CN114163643B - 一种多孔硅树脂及轻质柔性阻燃复合材料 - Google Patents
一种多孔硅树脂及轻质柔性阻燃复合材料 Download PDFInfo
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- CN114163643B CN114163643B CN202210005560.0A CN202210005560A CN114163643B CN 114163643 B CN114163643 B CN 114163643B CN 202210005560 A CN202210005560 A CN 202210005560A CN 114163643 B CN114163643 B CN 114163643B
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- silicone resin
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 69
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- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 59
- 239000002243 precursor Substances 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 51
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
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- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 8
- -1 triethoxysilyl Chemical group 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 6
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
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- XQEGZYAXBCFSBS-UHFFFAOYSA-N trimethoxy-(4-methylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=C(C)C=C1 XQEGZYAXBCFSBS-UHFFFAOYSA-N 0.000 claims description 6
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- NMDQPQZRIKCRDU-UHFFFAOYSA-N 3-chloro-2-dodecylpyridine Chemical compound CCCCCCCCCCCCC1=NC=CC=C1Cl NMDQPQZRIKCRDU-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- ZHALDANPYXAMJF-UHFFFAOYSA-N octadecanoate;tris(2-hydroxyethyl)azanium Chemical compound OCC[NH+](CCO)CCO.CCCCCCCCCCCCCCCCCC([O-])=O ZHALDANPYXAMJF-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229940029614 triethanolamine stearate Drugs 0.000 claims description 3
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 3
- PADYPAQRESYCQZ-UHFFFAOYSA-N triethoxy-(4-methylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C(C)C=C1 PADYPAQRESYCQZ-UHFFFAOYSA-N 0.000 claims description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
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- C08G77/08—Preparatory processes characterised by the catalysts used
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Abstract
本发明提供一种多孔硅树脂及轻质柔性阻燃复合材料,属于纳米多孔材料技术领域;其中,多孔硅树脂前驱体溶液包括阻燃剂、表面活性剂、硅氧烷单体、催化剂、助剂和溶剂;所述多孔硅树脂前驱体溶液是首先通过将阻燃剂、表面活性剂溶解于溶剂中,然后再加入硅氧烷单体、催化剂和助剂混合均匀得到;本发明的多孔硅树脂由上述多孔硅树脂前驱体溶液经固化工序、干燥工序制备得到。通过本发明制备得到的多孔硅树脂和轻质柔性阻燃复合材料具备高孔隙率、高阻燃、高弹性和高应变的优异性能。
Description
技术领域
本发明属于纳米多孔材料技术领域,具体涉及一种多孔硅树脂及轻质柔性阻燃复合材料,更具体涉及一种多孔硅树脂及其制备方法,以及基于多孔硅树脂作为基体的轻质柔性阻燃复合材料及其制备方法。
背景技术
在热防护、热密封和阻燃材料领域,有机硅材料常用作耐高温密封材料、高温隔热材料、抗氧化涂层材料、耐氧化烧蚀材料等诸多领域。有机硅树脂具有优异的耐高温、抗氧化和优良施工性能,被广泛应用于消防、建筑、极端火环境等技术领域。比如:高铁内饰阻燃材料、防热涂层的基体树脂、关键部位的热密封、抗氧化涂层等。随着消防领域火安全、电子产品热密封等领域对材料减重、长时隔热、低介电损耗等功能的需求,传统的致密材料已渐渐不能满足先进防火、阻燃和热密封材料需求,从而使得以有机硅树脂为基体的复合材料不断向低热导率、低密度的方向发展。
现有技术中,通过在有机硅树脂基体中引入空穴结构,从而降低材料的密度和热导率。比如:文献《神舟飞船防热结构的研制》公开了一种有机硅树脂,通过在硅橡胶基体中加入空心粒子,使得材料密度降至0.5g/cm3左右,热导率为0.25W/(m·K)左右(航天器工程,2004,13(3):14-19);专利ZL01117235.5公开实施例中,通过在有机硅树脂基体中引入发泡剂,交联固化后通过高温处理使有机组分分解,从而形成多孔硅树脂陶瓷体,然而无论是加入空心粒子还是这种直接高温发泡成孔制备得到的多孔硅树脂较脆,容易开裂,难以用作高温烧蚀体。
专利CN105692631B公开了一种二氧化硅气凝胶的常压制备方法,通过采用金属盐类化合物对老化后的二氧化硅湿凝胶进行修饰得到修饰后的湿凝胶,然后直接进行常压干燥得到二氧化硅气凝胶。专利CN110922095B公开了一种复合二氧化硅气凝胶毡的制备方法,通过将水、二氧化硅气凝胶粉、树脂、固化剂、低密度微球混合均匀,得到气凝胶浆料;然后分别将多个单层纤维毡浸渍于气凝胶浆料中并将其叠加在一起,得到多层气凝胶纤维毡;最后在一定条件下进行固化得到复合二氧化硅气凝胶毡。虽然上述专利均是以小分子硅氧烷单体作为硅源,通过溶胶凝胶法制备得到刚性或柔性的硅气凝胶;但是上述方法制备得到的硅气凝胶,在极端火环境下易发生燃烧、烧蚀剥落,不具有阻燃性能,无法满足热防护材料阻燃、超轻质、高强度等多方面的需求。
发明内容
针对现有技术存在的不足及缺陷,本发明旨在提供一种多孔硅树脂及其制备方法,以及基于多孔硅树脂作为基体的轻质柔性阻燃复合材料及其制备方法;通过本发明制备得到的多孔硅树脂和轻质柔性阻燃复合材料具备高孔隙率、高阻燃、高弹性和高应变的优异性能。
为了实现上述目的,采用如下的技术方案:
本发明第一方面提供了一种多孔硅树脂前驱体溶液,包括阻燃剂、表面活性剂、硅氧烷单体、催化剂、助剂和溶剂;其中,所述多孔硅树脂前驱体溶液是首先通过将阻燃剂、表面活性剂溶解于溶剂中,然后再加入硅氧烷单体、催化剂和助剂混合均匀得到。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述溶剂为水或者醇类;优选地,所述溶剂为水、乙醇、丙醇中的至少一种;优选地,所述硅氧烷单体与所述溶剂的质量比为1:(0.1~5)(比如1:0.5、1:1、1:2、1:3、1:4)。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述表面活性剂为阳离子表面活性剂;优选地,所述表面活性剂为十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、三乙醇胺硬脂酸酯、氯化十二烷基吡啶、四丁基氟化铵中的一种或多种;优选地,所述表面活性剂与所述硅氧烷单体的质量比为1:(5~50)(比如1:8、1:15、1:20、1:30、1:40)。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述阻燃剂为氢氧化镁、氢氧化铝、红磷、改性埃洛石管中的一种或两种;优选地,所述阻燃剂与所述硅氧烷单体的质量比为1:(5~100)(比如1:8、1:20、1:50、1:70、1:85)。
本发明中的改性埃洛石管是指在埃洛石管的基础上,通过偶联剂改性、插层改性、负载改性、自由基改性、表面活性剂改性等方法得到改性埃洛石管。通过化学修饰改性后埃洛石管能够溶解或均匀分散在有机溶剂或水溶液中,或者与树脂基体发生化学反应。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述硅氧烷单体包括:二甲基二甲氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、二甲基二乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、三甲氧基硅烷基笼型低聚倍半硅氧烷(POSS)、三乙氧基硅烷基笼型低聚倍半硅氧烷(POSS)、苯基三甲氧基硅烷、苯基三乙氧基硅烷、二苯基二乙氧基硅烷、对甲基苯基三甲氧基硅烷、对甲基苯基三乙氧基硅烷中的三种以上且必须至少含有一种带苯环的硅氧烷单体;三种以上硅氧烷单体可以以任意比例混合。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述三甲氧基硅烷基笼型低聚倍半硅氧烷的结构通式为:(R-SiO1.5)n,其中,n为4~20的自然数,R为如下官能团的一种:
其中,m为2~6的自然数。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述三乙氧基硅烷基笼型低聚倍半硅氧烷的结构通式为:(R-SiO1.5)n,其中,n为4~20的自然数,R为如下官能团的一种:
其中,m为2~6的自然数。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述催化剂为酸类催化剂;优选地,所述催化剂为稀盐酸、稀硝酸、冰醋酸、草酸中的至少一种;优选地,所述催化剂的摩尔浓度为0.005~1.0mol/L(比如0.008mol/L、0.01mol/L、0.05mol/L、0.1mol/L、0.5mol/L);优选地,所述催化剂与所述硅氧烷单体的物质的量的比为1:(1~500)(比如1:10、1:50、1:100、1:300、1:400)。
在上述多孔硅树脂前驱体溶液中,作为一种优选实施方式,所述助剂为弱碱类物质;优选地,所述助剂为稀氨水、尿素、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、六亚甲基四胺、三聚氰胺中的至少一种;优选地,所述助剂与所述硅氧烷单体的物质的量的比为1:(0.25~5)(比如1:0.5、1:1、1:2、1:3、1:4)。
本发明第二方面提供一种多孔硅树脂,所述多孔硅树脂由上述多孔硅树脂前驱体溶液经固化工序、干燥工序制备得到。
在上述多孔硅树脂中,作为一种优选实施方式,所述多孔硅树脂的密度为0.1~0.6g/cm3(比如0.2g/cm3、0.3g/cm3、0.4g/cm3、0.5g/cm3),室温热导率≤0.1W/(m·K)(比如0.04W/(m·K)、0.05W/(m·K)、0.06W/(m·K)、0.08W/(m·K)),平均孔径为100nm~500μm(比如200nm、500nm、50μm、100μm、200μm、300μm),孔隙率≥50%(比如55%、60%、62%、65%),极限氧指数≥28%(比如30%、31%、32%、35%)。
本发明中,通过硅氧烷单体间进行水解、缩聚化学反应从而制备得到多孔硅树脂,可反应的硅氧烷单体中必须至少含有一种带苯环的硅氧烷单体的原因在于,带苯环的硅氧烷单体能够提高多孔硅树脂的阻燃性能;本发明中选择三种以上的硅氧烷单体的原因在于,发明人发现,选择上述任意一种硅氧烷单体得到的多孔硅树脂其满足不了高弹性的性能要求,选择上述任意两种硅氧烷单体得到的多孔硅树脂其阻燃性能达不到使用要求;再比如采用正硅酸四乙酯制备硅树脂时,根本得不到多孔硅树脂,只能得到粉末状的硅气凝胶。
本发明中阻燃剂的加入能够进一步提高材料的阻燃性能;催化剂用于催化硅氧烷单体间进行水解、缩聚化学反应,加入的量太多,则会使得反应速率过高,从而不利于材料均匀多孔结构的形成,加入的量太少,则会使得反应速率太慢;助剂的主要作用是中和反应体系释放的多余氢离子,助剂的加入量过多或过少都会影响材料的微观结构,进而影响材料的宏观性能;本发明中选择水或者醇类作为前驱体溶液溶剂的主要原因在于,在水或者醇类作为溶剂时,更有利于硅氧烷单体发生水解,溶剂的加入量过多或过少都会对材料的强度、孔隙率以及力学性能造成影响;加入表面活性剂的主要作用在于能够减小后续干燥工序时的表面张力,表面活性剂的加入量过多或过少都会影响材料的微观结构,进而影响材料的孔隙率、平均孔径。
本发明第三方面提供一种上述多孔硅树脂的制备方法,包括:
(1)多孔硅树脂前驱体溶液的制备:首先将阻燃剂、表面活性剂加入到溶剂中搅拌10~20min(比如12min、15min、17min),然后加入硅氧烷单体、催化剂和助剂,再剧烈搅拌30~300min(比如70min、90min、150min、200min、260min),得到多孔硅树脂前驱体溶液;
(2)固化工序:在密封条件下,将上述多孔硅树脂前驱体溶液在60-120℃(比如75℃、90℃、110℃),保温12-72h(比如24h、36h、48h、56h)进行固化,然后冷却至室温得到多孔硅树脂凝胶;
(3)干燥工序:将步骤(2)湿的多孔硅树脂凝胶进行干燥,得到多孔硅树脂。
在上述多孔硅树脂的制备方法中,作为一种优选实施方式,所述干燥包括:先将步骤(2)湿的多孔硅树脂凝胶进行室温晾置24小时以上,然后在60~80℃(比如65℃、70℃、75℃)的烘箱中干燥48小时以上,直至重量不再减少,得到多孔硅树脂。
本发明中干燥步骤除了常压干燥外,还可以二氧化碳超临界干燥方式进行干燥。
本发明第四方面提供了一种轻质柔性阻燃复合材料,包括轻质柔性纺织品以及分布在所述轻质柔性纺织品表面和孔隙中的上述多孔硅树脂。
在上述轻质柔性阻燃复合材料中,作为一种优选实施方式,所述多孔硅树脂与轻质柔性纺织品的质量比为1:(1~9)(比如1:3、1:4、1:5、1:6、1:7)。
在上述轻质柔性阻燃复合材料中,作为一种优选实施方式,所述复合材料的密度为0.15~0.50g/cm3(比如0.2g/cm3、0.3g/cm3、0.4g/cm3、0.45g/cm3),室温热导率为≤0.10W/(m·K)(比如0.04W/(m·K)、0.05W/(m·K)、0.06W/(m·K)、0.08W/(m·K)),平均孔径为100nm~500μm(比如200nm、500nm、50μm、100μm、200μm、300μm),孔隙率为≥50%(比如55%、60%、62%、65%),极限氧指数≥30%(比如32%、35%、36%、38%),拉伸断裂应变≥20%(比如25%、28%、30%、32%)。
在上述轻质柔性阻燃复合材料中,作为一种优选实施方式,所述轻质柔性纺织品为纤柔性二维布、柔性无纺织造立体织物、立体柔性织物中的至少一种。
本发明第五方面提供一种上述轻质柔性阻燃复合材料的制备方法,包括:
(1)多孔硅树脂前驱体溶液的制备:首先将阻燃剂、表面活性剂加入到溶剂中搅拌10~20min(比如12min、15min、17min),然后加入硅氧烷单体、催化剂和助剂,再剧烈搅拌30~300min300 min(比如70min、90min、150min、200min、260min),得到多孔硅树脂前驱体溶液;
(2)浸渍工序:将轻质柔性纺织品真空浸渍于上述多孔硅树脂前驱体溶液中,浸渍压力为0.05-0.5MPa(比如0.1MPa、0.25MPa、0.3MPa、0.4MPa),浸渍时间为30~60min(比如35min、40min、50min);
(3)固化工序:在密封条件下,60-120℃(比如75℃、90℃、110℃)保温12-72小时(比如24h、36h、48h、56h)进行固化,然后冷却至室温得到复合材料的凝胶;
(4)干燥工序:将上述复合材料的凝胶进行干燥,得到轻质柔性阻燃复合材料。
在上述轻质柔性阻燃复合材料的制备方法中,作为一种优选实施方式,所述干燥包括:将上述复合材料的凝胶室温晾置24小时以上,然后再在60~80℃(比如65℃、70℃、75℃)的烘箱中干燥48小时以上,直至重量不再减少,得到轻质柔性阻燃复合材料。
本发明中干燥步骤除了常压干燥外,还可以二氧化碳超临界干燥方式进行干燥。
本发明与现有技术相比具有如下有效效果:
(1)本发明制备得到的多孔硅树脂为多孔类材料,平均孔径为100nm~500μm,压缩应变≥50%,拉伸断裂应变≥30%,可用作航天热防护材料和防火材料的高性能基体树脂。
(2)本发明制备得到的轻质柔性阻燃复合材料,具有耐高温烧蚀、阻燃、低密度和低热导率的优异性能,能够满足极端热环境下的热防护、防火、隔热、保暖等需求。
(3)本发明通过溶胶-凝胶方法制备得到多孔硅树脂及轻质柔性阻燃复合材料,反应条件温和且原料廉价易得,具有适用性广的特点,通过常压干燥的方式即可获得低收缩率的材料(若干燥过程后得到的材料的收缩率太大,则意味着材料的多孔结构坍塌,结构和性能降,不可控)。
(4)本发明制备得到的多孔硅树脂及轻质柔性阻燃复合材料在航天飞行器、热防护、防火、保暖隔热等领域具有重大的应用价值。
附图说明
图1为本发明实施例1制备得到的多孔硅树脂的扫描电子显微镜(SEM)图片。
图2为本发明实施例2制备得到的轻质柔性阻燃复合材料的扫描电子显微镜(SEM)图片。
图3为本发明实施例2制备得到的轻质柔性阻燃复合材料的TG-DSC曲线。
图4和图5为本发明实施例3制备得到的轻质柔性阻燃复合材料的扫描电子显微镜(SEM)图片。
图6为本发明实施例3制备得到的轻质柔性阻燃复合材料的循环压缩应力-应变曲线。
具体实施方式
下面结合附图和实施例对本发明的高孔隙率、高阻燃、高弹性的多孔硅树脂及其制备方法,以及基于多孔硅树脂作为基体的轻质柔性阻燃复合材料及其制备方法进行说明。应理解,这些实施例仅用于解释本发明而不用于限制本发明的范围。对外应理解,在阅读了本发明的内容之后,本领域技术人员对本发明作各种改动和修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
以下实施例中所述的小分子硅氧烷单体可从公开商业途径获得,所述的三甲氧基硅烷基笼型低聚倍半硅氧烷或者三乙氧基硅烷基笼型低聚倍半硅氧烷可按照公开文献报道途径实验室合成。所用其他原料都可以从市场上购得。
本发明的具体实施方式提供一种多孔硅树脂,其制备方法,包括:
(1)多孔硅树脂前驱体溶液的制备:首先将阻燃剂、表面活性剂加入到溶剂中搅拌10~20min,然后加入硅氧烷单体、催化剂和助剂,再剧烈搅拌30~300min,得到多孔硅树脂前驱体溶液;
(2)固化工序:在密封条件下,将上述多孔硅树脂前驱体溶液在60-120℃,保温12-72h进行固化,然后冷却至室温得到多孔硅树脂凝胶;
(3)干燥工序:将步骤(2)湿的多孔硅树脂凝胶先进行室温晾置24小时以上,然后再在60~80℃的烘箱中干燥48小时以上,直至重量不再减少,得到多孔硅树脂。
本发明另一实施例中提供一种轻质柔性阻燃复合材料,其制备方法,包括:
(1)多孔硅树脂前驱体溶液的制备:首先将阻燃剂、表面活性剂加入到溶剂中搅拌10~20min,然后加入硅氧烷单体、催化剂和助剂,再剧烈搅拌30~300min,得到多孔硅树脂前驱体溶液;
(2)浸渍工序:将轻质柔性纺织品浸渍于上述多孔硅树脂前驱体溶液中,浸渍压力为0.05-0.5MPa,浸渍时间为30~60min;
(3)固化工序:在密封条件下,60-120℃保温12-72小时进行固化,然后冷却至室温得到复合材料的凝胶;
(4)干燥工序:将上述复合材料的凝胶进行室温晾置24小时以上,然后再在60~80℃的烘箱中干燥48小时以上,直至重量不再减少,得到轻质柔性阻燃复合材料。
其中,本发明多孔硅树脂或者轻质柔性阻燃复合材料的制备中,所述多孔硅树脂前驱体溶液包括阻燃剂、表面活性剂、硅氧烷单体、催化剂、助剂和溶剂;其中,所述多孔硅树脂前驱体溶液是首先通过将阻燃剂、表面活性剂溶解于溶剂中,然后再加入硅氧烷单体、催化剂和助剂混合均匀得到。
具体地,所述溶剂为水或者醇类;优选地,所述溶剂为水、乙醇、丙醇中的至少一种;优选地,所述硅氧烷单体与所述溶剂的质量比为1:(0.1~5)。
具体地,所述表面活性剂为阳离子表面活性剂;优选地,所述表面活性剂为十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、三乙醇胺硬脂酸酯、氯化十二烷基吡啶、四丁基氟化铵中的一种或多种;优选地,所述表面活性剂与所述硅氧烷单体的质量比为1:(5~50)。
具体地,所述阻燃剂为氢氧化镁、氢氧化铝、红磷、改性埃洛石管中的一种或两种;优选地,所述阻燃剂与所述硅氧烷单体的质量比为1:(5~100)。
具体地,所述硅氧烷单体包括二甲基二甲氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、二甲基二乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、三甲氧基硅烷基笼型低聚倍半硅氧烷(POSS)、三乙氧基硅烷基笼型低聚倍半硅氧烷(POSS)、苯基三甲氧基硅烷、苯基三乙氧基硅烷、二苯基二乙氧基硅烷、对甲基苯基三甲氧基硅烷、对甲基苯基三乙氧基硅烷中的三种以上且必须至少含有一种带苯环的硅氧烷单体,以任意比例混合。本发明实施例中的硅氧烷单体和POSS包括但不限于以上所提到的单体。
具体地,所述催化剂为酸类催化剂;优选地,所述催化剂为稀盐酸、稀硝酸、冰醋酸、草酸中的至少一种;优选地,所述催化剂的摩尔浓度为0.005~1.0mol/L;优选地,所述催化剂与所述硅氧烷单体的物质的量的比为1:(1~500)。
具体地,所述助剂为弱碱类物质;优选地,所述助剂为稀氨水、尿素、碳酸钠、碳酸氢钠、六亚甲基四胺、三聚氰胺中的至少一种;优选地,所述助剂与所述硅氧烷单体的物质的量的比为1:(0.25~5)。
下面结合具体实施例对本发明作进一步详细地描述。
实施例1:多孔硅树脂,其制备方法包含如下步骤:
(1)多孔硅树脂前驱体溶液的制备:首先称量1.5g氢氧化镁,0.3g十六烷基三甲基氯化铵和8.0g的去离子水,放入烧杯中,搅拌5~10分钟,形成透明溶液;然后称量5.0g甲基三乙氧基硅烷,2.0g二甲基二乙氧基硅烷,1.0g苯基三乙氧基硅烷,剧烈搅拌30~40分钟;边滴加边搅拌0.1mol/L盐酸溶液5ml,至pH为5左右;加入的HCl与总的硅氧烷单体的摩尔比约为1:9。继续搅拌,水解60min后加入0.1mol/L氨水溶液,调节溶液pH在7.0左右,得到多孔硅树脂前驱体溶液;
(2)固化工序:将上述多孔硅树脂前驱体溶液转移至PP管中密封,然后放置在60℃的烘箱中固化48小时,然后冷却至室温得到多孔硅树脂凝胶;
(3)干燥工序:将上述湿的多孔硅树脂室温自然晾置24小时,然后转移至80℃的烘箱中干燥48小时,得到多孔硅树脂。
实施1制备得到的多孔硅树脂的SEM图片如图1所示,可以看出呈现疏松多孔状态,平均孔径为200μm。将上述得到的多孔硅树脂进行压缩循环试验,10次压缩循环后应变仍可回复到90%,显示出高弹性。
实施例2:轻质柔性阻燃复合材料,其制备方法包含如下步骤:
(1)多孔硅树脂前驱体溶液的制备:首先将5.0g氢氧化镁,4g十六烷基三甲基氯化铵加入到50g去离子水的烧杯中,搅拌10分钟,形成均一透明溶液,然后再向烧杯中加入30g甲基三甲氧基硅烷,20g乙烯基三乙氧基硅烷,7.0g对甲基苯基三甲氧基硅烷,剧烈搅拌,之后边搅拌边滴加0.1mol/L冰醋酸溶液100ml,30min内滴加完毕后,继续搅拌30min,最后加入20g尿素,继续搅拌10min,得到均一的多孔硅树脂前驱体溶液;
(2)浸渍工序:将尺寸为10cm×10cm×0.5cm,的轻质柔性石英纤维无纺布(柔性无纺织立体织物),质量为7.55g,放入10cm×10cm的钢制模具中,抽真空,将上述多孔硅树脂前驱体溶液导入模具中,直至溶液充满模具型腔,于0.15MPa的压力下,浸渍30min,浸渍完成后密封;
(3)固化工序:在80℃的烘箱中,保温24h进行固化,然后冷却至室温,放置48h,得到复合材料的凝胶;
(4)干燥工序:将上述复合材料的凝胶放入甲醇/正己烷=1/1的溶剂中,浸泡、洗涤三次,然后室温自然晾置干燥,得到轻质柔性阻燃复合材料,质量为11.82g。
实施例2制备得到的轻质柔性阻燃复合材料中多孔硅树脂与柔性纺织品的质量比约为1:1.77,其SEM图片如图2所示,可以看出呈现疏松多孔状态,平均孔径为100~300μm之间;图3为惰性气氛下的TG-DSC曲线,800℃残重高达60%;上述得到的轻质柔性阻燃复合材料进行压缩循环试验,10次压缩循环后仍具有90%以上的回弹率,显示出高弹性。
实施例3:轻质柔性阻燃复合材料,其制备方法包含如下步骤:
(1)多孔硅树脂前驱体溶液的制备:首先将500g氢氧化镁,500g十六烷基三甲基溴化铵,加入到1000g甲醇的容器中,搅拌20分钟,形成均一透明溶液,然后再向容器中加入2000g甲基三甲氧基硅烷,1200g二甲基二甲氧基硅烷,500g对甲基苯基三甲氧基硅烷,500g三甲氧基硅烷基笼型低聚倍半硅氧烷(参照文献Langmuir,Facile Fabrication ofFlexible,Robust and Superhydrophobic Hybrid Aerogel,2019,39:8692-8698.合成),化学式为((CH3O)3Si(CH2)3SCH2CH2-SiO1.5)8,分子量为2200g/mol,剧烈搅拌,之后边搅拌边滴加0.5mol/L冰醋酸溶液400ml,40min内滴加完毕后,继续搅拌20min,最后加入600g尿素,继续搅拌30min,得到均一的多孔硅树脂前驱体溶液;
(2)浸渍工序:将尺寸为20cm×20cm×0.5cm的轻质柔性石英纤维无纺布,质量为31.4g,放入20cm×20cm的钢制模具中,抽真空,将上述多孔硅树脂前驱体溶液导入模具中,直至溶液充满模具型腔,于0.3MPa的压力下,浸渍45min,浸渍完成后密封;
(3)固化工序:在70℃的烘箱中,保温36h进行固化,然后冷却至室温,放置48h,得到复合材料的凝胶;
(4)干燥工序:将上述复合材料的凝胶放入甲醇/正己烷=1/1的溶剂中,浸泡、洗涤三次,然后室温晾置干燥,得到轻质柔性阻燃复合材料,质量为48.6g,多孔硅树脂与轻质柔性石英纤维无纺布的质量比约为5:9。
实施例3制备得到的轻质柔性阻燃复合材料的SEM图片如图4和图5所示,可以看出呈现疏松多孔状态,平均孔径为300~500μm之间,图6为轻质柔性阻燃复合材料的循环压缩应力-应变曲线,经过10次压缩循环后仍具有90%以上的回弹率,显示出高弹性。
实施例4:轻质柔性阻燃复合材料,其制备方法包含如下步骤:
(1)多孔硅树脂前驱体溶液的制备:首先将100g质量浓度为25%的表面羟基改性埃洛石管悬浮液,15g四丁基氟化铵加入到烧杯中,搅拌30分钟,形成均一悬浮液,然后再向烧杯中加入50g甲基三甲氧基硅烷,200g二甲基二甲氧基硅烷,25g乙烯基三甲氧基硅烷,10g对甲基苯基三甲氧基硅烷,剧烈搅拌,之后边搅拌边滴加0.5mol/L冰醋酸溶液50ml,20min内滴加完毕后,继续搅拌20min,最后加入25g尿素,继续搅拌30min,得到均一的多孔硅树脂前驱体溶液;
(2)将尺寸为10cm×10cm×0.5cm的轻质柔性石英纤维布和无纺布(纤柔性二维布与柔性无纺织立体织物)的组合柔性纺织品,质量为9.91g,放入10cm×10cm的钢制模具中,抽真空,将上述多孔硅树脂前驱体溶液导入模具中,直至溶液充满模具型腔,于0.2MPa的压力下,浸渍45min,浸渍完成后密封;
(3)固化工序:在80℃的烘箱中,保温24h进行固化,然后冷却至室温,放置36h,得到复合材料的凝胶;
(4)干燥工序:将上述复合材料的凝胶放入甲醇/正己烷=1/1的溶剂中,浸泡、洗涤三次,然后室温晾置干燥,得到轻质柔性阻燃复合材料,质量为13.2g,其中,多孔硅树脂与轻质柔性纺织品质量比约为1:3。
实施例4得到的轻质柔性阻燃复合材料为疏松多孔态,平均孔径为300~500μm之间;上述得到的多孔硅树脂进行压缩循环试验,10次压缩循环后仍具有85%以上的回弹率,显示出高弹性。
性能数据测试
将本发明实施例1-4制备得到的多孔硅树脂及轻质柔性阻燃复合材料分别进行密度试验(按照GB/T 1463-2005《纤维增强塑料密度和相对密度试验方法》)、室温热导率测定(按照ISO 22007《瞬态平面热源法测定材料的导热系数》)、孔隙率测定(按照GB/T 3365-2008《碳纤维增强塑料孔隙含量和纤维体积含量试验方法》)、极限氧指数测定(按照ISO-4589《塑料–用氧指数法测定燃烧行为–第2部分:室温测试》、拉伸强度测定(按照GB/T1477-2005《纤维增强塑料拉伸性能试验方法》),检测结果如表1所示。
表1本发明实施例1-4制备得到的多孔硅树脂及轻质柔性阻燃复合材料的性能数据
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均在本发明待批权利要求保护范围之内。
Claims (19)
1.一种多孔硅树脂前驱体溶液,其特征在于,包括阻燃剂、表面活性剂、硅氧烷单体、催化剂、助剂和溶剂;其中,所述多孔硅树脂前驱体溶液是通过如下制备方法得到的:首先将阻燃剂、表面活性剂加入到溶剂中搅拌10~20 min,然后加入硅氧烷单体、催化剂和助剂,再剧烈搅拌30 ~ 300 min,得到多孔硅树脂前驱体溶液;
所述硅氧烷单体选自二甲基二甲氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、二甲基二乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、三甲氧基硅烷基笼型低聚倍半硅氧烷、三乙氧基硅烷基笼型低聚倍半硅氧烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、二苯基二乙氧基硅烷、对甲基苯基三甲氧基硅烷、对甲基苯基三乙氧基硅烷中的三种以上且必须至少含有一种带苯环的硅氧烷单体;三种以上硅氧烷单体以任意比例混合;
所述阻燃剂为氢氧化镁、氢氧化铝、表面羟基改性埃洛石管中的一种或两种;
所述阻燃剂与所述硅氧烷单体的质量比为1 : (5~100);
所述表面活性剂为十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、三乙醇胺硬脂酸酯、氯化十二烷基吡啶、四丁基氟化铵中的一种或多种;
所述表面活性剂与所述硅氧烷单体的质量比为1 : (5 ~ 50);
所述催化剂为酸类催化剂;
所述催化剂与所述硅氧烷单体的物质的量的比为1: (1 ~ 500);
所述助剂为弱碱类物质;
所述助剂与所述硅氧烷单体的物质的量的比为1: (0.25 ~ 5)。
2.根据权利要求1所述的多孔硅树脂前驱体溶液,其特征在于,所述溶剂为水或者醇类。
3.根据权利要求1所述的多孔硅树脂前驱体溶液,其特征在于,所述溶剂为水、乙醇、丙醇中的至少一种。
4.根据权利要求1所述的多孔硅树脂前驱体溶液,其特征在于,所述硅氧烷单体与所述溶剂的质量比为1 : (0.1 ~ 5)。
7.根据权利要求1所述的多孔硅树脂前驱体溶液,其特征在于,所述催化剂为稀盐酸、稀硝酸、冰醋酸、草酸中的至少一种。
8.根据权利要求1所述的多孔硅树脂前驱体溶液,其特征在于,所述催化剂的摩尔浓度为0.005~1.0 mol/L。
9.根据权利要求1所述的多孔硅树脂前驱体溶液,其特征在于,所述助剂为稀氨水、尿素、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、六亚甲基四胺、三聚氰胺中的至少一种。
10.一种多孔硅树脂,其特征在于,所述多孔硅树脂由上述权利要求1-9中任一项所述的多孔硅树脂前驱体溶液经固化工序、干燥工序制备得到。
11.根据权利要求10所述的多孔硅树脂,其特征在于,所述多孔硅树脂的密度为0.1~0.6g/cm3,室温热导率≤0.1W/(m·K),平均孔径为100 nm~500 μm,孔隙率≥50%,极限氧指数≥28%。
12.一种如权利要求10或11所述的多孔硅树脂的制备方法,其特征在于,包括:
(1)多孔硅树脂前驱体溶液的制备:首先将阻燃剂、表面活性剂加入到溶剂中搅拌10~20 min,然后加入硅氧烷单体、催化剂和助剂,再剧烈搅拌30 ~ 300 min,得到多孔硅树脂前驱体溶液;
(2)固化工序:在密封条件下,将上述多孔硅树脂前驱体溶液在60-120℃,保温12-72h进行固化,然后冷却至室温得到多孔硅树脂凝胶;
(3)干燥工序:将步骤(2)湿的多孔硅树脂凝胶进行干燥,得到多孔硅树脂。
13.根据权利要求12所述的多孔硅树脂的制备方法,其特征在于,所述干燥包括:先将步骤(2)湿的多孔硅树脂凝胶进行室温晾置24小时以上,然后在60~80℃的烘箱中干燥48小时以上,直至重量不再减少,得到多孔硅树脂。
14.一种轻质柔性阻燃复合材料,其特征在于,包括轻质柔性纺织品以及分布在所述轻质柔性纺织品表面和孔隙中的如权利要求10或11所述的多孔硅树脂。
15.根据权利要求14所述的轻质柔性阻燃复合材料,其特征在于,所述多孔硅树脂与所述轻质柔性纺织品的质量比为1: (1~9)。
16.根据权利要求14所述的轻质柔性阻燃复合材料,其特征在于,所述轻质柔性阻燃复合材料的密度为0.15~ 0.50 g/cm3,室温热导率为≤0.10W/(m·K),平均孔径为100 nm~500 μm,孔隙率为≥50%,极限氧指数≥30%,拉伸断裂应变≥20%。
17.根据权利要求14所述的轻质柔性阻燃复合材料,其特征在于,所述轻质柔性纺织品为纤柔性二维布、柔性无纺织造立体织物、立体柔性织物中的至少一种。
18.一种如权利要求14-17任一项所述的轻质柔性阻燃复合材料的制备方法,其特征在于,包括:
(1)多孔硅树脂前驱体溶液的制备:首先将阻燃剂、表面活性剂加入到溶剂中搅拌10~20 min,然后加入硅氧烷单体、催化剂和助剂,再剧烈搅拌30 ~ 300min,得到多孔硅树脂前驱体溶液;
(2)浸渍工序:将轻质柔性纺织品真空浸渍于上述多孔硅树脂前驱体溶液中,浸渍压力为0.05-0.5MPa,浸渍时间为30~60 min;
(3)固化工序:在密封条件下,60-120℃保温12-72小时进行固化,然后冷却至室温得到复合材料的凝胶;
(4)干燥工序:将上述复合材料的凝胶进行干燥,得到轻质柔性阻燃复合材料。
19.根据权利要求18所述的轻质柔性阻燃复合材料的制备方法,其特征在于,所述干燥包括:将上述复合材料的凝胶室温晾置24小时以上,然后再在60~80℃的烘箱中干燥48小时以上,直至重量不再减少,得到轻质柔性阻燃复合材料。
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