【作者】 黄坤；

【导师】 周永红；

【作者基本信息】 中国林业科学研究院 ， 林产化学加工工程， 2014， 博士

【摘要】 环氧树脂行业近年发展迅猛，天然可再生资源替代化石资源，同样是环氧树脂行业可持续发展的必然趋势。本研究针对天然植物油脂及其衍生物，如桐油、聚合脂肪酸和腰果酚等农林产品在环氧树脂领域的研究和应用方面的缺点和不足，利用这些天然产物的羧基、双键、酚羟基等活性基团，采用环氧化、Diels-Alder反应、威廉姆逊醚化反应、Mannich反应等经典化学反应来对固化剂或者是环氧树脂进行结构设计、化学改性、引入其他交联方式、或者是采用不同结构的环氧树脂进行复合调配，制备出一些具有浅色化、高模量、高韧性、双重固化和自我交联的环氧树脂或者固化剂单体，并对它们的结构和性能的相互关系进行了详细研究与探讨。本研究为天然植物油脂的高效利用和环氧树脂行业可持续发展提供了理论基础和文献参考，具体研究工作分为以下五个部分：1.以腰果酚丁基醚、甲醛和二乙烯三胺为原料合成了一种浅色的腰果酚环氧固化剂（MBCBE）。为了比较，一种具有相似结构的腰果酚酚醛胺固化剂（PKA）也按照相同方法合成。腰果酚醚化可以改善腰果酚环氧固化剂的色泽。GC-MS和FT-IR用来表征产物的结构。差示扫描量热法（DSC）用来研究了双酚A二缩水甘油醚（DGEBA）与这两种固化剂的固化行为。DSC结果表明MBCBE反应活性稍低于腰果酚酚醛胺。扫描电子显微镜（SEM）显示MBCBE/DGEBA固化物的相结构中存在孔洞分布于连续的环氧相中。这些孔洞的出现显著提高了固化物的拉伸剪切强度和冲击强度。傅里叶转换红外光谱（FT-IR）、索氏提取和热重分析（TGA）表明相分离是未反应的CBE在固化过程中析出造成的。与PKA/DGEBA的固化物相比，MBCBE/DGEBA固化物具有明显的双阶段热分解特征，这主要是由于分散相中析出的CBE蒸发造成的。2.用桐油脂肪酸分别与丙烯酸、富马酸通过Diels-Alder反应合成了一种21碳的二元酸（C21DA）和22碳的三元酸（C22TA），然后将它们转化为相应的二缩水甘油酯（DGEC21）和三缩水甘油酯（TGEC22）。合成过程中，引入CaO用作吸水剂可以有效避免副反应的发生，提高产物的环氧基含量。产物的化学结构用核磁共振氢谱（1H-NMR）、核磁共振碳谱（13C-NMR）和电喷雾质谱（ESI-MS）进行了表征。这两种缩水甘油酯的固化行为用DSC进行了研究。固化树脂的弯曲强度、冲击强度和动态力学性能分别用万能试验机和动态力学热分析（DMA）进行了测试。一种商品化的双酚A环氧树脂（DER332）和一种环氧大豆油（ESO）在本研究中用于性能比较。结果表明DGEC21和TGEC22的固化物的综合性能都要比ESO固化物的性能优异。值得注意的是，TGEC22表现出与DER332相当的强度、模量和玻璃化温度。3.用桐油脂肪酸和环氧氯丙烷合成了一种含有共轭双键的新型生物基环氧单体，桐酸缩水甘油酯（GEEA），并且用1H和13C-NMR进行了表征。DSC和FT-IR用来研究GEEA与亲二烯体和酸酐的固化过程。DSC表明GEEA可以与亲二烯体和酸酐通过Diels-Alder反应和环氧/酸酐开环反应这两种方式交联。而且，固化过程中，Diels-Alder交联方式要比环氧/酸酐开环反应更容易发生。FT-IR也证明了GEEA的确与亲二烯体和酸酐以这两种方式发生了交联。DMA和拉伸性能测试用来研究了GEEA与马来酸酐、甲基纳迪克酸酐和1,1’-（亚甲基-二-4,1-亚苯基）双马来酰亚胺固化物的热力学性能。通过热失重分析（TGA）考察了固化物的热稳定性。性能数据表明，由于亲二烯体和酸酐这两类固化剂可以彼此独立地进行反应，通过调节这两种固化剂的组成，可以得到一系列具有不同性能的热固性聚合物。4.在第3部分基础上，以GEEA和马来酸酐通过Diels-Alder反应合成了一种同时含有环氧基和酸酐基团的单体（GEMA）。产物的结构用1H-NMR、13C-NMR和极化转移无畸变增强(DEPT)13C-NMR进行了表征确认。DSC用来评价合成过程的可行性以及GEMA在叔胺催化剂存在下的固化行为。FT-IR研究了GEMA合成过程中的化学变化。DMA和拉伸性能测试分别考察了GEMA固化物的热力学性能、拉伸强度、模量和断裂伸长率。结果表明在GEMA合成过程中，只发生Diels-Alder反应，环氧基和酸酐不发生反应。GEMA的固化反应和普通的缩水甘油酯环氧树脂与酸酐的固化反应基本相同。GEMA固化物的玻璃化温度达到108°C，其拉伸强度、断裂伸长率和弹性模量分别达到42.5MPa,3.2%和1930.3MPa。5.用第2部分的合成方法，将二聚脂肪酸和丙烯海松酸分别转化成成二缩水甘油酯型环氧树脂DGEDA和DGEAPA，产物的化学结构用1H-NMR、FT-IR和ESI-MS进行了表征。柔性DGEDA和刚性DGEAPA按照不同质量比配成一系列环氧树脂混合物，以甲基纳迪克酸酐作为固化剂固化。用DSC研究了不同环氧树脂的固化行为。用三点弯曲测试和DMA测试了固化物的弯曲性能和动态力学性能。通过TGA考察了固化物的热稳定性。结果表明刚性的松香环氧树脂和柔性的二聚脂肪酸环氧树脂在弯曲强度和弹性模量两方面具有互补性。当DGEAPA：DGEDA质量比为5:3时，可以得到弯曲强度最高的材料。更多还原

【Abstract】 The development of epoxy resin industry and business is growing rapidly in recent years,it is also a tendency that the renewable resources replace the fossil resources for the sustainableprogress of epoxy resins. However, there were indeed many disadvantages or drawbacks ofnatural plant oils derivatives such as tung oil, polymerized fatty acids, and cardanols whenthese agriculture and forest products were applied in epoxy resins for research anddevelopment. Therefore, the aim of this work is to develop light color, high modulus, hightoughness, dual crosslinked, and self-crosslinked epoxy resins or curing agents. By using thecarboxyl, double bonds, and phenol hydroxyl of these natural products, a series of classicchemical reactions such as epoxidization, Diels-Alder reaction, Williamson ether synthesis, andMannich reaction were used to design or modify the molecules of epoxy resins and curingagents. Some other curing method was also introduced into the epoxy curing process. Otherepoxy resin with different structures was also blended with oil based epoxy resins to get afomulation with the optimal properties. The relationships between the structures and propertieswere studied and disscussed in detail in this work as well. This work offered theoretical basisand references for the efficient utilization of natural plant oils and the sustainable progress ofepoxy industry. The specific contents are the following five parts:1. a light color cardanol-based epoxy curing agent (MBCBE) was synthesized fromcardanol butyl ether, formaldehyde and diethylenetriamine. In comparison, a phenalkamine(PKA) with a similar structure was also prepared. MBCBE has a much lighter color than thatof PKA. The chemical structures of MBCBE were confirmed by GC-MS and FT-IR. The curebehaviors of diglycidyl ether of bisphenol A (DGEBA) with these two curing agents wasstudied by differential scanning calorimetry (DSC). The morphology, mechanical properties,thermal properties of the cured epoxies were also investigated. The DSC results indicated thatMBCBE is less reactive than the phenalkamine. The morphology of the cured MBCBE/DGEBA consisted of cavities dispersed within a continuous epoxy matrix which wereobserved by scanning electron microscope (SEM). The infrared spectra (FT-IR), soxhletextraction and thermogravimetric analysis (TGA) results confirmed that the phase separationwas arised by the unreacted CBE separated out from the epoxy matrix during the cure. Thecavities markedly improved the lap shear strength and impact strength of the cured resin.Compared with PKA/DGEBA, MBCBE/DGEBA showed an obvious two-stage weight losscurve, the first stage was mainly resulted from the dispersed phase filled with the unreactedCBE separated out from the epoxy matrix.2. In this work, a21-carbon dicarboxylic acid (C21DA) and a22-carbon tricarboxylic acid(C22TA) were prepared by the Diels-Alder addition of tung oil fatty acids with acrylic acid andfumaric acid, respectively, and subsequently converted into corresponding di-and triglycidylesters. There were no solvents used in the addition and glycidylation reactions. The excessepichlorohydrin used in the latter reaction was reused. Furthermore, for the first time calciumoxide was introduced as a water scavenger in the gycidylation process to effectively avoid theside reactions. The chemical structures of the products were confirmed using1H nuclearmagnetic resonance (1H-NMR),13C nuclear magnetic resonance (13C-NMR)and electrospray ionization mass spectrometry (ESI-MS) analyses. The curing behaviors ofthe di-and triglycidyl esters were studied using DSC. Flexural, impact and dynamicmechanical properties of the cured resins were also determined. A commercial bisphenol Aepoxy DER332and an epoxidized soybean oil (ESO) were used as performance comparison inthe study. Results indicated that the diglycidyl and triglycidyl esters had overall superiorperformance to ESO for epoxy applications. Particularly, the triglycidyl ester of the C22TAdisplayed comparable strength, modulus and glass transition temperature to that of DER332.3. A novel bio-based epoxy monomer with conjugated double bonds, glycidyl ester ofeleostearic acid (GEEA) was synthesized from tung oil fatty acids and epichlorohydrin, andthen characterized by1H-NMR and13C-NMR. DSC and FT-IR were utilized to investigate thecuring process of GEEA with dienophiles and anhydrides. DSC indicated that GEEA could crosslink with both dienophiles and anhydrides through these two synergetic ways: Diels-Alderreaction and epoxy/anhydride ring-opening reaction. Furthermore, Diels-Alder reaction wasmuch more active than the ring-opening of epoxy and anhydride in the curing process. FT-IRalso revealed that GEEA successively reacted with dienophiles and anhydrides in bothcrosslinking methods. DMA and mechanical tensile testing were used to study the thermal andmechanical properties of GEEA cured by maleic anhydride, nadic methyl anhydride (NMA)and1,1’-(methylenedi-4,1-phenylene)bismaleimide. Due to the independence between thecuring agents, dienophile and anhydride, a series of thermosetting polymers with variousproperties could be obtained by adjusting the composition of these two curing agents.4. Based on part3, a self-crosslinking monomer with both epoxy and anhydride groups(GEMA) was synthesized from GEEA and maleic anhydride. The structure of GEMA wasconfirmed by1H-NMR,13C-NMR, and distortionless enhancement by polarization transfer(DEPT)13C-NMR. The feasibility of the synthesis and the chemical reaction during thesynthesis were investigated by DSC and FT-IR, respectively. The curing behavior of GEMA inthe presence of tertiary amine was also studied by DSC. The dynamic mechanical propertiesand tensile properties were measured by DMA and tensile test. The results showed that therewas no epoxy/annydride reaction but only Diels-Alder raction during the synthesis of GEMA.The cure mechanism of GEMA was similar to that of conventional glycidyl ester epoxy resinand anhydride. The glass transition temperature of cured GEMA is108°C. The tensile strength,strain, and the elastic modulus of cured GEMA are42.5MPa,3.2%, and1930.3MPa,respectively.5. In this work, a rosin-derived diacid and a dimerized fatty acid were converted todiglycidyl ester type epoxies through the synthesis method offered in part2, respectively, andthe chemical structures of the products were confirmed by1H-NMR, FT-IR and ESI-MS. NMAwas used as curing agent to cure these two biobased epoxies and their mixtures in differentweight ratios. The cure behavior of these two epoxies with NMA was studied using DSC.Flexural and dynamic mechanical properties of the cured resins were determined using three point bending test and DMA. Thermal degradation of the cured resins was examined usingthermogravimetric analysis (TGA). Results suggest that the rigid rosin-derived epoxy and theflexible dimer acid-derived are complementary between flexural strength and flexural modulus.The combination of DGEAPA:DGEDA (5:3) by weight could result in resins with the bestflexural strength.更多还原