CN106633171B - 氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶材料的制备方法 - Google Patents
氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶材料的制备方法 Download PDFInfo
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Abstract
本发明属于纳米多孔气凝胶材料制备技术领域,具体涉及一种密度超低、低收缩率,高强度、低热导交联聚酰亚胺气凝胶材料制备方法。本发明采用溶胶凝胶法,以二酐和二胺为单体合成聚酰胺酸溶液,以笼型氨基苯基硅倍半氧烷或环梯形氨基苯基硅倍半氧烷等作为交联剂,经过化学亚胺化形成凝胶,结合超临界干燥工艺,制备出聚酰亚胺气凝胶材料。本发明反应过程简单,所得气凝胶制品具有纳米介孔结构,样品收缩率小于2%,密度最低可达到10mg/cm3,力学性能优异,热导率最低达到22mW/(m K),克服了传统交联型聚酰亚胺气凝胶制备过程中收缩率大,产品形状不可控的缺陷。所得低收缩、轻质、低热导、高强的聚酰亚胺气凝胶可作为绝热材料、高吸附材料等实现广阔应用。
Description
技术领域
本发明属于气凝胶材料制备技术领域,具体涉及一种密度超低、低收缩率,高强度、低热导交联聚酰亚胺气凝胶的简单制备方法。
背景技术
气凝胶是一种有着纳米多级结构的特殊多孔材料,由于其独特的结构和诸多优越的性能,在隔热材料、吸附性材料、绝缘材料等许多领域有着广泛的应用前景。然而对于目前研究最为成熟的二氧化硅气凝胶,其较差的力学性能制约了其在工业化生产及应用的前景。而应用普遍的聚合物改性二氧化硅气凝胶的产品,往往受聚合物限制,使用温度低于200℃。聚酰亚胺气凝胶作为一种力学性能较好、热稳定性高、隔热性能较好的有机气凝胶近年来受到人们的广泛研究和关注。
通常线性聚酰亚胺气凝胶是通过等摩尔的初始单体二酐和二胺合成,其主要缺点在于样品收缩大,力学性能较差,热稳定性不好。相较之下,交联型聚酰亚胺气凝胶有着更为优异的性能,这是由于在其凝胶网络中引入了某些功能化的胺类,即交联剂。交联剂的引入使得聚酰亚胺聚合物链通过共价键进行结合,互相缠结形成丰富的三维网络结构,确保了气凝胶较好的结构稳定性,同时可以极大降低样品的密度和热导率,提升其力学性能和热稳定性。然而,聚合物链的刚性是制约聚酰亚胺气凝胶低密度极限的重要因素,现有的条件和方法下,最低可以得到密度为60mg/cm3的聚酰亚胺气凝胶,如何选择一种多元胺交联剂能够增强聚合物链的刚性,帮助改善聚酰亚胺气凝胶的各项性质,满足高端应用需求,是一个有待解决的问题。
具有笼型结构的氨基苯基硅倍半氧烷(OAPS)、梯形结构的氨基苯基硅倍半氧烷(L-PAPSQ)以及环梯形结构氨基苯基硅倍半氧烷(CL-PAPSQ)作为一类新型多元胺,其分子结构上既含有无机硅氧烷的“骨架”结构,又在侧基上引进了有机基团,密度较大的无机含硅内核能抑制它的链运动而赋予其良好的耐热性能,相应的有机侧基则赋予其良好的韧性和可加工性,这种典型的无机-有机杂化材料同时具备有机聚合物和无机陶瓷的基本特征,作为聚合物助剂具有良好的增强、耐热、阻燃效果。因此,采用氨基苯基硅倍半氧烷作为交联剂提高聚合物链的刚性,帮助改善聚酰亚胺气凝胶的各项性质,获得密度超低、低收缩率,高强度、低热导的聚酰亚胺气凝胶成为学者们研究的一大方向。
发明内容
本发明的目的在于提供一种适用范围广、反应周期短、可能工业放大的轻质高强交联型聚酰亚胺气凝胶材料的制备方法。其基本思路在于通过添加氨基苯基硅倍半氧烷作为交联剂,首先采用适当配比的二酐和二胺反应生成酐封端的聚酰胺酸低聚物溶液,接着聚酰胺酸低聚物通过端酐基和氨基苯基硅倍半氧烷的氨基发生反应实现相互交联,随后经过化学亚胺过程形成聚酰亚胺湿凝胶,最后经二氧化碳超临界干燥得到交联型聚酰亚胺气凝胶。具体内容如下:
本发明提出了一种轻质高强交联型聚酰亚胺气凝胶材料的制备方法,其特征在于采用溶胶凝胶法,具体步骤如下:
(1)将二酐和二胺单体溶于有机溶剂中,在室温下超声震荡或快速搅拌10分钟,配制出聚酰亚胺酸溶液,溶液中溶质的质量分数为1~12wt%;
向步骤(1)所得的聚酰亚胺溶液加入一定量的交联剂震荡或搅拌均匀,再加入脱水剂,震荡或搅拌均匀,在室温下静置后得到湿凝胶;其中:二酐、二胺和交联剂中氨基基团的添加比例为6.2mmol:6.0mmol:0.4mmol;
(2)将步骤(2)所得凝胶在常温下老化24小时后干燥,获得交联型聚酰亚胺气凝胶;
其中:步骤(1)中的有机溶剂为N-甲基吡咯烷酮。
步骤(2)中的交联剂为笼型八氨基苯基硅倍半氧烷、梯形氨基苯基硅倍半氧烷、环梯形氨基苯基硅倍半氧烷及其任意比例的混合物。
本发明中,步骤(2)中的脱水剂为乙酸酐和吡啶组合的混合液。
本发明中,步骤(3)中所述干燥方法为超临界流体干燥、冷冻干燥、加热脱气干燥或常压自然干燥等方式。
本发明中,步骤(1)中所述的二酐为3,3’,4,4’-联苯四甲酸二酐、3,3’,4,4’二苯酮四酸二酐、4,4’-(六氟异丙基)双邻苯四酸二酐及其任意比例的混合物。
本发明中,步骤(1)中所述的二胺为4,4’-二氨基二苯醚、对苯二胺、2,2’-二甲基联苯胺及其任意比例的混合物。
本发明的有益效果在于:
本发明具有适用性广泛、反应过程简单、产品形状可设计性好等特点,所得到的聚酰亚胺气凝胶材料具有纳米介孔结构,尺寸、结构稳定性好,样品收缩率小于2%,密度最低可达到10mg/cm3,力学性能优异,热导率最低达到22mW/(m K),克服了传统交联型聚酰亚胺气凝胶制备过程中收缩率大,产品形状不可控的缺陷。所得密度超低、低收缩率、高强度、低热导的聚酰亚胺气凝胶可作为绝热材料、高吸附材料等实现广阔应用。
附图说明
图1为实施例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶实物图;
图2为实施例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶FT-IR谱图;
图3为实施例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶扫描电子显微镜照片;
图4为实施例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶压缩过程应力应变曲线;
图5为实施例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶热导系数随温度变化曲线;
具体实施方式
下面通过实例对本发明作进一步说明,但实施例并不限制本发明的保护范围。(各原料均为市售分析纯)
实施例1
1)将二胺和二酐(4,4’-二氨基二苯醚:3,3’,4,4’-联苯四甲酸二酐=6.0mmol:6.2mmol)溶于290mL的N-甲基吡咯烷酮中,超声震荡10min至澄清,得到聚酰胺酸溶液,随后加入带有0.4mmol氨基的笼型氨基苯基硅倍半氧烷(OAPS)或环梯形氨基苯基硅倍半氧烷(CL-PAPSQ)作为交联剂,超声震荡5min至混匀,再加入脱水剂8.70mL(乙酸酐:吡啶=4.68:4.02mL),快速搅拌均匀,倒入磨具中置于室温下凝胶,凝胶时间约为2h,老化24h。
2)将步骤1)得到的凝胶用乙醇和N-甲基吡咯烷酮的混合溶剂进行溶剂置换,浸泡8h后再用纯乙醇进行3~5次溶剂置换,每次8~12h,最后进行超临界二氧化碳干燥,超临界条件为10MPa,50℃,150mL/min出流量下干燥12h,得到体积收缩率低于2%,密度约为10mg/cm3的聚酰亚胺气凝胶。实物图如图1所示。
图2为例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶样品的FT-IR谱图,1372,1714,1777,1082,717cm-1为聚酰亚胺的红外特征峰,1660cm-1处聚酰胺酸C=O伸缩振动特征峰消失,证明亚胺化完全。图3的样品扫描电子显微镜照片中可以看出,气凝胶样品的微观结构是聚合物纳米纤维状链缠结形成的3D网络结构,纤维间的孔大小在10~50nm之间属于纳米介孔结构。
图4为例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶样品压缩过程应力应变曲线,可以看出压缩过程分为三个阶段:初期应力应变线性增长的弹性阶段;中期应力维持恒定的孔结构坍缩阶段,末期应力指数级增长的塑性变形阶段,最终气凝胶保持完整未碎裂,力学性能优异。图5为实施例1制备的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶样品样品热导系数随温度变化曲线,常温导热系数仅为22mW/(m K)左右,150℃下导热系数也仅有28mW/(m K)左右,远远低于常见的有机泡沫类隔热材料。
实施例2
1)将二胺和二酐(4,4’-二氨基二苯醚:3,3’,4,4’二苯酮四酸二酐=6.0mmol:6.2mmol)溶于95mL的N-甲基吡咯烷酮中,超声震荡10min至澄清,得到聚酰胺酸溶液,随后加入带有0.4mmol氨基的笼型氨基苯基硅倍半氧烷(OAPS)作为交联剂,超声震荡5min至混匀,再加入脱水剂8.70mL(乙酸酐:吡啶=4.68:4.02mL),快速搅拌均匀,倒入磨具中置于室温下凝胶,凝胶时间约为45min,老化24h。
2)将步骤1)得到的凝胶用乙醇和N-甲基吡咯烷酮的混合溶剂进行溶剂置换,浸泡8h后再用纯乙醇进行3~5次溶剂置换,每次8~12h,最后进行超临界二氧化碳干燥,超临界条件为10MPa,50℃,150mL/min出流量下干燥12h,得到体积收缩率低于2%,密度约为31mg/cm3的聚酰亚胺气凝胶。
实施例3
1)将二胺和二酐(2,2’-二甲基联苯胺:3,3’,4,4’-联苯四甲酸二酐=6.0mmol:6.2mmol)溶于72.5mL的N-甲基吡咯烷酮中,超声震荡10min至澄清,得到聚酰胺酸溶液,随后加入带有0.4mmol氨基的梯形氨基苯基硅倍半氧烷(L-PAPSQ)作为交联剂,超声震荡5min至混匀,再加入脱水剂8.70mL(乙酸酐:吡啶=4.68:4.02mL),快速搅拌均匀,倒入磨具中置于室温下凝胶,凝胶时间约为15min,老化24h。
2)将步骤1)得到的凝胶用乙醇和N-甲基吡咯烷酮的混合溶剂进行溶剂置换,浸泡8h后再用纯乙醇进行3~5次溶剂置换,每次8~12h,最后进行超临界二氧化碳干燥,超临界条件为10MPa,50℃,150mL/min出流量下干燥12h,得到体积收缩率低于3%,密度约为41mg/cm3的聚酰亚胺气凝胶。
实施例4
1)将二胺和二酐(4,4’-二氨基二苯醚:3,3’,4,4’-联苯四甲酸二酐=6.0mmol:6.2mmol)溶于40mL的N-甲基吡咯烷酮中,超声震荡10min至澄清,得到聚酰胺酸溶液,随后加入带有0.4mmol氨基的环梯形氨基苯基硅倍半氧烷(CL-PAPSQ)作为交联剂,超声震荡5min至混匀,再加入脱水剂8.70mL(乙酸酐:吡啶=4.68:4.02mL),快速搅拌均匀,倒入磨具中置于室温下凝胶,凝胶时间约为10min,老化24h。
2)将步骤1)得到的凝胶用乙醇和N-甲基吡咯烷酮的混合溶剂进行溶剂置换,浸泡8h后再用纯乙醇进行3~5次溶剂置换,每次8~12h,最后进行超临界二氧化碳干燥,超临界条件为10MPa,50℃,150mL/min出流量下干燥12h,得到体积收缩率低于3%,密度约为60mg/cm3的聚酰亚胺气凝胶。
实施例5
1)将二胺和二酐(对苯二胺:3,3’,4,4’-联苯四甲酸二酐=6.0mmol:6.2mmol)溶于25mL的N-甲基吡咯烷酮中,超声震荡10min至澄清,得到聚酰胺酸溶液,随后加入带有0.4mmol氨基的环梯形氨基苯基硅倍半氧烷(CL-PAPSQ)作为交联剂,超声震荡5min至混匀,再加入脱水剂8.70mL(乙酸酐:吡啶=4.68:4.02mL),快速搅拌均匀,倒入磨具中置于室温下凝胶,凝胶时间约为5min,老化24h。
2)将步骤1)得到的凝胶用乙醇和N-甲基吡咯烷酮的混合溶剂进行溶剂置换,浸泡8h后再用纯乙醇进行3~5次溶剂置换,每次8~12h,最后进行超临界二氧化碳干燥,超临界条件为10MPa,50℃,150mL/min出流量下干燥12h,得到体积收缩率低于3%,密度约为100mg/cm3的聚酰亚胺气凝胶。
Claims (3)
1.一种氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶材料的制备方法,其特征在于制备方法如下:
(1)将二酐和二胺单体溶于有机溶剂中,在室温下超声震荡或快速搅拌10分钟,配制出聚酰胺酸前驱体溶液;
(2)向步骤(1)所得的聚酰亚胺溶液加入一定量的交联剂震荡或搅拌均匀,再加入脱水剂,震荡或搅拌均匀,在室温下静置后得到湿凝胶;其中:二酐、二胺和交联剂中氨基基团的添加比例为6.2mmol:6.0mmol:0.4mmol;
(3)将步骤(2)所得凝胶在常温下老化24小时后干燥,获得交联型聚酰亚胺气凝胶;
其中:
步骤(1)中的有机溶剂为N-甲基吡咯烷酮,所述的二胺为4,4’-二氨基二苯醚、1,4-对苯二胺、2,2’-二甲基联苯胺及其任意比例的混合物;
步骤(2)中的脱水剂为乙酸酐和吡啶组合的混合液,所述交联剂为梯形氨基苯基硅倍半氧烷L-PAPSQ、环梯形氨基苯基硅倍半氧烷及其任意比例的混合物CL-PAPSQ。
2.根据权利要求1所述的氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶材料的制备方法,其特征在于步骤(3)中所述干燥方法为超临界流体干燥、冷冻干燥、加热脱气干燥或常压自然干燥。
3.根据权利要求1所述的一种氨基苯基硅倍半氧烷交联聚酰亚胺气凝胶材料的制备方法,其特征在于步骤(1)中所述的二酐为3,3’,4,4’-联苯四甲酸二酐、3,3’,4,4’-二苯酮四酸二酐、4,4’-(六氟异丙基)双邻苯四酸二酐及其任意比例的混合物。
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