【作者】 吴国民；

【导师】 蒋剑春；

【作者基本信息】 中国林业科学研究院 ， 林产化学加工工程， 2012， 博士

【摘要】 双组分水性聚氨酯将双组分溶剂型聚氨酯的高性能和水性树脂的低VOC含量相结合，有望取代溶剂型聚氨酯广泛应用于汽车、木器、塑料、工业维护等诸多领域的表面装饰、防护和黏接。我国是松节油的主要生产国，松节油年产量可达8-10万吨，目前主要作为溶剂使用，深加工利用率较低。本论文以来源于松节油的萜烯基环氧树脂（TME）为基体树脂，对其进行亲水化、羟基化改性合成水性萜烯基环氧树脂多元醇，再与多异氰酸酯交联，制备双组分水性萜烯基环氧树脂（EP）/聚氨酯（PU）复合聚合物。主要研究了水性萜烯基环氧树脂多元醇的合成工艺、结构表征，多元醇水分散体的稳定性、流变性、粒子形态、粒径分布等；水性萜烯基EP/PU复合体系的交联反应动力学及其反应机理与多元醇化学结构的内在关系；复合体系的流变特性、成膜过程及其复合产物的性能与结构的内在关系。为实现我国天然萜烯可再生资源的高值化高效综合利用及其在环境友好型高分子材料中的应用提供良好的理论基础。1.以聚乙二醇（PEG）改性TME制备了非离子型萜烯基环氧树脂多元醇水分散体。通过合成反应影响因素分析，得到制备NTP的最佳合成条件：以相对分子质量为6000的PEG作为亲水改性剂，用量为TME质量的8%，以质子酸硫酸为催化剂，用量为TME质量的1.5%，反应温度为110-120℃，反应时间为1h。NTP为黄色透明固体树脂，羟值100mg/g，羟基含量3.04%；NTP水分散体为乳白液体，固含量40%，黏度150mPa.s，Z均粒子粒径约为200nm。NTP水分散体的黏度随着剪切速率的增大而减小，呈现假塑性流体特性。2.以二乙醇胺（DEA）改性TME制备了阳离子型萜烯基环氧树脂多元醇水分散体。通过合成反应影响因素分析，得到制备阳离子型环氧树脂基多元醇的最佳合成条件：DEA用量为TME质量的12%，扩链剂用量为小分子二元醇与TME（与DEA氨基反应后的量）物质的量比为1-1.2∶1，催化剂用量为TME质量的2%，反应温度100℃，反应时间6-7h。阳离子型多元醇为黄色透明固体树脂，羟值230-260mg/g，羟基含量6.97%-7.88%；阳离子型多元醇水分散体为黄色透明液体，固含量30%，黏度1700-3700mPa.s，Z均粒子粒径约为20-40nm。水分散体的黏度随着剪切速率的增大变化不明显，属于牛顿流体。3.以对氨基苯甲酸（PABA）改性TME制备了阴离子型萜烯基环氧树脂多元醇（T-PABA）水分散体。通过合成反应影响因素分析，得到制备T-PABA的最佳合成条件：PABA/TME摩尔配比为1.6-1.8∶1，以丁酮为反应溶剂，用量为PABA质量的1.5倍，反应温度为丁酮回流温度80-90℃，反应时间为3h。T-PABA为黄色透明固体树脂，羟值170mg/g，胺值126mg/g，活泼氢含量0.525mol/100g； T-PABA水分散体为黄色透明液体，固含量30%，黏度400mPa.s，Z均粒子粒径约为30nm。T-PABA水分散体的剪切黏度随着剪切速率的增大保持不变，属于牛顿流体。4.将萜烯基环氧树脂多元醇水分散体与多异氰酸酯复合组成双组分水性EP/PU复合体系，利用低温冷冻干燥法除去分散介质水，以示差量热扫描仪（DSC）研究水性复合体系在无溶剂存在下的本体反应动力学，分别以Kissinger-Crane方法和Málek方法求取复合体系的交联反应动力学方程。研究发现，以Kissinger-Crane方法得到的n级反应动力学模型来拟合计算值和实验值时，发现计算曲线和实验曲线偏差较大。而以自催化动力学模型来拟合计算值和实验值时，计算曲线与实验曲线吻合较好。在实验考查的升温速率范围内，由Málek方法求得的自催化反应动力学模型能较好的描述水性萜烯基EP/PU复合体系的交联反应过程。以介电固化法研究水性萜烯基EP/PU复合体系的等温交联反应过程，并离子黏度曲线验证由非等温DSC法得到的动力学方程。用非等温动力学方程计算得到的交联度与时间曲线对等温介电固化离子黏度曲线进行拟合。结果显示两者的拟合效果较好，曲线随时间的变化趋势基本一致。这也说明了所得的自催化动力学模型能较好的描述水性复合体系的交联反应过程。5.水性萜烯基EP/PU复合体系的流变特性与所对应的水性多元醇的流变特性一致。多元醇与多异氰酸酯搅拌混合过程中，多元醇水分散体对多异氰酸酯有乳化作用，两者混合后重新分散形成了新的粒子。成膜过程包括可挥发物溶剂、水的挥发，多元醇和多异氰酸酯粒子的融合，多异氰酸酯和多元醇、水的反应。复合产物表面存在的粒子痕迹从侧面反映了膜结构内部保留粒子痕迹，验证了双组分水性聚氨酯体系粒子堆积成膜机理。复合产物性能与多元醇结构密切相关。非离子型复合体系的干燥时间较长；阳离子型多元醇由于叔胺基团的催化作用，其配合体系干燥快；阴离子型多元醇结构中含有仲胺基团，复合体系的干燥时间较短。由于多元醇都含有萜烯脂环结构，复合产物都具有较好的光泽度、冲击强度、附着力、柔韧性、耐污、耐热、抗粘连性能。阴离子型多元醇分子引入了苯环结构，其复合产物的关泽度、硬度最高。由于多元醇分子结构都经过亲水改性，复合产物的耐水性能稍差。随着NCO/OH物质的量比的增加，体系的干燥时间增加延长，复合产物的硬度、耐水、耐热性能增强。更多还原

【Abstract】 Two-component waterborne polyurethanes (2K-WPUs) which combine high performanceof two-component solvent based polyurethanes and environmental friendliness, safety ofwaterborne systems together, have been grown as hotspots of coating research in both domesticand overseas, and have been increasingly applied in surface finishing, protection and adhesionfor cars, wood, plastic, industrial maintenance, etc. China is the main turpentine producingcountry, and its turpentine annual output is80000-100000tons. Turpentine is widely used assolvent due to the low level of deep processing and utilization.Terpene-maleic ester type epoxy resin (TME) which is an alicyclic epoxy resin withendocyclic structure was synthesized from the raw material turpentine. In this paper,waterborne polyols were synthesized from TME by hydroxylation and hydrophilization. Thenthe TME-based polyols were crosslinked with polyisocyanate to prepare two-componentwaterborne epoxy resin/polyurethane composite systems. The main topics of this thesis are asfollows:(1)the synthesis and characterization of TME-based polyols, and the stability,rheological property and particle size distribution of the polyol dispersions;(2)the kinetics ofcrosslinking reaction between TME-based polyols and polyisocyanate, and the effects of polyolstructures on reaction mechanism;(3)the rheological property and film formation of thewaterborne composite systems, and the effects of polymer structures on properties of thecomposite products. The purpose of this study is to provide favorable theoretical basis forhigher value and more efficient application of the renewable terpene resource on preparationfor environment-friendly polymer materials.1. Nonionic TME-based polyol (NTP) dispersion was prepared by modifying TME withpolyethylene glycol. The best synthesis condition of polyols was confirmed by studying aboutreaction influence factors. When reacted at110-120℃for about1h,good quality product canbe obtained by using polyethylene glycol with molecular weight of6000as hydrophilic segment which desirably accounts for8%by weight based on the weight of TME, andsulphuric acid as catalyst which accounts for1.5%by weight based on the weight of TME.NTP is transparent yellow solid with hydroxyl value of100mg/g, hydroxyl group content of3.04%. NTP dispersion is milk-white liquid with solid content of40%, viscosity of150mPa·s,Z-average particle size of200nm. The apparent viscosity of NTP dispersion decreases with theincreasing of shear rate, which indicates NTP dispersion is Pseudoplastic fluid.2. Cationic TME-based polyol dispersions were prepared by modifying TME withdiethanolamine. Suitable synthesis condition of polyols was confirmed by studying on factorsof synthesis reaction. Good quality polyols can be obtained by TME reacting withdiethanolamine in the amount of12%of TME by weight and chain extenders whose molarratio to TME (the quantities after reacting with amido of diethanolamine) is1–1.2:1attemperature of100℃for about6–7h in the present of ZnCl2as catalyst with the amount about2%of TME by weight. Cationic TME-based polyols are transparent yellow solids withhydroxyl value of230-260mg/g, hydroxyl group content of6.97-7.88%. Cationic TME-basedpolyol dispersions are transparent yellow liquids with solid content of30%, viscosity of1700-3700mPa·s, Z-average particle size of20-40nm. The apparent viscosity of cationicpolyol dispersions remains constant with the increasing of shear rate, which indicates cationicpolyol dispersions are Newton fluid.3. Anionic TME-based polyol (T-PABA) dispersion was prepared by modifying TME withpara-aminobenzoic acid. And suitable synthesis condition of polyol was confirmed by studyingon factors of synthesis reaction. When reacted at80-90℃for about3h,good quality T-PABAcan be obtained by TME reacting with para-aminobenzoic acid whose molar ratio to TME is1.6–1.8∶1,and using butanone as reaction solvent which desirably accounts for150%byweight based on the weight of para-aminobenzoic acid. T-PABA is transparent yellow solidwith hydroxyl value of170mg/g, amine value of126mg/g, and active hydrogen content of0.525mol/100g. T-PABA dispersion is transparent yellow liquid with solid content of30%,viscosity of400mPa·s, Z-average particle size of30nm. The apparent viscosity of T-PABA dispersion remains constant with the increasing of shear rate, which indicates T-PABAdispersion is Newton fluid.4. A kinetics analysis method for the bulk crosslinking reaction of waterborne epoxyresin/polyurethane composite systems prepared with TME-based polyol dispersions andhydrophilically modified hexamethylene diisocyanate (HDI) tripolymer was investigated withfreeze-drying and differential scanning calorimetry (DSC). And the data fit was realized withthe nth order kinetics equation and Málek’s mechanism function method, respectively. Theresults showed that the nth order kinetics equations from Kissinger and Crane Equations werenot able to well describe the nonisothermal reaction rates of the waterborne composite systems.While the simulated curves acquired from Málek’s mechanism function method matched wellwith the experimental dots in the investigated heating rate range. These results reflected thatthe autocatalytic model from Málek’s method could be used well for the investigatedcrosslinking systems. The kinetic equations acquired from this model can be used to direct thetechnological parameters optimization of the2K-WPUs crosslinking process.In order to validate whether the kinetics models acquired from Málek’s method can directthe isothermal crosslinking process, conversion coefficient curves calculated from obtainedkinetics equations were compared with ion viscosity curves from dielectric analysis. It could beobserved that these two types of curves matched quite well with each other. This resultindicated that the kinetics models gained from the Málek’s mechanism function method couldwell describe the actual crosslinking reaction processes of the studied crosslinking systems.5. The rheological properties of the waterborne epoxy resin/polyurethane compositesystems were in conformity with that of the used polyol dispersions. Polyol dispersions couldemulsify the HDI tripolymer and reform new particles when the two components were mixed.The film formation process of2K-WPUs is as the following:(1) solvent, water volatilizing,(2)polyol particles and HDI particles merging together,(3) polyisocyanate reacting with polyoland water. The particle trails on the surface of composite products indicated that there were particle trails in the body of the film. This result confirmed the particles piling film formationmechanism of the2K-WPUs.The properties of the composite products are closely related to the chemical structures ofthe TME-based polyols. There is only secondary hydroxyl group whose reactivity is low whenreacting with isocyanate group in NTP structure. Therefore, the drying time of the compositesystem from NTP is long. T-PABA contains secondary amine group having high reactivity withisocyanate group, so the drying time of the composite system from T-PABA is short. CationicTME-based polyols have tertiary amine in structure, which can catalyze the reaction ofhydroxyl group and isocyanate group. The drying time of their composite systems is short too.Due to the presence of endocyclic structure of terpene, the composite products of thecomposite systems have many eximious properties, such as high gloss, good impact strength,adhesion, flexibility, antifouling, heat resistance and blocking resistance. The compositeproduct of T-PABA with benzene ring structure has the highest gloss and pencil hardness. Thewater resistance of the composite products is slightly inferior as a result of the presence ofhydrophilic groups. The drying time, pencil hardness, water-resistant and thermal-resistantproperties of the composite products increase with the molar ratio of NCO group to OH group.更多还原