CN105542120A - 一种阻燃聚氨酯树脂及其制备方法 - Google Patents
一种阻燃聚氨酯树脂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种阻燃聚氨酯树脂，其原料按重量份包括：有机磷聚酯多元醇37～40份，改性甲苯二异氰酸酯52～55份，一缩二乙二醇2.5～4份，酒石酸1.3～1.6份，环氧树脂7～10份，辛酸钴0.4～0.7份，二甲基乙醇胺3～4份，双(2-羟乙基)苯胺3.5～5份。本发明还公开了一种阻燃聚氨酯树脂，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温，保温，降温后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温，保温得到物料a；将物料a降温后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温，保温得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
Description
技术领域
本发明涉及聚氨酯树脂技术领域，尤其涉及一种阻燃聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯最早由德国的Schlack在1943年合成，而那时的水性聚氨酯材料主要是靠强烈的机械搅拌以及大量的乳化剂强制性的将聚氨酯分散在水中，这种方法合成的水性聚氨酯分散不够完全，粒径较大，稳定性较差，导致其性能在应用时上不能满足生产的需求。此后通过人们的研究开发，将亲水基团引入聚氨酯，合成了可以自分散于水中的水性聚氨酯。水性聚氨酯作为一种新型的材料与传统的溶剂型聚氨酯相比，气味更小，更加的环保，容易操作，而性能方面与传统的溶剂型聚氨酯相当，并且由于水性聚氨酯的化学结构中通常含有羟基、羧基，可以与多种树脂复合来改变其性能，以满足更高的生产需求。
发明内容
本发明提出了一种阻燃聚氨酯树脂及其制备方法，所得阻燃聚氨酯树脂具有优异的阻燃耐热性能，而且耐水性能优秀，同时黏度和断裂伸长率小，拉伸强度、硬度、韧性高。
本发明提出的一种阻燃聚氨酯树脂，其原料按重量份包括：有机磷聚酯多元醇37～40份，改性甲苯二异氰酸酯52～55份，一缩二乙二醇2.5～4份，酒石酸1.3～1.6份，环氧树脂7～10份，辛酸钴0.4～0.7份，二甲基乙醇胺3～4份，双(2-羟乙基)苯胺3.5～5份。
优选地，有机磷聚酯多元醇的制备方法如下：将2-磷酸基-1,2,4-三羧基丁烷和1,6-己二醇混合后，通入N2作为保护气体，接着升温至112～115℃，保温1.7～2h，再加入辛酸亚锡，升温至156～159℃，保温4.8～5.1h，真空保温1.2～1.5h得到有机磷聚酯多元醇。
优选地，有机磷聚酯多元醇制备方法中，按摩尔份将1～2份2-磷酸基-1,2,4-三羧基丁烷和3～4份1,6-己二醇混合后，通入N2作为保护气体，接着升温至112～115℃，保温1.7～2h，再加入0.1～0.2份辛酸亚锡，升温至156～159℃，保温4.8～5.1h，真空保温1.2～1.5h得到有机磷聚酯多元醇。
优选地，有机磷聚酯多元醇、改性甲苯二异氰酸酯、酒石酸、二甲基乙醇胺、双(2-羟乙基)苯胺的重量比为38～39：53～54：1.4～1.5：3.4～3.6：4～4.5。
优选地，改性甲苯二异氰酸酯按如下方法制备：将甲苯二异氰酸酯和1,2-二甲基咪唑混合后，升温至205～208℃，保温2～2.3h，接着减压蒸馏，冷却至84～88℃进行熟化得到改性甲苯二异氰酸酯。
优选地，改性甲苯二异氰酸酯制备方法中，按重量份将82～85份甲苯二异氰酸酯和1.5～1.8份1,2-二甲基咪唑混合后，升温至205～208℃，保温2～2.3h，接着减压蒸馏，冷却至84～88℃进行熟化得到改性甲苯二异氰酸酯。
优选地，其原料按重量份包括：有机磷聚酯多元醇38～39份，改性甲苯二异氰酸酯53～54份，一缩二乙二醇3～3.5份，酒石酸1.4～1.5份，环氧树脂8～9份，辛酸钴0.5～0.6份，二甲基乙醇胺3.4～3.6份，双(2-羟乙基)苯胺4～4.5份。
本发明还提出的上述阻燃聚氨酯树脂的制备方法，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温，保温，降温后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温，保温得到物料a；将物料a降温后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温，保温得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
优选地，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温至82～85℃，保温2～2.5h，降温至37～40℃后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温至77～80℃，保温3～4h得到物料a；将物料a降温至30～40℃后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温至72～75℃，保温1.8～2.1h得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
本发明将甲苯二异氰酸酯和1,2-二甲基咪唑混合后，升温，使甲苯二异氰酸酯中-NCO基团在1,2-二甲基咪唑的催化作用下发生缩合反应，两个异氰酸酯基团缩合生成碳化二亚胺基团(-N＝C＝N-)，所得改性甲苯二异氰酸酯黏度低，为后续阻燃聚氨酯树脂合成做铺垫。
本发明采用2-磷酸基-1,2,4-三羧基丁烷和1,6-己二醇进行酯化聚合得到有机磷聚酯多元醇；然后采用有机磷聚酯多元醇和改性甲苯二异氰酸酯进行制备阻燃聚氨酯树脂，改性甲苯二异氰酸酯在聚氨酯结构上引入长碳侧链基团，而有机磷聚酯多元醇在聚氨酯结构上引入长碳侧链和含磷的基团，长碳侧链基团可以相互缠绕，使阻燃聚氨酯树脂的黏度和断裂伸长率小，进一步提高拉伸强度、硬度、韧性，不仅提高了阻燃聚氨酯树脂的亲油性，使本发明固化时亲油基向外对空气排布，亲水基向内排布，从而使得接触角增大，水难以在本发明所形成的涂层表面铺展润湿，同时后期可在空气中进行氧合作用，产生自交联现象，使体系交联度增加，刚性结构增多，改善由于含磷基团的引入而导致涂层变软、附着力变差的缺点，从而使本发明的耐水、耐热和耐拉伸性能得到进一步增强；而其中的碳化二亚胺基团提高了阻燃聚氨酯树脂的极性，提高了反应活性，提高反应速度和交联度，提高了阻燃聚氨酯树脂的硬度和附着力，同时含磷基团的引入，使本发明在燃烧过程中，由于C-C键的键能大于C-P的键能要大，受热能力差的含磷化合物率先分解出磷酸以及多种有机膦酸起到覆盖作用，还引起多羟基聚合物脱水形成隔热、隔氧的炭层，从而提高本发明的阻燃性能；而环氧树脂含有活泼的环氧基团，环氧基团可断裂形成羟基与-NCO反应，生成具有交联网状结构的聚氨酯，分子链运动受到限制，且大范围的交联使得分子间空隙变小，水分子难以进入聚氨酯分子内部，表现为树脂的吸水率不断下降，耐水性提高，环氧树脂的引入使得聚氨酯交联程度增加，内聚能变大，提高了本发明的热稳定性和硬度。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种阻燃聚氨酯树脂，其原料按重量份包括：有机磷聚酯多元醇37份，改性甲苯二异氰酸酯55份，一缩二乙二醇2.5份，酒石酸1.6份，环氧树脂7份，辛酸钴0.7份，二甲基乙醇胺3份，双(2-羟乙基)苯胺5份。
有机磷聚酯多元醇的制备方法如下：按摩尔份将1份2-磷酸基-1,2,4-三羧基丁烷和4份1,6-己二醇混合后，通入N2作为保护气体，接着升温至112℃，保温2h，再加入0.1份辛酸亚锡，升温至159℃，保温4.8h，真空保温1.5h得到有机磷聚酯多元醇。
改性甲苯二异氰酸酯按如下方法制备：按重量份将82份甲苯二异氰酸酯和1.8份1,2-二甲基咪唑混合后，升温至205℃，保温2.3h，接着减压蒸馏，冷却至84℃进行熟化得到改性甲苯二异氰酸酯。
本发明还提出的上述阻燃聚氨酯树脂的制备方法，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温至85℃，保温2h，降温至40℃后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温至77℃，保温4h得到物料a；将物料a降温至30℃后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温至75℃，保温1.8h得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
实施例2
本发明提出的一种阻燃聚氨酯树脂，其原料按重量份包括：有机磷聚酯多元醇40份，改性甲苯二异氰酸酯52份，一缩二乙二醇4份，酒石酸1.3份，环氧树脂10份，辛酸钴0.4份，二甲基乙醇胺4份，双(2-羟乙基)苯胺3.5份。
有机磷聚酯多元醇的制备方法如下：按摩尔份将2份2-磷酸基-1,2,4-三羧基丁烷和3份1,6-己二醇混合后，通入N2作为保护气体，接着升温至115℃，保温1.7h，再加入0.2份辛酸亚锡，升温至156℃，保温5.1h，真空保温1.2h得到有机磷聚酯多元醇。
改性甲苯二异氰酸酯按如下方法制备：按重量份将85份甲苯二异氰酸酯和1.5份1,2-二甲基咪唑混合后，升温至208℃，保温2h，接着减压蒸馏，冷却至88℃进行熟化得到改性甲苯二异氰酸酯。
本发明还提出的上述阻燃聚氨酯树脂的制备方法，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温至82℃，保温2.5h，降温至37℃后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温至80℃，保温3h得到物料a；将物料a降温至40℃后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温至72℃，保温2.1h得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
实施例3
本发明提出的一种阻燃聚氨酯树脂，其原料按重量份包括：有机磷聚酯多元醇38份，改性甲苯二异氰酸酯54份，一缩二乙二醇3份，酒石酸1.5份，环氧树脂8份，辛酸钴0.6份，二甲基乙醇胺3.4份，双(2-羟乙基)苯胺4.5份。
有机磷聚酯多元醇的制备方法如下：按摩尔份将1.2份2-磷酸基-1,2,4-三羧基丁烷和3.8份1,6-己二醇混合后，通入N2作为保护气体，接着升温至113℃，保温1.9h，再加入0.14份辛酸亚锡，升温至158℃，保温4.9h，真空保温1.4h得到有机磷聚酯多元醇。
改性甲苯二异氰酸酯按如下方法制备：按重量份将83份甲苯二异氰酸酯和1.7份1,2-二甲基咪唑混合后，升温至206℃，保温2.2h，接着减压蒸馏，冷却至85℃进行熟化得到改性甲苯二异氰酸酯。
本发明还提出的上述阻燃聚氨酯树脂的制备方法，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温至84℃，保温2.2h，降温至39℃后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温至78℃，保温3.7h得到物料a；将物料a降温至34℃后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温至74℃，保温1.9h得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
实施例4
本发明提出的一种阻燃聚氨酯树脂，其原料按重量份包括：有机磷聚酯多元醇39份，改性甲苯二异氰酸酯53份，一缩二乙二醇3.5份，酒石酸1.4份，环氧树脂9份，辛酸钴0.5份，二甲基乙醇胺3.6份，双(2-羟乙基)苯胺4份。
有机磷聚酯多元醇的制备方法如下：按摩尔份将1.8份2-磷酸基-1,2,4-三羧基丁烷和3.5份1,6-己二醇混合后，通入N2作为保护气体，接着升温至114℃，保温1.8h，再加入0.16份辛酸亚锡，升温至157℃，保温5h，真空保温1.3h得到有机磷聚酯多元醇。
改性甲苯二异氰酸酯按如下方法制备：按重量份将84份甲苯二异氰酸酯和1.6份1,2-二甲基咪唑混合后，升温至207℃，保温2.1h，接着减压蒸馏，冷却至87℃进行熟化得到改性甲苯二异氰酸酯。
本发明还提出的上述阻燃聚氨酯树脂的制备方法，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温至83℃，保温2.4h，降温至38℃后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温至79℃，保温3.3h得到物料a；将物料a降温至38℃后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温至73℃，保温2h得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种阻燃聚氨酯树脂，其特征在于，其原料按重量份包括：有机磷聚酯多元醇37～40份，改性甲苯二异氰酸酯52～55份，一缩二乙二醇2.5～4份，酒石酸1.3～1.6份，环氧树脂7～10份，辛酸钴0.4～0.7份，二甲基乙醇胺3～4份，双(2-羟乙基)苯胺3.5～5份。
2.根据权利要求1所述阻燃聚氨酯树脂，其特征在于，有机磷聚酯多元醇的制备方法如下：将2-磷酸基-1,2,4-三羧基丁烷和1,6-己二醇混合后，通入N2作为保护气体，接着升温至112～115℃，保温1.7～2h，再加入辛酸亚锡，升温至156～159℃，保温4.8～5.1h，真空保温1.2～1.5h得到有机磷聚酯多元醇。
3.根据权利要求1或2所述阻燃聚氨酯树脂，其特征在于，有机磷聚酯多元醇制备方法中，按摩尔份将1～2份2-磷酸基-1,2,4-三羧基丁烷和3～4份1,6-己二醇混合后，通入N2作为保护气体，接着升温至112～115℃，保温1.7～2h，再加入0.1～0.2份辛酸亚锡，升温至156～159℃，保温4.8～5.1h，真空保温1.2～1.5h得到有机磷聚酯多元醇。
4.根据权利要求1-3任一项所述阻燃聚氨酯树脂，其特征在于，有机磷聚酯多元醇、改性甲苯二异氰酸酯、酒石酸、二甲基乙醇胺、双(2-羟乙基)苯胺的重量比为38～39：53～54：1.4～1.5：3.4～3.6：4～4.5。
5.根据权利要求1-4任一项所述阻燃聚氨酯树脂，其特征在于，改性甲苯二异氰酸酯按如下方法制备：将甲苯二异氰酸酯和1,2-二甲基咪唑混合后，升温至205～208℃，保温2～2.3h，接着减压蒸馏，冷却至84～88℃进行熟化得到改性甲苯二异氰酸酯。
6.根据权利要求1-5任一项所述阻燃聚氨酯树脂，其特征在于，改性甲苯二异氰酸酯制备方法中，按重量份将82～85份甲苯二异氰酸酯和1.5～1.8份1,2-二甲基咪唑混合后，升温至205～208℃，保温2～2.3h，接着减压蒸馏，冷却至84～88℃进行熟化得到改性甲苯二异氰酸酯。
7.根据权利要求1-6任一项所述阻燃聚氨酯树脂，其特征在于，其原料按重量份包括：有机磷聚酯多元醇38～39份，改性甲苯二异氰酸酯53～54份，一缩二乙二醇3～3.5份，酒石酸1.4～1.5份，环氧树脂8～9份，辛酸钴0.5～0.6份，二甲基乙醇胺3.4～3.6份，双(2-羟乙基)苯胺4～4.5份。
8.一种如权利要求1-7任一项所述阻燃聚氨酯树脂的制备方法，其特征在于，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温，保温，降温后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温，保温得到物料a；将物料a降温后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温，保温得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
9.根据权利要求8所述阻燃聚氨酯树脂的制备方法，其特征在于，将有机磷聚酯多元醇和改性甲苯二异氰酸酯混合均匀后，升温至82～85℃，保温2～2.5h，降温至37～40℃后加入一缩二乙二醇、酒石酸、环氧树脂和丙酮混合均匀，再加入辛酸钴，升温至77～80℃，保温3～4h得到物料a；将物料a降温至30～40℃后，再滴加含二甲基乙醇胺、双(2-羟乙基)苯胺的溶液，升温至72～75℃，保温1.8～2.1h得到物料b；将物料b调节pH至中性后，真空脱除丙酮得到阻燃聚氨酯树脂。
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