酚醛环氧防腐涂料用固化体系研究进展

综述了近年来国内外酚醛环氧防腐涂料用固化体系的研究现状和进展,包括苯酚-甲醛、双酚A-甲醛树脂和腰果酚-苯酚-甲醛树脂等酚醛树脂固化体系,苯酚-甲醛、双酚A-甲醛改性胺和腰果酚缩醛胺固化体系及其他固化体系。认为腰果酚改性胺固化剂是一种性能优异的环氧树脂固化剂,它对开发新型高性能、多用途、低成本和环保型的重防腐环氧树脂涂料固化技术提供了新思路。     

树脂制备工艺对腰果酚改性酚醛树脂胶接性能影响研究

采用腰果酚、苯酚和甲醛为原料,氨水为催化剂,制备了三种腰果酚含量40%的热固性腰果酚改性酚醛树脂:腰果酚-甲醛/苯酚-甲醛共混酚醛树脂(CF-PF)、腰果酚-苯酚-甲醛共聚酚醛树脂(PCF-A)和混酚(腰果酚-苯酚-双酚)-甲醛共聚酚醛树脂(PCF-B)。借助DSC、TGA、剪切强度等手段对合成树脂性能进行了表征。DSC分析结果表明:三种改性树脂中PCF-B树脂的固化反应活性最高,初始温度、峰温和终温分别为146℃、190℃和259℃,固化反应活性顺序是PCF-BPCF-ACF-PF。TGA结果表明,PCF-A和PCF-B树脂的耐热性能相当,2%和5%失重温度分别是340℃左右和400℃左右,CF-PF树脂耐热性能较低,2%和5%失重温度分别为316℃和376℃。PCF-B的室温和150℃剪切强度分别为8.31MPa和7.74MPa,较PF树脂分别提高27%和71%,增韧效果明显;CF-PF的高温粘接性能最好,250℃和300℃剪切强度分别为5.07MPa和5.15MPa,分别是PF树脂250℃和300℃剪切强度的96%和141%。     

腰果酚曼尼希改性胺-环氧树脂热固化性能的研究

为了得到一种具有内增韧的同时也能具有良好的耐热性的固化剂,制备了腰果酚酚醛胺、腰果酚-苯酚混酚酚醛胺、苯酚酚醛胺3种固化剂。主要研究了固化剂与环氧树脂加热固化物的固化度、粘接性能和综合力学性能(压缩性能、冲击性能、拉伸性能等)。结果表明,制备的腰果酚-苯酚混酚酚醛胺固化剂保留了腰果酚醛胺固化剂优良的冲击韧性、较长的适用期等优点,同时也保留了苯酚酚醛胺固化剂较高的力学性能和胶接性能,是一种综合性能较佳的环氧固化剂。     

腰果酚改性胺-环氧树脂室温固化性能的研究

为了实现固化剂的内增韧,采用腰果酚、苯酚、甲醛和三乙烯四胺为原料,利用傅克烷基化反应和曼尼希反应制备了腰果酚-苯酚混酚改性胺固化剂。主要研究了固化剂与环氧树脂的室温固化工艺性能,室温固化物的固化度、粘接性能和综合力学性能(压缩性能、冲击性能、拉伸性能、硬度等)。结果表明,制备的腰果酚-苯酚混酚酚醛胺固化剂具有优良的冲击韧性、较长的适用期、室温快速固化能力、较高的力学性能和胶接性能优点,是一种综合性能较佳的环氧固化剂,有很好的应用前景。     

改性邻苯二甲腈酚醛树脂胶黏剂的研究

采用4-硝基邻苯二甲腈和线型酚醛树脂反应,制备出邻苯二甲腈酚醛树脂。采用改性树脂和增韧剂对邻苯二甲腈酚醛树脂进行改性,制备出改性邻苯二甲腈酚醛树脂胶黏剂。并借助IR、DSC、TG对合成树脂及胶黏剂进行表征。该胶黏剂可在200℃温度下固化,固化产物具有较高的耐热性能和粘接性能。     

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。     

花生壳苯酚液化产物-尿素-甲醛树脂胶黏剂的研究

以花生壳苯酚液化产物为原料,制备花生壳苯酚液化产物-尿素-甲醛（PLPUF）树脂胶黏剂。采用正交试验探讨了制备PLPUF树脂胶黏剂的最优配比,以提高其综合性能,结果表明：第一批尿素（U₁）/第二批尿素（U₂）物质的量比、液化产物（PL）/尿素（U_总）物质的量比以及液化产物和尿素总用量（PL+U_总）与甲醛（F）物质的量比为3：1、1：1.5和1：1是PLPUF树脂胶黏剂制备的最佳配比;此配比下胶合强度达到了0.83 MPa,含固体量为47.11%,游离甲醛的量为0.05%,以酚醛树脂胶黏剂为标准,PLPUF树脂胶黏剂能满足木材工业树脂的使用要求。PLPUF树脂在贮存过程中黏度逐渐上升,贮存5~15 d胶合强度为0.87~1.15 MPa,22 d后胶合强度降低至0.74 MPa,仍可满足使用条件。PLPUF树脂的FT-IR图中出现酰胺C=O和C—N等伸缩振动峰,表明尿素参与反应、改性树脂,而加入固化剂前后树脂的FT-IR吸收峰相同,结合DSC曲线表明固化剂的加入不改变树脂结构,但可以改善PLPUF树脂的固化过程,降低固化温度和固化反应热。     

腰果酚制备可发性酚醛树脂的合成工艺研究

以苯酚、腰果酚、甲醛为原料,NaOH为催化剂,乙二醇为助剂,合成了可发性酚醛树脂,通过粘度,固含量,韧性测试研究了原料的配比,腰果酚替代苯酚的比例,催化剂用量,反应时间,反应温度及乙二醇用量对合成树脂性能的影响并通过IR,TG分析对树脂结构及耐热性进行了表征。结果表明,适宜的反应条件为:F/P比(甲醛与总酚物质的量比值)1.6,腰果酚替代量20%,催化剂用量1%,反应时间3 h,反应温度80℃,乙二醇质量分数10%～15%。以腰果酚制备的CPF树脂耐热性变化不明显,拉伸强度为22.34 MPa,断裂伸长率3.08%,冲击强度3.56 kJ/m2,较PF树脂有很大提高。     

微波辐射法合成葡萄糖苯酚树脂胶黏剂

以葡萄糖代替甲醛合成一种新的环保型酚醛树脂胶黏剂。在碱性条件下以微波加热法合成葡萄糖苯酚树脂胶黏剂、通过正交实验获得最佳反应条件，同时以此方法对树脂的固化条件进行了研究。微波加热条件下合成葡萄糖苯酚树脂胶黏剂的最佳条件是：葡萄糖：苯酚=7：1；pH：12；催化剂用量：1．4％；反应时间：6min。实验证明，微波辐射波法可以成功合成葡萄糖苯酚树脂胶黏剂，且该胶黏剂是一种环保型胶黏剂。     

腰果酚缩水甘油醚改性环氧树脂胶接性能的研究

制备了腰果酚缩水甘油醚,主要研究了腰果酚缩水甘油醚改性环氧树脂胶黏剂的室温固化工艺性能、室温固化度、室温固化胶接性能和综合力学性能(压缩性能、冲击性能、硬度、拉伸性能)。腰果酚缩水甘油醚的添加量为10份时,固化1d的剪切强度与纯环氧树脂相比增加约164%,固化7d的冲击强度达到了10.36kJ/m~2,剥离强度与纯环氧树脂增加约178%。结果表明,腰果酚缩水甘油醚是一种综合性能良好的环氧树脂改性剂。腰果酚缩水甘油醚改性环氧树脂具有较好的使用工艺性能、胶接性能和力学性能。     

腰果酚醛树脂的合成

以Ba（OH）2为催化剂,合成腰果酚醛树脂,通过溶解性实验探讨了反应时间、反应温度及催化剂用量对腰果酚醛树脂溶解性、粘度的影响,并对腰果酚醛树脂进行IR、GPC表征。结果表明：反应时间、温度及催化剂用量等均对腰果酚醛树脂的性能具有明显的影响,随着反应物比例、反应温度及反应时间的增大,总体上腰果酚醛树脂的相对分子质量随之增大。     

酚醛树脂基耐磨复合材料的改性及性能

采用原位改性法合成腰果酚改性酚醛树脂,并与粒径不同的碳化硅(SiC)混合物复配制备了腰果酚改性酚醛树脂基耐磨复合材料。通过红外光谱证明成功合成了腰果酚改性酚醛树脂,且树脂符合磨具磨料用液体树脂的基本要求。扫描电镜SEM图及力学性能测试结果表明,与普通酚醛树脂相比,腰果酚改性酚醛树脂粘结Si C的能力更强,且偶联剂的加入能提高树脂与碳化硅之间的相容性。在腰果酚含量为15%时,固化剂含量为10%,偶联剂含量为2.5%时,改性酚醛树脂基复合材料的拉伸、弯曲等力学性均能达到最优。通过分析耐磨测试结果发现,二硫化钼的添加能有效降低复合材料的磨损率,提高腰果酚改性酚醛树脂基耐磨复合材料的耐磨性。     

Studies on the adhesive properties of neoprene–phenolic blends

Polychloroprene (neoprene) rubber in combination with phenolic resins is a versatile adhesive formulation. The phenolic resin used in this case was derived from a mixture of cardanol, a meta-substituted naturally-occurring substance, and phenol. Cardanol is the main ingredient of cashew nut shell liquid (CNSL), a renewable resource. This study aims to investigate the adhesive properties of cardanol-based resin when used in combination with two grades of polychloroprene rubber. The effects of varying the solid content and resin content, choice of resin, fillers, crosslinking agents, adhesion promoters, solvents, etc. in the adhesive formulations were also studied. Moreover, relative proportions of rubber and resin that give optimum adhesion performance were identified. The results show that cardanol-phenol-formaldehyde resin is an effective ingredient in adhesives for bonding aluminium to aluminium and SBR to SBR. The addition of 3-aminopropyltriethoxysilane to the formulation improves the bond strength of metal-to-metal specimens.     

Hybrid Polymer Networks of Epoxy Resin and Substituted Phenolic Novolacs

Hybrid polymer networks of diglycidyl ether of bisphenol (DGEBA) resin and phenolic novolac resins were prepared and tested for mechanical properties, hardness, and water absorption. The novolacs employed were based on each of phenol and substituted phenols such as p-cresol, t-butyl phenol, and cardanol. Cardanol is the main constituent of cashew nut shell liquid (CNSL), a renewable resource. Blends containing 10–15 wt% of novolac resin show substantial improvement in properties. These properties show a declining trend with higher novolac loading. The stoichiometric ratio between phenol and formaldehyde in the novolacs was optimized (1:0.8) for maximum property enhancement. The property profiles of the epoxy/novolac networks show that novolacs are effective modifiers for commercial epoxy resin. Incorporation of novolacs of substituted phenols results in relatively greater improvement in energy absorption during failure.     

腰果酚改性甲阶酚醛树脂的合成及其泡沫性能研究

用腰果酚代替部分苯酚改性酚醛树脂,制备可发性甲阶酚醛树脂。并讨论了腰果酚替代量对改性酚醛树脂性能及其泡沫性能的影响,通过红外光谱仪、热重分析仪对树脂结构及热稳定性进行表征,运用万能电子试验机对甲阶酚醛树脂泡沫的力学性能进行了研究。结果表明:当腰果酚替代量为10%时,制得的树脂黏度为4650mPa·s,树脂中游离苯酚含量从6.72%降为5.45%,游离甲醛含量从1.17%降为0.68%,甲阶酚醛树脂泡沫压缩强度达到最大值0.20MPa,但树脂热稳定性及甲阶酚醛树脂泡沫阻燃性有所下降。     

Preparation of cardanol–formaldehyde resins from cashew nut shell liquid for the reinforcement of natural rubber

Natural rubber was reinforced with a high loading of a cardanol–formaldehyde resin prepared from cashew nut shell liquid. Cardanol–formaldehyde resins, both resoles and novolaks, were synthesized from cardanol, which was extracted from cashew nut shells. This was done by the condensation polymerization of cardanol and formaldehyde in the presence of base and acid catalysts. The cardanol–formaldehyde resole with the highest yield (ca. 75%) was prepared with a formaldehyde/cardanol molar ratio of 2.0 at pH 8.0 and 90°C for 8 h. The cardanol–formaldehyde novolak with the highest yield (ca. 80%) was prepared with a formaldehyde/cardanol molar ratio of 0.8 at pH 2.2 and 100°C for 7 h. Fourier transform infrared and ¹³C‐NMR were employed to characterize the chemical structures of the obtained cardanol–formaldehyde resins. The resins were compatible with natural rubber in various formulations. The cured behaviors of natural rubber blended with the cardanol–formaldehyde resole and novolak resins were investigated. The cured behaviors of cardanol–formaldehyde resole and cardanol–formaldehyde novolak samples were different, reflecting differences in their chemical reactivities. Furthermore, the incorporation of cardanol–formaldehyde resins into natural rubber provided significant improvements in mechanical properties such as the hardness, tensile strength, modulus at 100 and 300% elongation, and abrasion resistance. However, the elongation at break and compression set of the blends decreased as expected. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1997–2002, 2007     

Epoxy resin from cardanol as partial replacement of bisphenol-A-based epoxy for coating application

With continuous depletion of petrochemical feedstock and their rising prices, the chemical industry is now looking for alternative renewable and sustainable materials. Such materials could be processed with various chemistries to produce high performance functional materials for a range of applications, such as plastics, coatings, constructions, pharmaceuticals, and food applications. Cardanol derived from cashew nut shell liquid has a reactive phenolic group and aliphatic double bond that could be exploited to produce novel functional materials for polymer and coating applications. It has previously been used for preparation of phenolics, epoxy, and phenalkamine hardeners. In this study, we report on the preparation of novel epoxy resin from cardanol via simple a two-step reaction. The prepared resin with epoxy equivalent weight of 210–220 gm/eq was analyzed using FTIR and NMR spectroscopy. The epoxy resin was then used as binder along with bisphenol-A-based epoxy resin (DGEBPA) at various weight proportions and cured with different amine hardeners. The cured coatings were analyzed for physical, mechanical, and chemical properties for optimization of the coating formulation. The study conducted showed that 40–60% of DGEBPA resulted in comparable properties to that of completely DGEBPA-based system. Further, thermal and anticorrosive properties of the optimized coatings were also evaluated.     

Adhesive properties of blends of phenol/cardanol–formaldehyde copolymer resin with polychloroprene rubber

This is a continuation of an earlier study on the adhesive properties of neoprene–phenolic resin blends. The phenolic resin used is derived from a mixture of phenol and cardanol, a renewable resource. Having established the utility of cardanol for formulating adhesives, this study investigates the effect of varying the phenol: cardanol ratio in the formulation. The effect of varying the total resin content at various phenol/cardanol ratios is also studied. It is found that a phenol/cardanol ratio of 80:20 is optimum for shear strength of aluminum–aluminum bonds, while a 60:40 ratio is the best for peel properties. For SBR–SBR and SBR–Al bonds, a 60:40 ratio is optimum for both peel as well as shear strength. Further, an 80 phr total resin content in the primer and a 40 phr resin content in the adhesive are found to give the best shear and peel strengths for SBR–Al bonds. The study reveals that the copolymer based on phenol, cardanol and formaldehyde is a better choice for the resin than either of the individual condensation products of phenol or cardanol with formaldehyde.     

腰果酚改性酚醛树脂的UV光固化研究

合成了腰果酚改性酚醛树脂,得到了优化反应时间为4h,催化剂的用量为1．2％～1．4％（质量百分比）。研究了涂膜紫外光固化的过程,实验结果表明：uV固化膜的物理性能优于热固化膜。