氢化萜烯基环氧树脂及其多元醇衍生物的合成、交联反应与性能研究
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摘要
本文以松节油及其合成樟脑等产品的副产物双戊烯为原料，研究了饱和萜烯基环氧树脂的合成及其固化产物性能和环氧树脂基多元醇的合成及其交联产物的性能。主要内容和结论如下：
1．以萜烯-马来酸酐加成物的氢化产物(HTMA)为原料与环氧氯丙烷(ECH)反应合成了氢化萜烯酯型环氧树脂(HTME)。通过研究合成反应影响因素，确定了HTME最佳合成反应条件：酯化反应阶段，ECH与HTMA摩尔比为10：1，加入HTMA质量的1％～1.5％催化剂，在100℃左右共沸回流反应2 h：闭环反应阶段，采用ECH为闭环溶剂，以固体NaOH闭环，用量为HTMA摩尔量的1.8～1.9倍，在2 h内分批加入，加碱时反应温度为50℃，加碱后再反应2 h，反应温度为70℃。并经FT-IR及NMR光谱表征了HTME的化学结构为具有桥环结构的缩水甘油酯型饱和脂环基环氧树脂。该环氧树脂为浅黄色透明液体，环氧值0.35～0.39 mol/100g、黏度1.7 Pa·S(50℃)、酸值＜0.5 mg/g。
2．通过DSC热分析测得HTME与酸酐固化剂甲基六氢苯酐(MeHHPA)的固化反应放热焓为153.5J／g。通过凝胶时间的测定研究了HTME／MeHHPA体系的固化反应活性。经FT-IR光谱法定性分析与固化度测定法定量分析，表征了HTME／MeHHPA体系的固化反应行为及固化反应条件。比较了HTME、TME及环氧树脂6101与MeHHPA固化产物的冲击强度、弯曲强度等机械力学性能，实验结果表明三者的机械性能相似。
3．将HTME与带活泼氢的(羟基)化合物(二乙醇胺，N-甲基单乙醇胺，二乙胺)在一定条件下反应，制备了3种环氧树脂基多元醇，分别为HTME-DEA多元醇(羟值300±20mg/g)，HTME-MEA多元醇(羟值260±20 mg/g)，HTME-DeA多元醇(羟值200±10mg/g)。通过合成反应影响因素分析，确定了环氧树脂基多元醇的最佳合成反应条件：反应温度为60-70℃，反应时间为2 h，以无水乙醇为反应溶剂，用量为反应物总质量的40％。采用化学分析和红外光谱方法表征了环氧树脂基多元醇的化学结构。
4．通过粘度测定、FT-IR光谱分析方法表征了环氧树脂基多元醇与聚二异氰酸酯交联反应的特性。通过对交联反应影响因素分析，发现多元醇分子结构中的叔胺基团可自催化羟基与异氰酸酯基快速反应。测定了交联固化产物(涂膜)的机械性能和耐液体介质性能。实验结果表明，环氧树脂基多元醇与聚异氰酸酯交联产物具有优异的柔韧性、附着力、抗冲击性能和耐水、耐盐水、耐碱性能。
本论文的主要创新点如下：
1．利用林产品可再生资源松节油为原材料合成了具有饱和桥环结构的萜烯基环氧树脂，与通用的双酚A型环氧树脂相比，其分子结构以饱和的桥环骨架代替了苯环骨架，因而该环氧树脂除具有通用环氧树脂优良的机械力学性能，还具有良好的耐紫外、耐候性能。该合成方法工艺简单，反应效果好，产率高。
2．传统的聚氨酯增韧环氧树脂的方法主要是通过形成环氧树脂／聚氨酯互穿网络聚合物实现的。该方法涉及环氧树脂及其固化剂、多元醇及二异氰酸酯四种反应物共同反应，过程复杂，反应难以控制。本文从分子设计入手，利用HTME与带活泼氢的(羟基)化合物合成环氧树脂基多元醇，再与聚异氰酸酯交联，形成环氧树脂／聚氨酯复合材料，使饱和萜烯脂环结构环氧树脂的刚性、耐候性与聚氨酯树脂的弹性、韧性有机结合，实现对环氧树脂的增韧改性。
上述思路和基础研究成果为特种环氧树脂的制备与应用、环氧树脂的增韧改性以及林产品可再生资源制备高分子材料的应用创造良好的理论基础。
In this paper, it was reviewed on the applications of synthesis of epoxy resin andpolyurethane from turpentine, and the development and progress of epoxy resin andpolyurethane modified with eath other. A novel idea of synthesis, crosslinking reaction andproperties of alicyclolic epoxy resin with endocyclic structure from turpentine or dipentene andits polyol derivatives was provided. The main contents and conclusions of this paper are listedas follows:
1. An alicyclolic epoxy resin with endocyclic structure, hydrogenated terpinene-maleic estertype epoxy (HTME), was synthesized from the raw material hydrogenated terpinene-maleicanhydride (HTMA). The best synthesis conditions were confirmed by studying about theeffects on synthesis reaction of ratio of material, reaction temperature and time, dosage ofcatalyst, the dosage and concentration of alkali and the type of solvents. In the stage ofesterification reaction, when reacted at about 100℃for longer than 2h, the esterification cantake place more completely at the epichlorohydrin (ECH) /HTMA mol ratio of 10/1 and byadding catalyst in amount from 1% to 1.5% by weight based on the weight of HTMA. At thering-closing reaction stage, when using ECH as solvent and solid alkali at the OH/HTMA molratio of 1.8～1.9, more desirable effects can be obtained by adding solid alkali in batches in 2hat 50℃and after finishing it maintaining at 70℃for additional 2h. The epoxy resin wastransparent pale yellow liquid with epoxy value 0.35～0.39 mol/100g, viscosity at 50℃1.7Pa.S and acid value＜0.5 mg/g determined by chemical analysis methods, and its chemicalstructure was also characterized by FT-IR and NMR spectra.
2. It is widely known that the excellent properties of epoxy resin could not be obtained untilcured with curing agents, such as amine and anhydride. In this paper, the activity of curingreaction between HTME and methyl hexahydrophthalic anhydride (MeHHPA) wasinvestigated by means of DSC and gelatin time determination. The enthalpy of the curingreaction is 153.5J/g. The curing behaviors of HTME/MeHHPA system were studied byqualitative analysis of FT-IR spectrum and quantitative analysis of curing degreedetermination. The mechanic properties of HTME cured with MeHHPA were compared withthat of TME and epoxy resin 6101 at the same condition and found that all of them were aboutthe same.
3. To improving the toughness of epoxy resin with polyurethane, three kinds of polyols weresynthesized by reacting HTME with active hydrogen containing compounds, such asdiethylamine(DEA), N-methylethanolamine(MEA) and diethanolamine(DeA). They can beused in place of the commonly used polyols, such as polyether glycols and polyester polyols, toprepare two-component polyurethanes. The best synthesis conditions were confirmed bystudying about the effects on synthesis reaction of the ratio of material, reaction temperatureand time, the type and the dosage of solvents. When reacted at 60～70℃for about 2h, betterquality products can be obtained by using ethanol as solvent which desirably accounts for 40%by weight based on the weight of reactants. The chemical structures of the polyols from HTMEwere characterized by chemical analysis methods and FT-IR spectra.
4. The effects of catalyst,temperature and polarity of solvents on reactivity of the threepolyols crosslinked with polyisocyanate were examined by viscosity method. It was found thatthe reactions could be catalyzed by the tertiary amine groups included in the polyols. And thecrosslinking processes of the reactions between the polyols and polyisocyanate werecharacterized with FT-IR spectra by observing the change of -N=C=O stretch peaks. Themechanical, water-resistant and chemicals-resistant properties of the crosslinked products wereevaluated according to standard tests.The results showed the crosslinked products which can becalled epoxy-urethane polymers had excellent impact strength, flexibility and water-resistant,chemicals-resistant properties. It is indicated that these epoxy-urethane polymers have madeepoxy resin and polyurethane modified with each other successfully.
The creative achievements of this work are summarized as follows:
1. An alicyclolic epoxy resin with endocyclic structure, HTME, has been synthesized fromturpentine, one of the renewable resource of forest products. In contrast to the commonly usedbisphenol A epoxy resin, HTME has excellent weatherability property, because it containssaturated endocyclic structure instead of the structure of the benzene ring in bisphenol A epoxyresin. And this synthetic method of HTME is superior with uncomplicated technology and highyield.
2. The normally methods to modify epoxy resin with polyurethane are the EP/PUinterpenetrating polymer networks, the processes of which are quite complex and difficult tocontrol. In this paper polyols based on HTME have been synthesized to crosslink withpolyisocyanate in place of the commonly used polyols. The crosslinked systems which can becalled epoxy-urethane polymers combine the rigidity and weatherability of the saturated terpinene alicyclic epoxy resin(HTME) with the flexibility and tenacity of the polyurethaneperfectly.
The purpose of the present study was to provide favorable theoretical basis for the synthesismethod, toughening technology of epoxy resin, and the application of the renewable resourceof forest products on preparation for special polymers.
1．以萜烯-马来酸酐加成物的氢化产物(HTMA)为原料与环氧氯丙烷(ECH)反应合成了氢化萜烯酯型环氧树脂(HTME)。通过研究合成反应影响因素，确定了HTME最佳合成反应条件：酯化反应阶段，ECH与HTMA摩尔比为10：1，加入HTMA质量的1％～1.5％催化剂，在100℃左右共沸回流反应2 h：闭环反应阶段，采用ECH为闭环溶剂，以固体NaOH闭环，用量为HTMA摩尔量的1.8～1.9倍，在2 h内分批加入，加碱时反应温度为50℃，加碱后再反应2 h，反应温度为70℃。并经FT-IR及NMR光谱表征了HTME的化学结构为具有桥环结构的缩水甘油酯型饱和脂环基环氧树脂。该环氧树脂为浅黄色透明液体，环氧值0.35～0.39 mol/100g、黏度1.7 Pa·S(50℃)、酸值＜0.5 mg/g。
2．通过DSC热分析测得HTME与酸酐固化剂甲基六氢苯酐(MeHHPA)的固化反应放热焓为153.5J／g。通过凝胶时间的测定研究了HTME／MeHHPA体系的固化反应活性。经FT-IR光谱法定性分析与固化度测定法定量分析，表征了HTME／MeHHPA体系的固化反应行为及固化反应条件。比较了HTME、TME及环氧树脂6101与MeHHPA固化产物的冲击强度、弯曲强度等机械力学性能，实验结果表明三者的机械性能相似。
3．将HTME与带活泼氢的(羟基)化合物(二乙醇胺，N-甲基单乙醇胺，二乙胺)在一定条件下反应，制备了3种环氧树脂基多元醇，分别为HTME-DEA多元醇(羟值300±20mg/g)，HTME-MEA多元醇(羟值260±20 mg/g)，HTME-DeA多元醇(羟值200±10mg/g)。通过合成反应影响因素分析，确定了环氧树脂基多元醇的最佳合成反应条件：反应温度为60-70℃，反应时间为2 h，以无水乙醇为反应溶剂，用量为反应物总质量的40％。采用化学分析和红外光谱方法表征了环氧树脂基多元醇的化学结构。
4．通过粘度测定、FT-IR光谱分析方法表征了环氧树脂基多元醇与聚二异氰酸酯交联反应的特性。通过对交联反应影响因素分析，发现多元醇分子结构中的叔胺基团可自催化羟基与异氰酸酯基快速反应。测定了交联固化产物(涂膜)的机械性能和耐液体介质性能。实验结果表明，环氧树脂基多元醇与聚异氰酸酯交联产物具有优异的柔韧性、附着力、抗冲击性能和耐水、耐盐水、耐碱性能。
本论文的主要创新点如下：
1．利用林产品可再生资源松节油为原材料合成了具有饱和桥环结构的萜烯基环氧树脂，与通用的双酚A型环氧树脂相比，其分子结构以饱和的桥环骨架代替了苯环骨架，因而该环氧树脂除具有通用环氧树脂优良的机械力学性能，还具有良好的耐紫外、耐候性能。该合成方法工艺简单，反应效果好，产率高。
2．传统的聚氨酯增韧环氧树脂的方法主要是通过形成环氧树脂／聚氨酯互穿网络聚合物实现的。该方法涉及环氧树脂及其固化剂、多元醇及二异氰酸酯四种反应物共同反应，过程复杂，反应难以控制。本文从分子设计入手，利用HTME与带活泼氢的(羟基)化合物合成环氧树脂基多元醇，再与聚异氰酸酯交联，形成环氧树脂／聚氨酯复合材料，使饱和萜烯脂环结构环氧树脂的刚性、耐候性与聚氨酯树脂的弹性、韧性有机结合，实现对环氧树脂的增韧改性。
上述思路和基础研究成果为特种环氧树脂的制备与应用、环氧树脂的增韧改性以及林产品可再生资源制备高分子材料的应用创造良好的理论基础。
In this paper, it was reviewed on the applications of synthesis of epoxy resin andpolyurethane from turpentine, and the development and progress of epoxy resin andpolyurethane modified with eath other. A novel idea of synthesis, crosslinking reaction andproperties of alicyclolic epoxy resin with endocyclic structure from turpentine or dipentene andits polyol derivatives was provided. The main contents and conclusions of this paper are listedas follows:
1. An alicyclolic epoxy resin with endocyclic structure, hydrogenated terpinene-maleic estertype epoxy (HTME), was synthesized from the raw material hydrogenated terpinene-maleicanhydride (HTMA). The best synthesis conditions were confirmed by studying about theeffects on synthesis reaction of ratio of material, reaction temperature and time, dosage ofcatalyst, the dosage and concentration of alkali and the type of solvents. In the stage ofesterification reaction, when reacted at about 100℃for longer than 2h, the esterification cantake place more completely at the epichlorohydrin (ECH) /HTMA mol ratio of 10/1 and byadding catalyst in amount from 1% to 1.5% by weight based on the weight of HTMA. At thering-closing reaction stage, when using ECH as solvent and solid alkali at the OH/HTMA molratio of 1.8～1.9, more desirable effects can be obtained by adding solid alkali in batches in 2hat 50℃and after finishing it maintaining at 70℃for additional 2h. The epoxy resin wastransparent pale yellow liquid with epoxy value 0.35～0.39 mol/100g, viscosity at 50℃1.7Pa.S and acid value＜0.5 mg/g determined by chemical analysis methods, and its chemicalstructure was also characterized by FT-IR and NMR spectra.
2. It is widely known that the excellent properties of epoxy resin could not be obtained untilcured with curing agents, such as amine and anhydride. In this paper, the activity of curingreaction between HTME and methyl hexahydrophthalic anhydride (MeHHPA) wasinvestigated by means of DSC and gelatin time determination. The enthalpy of the curingreaction is 153.5J/g. The curing behaviors of HTME/MeHHPA system were studied byqualitative analysis of FT-IR spectrum and quantitative analysis of curing degreedetermination. The mechanic properties of HTME cured with MeHHPA were compared withthat of TME and epoxy resin 6101 at the same condition and found that all of them were aboutthe same.
3. To improving the toughness of epoxy resin with polyurethane, three kinds of polyols weresynthesized by reacting HTME with active hydrogen containing compounds, such asdiethylamine(DEA), N-methylethanolamine(MEA) and diethanolamine(DeA). They can beused in place of the commonly used polyols, such as polyether glycols and polyester polyols, toprepare two-component polyurethanes. The best synthesis conditions were confirmed bystudying about the effects on synthesis reaction of the ratio of material, reaction temperatureand time, the type and the dosage of solvents. When reacted at 60～70℃for about 2h, betterquality products can be obtained by using ethanol as solvent which desirably accounts for 40%by weight based on the weight of reactants. The chemical structures of the polyols from HTMEwere characterized by chemical analysis methods and FT-IR spectra.
4. The effects of catalyst,temperature and polarity of solvents on reactivity of the threepolyols crosslinked with polyisocyanate were examined by viscosity method. It was found thatthe reactions could be catalyzed by the tertiary amine groups included in the polyols. And thecrosslinking processes of the reactions between the polyols and polyisocyanate werecharacterized with FT-IR spectra by observing the change of -N=C=O stretch peaks. Themechanical, water-resistant and chemicals-resistant properties of the crosslinked products wereevaluated according to standard tests.The results showed the crosslinked products which can becalled epoxy-urethane polymers had excellent impact strength, flexibility and water-resistant,chemicals-resistant properties. It is indicated that these epoxy-urethane polymers have madeepoxy resin and polyurethane modified with each other successfully.
The creative achievements of this work are summarized as follows:
1. An alicyclolic epoxy resin with endocyclic structure, HTME, has been synthesized fromturpentine, one of the renewable resource of forest products. In contrast to the commonly usedbisphenol A epoxy resin, HTME has excellent weatherability property, because it containssaturated endocyclic structure instead of the structure of the benzene ring in bisphenol A epoxyresin. And this synthetic method of HTME is superior with uncomplicated technology and highyield.
2. The normally methods to modify epoxy resin with polyurethane are the EP/PUinterpenetrating polymer networks, the processes of which are quite complex and difficult tocontrol. In this paper polyols based on HTME have been synthesized to crosslink withpolyisocyanate in place of the commonly used polyols. The crosslinked systems which can becalled epoxy-urethane polymers combine the rigidity and weatherability of the saturated terpinene alicyclic epoxy resin(HTME) with the flexibility and tenacity of the polyurethaneperfectly.
The purpose of the present study was to provide favorable theoretical basis for the synthesismethod, toughening technology of epoxy resin, and the application of the renewable resourceof forest products on preparation for special polymers.
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