CN115612389A - 一种无氟生物基聚氨酯涂料及其制备方法 - Google Patents
一种无氟生物基聚氨酯涂料及其制备方法 Download PDFInfo
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Abstract
本申请公开了一种无氟生物基聚氨酯涂料,属于涂料技术领域。按质量份数计,无氟生物基聚氨酯涂料包括如下组分:聚酯多元醇5~20份,生物基多元醇10~50份,有机硅多元醇1~10份,丙烯酸多元醇30~60份,固化剂,钛白粉10‑40份,硫酸钡10~20份,分散剂0.2~3份,流平助剂0.1~2份,有机溶剂20~30份。本发明的无氟生物基聚氨酯涂料环保,耐候性优良。
Description
技术领域
本发明涉及涂料技术领域,尤其涉及一种无氟生物基聚氨酯涂料。
背景技术
太阳能光伏组件是太阳能光伏发电的核心,太阳能电池背板作为太阳能光伏组件的重要辅材之一,主要对太阳能光伏组件起到支撑和保护作用,需具有可靠的机械性能,绝缘性,阻隔水汽性,耐老化性能等性能。涂覆型背板由于工艺简单、性能容易调整和成本低等特点,逐渐受到市场的青睐。
含氟材料具有优良的耐候性能被大量用于涂覆型背板中,但是含氟材料的化学性质稳定,无法降解,燃烧后会释放出有毒有害的气体,目前尚无有效的回收方案和技术。
发明专利一种涂覆太阳能电池背板的聚氨酯基涂料及其制备方法(公开号为CN108504273A)公开了将天然改性的松香树脂作为聚酯多元醇的材料,即在聚氨酯涂料中引入生物,从而达到后期降解的可能。但是,松香树脂改性的聚酯的耐候性能难以达到光伏组件的长期耐候要求,该发明中仍然使用了含氟树脂,且含氟树脂的比例不能太低。
发明内容
本发明针对上述问题,提出了一种环保且耐候性优良的无氟生物基聚氨酯涂料。
本发明采取的技术方案如下:本发明提供一种无氟生物基聚氨酯涂料,按质量份数计,包括如下组分:聚酯多元醇5~20份,生物基多元醇10~50份,有机硅多元醇1~10份,丙烯酸多元醇30~60份,固化剂40~60份,钛白粉10-40份,硫酸钡10~20份,分散剂0.2~3份,流平助剂0.1~2份,有机溶剂20~30份。
本发明的涂料中,固含量大于70%,相对于传统的溶剂型涂料,高固含的涂料能有效的降低VOC排放以及焚烧产生的二氧化碳的排放,更加环保。一般体系的粘度随着固含量的提高增加,传统的溶剂型涂料体系粘度太大随着固含超过60以上,失去了施工的意义。因此高固低粘是高固含涂料的核心要求,并且能够满足涂层的其他的技术指标。
对聚酯多元醇、生物基多元醇、有机硅多元醇和这三者复配的树脂进行水滴角测试,其中,聚酯多元醇的水滴角为91.838,生物基多元醇的水滴角为99.933,有机硅多元醇的水滴角为116.241,复配树脂(三者复配)的水滴角为102.646,说明生物基多元醇和有机硅多元醇的加入可以显著改善聚酯多元醇的疏水性和表面张力,水在产品表面停留时间变短,从而提高产品的稳定性及耐候性。
可选地,生物基多元醇为植物基多元醇。本发明中的生物基多元醇其来源来着植物界的油,通过氧化、羟基化技术处理改性后得到,既保留了天然产物的特点环保,可以在合适的条件下发生降解反应,有助于后期回收等,同时生物基来源的材料有别于石油基的材料,因为中间减少了生产加工中的环节,可以明显降碳排放。此外,基于生物基多元醇的聚氨酯涂层能够赋予基材表面耐冲击、耐摩擦、耐腐蚀、耐潮湿水解、耐高低温变化等优异性能,同时致密的分子结构阻止了小分子渗透,达到耐脏污、易清洁的目的。
具体地,生物基多元醇为改性后的蓖麻油多元醇、腰果油多元醇、棕榈油多元醇中的一种或多种。蓖麻油多元醇、腰果油多元醇、棕榈油多元醇能够显著提高聚氨酯体系的疏水性,因而能够有效地提高涂层系统的耐水性能,具有优异的耐溶剂性、耐碱性、耐酸性和耐水性、良好的尺寸稳定性和较好的物理性能(如抗拉强度)。
可选地,有机硅多元醇为两端带有醇羟基的线性聚二甲基硅氧烷,且其分子量为2000~10000,粘度适中,柔韧性优异。Si-O键能够使得玻璃化转变温度低,比较柔软,能够显著的改善聚氨酯涂层的柔韧性、疏水性以及耐老化性能,同时可以帮助提高耐磨性和耐刮擦性,并且具有良好的透气性能。其中,线性聚二甲基硅氧烷的小于2000,分子量过小,交联密度小,耐候不佳;分子量大于10000,分子量过大,交联密度过大,柔韧性不够,甚至是固体,失去作为液体涂料的优势,而且会影响反应活性。
可选地,聚酯多元醇由至少一种多元酸和至少两种多元醇通过缩聚反应制得。聚酯多元醇包括线型和支化型结构,也可以是超支化结构。聚酯多元醇的引入可以平衡体系的油水平衡,既能保证足够的疏水性能同时保持一个较为高的表面张力,可以满足和EVA胶水黏合强度,保证器件间的稳定性以及耐候性。现有的采用己二酸和己二醇缩聚形成的聚酯多元醇耐候性较差。
具体地,本申请采用了至少两种多元醇,其中一种所述多元醇为2,2,4,4-四甲基-1,3-环丁二醇(TMCD),TMCD作为其中的一种多元醇,与多元酸反应制备得到超支化的聚酯多元醇。TMCD中的四甲基结构让聚酯材料溶解性更佳,与其他组分有很好的兼容性,让涂料以更低的粘度获得更高的固含。此外,TMCD中带有的仲醇羟基有助于提高耐污渍和耐化学性能,并赋予最终的涂料水解稳定性。脂环结构在保证聚合物硬度和刚性的同时,即使在高于玻璃化转变温度的情况下使其仍然具有优异的柔韧性。此外,超支化的聚酯可以显著降低体系的粘度,搭配使用可以制备高固含低粘度的涂料体系。
丙烯酸树脂由于其优良的耐候性能,以及价格相对便宜而得到了广泛的应用,其表面张力一般在30~40达因,因此能够和粘合剂具有优良的结合力,且具有较好的润湿以及贴合强度。固化剂为异氰酸酯类固化剂,能够提供交联。
可选地,按质量份数计,本发明的无氟生物基聚氨酯涂料还包括如下组分:催化剂0.2~2份,紫外吸收剂0.5~3份,消光粉5~10份,消泡剂0.1~0.5份。
紫外吸收剂是指能够吸收紫外线的一种小分子化合物,可以选用苯并三氮唑以及三嗪类化学品,能够有效的吸收260nm到400nm的紫外线,从而提高的体系的耐老化能力。本申请中的有机溶剂可以使用指乙酸乙酯、醋酸丁酯、三甲苯、二甲苯、甲苯、100号汽油或者其他的常用有机溶剂和体系由良好的相容性。催化剂为有机锡、有机铋、有机锌等。
本发明还提供一种无氟生物基聚氨酯涂料的制备方法,具体包括如下步骤:
将聚酯多元醇、生物基多元醇、有机硅多元醇、丙烯酸多元醇分别加入溶剂中,搅拌均匀后分别加入消泡剂、流平助剂、催化剂、分散剂,混合均匀后分别加入钛白粉、硫酸钡、消光粉得到混合液;
将上述混合液放入研磨机进行研磨,直至分散体的颗粒度或者细度达到8-12μm,然后通过300~400目的滤网过滤;
加入紫外吸收剂,并且用有机溶剂调节粘度至50~200mPa.s,得到A组分;
将异氰酸酯固化剂用有机溶剂稀释后得到B组分,其中,异氰酸酯固化剂和有机溶剂的稀释比为50%~80%;
将A组分和B组分按照NCO/OH=1~1.1的比例混合并且充分搅拌均匀制得涂料。
其中,异氰酸酯固化剂是指脂肪族的异氰酸酯固化剂,因为其无黄变聚异氰酸酯且有优秀的耐候性能,比如六亚甲基二异氰酸酯(HDI)类的三聚体以及缩二脲等,也可以是异佛尔酮二异氰酸酯(IPDI),本申请中的异氰酸酯固化剂可以按照需要单独使用其中的一种,也可以是多种的混合物。
具体地,本申请中的丙烯酸多元醇为同德树脂的6851A,6750,6688,6696;聚酯多元醇为伊斯曼的AC1001,IC3020;有机硅多元醇为崇耀科技SL-7510,SL-7540;生物基多元醇为NX-9212x,巴斯夫750;分散剂为BYK163;消泡剂为BYKA501,A530;流平剂为BYK354;催化剂为二月桂酸二丁基锡。
本发明的有益效果是:本发明的无氟生物基聚氨酯涂料不含氟材料,且能够达到现有含氟材料的涂料相当的技术指标,耐候性能优异。此外,本发明的涂料固含量大于70%,能有效的降低VOC排放以及焚烧产生的二氧化碳的排放,更加环保。
附图说明
图1是本发明的无氟生物基聚氨酯涂料固化后形成的涂层的水滴角测试图;
图2是市售的含氟光伏涂层样品水滴角测试图。
具体实施方式
下面结合各附图,通过具体实施例,对本发明进行详细、完整的描述。
实施例1
将30份丙烯酸多元醇(羟基160),10份聚酯多元醇(羟基160),3份有机硅多元醇(羟基120),40份生物基多元醇(羟基300)以及10份溶剂(乙酸乙酯:乙酸丁酯:三甲苯=2:1:1)混合;然后将1份分散剂,0.1份消泡剂,0.1流平剂,0.1催化剂以及5份溶剂混合。然后将上面的混合并且搅拌均匀,然后将60份钛白粉加入上述的混合物,然后用分散机分散均匀。接着将混合君和混合物放入球型研磨机研磨,转速为3000转/分,控制研磨的温度在30度一下,并且用细度板来检测过程中的细度,等细度低于10微米后,停止研磨,大概需要3个小时,过滤后,加入1份的紫外吸收剂(三嗪类)以及0.5分紫外捕捉剂(受阻胺类)做成A组分。然后加入55份的六亚甲基二异氰酸酯三聚体固化剂(NCO%为22%)和5份的溶剂混合物。最终的涂料的固含在80%,对应的粘度在400cps,细度小于10微米。
实施例2
将40份丙烯酸多元醇(羟基160),5份有机硅多元醇(羟基120),35份生物基多元醇(羟基300)以及10份溶剂(乙酸乙酯:乙酸丁酯:三甲苯=2:1:1)混合;然后将1份分散剂,0.1份消泡剂,0.1流平剂,0.1催化剂以及5份溶剂混合。然后将上面的混合并且搅拌均匀,然后将60份钛白粉加入上述的混合物,然后用分散机分散均匀。接着将混合君和混合物放入球型研磨机研磨,转速为3000转/分,控制研磨的温度在30度一下,并且用细度板来检测过程中的细度,等细度低于10微米后,停止研磨,大概需要3个小时,过滤后,加入1分的紫外吸收剂(三嗪类)以及0.5分紫外捕捉剂(受阻胺类)做成A组分。然后加入60份的六亚甲基二异氰酸酯三聚体固化剂(NCO%为22%)和5份的溶剂混合物。最终的涂料的固含在80%,对应的粘度在350cps,细度小于10微米。
实施例3
将40份丙烯酸多元醇(羟基160),5份有机硅多元醇(羟基120),35份生物基多元醇(羟基300)以及10份溶剂(乙酸乙酯:乙酸丁酯:三甲苯=2:1:1)混合;然后将1份分散剂,0.1份消泡剂,0.1流平剂,0.1催化剂以及5份溶剂混合。然后将上面的混合并且搅拌均匀,然后将40份钛白粉加入上述的混合物,然后用分散机分散均匀。接着将混合君和混合物放入球型研磨机研磨,转速为3000转/分,控制研磨的温度在30度一下,并且用细度板来检测过程中的细度,等细度低于10微米后,停止研磨,大概需要3个小时,过滤后,加入1分的紫外吸收剂(三嗪类)以及0.5分紫外捕捉剂(受阻胺类)做成A组分。然后加入60份的六亚甲基二异氰酸酯三聚体固化剂(NCO%为22%)和5份的溶剂混合物。最终的涂料的固含在70%,对应的粘度在300cps,细度小于10微米。
表1为本发明的无氟生物基聚氨酯涂料固化后形成的涂层的性能测试
对比例1
按照光伏行业的要求对涂层进行测试,包括接触角,耐溶剂,耐酸,耐碱,耐热,水煮等实验室将本发明无氟生物基涂液以及市面上典型的涂液1和2分别涂布在188umPET涂布8um光伏涂层(干重),固化条件为150℃下3分钟,然后熟化1天后测试。本发明的无氟生物基涂层都能达到光伏行业的要求,在耐溶剂方面则比市面的含氟涂液1和2更好。具体如说明书附图1以及表2和表3所示。
表2为市售含氟涂层1的测试结果
表3为本发明的聚氨酯涂料固化后的涂层和市售含氟涂层2的对比结果
以上所述仅为本发明的优选实施例,并非因此即限制本发明的专利保护范围,凡是运用本发明说明书及附图内容所作的等效结构变换,直接或间接运用在其他相关的技术领域,均同理包括在本发明的保护范围内。
Claims (8)
1.一种无氟生物基聚氨酯涂料,其特征在于,按质量份数计,包括如下组分:
聚酯多元醇5~20份,生物基多元醇10~50份,有机硅多元醇1~10份,丙烯酸多元醇30~60份,固化剂40~60份,钛白粉10-40份,硫酸钡10~20份,分散剂0.2~3份,流平助剂0.1~2份,有机溶剂20~30份。
2.根据权利要求1所述的无氟生物基聚氨酯涂料,其特征在于,所述生物基多元醇为植物基多元醇。
3.根据权利要求2所述的无氟生物基聚氨酯涂料,其特征在于,所述生物基多元醇为改性后的蓖麻油多元醇、腰果油多元醇、棕榈油多元醇中的一种或多种。
4.根据权利要求1所述的无氟生物基聚氨酯涂料,其特征在于,所述有机硅多元醇为两端带有醇羟基的线性聚二甲基硅氧烷,且其分子量为2000~10000。
5.根据权利要求1所述的无氟生物基聚氨酯涂料,其特征在于,所述聚酯多元醇由至少一种多元酸和至少两种多元醇通过缩聚反应制得。
6.根据权利要求5所述的无氟生物基聚氨酯涂料,其特征在于,其中一种所述多元醇为2,2,4,4-四甲基-1,3-环丁二醇。
7.根据权利要求1-6任意一项所述的无氟生物基聚氨酯涂料,其特征在于,按质量份数计,还包括如下组分:
催化剂0.2~2份,紫外吸收剂0.5~3份,消光粉5~10份,消泡剂0.1~0.5份。
8.一种无氟生物基聚氨酯涂料的制备方法,其特征在于,具体包括如下步骤:
将聚酯多元醇、生物基多元醇、有机硅多元醇、丙烯酸多元醇分别加入溶剂中,搅拌均匀后分别加入消泡剂、流平助剂、催化剂、分散剂,混合均匀后分别加入钛白粉、硫酸钡、消光粉得到混合液;
将上述混合液放入研磨机进行研磨,直至分散体的颗粒度或者细度达到8-12μm,然后通过300~400目的滤网过滤;
加入紫外吸收剂,并且用有机溶剂调节粘度至50~200mPa.s,得到A组分;
将异氰酸酯固化剂用有机溶剂稀释后得到B组分,其中,异氰酸酯固化剂和有机溶剂的稀释比为50%~80%;
将A组分和B组分按照NCO/OH=1~1.1的比例混合并且充分搅拌均匀。
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