CN113833140B - 一种三相复合结构隔热材料及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种三相复合结构隔热材料及其制备方法和应用，涉及隔热材料技术领域。该材料包括三维间隔织物及所述三维间隔织物中填充的聚氨酯；所述三维间隔织物上还包覆有气凝胶层。本发明是基于三维间隔织物‑聚氨酯‑SiO2气凝胶三相复合成一定结构的隔热材料，将疏水的二氧化硅气凝胶复合在与聚氨酯结合的间隔织物之中，形成复合结构，可以在有很好的隔热能力的同时提高其阻燃性能。
Description
技术领域
本发明涉及隔热材料技术领域，具体涉及一种三相复合结构隔热材料及其制备方法和应用。
背景技术
聚氨酯导热系数低，热工性能好。当硬质聚氨酯密度为35～40kg/m3时，导热系数仅为0.018～0.024W/(m·k)，约相当于聚苯乙烯泡沫(EPS)的一半，是及其优异的保温隔热材料。聚氨酯具有防潮、防水性能。硬质聚氨酯的闭孔率在90％以上，属于憎水性材料，不会因吸潮增大导热系数，墙面也不会渗水。由于聚氨酯板材具有优良的隔热性能，在达到同样保温要求下，可使减少建筑物外围护结构厚度，从而增加室内使用面积。但是，聚氨酯有易燃的特性，虽能够起到保温的效果，可是难以起到阻燃的效果。
为了实现上述目的，本领域技术人员通常将聚氨酯与阻燃材料进行复合使用而制造出兼有保温和阻燃性能的材料，但是现有基于聚氨酯的隔热材料结构复杂，且制备的方案也较为复杂，同时也牺牲了部分隔热性能。
发明内容
本发明的目的是为了解决上述背景技术中的不足，本发明提供了一种三相复合结构隔热材料及其制备方法和应用，该材料是基于三维间隔织物-聚氨酯-SiO2气凝胶复合成一定结构的隔热材料，结构设计合理，制造工艺简单，提升了隔热性能和制造的简单性。
本发明第一个目的是提供一种三相复合结构隔热材料，包括三维间隔织物及所述三维间隔织物中填充的聚氨酯；所述三维间隔织物上还包覆有气凝胶层。
优选的，所述气凝胶层材质为SiO2气凝胶。
优选的，所述三维间隔织物的下表层和上表层均为编链组织和衬纬组织复合形成的针织物；所述三维间隔织物的下表层与上表层通过复数根连续的间隔丝进行连接。
更优选的，所述编链组织的编链纱为涤纶；所述衬纬组织的衬纬纱为碳纤维丝束。
本发明第二个目的是提供一种三相复合结构隔热材料的制备方法，包括以下步骤：
将三维间隔织物浸入聚氨酯前驱溶液中进行发泡，获得三维间隔织物-聚氨酯复合物；
再将三维间隔织物-聚氨酯复合物浸没于气凝胶前驱体溶液中，待凝胶后，洗涤，并用无水乙醇浸没24～48h；随后于-55～-65℃下预冻4～6h，然后进行真空冷冻干燥，得到所述三相复合结构隔热材料。
优选的，所述聚氨酯前驱溶液是将异氰酸酯和聚醚多元醇按照体积比1：1混合配制而得。
优选的，所述气凝胶前驱体溶液是将水玻璃试剂、甲酰胺试剂、乙二醇、水按照体积比为35～50：11.72：5.28：55混合配制而得。
更优选的，所述凝胶过程是在相对湿度60～65％、温度22～28℃的条件下静置20～24h。
优选的，真空冷冻干燥时的温度-100℃，时间36～48h，压强为-200Pa。
本发明第三个目的是提供一种三相复合结构隔热材料在建筑隔热中的应用。
与现有技术相比，本发明的有益效果是：
本发明提供的一种三相复合结构隔热材料，该材料是基于三维间隔织物-聚氨酯-SiO2气凝胶三相复合成一定结构的隔热材料，将疏水的二氧化硅气凝胶复合在与聚氨酯结合的间隔织物之中，形成复合结构，可以在有很好的隔热能力的同时提高其阻燃性能。通过三维间隔织物增强聚氨酯基体，可以增强基体的应力，还可以减少燃起时的烟雾，同时使材料有燃烧自熄性，同时构成微穿孔结构还可以有隔除噪音。
本发明提供的三相复合结构隔热材料制备方法，主要是将异氰酸酯与聚醚多元醇以体积比为1：1组成的聚氨酯前驱体溶液与三维间隔织物一起制备基体，增加了基体的抗压能力，为无机纳米粒子类型的二氧化硅气凝胶作为填料来增强PUF的抗压强度，复合材料抗压能力提高至486KPa，是纯聚氨酯(PUF)221KPa的220％。此外，二氧化硅气凝胶的加入保持了纯PUF的孔隙率，并在复合材料中构建了分级多孔结构，这进一步降低了热导率，同时降低了可燃性和烟雾释放。同时还有燃烧的自熄性。是一种很好的新型隔热复合材料。
本发明提供的隔热材料结构设计合理，可广泛应用于建筑隔热等方面，具有良好地应用前景。
附图说明
图1为本发明提供的三相复合结构隔热材料结构示意图。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案能予以实施，下面结合具体实施例和附图对本发明作进一步说明，但所举实施例不作为对本发明的限定。
需要说明的是，下述各实施例中所述实验方法如无特殊说明，均为常规方法；采用的试剂和材料，如无特殊说明，均可在市场上购买得到。
本发明提供的一种三相复合结构隔热材料，见图1所示，包括三维间隔织物1及三维间隔织物1中填充的聚氨酯2；三维间隔织物1上还包覆有气凝胶层3。
气凝胶层材质为SiO2气凝胶。
三维间隔织物1的下表层和上表层均为编链组织和衬纬组织复合形成的针织物；三维间隔织物1的下表层与上表层通过复数根连续的间隔丝11进行连接。
编链组织的编链纱为涤纶；衬纬组织的衬纬纱为碳纤维丝束。
间隔丝为直径0.2mm的涤纶单丝。
下述实施例中采用的三维间隔织物是采用双针床拉舍尔经编机进行织造。
下述各实施例将采用提供的三相复合结构隔热材料的制备方法进行说明。
实施例1
一种三相复合结构隔热材料的制备方法，包括以下步骤：
步骤1：三维间隔织物采用具有GB1～GB6共6把梳栉的双针床拉舍尔经编机织造，其中织物的上表层和下表层均为编链+衬纬的经编间隔织物，GB2、GB5上所带纱线为300D/96F的涤纶复丝，GB1、GB6上所带为碳纤维丝束，GB3、GB4上所带为直径0.2mm的涤纶单丝；GB1和GB2两把梳栉在前针床编织三维间隔织物的上表层，GB5和GB6两把梳栉则在后针床编织织物的下表层，GB3和GB4两把梳栉上携带着间隔丝，在前后两个针床交替编织以将三维间隔织物的上下表层用间隔丝连接，形成三维间隔织物；所得织物厚度为10mm，面密度为925g/m2；织物下机后，将三维间隔织物裁剪层所需尺寸；
步骤2：量取体积比为1；1的异氰酸酯及聚醚多元醇混合均匀至颜色变为白色时将裁剪的三维间隔织物加入进去进行发泡，获得三维间隔织物-聚氨酯复合物，再将其裁剪至所需的尺寸；
步骤3：量取50ml水玻璃试剂，量取55ml去离子水，混合均匀，至溶液呈透明状，然后在相对湿度60％下、温度25℃的条件下静置；同时，再量取甲酰胺11.725ml、乙二醇5.286ml，再用0.5mol/l的醋酸滴定至pH值至11,将步骤2裁剪后的三维间隔织物-聚氨酯复合物浸入其中，待凝胶后，用去离子水洗涤两天，再用无水乙醇浸没两天，随后在-60℃下预冻4h，然后于温度-100℃，时间48h，压强为-200Pa进行真空冷冻干燥，即得所述三相复合结构隔热材料。
实施例2
一种三相复合结构隔热材料的制备方法，包括以下步骤：
步骤1：三维间隔织物采用具有GB1～GB6共6把梳栉的双针床拉舍尔经编机织造，其中织物的上表层和下表层均为编链+衬纬的经编间隔织物，GB2、GB5上所带纱线为300D/96F的涤纶复丝，GB1、GB6上所带为碳纤维丝束，GB3、GB4上所带为直径0.2mm的涤纶单丝；GB1和GB2两把梳栉在前针床编织三维间隔织物的上表层，GB5和GB6两把梳栉则在后针床编织织物的下表层，GB3和GB4两把梳栉上携带着间隔丝，在前后两个针床交替编织以将三维间隔织物的上下表层用间隔丝连接，形成三维间隔织物；所得织物厚度为7.5mm，面密度为920g/m2；织物下机后，将三维间隔织物裁剪层所需尺寸；
步骤2：量取体积比为1；1的异氰酸酯及聚醚多元醇混合均匀至颜色变为白色时将裁剪的三维间隔织物加入进去进行发泡，获得三维间隔织物-聚氨酯复合物，再将其裁剪至所需的尺寸；
步骤3：量取50ml水玻璃试剂，量取55ml去离子水，混合均匀，至溶液呈透明状，然后在相对湿度65％下、温度25℃的条件下静置；同时，再量取甲酰胺11.725ml、乙二醇5.286ml，再用0.5mol/l的醋酸滴定至pH值至11,将步骤2裁剪后的三维间隔织物-聚氨酯复合物浸入其中，待凝胶后，用去离子水洗涤两天，再用无水乙醇浸没两天，随后在-60℃下预冻4h，然后于温度-100℃，时间36h，压强为-200Pa进行真空冷冻干燥，即得所述三相复合结构隔热材料。
本发明提供的一种三相复合结构隔热材料抗压能力提高至486KPa，是纯PUF221KPa的220％。此外，二氧化硅气凝胶的加入保持了纯PUF的孔隙率，并在复合材料中构建了分级多孔结构，这进一步降低了热导率，使热导率低至0.021w/(m.k)，比纯聚氨酯的0.024w/(m.k)更低，同时降低了可燃性和烟雾释放，使复合材料具有了自熄行，降低了聚氨酯易燃带来的危险性和有毒烟雾的释放。是一种很好的新型隔热复合材料。
综上，本发明提供的一种三相复合结构隔热材料，该材料是基于三维间隔织物-聚氨酯-SiO2气凝胶三相复合成一定结构的隔热材料，将疏水的二氧化硅气凝胶复合在与聚氨酯结合的间隔织物之中，形成复合结构，可以在有很好的隔热能力的同时提高其阻燃性能。通过三维间隔织物增强聚氨酯基体，可以增强基体的应力，还可以减少燃起时的烟雾，同时使材料有燃烧自熄性，同时构成微穿孔结构还可以有隔除噪音。
本发明提供的三相复合结构隔热材料制备方法，主要是将异氰酸酯与聚醚多元醇以体积比为1：1组成的聚氨酯前驱体溶液与三维间隔织物一起制备基体，增加了基体的抗压能力，为无机纳米粒子类型的二氧化硅气凝胶作为填料来增强PUF的抗压强度，
本发明提供的隔热材料结构设计合理，可广泛应用于建筑隔热等方面，具有良好地应用前景。
本发明描述了优选实施例及其效果。但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (6)
1.一种三相复合结构隔热材料，其特征在于，包括三维间隔织物及所述三维间隔织物中填充的聚氨酯；所述三维间隔织物上还包覆有气凝胶层；
所述的三相复合结构隔热材料的制备方法，包括以下步骤：
将三维间隔织物浸入聚氨酯前驱溶液中进行发泡，获得三维间隔织物-聚氨酯复合物；
再将三维间隔织物-聚氨酯复合物浸没于气凝胶前驱体溶液中，待凝胶后，洗涤，并用无水乙醇浸没24～48h；随后于-55～-65℃下预冻4～6h，然后进行真空冷冻干燥，得到所述三相复合结构隔热材料；
所述气凝胶前驱体溶液是将水玻璃试剂、甲酰胺试剂、乙二醇、水按照体积比为35～50：11.72：5.28：55混合配制而得；
所述气凝胶层材质为SiO2气凝胶；
所述凝胶过程是在相对湿度60～65％、温度22～28℃的条件下静置20～24h。
2.根据权利要求1所述的三相复合结构隔热材料，其特征在于，所述三维间隔织物的下表层和上表层均为编链组织和衬纬组织复合形成的针织物；所述三维间隔织物的下表层与上表层通过复数根连续的间隔丝进行连接。
3.根据权利要求2所述的三相复合结构隔热材料，其特征在于，所述编链组织的编链纱为涤纶；所述衬纬组织的衬纬纱为碳纤维丝束。
4.根据权利要求1所述的三相复合结构隔热材料，其特征在于，所述聚氨酯前驱溶液是将异氰酸酯和聚醚多元醇按照体积比1：1混合配制而得。
5.根据权利要求1所述的三相复合结构隔热材料，其特征在于，真空冷冻干燥时的温度-100℃，时间36～48h，压强为-200Pa。
6.一种权利要求1～5任一项所述的三相复合结构隔热材料在建筑隔热中的应用。
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