酚醛树脂胶粘剂研究进展

酚醛树脂胶粘剂具有优良的耐水性、耐热性、耐候性,粘接强度高及化学稳定性好等优点而被用于诸多领域。但是其还存在固化温度高、热压时间长、易透胶、有甲醛释放、原料成本高且不可再生等缺点。综述了快速固化和低游离甲醛含量酚醛胶粘剂,三聚氰胺、尿素、木质素、生物质焦油以及其他改性酚醛树脂胶粘剂,并对其存在问题和发展前景作了分析和展望。     

三聚氰胺草酸盐与氯化铵作为UF固化剂的性能对比

以三聚氰胺草酸盐(MOX)和氯化铵分别作为脲醛树脂(UF)的固化剂,然后以相应的改性UF胶粘剂压制胶合板,并探讨了不同固化剂对UF的固化时间、胶合板的胶接强度和甲醛释放量等影响。结果表明:以MOX作为固化剂时,相应UF的固化速率相对较慢,由该改性UF胶粘剂压制而成的胶合板,其胶接强度相对较高,甲醛释放量略高于含氯化铵体系;含MOX固化剂的UF胶粘剂,其DSC曲线峰顶温度(86.22℃)和吸热量(51.14 J/mg)低于含氯化铵体系,并且含MOX体系的固化反应比较平稳。     

尿素改性酚醛树脂胶粘剂的研究

以苯酚、尿素、甲醛为原料采用合理的工艺进行了尿素对酚醛树脂改性,对其可行性进行了初步分析。试验结果表明,所合成的尿素改性酚醛树脂贮存性好;可以在低于酚醛树脂25℃的固化温度下固化;在相同的固化温度下,UPF树脂的固化速度要快于PF树脂;用尿素改性酚醛树脂压制桦木三合板,其所压制的胶合板的各项物理力学性能与常规PF树脂胶合板性能相近,能达到GB/T 9846-1988对I类胶合板理化性能的要求;板材中的甲醛释放量低于GB 18580-2001中的E1级的要求。由于尿素的加入降低了胶粘剂的成本,尿素改性酚醛树脂综合性能优于PF树脂。     

低甲醛释放量人造板用改性脲醛树脂制备及应用研究

为了降低脲醛树脂的游离甲醛含量及其胶接制品的甲醛释放量,本研究在脲醛树脂合成过程中加入改性剂代替部分甲醛,通过尿素-甲醛-改性剂发生共缩聚反应,合成了改性脲醛树脂。研究了改性剂取代甲醛的摩尔比对改性脲醛树脂固化速度、游离甲醛含量的影响,以及在不同的热压条件下,对胶接胶合板的胶合强度和甲醛释放量的影响。研究结果表明,改性剂的加入不仅能有效降低改性脲醛树脂的游离甲醛含量及其胶合板的甲醛释放量,还能提高胶合板的胶合强度和耐水性。     

基于改性橡子淀粉制备的UF胶粘剂用填料性能研究

以改性橡子淀粉、茶叶废料粉和无机矿物粉组成的复合无机填料作为面粉的替代物,配制胶合板用脲醛树脂(UF)胶粘剂。着重探讨了复合无机填料的种类及含量对UF胶粘剂和胶合板的固化速率、预压性能、热稳定性能、胶合强度及其甲醛释放量等影响。结果表明:以复合无机填料替代面粉制成的胶合板用UF胶粘剂,具有预压性能良好、胶合板胶合强度更高且甲醛释放量更低等优点,其应用前景良好。     

秸秆乙醇副产物酚醛树脂的制备与应用

以秸秆乙醇副产物、苯酚、甲醛为原料,NaOH为催化剂,通过逐步共聚制备了秸秆乙醇副产物改性酚醛树脂胶粘剂,并进行了中试放大试验和人造板生产试验。通过工艺优化发现,秸秆乙醇副产物最高可替代50%质量的苯酚,且不影响酚醛树脂胶粘剂的性能,其游离甲醛含量0.22%;制备的桉杨三层胶合板100℃水煮3 h,粘接强度为0.98 MPa,达到国家Ⅰ类板要求;甲醛释放量为0.23 mg/L,达到E0级。     

丙二酸二乙酯改性酚醛树脂胶粘剂的制备与性能研究

以甲醛和苯酚为主要原料、丙二酸二乙酯为改性剂,制备碱催化水溶性酚醛树脂(PF)胶粘剂;采用DMA(动态力学分析)法、DSC(差示扫描量热)法、FT-IR(红外光谱)法和TGA(热失重分析)法等对改性PF的性能进行了表征。结果表明:适量改性剂的引入,能有效提高改性PF胶粘剂的韧性,但其固化温度和胶合板的胶接强度下降;当w(改性剂)=0.015%(相对于苯酚质量而言)时,改性体系的固化温度下降了4℃,相应胶合板的胶接强度(>0.80 MPa)仍满足GB/T 9846—2004标准中I类胶合板的指标要求。     

高邻位线性钼酸改性酚醛树脂胶黏剂的研制

以苯酚、甲醛为原料,钼酸为改性催化剂,制备了高邻位钼酸改性酚醛树脂胶黏剂,分析了催化剂种类、酚醛比、合成时间以及钼酸改性剂对酚醛树脂胶黏剂的影响,并考察了高邻位钼酸改性酚醛树脂胶黏剂的粘接性能和耐热性能。结果表明,以氧化锌为催化剂,钼酸为改性催化剂,当酚醛比为1.7、合成时间为6h时,制备的高邻位酚醛树脂胶黏剂的性能较好。     

木焦油改性生物油-酚醛树脂胶粘剂的工艺条件研究

以木焦油作为BOPF(生物油-酚醛树脂)的改性剂,制备BTPF(木焦油改性生物油-酚醛树脂)胶粘剂,并用于胶合板的制备。以木焦油加入量、催化剂(NaOH)含量和反应时间作为试验因素,以胶接强度、黏度和凝胶时间作为评价指标,采用正交试验法优选出制备BTPF胶粘剂的最佳工艺条件。结果表明:当w(木焦油)=15%、w(NaOH)=4%和反应时间为40 min时,BTPF胶粘剂的综合性能相对最好,并且完全满足GB/T 14732-2006标准中的指标要求,相应胶合板的胶接强度(1.54 MPa)和甲醛释放量(0.25 mg/L)达到了GB/T 18580—2001标准中的Eo级指标要求。     

中温固化酚醛胶粘剂固化工艺及粘接性能研究

在合成改性酚醛树脂的过程中引入了活性单体间苯二酚,以多聚甲醛为固化剂,辅以耐热无机填料制备了可中温固化的耐高温改性酚醛胶粘剂。在此基础上考察了苯酚和间苯二酚的配比、固化温度和固化剂用量对体系凝胶特性和粘接性能的影响,同时对试片处理方式、溶剂烘除时间和固化压力等因素展开研究。结果表明,苯酚和间苯二酚为2∶1、多聚甲醛用量为16.5phr、固化压力不小于0.3MPa时,胶粘剂粘接喷砂处理的试片在100℃下固化6h可获得较高的粘接强度,常温剪切强度在10MPa以上,700℃仍有约2MPa的强度。     

Properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde resin

The aim of this research was to investigate the physical and mechanical properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde (LPF) resin. For this purpose, soda bagasse lignin was modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid, and then, various contents of modified lignins (10, 15, and 20 wt%) were added as a substitute of phenol in phenol–formaldehyde (PF) resin synthesis. The properties of the synthesized resin were compared with those of a control PF resin. The changes in curing behavior of the resins prepared were analyzed by differential scanning calorimetry (DSC). The physical properties of the resins prepared, as well as the water absorption, thickness swelling, shear strength, and formaldehyde emission of the plywood panels bonded with these adhesives, were measured according to standard methods. DSC analysis indicated that in comparison with PF resins, curing of the LPF resin occurred at lower temperatures. The physical properties of the synthesized resins indicated that viscosity and solid content increased, while gel time and density decreased by addition of treated lignin to the PF resin. Although the panels containing resins with modified lignin yielded low formaldehyde emission, their dimensional stability was worse than those bonded with a commercial PF adhesive. The plywood prepared using IL-treated lignin PF resins has shear strength, which satisfy the requirements of the relevant standards specifications and significantly better than that of panels prepared with the control PF resin. The mechanical properties of the panels could be significantly enhanced with increased percentage of treated lignin content from 0 to 20 wt%.     

改性葫芦巴蛋白质降低酚醛树脂胶粘剂成本的研究

酚醛树脂固化后具有较好的胶合强度和优良的耐候性,是室外结构用胶合板等人造板常用胶粘剂。但是,酚醛树脂胶粘剂同时存在着成本高等缺点,限制了其更广泛的应用。研究通过添加葫芦巴残渣来达到降低酚醛树脂成本的目的。实验表明:用改性葫芦巴残渣代替部分酚醛树脂在不降低固化速度,也不影响胶合板的胶合强度的情况下,树脂成本可以得到较大降低。     

Soybean meal-based adhesive enhanced by MUF resin

Soybean meal flour, polyethylene glycol (PEG), sodium hydroxide (NaOH), and a melamine-urea-formaldehyde (MUF) resin were used to formulate soybean meal/MUF resin adhesive. Effects of the adhesive components on the water resistance and formaldehyde emission were measured on three-ply plywood. The viscosity and solid content of the different adhesive formulations were measured. The functional groups of the cured adhesives were evaluated. The results showed that the wet shear strength of plywood bonded by soybean meal/NaOH adhesive increased by 33% to 0.61 MPa after adding NaOH into the adhesive formulation. Addition of PEG reduced the viscosity of the soybean meal/NaOH/PEG adhesive by 91% to 34,489 cP. By using the MUF resin, the solid content of the soybean meal/MUF resin adhesive was improved to 39.2%, the viscosity of the adhesive was further reduced by 37% to 21,727 cP, and the wet shear strength of plywood bonded by the adhesive was increased to 0.95 MPa, which met the interior plywood requirements (≥0.7 MPa). The formaldehyde emission of plywood bonded by the soybean meal/MUF resin adhesive was obtained at 0.28 mg/L, which met the strictest requirement of the China National Standard (≤0.5 mg/L). FTIR showed using the MUF resin formed more  CH₂ group in the cured adhesive. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

纳米碳酸钙影响UF树脂性能的研究

实验对纳米CaCO3对UF树脂固化时间,游离甲醛含量及胶合强度的影响进行研究,结果表明:纳米CaCO3延长了树脂的固化时间,游离甲醛含量随加入量的增加而逐渐减少,纳米CaCO3对胶合板的胶合强度贡献不大。     

Improving the properties of ionic liquid-treated lignin-urea-formaldehyde resins by a small addition of isocyanate for wood adhesive

The aim of this research was to investigate the effect of polymeric 4, 4 diphenyl methane diisocyanate (pMDI) on the physical and mechanical properties of plywood panels bonded with an ionic liquid (IL)-treated lignin-urea-formaldehyde resin. Soda lignin modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) IL was added to a urea formaldehyde (UF) resin during resin synthesis to prepare a lignin-urea-formaldehyde (LUF) resin. pMDI at various contents (2, 4, and 6% on resin solids) was then added to prepare a LUF resin. The thermal and physicochemical properties of the resins prepared as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels bonded with them were measured according to standard methods. DSC analysis indicated that the addition of pMDI decreases the gel onset and curing temperatures of the LUF resin. According to the results obtained, the addition of pMDI significantly increased the viscosity and solid content and accelerated the gelation time of LUF resins. Based on the findings of this research, the addition of pMDI dramatically improves the performance of LUF resins as a new adhesive for wood-based panels. The LUF resins with isocyanate added yielded panels presenting lower formaldehyde emission and lower water absorption content when compared to those bonded with the control LUF resins. Greater dry and wet shear strength can be obtained by a small addition of pMDI to LUF resins.     

茶叶废料在脲醛树脂中的应用研究

将不同颗粒度的茶叶废料粉添加到脲醛树脂胶中,研究了茶叶废料的颗粒度、加入量等对脲醛树脂胶黏剂的游离甲醛含量、黏接胶合板的甲醛释放量及胶合强度的影响。实验结果表明,茶叶废料作为填料添加到脲醛树脂胶黏剂中,能够降低其游离甲醛含量以及其黏接胶合板的甲醛释放量;茶叶废料颗粒度越小,与脲醛树脂混合性越好,消除甲醛效果越显著;茶叶废料的适量加入不会降低胶合板胶合强度。