CN110452608A - 一种稀土改性聚氨酯-环氧防污防辐射水性树脂及其制备方法 - Google Patents
一种稀土改性聚氨酯-环氧防污防辐射水性树脂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种稀土改性聚氨酯‑环氧防污防辐射水性树脂及其制备方法,其由二异氰酸酯、环氧树脂、4‑氨基邻苯二甲酰肼、六氟‑2‑甲基异丙醇、低聚物多元醇、多元醇、二羟甲基丙酸、稀土溶液、甲醇0.5~6.0份与中和剂通过反应制得,其玻璃化温度Tg为40~70℃、乳液粒径为100~300nm、pH值7.5~8.0;本发明制得的一种稀土改性聚氨酯‑环氧防污防辐射水性树脂,其交联密度高,具有优异的附着力、耐磨性以及防污性能,无需额外添加防辐射材料,其所制成的涂料具有良好的防辐射性能。
Description
技术领域
本发明涉及一种防污防辐射水性树脂,尤其涉及到一种稀土改性聚氨酯-环氧防污防辐射水性树脂及其制备方法,属于特种水性树脂技术领域。
背景技术
随着科学技术的发展,单一性质的材料已不能满足人们的需求,复合化、低维化、智能化是现代材料发展的趋势和信息技术发展的迫切需要。通过两种或多种材料的功能复合、性能互补和优化,可以制备出性能优异的杂化材料。因此兼具无机、有机两类材料优点的有机-无机高分子树脂杂化材料逐渐被人所重视。研究中发现,把稀土配合物与聚合物材料复合起来,制成稀土配合物-聚合物复合材料是发展稀土功能材料的一个重要方面。
而将稀土离子嫁接于高分子材料上,高分子材料的结构决定其性能,对其结构的控制和改性,可获得性能不同的材料,高分子独特的结构和易改性,以及易加工等特点,使其具有其他材料无法比拟的优越性,不可取代性,从而广泛应用在各个科学领域,聚氨酯具有优异的耐腐性、附着力、耐化学药品性、耐候性,在胶粘剂、涂料等领域得到广泛的应用。但溶剂型的聚氨酯含有大量的溶剂,如甲苯、二甲基酰胺等,都会造成严重的环境污染。而水性聚氨酯以水为溶剂,不仅具有溶剂型聚氨酯胶粘剂所具有的耐寒、耐候、弹性好、光泽高、软硬段温度可调等基本特性外,还具有无毒、无污染等优点。
中国专利CN107814895A公开了一种稀土金属配位改性水性聚氨酯发光树脂及其制备方法,玻璃化温度Tg为30~65℃、分子量为18000~30000、乳液粒径为0.3~0.8μm、pH值7~8.5;所述聚氨酯发光树脂由以下质量份数的配方组成:多异氰酸酯单体15~22份、小分子多元醇3~8份、低聚物多元醇5~12份、3~8份2-吡咯烷酮、Eu(NO3)3乙醇溶液2~8份、催化剂0.05~0.5份、丙酮8~15份、有机胺扩链剂0.2~1份、去离子水55~77份。此发明虽然采用稀土铕改性聚氨酯树脂,但其稀土离子直接与聚氨酯主链相连,稀土离子容易被包覆而影响其性能,且树脂表面张力较大,易被污染物污染,从而破坏涂层,导致涂层性能下降。
中国专利CN105820604A公开了一种环保型防辐射涂料,其由硫酸钡或重晶石为主料、以金属铁或其衍生物、铜或其衍生物、锡或其衍生物、铋或其衍生物、钨或其衍生物和稀土元素或其衍生物的混合粉为辅料,且以高分子胶粉为粘接剂。与现有技术相比,本发明提供的环保型防辐射涂料具有防辐射性能好,能吸收散射线;粉刷层薄,不会龟裂、脱落;不含铅,环保无毒、施工方便等优势,可取代铅板做新型射线防护材料,具有很大市场前景。其防辐射材料采用掺杂的方式加入,其存在分散不均,使用时间较长时,防辐射材容易脱落,对防辐射性能造成影响。
针对上述问题,本发明将稀土离子直接引入到高分子树脂端链上,形成复合材料,有效解决了稀土离子在水性树脂中分散不均、使用寿命短、易被包覆等问题。
发明内容
针对上述所述的技术问题,本发明首先合成聚氨酯-环氧树脂主链,然后引入氟元素与配位基团进行封端,将稀土离子直接引入到聚氨酯-环氧树脂中,稀土离子与聚氨酯-环氧树脂端链上的配位基团形成配位键,能有效实现高分子材料与稀土离子之间能量的传递,使其兼具聚氨酯-环氧树脂与稀土离子的特性。同时在聚氨酯分子结构上引入二羟甲基丙酸,使其能在水中均匀分散。
本发明将氟元素引入聚氨酯-环氧树脂的一端,有效的解决涂层由于表面张力过大而造成漆膜易被污染物覆盖而影响漆膜性能,在涂料成膜时,氟元素能富集表面,不易被高分子所包覆,充分发挥氟元素低表面能的特性。
为了解决所述的技术问题,所采用的稀土离子为防辐射性能好的铕(Eu)、钆(Gd)、钐(Sm)、镝(Dy),同时需控制好稀土离子用量,如稀土离子用量太多,容易造成树脂凝胶沉淀,导致树脂分散不均匀,如用量过少,将影响防辐射性能。
为消耗剩余以及游离的NCO,本发明加入甲醇,同时提高树脂储存稳定性。
本发明的目的旨在提供一种稀土改性聚氨酯-环氧防污防辐射水性树脂。
本发明的另一目的提供一种稀土改性聚氨酯-环氧防污防辐射水性树脂的其制备方法。
为满足本发明的一种稀土改性聚氨酯-环氧防污防辐射水性树脂,按重量份计,其组成为:二异氰酸酯30.0~80.0份、环氧树脂10.0~20.0份、4-氨基邻苯二甲酰肼2.0~10.0份、六氟-2-甲基异丙醇2.0~10.0份、低聚物多元醇10.0~25.0份、多元醇4.0~10.0份、二羟甲基丙酸2.5~6.5份、稀土溶液0.8~5.0份、二月桂酸二丁基锡0.01~0.1份、丙酮10.0~25.0份、甲醇0.5~6.0份、中和剂2.0~7.0份、氢氧化钠水溶液0.5~4.0份、去离子水100.0~200.0份。
本发明的一种稀土改性聚氨酯-环氧防污防辐射水性树脂,设计玻璃化温度Tg为40~70℃、乳液粒径为100~300nm、pH值7.5~8.0。
其中,优选二异氰酸酯与二羟甲基丙酸的质量比为8.0~12.0:1。
所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或几种的组合。
所述的低聚物多元醇为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚环氧乙烷多元醇、聚醚二元醇、聚乙二醇、聚环氧丙烷多元醇中的一种或几种的组合;所述的低聚物多元醇分子量为1000~3000。
所述的多元醇为乙二醇、丁二醇、1,4-环己二甲醇、新戊二醇、二缩二乙二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、三羟甲基丙烷、三羟甲基乙烷中的一种或几种的组合。
所述的稀土溶液为0.1mol·L-1的铕乙醇溶液、钆乙醇溶液、钐乙醇溶液、镝乙醇溶液中的一种或几种的组合。
所述的环氧树脂为脱水双酚A环氧树脂。
所述的稀土改性聚氨酯-环氧防污防辐射水性树脂,其制备工艺如下:
a)、在装有温度计、冷凝管、搅拌器的四口反应器中,按配方重量份,依次加入低聚物多元醇、多元醇、二羟甲基丙酸,升温至110~120℃,真空下脱水1.5~2.0h;
b)、降温至60~70℃,缓慢加入二异氰酸酯和环氧树脂后通入N2,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,然后升温到80~82℃反应2.0~2.5h,视体系粘度补充丙酮;
c)、降温至70~75℃,加入4-氨基邻苯二甲酰肼和六氟-2-甲基异丙醇,保温反应1.5~2.0h,检测,当NCO值达到规定的设计值时为止,加入适量甲醇;
d)、继续搅拌将温度降至40℃以下,缓慢滴加中和剂,高速搅拌反应,加入计算量去离子水,高速搅拌分散均匀,脱丙酮,得到聚氨酯-环氧树脂水性分散体;
e)、将聚氨酯-环氧树脂水性分散体加入到三口烧瓶中,然后升温至62~65℃,然后滴加稀土溶液,用氢氧化钠水溶液缓慢调节混合物pH值至7.5~8.0之间,继续反应2h,停止反应后,过滤,即得稀土改性聚氨酯-环氧防污防辐射水性树脂。
本发明制得的一种稀土改性聚氨酯-环氧防污防辐射水性树脂,其交联密度高,具有优异的附着力、耐磨性以及防污性能,无需额外添加防辐射材料,其所制成的涂料具有良好的防辐射性能。
具体实施方式
本发明结合以下实施例对稀土改性聚氨酯-环氧防污防辐射水性树脂做进一步的描述。
实施例1
制备稀土改性聚氨酯-环氧防污防辐射水性树脂,其步骤如下:
a)、在装有温度计、冷凝管、搅拌器的四口反应器中,按配方重量份,依次加入聚四氢呋喃二元醇25.0份、1,4-环己二甲醇5.0份、二羟甲基丙酸4.5份,升温至115℃,真空下脱水2.0h;
b)、降温至65℃,缓慢加入异佛尔酮二异氰酸酯45.0份和环氧树脂12.0份后通入N2,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡0.05份,然后升温到80~82℃反应2.0h,视体系粘度补充丙酮15.0份;
c)、降温至72℃,加入4-氨基邻苯二甲酰肼4.0份和六氟-2-甲基异丙醇4.0份,保温反应2.0h,检测,当NCO值达到规定的设计值时为止,加入甲醇2.5份;
d)、继续搅拌将温度降至40℃以下,缓慢滴加中和剂4.2份,高速搅拌反应,加入计算量去离子水145.0份,高速搅拌分散均匀,脱丙酮,得到聚氨酯-环氧树脂水性分散体;
e)、将聚氨酯-环氧树脂水性分散体加入到三口烧瓶中,然后升温至64℃,然后滴加铕乙醇溶液4.2份,用氢氧化钠水溶液3.5份缓慢调节混合物pH值至7.5~8.0之间,继续反应2h,停止反应后,过滤,即得稀土改性聚氨酯-环氧防污防辐射水性树脂,记为样品1。
实施例2
制备稀土改性聚氨酯-环氧防污防辐射水性树脂,其步骤如下:
a)、在装有温度计、冷凝管、搅拌器的四口反应器中,按配方重量份,依次加入聚碳酸酯二元醇20.0份、丁二醇5.2份、二羟甲基丙酸5.0份,升温至120℃,真空下脱水2.0h;
b)、降温至66℃,缓慢加入甲苯二异氰酸酯42.0份和环氧树脂10.0份后通入N2,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡0.05份,然后升温到80反应2.5h,视体系粘度补充丙酮13.0份;
c)、降温至72℃,加入4-氨基邻苯二甲酰肼5.0份和六氟-2-甲基异丙醇5.0份,保温反应2.0h,检测,当NCO值达到规定的设计值时为止,加入甲醇3.0份;
d)、继续搅拌将温度降至40℃以下,缓慢滴加中和剂5.2份,高速搅拌反应,加入计算量去离子水135.5份份,高速搅拌分散均匀,脱丙酮,得到聚氨酯-环氧树脂水性分散体;
e)、将聚氨酯-环氧树脂水性分散体加入到三口烧瓶中,然后升温至62℃,然后滴加钆乙醇溶液3.0份,用氢氧化钠水溶液2.5份缓慢调节混合物pH值至7.5~8.0之间,继续反应2h,停止反应后,过滤,即得稀土改性聚氨酯-环氧防污防辐射水性树脂,记为样品2。
实施例3
制备稀土改性聚氨酯-环氧防污防辐射水性树脂,其步骤如下:
a)、在装有温度计、冷凝管、搅拌器的四口反应器中,按配方重量份,依次加入聚己内酯二元醇15.0份、新戊二醇3.0份、三羟甲基丙烷2.0份、二羟甲基丙酸5.5份,升温至110℃,真空下脱水2.0h;
b)、降温至68℃,缓慢加入六亚甲基二异氰酸酯55.0份和环氧树脂20.0份后通入N2,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡0.06份,然后升温到82℃反应2.0h,视体系粘度补充丙酮19.0份;
c)、降温至75℃,加入4-氨基邻苯二甲酰肼6.0份和六氟-2-甲基异丙醇5.0份,保温反应1.5h,检测,当NCO值达到规定的设计值时为止,加入甲醇4.0份;
d)、继续搅拌将温度降至40℃以下,缓慢滴加中和剂6.0份,高速搅拌反应,加入计算量去离子水150.0份,高速搅拌分散均匀,脱丙酮,得到聚氨酯-环氧树脂水性分散体;
e)、将聚氨酯-环氧树脂水性分散体加入到三口烧瓶中,然后升温至65℃,然后滴加钐乙醇溶液4.0份,用氢氧化钠水溶液3.6份缓慢调节混合物pH值至7.5~8.0之间,继续反应2h,停止反应后,过滤,即得稀土改性聚氨酯-环氧防污防辐射水性树脂,记为样品3。
性能指标测试:将上述实例中样品1、样品2与样品3,按照表1的原料配方制备成涂料,对应的涂料样品分别记为涂料1、涂料2与涂料3,并分别测试其性能。
表1:涂料配方
原料名称 | 规格 | 用量/% |
水 | 去离子水 | 15 |
润湿剂 | pe100 | 0.3 |
乳液 | 乳液 | 80.0 |
成膜助剂 | 醇酯十二 | 4.3 |
消泡剂 | WC-DF505 | 0.1 |
流平剂 | RM-2020 | 0.3 |
将配置好的涂料按照相关标准,《漆膜耐水性测定法》(GB/T1733-1993)、《色漆和清漆漆膜的划格试验》(GB/T9286-1998)、《漆膜柔韧性测定法》(GB/T1731-1993)、铅笔硬度(GB/T6739-1996)、《色漆和清漆耐中性盐雾性能的测定》(GB/T1771-2007)、《漆膜耐冲击性测定法》(GB/T1732-1993)、接触角(GB/T30693-2014)、防辐射性(GB/T25471-2010)、涂膜耐玷污性参照克莱恩公司的耐玷污测试方法等进行性能指标测试,测试结果如表2所示。
表2:涂层的性能技术指标
检测项目 | 涂料1 | 涂料2 | 涂料3 |
耐水性 | 15d | 15d | 15d |
贮存稳定性 | 3年 | 3年 | 3年 |
附着力 | 0级 | 0级 | 0级 |
柔韧性/mm | 1 | 1 | 1 |
硬度 | 2H | 2H | 2H |
耐盐雾性 | 1000h | 1000h | 1000h |
耐碱性(10%NaOH) | 800h | 800h | 800h |
耐酸性(10%HCl) | 800h | 800h | 800h |
热中子透过率 | 0.3% | 0.37% | 0.32% |
X射线吸收率 | 99.6% | 99.2% | 99.4% |
防辐射性 | 良好 | 良好 | 良好 |
接触角 | 124° | 130° | 132° |
耐沾污性(%) | 3.2 | 2.8 | 2.8 |
按上述原料配方制备成的涂料,采用色谱、质谱法、元素分析仪检测样品中稀土离子含量,其初始含量与涂层模拟3年自然老化后稀土离子含量基本保持不变,这是由于稀土离子是通过配位键方式固定在树脂结构上,不易脱落,粉化。
以实施例1为例,在室温条件下,调节入射和出射光的狭缝均为5.0nm,电压为400V,采用荧光光谱仪测定本发明实施例1荧光光谱如下图1所示:
图1:实施例1荧光光谱
其中,a为激发光谱,b为发射光谱。
由图1可知,其发射光谱为稀土铕的特征荧光光谱,这表明其能量传递性能好,没有被高分子树脂所包覆,充分体现了稀土铕离子的特性。
尽管本发明已作了详细说明并引证了实施例,但对于本领域的普通技术人员,显然可以按照上述说明而做出的各种方案、修改和改动,都应该包括在权利要求的范围之内。
Claims (7)
1.一种稀土改性聚氨酯-环氧防污防辐射水性树脂,其特征在于,按重量份计,其组成为:二异氰酸酯30.0~80.0份、环氧树脂10.0~20.0份、4-氨基邻苯二甲酰肼2.0~10.0份、六氟-2-甲基异丙醇2.0~10.0份、低聚物多元醇10.0~25.0份、多元醇4.0~10.0份、二羟甲基丙酸2.5~6.5份、稀土溶液0.8~5.0份、二月桂酸二丁基锡0.01~0.1份、丙酮10.0~25.0份、甲醇0.5~6.0份、中和剂2.0~7.0份、氢氧化钠水溶液0.5~4.0份、去离子水100.0~200.0份;
其中,优选二异氰酸酯与二羟甲基丙酸的质量比为8.0~12.0:1;
所述的稀土改性聚氨酯-环氧防污防辐射水性树脂,其设计玻璃化温度Tg为40~70℃、乳液粒径为100~300nm、pH值7.5~8.0。
2.根据权利要求1所述的稀土改性聚氨酯-环氧防污防辐射水性树脂,其特征在于,所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或几种的组合。
3.根据权利要求1所述的稀土改性聚氨酯-环氧防污防辐射水性树脂,其特征在于,所述的低聚物多元醇为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚环氧乙烷多元醇、聚醚二元醇、聚乙二醇、聚环氧丙烷多元醇中的一种或几种的组合;所述的低聚物多元醇分子量为1000~3000。
4.根据权利要求1所述的稀土改性聚氨酯-环氧防污防辐射水性树脂,其特征在于,所述的多元醇为乙二醇、丁二醇、1,4-环己二甲醇、新戊二醇、二缩二乙二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、三羟甲基丙烷、三羟甲基乙烷中的一种或几种的组合。
5.根据权利要求1所述的稀土改性聚氨酯-环氧防污防辐射水性树脂,其特征在于,所述的稀土溶液为0.1mol·L-1的铕乙醇溶液、钆乙醇溶液、钐乙醇溶液、镝乙醇溶液中的一种或几种的组合。
6.根据权利要求1所述的稀土改性聚氨酯-环氧防污防辐射水性树脂,其特征在于,所述的环氧树脂为脱水双酚A环氧树脂。
7.根据权利要求1所述的稀土改性聚氨酯-环氧防污防辐射水性树脂的制备方法,其特征在于,所述的制备工艺如下:
a)、在装有温度计、冷凝管、搅拌器的四口反应器中,按配方重量份,依次加入低聚物多元醇、多元醇、二羟甲基丙酸,升温至110~120℃,真空下脱水1.5~2.0h;
b)、降温至60~70℃,缓慢加入二异氰酸酯和环氧树脂后通入N2,搅拌反应0.5h,滴加配方量的二月桂酸二丁基锡,然后升温到80~82℃反应2.0~2.5h,视体系粘度补充丙酮;
c)、降温至70~75℃,加入4-氨基邻苯二甲酰肼和六氟-2-甲基异丙醇,保温反应1.5~2.0h,检测,当NCO值达到规定的设计值时为止,加入适量甲醇;
d)、继续搅拌将温度降至40℃以下,缓慢滴加中和剂,高速搅拌反应,加入计算量去离子水,高速搅拌分散均匀,脱丙酮,得到聚氨酯-环氧树脂水性分散体;
e)、将聚氨酯-环氧树脂水性分散体加入到三口烧瓶中,然后升温至62~65℃,然后滴加稀土溶液,用氢氧化钠水溶液缓慢调节混合物pH值至7.5~8.0之间,继续反应2h,停止反应后,过滤,即得稀土改性聚氨酯-环氧防污防辐射水性树脂。
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