CN112625244B - 一种超支化含磷有机硅膨胀型阻燃剂、制备方法及阻燃高分子涂层组合物 - Google Patents
一种超支化含磷有机硅膨胀型阻燃剂、制备方法及阻燃高分子涂层组合物 Download PDFInfo
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Abstract
本发明公开了一种超支化含磷有机硅膨胀型阻燃剂,具有含硅原子的分子骨架和化学键合到分子骨架的硅原子上的含磷基团,获得步骤为:将具有三个或更多个缩合性官能团的硅烷化合物A与至少一种能与硅烷化合物A的缩合性官能团进行缩合反应的化合物B进行缩合反应,形成超支化含磷硅阻燃剂,化合物B至少含有一个磷元素和至少含有1个能和硅烷化合物A进行缩合反应的可缩合性官能团。阻燃剂在分子层面上集合酸源、碳源和气源为一体,阻燃效率更高。应用到透明阻燃涂料,特别是水性透明阻燃涂料中,其疏水性的有机硅内核能够有效保护磷(氧)阻燃基团不容易被水解,分布在超支化聚合物分子表面的亲水性的基团提供阻燃剂在水中的分散性能。
Description
技术领域
本发明涉及阻燃剂技术领域,涉及一种超支化含磷有机硅膨胀型阻燃剂,及其制备方法。还涉及所述的一种超支化含磷有机硅膨胀型阻燃剂在阻燃高分子涂层组合物中的应用。
背景技术
高分子材料具有质地轻、化学稳定性好、易于加工等优异的特点,已经成为航空航天、交通运输、电工电子、建筑材料的等领域重要的基体材料。但是,绝大部分高分子材料都属于易燃材料,因此高分子材料在提供了便捷的同时也增加了很大的安全隐患。火灾是威胁公共安全的主要灾害之一,每年造成大量的人员伤亡和巨额经济损失。仅 2017 年 1 至10 月,全国共接报火灾 21.9 万起,亡 1065 人、伤 679 人,已核直接财产损失 26.2 亿元。2001年我国颁布和实施了《消防法》,在法律层面上将防火和阻燃要求公共安全是国家安全和社会稳定的基石。
目前最常用最有效的阻燃涂层胶仍然是溴锑型体系。溴锑型阻燃体系在气相阻燃方面性能优异,性价比高,而广受欢迎。向溴化阻燃剂中加入锑,如最常用的氧化锑,实现溴锑协效可大幅提高阻燃体系的阻燃效率并减少阻燃剂的使用量。虽然卤系阻燃剂有很多优异的性能,但含有该阻燃剂的高聚物在燃烧时会释放出来大量的烟及有毒、腐蚀性气体(卤化氢气体),部分在热分解时生成多卤代二苯并二噁烷及多卤代二苯并呋喃的致癌物。多种含溴有机化合物具有生物累积性,会影响生物的神经系统、免疫系统和生殖系统,是一类全球性环境污染物。
膨胀型含磷复合阻燃体系替代溴锑型阻燃剂也是近年来我国阻燃领域广为关注的新型复合阻燃剂。膨胀型复合阻燃剂采用酸源、碳源、气源协同增效阻燃,是阻燃领域又一经典的协效组合。膨胀型阻燃体系可以通过凝聚相阻燃实现高效成炭阻燃。在织物表面形成致密的多孔泡沫炭层,既可阻止内层高聚物的进一步降解及可燃物向表面的释放,又可阻止热源向高聚物的传递以及隔绝氧源,从而阻止火焰的蔓延和传播。膨胀型阻燃剂虽然具有无卤、低烟、低毒、防熔滴和无腐蚀性气体的优点,但在阻燃效率、耐热性和耐水洗性能等方面还不如溴锑阻燃体系。
随着人们对环保和美观的重视,水性透明阻燃涂层需求越来越广泛。然而,目前市场上的含磷无卤阻燃剂在水性透明阻燃涂层中的应用存在各种各样的缺陷。如耐水性、在水中的分散稳定性、透明性、阻燃效率都不尽如人意。目前市场上急需一种集合或部分集合溴锑阻燃体系和膨胀型含磷复合阻燃体系优点并克服它们缺点,无卤的透明阻燃剂体系。
同时,超支化聚合物是具有树枝状的、超支化的、3D结构的,空间结构呈现球形,表面可以构造带有大量不同的活性官能团的聚合物。其特殊的结构赋予了其特殊的性质,目前超支化聚合物已在涂料、阻燃剂、纳米科技、生物材料、工程塑料等诸多领域都显现出巨大的应用价值。
发明内容
本发明提高了一种超支化含磷有机硅膨胀型阻燃剂,该阻燃剂其具有含硅原子的分子骨架和化学键合到所述分子骨架的硅原子上的含磷基团,其中所述超支化含磷有机硅膨胀型阻燃剂是通过如下步骤获得的:将具有三个或更多个缩合性官能团的硅烷化合物A与至少一种能与硅烷化合物A的缩合性官能团进行缩合反应的化合物B进行缩合反应,从而形成所述的超支化含磷有机硅膨胀型阻燃剂;并且所述的化合物B具有如下特征:
c.至少含有一个磷元素,
d.至少含有1个能和硅烷化合物A进行缩合反应的可缩合性官能团。
所述的化合物B具有如下特征:
a.至少含有一个磷元素,
b.至少含有2个能和硅烷化合物A进行缩合反应的可缩合性官能团。
所述的化合物B的能和硅烷化合物A进行缩合反应的可缩合性官能团选自羟基官能团。
所述化合物B选自同时含有至少一个磷元素和至少一个氮元素的化合物或有至少含一个磷元素的化合物和至少含一个氮元素的化合物的混合物 。
所述化合物B为含有至少一个磷元素或至少同时含有一个磷元素和一个氮元素的多元醇或多元酚或其混合物,可选自如下结构的化合物:
所述具有三个或更多个缩合性官能团的硅烷化合物包括四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四丁氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、苯基三甲氧基硅烷、十六烷基三甲氧基硅烷、辛基三乙氧基硅烷、巯丙基三甲氧基硅烷、N-氨酰基-3-氨丙基三乙氧基硅烷、胺丙基三乙氧基硅烷、乙烯基三乙氧基硅烷、缩水甘油醚氧基丙基三甲氧基硅烷、甲基三乙酰氧基硅烷、甲基三丁酮肟基硅烷、甲基三异丙烯氧硅烷、α-单甲基,ω-三甲氧基聚二甲基硅氧烷、α-单甲基,ω-三乙氧基聚二甲基硅氧烷或α-单甲基,ω-三丙氧基聚二甲基硅氧烷或上述化合物的组合。
所述化合物B为N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯,结构式如下:
所述硅烷化合物A与化合物B进行的缩合反应在无溶剂条件下进行。
所述硅烷化合物A与化合物B进行的缩合反应在无催化剂条件下进行。
超支化含磷有机硅膨胀型阻燃剂的制备方法为:
将具有三个或更多个缩合性官能团的硅烷化合物A与至少一种羟基化合物B进行缩合反应,从而形成超支化含磷有机硅膨胀型阻燃剂;其中,所述具有三个或更多个缩合性官能团的硅烷化合物A的缩合性官能团和所述羟基化合物B的羟基的摩尔比在1:4至4:1的范围内,优选的在1:3至3:1的范围内,更优选的在1:2.5至2.5:1的范围内;并且所述的羟基化合物B含有至少一个磷元素。
尽管并不希望受缚于任何理论,发明人相信,过量的硅烷化合物A(如:四乙氧基硅烷)和羟基化合物B(如:二元醇)按照如下示意式(I)所表示的反应:
尽管并不希望受缚于任何理论,发明人相信,硅烷化合物A(如:四乙氧基硅烷)和过量的羟基化合物B(如:二元醇)按照如下示意式(II)所表示的反应:
其中Ο代表羟基化合物的骨架。
所述能与硅烷化合物A的缩合性官能团进行缩合反应的羟基化合物B选自同时含有至少一个磷元素和至少一个氮元素的化合物或有至少含一个磷元素的化合物和至少含一个氮元素的化合物的混合物 。
本发明制备方法被描述为包括或包含特定工艺步骤的情况下,预计该方法中并不排除本发明未涉及的可选工艺步骤,并且预计该方法可由所涉及的工艺步骤构成或组成。例如,作为本发明的一种用于制备含磷氧基官能化的硅基树脂的方法的其中一个的反应式示意式E如下所示:
一种阻燃高分子涂层组合物,其包含权利要求1-11中任意一项所述的超支化含磷有机硅膨胀型阻燃剂、任选成膜物质、任选阻燃剂、附加添加剂。
本发明的超支化含磷氮有机硅阻燃剂在分子层面上集合酸源、碳源和气源为一体,阻燃效率更高。应用到透明阻燃涂料,特别是水性透明阻燃涂料中,其疏水性的有机硅内核能够有效保护磷(氧)阻燃基团不容易被水解,分布在超支化聚合物分子表面的亲水性的基团提供阻燃剂在水中的分散性能。
附图说明
图1是实施例1反应原料和反应产物的FTIR图谱;
图2是实施例3反应原料和反应产物的FTIR图谱;
图3是实施例4反应原料和反应产物的FTIR图谱;
图4是实施例5所制试样燃烧20s后的效果图;
图5是实施例6所制试样燃烧20s后的效果图。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,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。
1.实施例1
具体实施例如下:将83.4g(0.40mol)的四乙氧基硅烷和89.2g(0.35mol) 的N,N-二羟乙基胺甲基膦酸二乙酯在室温下添加到安装有温度计、顶部搅拌器、气体入口和蒸馏装置的四口烧瓶中。该反应在通过反应器的气体入口引入的无水氮气流的保护下进行。然后将反应混合物加热至150℃,并且保持在该温度下,直到有馏出物从反应混合物中馏出。继续加热并且逐步将反应混合物的温度升高至180℃,直到乙醇馏出完全。所得的硅基树脂上引入含磷(氧)含氮基,从而形成含磷 (氧)含氮基官能化的硅基树脂。
这样,得到含有羟基的磷氮一体化超支化聚硅氧烷。其红外图谱FTIR结果示于图1中(TEOS:四乙氧基硅烷;FR-6:N,N-二羟乙基胺甲基膦酸二乙酯;CZH-1:反应产物,即磷氮一体化超支化聚硅氧烷)。
2.实施例2
本发明的一个实施方式中,四乙氧基硅烷作为具有三个或更多个缩合性官能团的硅烷化合物。N,N-二羟乙基胺甲基膦酸二乙酯作为多元醇,且该多元醇具有含量较高的磷、氮阻燃元素,增大其含量理论上可进一步增强反应产物的阻燃效果。
将41.7g (0.20mol) 的四乙氧基硅烷和178.4g (0.70mol) 的N,N-二羟乙基胺甲基膦酸二乙酯在室温下添加到安装有温度计、顶部搅拌器、气体入口和蒸馏装置的四口烧瓶中。该反应在通过反应器的气体入口引入的无水氮气流的保护下进行。然后将反应混合物加热至150℃,并且保持在该温度下,直到有馏出物从反应混合物中馏出。继续加热并且逐步将反应混合物的温度升高至180℃,直到乙醇馏出完全。这样,得到含有羟基的高磷氮含量的一体化超支化聚硅氧烷。
3.实施例3
具体实施例如下:将83.4g (0.40mol) 的四乙氧基硅烷和129.6g (0.40mol) 的DOPO-HQ在室温下添加到安装有温度计、顶部搅拌器、气体入口和蒸馏装置的四口烧瓶中。该反应在通过反应器的气体入口引入的无水氮气流的保护下进行。然后将反应混合物加热至150℃,并且保持在该温度下,直到有馏出物从反应混合物中馏出。继续加热并且逐步将反应混合物的温度升高至180℃,直到乙醇馏出完全。这样,得到含有羟基的含磷基官能团化超支化聚硅氧烷。其红外图谱FTIR结果示于图2中(TEOS:四乙氧基硅烷;DOPO-HQ:10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物;CZH-2:反应产物,即含有羟基的含磷基官能团化超支化聚硅氧烷);
4.实施例4
具体实施例如下:将62.6g (0.30mol) 的四乙氧基硅烷和75.5g (0.23mol)DOPO-HQ,60.8g (0.23mol) 的三羟乙基异氰尿酸酯在室温下添加到安装有温度计、顶部搅拌器、气体入口和蒸馏装置的四口烧瓶中。该反应在通过反应器的气体入口引入的无水氮气流的保护下进行。然后将反应混合物加热至150℃,并且保持在该温度下,直到有馏出物从反应混合物中馏出。继续加热并且逐步将反应混合物的温度升高至180℃,直到乙醇馏出完全。这样,得到含有羟基的含磷氮基官能团化超支化聚硅氧烷。其红外图谱FTIR结果示于图3中(TEOS:四乙氧基硅烷; CZH-3:反应产物,即含有羟基的含磷氮基官能团化超支化聚硅氧烷);
5.实施例5
在本发明的另一方面中,提供了一种环保无卤织物阻燃涂层胶,其包含本发明所述的一种超支化含磷(氧)基官能化的硅基树脂阻燃剂,将其与其他阻燃剂和丙烯酸酯乳液复配制备,用于涤纶沙发布阻燃。
将环状磷酸酯(PCU)、聚磷酸铵II型(APP)、本发明实施例1制备的超支化阻燃剂(CZH-1)、硼酸锌、三嗪成炭剂(CFA)、酚醛树脂按照1.5:5.0:2.0:2.0:2.5:2.0的质量配比,总用量为15.0g,加入到调和容器中,另加入26g丙烯酸酯乳液(乳液固含量为50%),加入15g水、0.5g乳化剂和0.5g消泡剂,高速研磨分散均匀,制得阻燃涂层胶。
将上述阻燃涂层胶刮涂到织物背面(织物为本白涤纶布,克重200g,即每平方米布的重量为200g),烘焙(150℃,180s),得到低烟毒高效率阻燃涤纶沙发纺织织物,克增重为100.3g(即每平方米布涂覆质量为100.3g的涂层胶)。
6.对比实施例6
重复实施例5,把本发明的超支化含磷有机硅膨胀型阻燃剂(CZH-1)等量替换为APP。对比样为环状磷酸酯(PCU)、疏水性聚磷酸铵(APP)、硼酸锌、三嗪成炭剂(CFA)、酚醛树脂按照1.5:7.0: 2.0:2.5:2.0的质量配比,总用量为15.0g,其他步骤相同,同样将阻燃涂层胶刮涂到本白涤纶布背面,克增重为100.4g。
参考BS5852阻燃测试标准,将试样分别覆盖于规定的聚氨酯海绵,并置于规定的燃烧器下点燃,丁烷火焰高度35mm,稳定火苗30s后,用火焰持续燃烧试样20s,测试试样的阻燃性能。其中含超支化阻燃剂的式样燃烧20s后离火即熄,通过BS5852标准;未添加超支化阻燃剂的对比试样20s内烧穿,且火焰持续燃烧不自熄,不能通过标准。
7.实施例7
重复实施例5,把本发明的超支化含磷有机硅膨胀型阻燃剂(CZH-1)替换成本发明的其它超支化含磷有机硅膨胀型阻燃剂,也得到类似的阻燃效果。
以上所述,仅是本发明的较佳实施例而已,并非对本发明的技术方案作任何形式上的限制。凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均落入本发明的保护范围内。
Claims (6)
1.一种超支化含磷有机硅膨胀型阻燃剂,其具有含硅原子的分子骨架和化学键合到所述分子骨架的硅原子上的含磷基团,其特征在于:所述超支化含磷有机硅膨胀型阻燃剂是通过如下步骤获得的:将具有三个或更多个缩合性官能团的硅烷化合物A与至少一种羟基化合物B进行缩合反应,从而形成所述的超支化含磷有机硅膨胀型阻燃剂;所述硅烷化合物A与羟基化合物B进行的缩合反应在无溶剂、无催化剂条件下进行,并且所述的羟基化合物B具有如下特征:
所述羟基化合物B为含有至少一个磷元素或至少同时含有一个磷元素和一个氮元素的多元醇或多元酚或其混合物,选自如下结构的化合物:
所述具有三个或更多个缩合性官能团的硅烷化合物A包括四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四丁氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、苯基三甲氧基硅烷、十六烷基三甲氧基硅烷、辛基三乙氧基硅烷、巯丙基三甲氧基硅烷、N-氨酰基-3-氨丙基三乙氧基硅烷、胺丙基三乙氧基硅烷、乙烯基三乙氧基硅烷、缩水甘油醚氧基丙基三甲氧基硅烷、甲基三乙酰氧基硅烷、甲基三丁酮肟基硅烷、甲基三异丙烯氧硅烷、α-单甲基,ω-三甲氧基聚二甲基硅氧烷、α-单甲基,ω-三乙氧基聚二甲基硅氧烷或α-单甲基,ω-三丙氧基聚二甲基硅氧烷或上述化合物的组合。
2.根据权利要求1所述的超支化含磷有机硅膨胀型阻燃剂,其特征在于:其制备方法为:
将具有三个或更多个缩合性官能团的硅烷化合物A与至少一种羟基化合物B进行缩合反应,从而形成超支化含磷有机硅膨胀型阻燃剂;其中,所述具有三个或更多个缩合性官能团的硅烷化合物A的缩合性官能团和所述羟基化合物B的羟基的摩尔比在1:4至4:1的范围内;并且所述的羟基化合物B含有至少一个磷元素。
3.根据权利要求2所述的超支化含磷有机硅膨胀型阻燃剂,其特征在于:所述具有三个或更多个缩合性官能团的硅烷化合物A的缩合性官能团和所述羟基化合物B的羟基的摩尔比在1:3至3:1的范围内。
4.根据权利要求3所述的超支化含磷有机硅膨胀型阻燃剂,其特征在于:所述具有三个或更多个缩合性官能团的硅烷化合物A的缩合性官能团和所述羟基化合物B的羟基的摩尔比在1:2.5至2.5:1的范围内。
6.一种阻燃高分子涂层组合物,其特征在于:其包含权利要求1-5中任意一项所述的超支化含磷有机硅膨胀型阻燃剂、任选成膜物质、任选阻燃剂、附加添加剂。
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