resins with a higher F/(M + U) molar ratio, leading to increased bond strength and formaldehyde emission. There is no significant difference in the linkage structure of the cured resins with the same F/(M + U) and different M/U molar ratios except the ratios of carbonyl carbon of urea and triazine carbon of melamine. Therefore, the lower formaldehyde emission from cured MUF resins with a higher M/U molar ratio might be ascribed to the stronger linkages between triazine carbons of melamine than those of urea carbons. Consequently, the melamine contributed to strong crosslinking linkages in the cured resin structures, leading to lower formaldehyde emission and better bond performance.Part of this work was presented at the 48th Annual Meeting of the Japan Wood Research Society, Shizuoka, April 1998     

Technological properties and fire performance of medium density fibreboard (MDF) treated with selected polyphosphate-based fire retardants

ABSTRACT

The objective of the work was to evaluate the efficacy of two new polyphosphate-based fire retardants (FRs) and one commercial product named Siriono^® on the fire performance and physical–mechanical properties of medium density fibreboard (MDF) fabricated in the laboratory from Scots pine (Pinus sylvestris L.) wood. The fibres were treated with aqueous solutions of fire retardants, at 12% loading (dry salt on dry wood), and bonded with a melamine urea formaldehyde (MUF) adhesive. The physical and mechanical properties of panels were assessed using the European standards, whereas their fire performance was evaluated using an in-house method and the Cone calorimeter. In overall, the chemicals added enhanced the fire and smoke properties of the panels to varying degrees. Critical FR parameters such as peak heat release rate (peak HRR), total heat release (THR) and total smoke production (TSP) were significantly improved in the FR-treated panels, as exhibited in cone calorimeter tests. However, the internal bond strength of treated panels largely decreased by the addition of fire retardants, while thickness swell and water absorption negatively affected to a significant extent. In contrast, the formaldehyde release of the panels was considerably decreased at the E1 class level, with the incorporation of the polyphosphate-based additives.     

Effects of sealed press on improving the properties of particleboard

To improve the properties of particleboard, boards were produced using a sealed press. With the sealed press, boards were processed under high-temperature and high-pressure steam. This increased the saturation temperature, causing a dramatic rise in temperature inside the board, faster curing of the binder, and a shorter pressing time. The boards were bonded with urea formaldehyde resin, melamine urea formaldehyde resin, or poly(methylene diphenyl diisocyanate) (PMDI). The sealed press improved the internal bond strength and thickness swelling of boards regardless of the binder used during the reduced pressing time. The increased bonding strength improved the board properties, allowing PMDI with a lower resin content to be used for bonding the boards.     

低分子量酚醛树脂与阻燃剂复配改性大青杨木材的研究

用低分子量酚醛树脂分别与阻燃剂ＦＲＤＬ－１１２或硼酸复配改性大青杨木材的研究表明,ＰＦ树脂与ＦＲＤＬ－１１２复配使用时的渗透性优于与硼酸复配;对处理材的顺纹抗压强度和硬度有降低作用,但与未处理素材相比仍有提高,与硼酸复配对处理材的阻湿性和抗胀缩性能有较大负面影响。阻燃效果是ＦＲＤＬ－１１２明显优于硼酸;与ＦＲＤＬ０－１１２复配可处理材的防腐能力下降,与硼酸复配处理材的防腐效果优于单纯的酚醛树脂处理     

The influence of curing conditions on the chemical distribution in wood modified with thermosetting resins

Scots pine (Pinus sylvestris L.) sapwood was impregnated with aqueous solutions of phenol formaldehyde and methylated melamine formaldehyde resins and subsequently cured in an oven. One set of specimens was cured in plastic bags to avoid drying (wet curing) while another set of samples was heated and water was allowed to freely evaporate (dry curing). Macroscopic resin distribution was investigated using X-ray densitometry and infrared spectroscopy (FTIR-ATR). During dry curing, the resins migrated to the wood surface resulting in a gradient. Wet curing resulted in even distribution of the resins because it was immobilized due to condensation and precipitation in the wood. Neither densitometry nor FTIR-ATR was found to be generally applicable for investigating resin distribution in modified wood. Wet curing resulted in low cell wall bulking as compared to dry curing, probably because resin precipitated before drying. Storing impregnated wood prior to curing under non-drying conditions (“diffusion phase”) also reduced cell wall penetration and bulking.     

热固性PMUF树脂胶黏剂贮存稳定性研究

以酚醛、尿素、三聚氰胺和甲醛为原料,采用缩聚的方法制备了热固性PMUF树脂胶黏剂。考察了原料配比和初始黏度对PMUF树脂贮存稳定性的影响,以及贮存时间对PMUF树脂性能的影响,并采用FT-IR对其进行了表征。结果表明在一定范围内,减少尿素和甲醛的用量,增加苯酚和NaOH的用量,降低初始黏度可以提高PMUF树脂胶黏剂的贮存稳定性。随着贮存时间的增加,PMUF树脂胶黏剂的游离甲醛含量增加,游离苯酚含量减少,黏度变化速率上升,用其压制的胶合板甲醛释放量略有下降。