酚醛树脂胶粘剂快速固化研究进展

从酚醛树脂胶粘剂的合成催化剂选择、合成工艺改进、固化促进剂添加等几个方面,综述了近年来酚醛树脂胶粘剂快速固化研究进展。     

我国木材胶粘剂发展概况

综述中国木材胶粘剂概况．报告了脲醛树脂、酚醛树脂、三聚氰胺－甲醛树脂、单宁胶、本素胶、木材的本体聚合等胶粘剂与粘合技术的改进，并提出有关建议。     

落叶松生物油-酚醛树脂胶粘剂的研制及性能研究

为了降低酚醛树脂胶粘剂成本,提高其环保性能,研制了新型的落叶松快速热解生物油-酚醛树脂胶粘剂。选用生物油替代率、n甲醛／n苯酚以及nN2OH／n苯酚为试验因子,探讨这3个因子对生物油-酚醛树脂胶粘剂主要性能的影响,得出生物油-酚醛树脂胶粘剂的最佳合成工艺。     

酚醛树脂胶粘剂的研究进展

主要介绍了酚醛树脂胶粘剂的研究现状与进展方向,综述了酚醛树脂和酚醛树脂胶粘剂的改性方法。性能的改善提高了酚醛树脂胶粘剂的应用价值,扩大了其使用范围。     

一种汽车刹车片胶粘剂的研制及性能研究

以丁腈橡胶和酚醛树脂为主要原材料制备了一种汽车刹车片胶粘剂,介绍了其固化工艺,并讨论了该胶粘剂主要成分对拉伸剪切强度的影响。从试验结果可知,热固型液态酚醛树脂和丁腈橡胶用量均在100份时较为适宜,刹车片胶粘剂显示出较好的粘附性、耐热性。     

我国木材工业用胶粘剂的现状、存在问题及对策

本文介绍了脲醛树脂胶粘剂、酚醛树脂胶粘剂、三聚氰胺甲醛树脂胶粘剂、聚醋酸乙烯乳液胶粘剂、聚氨酯胶粘剂、热熔胶粘剂等木材工业用胶粘剂的现状和研究进展。分析了目前木材工业用胶粘剂存在的问题,初步提出了解决问题的对策。     

耐高温胶粘剂研究进展

综述了国内外耐高温胶粘剂的发展概况,对环氧树脂(EP)、聚酰亚胺(PI)、酚醛树脂(PF)、聚氨酯(PU)等耐高温有机胶粘剂和磷酸盐、硅酸盐等耐高温无机胶粘剂的合成和改性研究现状作了详细论述,并对今后耐高温胶粘剂的发展趋势进行了展望。     

生物油-酚醛树脂改性淀粉胶粘剂的研究

为了提高淀粉胶粘剂的耐水性和降低其生产成本,以生物油-PF(酚醛树脂)作为淀粉胶粘剂的改性剂,采用单因素分析法探讨了氧化剂种类、聚合反应温度及固化剂用量等因素对改性淀粉胶粘剂主要性能的影响。结果表明:制备改性淀粉胶粘剂的较佳工艺条件是以高锰酸钾和硫酸为氧化剂,聚合反应温度为75℃,w(固化剂)=12%(相对于胶粘剂总质量而言);在较佳工艺条件下制成的改性淀粉胶粘剂具有良好的胶接性能,并且克服了传统淀粉胶粘剂遇水易开胶、传统PF胶粘剂中游离醛释放量较高等缺点,可广泛用于Ⅱ类胶合板的生产。     

脲醛树脂胶粘剂及其制品低毒化研究新进展

从脲醛树脂胶粘剂的配方改进、胶粘剂合成工艺改进、胶粘剂调胶及人造板热压工艺改进、甲醛吸附材料与人造板等的复合、人造板及其制品的后处理等几个方面,综述了近几年来脲醛树脂胶粘剂及其制品低毒化研究新进展。     

酚醛-环氧结构胶粘剂的研制

论述了酚醛－环氧结构胶粘剂的制备原理及工艺，讨论了影响酚醛－环氧结构胶粘剂的性能因素，在环氧树脂中加入酚醛树脂后，二者形成了一个体型缩聚物，再加入聚砜进行改性，使制得的酚醛－环氧结构胶粘剂具有较高的剪切强度和耐热性，且具有一定的韧性和抗氧化性。     

胶合板用尿素改性酚醛树脂胶合性能的研究

制备了不同尿素用量的系列尿素改性酚醛（PUF）树脂体系（当尿素用量为苯酚质量的0、25%、43%、66%时分别记为PF、PUF-1、PUF-2、PUF-3）,并将其用于制备胶合板,研究树脂在胶合板加工过程中的变化。结果表明：PUF-3树脂与桉木和杨木的接触角为79.6°和81.1°,小于PF树脂的,PUF对桉木相容性比杨木优良,PF树脂则相反;对4种树脂进行DSC分析显示,PF、PUF-1、PUF-2、PUF-3固化速率最大温度分别为146.8、171.4、171.8和171.8℃;PUF-3和面粉共混体系的流变行为显示该共混体系110℃开始发生固化反应,（130±5）℃为较合适的热压温度;对热压前后PF和PUF-3进行热重分析,结果发现PUF的耐高温性能优于PF,热压后形成的结构耐热性也更好;4种树脂压制的胶合板性能达到E₀级,甲醛释放量均小于0.5mg/L,胶合强度分别为1.42、1.11、0.98和0.92MPa。     

Wood-induced catalytic activation of PF adhesives autopolymerization vs. PF/wood covalent bonding

The reaction of polycondensation of phenol-formaldehyde (PF) resins in the presence of wood was confirmed to have a lower energy of activation than of the PF resin alone. Under the low temperature and short curing times characteristic of the application of PF resins as thermosetting wood adhesives DSC, TGA, chemical kinetics, and IR of PF resins and relevant model compounds were carried out. These indicated that two effects appear to be present when a PF resin cures on a wood surface, both induced by the polymeric constituents of the substrate, namely carbohydrates and lignin. These appear to be (1) the catalytic activation of the resin self-condensation induced particularly by carbohydrates such as crystalline and amorphous cellulose and hemicelluloses and (2) the formation of resin/substrate covalent bonding, particularly in the case of lignin. The first appears to be, by far, the major cause of the lowering of the activation energy of PF resins curing. The contribution of the second has been found to be very small and often negligble under the conditions pertaining to thermosetting wood adhesives applications. Molecular mechanics results appear to indicate that the marked catalytic activation of PF resins autocondensation and curing appears to be induced by the strong set of PF adhesive/substrate secondary forces interactions which appear to weaken bonds which, by cleavage, lead to PF resins autocondensation. © 1994 John Wiley & Sons, Inc.     

Phenol–formaldehyde‐type resins made from phenol‐liquefied wood for the bonding of particleboard

Liquefaction of southern pine wood in phenol in 30–40 : 70–60 weight ratios resulted in homogeneous liquefied materials, which were directly used to synthesize phenol–formaldehyde (PF)‐type resins. The synthesized resins showed good physical and handling properties: low viscosity, stability for storage and transportation, and resin applicable by a common sprayer. Particleboard panels bonded with the synthesized resins showed promising physical properties and significantly lower formaldehyde emission values than those bonded with the urea–formaldehyde resin control. One deficiency observed for the synthesized resins was lower internal bond values, which might be overcome the use of a hot‐stacking procedure. Overall, the process of wood liquefaction with limited amounts of phenol as a solvent was shown to have the potential of providing practical, low‐cost PF‐type resins with very low formaldehyde emission potentials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

加快绿色化 迎接新世纪

在知识经济走向我们的时代 ,木材胶粘剂加快绿色化 ,成为生态材料 ,进入高技术产业行列。在我国 ,下世纪前十年内 ,低毒脲醛胶将成为主流产品 ;现用树脂胶的改性技术日益成熟 ,如三聚氰胺改性脲醛 (MUF)、苯酚改性脲醛 (PUF)等 ;利用天然资源制造的可降解胶粘剂用量提高 ,如木素胶、单宁胶、豆蛋白胶等 ;新产品用胶不断出现 ,如水性异氰酸酯等。另外 ,集科研、开发、生产于一体的专业胶粘剂产业将较快增长。     

Curing Behavior of Wood Adhesives Under High Steam Pressure

Steam-injection pressing is a recent development for manufacturing wood products. The curing mechanism and behavior of wood adhesives during steam-injection heating and hot-platen heating may cause differences in both chemical and physical aspects. The curing of wood adhesives under high steam pressure using an especially designed reaction cell is discussed. The adhesives used in this study were phenol-formaldehyde (PF), urea-formaldehyde (UF), melamine-formaldehyde (MF), and isocyanate (IC) resins. At different curing times, the heating temperature (steam pressure) applied to cure the adhesives was 160°C (6 kgf/cm²). Results were examined by analytical methods using FR-IR, ¹³C-NMR, dynamic mechanical analysis and solvent extraction. (1) By steam-injection heating, PF resin immediately cured to some degree in a few minutes and maintained an equilibrium situation. In this case, the reaction was accompanied by the disappearance of the ether structure. (2) In UF resin, results from IR data clarified different reactions between hot-platen heating and steam-injection heating. During steam-injection heating, as heating time increased, UF resin returned to its liquid state under the influence of hydrolysis. (3) MF resin was almost cured under steam-injection in a short heating time compared with hot-platen heating. (4) IC resin foamed and cured in a short heating time under steam-injection. It was proved that steam-injection heating was more effective than by hot-platen heating for IC resin.     

Physicomechanical and thermal properties of moldings made from liquefied wood‐based novolak PF resins under various hot‐pressing conditions

The wood powder of Cryptomeria japonica (Japanese cedar) was liquefied in phenol, with H₂SO₄ and HCl as a catalyst. The liquefied wood was used to prepare the liquefied wood‐based novolak phenol formaldehyde (PF) resins by reacting with formalin. Furthermore, novolak PF resins were mixed with wood flour, hexamethylenetetramine, zinc stearate as filler, curing agent, and lubricating agent, respectively, and hot‐pressed under 180 or 200°C for 5 or 10 min to manufacture moldings. The results showed that physicomechanical properties of moldings were influenced by the hot‐pressing condition. The molding made with hot‐pressing temperature of 200°C for 10 min had a higher curing degree, dimensional stability, and internal bonding strength. The thermal analysis indicated that using a hot‐pressing temperature of 180°C was not sufficient for the liquefied wood‐based novolak PF resins to completely cure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

烯丙基酚醛树脂固化行为的研究

利用酚醛树脂与氯丙烯反应,合成出了烯丙基酚醛树脂（APF）,并对其固化过程进行了研究。结果表明,烯丙基酚醛树脂不仅能溶于极性溶剂,还能溶于非极性溶剂,其起始固化温度为180℃,比普通的酚醛树脂高。烯丙基酚醛树脂的固化窗口为44℃,其固化是通过双键的加成反应来实现的,固化后树脂为连续相结构。     

落叶松树皮生物油改性酚醛树脂胶粘剂固化动力学研究

采用差热分析(DTA)技术测定了普通酚醛树脂(PF)和生物油改性PF在固化反应过程中的热行为,综合运用Kissinger方程、Ozawa方程和Crane方程计算出两者的固化反应动力学参数。研究结果表明,普通PF和生物油改性PF的反应级数分别为0.95和0.93,平均活化能分别为118.24kJ/mol和83.62kJ/mol,指前因子分别为8.302×1010s-1和6.235×103s-1;两者的反应级数较为接近,均可归结为复杂反应,说明生物油改性PF和普通PF的固化反应模式基本相同;与普通PF相比,生物油改性PF具有相对较低的平均活化能(即固化能耗相对较低)。     

Reduction of formaldehyde emission from plywood

The aim of this work is to evaluate performances of tannin-based resins designed as adhesive in the plywood production. For this purpose, a part of phenol formaldehyde (PF) and melamine formaldehyde (MF) in the classic adhesive formulation was replaced by tannin. The physical properties of the formulated resins (rheological characterization, etc.) were measured. In order to analyze the mechanical performance of tannin-based resins, plywood panels were produced and the mechanical properties including tensile strength wood failure and three-point bending strength were investigated. The performance of these panels is comparable to those of plywood panels made by commercial PF and MF. The results showed that the plywood panels bonded with tannin–PF (PFT) and tannin–MF (MFT) resins exhibited better mechanical properties in comparison to the plywood panels made of commercials PF and MF. The introduction of small properties of tannin in PF and MF resins contribute to the improvement of the water performance of these adhesives. The formaldehyde emission levels obtained from panels bonded with tannin-based resins were lower than those obtained from panels bonded with control PF and MF. Although there are no actual reaction at all between PF, MF, and tannin, addition of tannin significantly improves the water resistance of PF and MF resins. This is a novel finding that manifests the possibility of replacing a convention PF and MF resins by tannin. Modified adhesive is one of the goals in the plywood production without changing any of their production conditions with improvement to their overall properties.