耐高温酚醛树脂胶粘剂研究进展

综述耐高温PF(酚醛树脂)胶粘剂的研究进展,包括其在航空、航天领域的应用以及PF胶粘剂的耐高温改性。耐高温改性主要集中在硼改性、有机硅改性、无机填料改性以及有机/无机复合改性等方面。最后对耐高温PF胶粘剂的发展方向进行了展望。     

复合催化间苯二酚/膨润土改性酚醛树脂胶粘剂研究

以苯酚和甲醛为原料,选取氢氧化钡[Ba(OH)2]/氢氧化钠(NaOH)为复合催化剂,采用两步加入甲醛法合成了中温固化酚醛树脂(PF)胶粘剂;然后以间苯二酚、膨润土为改性剂,探讨了改性剂含量、反应时间等对改性PF胶粘剂性能的影响,并通过对改性PF胶粘剂的黏度、密度、固含量以及胶接强度等测试,比较了改性PF胶粘剂合成条件的影响。研究结果表明:间苯二酚作为改性剂可明显提高胶粘剂的耐水性能;合成的改性PF胶粘剂的储存期超过60 d,但延长反应时间会使PF胶粘剂的储存期缩短;膨润土对PF胶粘剂性能的影响较复杂;间苯二酚与膨润土同时加入时,前者对PF胶粘剂的性能改进起决定作用。     

改性耐高温胶粘剂的研究进展

综述了近年来国内外改性耐高温胶粘剂的发展现状,对环氧树脂(EP)、酚醛树脂(PF)、有机硅、含氮杂环以及无机耐高温胶粘剂的性能、应用和改性方法进行了详细的论述,主要介绍了提高各种胶粘剂耐高温性能的改性方法和技术途径,并对今后改性耐高温胶粘剂的发展趋势作了展望。     

耐高温环氧树脂胶粘剂的研究进展

介绍了耐高温环氧树脂(EP)胶粘剂中无机填料、热塑性树脂、酚醛树脂(PF)、纳米粒子和结构调整等EP改性方法的研究进展,特别对双马来酰亚胺(BMI)改性EP及有机硅改性EP进行了综述。最后对耐高温EP胶粘剂的发展前景进行了展望。     

单宁改性酚醛树脂胶粘剂研究进展

在介绍可再生的绿色环保型生物质原料单宁的基础上,综述了黑荆树栲胶、落叶松栲胶以及马占相思栲胶等富含缩合单宁的生物质原料改性PF(酚醛树脂)胶粘剂的研究进展,并指出了单宁改性PF胶粘剂存在胶液黏度过大、单宁/甲醛的反应活性过高和胶液适用期过短等缺点。最后对单宁改性PF胶粘剂的研究方向进行了展望,指出利用单宁与改性木质素、玉米淀粉和生物油等生物质原料复配改性PF胶粘剂将成为重要的研究方向。     

水溶性中温快速固化酚醛树脂胶粘剂的工艺优化研究

以氢氧化钡[Ba(OH)2]和氢氧化钠(Na OH)作为复合催化剂,采用两步甲醛(F)加入法制备了高邻位羟甲基含量的PF(酚醛树脂)胶粘剂。以Na OH掺量、Ba(OH)2掺量和Ba(OH)2加入时间作为试验因素,PF胶粘剂的黏度、水溶倍数和固化时间作为考核指标,采用正交试验法优选出制备PF胶粘剂的最佳工艺条件。研究结果表明:同时采用Na OH和Ba(OH)2作为催化剂时,Na OH的催化效果优于Ba(OH)2;Na OH掺量是影响PF胶粘剂的黏度、水溶倍数和固化时间的最显著因素,Ba(OH)2加入时间是不显著因素;合成PF胶粘剂的最佳工艺条件是n(Na OH)=0.30 mol、n[Ba(OH)2]=0.03 mol和Ba(OH)2加入时间为40 min。     

有机硅改性木薯淀粉胶粘剂的制备及性能研究

以木薯淀粉和丙烯酰胺(AM)为主要原料、过氧化氢为木薯淀粉的氧化剂、过硫酸铵(APS)为引发剂和有机硅为改性剂,制备了有机硅改性木薯淀粉木材胶粘剂。采用单因素试验和正交试验法优选出合成该木材胶粘剂的最佳工艺条件,并采用红外光谱(FT-IR)法对制胶过程的化学机制进行了分析。研究结果表明:当V(有机硅)=6.0 m L、m(AM)=14.0 g、m(引发剂)=0.30 g和反应温度为60℃时,制胶工艺条件相对最佳,相应胶粘剂的应用性能(粘接强度达到4.65 MPa、耐水时间超过32.0 h、黏度为1 050 m Pa·s)基本符合GB/T14732—2006标准要求。     

酚醛树脂耐热改性研究进展

对酚醛树脂(PF)耐热性的改性研究进行了综述,改性后的PF耐热性得到了显著提高。耐热改性方法包括苯并噁嗪化合物改性PF、纳米材料改性PF、硼(B)改性PF、钼(Mo)改性PF、双马来酰亚胺(BMI)改性PF和有机硅改性PF等。     

助剂对脱脂豆粉胶粘剂粘接性能及工艺性能的影响

传统大豆蛋白胶粘剂具有黏度大、工艺性能差和易干胶沙化等缺点,导致胶粘剂的粘接性能和耐水性较差。以脱脂豆粉为基体、MPA(改性聚酰胺)为交联改性剂、Na Cl(氯化钠)为改性剂和甘油为保水剂,采用单因素试验法优选出制备胶合板用大豆蛋白木材胶粘剂的最佳工艺条件。研究结果表明:低固含量MPA可改善胶粘剂的耐水性、工艺性能,并且能有效降低胶粘剂的黏度;引入适当的助剂,可延长胶粘剂的适用期、改善工艺性能;Na Cl和甘油能有效改善豆胶的沙化现象。当m(脱脂豆粉)∶m(MPA)=1∶0.6、w(Na Cl)=1%和w(甘油)=5%(均相对于干固胶粘剂质量而言)时,制成的胶粘剂可用于胶合板的压制,并且该胶合板经煮-烘-煮28 h循环处理后的剪切强度为0.90 MPa。     

大豆蛋白基木材胶粘剂的制备与应用性能研究

以SPI(大豆蛋白)粉、自制混合改性剂为主要原料,制备了SPI胶粘剂;然后以改性异氰酸酯为固化剂,并引入不同的填料,配制胶合板用胶粘剂。研究结果表明:采用单因素试验法优选出制备SPI胶粘剂的最佳工艺条件是w(混合改性剂B)=10%(相对于SPI粉质量而言)、w(固化剂)=10%(相对于SPI胶粘剂质量而言)、混合填料中m(蒙脱土)∶m(小麦面粉)=4∶1且w(混合填料)=10%(相对于SPI胶粘剂质量而言);此时改性胶粘剂的综合性能相对较好,其黏度适中、适用期较长,并且由其压制而成的胶合板具有相对较大的胶接强度和相对较好的耐水性。     

Effects of Pinus pinaster bark extracts content on the cure properties of tannin-modified adhesives and on bonding of exterior grade MDF

Phenol-urea-formaldehyde-tannin (PUFT) adhesives with different degrees of phenol substitution by Pinus pinaster bark tannins were thermally characterized by dynamic mechanical thermal analysis (DMTA) and by differential scanning calorimetry (DSC). They were employed to prepare exterior grade Medium Density Fiberboards (MDF) according to European Standards. DMTA and DSC experiments showed, first, that the tannin-modified adhesives hardened in the low temperature range (30-110°C) and, second, that increasing the tannin content of the adhesives reduced the curing temperature, obtaining at least the same mechanical strength (stiffness) and higher curing enthalpies (ΔH) than the commercial phenolic resin. Although only the MDF boards made using the lowest viscosity tannin-modified adhesive (PUFT-10), with a 44% phenol replacement by tannin, met the outdoor requirements, all the other tannin-modified adhesives boards met the interior grade specifications. Among the board properties evaluated, the low value of thickness swelling after 24-h water immersion of MDF boards prepared using the PUFT-10 (6.6%) is particularly noticeable, which means an improvement of almost 50% compared to that of the commercial PF (12.6%).     

Preparation and performance of lignin–phenol–formaldehyde adhesives

Steam explosion lignin phenol formaldehyde (SEL–PF) adhesives were prepared by ternary gradual copolymerization. The parameters for the phenolate of steam explosion lignin (SEL) and preparation of SEL–PF adhesives were optimized. Under the optimum phenolate conditions, the phenolic hydroxyl content of lignin increased by 130%, whilst the methoxyl content was reduced by 68%. The SEL–PF adhesives were used to prepare plywoods by hot-pressing. The pH value, viscosity, solid content, free phenol content and free formaldehyde content of SEL–PF adhesives were investigated. The bonding strengths of the plywoods glued with SEL–PF adhesives were determined. The maximum SEL replacement percentage of phenol reached 70 wt%, and the properties of adhesives and plywoods met the Chinese National Standard (GB/T 14732-2006) for first grade plywood.     

H2O2改性稻杆作为Pb2+吸附剂的工艺优化

H₂O₂改性稻杆作为Pb²⁺吸附剂,具有改性工艺环保、简单、成本低,以及对Pb²⁺吸附率高等特点,是一种优良的改性剂。优化改性工艺,制备优良吸附性能的H₂O₂改性稻杆具有较强的实用价值。详细探讨了改性工艺的影响因素如pH值、H₂O₂用量、Fe²⁺/H₂O₂物质的量之比、改性温度、改性时间、稻杆颗粒度和稻杆用量等对改性效果的影响,在单因素实验的基础上,通过正交实验和对比实验对改性工艺进行了进一步优化。得出最适宜的改性工艺为：在100 mL的溶液中,不加FeSO₄的情况下,稻杆用量为3 g,改性pH值为8,H₂O₂用量为稻秆用量的30%,稻杆颗粒度为40目,改性温度为20℃,改性时间为4 h。用2 g H₂O₂改性稻秆处理100 mL 200 mg/L的Pb²⁺废水时,对Pb²⁺的吸附率为94.45%,吸附容量为9.445 mg/g,表明H₂O₂改性稻秆具有优良的吸附性能。     

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%.     

Effect of the evolution of phenol–formaldehyde resin on the high-temperature bonding

The novel high-temperature adhesives (HTAs) were prepared using phenol–formaldehyde (PF) resin as matrix and elemental silicon or boron carbide as modification additives. The bonding properties of the above adhesives were investigated by the bonding experiment on graphite substrate. The graphite joints were heat treated at high temperatures ranging from 200 to 1500 °C. It was shown that the degradation and the content of PF resin had important influences on the bonding properties of the HTAs. The pyrolysis and degradation of the organic resin led to the drastic volume shrinkage and the decrease of mechanical strength of resin matrix. It is the main reason leading to the failure of the joints treated at high temperatures, especially in the range of 400–650 °C. It is concluded that the satisfactory bonding property of the novel organic resin matrix HTAs lies in two aspects: (i) the selection of additives with good modification effect, and (ii) the optimized ratio between resin matrix and modification additives.     

胶合板用脲醛树脂胶粘剂的纳米改性

以MMT(蒙脱土)或OMMT(有机蒙脱土)作为改性剂,两者分别在UF(脲醛树脂)合成的不同阶段(加成阶段、缩聚阶段和缩聚后期)中以同一投料比引入体系中,制备相应的改性UF胶粘剂。研究结果表明:当n(F):n(U)=1.2:1、w(MMT或OMMT)=2%(相对于尿素总质量而言)时,MMT和OMMT的引入,能使相应改性UF胶粘剂的某些性能(如黏度、固含量、胶接强度和固化时间等)增加、游离甲醛含量降低;OMMT的改性效果优于MMT,并且OMMT在加成阶段投入时降醛效果明显,在缩聚阶段投入时补强效果明显。     

^60Coγ辐照水稻秸秆制备阳离子吸附剂的研究

采用辐照法将二甲基二烯丙基氯化铵接枝共聚于预处理的水稻秸秆,考察了产物对于阴离子染料和COD的吸附性能,结果表明接枝后秸秆有吸附阴离子的效果.研究了溶液pH值、吸附时间和温度对吸附过程的影响,吸附剂对于阴离子染料与COD的最大吸附量分别为335 mg/g和73 mg/g.     

马来酰亚胺改性酚醛树脂研究进展

综述了近年来马来酰亚胺(MI)对酚醛树脂(PF)的常见改性方法。重点分析和总结了双马来酰亚胺(BMI)改性PF的机制、方法,并介绍了应用新型MI结构聚合物改性PF及PF胶粘剂。最后展望了MI改性PF的未来发展方向。     

改性热塑性酚醛树脂的制备及残炭率的影响因素

在苯酚和甲醛原料中加入一定量的SiO2粉体改性剂,可成功制备出改性热塑性PF(酚醛树脂)。以热塑性PF的残炭率为考核指标,采用单因素试验法优选出制备硅改性PF的最优方案。结果表明,当m(苯酚)∶m(甲醛)=(1.30～1.36)∶1时,硅改性PF的残炭率较高且变化不大;当w(SiO2粉体)=0.9%、反应温度为90℃和反应时间为3 h时,改性热塑性PF的残炭率相对较高;此时,Si元素已均匀分布在PF基体树脂上,掺杂的SiO2有助于提高热塑性PF的耐热性能。     

无卤阻燃PF/EP/GF布复合材料的固化性能和阻燃性能

采用环氧树脂(EP)作固化剂,2,4,6-三(二甲胺基甲基)-苯酚(DMP30)作固化促进剂改善酚醛树脂(PF)的固化性能,以氢氧化铝和有机磷阻燃剂协同改性其阻燃性能,将其涂覆于玻璃纤维(GF)布上,压制成无卤阻燃PF/EP/GF布复合材料.用傅立叶变换红外光谱(FTIR)仪和差示扫描量热(DSC)仪对无卤阻燃PF/EP/GF布复合材料的固化反应机理、固化反应动力学进行了分析研究,并测试了该复合材料的阻燃性能.结果表明,无卤阻燃PF/EP/GF布复合材料的固化反应表观活化能Ea=75.7 kJ/mol、反应级数n=0.91,起始固化温度、固化峰顶温度、固化终止温度分别为108.6、133.2、152.9℃;当氢氧化铝质量分数为14%、DMP30质量分数为1%、有机磷阻燃剂质量分数为4.8%时,无卤阻燃PF/EP/GF布复合材料的固化性能、阻燃性能均达到较佳状态.