CN112457762A - 一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法 - Google Patents

一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法 Download PDF

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CN112457762A
CN112457762A CN202011435835.1A CN202011435835A CN112457762A CN 112457762 A CN112457762 A CN 112457762A CN 202011435835 A CN202011435835 A CN 202011435835A CN 112457762 A CN112457762 A CN 112457762A
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agent
coating
weight
fluorine
parts
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刘霞
赵晓礼
杨小牛
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法，属于涂料技术领域。解决了现有聚氨酯涂料在湿热、高低温冲击等恶劣环境下，附着力失效的问题。本发明的防护涂料，包括涂料A剂和涂料B剂；按重量份计，涂料A剂包括10‑15份聚多元醇、6‑15份扩链剂、0.5‑2份含氟醇、0.1‑0.2份催化剂、1‑2.5份附着力促进剂、0.01‑0.05份流平剂、0.1‑0.5份润湿剂、0.4‑0.8份防晒剂、0.5‑1份抗菌剂和40‑50份溶剂，涂料B剂包括20‑40份脂肪族二异氰酸酯。该防护涂料固化后，聚氨酯硬段含量在70％‑95％，具有优异的附着力，良好疏水和耐候性能，能在湿热环境下保持良好的附着力。

Description

一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使 用方法
技术领域
本发明属于涂料技术领域，具体涉及一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法。
背景技术
聚氨酯涂料是以聚氨酯树脂为成膜物质的一种涂料，可以分为单组分聚氨酯涂料和双组分聚氨酯涂料。单组分聚氨酯涂料施工方便，但由于其储存时间短、对固化条件要求较高(如潮固化性的单组重量份聚氨酯涂料，要求在高湿度环境下干燥成膜，仅局限于阴雨天和潮湿环境使用；封闭型的单组分聚氨酯涂料，需在热烘烤下固化结膜)且固化时间长等问题致使该类涂料应用面不如双组分涂料广，目前主要用于地板涂料、防腐涂料、预卷材涂料等。双组分聚氨酯涂料一般是由异氰酸酯预聚物和含羟基树脂两部分组成，通常称为固化剂组分和主剂组分。双组分聚氨酯涂料具有成膜温度低、附着力强、耐磨性好、硬度大以及耐化学品、耐候性好等优越性能，广泛作为工业防护、木器家具和汽车涂料。
脂肪族二异氰酸酯合成的聚氨酯，由于不含苯环，在紫外光照射下，不会发生氧化变黄，可用于制作透明耐黄变的聚氨酯产品。但现有的透明聚氨酯很难长久地保持良好的附着力，尤其在湿热环境、高低温冲击等恶劣的环境下，水分子容易渗透到涂层和基底间，破坏涂层与基底间的化学与物理键合，造成涂层的附着力失效。因此，亟需开发出一种高附着力、疏水、恶劣环境下依然能保持良好附着力的聚氨酯透明涂层。
发明内容
本发明的目的是为了解决现有的聚氨酯涂料在湿热、高低温冲击等恶劣的环境下，水分子容易渗透到涂层和基底间，破坏涂层与基底间的化学与物理键合，造成涂层的附着力失效的问题，而提供一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法。
为解决上述技术问题，本发明采取的技术方案如下。
本发明提供一种高附着力的含氟疏水聚氨酯透明防护涂料，包括涂料A剂和涂料B剂；
所述涂料A剂包括10-15重量份聚多元醇、6-15重量份扩链剂、0.5-2重量份含氟醇、0.1-0.2重量份催化剂、1-2.5重量份附着力促进剂、0.01-0.05重量份流平剂、0.1-0.5重量份润湿剂、0.4-0.8重量份防晒剂、0.5-1重量份抗菌剂和40-50重量份溶剂；
所述涂料B剂包括20-40重量份脂肪族二异氰酸酯；
该聚氨酯透明涂料固化后，聚氨酯硬段含量在70％-95％。
优选的是，所述含氟醇为氟甲醇、三氟乙醇、全氟丙基乙醇、全氟丁基乙醇、全氟戊基乙醇、全氟己基乙基醇、全氟庚基乙醇、全氟辛基乙醇、六氟异丙醇、全氟叔丁醇、八氟-1,6-己二醇中的一种或多种的混合物。
优选的是，所述聚多元醇为聚酯多元醇、聚醚多元醇中的一种或几种的混合物，聚酯多元醇和聚醚多元醇的分子量均为400-2000g/mol。
优选的是，所述脂肪族二异氰酸酯为六亚甲基二异氰酸酯(HDI)、异氟尔酮二异氰酸酯(IPDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯二聚体、六亚甲基二异氰酸酯三聚体中的一种或几种的混合物。
优选的是，所述扩链剂为乙二醇、二甘醇、1，3-丙二醇、乙二胺、2-甲基1，5-戊二胺、乙醇胺、1,4-丁二醇、1,2,4-丁三醇中的一种或几种的混合物。
优选的是，所述催化剂为叔胺类催化剂或有机锡类催化剂。
优选的是，所述附着力促进剂是双酚A型环氧树脂，双酚A型环氧树脂的分子量≤500g/mol，环氧值＞0.42。
优选的是，所述流平剂为改性硅烷类流平剂或丙烯酸酯类流平剂。
优选的是，所述润湿剂为改性硅烷类润湿剂或丙烯酸酯类润湿剂。
优选的是，所述防晒剂为纳米二氧化钛，纳米二氧化钛的粒径为20nm。
优选的是，所述抗菌剂为LF-1194。
本发明还提供一种高附着力的含氟疏水聚氨酯透明防护涂料的制备方法，包括以下步骤；
步骤一、按照组成和重量份，称取聚多元醇、扩链剂、含氟醇、催化剂、附着力促进剂、流平剂、润湿剂、防晒剂、抗菌剂和溶剂，混合均匀，得到涂料A剂；
步骤二、按照组成和重量份，取脂肪族二异氰酸酯，得到涂料B剂。
本发明还提供一种高附着力的含氟疏水聚氨酯透明防护涂料的使用方法，将涂料A剂和涂料B剂倒入搅拌反应釜中，控温24-26℃反应1.5-2.5h，静置20-30min除气泡，涂覆后固化，得到高附着力的含氟疏水聚氨酯透明防护涂层。
与现有技术相比，本发明的有益效果为：
本发明提供的高附着力的含氟疏水聚氨酯透明防护涂料，采用的含氟醇中氟元素的颠电负性最大，原子半径很小、形成的碳氟键键长较短、键能大；将氟元素引入涂层材料中，一方面，由于氟元素会迁移到涂层表面，使得涂层表面具有很低的表面能，兼具有疏水和自清洁功能；另一方面，氟元素极性大，容易与基底形成氢键，使涂层与基底形成物理键合，增加涂层附着力。同时，调控涂层合适的分子结构，增加涂层的交联密度，可防止水汽侵袭，可更好的抵抗湿热环境。经试验检测，该防护涂料60℃水煮12h条件下附着力没有下降，依然保持5B。
本发明提供的高附着力的含氟疏水聚氨酯透明防护涂料，一方面，通过引入双酚A型环氧树脂作为附着力促进剂增强了涂层的附着力；另一方面，通过控制聚氨酯硬段含量来调控聚氨酯硬度(硬段含量70％-95％)来进一步提高涂层的附着力，同时保证了涂层的力学性能和耐环境侵蚀性。
本发明提供的高附着力的含氟疏水聚氨酯透明防护涂料，采用的异氰酸酯为脂肪族二异氰酸酯，不含苯环，在紫外光照射下，不会发生氧化变黄，同时，涂料中添加纳米二氧化钛作为防晒剂，二氧化钛纳米粒子由于其粒径小，活性大，既能反射、散射紫外线，又能吸收紫外线，从而对紫外线有很强的阻隔能力，可提高涂料耐老化能力的同时，又不影响涂层透明的性质。
本发明提供的高附着力的含氟疏水聚氨酯透明防护涂料，不改变基底透光性的同时，提高涂层的寿命，实现其良好的使用效果及保护功效。
本发明提供的高附着力的含氟疏水聚氨酯透明防护涂料，通过各组分配合，使聚氨酯涂层在具有优异的力学性能的同时，具有良好的附着力和疏水性能，能够抵抗各种环境冲蚀，例如高温、低温、高低温冲击、湿热、太阳辐照、霉菌等，提高产品的使用效果及保护功效。可用于恶劣环境下玻璃(或有机玻璃)保护膜。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1中，(a)和(b)分别为本发明实施例4和对比例1的聚氨酯防护涂料固化后得到的聚氨酯涂层的水接触角。
具体实施方式
为了进一步理解本发明，下面对本发明的实施方式进行详细描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
本发明提供一种高附着力的含氟疏水聚氨酯透明防护涂料，包括涂料A剂和涂料B剂，也可以仅由涂料A剂和涂料B剂组成。其中，
涂料A剂包括10-15重量份聚多元醇、6-15重量份扩链剂、0.5-2重量份含氟醇、0.1-0.2重量份催化剂、1-2.5重量份附着力促进剂、0.01-0.05重量份流平剂、0.1-0.5重量份润湿剂、0.4-0.8重量份防晒剂、0.5-1重量份抗菌剂和40-50重量份溶剂；
涂料B剂包括20-40重量份脂肪族二异氰酸酯(涂料A剂和涂料B剂中的重量份的标准统一)；涂料B剂也可以仅由上述组分组成。
上述技术方案中，聚氨酯透明涂料固化后，聚氨酯硬段含量在70％-95％，此时的聚氨酯涂层具有良好的附着力、力学性能和耐环境侵蚀性。附着力是由涂层中聚合物的极性基团与基材表面的极性基团相互作用而形成的，聚氨酯涂层中的极性基团数量随硬段含量增加而增加，所以高硬段含量聚氨酯涂层的附着力更高；但是随着硬段含量的继续增加，涂层的模量增加，侵蚀过程会产生应力集中，涂层被破坏的可能增大；同时，硬段含量高，涂层密度大，可防止水汽侵袭，可更好的抵抗湿热环境。
上述技术方案中，聚多元醇为聚酯多元醇、聚醚多元醇中的一种或几种的混合物，聚酯多元醇和聚醚多元醇的分子量均为400-2000g/mol。聚酯多元醇优选为聚碳酸酯多元醇或聚己内酯多元醇，聚醚多元醇优选为聚氧化丙烯二醇或聚氧四亚甲基二醇。
上述技术方案中，脂肪族二异氰酸酯与聚多元醇聚合生成聚氨酯。脂肪族二异氰酸酯没有特殊限制，为本领域技术人员熟知物质，优选为六亚甲基二异氰酸酯(HDI)、异氟尔酮二异氰酸酯(IPDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯二聚体、六亚甲基二异氰酸酯三聚体中的一种或几种的混合物。本发明采用脂肪族二异氰酸酯合成聚氨酯，由于不含苯环，在紫外光照射下，不会发生氧化变黄，可用于制作透明耐黄变的聚氨酯产品。上述技术方案中，扩链剂与聚氨酯分子链上的官能团反应而使聚氨酯分子链扩展、分子量增大。扩链剂没有特殊限制，为本领域技术人员熟知物质，优选为乙二醇、二甘醇、1，3-丙二醇、乙二胺、2-甲基1，5-戊二胺、乙醇胺、1,4-丁二醇、1,2,4-丁三醇中的一种或几种的混合物。
上述技术方案中，含氟醇为三氟乙醇、全氟丙基乙醇、全氟丁基乙醇、全氟戊基乙醇、全氟己基乙基醇、全氟庚基乙醇、全氟辛基乙醇、六氟异丙醇、全氟叔丁醇、八氟-1,6-己二醇中的一种或几种的混合物。优选八氟-1,6-己二醇。采用的含氟醇中氟元素的颠电负性最大，原子半径很小、形成的碳氟键键长较短、键能大；将氟元素引入涂层材料中，一方面，由于氟元素会迁移到涂层表面，使得涂层表面具有很低的表面能，兼具有疏水和自清洁功能；另一方面，氟元素极性大，容易与基底形成氢键，使涂层与基底形成物理键合，增加涂层附着力。同时，调控涂层合适的分子结构，增加涂层的交联密度，可防止水汽侵袭，可更好的抵抗湿热环境。
上述技术方案中，催化剂加速聚合反应的进行。催化剂没有特殊限制，为本领域技术人员熟知物质，如叔胺类催化剂或有机锡类催化剂，叔胺类催化剂优选为三乙胺或四甲基丁二胺，有机锡类催化剂优选为辛酸亚锡或二丁基锡二月桂酸酯。
上述技术方案中，附着力促进剂是双酚A型环氧树脂，优选分子量≤500g/mol，环氧值＞0.42。双酚A型环氧树脂能与脂肪族二异氰酸酯形成高粘结强度的固化物，从而增强了涂层的附着力。
上述技术方案中，溶剂用于溶解各原料。溶剂没有特殊限制，能起到相应作用即可，溶剂优选为乙酸乙酯、乙酸丁酯、丁酮、甲苯、二甲苯、二异丁基酮、二乙二醇醚、N,N二甲基甲酰胺、N,N二甲基乙酰胺中的一种或几种的混合物。
上述技术方案中，流平剂能促使涂料在固化后形成一个平整、光滑、均匀的涂层。流平剂没有特殊限制，为本领域技术人员熟知物质，可以为改性硅烷类流平剂，也可以为非硅烷类流平剂。改性硅烷类流平剂优选为聚醚改性聚二甲基硅氧烷。非硅烷类流平剂优选为聚丙烯酸酯流平剂。
上述技术方案中，润湿剂降低原料表面张力，增加分散性。润滑剂没有特殊限制，为本领域技术人员熟知物质，润湿剂可以为改性硅烷类润湿剂，也可以为非硅烷类润湿剂。改性硅烷类润湿剂优选为聚醚改性聚有机硅氧烷润湿剂。非硅烷类润湿剂优选为聚丙烯酸酯润湿剂。
上述技术方案中，防晒剂为纳米二氧化钛，纳米二氧化钛的粒径优选为20nm，二氧化钛纳米粒子由于粒径小，活性大，既能反射、散射紫外线，又能吸收紫外线，从而对紫外线有很强的阻隔能力，可提高涂料耐老化能力的同时，又不影响涂层透明的性质。
上述技术方案中，抗菌剂优选为LF-1194。LF-1194可以缓慢释放“正电纳米银”，牢牢吸附并穿透细菌、霉菌的细胞壁，破坏微生物电子传输系统、呼吸系统、物质传输系统从而迅速杀死菌体，当细菌体失去活性后，银离子又会从菌体中游离出来，重复进行杀菌活动。
本发明还提供一种高附着力的含氟疏水聚氨酯透明防护涂料的制备方法，包括以下步骤；
步骤一、按照组成和重量份，称取聚多元醇、扩链剂、含氟醇、催化剂、附着力促进剂、流平剂、润湿剂、防晒剂、抗菌剂和溶剂，混合均匀，得到涂料A剂；
步骤二、按照组成和重量份，取脂肪族二异氰酸酯，得到涂料B剂。
本发明还提供一种高附着力的含氟疏水聚氨酯透明防护涂料的使用方法，将涂料A剂和涂料B剂倒入搅拌反应釜中，控温24-26℃反应1.5-2.5h，静置20-30min除气泡，涂覆后固化，得到高附着力的含氟疏水聚氨酯透明防护涂层。
在本发明中所使用的术语，一般具有本领域普通技术人员通常理解的含义，除非另有说明。为了使本领域的技术人员更好地理解本发明的技术方案，下面将结合实施例对本发明作进一步的详细介绍。
在以下实施例中，未详细描述的各种过程和方法是本领域中公知的常规方法。下述实施例中所用的材料、试剂、装置、仪器、设备等，如无特殊说明，均可从商业途径获得。
实施例1
高附着力的含氟疏水聚氨酯透明防护涂料，由涂料A剂和涂料B剂组成；涂料A剂由聚氧四亚甲基二醇(PTMG、分子量650)13.90重量份、1,2,4-丁三醇8.34重量份、六氟异丙醇0.83重量重量份、辛酸亚锡0.13重量份、双酚A型环氧树脂2.18重量份、聚醚改性聚二甲基硅氧烷0.03重量份、聚醚改性聚有机硅氧烷0.27重量份、纳米二氧化钛0.55重量份(粒径为20nm)、LF-1194抗菌剂0.56重量份和N,N二甲基甲酰胺41.70重量份组成；涂料B剂为异佛尔酮二异氰酸酯31.51重量份。该聚氨酯透明涂料固化后，聚氨酯硬段含量为73％。
上述高附着力的耐环境冲蚀的聚氨酯透明涂料的制备方法：
步骤一、按照组成和重量份，称取聚多元醇、扩链剂、含氟醇、催化剂、附着力促进剂、流平剂、润湿剂、防晒剂、抗菌剂和溶剂，混合均匀，得到涂料A剂；
步骤二、按照组成和重量份，取脂肪族二异氰酸酯，得到涂料B剂。
实施例2
高附着力的含氟疏水聚氨酯透明防护涂料，由涂料A剂和涂料B剂组成；涂料A剂由聚氧化丙烯二醇(PPG分子量400)16.63重量份、1,2,4-丁三醇9.98重量份、六氟异丙醇1.00重量份、二丁基锡二月桂酸酯0.13重量份、双酚A型环氧树脂2.18重量份、聚醚改性聚二甲基硅氧烷0.03重量份、聚醚改性聚有机硅氧烷0.27重量份、纳米二氧化钛0.55重量份(粒径为20nm)、LF-1194抗菌剂0.67重量份和N,N二甲基甲酰胺41.56重量份组成；涂料B剂为六亚甲基二异氰酸酯(HDI)27.01重量份。该聚氨酯透明涂料固化后，聚氨酯硬段含量为83.51％。
上述高附着力的耐环境冲蚀的聚氨酯透明涂料的制备方法同实施例1。
实施例3
高附着力的含氟疏水聚氨酯透明防护涂料，由涂料A剂和涂料B剂组成；涂料A剂由聚碳酸酯多元醇(PCDL，分子量550)13.41重量份、1,2,4-丁三醇8.14重量份、六氟异丙醇0.67重量份、三乙胺0.14重量份、双酚A型环氧树脂2.24重量份、聚醚改性聚二甲基硅氧烷0.03重量份、聚醚改性聚有机硅氧烷0.28重量份、纳米二氧化钛0.56重量份(粒径为20nm)、LF-1194抗菌剂0.54重量份和N,N二甲基甲酰胺40.22重量份组成；涂料B剂为4,4'-二环己基甲烷二异氰酸酯(HMDI)33.87重量份。该聚氨酯透明涂料固化后，聚氨酯硬段含量为74.86％。
上述高附着力的耐环境冲蚀的聚氨酯透明涂料的制备方法同实施例1。
实施例4
高附着力的含氟疏水聚氨酯透明防护涂料，由涂料A剂和涂料B剂组成；涂料A剂由聚己内酯多元醇(PCL,分子量850)13.83重量份、1,4-丁二醇12.45重量份、六氟异丙醇0.69重量份、四甲基丁二胺0.14重量份、双酚A型环氧树脂2.19重量份、聚醚改性聚二甲基硅氧烷0.03重量份、聚醚改性聚有机硅氧烷0.27重量份、纳米二氧化钛(粒径为20nm)0.55重量份、LF-1194抗菌剂0.55重量份和N,N二甲基甲酰胺41.50重量份组成；涂料B剂为六亚甲基二异氰酸酯(HDI)27.79重量份。该聚氨酯透明涂料固化后，聚氨酯硬段含量为73.48％。
上述高附着力的耐环境冲蚀的聚氨酯透明涂料的制备方法同实施例1。
对比例1
不含氟的聚氨酯透明防护涂料，由涂料A剂和涂料B剂组成；涂料A剂由聚己内酯多元醇(PCL,分子量850)14.51重量份、1,4-丁二醇13.88重量份、四甲基丁二胺0.14重量份、双酚A型环氧树脂2.19重量份、聚醚改性聚二甲基硅氧烷0.03重量份、聚醚改性聚有机硅氧烷0.27重量份、纳米二氧化钛(粒径为20nm)0.55重量份、LF-1194抗菌剂0.58重量份和N,N二甲基甲酰胺41.50重量份；涂料B剂为六亚甲基二异氰酸酯(HDI)26.35重量份。该聚氨酯透明涂料固化后，聚氨酯硬段含量为73.48％。
上述高附着力的耐环境冲蚀的聚氨酯透明涂料的制备方法同实施例1。
将实施例1-4和对比例1的聚氨酯透明涂料中的涂料A剂和涂料B剂倒入搅拌反应釜中，控温24-26℃反应1.5-2.5h，静置20-30min除气泡，涂覆在PMMA板上，固化，得到聚氨酯涂层。采用胶带法进行测试(ASTMD3359-17)附着力，结果如表1所示。并检测聚氨酯涂层的疏水性，结果如图1所示。
表1实施例1-4和对比例1的聚氨酯透明涂料的附着力
Figure BDA0002828104140000091
从表1可以看出，本发明制备的聚氨酯涂层在60℃水煮12h条件下附着力均没有下降，依然保持5B；而对比例1的聚氨酯涂层附着力降低到0B。
图1中，(a)是实施例4的聚氨酯防护涂料制备的聚氨酯涂层的水接触角，为128.9°，说明该聚氨酯涂层的疏水作用较强，能有效阻止水分子浸入到涂层中；(b)是对比例1的聚氨酯防护涂层制备的聚氨酯涂层的水接触角，为77.5°，说明该聚氨酯涂层的疏水作用不明显，分子相对容易浸入涂层与基底间，破坏涂层与基底间的附着力。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明范围的限制，但凡采用等同替换或等效变换的形式所获得的的技术方案，均应在本发明的保护范围内。

Claims (10)

1.一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，包括涂料A剂和涂料B剂；
所述涂料A剂包括10-15重量份聚多元醇、6-15重量份扩链剂、0.5-2重量份含氟醇、0.1-0.2重量份催化剂、1-2.5重量份附着力促进剂、0.01-0.05重量份流平剂、0.1-0.5重量份润湿剂、0.4-0.8重量份防晒剂、0.5-1重量份抗菌剂和40-50重量份溶剂；
所述涂料B剂包括20-40重量份脂肪族二异氰酸酯；
该防护涂料固化后，聚氨酯硬段含量在70％-95％。
2.根据权利要求1所述的一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，所述含氟醇为氟甲醇、三氟乙醇、全氟丙基乙醇、全氟丁基乙醇、全氟戊基乙醇、全氟己基乙基醇、全氟庚基乙醇、全氟辛基乙醇、六氟异丙醇、全氟叔丁醇、八氟-1,6-己二醇中的一种或多种的混合物。
3.根据权利要求1所述的一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，所述聚多元醇为聚酯多元醇、聚醚多元醇中的一种或几种的混合物，聚酯多元醇和聚醚多元醇的分子量均为400-2000g/mol；
所述脂肪族二异氰酸酯为六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯二聚体、六亚甲基二异氰酸酯三聚体中的一种或几种的混合物；
所述扩链剂为乙二醇、二甘醇、1，3-丙二醇、乙二胺、2-甲基1，5-戊二胺、乙醇胺、1,4-丁二醇、1,2,4-丁三醇中的一种或几种的混合物。
4.根据权利要求1所述的一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，所述催化剂为叔胺类催化剂或有机锡类催化剂。
5.根据权利要求1所述的一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，所述附着力促进剂是双酚A型环氧树脂，双酚A型环氧树脂的分子量≤500g/mol，环氧值＞0.42。
6.根据权利要求1所述的一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，所述流平剂为改性硅烷类流平剂或丙烯酸酯类流平剂；
所述润湿剂为改性硅烷类润湿剂或丙烯酸酯类润湿剂。
7.根据权利要求1所述的一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，所述防晒剂为纳米二氧化钛，纳米二氧化钛的粒径为20nm。
8.根据权利要求1所述的一种高附着力的含氟疏水聚氨酯透明防护涂料，其特征在于，所述抗菌剂为LF-1194。
9.权利要求1-8任何一项所述的一种高附着力的含氟疏水聚氨酯透明防护涂料的制备方法，其特征在于，包括以下步骤；
步骤一、按照组成和重量份，称取聚多元醇、扩链剂、含氟醇、催化剂、附着力促进剂、流平剂、润湿剂、防晒剂、抗菌剂和溶剂，混合均匀，得到涂料A剂；
步骤二、按照组成和重量份，取脂肪族二异氰酸酯，得到涂料B剂。
10.权利要求1-8任何一项所述的一种高附着力的含氟疏水聚氨酯透明防护涂料的使用方法，将涂料A剂和涂料B剂倒入搅拌反应釜中，控温24-26℃反应1.5-2.5h，静置20-30min除气泡，涂覆后固化，得到高附着力的含氟疏水聚氨酯透明防护涂层。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113912814A (zh) * 2021-10-29 2022-01-11 山东圳谷新材料科技有限公司 一种有机氟与环氧树脂协同改性水性聚氨酯的制备方法
CN114957616A (zh) * 2022-06-28 2022-08-30 清远高新华园科技协同创新研究院有限公司 一种含氟羟基树脂及其制备方法与应用
CN115093532A (zh) * 2022-05-12 2022-09-23 广州冠志新材料科技有限公司 一种阳离子型羟基聚氨酯分散体、水性木器涂料及其制备方法和应用
CN117050628A (zh) * 2023-07-05 2023-11-14 浙江大学 透明疏水型有机硅聚氨酯防污防腐涂层材料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040192835A1 (en) * 2002-02-27 2004-09-30 Norbert Steidl Aqueous fluoromodified polyurethane system for anti-graffiti and anti-soiling coatings
WO2005047358A1 (en) * 2003-11-11 2005-05-26 Omnova Solutions Inc. Aqueous hydrophobic and oleophobic coating compositions, methods and uses
CN101585902A (zh) * 2009-06-26 2009-11-25 湖南大学 一种氟化聚氨酯纳米复合材料及其制备
CN111303754A (zh) * 2020-04-17 2020-06-19 中国科学院长春应用化学研究所 一种高附着力的抗刮耐磨聚氨酯透明涂料
CN111763474A (zh) * 2020-07-08 2020-10-13 中国科学院长春应用化学研究所 一种高附着力耐环境侵蚀聚氨酯透明涂料及其制备、使用方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040192835A1 (en) * 2002-02-27 2004-09-30 Norbert Steidl Aqueous fluoromodified polyurethane system for anti-graffiti and anti-soiling coatings
WO2005047358A1 (en) * 2003-11-11 2005-05-26 Omnova Solutions Inc. Aqueous hydrophobic and oleophobic coating compositions, methods and uses
CN101585902A (zh) * 2009-06-26 2009-11-25 湖南大学 一种氟化聚氨酯纳米复合材料及其制备
CN111303754A (zh) * 2020-04-17 2020-06-19 中国科学院长春应用化学研究所 一种高附着力的抗刮耐磨聚氨酯透明涂料
CN111763474A (zh) * 2020-07-08 2020-10-13 中国科学院长春应用化学研究所 一种高附着力耐环境侵蚀聚氨酯透明涂料及其制备、使用方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113912814A (zh) * 2021-10-29 2022-01-11 山东圳谷新材料科技有限公司 一种有机氟与环氧树脂协同改性水性聚氨酯的制备方法
CN115093532A (zh) * 2022-05-12 2022-09-23 广州冠志新材料科技有限公司 一种阳离子型羟基聚氨酯分散体、水性木器涂料及其制备方法和应用
CN114957616A (zh) * 2022-06-28 2022-08-30 清远高新华园科技协同创新研究院有限公司 一种含氟羟基树脂及其制备方法与应用
CN114957616B (zh) * 2022-06-28 2023-11-28 清远高新华园科技协同创新研究院有限公司 一种含氟羟基树脂及其制备方法与应用
CN117050628A (zh) * 2023-07-05 2023-11-14 浙江大学 透明疏水型有机硅聚氨酯防污防腐涂层材料的制备方法

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