CN112538148B - 一种硅溴协同反应型阻燃剂及其制备方法、热塑性聚氨酯弹性体及其制备方法 - Google Patents
一种硅溴协同反应型阻燃剂及其制备方法、热塑性聚氨酯弹性体及其制备方法 Download PDFInfo
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- CN112538148B CN112538148B CN201910889631.6A CN201910889631A CN112538148B CN 112538148 B CN112538148 B CN 112538148B CN 201910889631 A CN201910889631 A CN 201910889631A CN 112538148 B CN112538148 B CN 112538148B
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Abstract
本发明涉及一种硅溴协同反应型阻燃剂及其制备方法、热塑性聚氨酯弹性体及其制备方法，所述硅溴协同反应型阻燃剂通过四溴双酚A双(2‑羟乙基)醚和二甲基二卤硅烷在催化剂一的催化下制备而成，该热塑性聚氨酯弹性体的制备方法为：将聚多元醇、扩链剂、硅溴协同反应型阻燃剂、二异氰酸酯、催化剂加入反应器中，充分混合反应制备硅溴协同阻燃热塑性聚氨酯弹性体。本发明的硅溴协同阻燃热塑性聚氨酯同时引入硅、溴两种元素，两种元素通过不同的阻燃机理进行协同增效阻燃。本发明的硅溴协同阻燃热塑性聚氨酯还具备较好的疏水性能，可以广泛应用于电线和电缆护套、薄膜、纤维、汽车中的面板、电缆插头、牵引索、垫圈、泡沫、水管、消防水袋等领域。
Description
技术领域
本发明涉及阻燃剂及聚氨酯领域，具体涉及一种硅溴协同反应型阻燃剂及其制备方法、热塑性聚氨酯弹性体及其制备方法。
背景技术
热塑性聚氨酯弹性体广泛应用于电线和电缆护套、薄膜、纤维、汽车中的面板、电缆插头、牵引索、垫圈、泡沫、水管、消防水袋。但热塑性聚氨酯弹性体属于易燃物质，遇火会燃烧并引发火灾，对生命财产安全造成威胁。因此，制备阻燃热塑性聚氨酯弹性体具有重要意义。制备阻燃热塑性弹性体可以引入阻燃剂，其中阻燃剂可以分为添加型阻燃剂和反应型阻燃剂。采用添加型阻燃剂生产热塑性聚氨酯工艺简单，现有技术多采用添加型阻燃剂为主，但是添加型阻燃剂存在添加量大、易迁移析出等缺点，前者会导致产品成本增加，后者会导致聚氨酯阻燃效果逐渐变差。反应型阻燃剂克服了添加型阻燃剂易迁移析出、不能持久保持阻燃效果、相容性差的缺点，而且反应型阻燃剂稳定性好、添加量小、阻燃效率高、毒性低，对聚合物的力学性能影响也小。
中国专利授权公告号CN103429646B和CN103476821B公开了采用反应型阻燃剂制备软质聚氨酯泡沫的方法。其中反应型阻燃剂为环上溴代的芳香族化合物的二酯二醇，包括四溴代邻苯二甲酸与C2至C6的多羟脂肪醇和C2至C8的氧化烯的一种二酯，例如四溴代邻苯二甲酸与二乙二醇和氧化乙烯或氧化丙烯的一种二酯。但是该反应型阻燃剂只有溴元素发挥阻燃作用，存在阻燃效果差的缺点。
中国专利授权公告号CN102585140B公开了采用反应型阻燃剂四溴双酚A双(烯丙基)醚作为一种反应型阻燃剂制备阻燃聚氨酯组合物、阻燃聚氨酯泡沫材料的方法。但是该反应型阻燃剂需和乙烯类单体共聚，并且需引发剂诱导聚合反应才能引入聚氨酯中，对反应体系要求高，反应过程复杂，且形成的聚氨酯为交联结构，不易回收利用。
发明内容
本发明的一个目的在于提供一种硅溴协同反应型阻燃剂及其制备方法，该阻燃剂为硅溴协同反应型阻燃剂，同时引入了硅、溴两种元素，从不同的阻燃机理产生协同阻燃作用，阻燃效果好。
本发明的另一个目的在于提供一种热塑性聚氨酯弹性体及其制备方法，该热塑性聚氨酯弹性体具备优异的拉伸强度、撕裂强度；并具备良好的阻燃性能和疏水性能，耐水解性高。
为达到以上目的，本发明采用如下技术方案：
本发明提供一种硅溴协同反应型阻燃剂，其结构式为：
其中n为1-10的一个整数，优选为1-6的一个整数，更优选1-3的一个整数。
本发明还提供一种硅溴协同反应型阻燃剂的制备方法，其步骤为：
将四溴双酚A双(2-羟乙基)醚、催化剂一和有机溶剂混合均匀，并通保护气，然后加入二甲基二卤硅烷，优选二甲基二氯硅烷，在45℃-90℃，优选60-70℃下充分反应。其中，保护气优选氮气。
四溴双酚A双(2-羟乙基)醚具备一定的阻燃效果，和二甲基二卤硅烷反应后，引入硅氧基团，其中硅氧基团能够促进材料在高温下成炭，显著提高材料的抗高温氧化性能，从而达到硅溴协同阻燃目的。
本发明的一些优选实施方式中，所述的硅溴协同反应型阻燃剂的制备方法为：将四溴双酚A双(2-羟乙基)醚、催化剂一和有机溶剂在室温下混合均匀，并通氮气保护，向四溴双酚A双(2-羟乙基)醚的溶液中加入二甲基二氯硅烷，并在60-70℃下充分反应。反应结束后，抽滤，滤液加入蒸馏水洗涤、分液，分离出的有机层用干燥剂进行干燥，过滤除去干燥剂。得到的滤液进行减压蒸馏，除去有机溶剂，粗产物经柱层析(氯仿/石油醚)提纯获得产物。
本发明的一些优选实施方式中，二甲基二卤硅烷通过注射泵加入到四溴双酚A双(2-羟乙基)醚的溶液中，加入速度为10mL/h-50mL/h，优选的，注射过程中控制溶液温度小于40℃。
本发明的一些优选实施方式中，所述四溴双酚A双(2-羟乙基)醚与二甲基二卤硅烷的摩尔比为1.1:1-2:1，优选(m+1)：m，其中m为1-10的一个整数，更优选的m＝n。
本发明的一些优选实施方式中，所述四溴双酚A双(2-羟乙基)醚与二甲基二卤硅烷的摩尔比为2:1、3:2、4:3、5:4、6:5、7:6、8:7、9:8、10:9、11:10，分别获得二甲基硅基数目n＝1、2、3、4、5、6、7、8、9、10的硅溴协同反应型阻燃剂，优选二甲基硅基数目n＝1、2、3。本发明中，所述催化剂一为碱性催化剂，例如三乙胺、氢氧化钠或氢氧化钾中的一种或多种，更优选三乙胺。
本发明中，所述催化剂一与二甲基二卤硅烷的摩尔比为2-2.6，优选2.1-2.3。
本发明还提供一种硅溴协同阻燃热塑性聚氨酯弹性体，由包括以下原料的反应制得：
所述硅溴协同反应型阻燃剂为上述的硅溴协同反应型阻燃剂或上述制备方法制备的硅溴协同反应型阻燃剂。
本发明中，所述多异氰酸酯为芳香族多异氰酸酯、脂肪族多异氰酸酯、脂环族多异氰酸酯中的一种或几种；优选的多异氰酸酯包括4,4’-二苯基甲烷二异氰酸酯、2,4-二苯基甲烷二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,5-萘二异氰酸酯、1,4-苯二异氰酸酯、间苯二亚甲基二异氰酸酯、二苯甲烷-3,3’-二甲氧基-4,4’-二异氰酸酯、1,6-六亚甲基二异氰酸酯、1,10-癸二异氰酸酯、1,3-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、2,4-六氢甲苯二异氰酸酯、2,6-六氢甲苯二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、2,2’-二环己基甲烷二异氰酸酯和2,4-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种，更优选4,4’-二苯基甲烷二异氰酸酯。
本发明中，所述聚多元醇为聚醚型多元醇、聚酯型多元醇或聚碳酸酯型多元醇，聚醚多元醇优选为聚氧化丙烯、聚四氢呋喃、共聚醚多元醇中的一种或几种，更优选聚四氢呋喃；所述聚酯型多元醇为聚己二酸乙二醇酯、聚己二酸-1,2-丙二醇酯、聚己二酸-1,4-丁二醇酯、聚己二酸乙二醇丙二醇酯、聚己二酸新戊二醇酯、聚己二酸-1,6-己二醇酯、聚己二酸二乙二醇酯、聚邻苯二甲酸乙二醇酯、聚邻苯二甲酸二乙二醇酯、聚邻苯二甲酸-1,4-丁二醇酯、聚邻苯二甲酸-1,6-己二醇酯、聚间苯二甲酸乙二醇酯、聚间苯二甲酸二乙二醇酯、聚间苯二甲酸-1,4-丁二醇酯、聚间苯二甲酸-1,6-己二醇酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸二乙二醇酯、聚对苯二甲酸-1,4-丁二醇酯、聚对苯二甲酸-1,6-己二醇酯、聚己二酸-1,2-丙二醇酯、聚β-丙内酯、聚γ-丁内酯、聚ε-己内酯、聚甲基-ε-己内酯中的一种或几种，更优选聚己二酸乙二醇酯、聚己二酸-1,2-丙二醇酯、聚己二酸-1,4-丁二醇酯、聚己二酸乙二醇丙二醇酯；所述聚碳酸酯多元醇为二醇和二芳基碳酸酯如碳酸二苯酯、碳酸亚烷基酯或碳酰氯反应的产物，合适的二醇包括1,2-乙二醇，1,3-丙二醇，1,4-丁二醇，1,5-戊二醇，1,6-己二醇，二甘醇或者四甘醇中的一种或几种。更优选为1,4-丁二醇和/或1,5-戊二醇。
本发明中，所述小分子扩链剂为脂肪族和/或芳香族小分子扩链剂，优选乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,2-戊二醇、1,3-戊二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、二乙二醇、三乙二醇、二丙二醇、三丙二醇、1,4-二(羟基甲基)苯、1,4-二(羟基乙基)苯、1,4-二(2-羟基乙氧基)苯中的一种或几种，更优选乙二醇、1,4-丁二醇、1,6-己二醇作为扩链剂。
本发明中，所述热塑性聚氨酯弹性体的原料还包括催化剂二，所述催化剂二的加入量为0.0001-8wt％，优选为0.0003-5wt％，基于聚氨酯总重量。所述的催化剂二包括有机金属化合物，优选为以下化合物：钛酯、铁化合物，例如乙酰丙酮铁；锡化合物，例如乙酸亚锡、辛酸亚锡、二月桂酸亚锡或有机羧酸的二烷基锡盐，所述有机羧酸的二烷基锡盐优选二乙酸二丁基锡、二月桂酸二丁基锡、二乙酸二辛基锡或其混合物；碱金属氢氧化物，如氢氧化钠；碱金属醇化物，如甲醇钠和异丙醇钾；强碱性胺催化剂：脒，例如2,3-二甲基-3,4,5,6-四氢嘧啶；叔胺，例如三乙胺、三丁胺、二甲基苄胺、二环己基甲基胺、二甲基环己基胺、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-四甲基丁二胺、N,N,N’,N’-四甲基已二胺、五甲基二亚乙基三胺、N-甲基吗啉、N-乙基吗啉和N-环已基吗啉、四甲基二氨基乙基醚；酸性催化剂如磷酸、苯甲酰氯。催化剂二可单独使用或作为混合物使用。本发明使用的催化剂二更优选辛酸亚锡、二月桂酸二丁基锡和磷酸。
本发明还提供上述聚氨酯弹性体的制备方法，包括以下步骤：将聚多元醇、扩链剂、硅溴协同反应型阻燃剂、二异氰酸酯、催化剂二加入反应器中，充分混合反应制备硅溴协同阻燃热塑性聚氨酯弹性体。
本发明的聚氨酯弹性体还可采用其他本领域公知的制备方法制得，其反应原料包含上述硅溴协同反应型阻燃剂，在此不作赘述。本发明的阻燃热塑性聚氨酯弹性体能够应用于对阻燃要求较高的电线和电缆护套、薄膜、纤维、电缆插头、汽车中的面板、电缆插头、牵引索、垫圈、泡沫等领域，也能用于水管、消防水袋等领域。
与现有技术相比，本发明的有益效果在于：
一、本发明采用硅溴协同反应型阻燃剂制备热塑性聚氨酯，阻燃剂被固定在聚氨酯主链中，成为聚氨酯的一部分，克服了添加型阻燃剂易迁移析出的缺点，能够持久阻燃。
二、本发明采用的硅溴协同反应型阻燃剂不同于添加型阻燃剂，不存在和聚合物材料相容性差的问题，对聚合物材料本身的力学性能影响小。
三、本发明的热塑性聚氨酯为阻燃型热塑性聚氨酯，引入了硅、溴两种元素，硅能促进材料在高温下成炭；溴在燃烧过程中生成溴化氢，起到气相阻燃作用。硅、溴两种元素协同阻燃，通过这种硅溴协同反应型阻燃剂制备的产品耐热性好，氧指数高，不易燃烧，具有出色的阻燃性能。
四、本发明的阻燃型热塑性聚氨酯由于引入了新的硅溴协同反应型阻燃剂，具有优异的疏水性能，材料的耐水解性提高。相比普通的聚氨酯，接触角增大5°到9°，疏水性的提高，有助于提高材料的耐水解性，对于需要长期浸水的聚氨酯材料具有重要价值，如聚氨酯消防水袋、聚氨酯水管等。
附图说明
为了进一步说明产品的结构和性能特给出如下附图。
图1为实施例1制备的硅溴协同反应型阻燃剂A的红外光谱；
图1表明，3080cm-1处的信号峰为苯环上C-H的伸缩振动吸收峰，2985-2864cm-1处的信号峰为饱和C-H伸缩振动吸收峰，位于1000-1100cm-1处的信号峰为Si-O和C-O伸缩振动吸收峰重叠。位于1587cm-1、1537cm-1、1468cm-1、1444cm-1处的信号峰为苯环骨架振动吸收峰。
图2为实施例1制备的硅溴协同反应型阻燃剂A的核磁谱图；
图2表明，氘代二甲基亚砜做溶剂，7.49ppm处为苯环上质子信号峰，4.0ppm附近为苯环醚键邻位亚甲基质子信号峰的重叠，3.8ppm处为另外亚甲基质子信号峰的重叠，0.08ppm处为-Si(CH3)2的质子信号峰，2.5ppm处为氘代二甲基亚砜甲基质子信号峰，3.3ppm处为氘代二甲基亚砜中水的信号峰。
具体实施方式
下面我们结合具体的实施例对本发明做进一步的详细阐述，但是本发明的范围并不限于这些实施例。在不脱离本发明上述方法思想的情况下，根据本领域普通技术知识和惯用手段做出的各种替换或变更，均应包含在本发明的范围内。
原料来源：
四溴双酚A双(2-羟乙基)醚，阿拉丁试剂(上海)有限公司。
聚四氢呋喃二醇，Hannong Chemicals INC.，数均分子量为1000g/mol。
聚己二酸乙二醇酯二醇，万华化学集团股份有限公司，数均分子量为2000g/mol。
聚己二酸-1,2-丙二醇酯二醇，万华化学集团股份有限公司，数均分子量为5000g/mol。
聚己二酸-1,4-丁二醇酯二醇，万华化学集团股份有限公司，数均分子量为1000g/mol。
聚己二酸乙二醇丙二醇酯二醇，万华化学集团股份有限公司，数均分子量为2000g/mol。
实施例1
硅溴协同反应型阻燃剂A的制备：
在氮气保护下，向装有冷凝管的1L三口烧瓶中，加入四溴双酚A双(2-羟乙基)醚(101.1g，160mmol)、600mL甲苯和三乙胺(17.8g，176mmol)，并搅拌均匀。通过注射泵向四溴双酚A双(2-羟乙基)醚的溶液中加入二甲基二氯硅烷(10.3g，80mmol)，注射速率30mL/h，注射过程中控制反应温度不高于40℃。注射完毕后，将反应体系升温至65℃，保温8h，保证充分反应。反应结束后，冷却至室温，抽滤，滤液分别加入50mL蒸馏水，洗涤三次，分液。甲苯层用无水硫酸钠干燥，过滤除去无水硫酸钠，取滤液，通过减压蒸馏除去滤液中的甲苯，得粗产物。粗产物经柱层析(氯仿/石油醚)提纯得产物硅溴协同反应型阻燃剂A。
本实施例中四溴双酚A双(2-羟乙基)醚与二甲基二氯硅烷的摩尔比为2:1，三乙胺与二甲基二氯硅烷的摩尔比2.2:1，制备二甲基硅基数目n＝1的硅溴协同反应型阻燃剂A。
实施例2
硅溴协同反应型阻燃剂B：其制备方法与阻燃剂A的不同之处在于，四溴双酚A双(2-羟乙基)醚的加入量为94.8g，甲苯的加入量为600mL，三乙胺的加入量为21.2g，二甲基二氯硅烷的加入量为12.9g，得到的产物二甲基硅基数目n＝2。
实施例3
硅溴协同反应型阻燃剂C：其制备方法与阻燃剂A的不同之处在于，四溴双酚A双(2-羟乙基)醚的加入量为88.5g，甲苯的加入量为600mL，三乙胺的加入量为27.9g，二甲基二氯硅烷的加入量为15.5g，得到的产物二甲基硅基数目n＝6。
实施例4
硅溴协同反应型阻燃剂D：其制备方法与阻燃剂A的不同之处在于，四溴双酚A双(2-羟乙基)醚的加入量为69.5g，甲苯的加入量为600mL，三乙胺的加入量为22.3g，二甲基二氯硅烷的加入量为12.9g，得到的产物二甲基硅基数目n＝10。
硅溴协同阻燃热塑性聚氨酯弹性体制备实施例：
实施例5
将55份数均分子量为1000g/mol聚四氢呋喃二醇，6.99份1,4-丁二醇，3.50份硅溴协同反应型阻燃剂A，34.51份4,4’-二苯基甲烷二异氰酸酯和辛酸亚锡(13ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
实施例6
将60份数均分子量为2000g/mol聚己二酸乙二醇酯二醇，6.38份1,4-丁二醇，7.01份硅溴协同反应型阻燃剂B，26.61份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
实施例7
将38份数均分子量为5000g/mol聚己二酸-1,2-丙二醇酯二醇，11.16份1,4-丁二醇，14.5份硅溴协同反应型阻燃剂A，36.34份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
实施例8
将45份数均分子量为1000g/mol聚己二酸-1,4-丁二醇酯二醇，7.33份1,4-丁二醇，14.65份硅溴协同反应型阻燃剂C，33.02份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
实施例9
将63份数均分子量为2000g/mol聚己二酸乙二醇丙二醇酯二醇，5.80份1,4-丁二醇，5.63份硅溴协同反应型阻燃剂A，25.57份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
实施例10
将38份数均分子量为1000g/mol聚己二酸-1,4-丁二醇酯二醇，12.96份1,4-丁二醇，3.42份硅溴协同反应型阻燃剂D，45.62份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
对比例1
将55份数均分子量为1000g/mol聚四氢呋喃二醇，8.08份1,4-丁二醇，36.92份4,4’-二苯基甲烷二异氰酸酯和辛酸亚锡(13ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
对比例2
将60份数均分子量为2000g/mol聚己二酸乙二醇酯二醇，8.44份1,4-丁二醇，31.56份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
对比例3
将38份数均分子量为5000g/mol聚己二酸-1,2-丙二醇酯二醇，15.67份1,4-丁二醇，46.33份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
对比例4
将45份数均分子量为1000g/mol聚己二酸-1,4-丁二醇酯二醇，11.35份1,4-丁二醇，43.65份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
对比例5
将63份数均分子量为2000g/mol聚己二酸乙二醇丙二醇酯二醇，7.56份1,4-丁二醇，29.44份4,4’-二苯基甲烷二异氰酸酯和磷酸(4ppm)加入反应器，加热至80℃，采用桨式搅拌器高速搅拌，充分反应后迅速倒入模具中，放入80℃烘箱中熟化12h，冷却、粉碎。通过注塑加工制备试片，裁制不同形状的样条，进行基础物性的测试。阻燃性通过氧指数来衡量，接触角通过接触角测量仪测试。
实施例的力学性能和阻燃性能等见表1。
表1
对比例的力学性能和阻燃性能等见表2。
表2
通过表1和表2，从对比例与实施例的对比可以看出：在聚氨酯配方中加入硅溴协同反应型阻燃剂后，聚氨酯的力学性能没有显著变化，但是聚氨酯的氧指数有明显提高，接触角变大，疏水性增强。
Claims (21)
1.一种硅溴协同反应型阻燃剂，其特征在于，其结构式为：
其中n为1-10的一个整数。
2.根据权利要求1所述的阻燃剂，其特征在于，n为1-6的一个整数。
3.根据权利要求2所述的阻燃剂，其特征在于，n为1-3的一个整数。
4.一种权利要求1所述的硅溴协同反应型阻燃剂的制备方法，其特征在于，该制备方法为：
将四溴双酚A双(2-羟乙基)醚、催化剂一和有机溶剂混合均匀，并通保护气，然后加入二甲基二卤硅烷，在45℃-90℃下充分反应。
5.根据权利要求4所述的制备方法，其特征在于，所述二甲基二卤硅烷为二甲基二氯硅烷。
6.根据权利要求4所述的制备方法，其特征在于，反应温度为60-70℃。
7.根据权利要求4所述的制备方法，其特征在于，所述二甲基二卤硅烷的加入速度为10mL/h-50mL/h。
8.根据权利要求4所述的制备方法，其特征在于，所述四溴双酚A双(2-羟乙基)醚与二甲基二卤硅烷的摩尔比为1.1:1-2:1。
9.根据权利要求8所述的制备方法，其特征在于，所述四溴双酚A双(2-羟乙基)醚与二甲基二卤硅烷的摩尔比为(m+1)：m，其中m为1-10的一个整数。
10.根据权利要求9所述的制备方法，其特征在于，m＝n。
11.根据权利要求4所述的制备方法，其特征在于，所述催化剂一为碱性催化剂。
12.根据权利要求11所述的制备方法，其特征在于，所述催化剂一为三乙胺、氢氧化钠或氢氧化钾中的一种或多种。
13.根据权利要求4所述的制备方法，其特征在于，所述催化剂一与二甲基二卤硅烷的摩尔比为2-2.6。
14.根据权利要求13所述的制备方法，其特征在于，所述催化剂一与二甲基二卤硅烷的摩尔比为2.1-2.3。
15.一种热塑性聚氨酯弹性体，其特征在于，由包括以下原料的反应制得：
所述硅溴协同反应型阻燃剂为权利要求1-3任一项所述的硅溴协同反应型阻燃剂或权利要求4-14任一项所述制备方法制备的硅溴协同反应型阻燃剂。
16.根据权利要求15所述的热塑性聚氨酯弹性体，其特征在于，由包括以下原料的反应制得：
17.根据权利要求15所述的热塑性聚氨酯弹性体，其特征在于，所述热塑性聚氨酯弹性体的原料还包括催化剂二，所述催化剂二的加入量为0.0001-8wt％，基于聚氨酯总重量。
18.根据权利要求17所述的热塑性聚氨酯弹性体，其特征在于，所述催化剂二的加入量为0.0003-5wt％，基于聚氨酯总重量。
19.根据权利要求18所述的热塑性聚氨酯弹性体，其特征在于，所述的催化剂二包括有机金属化合物、碱金属氢氧化物、强碱性胺催化剂或酸性催化剂。
20.根据权利要求19所述的热塑性聚氨酯弹性体，其特征在于，所述有机金属化合物包括钛酯、铁化合物、锡化合物或碱金属醇化物；所述铁化合物包括乙酰丙酮铁；所述锡化合物包括乙酸亚锡、辛酸亚锡、二月桂酸亚锡、二乙酸二丁基锡、二月桂酸二丁基锡或二乙酸二辛基锡；
所述碱金属氢氧化物包括氢氧化钠；
所述碱金属醇化物包括甲醇钠或异丙醇钾；
所述强碱性胺催化剂包括脒或叔胺；所述脒为2,3-二甲基-3,4,5,6-四氢嘧啶；所述叔胺选自三乙胺、三丁胺、二甲基苄胺、二环己基甲基胺、二甲基环己基胺、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-四甲基丁二胺、N,N,N’,N’-四甲基已二胺、五甲基二亚乙基三胺、N-甲基吗啉、N-乙基吗啉、N-环已基吗啉或四甲基二氨基乙基醚；
所述酸性催化剂包括磷酸或苯甲酰氯。
21.一种权利要求15所述的热塑性聚氨酯弹性体的制备方法，其特征在于，包括以下步骤：将聚多元醇、扩链剂、硅溴协同反应型阻燃剂、多异氰酸酯加入反应器中，充分混合反应制备硅溴协同阻燃热塑性聚氨酯弹性体。
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