基于超支化技术的新型氰酸酯树脂体系的研究
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摘要
氰酸酯(CE)树脂是含有两个或两个以上氰酸酯官能团(—OCN)的酚衍生物,它的固化物具有优异的介电性能、高的耐热性和优良的力学性能。此外,其粘接性好、吸湿率低,因而被公认为―二十一世纪制备高性能结构/性能一体化材料最具竞争力的树脂品种‖,在航空航天、电子信息、交通运输等工业领域显示出巨大的应用潜力。然而,与其他热固性树脂一样,脆性大是CE树脂一个不可避免的缺陷,对于许多尖端领域的应用场合来说,脆性已经成为制约CE树脂应用的―瓶颈‖。
本文以KH-560为原料,通过水解缩合法设计制备了一种带有环氧活性官能团的超支化聚硅氧烷(HPSiE),并对其结构与性能进行表征。以HPSiE作为改性剂,制得HPSiE/CE树脂,研究了HPSiE含量对HPSiE/CE树脂的固化行为和性能的影响。为了提高HPSiE/CE树脂的热稳定性,通过共聚向树脂体系中引入具有突出耐热性的改性双马来酰亚胺/二烯丙级双酚A(记为BD)树脂,制备了CE/BD/HPSiE树脂,并对其性能进行系统的研究。
酸被用来作为水解的催化剂。为了研究水与KH-560的摩尔比(m)对HPSiE性能的影响,分别采用6个不同的m(1.1—1.6)进行水解。结果表明,产物的重均分子量(Mw)和粘度随着m的增大而变大。取m值为1.5的粘度适中的产物作为研究对象,IR、1H-NMR和29Si-NMR测试表明,通过KH-560的受控水解,可以实现甲氧基向硅氧基的转变,进而生成可溶性的超支化聚硅氧烷。
对于HPSiE/CE树脂体系,探讨了HPSiE含量对树脂的韧性、耐热性、介电性能及吸水率等关键性能的影响。研究结果表明,引入HPSiE不仅可以提高CE树脂的韧性和抗水性,同时对CE树脂的固化反应有着明显的催化作用,而且这些积极的效果随着HPSiE在树脂体系中含量的增加而更显著。此外,随着HPSiE含量的增加,介电常数和介电损耗稍微上升,耐热性有所降低。需要指出的是,HPSiE/CE树脂体系在800℃下的残炭率均高于纯CE,树脂的阻燃效果有所提高。由适当含量HPSiE组成的HPSiE/CE树脂具有比纯CE更佳的综合性能。
对于CE/BD/HPSiE树脂体系,重点研究了组成的配比对树脂的力学性能、介电性能、热性能等的影响。结果表明,BD和HPSiE之间存在一个最佳计量比使CE/BD/HPSiE树脂具有最大的冲击强度(大约为CE/BD树脂的1.5倍),与CE/BD树脂相比,CE/BD/HPSiE树脂体系具有更高的抗水性。随着HPSiE含量增加,CE/BD/HPSiE树脂体系的线性热膨胀系数逐渐升高,而热稳定性均呈逐渐降低趋势,但介电常数和损耗基本保持不变。值得注意的是,与HPSiE/CE树脂相比,当HPSiE在整个体系中的质量分数相当时,CE/BD/HPSiE树脂具有较高的起始热分解温度,表明CE/BD/HPSiE树脂具有较HPSiE/CE树脂高的热稳定性。由适当配比组成的CE/BD/HPSiE树脂也具有杰出的热性能和介电性能。固化树脂性能的变化与HPSiE的特殊结构和交联网络化学结构的改变有关。
Cyanate ester (CE) resins are derivatives of compounds containing two or more cyanate functional groups (?O?C≡N). Cured CE resins possess a good combination of excellent dielectric properties, high thermal stability and good mechanical property. In addition, CE resins have very good adhesion, and almost the lowest moisture absorption among thermosets. Therefore, CE resins have been considered as―the most competitive resin for preparing advanced structural and functional materials in 21st century‖, showing great potential in many fields including aviation and aerospace, electric and transportation. However, being a thermosetting resin, the inherent brittleness is the major drawback of CE resins, which are the major disadvantages to restrict further prosperity of CEs into the advanced industrial applications.
In this thesis, a reactive hyperbranched polysiloxane (HPSiE) with epoxy groups was designed and synthesized via the hydrolyzation of KH-560 and water, and its structure and properties were characterized. HPSiE was used to develop a novel high performance HPSiE/CE resin, in addition, the effect of HPSiE content on the processing characteristics and properties of HPSiE/CE resins were investigated intensively. In order to improve the thermal stability of HPSiE/CE resin, bismaleimide/diallyl bisphenol A (coded as BD) was introduced by copolymerizing to prepare
CE/BD/HPSiE resins, of which the key properties were systemicly investigated. Acid is used as the catalyst to speed up the hydrolysis process. In order to study the effect of molar ratio (m) of H2O and KH-560 on of the properties of HPSiE, six m (1.1—1.6) were designed. Reslults show that the molecular weight (Mw) and viscosity of HPSiE increase with the m value. Due to the moderate viscosity, HPSiE synthesized by using the m value of 1.5 was used as the example to study the synthesizing process. The results from IR,1H-NMR and 29Si-NMR indicate that methoxy groups have transformed into silicon oxidation groups successfully.
For HPSiE/CE resins, the effects of HPSiE concentration on key properties such as toughness, thermal and dielectric properties as well water resistance were discussed in detail. Results reveal that the addition of HPSiE in CE resin can not only improve the toughness and water resistance of CE resin, but also display obvious catalytic effect on the curing reaction of neat CE. Moreover, these positive effects increase with the increase of HPSiE concentration in HPSiE/CE resins. In addition, with the increase of HPSiE content in HPSiE/CE resins, both the dielectric constant and loss increase slightly, while the thermal resistance decreases. It is need to point that the char yields of HPSiE/CE resins were higher than neat CE resin, indicating better flame retardation. The HPSiE/CE resins with desirable HPSiE content have more outstanding integrate properties than neat CE resin.
For CE/BD/HPSiE resins, the effect of the formulations on key properties mainly including mechanical, dielectric and thermal properties, etc, was emphasized investigated. Results show that there is an optimum stoichiometry between BD and HPSiE for obtaining the maximum impact strength (which is about 1.5 times of that of original CE/BD resin), and CE/BD/HPSiE resins have much better water resistance than CE/BD resin. With the increase of HPSiE content in CE/BD/HPSiE resins, the coefficient of thermal expansion increases, and thermal resisitance decreases, while the dielectric constant and loss almost does not change. Comparing to HPSiE/CE resins, CE/BD/HPSiE resins with desirable HPSiE content show higher initial degradation temperature, or better thermal stability. In addition, these resins also have outstanding thermal and dielectric properties. These changes of properties are explained by an inherent feature of HPSiE, and the alteration of chemistry in network.
本文以KH-560为原料,通过水解缩合法设计制备了一种带有环氧活性官能团的超支化聚硅氧烷(HPSiE),并对其结构与性能进行表征。以HPSiE作为改性剂,制得HPSiE/CE树脂,研究了HPSiE含量对HPSiE/CE树脂的固化行为和性能的影响。为了提高HPSiE/CE树脂的热稳定性,通过共聚向树脂体系中引入具有突出耐热性的改性双马来酰亚胺/二烯丙级双酚A(记为BD)树脂,制备了CE/BD/HPSiE树脂,并对其性能进行系统的研究。
酸被用来作为水解的催化剂。为了研究水与KH-560的摩尔比(m)对HPSiE性能的影响,分别采用6个不同的m(1.1—1.6)进行水解。结果表明,产物的重均分子量(Mw)和粘度随着m的增大而变大。取m值为1.5的粘度适中的产物作为研究对象,IR、1H-NMR和29Si-NMR测试表明,通过KH-560的受控水解,可以实现甲氧基向硅氧基的转变,进而生成可溶性的超支化聚硅氧烷。
对于HPSiE/CE树脂体系,探讨了HPSiE含量对树脂的韧性、耐热性、介电性能及吸水率等关键性能的影响。研究结果表明,引入HPSiE不仅可以提高CE树脂的韧性和抗水性,同时对CE树脂的固化反应有着明显的催化作用,而且这些积极的效果随着HPSiE在树脂体系中含量的增加而更显著。此外,随着HPSiE含量的增加,介电常数和介电损耗稍微上升,耐热性有所降低。需要指出的是,HPSiE/CE树脂体系在800℃下的残炭率均高于纯CE,树脂的阻燃效果有所提高。由适当含量HPSiE组成的HPSiE/CE树脂具有比纯CE更佳的综合性能。
对于CE/BD/HPSiE树脂体系,重点研究了组成的配比对树脂的力学性能、介电性能、热性能等的影响。结果表明,BD和HPSiE之间存在一个最佳计量比使CE/BD/HPSiE树脂具有最大的冲击强度(大约为CE/BD树脂的1.5倍),与CE/BD树脂相比,CE/BD/HPSiE树脂体系具有更高的抗水性。随着HPSiE含量增加,CE/BD/HPSiE树脂体系的线性热膨胀系数逐渐升高,而热稳定性均呈逐渐降低趋势,但介电常数和损耗基本保持不变。值得注意的是,与HPSiE/CE树脂相比,当HPSiE在整个体系中的质量分数相当时,CE/BD/HPSiE树脂具有较高的起始热分解温度,表明CE/BD/HPSiE树脂具有较HPSiE/CE树脂高的热稳定性。由适当配比组成的CE/BD/HPSiE树脂也具有杰出的热性能和介电性能。固化树脂性能的变化与HPSiE的特殊结构和交联网络化学结构的改变有关。
Cyanate ester (CE) resins are derivatives of compounds containing two or more cyanate functional groups (?O?C≡N). Cured CE resins possess a good combination of excellent dielectric properties, high thermal stability and good mechanical property. In addition, CE resins have very good adhesion, and almost the lowest moisture absorption among thermosets. Therefore, CE resins have been considered as―the most competitive resin for preparing advanced structural and functional materials in 21st century‖, showing great potential in many fields including aviation and aerospace, electric and transportation. However, being a thermosetting resin, the inherent brittleness is the major drawback of CE resins, which are the major disadvantages to restrict further prosperity of CEs into the advanced industrial applications.
In this thesis, a reactive hyperbranched polysiloxane (HPSiE) with epoxy groups was designed and synthesized via the hydrolyzation of KH-560 and water, and its structure and properties were characterized. HPSiE was used to develop a novel high performance HPSiE/CE resin, in addition, the effect of HPSiE content on the processing characteristics and properties of HPSiE/CE resins were investigated intensively. In order to improve the thermal stability of HPSiE/CE resin, bismaleimide/diallyl bisphenol A (coded as BD) was introduced by copolymerizing to prepare
CE/BD/HPSiE resins, of which the key properties were systemicly investigated. Acid is used as the catalyst to speed up the hydrolysis process. In order to study the effect of molar ratio (m) of H2O and KH-560 on of the properties of HPSiE, six m (1.1—1.6) were designed. Reslults show that the molecular weight (Mw) and viscosity of HPSiE increase with the m value. Due to the moderate viscosity, HPSiE synthesized by using the m value of 1.5 was used as the example to study the synthesizing process. The results from IR,1H-NMR and 29Si-NMR indicate that methoxy groups have transformed into silicon oxidation groups successfully.
For HPSiE/CE resins, the effects of HPSiE concentration on key properties such as toughness, thermal and dielectric properties as well water resistance were discussed in detail. Results reveal that the addition of HPSiE in CE resin can not only improve the toughness and water resistance of CE resin, but also display obvious catalytic effect on the curing reaction of neat CE. Moreover, these positive effects increase with the increase of HPSiE concentration in HPSiE/CE resins. In addition, with the increase of HPSiE content in HPSiE/CE resins, both the dielectric constant and loss increase slightly, while the thermal resistance decreases. It is need to point that the char yields of HPSiE/CE resins were higher than neat CE resin, indicating better flame retardation. The HPSiE/CE resins with desirable HPSiE content have more outstanding integrate properties than neat CE resin.
For CE/BD/HPSiE resins, the effect of the formulations on key properties mainly including mechanical, dielectric and thermal properties, etc, was emphasized investigated. Results show that there is an optimum stoichiometry between BD and HPSiE for obtaining the maximum impact strength (which is about 1.5 times of that of original CE/BD resin), and CE/BD/HPSiE resins have much better water resistance than CE/BD resin. With the increase of HPSiE content in CE/BD/HPSiE resins, the coefficient of thermal expansion increases, and thermal resisitance decreases, while the dielectric constant and loss almost does not change. Comparing to HPSiE/CE resins, CE/BD/HPSiE resins with desirable HPSiE content show higher initial degradation temperature, or better thermal stability. In addition, these resins also have outstanding thermal and dielectric properties. These changes of properties are explained by an inherent feature of HPSiE, and the alteration of chemistry in network.
引文
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