CN107903375A - 一种耐低温阻尼涂料用水性聚氨酯乳液及其制备方法 - Google Patents

一种耐低温阻尼涂料用水性聚氨酯乳液及其制备方法 Download PDF

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CN107903375A
CN107903375A CN201711210928.2A CN201711210928A CN107903375A CN 107903375 A CN107903375 A CN 107903375A CN 201711210928 A CN201711210928 A CN 201711210928A CN 107903375 A CN107903375 A CN 107903375A
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aqueous polyurethane
polyurethane emulsion
low temperature
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damping paint
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单久航
周超
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Changchun University of Technology
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Abstract

本发明公开了一种耐低温阻尼涂料用水性聚氨酯乳液及其制备方法，属于涂料技术领域。该水性聚氨酯乳液按重量份数计，包括聚醚多元醇30～90份，多异氰酸酯类单体20～60份，蓖麻油10～60份，小分子扩链剂5～12份，亲水扩链剂5～14份，成盐剂4～8份。本发明还公开了一种耐低温阻尼涂料用水性聚氨酯乳液的制备方法，该方法将聚醚多元醇、多异氰酸酯类单体、蓖麻油以及亲水扩链剂按照一定比例进行逐步聚合，通过自乳化法合成阴离子型水性聚氨酯乳液。本发明所述耐低温阻尼涂料用水性聚氨酯乳液涂饰成膜后，tanδ>0.3初始温度低，有阻尼温域宽。

Description

一种耐低温阻尼涂料用水性聚氨酯乳液及其制备方法
技术领域
本发明属于涂料技术领域，具体涉及一种耐低温阻尼涂料用水性聚氨酯乳液及其制备方法。
背景技术
随着人们环保意识的增强，对噪音污染的治理已成为当今社会的热点话题，减振降噪材料也随之发展起来。阻尼涂料通过高分子材料独特的内部结构，能将外场作用(机械振动和声波振动)转化为热能散发掉，从而达到减振降噪的目的。
传统的溶剂型阻尼涂料无论在生产和施工中都存在着有毒气体和液体的排放问题，对环境资源造成严重的污染。而水性聚氨酯阻尼涂料中使用的水性聚氨酯乳液以水为分散介质，通过一系列手段改性后的水性聚氨酯更具有优良的耐水性、耐候性、耐燃性、耐化学腐蚀以及造价低廉等等优点。以水性涂料代替溶剂型涂料将是一种必然趋势。
公开号为CN 101250246A公开了一种宽温域高阻尼丙烯酸乳液材料的制备方法，该方法制得的乳液有效阻尼(tanδ>0.3)初始温度为-23℃，不能满足低温使用的需求。公开号为CN 106565894A公开了一种阻尼涂料用的丙烯酸乳液，该乳液制备工艺较为复杂，增加了工业化生产的难度。
发明内容
本发明提供一种耐低温阻尼涂料用水性聚氨酯乳液及其制备方法，该乳液涂饰成膜具有优异的阻尼性能。
本发明首先提供一种耐低温阻尼涂料用水性聚氨酯乳液，按重量份数计，包括如下：
优选的是，所述的聚醚多元醇选自聚氧化乙烯二醇、聚氧化丙烯二醇、聚氧化丙烯三醇或聚四氢呋喃二醇中的一种或几种。
优选的是，所述的聚醚多元醇数均分子量为1000～3000。
优选的是，所述的多异氰酸酯类单体选自六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或四甲基苯二甲基二异氰酸酯中的一种或几种。
优选的是，所述的小分子扩链剂选自乙二醇、1，4-丁二醇、1，6-己二醇或一缩二乙二醇中的一种或几种。
优选的是，所述的亲水扩链剂选自二羟甲基丙酸、二羟基半脂、乙二胺基乙磺酸钠、二乙烯三胺或甲基二乙醇胺中的一种或几种。
优选的是，所述的成盐剂选自三乙胺、盐酸、醋酸种环氧丙烷中的一种或几种。
本发明还提供一种耐低温阻尼涂料用水性聚氨酯乳液的制备方法，包括如下：
步骤一：在四口烧瓶中加入聚醚多元醇、异氰酸酯单体、蓖麻油、小分子扩链剂、亲水扩链剂和催化剂，在70～90℃条件下反应2～3h，得到预聚物；
步骤二：将体系迅速降温至30～50℃，加入成盐剂反应10～20min，然后加入去离子水高速搅拌30～50min，得到水性聚氨酯乳液。
优选的是，所述的催化剂选自辛酸亚锡、二月桂酸二丁基锡、三乙醇胺或二甲基乙醇胺中的一种或几种。
优选的是，所述的步骤一中，在四口烧瓶中先加入聚醚多元醇，在80～120℃条件下真空脱水1～2h，然后加入异氰酸酯单体、小分子扩链剂、亲水扩链剂和催化剂，逐步升温至70～90℃反应20-40min，最后加入蓖麻油继续反应70～100min。
本发明的有益效果
本发明首先提供一种耐低温阻尼涂料用水性聚氨酯乳液，该乳液选用聚醚多元醇和蓖麻油为软段，通过两种软段不同比例的配比，达到拓宽有效阻尼(tanδ>0.3)温度范围的效果。通过对软硬段比例的调整，克服了聚氨酯材料低温硬的缺点，有效阻尼(tanδ>0.3)初始温度低。同时，该乳液以水为分散介质，所含有机溶剂极少，应用于涂料时，较溶剂型聚氨酯(VOC)排放低，是一种环境友好型涂料用乳液。
本发明还提供一种耐低温阻尼涂料用水性聚氨酯乳液制备方法，该方法属于一步法，其工艺简单，合成条件易于达成，降低了工业化生产的难度，生产过程中以水为介质，所含有机溶剂少，不污染环境。
附图说明
图1为本发明实例1制备的一种耐低温阻尼涂料用水性聚氨酯乳液所制胶膜的红外光谱图；
图2为本发明实例1制备的一种耐低温阻尼涂料用水性聚氨酯乳液所制胶膜的动态力学测试曲线。
具体实施方式
为进一步了解本发明，下面结合具体实施方式对本发明的优选方案进行描述，但应该了解，这些描述只是为进一步说明本发明的优点和特征，并非对专利要求的限制。
本发明首先提供一种耐低温阻尼涂料用水性聚氨酯乳液，按重量份数计，包括如下：
聚醚多元醇30～90份，多异氰酸酯类单体20～60份，蓖麻油10～60份，小分子扩链剂5～12份，亲水扩链剂5～14份，成盐剂4～8份。优选的是，聚醚多元醇36～80份，多异氰酸酯类单体40～56份，蓖麻油15～44份，小分子扩链剂7～9份，亲水扩链剂12～14份，成盐剂5份。
按照本发明，所述的聚醚多元醇优选选自聚氧化乙烯二醇、聚氧化丙烯二醇、聚氧化丙烯三醇或聚四氢呋喃二醇中的一种或几种。所述的聚醚多元醇数均分子量优选为1000～3000。所述的聚醚多元醇的数均分子量为该配方的关键因素，当聚醚多元醇数均分子量低于1000时，会导致聚合过程体系粘度过大，高温反应时发生凝结成块现象；当聚醚多元醇数均分子量高于3000时，相当于提高了体系中软段比例，所得乳液涂饰成膜后，胶膜物理性能较差，不具有实用价值。
按照本发明，所述的多异氰酸酯类单体优选选自六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或四甲基苯二甲基二异氰酸酯中的一种或几种。所述的多异氰酸酯类单体为脂肪族或脂环族，制得的聚氨酯乳液储存稳定性好，耐黄变。
按照本发明，所述的蓖麻油没有特殊限制，来源为商购，优选蓖麻油羟基平均官能度为2.7，所述的蓖麻油在聚氨酯乳液体系中既可以充当软段，又起到一定的交联作用，以提高材料的物理性能。
按照本发明，本发明的聚氨酯乳液体系选用聚醚多元醇和蓖麻油为软段，聚醚多元醇为软段的聚氨酯其玻璃化转变温度在高温区，而以蓖麻油为软段的聚氨酯其玻璃化转变温度在低温区，通过两种组分的相容性控制，使其在动态力学性能分析中表现为两种组分的Tg互相靠拢，曲线彼此叠加，曲线波谷位置也拥有有效阻尼，以达到扩宽阻尼温域的效果。
按照本发明，所述的小分子扩链剂优选选自乙二醇、1，4-丁二醇、1，6-己二醇或一缩二乙二醇中的一种或几种。
按照本发明，所述的亲水扩链剂优选选自二羟甲基丙酸、二羟基半脂、乙二胺基乙磺酸钠、二乙烯三胺或甲基二乙醇胺中的一种或几种。
按照本发明，所述的成盐剂优选选自三乙胺、盐酸、醋酸种环氧丙烷中的一种或几种。
本发明还提供一种耐低温阻尼涂料用水性聚氨酯乳液的制备方法，包括如下：
步骤一：在四口烧瓶中加入聚醚多元醇、异氰酸酯单体、蓖麻油、小分子扩链剂、亲水扩链剂和催化剂，在70～90℃条件下反应2～3h，得到预聚物；
步骤二：将体系迅速降温至30～50℃，加入成盐剂反应10～20min，然后加入去离子水高速搅拌30～50min，得到水性聚氨酯乳液。
按照本发明，在四口烧瓶中先加入聚醚多元醇，优选在80～120℃条件下真空脱水1～2h，然后加入异氰酸酯单体、小分子扩链剂、亲水扩链剂和催化剂，逐步升温至70～90℃反应20-40min，最后加入蓖麻油继续反应70～100min。所述的催化剂优选选自辛酸亚锡、二月桂酸二丁基锡、三乙醇胺或二甲基乙醇胺中的一种或几种。催化剂用量按重量份数计，优选为0.01～0.1份。
按照本发明，将体系迅速降温至30～50℃，加入丙酮75～95ml，用丙酮-二正丁胺法测定-NCO值达到理论值，加入成盐剂反应10～20min，然后加入去离子水高速搅拌30～50min，室温乳化得到水性聚氨酯乳液。所述的高速搅拌的速度优选为1000-1200rad/min。
下面结合实施例对本发明做进一步详细的描述。
实施例1
在装有搅拌装置、冷凝装置、温度计并通有氮气保护的四口烧瓶中，加入聚四氢呋喃二醇(数均分子量为1000)30g，在90℃条件下真空脱水1.5h，然后加入异佛尔酮二异氰酸酯51g、小分子扩链剂1，4-丁二醇7g、亲水扩链剂二羟甲基丙酸14g以及催化剂二月桂酸二丁基锡0.1g，将体系升温至75℃反应30min，加入蓖麻油10g，反应100min，得到预聚物；
将体系迅速降温至30℃，加入丙酮80ml以降低粘度，待体系-NCO值达到理论值，加入成盐剂三乙胺5g，继续反应10min，然后加入去离子水，将搅拌装置转数调整至1000rad/min，室温乳化30min得到水性聚氨酯乳液。
图1为本发明实例1制备的一种耐低温阻尼涂料用水性聚氨酯乳液所制胶膜的红外光谱图，从图1中可以看出，本发明成功制备了蓖麻油改性的水性聚氨酯乳液；
图2为本发明实例1制备的一种耐低温阻尼涂料用水性聚氨酯乳液的动态力学分析曲线，从图2中可以看出，本发明制备的水性聚氨酯有效阻尼(tanδ>0.3)初始温度为-43℃，且在材料升温软化(70℃)失去弹性之前始终具有有效阻尼性能。
实施例2
在装有搅拌装置、冷凝装置、温度计并通有氮气保护的四口烧瓶中，加入聚氧化丙烯二醇(数均分子量为2000)56g，在90℃条件下真空脱水1.5h，然后加入四甲基苯二甲基二异氰酸酯56g、小分子扩链剂1，6-己二醇9g、亲水扩链剂二羟甲基丙酸14g以及催化剂二月桂酸二丁基锡0.1g，将体系升温至80℃反应20min，加入蓖麻油15g，反应100min，得到预聚物；
将体系迅速降温至35℃，加入丙酮100ml以降低粘度，待体系-NCO值达到理论值，加入成盐剂三乙胺5g，继续反应10min，然后加入去离子水，将搅拌装置转数调整至1000rad/min，室温乳化30min得到水性聚氨酯乳液。
实验结果表明：本发明实施例2制备的水性聚氨酯有效阻尼(tanδ>0.3)初始温度为-28℃，且在材料升温软化(70℃)失去弹性之前始终具有有效阻尼性能。
实施例3
在装有搅拌装置、冷凝装置、温度计并通有氮气保护的四口烧瓶中，加入聚四氢呋喃二醇(数均分子量为2000)80g，在100℃条件下真空脱水2h，然后加入异佛尔酮二异氰酸酯40g、小分子扩链剂1，4-丁二醇7g、亲水扩链剂二羟甲基丙酸14g以及催化剂二月桂酸二丁基锡0.1g，将体系升温至75℃反应30min，加入蓖麻油44g，反应90min，得到预聚物；
将体系迅速降温至35℃，加入丙酮95ml以降低粘度，待体系-NCO值达到理论值，加入成盐剂三乙胺5g，继续反应10min，然后加入去离子水，将搅拌装置转数调整至1200rad/min，室温乳化50min得到水性聚氨酯乳液。
实验结果表明：本发明实施例3制备的水性聚氨酯有效阻尼(tanδ>0.3)初始温度为-15℃，且在材料升温软化(70℃)失去弹性之前始终具有有效阻尼性能。
实施例4
在装有搅拌装置、冷凝装置、温度计并通有氮气保护的四口烧瓶中，加入聚氧化乙烯二醇(数均分子量为3000)36g，在100℃条件下真空脱水1h，然后加入二环己基甲烷二异氰酸酯48g、小分子扩链剂乙二醇9g、亲水扩链剂甲基二乙醇胺12g以及催化剂二月桂酸二丁基锡0.1g，将体系升温至80℃反应40min，加入蓖麻油26g，反应80min，得到预聚物；
将体系迅速降温至30℃，加入丙酮90ml以降低粘度，待体系-NCO值达到理论值，加入成盐剂三乙胺5g，继续反应10min，然后加入去离子水，将搅拌装置转数调整至1000rad/min，室温乳化50min得到水性聚氨酯乳液。
实验结果表明：本发明实施例4制备的水性聚氨酯有效阻尼(tanδ>0.3)初始温度为-33℃，且在材料升温软化(70℃)失去弹性之前始终具有有效阻尼性能。

Claims (10)

1.一种耐低温阻尼涂料用水性聚氨酯乳液，其特征在于，按重量份数计，包括如下：
2.根据权利要求1所述的一种耐低温阻尼涂料用水性聚氨酯乳液，其特征在于，所述的聚醚多元醇选自聚氧化乙烯二醇、聚氧化丙烯二醇、聚氧化丙烯三醇或聚四氢呋喃二醇中的一种或几种。
3.根据权利要求1或2所述的一种耐低温阻尼涂料用水性聚氨酯乳液，其特征在于，所述的聚醚多元醇数均分子量为1000～3000。
4.根据权利要求1所述的一种耐低温阻尼涂料用水性聚氨酯乳液，其特征在于，所述的多异氰酸酯类单体选自六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或四甲基苯二甲基二异氰酸酯中的一种或几种。
5.根据权利要求1所述的一种耐低温阻尼涂料用水性聚氨酯乳液，其特征在于，所述的小分子扩链剂选自乙二醇、1，4-丁二醇、1，6-己二醇或一缩二乙二醇中的一种或几种。
6.根据权利要求1所述的一种耐低温阻尼涂料用水性聚氨酯乳液，其特征在于，所述的亲水扩链剂选自二羟甲基丙酸、二羟基半脂、乙二胺基乙磺酸钠、二乙烯三胺或甲基二乙醇胺中的一种或几种。
7.根据权利要求1所述的一种耐低温阻尼涂料用水性聚氨酯乳液，其特征在于，所述的成盐剂选自三乙胺、盐酸、醋酸种环氧丙烷中的一种或几种。
8.根据权利要求1所述的一种耐低温阻尼涂料用水性聚氨酯乳液的制备方法，其特征在于，包括如下：
步骤一：在四口烧瓶中加入聚醚多元醇、异氰酸酯单体、蓖麻油、小分子扩链剂、亲水扩链剂和催化剂，在70～90℃条件下反应2～3h，得到预聚物；
步骤二：将体系迅速降温至30～50℃，加入成盐剂反应10～20min，然后加入去离子水高速搅拌30～50min，得到水性聚氨酯乳液。
9.根据权利要求8所述的一种耐低温阻尼涂料用水性聚氨酯乳液的制备方法，其特征在于，所述的催化剂选自辛酸亚锡、二月桂酸二丁基锡、三乙醇胺或二甲基乙醇胺中的一种或几种。
10.根据权利要求8所述的一种耐低温阻尼涂料用水性聚氨酯乳液的制备方法，其特征在于，所述的步骤一中，在四口烧瓶中先加入聚醚多元醇，在80～120℃条件下真空脱水1～2h，然后加入异氰酸酯单体、小分子扩链剂、亲水扩链剂和催化剂，逐步升温至70～90℃反应20-40min，最后加入蓖麻油继续反应70～100min。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108912295A (zh) * 2018-05-28 2018-11-30 上海大学 无溶剂自流平室温成型聚氨酯阻尼材料及其制备方法
CN108948322A (zh) * 2018-06-01 2018-12-07 合肥科天水性科技有限责任公司 一种用于沙发革的水性聚氨酯树脂、制备方法及其应用
CN109180903A (zh) * 2018-09-11 2019-01-11 长春工业大学 一种水性高硬度木器涂料用水性聚氨酯乳液及其制备方法
CN112724347A (zh) * 2020-12-28 2021-04-30 上海汇得科技股份有限公司 一种生物基水性聚氨酯树脂及其制备方法和应用
CN115323085A (zh) * 2022-08-10 2022-11-11 上海金狮化工有限公司 一种辊涂补伤剂及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199255A (zh) * 2011-04-07 2011-09-28 合肥工业大学 一种热解封型聚氨酯-丙烯酸酯乳液及其制备方法
CN105131250A (zh) * 2015-08-29 2015-12-09 高明志 单组分自交联水性聚氨酯缓控释包膜材料
CN105131191A (zh) * 2015-09-04 2015-12-09 高明志 一种具有螯合功能的双组分改性聚氨酯缓控释包膜材料
CN105199076A (zh) * 2015-10-23 2015-12-30 青岛展辰新材料有限公司 一种水性紫外光固化的生物基聚氨酯丙烯酸酯树脂的制备方法
CN105418870A (zh) * 2015-11-30 2016-03-23 上海华谊涂料有限公司 一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液及其制备方法
CN106188457A (zh) * 2016-07-14 2016-12-07 武汉理工大学 一种内交联型蓖麻油基水性聚氨酯乳液及其制备方法
CN106589291A (zh) * 2016-12-29 2017-04-26 合众（佛山）化工有限公司 一种蓖麻油封端聚氨酯水性油墨树脂及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199255A (zh) * 2011-04-07 2011-09-28 合肥工业大学 一种热解封型聚氨酯-丙烯酸酯乳液及其制备方法
CN105131250A (zh) * 2015-08-29 2015-12-09 高明志 单组分自交联水性聚氨酯缓控释包膜材料
CN105131191A (zh) * 2015-09-04 2015-12-09 高明志 一种具有螯合功能的双组分改性聚氨酯缓控释包膜材料
CN105199076A (zh) * 2015-10-23 2015-12-30 青岛展辰新材料有限公司 一种水性紫外光固化的生物基聚氨酯丙烯酸酯树脂的制备方法
CN105418870A (zh) * 2015-11-30 2016-03-23 上海华谊涂料有限公司 一种蓖麻油/丙烯酸复合改性水性聚氨酯乳液及其制备方法
CN106188457A (zh) * 2016-07-14 2016-12-07 武汉理工大学 一种内交联型蓖麻油基水性聚氨酯乳液及其制备方法
CN106589291A (zh) * 2016-12-29 2017-04-26 合众（佛山）化工有限公司 一种蓖麻油封端聚氨酯水性油墨树脂及其制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108912295A (zh) * 2018-05-28 2018-11-30 上海大学 无溶剂自流平室温成型聚氨酯阻尼材料及其制备方法
CN108948322A (zh) * 2018-06-01 2018-12-07 合肥科天水性科技有限责任公司 一种用于沙发革的水性聚氨酯树脂、制备方法及其应用
CN109180903A (zh) * 2018-09-11 2019-01-11 长春工业大学 一种水性高硬度木器涂料用水性聚氨酯乳液及其制备方法
CN112724347A (zh) * 2020-12-28 2021-04-30 上海汇得科技股份有限公司 一种生物基水性聚氨酯树脂及其制备方法和应用
CN115323085A (zh) * 2022-08-10 2022-11-11 上海金狮化工有限公司 一种辊涂补伤剂及其制备方法

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