CN108285536A - 一种有机硅超疏水阻燃材料及其制备方法 - Google Patents
一种有机硅超疏水阻燃材料及其制备方法 Download PDFInfo
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Abstract
本发明属于超疏水材料和阻燃材料领域,具体涉及一种以有机硅为主体的超疏水涂层的制备方法。把八苯基硅倍半氧烷和硝酸进行反应得到八(苯基)倍半硅氧烷。将八(硝基苯基)倍半硅氧烷和三氯化铁、活性炭以及肼反应得到八(氨基苯基)倍半硅氧烷。最后把八(氨基苯基)倍半硅氧烷和聚二甲基硅烷反应得到聚二甲基硅烷包裹的八(氨基苯基)倍半硅氧烷超疏水阻燃材料。本发明制备的聚二甲基硅烷包裹的八(氨基苯基)倍半硅氧烷材料不仅具有超疏水性能还具有阻燃性能,通过浸渍在织物上能够广泛增加织物的应用领域,提高织物的使用价值。本发明所述合成方法简单易行,原料均可工业化生产,具有很好的推广应用价值。
Description
技术领域
本发明属于超疏水材料以及阻燃材料领域,具体涉及一种有机硅超疏水阻燃材料及其制备方法。
背景技术
易燃物的阻燃处理可以延迟点火并且阻止火的传播,因此可以减少火灾的发生。在这些阻燃材料中,阻燃织物引起了关注因为其可以广泛应用在制造业服饰,室内装饰品等。表面修饰方法对织物的内部结构破坏小,是非常好的阻燃改性方向。通常把接触角大于150o并且滚动角小于10o的表面称为超疏水表面。由于水滴在这种表面呈现良好的球形而无法润湿表面,因此使其具有良好的抗腐蚀,防雾,油水分离,自清洁等功能。
因此阻燃性能和超疏水性能的结合可以很大程度上减少织物洗涤的需要并且提供一种可行的办法去解决织物洗涤过程中阻燃成分的析出。增加了织物的适用范围,让织物能在苛刻的条件下使用。
笼状低聚倍半硅氧烷(Polyhedral Oligomeric Silsesquioxane,POSS)是一种以无机Si-O-Si结构为骨架核心,有机基团R包围的且具备三维笼状结构的新型杂化材料;具有对称均一、耐热阻燃、与基体相容性好、安全环保等独特的优点,通过点击化学在POSS表面接枝聚硅烷,制得笼状的低能表面物质。将织物浸渍在该低能表面物质的分散液中,在织物表面形成了具有阻燃效果的超疏水涂层。
发明内容
本发明的目的在于提供一种有机硅超疏水阻燃材料的制备方法。
本发明的目的是将八苯基硅倍半氧烷和硝酸进行反应得到八(硝基苯基)倍半硅氧烷。将八(硝基苯基)倍半硅氧烷和三氯化铁、活性炭以及肼反应得到八(氨基苯基)倍半硅氧烷。最后把八(氨基苯基)倍半硅氧烷和聚二甲基硅烷反应得到聚二甲基硅烷包裹的八(氨基苯基)倍半硅氧烷超疏水阻燃材料。
本发明提出的有机硅超疏水阻燃材料的制备方法,具体步骤如下:
(1)将质量分数为85%~95%的硝酸和八(苯基)倍半硅氧烷(质量比6:1)在冰水浴中反应30min~2h,接着在10~30oC之间反应10~24h;
(2)将步骤(1)所得溶液倒入到沉淀剂A中进行沉淀,把沉淀用溶液B洗涤至中性,得到八(硝基苯基)倍半硅氧烷;其中:沉淀剂A由沉淀剂和有机相组成,沉淀剂:有机相的体积比为(2~5):1;
(3)把步骤(2)得到的八(硝基苯基)倍半硅氧烷和三氯化铁、活性炭以及肼(质量比25:1:15)溶解在溶剂C中,反应在50oC ~150oC,在氮气气氛下冷凝回流3h~10h;
(4)用硅藻土过滤反应后的滤液,加入乙酸乙酯并用水洗涤;将有机层干燥后倒入沉淀剂D中,得到八(氨基苯基)倍半硅氧烷;
(5)将步骤(4)得到的八(氨基苯基)倍半硅氧烷和聚二甲基硅烷(摩尔比1:1)在溶剂E中60oC~120oC下反应8h~18h,得到有机硅超疏水阻燃材料。
本发明中,所述沉淀剂A为甲醇、水或正己烷的一种或几种。
本发明中,所述溶剂B为碳酸钠、水或乙醇的一种或几种。
本发明中,所述溶剂C为四氢呋喃、二氯甲烷或三氯甲烷的一种或几种。
本发明中,所述沉淀剂D为石油醚、甲醇或乙醚的一种或几种。
本发明中,所述溶剂E为四氢呋喃、二氯甲烷或甲苯的一种或几种。
本发明的有益效果在于:原料来源广泛,所使用的八苯基硅倍半氧烷、聚二甲基硅烷、三氯化铁、活性炭、溶剂和沉淀剂等均可工业化生产,合成方法简单易行。制备得到的聚二甲基硅烷包裹的八(氨基苯基)倍半硅氧烷具有超疏水和阻燃性能,通过浸渍在织物上能够提高织物的疏水性和阻燃性,广泛增加织物的应用领域,提高织物的使用价值。
具体实施方式
以下实施例是对本发明的进一步说明,而不是限制本发明的范围。
实施例1
将90ml质量分数为85%的硝酸和15g八(苯基)倍半硅氧烷在冰水浴中反应30min,接着在15oC时反应12h.将溶液倒入沉淀剂冰甲醇(沉淀剂:有机相=2:1,体积比)中进行沉淀,把沉淀用碳酸钠溶液洗涤至中性得到八(硝基苯基)倍半硅氧烷。把5g八(硝基苯基)倍半硅氧烷和40mg三氯化铁、5g活性炭以及肼溶解在二氯甲烷中,反应在70oC下氮气气氛中冷凝回流4h。用硅藻土过滤反应后的滤液加入乙酸乙酯并用水洗涤。将有机层干燥后倒入沉淀剂甲醇中,得到八(氨基苯基)倍半硅氧烷。八(氨基苯基)倍半硅氧烷和聚二甲基硅烷(摩尔比1:1.5,后者体积分数为5%)在四氢呋喃中60oC反应8h,得到有机硅超疏水阻燃材料。
实施例2
将90ml质量分数为90%的硝酸和12g八(苯基)倍半硅氧烷在冰水浴中反应55min,接着在20oC时反应18h.将溶液倒入沉淀剂冰水(沉淀剂:有机相=2:1,体积比)中进行沉淀,把沉淀用碳酸钠溶液洗涤至中性得到八(硝基苯基)倍半硅氧烷。把5g八(硝基苯基)倍半硅氧烷和60mg三氯化铁、3g活性炭以及肼溶解在四氢呋喃中,反应在100oC下氮气气氛中冷凝回流5h。用硅藻土过滤反应后的滤液加入乙酸乙酯并用水洗涤。将有机层干燥后倒入沉淀剂石油醚中,得到八(氨基苯基)倍半硅氧烷。八(氨基苯基)倍半硅氧烷和聚二甲基硅烷(摩尔比1:1.5,后者体积分数为5%)在二氯甲烷中80oC反应10h,得到有机硅超疏水阻燃材料。
实施例3
将90ml质量分数为92%的硝酸和13g八(苯基)倍半硅氧烷在冰水浴中反应75min,接着在25oC时反应11h.将溶液倒入沉淀剂冰水(沉淀剂:有机相=2:1,体积比)中进行沉淀,把沉淀用碳酸钠溶液洗涤至中性得到八(硝基苯基)倍半硅氧烷。把5g八(硝基苯基)倍半硅氧烷和55mg三氯化铁、3.4g活性炭以及肼溶解在四氢呋喃中,反应在60oC下氮气气氛中冷凝回流6h。用硅藻土过滤反应后的滤液加入乙酸乙酯并用水洗涤。将有机层干燥后倒入沉淀剂石油醚中,得到八(氨基苯基)倍半硅氧烷。八(氨基苯基)倍半硅氧烷和聚二甲基硅烷(摩尔比1:1.5,后者体积分数为5%)在甲苯中90oC反应13h,得到有机硅超疏水阻燃材料。
实施例4
将90ml质量分数为91%的硝酸和10g八(苯基)倍半硅氧烷在冰水浴中反应30min,接着在15oC时反应12h.将溶液倒入沉淀剂冰甲醇(沉淀剂:有机相=2:1,体积比)中进行沉淀,把沉淀用乙醇洗涤至中性得到八(硝基苯基)倍半硅氧烷。把5g八(硝基苯基)倍半硅氧烷和40mg三氯化铁、5g活性炭以及肼溶解在二氯甲烷中,反应在70oC下氮气气氛中冷凝回流4h。用硅藻土过滤反应后的滤液加入乙酸乙酯并用水洗涤。将有机层干燥后倒入沉淀剂甲醇中,得到八(氨基苯基)倍半硅氧烷。八(氨基苯基)倍半硅氧烷和聚二甲基硅烷(摩尔比1:1.5,后者体积分数为5%)在四氢呋喃中60oC反应8h,得到有机硅超疏水阻燃材料。
Claims (6)
1.一种有机硅超疏水阻燃材料的制备方法,其特征是具体步骤如下:
(1)将质量分数为85%~95%的硝酸和八(苯基)倍半硅氧烷(质量比6:1)在冰水浴中反应30min~2h,接着在10~30oC之间反应10~24h;
(2)将步骤(1)所得溶液倒入到沉淀剂A中进行沉淀,把沉淀用溶液B洗涤至中性,得到八(硝基苯基)倍半硅氧烷;其中:沉淀剂A由沉淀剂和有机相组成,沉淀剂:有机相的体积比为(2~5):1;
(3)把步骤(2)得到的八(硝基苯基)倍半硅氧烷和三氯化铁、活性炭以及肼(质量比25:1:15)溶解在溶剂C中,反应在50oC ~150oC,在氮气气氛下冷凝回流3h~10h;
(4)用硅藻土过滤反应后的滤液,加入乙酸乙酯并用水洗涤;将有机层干燥后倒入沉淀剂D中,得到八(氨基苯基)倍半硅氧烷;
(5)将步骤(4)得到的八(氨基苯基)倍半硅氧烷和聚二甲基硅烷(摩尔比1:1)在溶剂E中60oC~120oC下反应8h~18h,得到有机硅超疏水阻燃材料。
2.根据权利要求1所述的有机硅超疏水阻燃材料的制备方法,其特征是所述沉淀剂A为甲醇、水或正己烷的一种或几种。
3.根据权利要求1所述的有机硅超疏水阻燃材料的制备方法,其特征是所述溶剂B为碳酸钠、水或乙醇的一种或几种。
4.根据权利要求1所述的有机硅超疏水阻燃材料的制备方法,其特征是所述溶剂C为四氢呋喃、二氯甲烷或三氯甲烷的一种或几种。
5.根据权利要求1所述的有机硅超疏水阻燃材料的制备方法,其特征是所述沉淀剂D为石油醚、甲醇或乙醚的一种或几种。
6.根据权利要求1所述的有机硅超疏水阻燃材料的制备方法,其特征是所述溶剂E为四氢呋喃、二氯甲烷或甲苯的一种或几种。
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