CN114196019B - 一种形状可塑性高分子陶瓷先驱体的制备方法 - Google Patents

一种形状可塑性高分子陶瓷先驱体的制备方法 Download PDF

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CN114196019B
CN114196019B CN202111583207.2A CN202111583207A CN114196019B CN 114196019 B CN114196019 B CN 114196019B CN 202111583207 A CN202111583207 A CN 202111583207A CN 114196019 B CN114196019 B CN 114196019B
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吴金荣
韩文波
赵广东
武世斌
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Ningxia Qilicheng Machinery Technology Group Co ltd
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Abstract

一种形状可塑性高分子陶瓷先驱体的制备方法，本发明涉及一种形状可塑性高分子陶瓷先驱体的制备方法，本发明的目的是为了解决现有制备的陶瓷先驱体产率较低的问题，本发明以溶胶凝胶‑溶剂热方法合成多元聚合物先驱体为目的，重点解决在先驱体交联过程中，关于B、Zr、Si等元素键合为Si‑O‑Zr、Si‑O‑B和先驱体陶瓷最终产率的协调问题，得到一种具有形状可塑性高分子陶瓷先驱体，在此过程中，再通过对合成过程中的工艺参数的变化的微观调控，保证先驱体中各个元素的最大限度结合，得到形状可塑性高分子陶瓷先驱体，制备得到陶瓷先驱体的陶瓷产率80％。本发明适用于陶瓷先驱体制备领域。

Description

一种形状可塑性高分子陶瓷先驱体的制备方法
技术领域：
本发明涉及一种形状可塑性高分子陶瓷先驱体的制备方法。
背景技术：
先驱体转化陶瓷(polymer-derived ceramics，PDCs)是一类无需烧结助剂的陶瓷材料，具有卓越的高温抗氧化和耐热性能。在PDCs的研究中，主要以硅基陶瓷先驱体为研究对象。目前已知的先驱体陶瓷大体上可以分为二元体系陶瓷(Si3N4、SiC、ZrB2等)，三元体系陶瓷(SiOC、SiCN、BCN等)，四元体系陶瓷(SiBOC、SiBCN、SiZrOC等)和五元体系陶瓷(SiBOCN、SiAlOCN)。目前常用的具有较好流动性且浸渍后形状可塑性高的先驱体有聚碳硅烷、聚硅氮烷、聚硅硼氮碳烷等。但现有的陶瓷先驱体在实现有机-无机转化过程中，会释放过量的小分子物质，导致高温热解过程中容易产生气孔，出现裂纹，进而导致陶瓷产率降低等问题。
发明内容：
本发明的目的是为了解决现有制备的陶瓷先驱体产率较低的问题，提供了一种高陶瓷产率且具有形状可塑性高分子陶瓷先驱体的制备方法。
本发明一种形状可塑性高分子陶瓷先驱体的制备方法，按照下述步骤来进行：
一、在冰浴条件下，将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中，搅拌，再加入硼酸，在室温下搅拌，然后减压蒸馏得到先驱体粉末A；
二、用乙醇溶液溶解四氯化锆粉末，得到四氯化锆水解液；其中四氯化锆粉末与乙醇的物质的量比为3：(20-30)；
三、在冰浴条件下，向先驱体粉末A中加入四氢呋喃，搅拌均匀，得到先驱体溶液B；先驱体粉末A与四氢呋喃的质量比为3：(10-15)；
四、将四氯化锆水解液和先驱体溶液B混合，搅拌均匀，待恢复到室温，升温进行交联反应，得到先驱体溶液C；
五、将先驱体溶液C进行减压蒸馏，随后放入烘箱中进行干燥固化，得到陶瓷先驱体本发明以溶胶凝胶-溶剂热方法合成多元聚合物先驱体为目的，重点解决在先驱体交联过程中，关于B、Zr、Si等元素键合为Si-O-Zr、Si-O-B和先驱体陶瓷最终产率的协调问题，得到一种具有形状可塑性高分子陶瓷先驱体，在此过程中，再通过对合成过程中的工艺参数的变化的微观调控，保证先驱体中各个元素的最大限度结合，方便得到的大批量形状可塑性高分子陶瓷先驱体进行后续的陶瓷制备及其他研究工作。
本发明主要目标实现：在制备得到的形状可塑性高分子先驱体中，可以将B、Zr、Si、C等元素键合为一种大分子网络结构。通过优化固化温度，调整固化时间，引入带有苯环的硅烷增加反应性基团，增加先驱体分子交联程度，可以提高陶瓷产率，根据加入试剂摩尔比的不同可得到不同陶瓷产率的先驱体聚合物，按照上述步骤制备得到陶瓷先驱体的陶瓷产率80％。
附图说明
图1为实例1中所得形状可塑性高分子陶瓷先驱体的红外图片；
图2为实例1中所得形状可塑性高分子陶瓷的XRD图片；
图3为实例1中所得形状可塑性高分子陶瓷的SEM图片；
图4为实例1～3中所得形状可塑性高分子陶瓷先驱体的热解产率图片。
具体实施方式
具体实施方式一：本实施方式一种形状可塑性高分子陶瓷先驱体的制备方法，按照下述步骤来进行：
一、在冰浴条件下，将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中，搅拌，再加入硼酸，在室温下搅拌，然后减压蒸馏得到先驱体粉末A；
二、用乙醇溶液溶解四氯化锆粉末，得到四氯化锆水解液；其中四氯化锆粉末与乙醇的物质的量比为3：(20-30)；
三、在冰浴条件下，向先驱体粉末A中加入四氢呋喃，搅拌均匀，得到先驱体溶液B；先驱体粉末A与四氢呋喃的质量比为3：(10-15)；
四、将四氯化锆水解液和先驱体溶液B混合，搅拌均匀，待恢复到室温，升温进行交联反应，得到先驱体溶液C；
五、将先驱体溶液C进行减压蒸馏，随后放入烘箱中进行干燥固化，得到陶瓷先驱体。
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤一中甲基三氯硅烷、苯基三氯硅烷及硼酸物质的量比为10：5：1。其它与具体实施方式一相同。
具体实施方式三：本实施方式与具体实施方式一或二不同的是：步骤一中甲基三氯硅烷与甲苯的体积比为1：1。其它与具体实施方式一或二相同。
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：步骤一中冰浴的温度为1-3℃。其它与具体实施方式一至三之一相同。
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是：步骤一中将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中搅拌时间为20min。其它与具体实施方式一至四之一相同。
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是：步骤一中加入硼酸后室温搅拌30h，然后进行减压蒸馏，减压蒸馏温度为47℃。其它与具体实施方式一至五之一相同。
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是：步骤二中乙醇溶液由乙醇和水按物质的量比为2：1的比例搅拌混合而成，搅拌时间为20min。其它与具体实施方式一至六之一相同。
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：四氯化锆粉末与硼酸的物质质量比为1:(1～6)。其它与具体实施方式一至七之一相同。
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是：步骤四中以升温速率2℃/min升温至27℃，交联反应30h。其它与具体实施方式一至八之一相同。
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是：步骤五中固化温度为190～210℃，固化时间为8-12小时。其它与具体实施方式一至九之一相同。
通过以下试验验证本发明的有益效果：
实施例1、一种形状可塑性高分子陶瓷先驱体的制备方法，按照下述步骤来进行：
一、在圆底烧瓶中，冰浴条件下，将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中，搅拌20min，再加入硼酸，转移至室温搅拌30h，然后在69℃下减压蒸馏得到先驱体粉末A；其中甲基三氯硅烷、苯基三氯硅烷及硼酸物质的量比为10：5：1；甲基三氯硅烷与甲苯的体积比为1：1；
二、用乙醇溶液溶解四氯化锆粉末，得到四氯化锆水解液；四氯化锆粉末与乙醇的物质的量比为3：26；
三、在冰浴条件下，向先驱体粉末A中加入四氢呋喃，搅拌均匀，得到先驱体溶液B；先驱体粉末A与四氢呋喃的质量比为3：13；
四、将四氯化锆水解液和先驱体溶液B混合，搅拌均匀，待恢复到室温，然后控制升温速率以2℃/min升温至27℃，进行交联反应30h，得到先驱体溶液C；四氯化锆与步骤一加入的硼酸的物质质量比为1:3；
五、将先驱体溶液C在69℃下进行减压蒸馏，随后放入烘箱中进行干燥固化，固化温度为150℃，固化时间为2小时，得到陶瓷先驱体，在氩气气氛下，将陶瓷先驱体以5℃/min的升温速率加热到1000℃后，继续加热(3℃/min)达到目标温度1200或1400℃℃，在目标温度保温150min，再降温(3℃/min)到1000℃，冷却(5℃/min)到室温，最终得到所需的陶瓷材料。
图1为实例1中所得形状可塑性高分子陶瓷先驱体的红外图片，从图1可以得出B、Zr、Si、C等元素已交联为大分子网络结构。
图2为实例1中所得形状可塑性高分子陶瓷的XRD图片，其中●为SiC，◆为ZrO2；从图2可以得出在陶瓷完成转化后主要晶体相为SiC、ZrO2。
图3为实例1中所得形状可塑性高分子陶瓷的SEM图片，从图3可以看到热解后的表面无裂纹其气孔率较低的陶瓷先驱体微观组织形貌。
经过管式炉1200℃高温热处理，本实施例制备得到陶瓷先驱体的陶瓷产率为66.5％，1400℃高温热处理后，本实施例制备得到陶瓷先驱体的陶瓷产率为66.22％。
实施例2
一种形状可塑性高分子陶瓷先驱体的制备方法，按照下述步骤来进行：
一、在圆底烧瓶中，冰浴条件下，将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中，搅拌20min，再加入硼酸，转移至室温搅拌30h，然后在69℃下减压蒸馏得到先驱体粉末A；其中甲基三氯硅烷、苯基三氯硅烷及硼酸物质的量比为10：5：1；甲基三氯硅烷与甲苯的体积比为1：1；
二、用乙醇溶液溶解四氯化锆粉末，得到四氯化锆水解液；四氯化锆粉末与乙醇的物质的量比为3：26；
三、在冰浴条件下，向先驱体粉末A中加入四氢呋喃，搅拌均匀，得到先驱体溶液B；先驱体粉末A与四氢呋喃的质量比为3：13；
四、将四氯化锆水解液和先驱体溶液B混合，搅拌均匀，待恢复到室温，然后控制升温速率以2℃/min升温至27℃，进行交联反应30h，得到先驱体溶液C；四氯化锆与步骤一加入的硼酸的物质质量比为1:4；
五、将先驱体溶液C在69℃下进行减压蒸馏，随后放入烘箱中进行干燥固化，固化温度为150℃，固化时间为2小时，得到陶瓷先驱体，在氩气气氛下，将先驱体以5℃/min的升温速率加热到1000℃后，继续加热(3℃/min)达到目标温度1200或1400℃，在目标温度保温150min，再降温(3℃/min)到1000℃，冷却(5℃/min)到室温，最终得到所需陶瓷材料。
经过管式炉1200℃高温热处理，本实施例制备得到陶瓷先驱体的陶瓷产率为68.88％，1400℃高温热处理后，本实施例制备得到陶瓷先驱体的陶瓷产率为66.82％。
实施例3一种形状可塑性高分子陶瓷先驱体的制备方法，按照下述步骤来进行：
一、在圆底烧瓶中，冰浴条件下，将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中，搅拌20min，再加入硼酸，转移至室温搅拌30h，然后在69℃下减压蒸馏得到先驱体粉末A；其中甲基三氯硅烷、苯基三氯硅烷及硼酸物质的量比为10：5：1；甲基三氯硅烷与甲苯的体积比为1：1；
二、用乙醇溶液溶解四氯化锆粉末，得到四氯化锆水解液；四氯化锆粉末与乙醇的物质的量比为3：26；
三、在冰浴条件下，向先驱体粉末A中加入四氢呋喃，搅拌均匀，得到先驱体溶液B；先驱体粉末A与四氢呋喃的质量比为3：13；
四、将四氯化锆水解液和先驱体溶液B混合，搅拌均匀，待恢复到室温，然后控制升温速率以2℃/min升温至27℃，进行交联反应30h，得到先驱体溶液C；四氯化锆粉末还是水解液与步骤一加入的硼酸的物质质量比为1:5；
五、将先驱体溶液C在69℃下进行减压蒸馏，随后放入烘箱中进行干燥固化，固化温度为150℃，固化时间为2小时，得到陶瓷先驱体，在氩气气氛下，将先驱体以5℃/min的升温速率加热到1000℃后，继续加热(3℃/min)达到目标温度1200或1400℃，在目标温度保温150min，再降温(3℃/min)到1000℃，冷却(5℃/min)到室温，最终得到所需陶瓷材料。
经过管式炉1200℃高温热处理，本实施例制备得到陶瓷先驱体的陶瓷产率为80.06％，1400℃高温热处理，本实施例制备得到陶瓷先驱体的陶瓷产率为75％。
图4为实例1～3中所得形状可塑性高分子陶瓷先驱体的热解产率图片，其中a为1200℃下热解，b为1200℃下热解；从图4可以得出最高陶瓷产率已经达到80％。

Claims (10)

1.一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于该制备方法按照下述步骤来进行：
一、在冰浴条件下，将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中，搅拌，再加入硼酸，在室温下搅拌，然后减压蒸馏得到先驱体粉末A；
二、用乙醇溶液溶解四氯化锆粉末，得到四氯化锆水解液；其中四氯化锆粉末与乙醇的物质的量比为3：(20-30)；
三、在冰浴条件下，向先驱体粉末A中加入四氢呋喃，搅拌均匀，得到先驱体溶液B；先驱体粉末A与四氢呋喃的质量比为3：(10-15)；
四、将四氯化锆水解液和先驱体溶液B混合，搅拌均匀，待恢复到室温，升温进行交联反应，得到先驱体溶液C；
五、将先驱体溶液C进行减压蒸馏，随后放入烘箱中进行干燥固化，得到陶瓷先驱体。
2.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤一中甲基三氯硅烷、苯基三氯硅烷及硼酸物质的量比为10：5：1。
3.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤一中甲基三氯硅烷与甲苯的体积比为1：1。
4.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤一中冰浴的温度为1-3℃。
5.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤一中将甲基三氯硅烷和苯基三氯硅烷加入到甲苯中搅拌时间为20min。
6.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤一中加入硼酸后室温搅拌30h，然后进行减压蒸馏，减压蒸馏温度为47℃。
7.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤二中乙醇溶液由乙醇和水按物质的量比为2：1的比例搅拌混合而成，搅拌时间为20min。
8.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于四氯化锆粉末与硼酸的物质质量比为1:(1～6)。
9.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤四中以升温速率2℃/min升温至27℃，交联反应30h。
10.根据权利要求1所述的一种形状可塑性高分子陶瓷先驱体的制备方法，其特征在于步骤五中固化温度为190～210℃，固化时间为8-12小时。
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