环氧树脂用潜伏型固化剂的合成及性能
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摘要
环氧树脂是一种非常重要的热固性树脂，具有优异的耐化学腐蚀性、力学性能、黏结性、绝缘性等，广泛应用于工业中。环氧树脂由环氧预聚物和固化剂经固化反应而成，环氧树脂预聚物在使用中离不开固化剂，不同结构固化剂的使用会影响环氧树脂固化物的应用性能。潜伏型固化剂的出现使环氧树脂的使用和固化工艺过程变得更为简便，并扩大了环氧树脂的应用范围。在众多潜伏型固化剂中，含硼潜伏型固化剂，如BF3-胺络合物、含胺硼酸酯，不但具有优秀的潜伏性，而且对提高环氧树脂固化物热稳定性具有重要贡献。本文合成了多种含胺硼酸酯，对其潜伏性和固化活性进行评价，系统研究了其固化动力学及其固化物的热降解过程。
（1）采用硼酸、二甲基乙醇胺与不同的双羟基化合物反应，合成得到多种短链含胺硼酸酯，对其固化活性和潜伏性进行研究。在本文所合成的短链含胺硼酸酯中，由新戊二醇（NPG）、硼酸（BA）和二甲基乙醇胺（DMEA）等摩尔比反应合成的产物（NBD）具有较佳的的固化活性和潜伏性，其凝胶温度为150℃，并可与环氧预聚物E51混合后在60℃下稳定储存54天；DSC曲线显示，由NBD作为固化剂配制的单组份环氧树脂在室温常态下经过放置315天后，在200℃处出现明显的固化放热峰，表明其仍具有固化活性。
（2）采用二甘醇、硼酸、乙二醇（或新戊二醇）、乙二酸（或己二酸）和二甲基乙醇胺反应制得不同结构的长链含胺硼酸酯，对其固化活性和潜伏性能进行比较研究。研究表明，与短链硼胺固化剂NBD相比，长链含胺硼酸酯的凝胶温度降低了10℃，固化活性得到提高。其中，采用新戊二醇、硼酸、二甲基乙醇胺、乙二醇和乙二酸等摩尔合成得到的固化剂具有较好的固化活性和潜伏性，凝胶温度为140℃，可在60℃下稳定储存6天，且经过60℃下5天的放置后，其DSC曲线仍在200℃左右有明显固化放热峰。
（3）研究含胺硼酸酯NBD对环氧树脂预聚物的潜伏固化机制及固化动力学。恒温DSC表征以及恒温处理后样品的傅立叶红外光谱（FTIR）结果表明，当温度低于140℃，由于NBD其结构中的活性基团叔胺与硼原子形成络合结构而导致NBD的固化活性处于封闭状态，而当温度达到150℃后，NBD中硼胺络合结构解络合，固化活性得以恢复。且一旦固化反应开始进行，NBD对环氧树脂预聚物的固化速率明显高于DMEA。采用Avrami-Arrhenius方法以及Horowitz-Metzger方法对潜伏型固化剂NBD和显在型固化剂DMEA的固化动力学进行研究比较。单组份环氧树脂E51-NBD的固化反应表观活化能（Ea）大于E51-DMEA的Ea，说明E51-NBD的固化反应比E51-DMEA的固化反应难开始；E51-NBD的Avrami指数n的转折点对应着固化过程中固化机制的明显变化，n在170℃出现第一个转折点意味着体系凝胶点的到来，n在210℃出现第二个转折点，预示着固化反应的即将结束；Avrami-Arrhenius方法有助于判断环氧树脂固化体系的凝胶点，而Horowitz-Metzger方法可以预测固化完成阶段。
（4）研究了含胺硼酸酯NBD和DMEA对环氧树脂固化物（分别记为E51/NBD和E51/DMEA）热稳定性的影响，并采用Horowitz-Metzger法对环氧树脂固化物热降解反应表观活化能（Ea’）进行了计算。结果表明，硼酸酯结构的引入有效提高了环氧树脂固化物的热稳定性。与E51/DMEA相比，E51/NBD（100/9）将环氧树脂固化物热失重为5%时的温度（T5）由356.5℃提高到405.4℃，900℃时的残炭率由3.0%提高到14.8%。固化剂NBD加入量对环氧树脂固化物的热稳定性有一定影响，当E51:NBD的质量比低于100:12时，E51/NBD的热稳定性随NBD加入量增加而提高；当E51:NBD的质量比高于100:12时，E51/NBD的热稳定性随NBD加入量增加变化不大，甚至略有下降。E51:NBD的质量比为100:12时，E51/NBD具有较佳的热稳定性，其T5为423.7℃， Ea’为350.3kJ/mol，900℃时的残炭率为17.4%。SEM结果表明，环氧树脂固化物（E51/NBD）经过高温900℃热降解后得到的残渣呈多孔状结构，且这种封闭状孔洞能够有效阻止材料与外层氧气接触和抑制分解过程中产生可燃气体的扩散。
（5）将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）结构引入含胺硼酸酯中，反应得到无卤阻燃含胺硼酸酯潜伏型固化剂（DBD），并对其固化活性、潜伏性、阻燃性、热稳定性进行了研究。结果表明，DOPO结构的引入使得DBD结构中有较大体积基团存在，一方面对叔胺基团形成较大空间位阻，降低了固化剂的固化活性；另一方面该大体积基团的存在不利于硼胺络合结构的形成，使潜伏性能有所下降。DBD同时具备潜伏性和阻燃性，实现了环氧树脂用固化剂的高性能化。环氧树脂固化物E51/DBD3（100:20）的磷元素含量为1.29%，其阻燃效果可以达到V-0级，LOI值为35.3%，具有较好的阻燃性。同时具备一定的潜伏性，在60℃下可稳定存储9天。研究还发现，随固化剂DBD含量的增加，环氧树脂固化物E51/DBD的热稳定性呈下降趋势，而残炭率呈增加趋势。当E51:DBD的质量比由100:10增至100:25时，制备得环氧树脂固化物E51/DBD的T5由367.1℃下降至349.6℃，Tmax由435.1℃降至398.8℃，900℃时的残炭率由14.3%增至19.6%。
Epoxy resins, one of the most important industrial thermosetting resins, own manyexcellent properties including chemical resistance, good adhesion to many substrates,mechanical properties, and thus find extensive use in various industrial areas. As is wellknown, nearly all epoxy end-use products need reaction with a hardener, and the use ofdifferent hardeners may have different effects on the terminal properties of epoxy resins. Theapperance of latent hardeners enhanced storage stability of epoxy resins containing hardenersunder ambient conditions and extended the limits of application for epoxy resins. Amongvarious latent hardeners, boron-containing compounds, such as BF3-amine complexes andamine-containing borate esters, show not only good latent curing properties, but also animprovement in the thermal stability for epoxy resins.
Firstly, a series of short chain amine-containing borates were synthesized using boricacid (BA), N,N-dimethylethanolamine (DMEA) and different di-hydroxyl chemicals byone-step method. Their curing activity and latent properties were studied and compared. Theresults showed that the short chain amine-containing borate (named as NBD) synthesized byneopentyl glycol (NPG), boric acid (BA) and N,N-dimethylethanolamine (DMEA) exhibitedexcellent curing activity and latent properties, its triggered temperature of curing activity was150oC and could be kept stably when mixing with epoxy resins at60oC for54days; DSCcharacterization indicated that one-pot epoxy resin system using NBD as a hardener stillpossessed curing reactivity after being set under ambient conditions for more than315days,for an exothermic peak related with curing reaction was found at200oC on DSC curve.
Secondly, a series of long chain amine-containing borates were synthesized usingdi-ethylene glycol, boric acid (BA), ethylene glycol (or NPG), oxalic acid (or hexanedioicacid) and N,N-dimethylethanolamine (DMEA) by two-step method. Their curing activity andlatent properties were also studied and compared. The results exhibited that curingtemperature of long chain amine-containing borates were lower10oC than that of shortamine-containing borate, because the former presented higher curing activity than the latter.Among the long chain amine-containing borates, the product synthesized by NPG, BA,DMEA, glycol and oxalic acid presented high curing activity and good latent properties,whose triggered temperature of curing activity was140oC and pot life at60oC was6dayswhen mixing with epoxy resins; and DSC results suggested that the one-pot epoxy resins stillpossessed curing reactivity after being set at60oC for5days.
Thirdly, curing kinetics and curing process of epoxy resins using NBD as a hardenerwere investigated. Isothermal differential scanning calorimetry (DSC) results and fouriertransform infrared (FTIR) spectroscopy indicated that boron-nitrogen coordination in NBDstructure blocked the curing activity of tertiary amine group below140oC, and thecoordination disassociated above150oC. The curing processes of bisphenol A diglycidyl etherepoxy resins (E51) using NBD as a latent hardener in comparison with a common hardener,DMEA, were studied using Avrami-Arrhenius method as well as Horowitz-Metzger methodbased on DSC results. It could be found that NBD showed nearly no curing activity below140oC and exhibited evident curing reactivity when temperature exceeded160oC; and thecuring reactivity of one-pot epoxy resin E51-NBD became higher than E51-DMEA once thetriggering temperature was reached. The apparent activation energy associated with curereaction (Ea) for E51-NBD and E51-DMEA were calculated by Avrami-Arrhenius method orHorowitz-Metzger method. It could be noticed that whatever the method adopted, EaofE51-NBD was larger than that of E51-DMEA, suggesting the cure reaction of the formersystem was more difficult to start than that of the latter. Transition of Avrami exponent n wasconsidered to be related with significant changes of cure mechanism. n value of E51-NBDshowed the first transition at170oC, which had some relationship with its gel point, and thesecond transition occurred at210oC, which was related with the advent of end stage of curingreaction. Avrami-Arrhenius methods could reveal the transition associated with gel point, andHorowitz-Metzger method could disclose the transition associated with the end of curingreaction.
Fourthly, effects of different hardeners (NBD and DMEA) on thermal stability of curedepoxy resins (marked as E51/NBD and E51/DMEA respectively) were discussed, and theapparent activation energy associated with thermal degradation (Ea’) was calculated byHorowitz-Metzger method. It could be found the introduction of borate by NBD enhancedthermal stability of cured epoxy resins. Comparing with cured epoxy resins E51/DMEA, T5(the temperature at which weight loss is5%) of E51/NBD increased from356.5oC to405.4oC,and char yield at900oC of E51/NBD was14.8%, much higher than that of E51/DMEA(3.0%). It was also noticed that the content of NBD in cured epoxy resin also influenced itsthermal stability. When mass ratio of E51to NBD was lower than100:12, thermal stability ofE51/NBD was enhanced with NBD content increasing. However, when mass ratio of E51toNBD was higher than100:12, few differences could be found in thermal stability of E51/NBDwith NBD content increasing, and the increase of NBD content may induce the reduction ofthermal stability of E51/NBD. E51/NBD（100:12）possessed good thermal stability, whose T5 was423.7oC, Ea’ was350.3kJ/mol, and char yield at900oC was17.4%. SEM resultsindicated that E51/NBD after thermal decomposition at900oC presented porous structure,and the enclosed porous structure was helpful to prevent the contact between epoxy resins andoxygen and inhibit the release of flammable gas.
Finally,9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide (DOPO) structure wasintroduced into amine containing borate to synthesize one novel non-halogen flameretardance hardener (DBD), and its curing activity, latent property, flame resistance andthermal stability were investigated. The results displayed that the introduction of DOPOstructure led the formation of a sterically hindered structure, which blocked the curing activityof tertiary amine and the formation of boron-nitrogen coordination, thus induced loss ofcuring activity and latent property. E51/DBD(100:20), whose phosphorus content is1.29%,possessed good flame retardance (V-0), LOI value was35.3%, and could be kept stably at60oC for9days when mixing with E51. It could also be found that thermal stability of E51/DBDdecreased, yet char yield of E51/DBD increased as DBD content increasing. When mass ratioof E51to DBD increased from100:10to100:25, T5of cured epoxy resin E51/DBD decreasedfrom367.1o C to349.6oC, Tmaxdecreased from435.1oC to398.8oC, however char yield at900oC increased from14.3%to19.6%.
（1）采用硼酸、二甲基乙醇胺与不同的双羟基化合物反应，合成得到多种短链含胺硼酸酯，对其固化活性和潜伏性进行研究。在本文所合成的短链含胺硼酸酯中，由新戊二醇（NPG）、硼酸（BA）和二甲基乙醇胺（DMEA）等摩尔比反应合成的产物（NBD）具有较佳的的固化活性和潜伏性，其凝胶温度为150℃，并可与环氧预聚物E51混合后在60℃下稳定储存54天；DSC曲线显示，由NBD作为固化剂配制的单组份环氧树脂在室温常态下经过放置315天后，在200℃处出现明显的固化放热峰，表明其仍具有固化活性。
（2）采用二甘醇、硼酸、乙二醇（或新戊二醇）、乙二酸（或己二酸）和二甲基乙醇胺反应制得不同结构的长链含胺硼酸酯，对其固化活性和潜伏性能进行比较研究。研究表明，与短链硼胺固化剂NBD相比，长链含胺硼酸酯的凝胶温度降低了10℃，固化活性得到提高。其中，采用新戊二醇、硼酸、二甲基乙醇胺、乙二醇和乙二酸等摩尔合成得到的固化剂具有较好的固化活性和潜伏性，凝胶温度为140℃，可在60℃下稳定储存6天，且经过60℃下5天的放置后，其DSC曲线仍在200℃左右有明显固化放热峰。
（3）研究含胺硼酸酯NBD对环氧树脂预聚物的潜伏固化机制及固化动力学。恒温DSC表征以及恒温处理后样品的傅立叶红外光谱（FTIR）结果表明，当温度低于140℃，由于NBD其结构中的活性基团叔胺与硼原子形成络合结构而导致NBD的固化活性处于封闭状态，而当温度达到150℃后，NBD中硼胺络合结构解络合，固化活性得以恢复。且一旦固化反应开始进行，NBD对环氧树脂预聚物的固化速率明显高于DMEA。采用Avrami-Arrhenius方法以及Horowitz-Metzger方法对潜伏型固化剂NBD和显在型固化剂DMEA的固化动力学进行研究比较。单组份环氧树脂E51-NBD的固化反应表观活化能（Ea）大于E51-DMEA的Ea，说明E51-NBD的固化反应比E51-DMEA的固化反应难开始；E51-NBD的Avrami指数n的转折点对应着固化过程中固化机制的明显变化，n在170℃出现第一个转折点意味着体系凝胶点的到来，n在210℃出现第二个转折点，预示着固化反应的即将结束；Avrami-Arrhenius方法有助于判断环氧树脂固化体系的凝胶点，而Horowitz-Metzger方法可以预测固化完成阶段。
（4）研究了含胺硼酸酯NBD和DMEA对环氧树脂固化物（分别记为E51/NBD和E51/DMEA）热稳定性的影响，并采用Horowitz-Metzger法对环氧树脂固化物热降解反应表观活化能（Ea’）进行了计算。结果表明，硼酸酯结构的引入有效提高了环氧树脂固化物的热稳定性。与E51/DMEA相比，E51/NBD（100/9）将环氧树脂固化物热失重为5%时的温度（T5）由356.5℃提高到405.4℃，900℃时的残炭率由3.0%提高到14.8%。固化剂NBD加入量对环氧树脂固化物的热稳定性有一定影响，当E51:NBD的质量比低于100:12时，E51/NBD的热稳定性随NBD加入量增加而提高；当E51:NBD的质量比高于100:12时，E51/NBD的热稳定性随NBD加入量增加变化不大，甚至略有下降。E51:NBD的质量比为100:12时，E51/NBD具有较佳的热稳定性，其T5为423.7℃， Ea’为350.3kJ/mol，900℃时的残炭率为17.4%。SEM结果表明，环氧树脂固化物（E51/NBD）经过高温900℃热降解后得到的残渣呈多孔状结构，且这种封闭状孔洞能够有效阻止材料与外层氧气接触和抑制分解过程中产生可燃气体的扩散。
（5）将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）结构引入含胺硼酸酯中，反应得到无卤阻燃含胺硼酸酯潜伏型固化剂（DBD），并对其固化活性、潜伏性、阻燃性、热稳定性进行了研究。结果表明，DOPO结构的引入使得DBD结构中有较大体积基团存在，一方面对叔胺基团形成较大空间位阻，降低了固化剂的固化活性；另一方面该大体积基团的存在不利于硼胺络合结构的形成，使潜伏性能有所下降。DBD同时具备潜伏性和阻燃性，实现了环氧树脂用固化剂的高性能化。环氧树脂固化物E51/DBD3（100:20）的磷元素含量为1.29%，其阻燃效果可以达到V-0级，LOI值为35.3%，具有较好的阻燃性。同时具备一定的潜伏性，在60℃下可稳定存储9天。研究还发现，随固化剂DBD含量的增加，环氧树脂固化物E51/DBD的热稳定性呈下降趋势，而残炭率呈增加趋势。当E51:DBD的质量比由100:10增至100:25时，制备得环氧树脂固化物E51/DBD的T5由367.1℃下降至349.6℃，Tmax由435.1℃降至398.8℃，900℃时的残炭率由14.3%增至19.6%。
Epoxy resins, one of the most important industrial thermosetting resins, own manyexcellent properties including chemical resistance, good adhesion to many substrates,mechanical properties, and thus find extensive use in various industrial areas. As is wellknown, nearly all epoxy end-use products need reaction with a hardener, and the use ofdifferent hardeners may have different effects on the terminal properties of epoxy resins. Theapperance of latent hardeners enhanced storage stability of epoxy resins containing hardenersunder ambient conditions and extended the limits of application for epoxy resins. Amongvarious latent hardeners, boron-containing compounds, such as BF3-amine complexes andamine-containing borate esters, show not only good latent curing properties, but also animprovement in the thermal stability for epoxy resins.
Firstly, a series of short chain amine-containing borates were synthesized using boricacid (BA), N,N-dimethylethanolamine (DMEA) and different di-hydroxyl chemicals byone-step method. Their curing activity and latent properties were studied and compared. Theresults showed that the short chain amine-containing borate (named as NBD) synthesized byneopentyl glycol (NPG), boric acid (BA) and N,N-dimethylethanolamine (DMEA) exhibitedexcellent curing activity and latent properties, its triggered temperature of curing activity was150oC and could be kept stably when mixing with epoxy resins at60oC for54days; DSCcharacterization indicated that one-pot epoxy resin system using NBD as a hardener stillpossessed curing reactivity after being set under ambient conditions for more than315days,for an exothermic peak related with curing reaction was found at200oC on DSC curve.
Secondly, a series of long chain amine-containing borates were synthesized usingdi-ethylene glycol, boric acid (BA), ethylene glycol (or NPG), oxalic acid (or hexanedioicacid) and N,N-dimethylethanolamine (DMEA) by two-step method. Their curing activity andlatent properties were also studied and compared. The results exhibited that curingtemperature of long chain amine-containing borates were lower10oC than that of shortamine-containing borate, because the former presented higher curing activity than the latter.Among the long chain amine-containing borates, the product synthesized by NPG, BA,DMEA, glycol and oxalic acid presented high curing activity and good latent properties,whose triggered temperature of curing activity was140oC and pot life at60oC was6dayswhen mixing with epoxy resins; and DSC results suggested that the one-pot epoxy resins stillpossessed curing reactivity after being set at60oC for5days.
Thirdly, curing kinetics and curing process of epoxy resins using NBD as a hardenerwere investigated. Isothermal differential scanning calorimetry (DSC) results and fouriertransform infrared (FTIR) spectroscopy indicated that boron-nitrogen coordination in NBDstructure blocked the curing activity of tertiary amine group below140oC, and thecoordination disassociated above150oC. The curing processes of bisphenol A diglycidyl etherepoxy resins (E51) using NBD as a latent hardener in comparison with a common hardener,DMEA, were studied using Avrami-Arrhenius method as well as Horowitz-Metzger methodbased on DSC results. It could be found that NBD showed nearly no curing activity below140oC and exhibited evident curing reactivity when temperature exceeded160oC; and thecuring reactivity of one-pot epoxy resin E51-NBD became higher than E51-DMEA once thetriggering temperature was reached. The apparent activation energy associated with curereaction (Ea) for E51-NBD and E51-DMEA were calculated by Avrami-Arrhenius method orHorowitz-Metzger method. It could be noticed that whatever the method adopted, EaofE51-NBD was larger than that of E51-DMEA, suggesting the cure reaction of the formersystem was more difficult to start than that of the latter. Transition of Avrami exponent n wasconsidered to be related with significant changes of cure mechanism. n value of E51-NBDshowed the first transition at170oC, which had some relationship with its gel point, and thesecond transition occurred at210oC, which was related with the advent of end stage of curingreaction. Avrami-Arrhenius methods could reveal the transition associated with gel point, andHorowitz-Metzger method could disclose the transition associated with the end of curingreaction.
Fourthly, effects of different hardeners (NBD and DMEA) on thermal stability of curedepoxy resins (marked as E51/NBD and E51/DMEA respectively) were discussed, and theapparent activation energy associated with thermal degradation (Ea’) was calculated byHorowitz-Metzger method. It could be found the introduction of borate by NBD enhancedthermal stability of cured epoxy resins. Comparing with cured epoxy resins E51/DMEA, T5(the temperature at which weight loss is5%) of E51/NBD increased from356.5oC to405.4oC,and char yield at900oC of E51/NBD was14.8%, much higher than that of E51/DMEA(3.0%). It was also noticed that the content of NBD in cured epoxy resin also influenced itsthermal stability. When mass ratio of E51to NBD was lower than100:12, thermal stability ofE51/NBD was enhanced with NBD content increasing. However, when mass ratio of E51toNBD was higher than100:12, few differences could be found in thermal stability of E51/NBDwith NBD content increasing, and the increase of NBD content may induce the reduction ofthermal stability of E51/NBD. E51/NBD（100:12）possessed good thermal stability, whose T5 was423.7oC, Ea’ was350.3kJ/mol, and char yield at900oC was17.4%. SEM resultsindicated that E51/NBD after thermal decomposition at900oC presented porous structure,and the enclosed porous structure was helpful to prevent the contact between epoxy resins andoxygen and inhibit the release of flammable gas.
Finally,9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide (DOPO) structure wasintroduced into amine containing borate to synthesize one novel non-halogen flameretardance hardener (DBD), and its curing activity, latent property, flame resistance andthermal stability were investigated. The results displayed that the introduction of DOPOstructure led the formation of a sterically hindered structure, which blocked the curing activityof tertiary amine and the formation of boron-nitrogen coordination, thus induced loss ofcuring activity and latent property. E51/DBD(100:20), whose phosphorus content is1.29%,possessed good flame retardance (V-0), LOI value was35.3%, and could be kept stably at60oC for9days when mixing with E51. It could also be found that thermal stability of E51/DBDdecreased, yet char yield of E51/DBD increased as DBD content increasing. When mass ratioof E51to DBD increased from100:10to100:25, T5of cured epoxy resin E51/DBD decreasedfrom367.1o C to349.6oC, Tmaxdecreased from435.1oC to398.8oC, however char yield at900oC increased from14.3%to19.6%.
引文
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