CN106832387A - 一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶及其制备方法和应用 - Google Patents
一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶及其制备方法和应用 Download PDFInfo
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- CN106832387A CN106832387A CN201710012537.3A CN201710012537A CN106832387A CN 106832387 A CN106832387 A CN 106832387A CN 201710012537 A CN201710012537 A CN 201710012537A CN 106832387 A CN106832387 A CN 106832387A
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- sulfydryl
- vinyl
- polymer
- silsesquioxane
- obdurability
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Abstract
本发明公开了一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶及其制备方法和应用，该气凝胶主要由含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷与含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物在有机溶剂中按官能团摩尔比为1:0.5～4进行混合而制成。本发明气凝胶是以C‑S或C‑N键形成的交联结构，由于C‑S、C‑N键具有低的内旋转势垒可以赋予气凝胶很好的韧性；成块性好、具有纳米多孔结构、韧性好、密度低、比表面积高，热导率低、热稳定性好、力学比强度高，同时制备方法工艺简单、效率高、周期短，本发明制备的气凝胶可以规模化应用在建筑节能、高温隔热、石油化工或污水处理等领域。
Description
技术领域
本发明涉及化工材料，具体涉及一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶及其制备方法和应用
背景技术
二氧化硅气凝胶是一种具有三维纳米多孔结构的新材料，具有低密度(0.003～0.8g·cm-3)，高孔隙率(80～99.8％)，高比表面积(200～1000m2·g-1)，低热导率(～0.02W·m-1K-1)等性质，在航空航天、化工、节能建筑、军事、通讯、电子、冶金等应用领域有着十分广阔的前景。然而二氧化硅气凝胶并未得到广泛应用，这主要是因为二氧化硅气凝胶由弱应变性的硅氧共价键形成的三维网络结构，这种结构决定了二氧化硅气凝胶的弱应变性，在外力作用下容易断裂破碎，结构坍塌，导致力学性能差。
美国专利US7078359 B2，US8214980 B2和中国专利CN1803602A、CN101318659A、CN101671030A、CN101973752A采用纤维作为增强相来提高气凝胶的力学比强度(压缩模量与密度比)。虽然复合气凝胶的力学比强度有所提高，但是纤维直径比气凝胶孔径大得多，导致形成的网络结构不均匀，复合材料存在一定的缺陷。另外，增强相纤维材料与气凝胶基体的相容性也会影响材料的综合性能。美国Meador等人采用聚合物增强SiO2气凝胶，利用聚合物在SiO2粒子表面形成包覆层，通过增加粒子与粒子之间颈部的宽度来提高气凝胶的力学比强度，研究表明聚合物的引入可以将气凝胶的弹性模量提高两个数量级，增强效果显著。他们首先在SiO2凝胶表面修饰上特殊的官能团如氨基，通过溶剂交换后将修饰的凝胶浸入到某些有机单体的溶剂中，然后引发聚合和超临界干燥获得聚合物增强的SiO2气凝胶，如聚脲增强SiO2气凝胶、环氧增强SiO2气凝胶、聚苯乙烯增强SiO2气凝胶等。但该方法导致制备的气凝胶密度大(>0.4g·cm-3)，因此固相热传导作用较强，热导率较高(>0.04W·m-1·k-1)。
为了提高气凝胶的力学比强度而不大幅度增加气凝胶密度的情况下，Boday等人采用化学气相沉积的方法制备出聚氰基丙烯酸酯复合SiO2气凝胶。他们采用溶胶-凝胶法在SiO2凝胶表面修饰氨基，然后超临界干燥制备含氨基的SiO2气凝胶，通过化学气相沉积的方法将氰基丙烯酸酯以气体的形式扩散到气凝胶中，经过阴离子聚合反应得到聚氰基丙烯酸酯交联的SiO2复合气凝胶，制备的复合气凝胶具有低的密度(0.095-0.230g·cm-3)，比纯的氨基修饰的SiO2气凝胶比强度提高31倍。综上所述，目前的方法是先将SiO2凝胶表面进行修饰，再通过浸泡在有机单体溶液中经扩散平衡后进行交联反应或通过气相沉积的方法进行交联，获得力学增强的聚合物交联SiO2气凝胶。但是上述方法需要凝胶改性、溶剂交换和单体扩散的过程，周期长、制备效率低，不能从本质上解决硅基气凝胶本身的脆性问题。因此，需要一种工艺简单、效率高的生产方法制备出综合性能优异的气凝胶材料，推动气凝胶的规模化应用。
发明内容
发明目的：针对现有技术存在的问题，本发明是提供一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，该气凝胶成块性好、具有纳米多孔结构、韧性好、密度低、比表面积高，热导率低、热稳定性好、力学比强度高，以C-S或C-N键形成交联结构。
本发明的另一目的是提供一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的制备方法，该方法工艺简单、效率高。
最后，本发明还提供了一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的应用。
技术方案：为了实现上述目的，如本发明所述的一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，主要由含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷与含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物在有机溶剂中按官能团摩尔比为1:0.5～4进行混合而制成。
其中，所述的含反应性官能团的笼状倍半硅氧烷选自含氨基倍半硅氧烷、含乙烯基倍半硅氧烷或含巯基倍半硅氧烷中的至少一种。
作为优选，所述含氨基倍半硅氧烷选自六氨基丙基倍半硅氧烷、六氨基苯基倍半硅氧烷、八氨基丙基倍半硅氧烷、八氨基苯基倍半硅氧烷、十氨基丙基倍半硅氧烷、十氨基苯基倍半硅氧烷、十二氨基丙基倍半硅氧烷、或十二氨基苯基倍半硅氧烷中的至少一种。
作为优选，所述含乙烯基倍半硅氧烷选自六乙烯基倍半硅氧烷、八乙烯基倍半硅氧烷、十乙烯基倍半硅氧烷、十二乙烯基倍半硅氧烷中的至少一种；
作为优选，所述含巯基倍半硅氧烷选自六巯基倍半硅氧烷、八巯基倍半硅氧烷、十巯基倍半硅氧烷、十二巯基倍半硅氧烷中的至少一种。
其中，所述含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物选自含异氰酸酯基的有机单体或低聚物、含环氧基的有机单体或低聚物、含乙烯基有机单体或低聚物或含巯基的有机单体或低聚物中的至少一种。
所述含异氰酸酯基的有机单体或低聚物能与含氨基倍半硅氧烷反应，包括二异氰酸酯，优选六亚甲基二异氰酸酯、对苯二异氰酸酯、4，4'-亚甲基双(异氰酸苯酯)、4，4'-二异氰酸基-3，3'-二甲基联苯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、2，4-甲苯二异氰酸酯或2，6-甲苯二异氰酸酯；三异氰酸酯，优选为三苯基甲烷三异氰酸酯、L-赖氨酸三异氰酸酯；或者多聚异氰酸酯中的至少一种。
作为另一种优选，能与含氨基倍半硅氧烷反应的含反应性官能团的有机单体或低聚物还包括双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂、三缩水甘油基对氨基苯酚、三缩水甘油基三聚异氰酸酯、四缩水甘油基二氨基二苯基甲烷、四缩水甘油基二苯基二胺、四缩水甘油基-1,3-双氨基甲基环氧乙烷、四苯基缩水甘油醚基乙烷、三苯基缩水甘油醚基乙烷、溴化环氧树脂或氟化环氧树脂中的至少一种。
所述含乙烯基单体或低聚物能与含巯基倍半硅氧烷反应，包括异戊二烯、二烯丙基氨基甲酰氯、1,5-己二烯、二烯丙基二硫、1,5-环辛二烯、二聚环戊二烯、二烯丙基胺、2,4-己二烯、1-甲基-1,4-环己二烯、马来酸二烯丙酯、2,4-癸二烯酸乙酯、二烯丙基硫醚、甲基环戊二烯、2,5-二甲基-2,4-己二烯、2,4-庚二烯醛、2,4-癸二烯酸乙酯、亚油酸、聚丁二烯、五甲基环戊二烯、山梨酸、6-甲基-3,5-庚二烯-2-酮、邻苯二甲酸二丙烯酯、山梨酸酯、柠檬醛、双戊烯、二乙烯基四甲基二硅氧烷、聚乙二醇二甲基丙烯酸酯、1,5-戊二醇二丙烯酸酯、二丙烯酸新戊二醇酯、二丙烯酸1,6-己二醇、二丙烯酸乙二醇酯、三烯丙基胺、异氰脲酸三烯丙酯、乙氧基化三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三丙烯酸酯或四甲基四乙烯基环四硅氧烷中的至少一种。
所述含巯基单体或低聚物能与含乙烯基倍半硅氧烷反应，包括4,4'-硫代双苯硫酚、甲苯-3,4-二硫酚、1,2-乙二硫醇、1,3-丙二硫醇、2,3-丁二硫醇、1,5-戊二硫醇、1,6-己二硫醇、1,8-辛二硫醇、1,9-壬二硫醇、1，10-癸二硫醇、3,6-二氧-1,8-辛二硫醇、季戊四醇四巯基丙酸酯、三羟甲基丙烷三巯基丙酯、三聚硫氰酸或六元硫醇低聚物中的至少一种。
其中，所述有机溶剂为醇类、酮类、酰胺类、亚砜、呋喃、腈类或苯类有机溶剂。
所述有机溶剂为甲醇、乙醇、丙醇、异丙醇、叔丁醇、丙酮、甲酰胺、乙酰胺、二甲基亚砜、四氢呋喃、N-甲基吡咯烷酮、乙腈、丙腈、甲苯或二甲苯中的至少一种。
上述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，孔径分布为2～500nm，BET比表面积为100～1500m2·g-1，密度为0.01～0.45g·cm-3，密度优选为0.05～0.25g·cm-3，压缩模量为2～100MPa，弯曲模量为0.2～10MPa，弯曲形变40～95％，热导率为0.01～0.05W·m-1·k-1，在空气气氛中可耐400℃以上高温。
本发明所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的制备方法，包括如下步骤：
(1)将含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷与含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物在有机溶剂中按上述官能团摩尔比进行混合，配制成均一的溶液，然后40～100℃加热0.5～24h引发聚合反应得到聚合物/笼状倍半硅氧烷杂化湿凝胶；
(2)将湿凝胶在有机溶剂中进行老化，所述有机溶剂为步骤(1)有机溶剂中的至少一种，然后将湿凝胶进行干燥，制备得到强韧性聚合物/笼状倍半硅氧烷杂化气凝胶。
作为优选，步骤(1)所述均一的溶液中溶质的质量浓度为5g/L-400g/L，溶质为含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷与含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物。
作为优选，步骤(2)所述老化时间为4-72h，老化温度为30-100℃。
作为优选，步骤(2)所述干燥为超临界CO2干燥、真空冷冻干燥或常压干燥。
本发明所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶在建筑节能、高温隔热、石油化工或污水处理领域中的应用。
有益效果：与现有技术相比，本发明具有以下优点：
1.本发明的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶是以C-S或C-N键形成的交联结构，由于C-S、C-N键具有低的内旋转势垒可以赋予气凝胶很好的韧性；
2.本发明的气凝胶采用了笼状倍半硅氧烷为反应单体，由于笼状倍半硅氧烷分子具有刚性结构可以提高气凝胶材料的比强度；同时与传统的硅基气凝胶相比，本发明提供的气凝胶表面不存在硅羟基，在干燥过程中可以减小气凝胶的不可逆收缩，从而可以降低气凝胶的密度；
3.本发明的气凝胶因分子链中含有笼状倍半硅氧烷分子结构，与传统的聚合物复合硅基气凝胶相比具有更高的热稳定性。
4、本发明的气凝胶成块性好、具有纳米多孔结构、韧性好、密度低、比表面积高，热导率低、热稳定性好、力学比强度高，以C-S或C-N键形成交联结构，可以规模化应用；同时制备方法工艺简单、效率高、周期短。
附图说明
图1是实施例1制备的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的孔径分布图；
图2是实施例3制备的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的扫描电镜照片。
具体实施方式
以下结合附图和实施例对本发明作进一步说明。
实施例1
(1)将反应性官能团摩尔比为1:0.5的八氨基丙基倍半硅氧烷与对苯二异氰酸酯在甲酰胺溶剂中进行混合均匀，配制成溶质质量浓度为5g/L的溶液，然后40℃加热24h引发聚合反应得到聚合物/笼状倍半硅氧烷杂化湿凝胶；
2)将上述湿凝胶在丙酮中进行老化，老化时间4h，老化温度30℃，然后将湿凝胶超临界CO2干燥得到聚合物笼状倍半硅氧烷杂化气凝胶。
实施例1制备的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的孔径分布为2～250nm，BET比表面积为1500m2·g-1，密度为0.01g·cm-3，热导率为0.01W·m-1·k-1，压缩模量为2MPa，弯曲模量为0.2MPa，弯曲形变95％，在空气气氛中可耐500℃，其孔径分布如图1所示。
实施例2
1)将反应性官能团摩尔比为1:1的八氨基苯基倍半硅氧烷与双酚A型环氧树脂在丙酮溶剂中进行混合均匀，配制成溶质质量浓度为40g/L的溶液，然后50℃加热16h引发聚合反应得到聚合物笼状倍半硅氧烷杂化湿凝胶；
2)将上述湿凝胶在四氢呋喃中进行老化，老化时间24h，老化温度40℃，然后将湿凝胶在60℃下进行常压干燥得到聚合物笼状倍半硅氧烷杂化气凝胶。
实施例2制备的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的孔径分布为5～300nm，BET比表面积为1200m2·g-1，密度为0.05g·cm-3，热导率为0.02W·m-1·k-1，压缩模量为10MPa，弯曲模量为1MPa，弯曲形变85％，在空气气氛中可耐450℃。
实施例3
1)将反应性官能团摩尔比为1:1.5的十氨基丙基倍半硅氧烷与三苯基甲烷三异氰酸酯在乙酰胺溶剂中进行混合均匀，配制成溶质质量浓度为400g/L的溶液，然后60℃加热10h引发聚合反应得到聚合物/笼状倍半硅氧烷杂化湿凝胶；
2)将上述湿凝胶在丙酮中进行老化，老化时间4h，老化温度30℃，然后将湿凝胶超临界CO2干燥得到聚合物笼状倍半硅氧烷杂化气凝胶。
实施例3制备的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的孔径分布为2～500nm，BET比表面积为100m2·g-1，密度为0.45g·cm-3，热导率为0.05W·m-1·k-1，压缩模量为100MPa，弯曲模量为10MPa，弯曲形变40％，在空气气氛中可耐500℃，其扫描电镜照片如图2所示。
实施例4
1将反应性官能团摩尔比为1:2的六乙烯基倍半硅氧烷与三聚硫氰酸在N-甲基吡咯烷酮溶剂中进行混合均匀，配制成溶质质量浓度为200g/L的溶液，然后80℃加热5h引发聚合反应得到聚合物/笼状倍半硅氧烷杂化湿凝胶；
2)将上述湿凝胶在乙醇中进行老化，老化时间72h，老化温度60℃，然后将湿凝胶进行真空冷冻干燥得到聚合物笼状倍半硅氧烷杂化气凝胶。
实施例4制备的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的孔径分布为2～500nm，BET比表面积为800m2·g-1，密度为0.25g·cm-3，热导率为0.03W·m-1·k-1，压缩模量为50MPa，弯曲模量为5MPa，弯曲形变63％，在空气气氛中可耐410℃。
实施例5
1)将反应性官能团摩尔比为1:3的的八巯基倍半硅氧烷与异氰脲酸三烯丙酯在四氢呋喃溶剂中进行混合均匀，配制成溶质质量浓度为100g/L的溶液，然后70℃加热6h引发聚合反应得到聚合物/笼状倍半硅氧烷杂化湿凝胶；
2)将上述湿凝胶在N-甲基吡咯烷酮中进行老化，老化时间24h，老化温度100℃，然后将湿凝胶超临界CO2干燥得到聚合物/笼状倍半硅氧烷杂化气凝胶。
实施例5强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的孔径分布为2～500nm，BET比表面积为700m2·g-1，密度为0.15g·cm-3，热导率为0.025W·m-1·k-1，压缩模量为20MPa，弯曲模量为3.5MPa，弯曲形变77％，在空气气氛中可耐480℃。
实施例6
1)将反应性官能团摩尔比为1:4的十二氨基苯基倍半硅氧烷与三苯基甲烷三异氰酸酯在二甲基亚砜溶剂中进行混合均匀，配制成质量浓度为150g/L的溶液，然后100℃加热0.5h引发聚合反应得到聚合物笼状倍半硅氧烷杂化湿凝胶；
2)将上述湿凝胶在丙酮中进行老化，老化时间4h，老化温度50℃，然后将湿凝胶进行超临界CO2干燥得到聚合物/笼状倍半硅氧烷杂化气凝胶。
实施例6强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的孔径分布为2～500nm，BET比表面积为800m2·g-1，密度为0.20g·cm-3，热导率为0.028W·m-1·k-1，压缩模量为40MPa，弯曲模量为5.5MPa，弯曲形变72％，在空气气氛中可耐550℃以上高温。
实施例7
将实施例1至6制备的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶在建筑节能、高温隔热、石油化工或污水处理等领域中应用。
试验例1
通过对本发明实施例1至3制备的聚合物/笼状倍半硅氧烷杂化气凝胶的各项指标进行检测，包括密度、热导率、比强度(压缩模量与密度比)，韧性(弯曲模量和形变)、热稳定性，数据见各个实施例。同时将各个实施例与对比例进行对比，结果见表1。
对比例1采用实施例1的原料和方法，不同之处在于反应性官能团摩尔比为1:0.4。
对比例2采用实施例1的原料和方法，不同之处在于反应性官能团摩尔比为1:4.1。
表1有机气凝胶的各项指标
由表1可知，实施例1至3制备的聚合物/笼状倍半硅氧烷杂化气凝胶与对比例相比，本发明制备的聚合物/笼状倍半硅氧烷杂化气凝胶其密度更低、热导率更低，在空气气氛中可耐温度高热稳定性更好并且韧性更好。
Claims (10)
1.一种强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，其特征在于，主要由含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷与含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物在有机溶剂中按官能团摩尔比为1:0.5～4进行混合而制成。
2.根据权利要求1所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，其特征在于，所述含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷选自含氨基倍半硅氧烷、含乙烯基倍半硅氧烷或含巯基倍半硅氧烷中的至少一种；所述含氨基倍半硅氧烷选自六氨基丙基倍半硅氧烷、六氨基苯基倍半硅氧烷、八氨基丙基倍半硅氧烷、八氨基苯基倍半硅氧烷、十氨基丙基倍半硅氧烷、十氨基苯基倍半硅氧烷、十二氨基丙基倍半硅氧烷、或十二氨基苯基倍半硅氧烷中的至少一种；所述含乙烯基倍半硅氧烷选自六乙烯基倍半硅氧烷、八乙烯基倍半硅氧烷、十乙烯基倍半硅氧烷、十二乙烯基倍半硅氧烷中的至少一种；所述含巯基倍半硅氧烷选自六巯基倍半硅氧烷、八巯基倍半硅氧烷、十巯基倍半硅氧烷、十二巯基倍半硅氧烷中的至少一种。
3.根据权利要求1所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，其特征在于，所述含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物选自含异氰酸酯基的有机单体或低聚物、含环氧基的有机单体或低聚物、含乙烯基有机单体或低聚物或含巯基的有机单体或低聚物中的至少一种。
4.根据权利要求1所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，其特征在于，所述有机溶剂为醇类、酮类、酰胺类、亚砜、呋喃、腈类或苯类有机溶剂。
5.根据权利要求1所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶，其特征在于，所述有机溶剂为甲醇、乙醇、丙醇、异丙醇、叔丁醇、丙酮、甲酰胺、乙酰胺、二甲基亚砜、四氢呋喃、N-甲基吡咯烷酮、乙腈、丙腈、甲苯或二甲苯中的至少一种。
6.一种如权利要求1所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶的制备方法。其特征在于，包括如下步骤：
(1)将含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷与含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物在有机溶剂中按上述官能团摩尔比进行混合，配制成均一的溶液，然后40～100℃加热0.5～24h引发聚合反应得到聚合物/笼状倍半硅氧烷杂化湿凝胶；
(2)将湿凝胶在有机溶剂中进行老化，所述有机溶剂为步骤(1)有机溶剂中的至少一种，然后将湿凝胶进行干燥，制备得到强韧性聚合物/笼状倍半硅氧烷杂化气凝胶。
7.根据权利要求6所述的制备方法，其特征在于，步骤(1)所述均一的溶液中溶质的质量浓度为5g/L-400g/L，溶质为含氨基、乙烯基或巯基反应性官能团的笼状倍半硅氧烷与含异氰酸酯基、巯基、环氧基或乙烯基反应性官能团的有机单体或低聚物。
8.根据权利要求6所述的制备方法，其特征在于，步骤(2)所述老化时间为4-72h，老化温度为30-100℃。
9.根据权利要求6所述的制备方法，其特征在于，步骤(2)所述干燥为超临界CO2干燥、真空冷冻干燥或常压干燥。
10.一种如权利要求1所述的强韧性聚合物/笼状倍半硅氧烷杂化气凝胶在建筑节能、高温隔热、石油化工或污水处理领域中的应用。
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212032A (zh) * | 2018-01-18 | 2018-06-29 | 航天特种材料及工艺技术研究所 | 一种形状记忆气凝胶材料及其制备方法 |
| CN109553746A (zh) * | 2018-11-27 | 2019-04-02 | 射阳天源化工有限公司 | 一种四巯基倍半硅氧烷改性水性聚氨酯固色剂的制备方法 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492078A (zh) * | 2011-11-27 | 2012-06-13 | 吉林大学 | 丙烯酸与多面体笼型倍半硅氧烷共聚水凝胶及其制备方法和用途 |
| US20150141544A1 (en) * | 2012-02-03 | 2015-05-21 | U.S. Government as represented by the Administrator of the National Aeronautics and Spac | Porous cross-linked polyimide networks |
| CN105504331A (zh) * | 2014-09-23 | 2016-04-20 | 中国科学院大连化学物理研究所 | 一种多孔整体材料的制备方法 |
| CN106749378A (zh) * | 2016-12-28 | 2017-05-31 | 淮阴工学院 | 一种力学增强型聚倍半硅氧烷气凝胶及其制备方法 |
-
2017
- 2017-01-09 CN CN201710012537.3A patent/CN106832387B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492078A (zh) * | 2011-11-27 | 2012-06-13 | 吉林大学 | 丙烯酸与多面体笼型倍半硅氧烷共聚水凝胶及其制备方法和用途 |
| US20150141544A1 (en) * | 2012-02-03 | 2015-05-21 | U.S. Government as represented by the Administrator of the National Aeronautics and Spac | Porous cross-linked polyimide networks |
| CN105504331A (zh) * | 2014-09-23 | 2016-04-20 | 中国科学院大连化学物理研究所 | 一种多孔整体材料的制备方法 |
| CN106749378A (zh) * | 2016-12-28 | 2017-05-31 | 淮阴工学院 | 一种力学增强型聚倍半硅氧烷气凝胶及其制备方法 |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212032A (zh) * | 2018-01-18 | 2018-06-29 | 航天特种材料及工艺技术研究所 | 一种形状记忆气凝胶材料及其制备方法 |
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