CN106750080A - 一种自消光型改性水性聚氨酯涂料及其制备方法与应用 - Google Patents

一种自消光型改性水性聚氨酯涂料及其制备方法与应用 Download PDF

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CN106750080A
CN106750080A CN201710044087.6A CN201710044087A CN106750080A CN 106750080 A CN106750080 A CN 106750080A CN 201710044087 A CN201710044087 A CN 201710044087A CN 106750080 A CN106750080 A CN 106750080A
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castor oil
aqueous polyurethane
epoxy
organosilicon
modified aqueous
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庞浩
雍奇文
黄健恒
廖兵
莫文蔚
黄福仁
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Foshan Function High Polymer Materials & Fine Chemicals Professional Center
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Foshan Function High Polymer Materials & Fine Chemicals Professional Center
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Priority to CN201710044087.6A priority Critical patent/CN106750080A/zh
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Abstract

本发明属于水性涂料领域，公开了一种自消光型改性水性聚氨酯涂料及其制备方法。该方法通过调控蓖麻油和环氧树脂在反应过程中合成水性聚氨酯的交联和支化程度以达到控制乳液粒径的目的，并选择性引入有机硅，合成出粒径在400～2000nm的蓖麻油环氧双重改性水性聚氨酯和粒径在50～200nm的有机硅蓖麻油双重改性水性聚氨酯，并将得到的上述两组分进行物理共混和复配制得漆膜。相比于单组份的自消光型水性聚氨酯，合成的自消光型改性水性聚氨酯涂料由于蓖麻油和环氧树脂的支化和交联作用，使其具有更高的硬度，更好的耐刮擦性、耐水解性和热稳定性，尤其是有机硅的引入还赋予了自消光型改性水性聚氨酯漆膜良好的触感。

Description

一种自消光型改性水性聚氨酯涂料及其制备方法与应用
技术领域
本发明属于水性涂料领域，特别涉及一种自消光型改性水性聚氨酯涂料及其制备方法与应用。
背景技术
日常生活中具有消光效果的物品随处可见：在家中，在上班的路上，或在夜幕下的餐馆里都可见其踪影。室内家具多采用了消光面，覆盖于餐馆外部的木质板材基本也消光外表。当面临是选择亮光的还是消光的效果时，我们不仅仅局限于时尚和外观需求。实践证明，易清洁性，光亮效果及触摸感觉等方面的要求也影响着我们的选择。当我们抵达办公室，不论是驾车，乘公共汽车还是坐火车，都会发现各类交通工具的内部装饰面基本是消光的。从实用和安全的方面考虑，学校的黑板都是采用消光表面避免刺眼。轿车的内部也采用这类设计，一些经济实用的装置以及内部的装饰为了安全考虑均采用了不刺眼的消光漆。防反光是一项课题。摩天大楼表面一般不刷光亮的涂料，而是在钢或铝的基材上用预先涂漆的板材进行覆盖，且均使用消光涂料，以避免产生危险的反光，刺激行人或汽车司机的眼睛。此外，经济实用是选择涂料表面状态的另一个重要因素。比如，当某些基材被擦伤、有轻微凹坑以及弄脏时，采用消光涂料可以掩饰这些缺陷，而涂覆亮光漆却难以掩盖此类瑕疵。
所谓消光效果就是人眼接收到的光线极少，是我们的感官所形成的一种主观印象。具体来说，就是当一束光源(太阳光、灯光等)以一定的角度照射在某个物体上，绝大部分入射光线根据物体表面特性主要发生了吸收、折射、散射等，仅有极少部分光线反射出去被人眼接收到，人们再根据主观判断出这个物体是否具有消光效果。有研究发现，光线反射强度取决于物体表面的平整度。例如镜子，众所周知其表面十分细腻光滑，对光线反射率极高，具有极高的光泽。相反地，微观粗糙的漆膜表面散射光线，只反射极少部分光线，实现具有消光效果的外观。
浮石粉在过去用于打磨干燥漆膜的外表面。通过加工获得细微擦痕，使漆膜具有精细的、高贵的消光外表。现在有更多的材料用于制造消光表面。尽管有些加工过程较为复杂，但是却十分快捷。以硅石、石蜡、有机材料甚至填料为基础的添加剂，可以添加在涂料中，在干燥后能形成微观粗糙的漆膜表面。例如，美国专利US9353271B2结合了未处理硅、有机改性硅和蜡改性硅三种消光剂的协同消光作用赋予了丙烯酸类涂料的低光泽性和优异的物理性能。美国专利US8986791B2发明了水可溶性的聚环氧乙烷树脂充当有机消光剂与丙烯酸树脂搅拌混合后用于天然或合成革表面处理可降低表面光泽。传统地通过打磨干燥漆膜的外表面或外加一定量的消光剂到涂料里，使漆膜表面产生微观粗糙，从而实现其表面低光泽的效果。前者方法对人工费用和施工工艺的要求过高，后者方法受限于消光剂与基底树脂的匹配性(不同的基底树脂对消光剂的粒径、孔隙度、折光率等参数要求不同)、消光剂与基底树脂的相容性、消光剂的成本等问题，而且外加消光剂必然会致使漆膜损失部分光学透明性和一些物理化学性能。
随着世界工业技术日新月异，八九十年代沿袭下来的传统制造消光涂料的技术似乎并没有从根本上实现变革，正面临着与当代先进工业技术需求不相适的尴尬局面。为此，越来越多的世界各国涂料专家学者们开启了探讨制造消光涂料的新技术研究。他们期望利用化学反应合成控制、紫外光分步固化等手段实现构建微褶皱或微观粗糙的漆膜表面而不需要再外加消光剂便能产生良好的消光效果，这一新的技术被称之为化学消光或自消光，以便与传统的外加消光剂的物理消光方法相区别。美国专利US20140371384A1，US8906468B2采用双光束紫外灯分步固化原理分别得到了耐刮擦的消光涂料和低光泽军用航空涂料，均是首先利用波长较长、能量较低的汞灯对漆膜表面进行辐射固化产生微褶皱，再利用波长较短、能量较高的氙灯进行漆膜的深度完全辐射固化。这种方法的缺点是漆膜的厚度最好控制在20μm以内，否则紫外固化不完全；同时也需要特定的紫外设备和原料配方才能实现紫外固化成膜。中国专利CN103865031A，CN104193946A，CN103936959A利用化学反应合成控制相继发表了单组份的水性聚氨酯自消光树脂，其光泽度低，合成工艺简单，但漆膜硬度不够，易划伤，耐水性和热稳定性差。中国专利CN103626930A发表了一种具有相分离结构的水性丙烯酸聚氨酯消光树脂的制备方法，其工艺复杂，需要同时合成阴离子型封闭聚氨酯和非离子型聚氨酯，再引发丙烯酸酯类聚合反应，很难在工业上应用。
发明内容
为了克服现有的单组份的自消光型水性聚氨酯涂料的漆膜硬度低，易划伤，耐水性和热稳定性差等缺点与不足。本发明旨在提供一种自消光型改性水性聚氨酯涂料。该涂料在固化成膜后通过表面形成微粗糙结构而产生消光效果，不需要再添加二氧化硅消光粉或消光蜡等传统的物理消光剂。此外，该改性水性聚氨酯涂料形成的漆膜由于蓖麻油和环氧树脂的支化和交联作用，使其具有更高的硬度，更好的耐刮擦性、耐水解性和热稳定性，尤其是有机硅的引入还赋予了漆膜良好的触感。
本发明另一目的在于提供上述自消光型改性水性聚氨酯涂料的制备方法。该方法简单可控，通过调节两组分的用量比例也可获得不同硬度和不同光泽度的改性水性聚氨酯漆膜。
本发明再一目的在于提供上述自消光型改性水性聚氨酯涂料的应用。
本发明的目的通过下述技术方案实现：
一种自消光型改性水性聚氨酯涂料，包括蓖麻油环氧双重改性水性聚氨酯和有机硅蓖麻油双重改性水性聚氨酯。
优选地，所述蓖麻油环氧双重改性水性聚氨酯组分与有机硅蓖麻油双重改性水性聚氨酯组分的质量比为0.6～1.5:1。
一种上述自消光型改性水性聚氨酯涂料的制备方法，包括如下具体步骤：
S1.蓖麻油环氧双重改性水性聚氨酯的制备：
(a)将异氰酸酯、蓖麻油、聚合物多元醇、催化剂混合在60～90℃下通N2反应2～3小时；
(b)将小分子亲水单体、环氧树脂加入步骤S1(a)中继续反应2～4小时，并用丙酮调节反应体系的粘度，防止凝胶的生成；
(c)将步骤S1(b)得到的反应液降至30～50℃，加入中和剂，反应10～30分钟，得到蓖麻油环氧双重改性水性聚氨酯预聚体；
(d)将步骤S1(c)得到的蓖麻油环氧双重改性水性聚氨酯预聚体滴加到含有扩链剂的水溶液中进行充分扩链，并在1000～2000r/min转速下搅拌0.5～1小时，得到蓖麻油环氧双重改性水性聚氨酯；
S2.有机硅蓖麻油双重改性水性聚氨酯的制备：
(a)将异氰酸酯、蓖麻油、聚合物多元醇、催化剂混合在60～90℃下通N2反应2～3小时；
(b)将小分子亲水单体加入步骤S2(a)中继续反应2～4小时，用丙酮调节反应体系的粘度，防止凝胶的生成；
(c)将步骤S2(b)得到的反应液降至30～50℃，加入中和剂，反应10～30分钟，得到蓖麻油改性水性聚氨酯预聚体；
(d)接着将有机硅与去离子水混合后，滴加到步骤S2(c)得到的蓖麻油改性水性聚氨酯预聚体中并在1000～2000r/min转速下搅拌0.5～1小时，制得有机硅蓖麻油双重改性水性聚氨酯；
S3.将步骤S1所得蓖麻油环氧双重改性水性聚氨酯和步骤S2所得有机硅蓖麻油双重改性水性聚氨酯共混，在1000～2000r/min转速下搅拌15～30分钟后静置2～4小时，即得自消光型改性水性聚氨酯涂料。
优选地，步骤S1(a)和S2(a)中所述异氰酸酯为三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯；
优选地，步骤S1(a)和S2(a)中所述聚合物多元醇为聚氧化丙烯二醇、聚己内酯二醇、聚碳酸酯二醇或聚四氢呋喃二醇中的一种以上，所述聚氧化丙烯二醇、聚己内酯二醇、聚碳酸酯二醇或聚四氢呋喃二醇的分子量为400～4000；
优选地，步骤S1(a)和S2(a)中所述蓖麻油的羟值含量为175～185mg/g；所述催化剂为二月桂酸二丁基锡、异辛酸铋、月桂酸铋、新癸酸铋中的任意一种。
优选地，步骤S1(b)和S2(b)中所述小分子亲水单体为二羟甲基丙酸或二羟甲基丁酸；步骤S1(b)中所述环氧树脂为双酚A型环氧E-44树脂或环氧E-51树脂；步骤S1(c)和S2(c)中所述中和剂为三乙胺或三丙胺。
优选地，步骤S1(d)中所述扩链剂为乙二胺或水合肼；步骤S2(d)中所述有机硅为含氨基、羟基、环氧基的小分子有机硅氧烷类。
更为优选地，所述小分子有机硅氧烷类为含单氨基官能团的KH550、环氧基官能团的KH560、双氨基官能团的KH602或双氨基官能团的KH792。
优选地，步骤S1(a)中所述异氰酸酯与聚合物多元醇的摩尔比为1.2～1.8:1，所述蓖麻油的用量为聚合物多元醇的质量的5～8％，所述催化剂的用量为异氰酸酯、聚合物多元醇和蓖麻油总质量的0.3～0.6％；
优选地，步骤S1(b)中所述小分子亲水单体用量为异氰酸酯和聚合物多元醇的总质量的4～8％，所述环氧树脂的用量为异氰酸酯和聚合物多元醇的总质量的4～6％；
优选地，步骤S1(c)中所述中和剂与小分子亲水单体的摩尔比为0.8～1.2：1。
优选地，步骤S1(d)中所述扩链剂的用量为蓖麻油环氧双重改性水性聚氨酯预聚体中剩余异氰酸根的摩尔质量，所述蓖麻油环氧双重改性水性聚氨酯的固含量为15～30％。
优选地，步骤S2(a)中所述异氰酸酯与聚合物多元醇的摩尔比为1.4～2:1，所述蓖麻油的用量为聚合物多元醇的质量的3～5％；
优选地，步骤S2(b)中所述小分子亲水单体的用量为异氰酸酯和聚合物多元醇的总质量的3～6％；
优选地，步骤S2(c)中所述中和剂与小分子亲水单体的摩尔比为0.8～1.2：1；
优选地，步骤S2(d)中所述有机硅的用量为聚合物多元醇的质量的3～4％，得到的有机硅蓖麻油双重改性水性聚氨酯固含量为30～40％。
上述自消光型改性水性聚氨酯涂料在汽车内饰、木器、家具、纸张光油、天然和人造革表面处理领域中的应用。
本发明通过调控蓖麻油和环氧树脂在反应过程中合成水性聚氨酯的交联和支化程度以达到控制乳液粒径的目的，并选择性引入有机硅，分别合成出粒径在400～2000nm的蓖麻油环氧双重改性水性聚氨酯和粒径在50～200nm的有机硅蓖麻油双重改性水性聚氨酯。两者同为聚氨酯树脂系列，具有极其相似的物化性质及官能团结构，相容性较好，折光率接近，在共混后涂饰成膜具有较好的通透度，避免了外加消光剂出现的漆膜表面发白发花现象和储存稳定性差等问题。由于蓖麻油环氧双重改性水性聚氨酯的分子结构支链多，交联程度大，乳液胶束粒子具有较大体积，比重小，在成膜过程中容易浮在漆膜表面，提供了改性水性聚氨酯漆膜的消光效果。同时有机硅蓖麻油双重改性水性聚氨酯由于引入了有机硅和蓖麻油，使漆膜具有较好的耐水性、热稳定性和优异的触感等性能。
与现有技术相比，本发明具有以下优点及有益效果：
1.本发明制备的自消光型改性水性聚氨酯涂料，相比于单组份的自消光型水性聚氨酯，合成的自消光型改性水性聚氨酯涂料由于蓖麻油和环氧树脂的支化和交联作用以及环氧树脂的高模量、高强度等特点，使其具有更高的硬度，更好的耐刮擦性、耐水解性和热稳定性，尤其是有机硅的引入还赋予了改性水性聚氨酯漆膜良好的触感。
2.本发明制备的自消光型改性水性聚氨酯涂料在涂饰成膜后具有较好的通透度，避免了外加消光剂出现的漆膜表面发白发花现象和储存稳定性差等问题。
3.本发明通过调控蓖麻油和环氧树脂在反应过程中合成水性聚氨酯的交联和支化程度，以及引入有机硅改性，合成出自消光型改性水性聚氨酯涂料。该方法简单可控，成本低廉，不需要复杂的生产设备，通过调节两组分的用量比例可获得不同硬度和不同光泽度的漆膜。其消光效果由涂料本身在成膜后自动产生，也不需要外加物理消光剂。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
在以下实施例中采用如下方法进行测试：
1.乳液的固含量的测试：本发明依照GB/T 1725-79测量标准测试蓖麻油环氧双重改性水性聚氨酯和有机硅蓖麻油双重改性水性聚氨酯乳液的固含量。
2.乳液粒径的测试：本发明采用马尔文仪器公司Nano-60纳米粒度测定仪在25℃下测得蓖麻油环氧双重改性水性聚氨酯和有机硅蓖麻油双重改性水性聚氨酯乳液的粒径。
3.粘度的测试：本发明采用NDJ-1A粘度测量仪在20rpm-25℃下测量蓖麻油环氧双重改性水性聚氨酯和有机硅蓖麻油双重改性水性聚氨酯乳液的粘度。
4.光泽度的测试：本发明采用KGZ-60°标准光泽度仪器，根据标准GB 9754测量漆膜的光泽度。
实施例1
1.蓖麻油环氧双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚氧化丙烯二醇40g、异佛尔酮二异氰酸酯17.58g、蓖麻油1.38g和二月桂酸二丁基锡催化剂0.01g，在70℃下反应2h。然后再加入二羟甲基丙酸3.85g和E-44环氧树脂3.69g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至40℃，加入三乙胺2.91g中和30min后转移至滴液漏斗中，在2000r/min的高速搅拌下，逐滴快速滴加到乙二胺(1.72g)水溶液分散30min得乳白色蓖麻油环氧双重改性水性聚氨酯备用。测得乳液固含为20％，粘度为3500mPa.s，粒径为500～1000nm。
2.有机硅蓖麻油双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚氧化丙烯二醇20g、2000分子量聚己内酯二醇20g，异佛尔酮二异氰酸酯17.58g，蓖麻油1.2g和二月桂酸二丁基锡催化剂0.01g，在70℃下反应2h。然后再加入二羟甲基丁酸3.51g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至50℃，加入三乙胺2.4g中和30min。接着，在2000r/min的高速搅拌下加入有机硅类的KH792质量1.2g与去离子水的混合液，分散0.5～1h得有机硅蓖麻油双重改性水性聚氨酯备用。测得乳液固含为30％，粘度为500mPa.s，粒径为50～100nm。
3.蓖麻油环氧双重改性水性聚氨酯与有机硅蓖麻油双重改性水性聚氨酯复配：用高速剪切乳化剂在2000r/min的速度下将蓖麻油环氧双重改性水性聚氨酯100g和有机硅蓖麻油双重改性水性聚氨酯80g混合搅拌15min，静置消泡2h后，得自消光型改性水性聚氨酯涂料。测得粘度为2500mPa.s，离心测试无沉淀现象。
4.应用：将得到的自消光型改性水性聚氨酯涂料用线棒涂布器涂敷在未经处理的天然皮革上，在烘箱中50℃恒温2h，室温干燥1天后，测得60°下光泽度为3。
实施例2
1.蓖麻油环氧双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚氧化丙烯二醇40g、异佛尔酮二异氰酸酯17.58g、蓖麻油2.07g和催化剂二月桂酸二丁基锡0.01g，在75℃下反应2h。然后再加入二羟甲基丙酸3.85g和E-51环氧树脂3.18g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至50℃，加入三乙胺2.91g中和30min后转移至滴液漏斗中，在2000r/min的高速搅拌下，逐滴快速滴加到乙二胺水(1.58g)溶液分散30min，得乳白色蓖麻油环氧双重改性水性聚氨酯备用。测得乳液固含为15％，粘度为3200mPa.s，粒径为400～1200nm。
2.有机硅蓖麻油双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚碳酸酯二醇40g、异佛尔酮二异氰酸酯17g、蓖麻油1.6g和二月桂酸二丁基锡催化剂0.01g，在70℃下反应2h。然后再加入二羟甲基丁酸3.31g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至50℃，加入三乙胺2.26g中和30min。接着，在2000r/min的高速搅拌下加入有机硅类的KH550质量1.2g与去离子水的混合液搅拌1h，得有机硅蓖麻油双重改性水性聚氨酯备用。测得乳液固含为30％，粘度为800mPa.s，粒径为50～200nm。
3.蓖麻油环氧双重改性水性聚氨酯与有机硅蓖麻油双重改性水性聚氨酯复配：用高速剪切乳化剂在2000r/min的速度下将100g蓖麻油环氧双重改性水性聚氨酯和60g有机硅蓖麻油双重改性水性聚氨酯混合搅拌15min，静置消泡3h后，得自消光型改性水性聚氨酯涂料。测得粘度为2800mPa.s，离心测试无沉淀现象。
4.应用：将得到的自消光型改性水性聚氨酯涂料用涂布器涂敷在未经处理的天然皮革上，在烘箱中50℃恒温2h，室温干燥1天后，测得60°下光泽度为4。
实施例3
1.蓖麻油环氧双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚氧化丙烯二醇40g、异佛尔酮二异氰酸酯17.58g、蓖麻油2.76g和有机铋类催化剂-月桂酸铋0.01g，在70℃下反应2h。然后再加入二羟甲基丙酸3.85g和E-44环氧树脂1.85g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至50℃，加入三乙胺3.01g中和30min后转移至滴液漏斗中，在2000r/min的高速搅拌下，逐滴快速滴加到乙二胺(1.58g)水溶液分散30分钟得乳白色蓖麻油环氧双重改性水性聚氨酯备用。测得乳液固含为20％，粘度为3000mPa.s，粒径为800～1500nm。
2.有机硅蓖麻油双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚氧化丙烯二醇40g、三甲基六亚甲基二异氰酸酯13g、蓖麻油1.4g和二月桂酸二丁基锡催化剂0.01g，在75℃下反应2小时。然后再加入二羟甲基丁酸4.51g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至50℃，加入三乙胺3.1g中和30min。接着，在1500r/min的高速搅拌下加入有机硅类的KH560质量1.4g与去离子水的混合液分散1h，得有机硅蓖麻油双重改性水性聚氨酯备用。测得乳液固含为30％，粘度为600mPa.s，粒径为50～100nm。
3.蓖麻油环氧双重改性水性聚氨酯与蓖麻油环氧双重改性水性聚氨酯复配：用高速剪切乳化剂在1800r/min的速度下将蓖麻油环氧双重改性水性聚氨酯100g和蓖麻油环氧双重改性水性聚氨酯100g混合搅拌15min，静置消泡2h后，得自消光型改性水性聚氨酯涂料。测得粘度为2000mPa.s，离心测试无沉淀现象。
4.应用：将得到的自消光型改性水性聚氨酯涂料用涂布器涂敷在未经处理的天然皮革上，在烘箱中50℃恒温2h，室温干燥1天后，测得60°下光泽度为4。
实施例4
1.蓖麻油环氧双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚氧化丙烯二醇40g、异佛尔酮二异氰酸酯17.58g、蓖麻油2.76g和二月桂酸二丁基锡催化剂0.01g，在70℃下反应2h。然后再加入二羟甲基丁酸3.31g和E-51环氧树脂3.75g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至40℃，加入三乙胺2.26g中和30min后转移至滴液漏斗中，在2000r/min的高速搅拌下，逐滴快速滴加到乙二胺(1.8g)水溶液分散30min，得乳白色蓖麻油环氧双重改性水性聚氨酯备用。测得乳液固含为25％，粘度为3500mPa.s，粒径为500～1000nm。
2.有机硅蓖麻油双重改性水性聚氨酯的合成：向装有搅拌器、回流冷凝管并通有氮气的500ml四口烧瓶中加入2000分子量聚四氢呋喃二醇40g、异佛尔酮二异氰酸酯17g、蓖麻油1.8g和催化剂二月桂酸二丁基锡0.01g，在70℃下反应2h。然后再加入二羟甲基丁酸3.51g的丙酮溶液继续反应3h，期间加入丙酮调节粘度。降温至50℃，加入三乙胺2.4g中和30min。接着，在2000r/min的高速搅拌下加入有机硅类的KH792质量1.2g与去离子水的混合液搅拌1h，得有机硅蓖麻油双重改性水性聚氨酯备用。测得乳液固含为30％，粘度为800mPa.s，粒径为50～150nm。
3.蓖麻油环氧双重改性水性聚氨酯与蓖麻油环氧双重改性水性聚氨酯复配：用高速剪切乳化剂在2200r/min的速度下将蓖麻油环氧双重改性水性聚氨酯100g和有机硅蓖麻油双重改性水性聚氨酯60g混合搅拌15min，静置消泡2h后，得自消光型改性水性聚氨酯涂料。测得粘度为1800mPa.s，离心测试无沉淀现象。
4.应用：将得到的自消光型改性水性聚氨酯涂料用涂布器涂敷在未经处理的天然皮革上，在烘箱中50℃恒温2h，室温干燥1天后，测得60°下光泽度为5。
实施例5
本实施例与实施例1的区别在于：
所述的合成蓖麻油环氧双重改性水性聚氨酯中的蓖麻油用量为2.07g。
所述的合成蓖麻油环氧双重改性水性聚氨酯中的催化剂为月桂酸铋0.01g。
所述的合成蓖麻油环氧双重改性水性聚氨酯中的中和剂为三丙胺4.12g。
所述的合成蓖麻油环氧双重改性水性聚氨酯的固含为20％，粘度为2000mPa.s，粒径为600～1500nm。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的聚合物多元醇为2000分子量的聚己内酯二醇40g。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的反应温度为80℃。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的固含为35％，粘度为800mPa.s，粒径为100～200nm。
所述的制备工艺制得的自消光型改性水性聚氨酯涂料用在天然皮革上得到的光泽度为5。
实施例6
本实施与例实施例1的区别在于：
所述的合成蓖麻油环氧双重改性水性聚氨酯中的反应温度为80℃。
所述的合成蓖麻油环氧双重改性水性聚氨酯中的催化剂为异辛酸铋0.01g。
所述的合成蓖麻油环氧双重改性水性聚氨酯中的扩链剂为水合肼1.4g。
所述的合成蓖麻油环氧双重改性水性聚氨酯的固含量为20％，粘度为3000mPa.s，粒径为600～1000nm。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的聚合物多元醇为2000分子量的聚己内酯二醇40g。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的异氰酸酯为六亚甲基二异氰酸酯12.9g。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的有机硅类为KH602质量1.4g。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的固含为35％，粘度为600mPa.s，粒径为50～200nm。
所述的制备工艺制得的自消光型改性水性聚氨酯涂料用在天然皮革上得到的光泽度为3.5。
实施例7
本实施例与实施例1的区别在于：
所述的合成蓖麻油环氧双重改性水性聚氨酯中的环氧树脂为E-51环氧树脂3.18g。
所述的蓖麻油环氧双重改性水性聚氨酯中的扩链剂为水合肼1.4g。
所述的合成蓖麻油环氧双重改性水性聚氨酯的固含为20％，粘度为3500mPa.s，粒径为500～1500nm。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的聚合物多元醇为2000分子量的聚氧化丙烯二醇20g和1000分子量的聚四氢呋喃二醇10g。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的异氰酸酯为三甲基六亚甲基二异氰酸酯15.5g。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的有机硅类为KH560质量1.2g。
所述的合成有机硅蓖麻油双重改性水性聚氨酯的固含为35％，粘度为600mPa.s，粒径为50～100nm。
所述的制备工艺制得的自消光型改性水性聚氨酯涂料用在天然皮革上得到的光泽度为4.5。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

1.一种自消光型改性水性聚氨酯涂料，其特征在于，包括蓖麻油环氧双重改性水性聚氨酯和有机硅蓖麻油双重改性水性聚氨酯。
2.根据权利要求1所述自消光型改性水性聚氨酯涂料，其特征在于，所述蓖麻油环氧双重改性水性聚氨酯与有机硅蓖麻油双重改性水性聚氨酯的质量比为0.6～1.5:1。
3.一种根据权利要求1或2所述自消光型改性水性聚氨酯涂料的制备方法，其特征在于，包括如下具体步骤：
S1.蓖麻油环氧双重改性水性聚氨酯的制备：
(a)将异氰酸酯、蓖麻油、聚合物多元醇、催化剂混合后在60～90℃下通N2反应2～3小时；
(b)将小分子亲水单体、环氧树脂加入步骤S1(a)中继续反应2～4小时，
并用丙酮调节反应体系的粘度，防止凝胶的生成；
(c)将步骤S1(b)得到的反应液降至30～50℃，加入中和剂，反应10～30分钟，得到蓖麻油环氧双重改性水性聚氨酯预聚体；
(d)将步骤S1(c)得到的蓖麻油环氧双重改性水性聚氨酯预聚体滴加到含有扩链剂的水溶液中进行充分扩链，并在1000～2000r/min转速下搅拌0.5～1小时，得到蓖麻油环氧双重改性水性聚氨酯；
S2.有机硅蓖麻油双重改性水性聚氨酯的制备：
(a)将异氰酸酯、蓖麻油、聚合物多元醇、催化剂混合后在60～90℃下通N2反应2～3小时；
(b)将小分子亲水单体加入步骤S2(a)中继续反应2～4小时，用丙酮调节反应体系的粘度，防止凝胶的生成；
(c)将步骤S2(b)得到的反应液降至30～50℃，加入中和剂，反应10～30分钟，得到蓖麻油改性水性聚氨酯预聚体；
(d)接着将有机硅与去离子水混合后，滴加到步骤S2(c)得到的蓖麻油改性水性聚氨酯预聚体中，并在1000～2000r/min转速下搅拌0.5～1小时，制得有机硅蓖麻油双重改性水性聚氨酯；
S3.将步骤S1所得蓖麻油环氧双重改性水性聚氨酯和步骤S2所得有机硅蓖麻油双重改性水性聚氨酯共混，在1000～2000r/min转速下搅拌15～30分钟后静置2～4小时，即得自消光型改性水性聚氨酯涂料。
4.根据权利要求3所述自消光型改性水性聚氨酯涂料的制备方法，其特征在于，步骤S1(a)和S2(a)中所述异氰酸酯为三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯；
步骤S1(a)和S2(a)中所述聚合物多元醇为聚氧化丙烯二醇、聚己内酯二醇、聚碳酸酯二醇或聚四氢呋喃二醇中的一种以上，所述聚氧化丙烯二醇、聚己内酯二醇、聚碳酸酯二醇或聚四氢呋喃二醇的分子量为400～4000；
步骤S1(a)和S2(a)中所述蓖麻油的羟值含量为175～185mg/g；所述催化剂为二月桂酸二丁基锡、异辛酸铋，月桂酸铋或新癸酸铋中的任意一种。
5.根据权利要求3所述自消光型改性水性聚氨酯涂料的制备方法，其特征在于，步骤S1(b)和S2(b)中所述小分子亲水单体为二羟甲基丙酸或二羟甲基丁酸；步骤S1(b)中所述环氧树脂为双酚A型环氧E-44树脂或环氧E-51树脂；步骤S1(c)和S2(c)中所述中和剂为三乙胺或三丙胺。
6.根据权利要求3所述自消光型改性水性聚氨酯涂料的制备方法，其特征在于，步骤S1(d)中所述扩链剂为乙二胺或水合肼；步骤S2(d)中所述有机硅为含氨基、羟基、环氧基的小分子有机硅氧烷类。
7.根据权利要求6所述自消光型改性水性聚氨酯涂料的制备方法，其特征在于，所述小分子有机硅氧烷类为含单氨基官能团的KH550、环氧基官能团的KH560、双氨基官能团的KH602或双氨基官能团的KH792。
8.根据权利要求3所述自消光型改性水性聚氨酯涂料的制备方法，其特征在于，步骤S1(a)中所述异氰酸酯与聚合物多元醇的摩尔比为1.2～1.8:1，所述蓖麻油的用量为聚合物多元醇的质量的5～8％，所述催化剂的用量为异氰酸酯、聚合物多元醇和蓖麻油总质量的0.3～0.6％；
步骤S1(b)中所述小分子亲水单体用量为异氰酸酯和聚合物多元醇的总质量的4～8％，所述环氧树脂的用量为异氰酸酯和聚合物多元醇的总质量的4～6％；
步骤S1(c)中所述中和剂与小分子亲水单体的摩尔比为0.8～1.2：1；
步骤S1(d)中所述扩链剂的用量为蓖麻油环氧双重改性水性聚氨酯预聚体中剩余异氰酸根的摩尔量，所述蓖麻油环氧双重改性水性聚氨酯的固含量为15～30％。
9.根据权利要求3所述自消光型改性水性聚氨酯涂料的制备方法，其特征在于，步骤S2(a)中所述异氰酸酯与聚合物多元醇的摩尔比为1.4～2:1，所述蓖麻油的用量为聚合物多元醇的质量的3～5％；
步骤S2(b)中所述小分子亲水单体的用量为异氰酸酯和聚合物多元醇的总质量的3～6％；
步骤S2(c)中所述中和剂与小分子亲水单体的摩尔比为0.8～1.2：1；
步骤S2(d)中所述有机硅的用量为聚合物多元醇的质量的3～4％，得到的有机硅蓖麻油双重改性水性聚氨酯固含量为30～40％。
10.权利要求1或2所述自消光型改性水性聚氨酯涂料在汽车内饰、木器、家具、纸张光油、天然和人造革表面处理领域中的应用。
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276551A (zh) * 2017-12-26 2018-07-13 合肥科天水性科技有限责任公司 一种生物基多重交联改性水性聚氨酯树脂及其制备方法和用途
CN108330732A (zh) * 2018-01-31 2018-07-27 上海宏盾防伪材料有限公司 一种具有耐刮伤功能哑度可调的水性聚氨酯涂料
CN108546323A (zh) * 2018-04-18 2018-09-18 万华化学集团股份有限公司 阳离子自消光树脂及其制备方法和应用
CN109651588A (zh) * 2018-11-21 2019-04-19 万华化学集团股份有限公司 蓖麻油改性阳离子自交联聚氨酯聚脲水分散体及制备方法和应用
CN110976247A (zh) * 2019-12-16 2020-04-10 江苏靓时新材料科技股份有限公司 一种灯制超哑肤感板材的装置
CN111849337A (zh) * 2020-07-22 2020-10-30 清远市美佳乐环保新材股份有限公司 一种以油性消光树脂为核的自消光乳液制备方法
CN111848914A (zh) * 2020-06-10 2020-10-30 华南理工大学 一种低吸水率的自消光光固化水性聚氨酯丙烯酸酯固化膜及其制备方法与应用
CN112852278A (zh) * 2021-03-16 2021-05-28 天津中晶建筑材料有限公司 一种水性植物基抗指纹清漆及其制备方法与应用
CN114181577A (zh) * 2020-09-15 2022-03-15 广东华润涂料有限公司 水性木器涂料组合物以及由其制成的木制品
CN115819984A (zh) * 2022-12-29 2023-03-21 江西阿璐达新材料有限公司 一种高回弹氟硅橡胶材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102395612A (zh) * 2009-04-16 2012-03-28 巴斯夫欧洲公司 球形颗粒及其用途
CN103740250A (zh) * 2013-12-06 2014-04-23 四川达威科技股份有限公司 自消光型皮革水性聚氨酯涂饰剂的制备方法
CN104356342A (zh) * 2014-11-04 2015-02-18 佛山市功能高分子材料与精细化学品专业中心 有机硅改性水性聚氨酯皮革涂饰剂及制备方法
CN104356343A (zh) * 2014-11-04 2015-02-18 佛山市功能高分子材料与精细化学品专业中心 环氧树脂蓖麻油双重改性聚氨酯皮革涂饰剂及其制备方法
CN104893550A (zh) * 2015-06-16 2015-09-09 合肥吉科新材料有限公司 一种隔热涂料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102395612A (zh) * 2009-04-16 2012-03-28 巴斯夫欧洲公司 球形颗粒及其用途
CN103740250A (zh) * 2013-12-06 2014-04-23 四川达威科技股份有限公司 自消光型皮革水性聚氨酯涂饰剂的制备方法
CN104356342A (zh) * 2014-11-04 2015-02-18 佛山市功能高分子材料与精细化学品专业中心 有机硅改性水性聚氨酯皮革涂饰剂及制备方法
CN104356343A (zh) * 2014-11-04 2015-02-18 佛山市功能高分子材料与精细化学品专业中心 环氧树脂蓖麻油双重改性聚氨酯皮革涂饰剂及其制备方法
CN104893550A (zh) * 2015-06-16 2015-09-09 合肥吉科新材料有限公司 一种隔热涂料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
吕建平 等: "蓖麻油硅氧烷双重交联改善水性聚氨酯的耐水性", 《聚氨酯工业》 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276551A (zh) * 2017-12-26 2018-07-13 合肥科天水性科技有限责任公司 一种生物基多重交联改性水性聚氨酯树脂及其制备方法和用途
CN108330732A (zh) * 2018-01-31 2018-07-27 上海宏盾防伪材料有限公司 一种具有耐刮伤功能哑度可调的水性聚氨酯涂料
CN108546323B (zh) * 2018-04-18 2020-08-28 万华化学集团股份有限公司 阳离子自消光树脂及其制备方法和应用
CN108546323A (zh) * 2018-04-18 2018-09-18 万华化学集团股份有限公司 阳离子自消光树脂及其制备方法和应用
CN109651588B (zh) * 2018-11-21 2021-09-07 万华化学集团股份有限公司 蓖麻油改性阳离子自交联聚氨酯聚脲水分散体及制备方法和应用
CN109651588A (zh) * 2018-11-21 2019-04-19 万华化学集团股份有限公司 蓖麻油改性阳离子自交联聚氨酯聚脲水分散体及制备方法和应用
CN110976247A (zh) * 2019-12-16 2020-04-10 江苏靓时新材料科技股份有限公司 一种灯制超哑肤感板材的装置
CN111848914A (zh) * 2020-06-10 2020-10-30 华南理工大学 一种低吸水率的自消光光固化水性聚氨酯丙烯酸酯固化膜及其制备方法与应用
CN111849337A (zh) * 2020-07-22 2020-10-30 清远市美佳乐环保新材股份有限公司 一种以油性消光树脂为核的自消光乳液制备方法
CN111849337B (zh) * 2020-07-22 2021-11-23 清远市美佳乐环保新材股份有限公司 一种以油性消光树脂为核的自消光乳液制备方法
CN114181577A (zh) * 2020-09-15 2022-03-15 广东华润涂料有限公司 水性木器涂料组合物以及由其制成的木制品
CN112852278A (zh) * 2021-03-16 2021-05-28 天津中晶建筑材料有限公司 一种水性植物基抗指纹清漆及其制备方法与应用
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CN115819984A (zh) * 2022-12-29 2023-03-21 江西阿璐达新材料有限公司 一种高回弹氟硅橡胶材料及其制备方法
CN115819984B (zh) * 2022-12-29 2023-09-22 江西阿璐达新材料有限公司 一种高回弹氟硅橡胶材料及其制备方法

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