CN114058142B - 一种透明含氟聚合物薄膜 - Google Patents

一种透明含氟聚合物薄膜 Download PDF

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CN114058142B
CN114058142B CN202010770555.XA CN202010770555A CN114058142B CN 114058142 B CN114058142 B CN 114058142B CN 202010770555 A CN202010770555 A CN 202010770555A CN 114058142 B CN114058142 B CN 114058142B
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film
hydroxy
transparent
triazine
ultraviolet
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CN114058142A (zh
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刘伟
陈思献
潘东铭
蔡榕
李敏
张艳中
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
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Sinochem Lantian Co Ltd
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Abstract

本发明公开了一种透明含氟聚合物薄膜，所述透明含氟聚合物薄膜包括100份含氟树脂，0.5～15份高分子型紫外线吸收剂和0.2～2.5份三嗪类紫外线吸收剂，所述高分子型紫外线吸收剂是由含双键侧基的二苯甲酮类化合物、含双键侧基的苯并三唑类化合物中的至少一种与丙烯酸类共聚单体、丙烯酸酯类共聚单体、丙烯酰胺类共聚单体中的至少一种聚合形成。本发明的透明含氟聚合物薄膜具有紫外吸收范围宽，高紫外屏蔽性能持久，耐紫外老化性能好，耐抽提等优点，适于用作太阳能电池前板或背板膜、户外建筑或标牌保护用膜等。

Description

一种透明含氟聚合物薄膜
技术领域
本发明属于高分子材料领域，具体涉及一种持久性高紫外屏蔽的透明含氟聚合物薄膜及包含所述含氟聚合物透明薄膜的复合透明膜。
背景技术
含氟聚合物具有良好的化学稳定性、热稳定性、绝缘性、光学特性、不燃性和耐久性，使其具有广阔的应用前景。当透明含氟聚合物薄膜用作太阳能前板或背板膜、户外建筑结构(如标牌、遮阳棚、温室、房屋等)的保护用膜时，则必须具有良好的耐湿热老化性，高透明性，低水汽透过率，耐高温，耐水解，耐腐蚀性能，以及抵御紫外光照射能力。
为了防止紫外线对透明含氟聚合物薄膜以及透明含氟聚合物薄膜与基体间粘合层的降解，通常在含氟聚合物膜中加入紫外线吸收剂。专利US5254608A公开了在含氟聚合物膜中加入二苯甲酮和苯并三唑类紫外线吸收剂，所述紫外线吸收剂能够吸收紫外光并以热能的形式释放出去从而达到保护基材的目的。但该紫外线吸收剂与含氟树脂基体的相容性差，在薄膜加工、存储和使用过程中，容易向表面迁移析出并挥发，导致薄膜保护作用大幅降低。
专利CN110527223A公开了一种透明含氟聚合物膜，包括氟乙烯聚合物、2wt％至8wt％的丙烯酸酯聚合物以及0.1wt％至4wt％的三嗪紫外线吸收剂，该丙烯酸酯聚合物能够促进三嗪紫外线吸收剂与基体之间的相容性，在一定程度上延缓三嗪紫外线吸收剂的迁出，但其在使用过程中仍存在紫外线吸收剂的迁出现象。
目前，包含小分子型紫外线吸收剂的透明含氟聚合物薄膜表面容易发粘，与基体材料复合后的初始粘接力低，在透明含氟聚合物薄膜加工制备过程中，小分子型紫外线吸收剂易迁移析出到薄膜表面，影响其与基体材料之间的复合效果。另一方面，复合膜在紫外湿热老化后紫外屏蔽效果和层间粘接力大幅降低，在紫外湿热老化过程中迁移析出较为严重，影响了复合膜之间的粘接力。
发明内容
为了解决上述这些问题，本发明提供一种持久性高紫外屏蔽的透明透明含氟聚合物薄膜，不仅有效克服了小分子紫外线吸收剂迁移渗出的问题，同时拓宽了紫外吸收范围。
本发明是通过以下技术方案实现的：
一种透明含氟聚合物薄膜，所述透明含氟聚合物薄膜包括100份含氟树脂、0.5～15份高分子型紫外线吸收剂和0.2～2.5份三嗪类紫外线吸收剂，所述高分子型紫外线吸收剂如下式结构式(I)所示：
Figure BDA0002616438200000021
其中，R独立地选自H、C1～C4烷基、卤代C1～C4烷基；
R1选自C1～C16烷基、C1～C16羟烷基、C1～C16烷基环氧基；
R2独立地选自H或C1～C16烷基、C1～C16羟烷基或含氮官能基团；
a、b、c、d、e均为自然数，其对应的各聚合单元的顺序是任意的，a和b不同时为0，c、d和e不同时为0，且20≤a+b≤1500，20≤c+d+e≤1200，0.1≤(a+b)/(a+b+c+d+e)≤0.9。
优选地，200≤a+b≤1200，200≤c+d+e≤1000，0.3≤(a+b)/(a+b+c+d+e)≤0.8；更为优选地，500≤a+b≤1000，500≤c+d+e≤800，0.5≤(a+b)/(a+b+c+d+e)≤0.7。
根据上述的透明含氟聚合物薄膜，所述含氟树脂选自聚氟乙烯、聚偏氟乙烯、聚三氟氯乙烯、乙烯-三氟氯乙烯共聚物、乙烯-四氟乙烯共聚物中的至少一种；更为优选地，所述含氟树脂选自聚氟乙烯。
所述三嗪类紫外线吸收剂选自2-[4-[2-羟基-3-十三烷氧基丙基]氧基]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[4-[2-羟基-3-十二烷氧基丙基]氧基]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-[3-(2-乙基己氧基)-2-羟基丙氧基]苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-二[2-羟基-4-(2-乙基己氧基)苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪、2-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-辛氧基酚、2-(4,6-二苯基-1,3,5-三嗪-2)-5-正己烷氧基苯酚、2-[4,6-二(4-联苯基)-1,3,5-三嗪-2-基]-5-[(2-乙基己基)氧基]苯酚、4,4',4”-(1,3,5-三嗪-2,4,6-三亚氨基)三苯甲酸三(2-乙基己基)酯、二乙基己基丁酰胺基三嗪酮中的至少一种；更为优选地，所述三嗪类紫外线吸收选自2,4-二[2-羟基-4-(2-乙基己氧基)苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪、2-[4,6-二(4-联苯基)-1,3,5-三嗪-2-基]-5-[(2-乙基己基)氧基]苯酚、4,4',4”-(1,3,5-三嗪-2,4,6-三亚氨基)三苯甲酸三(2-乙基己基)酯、二乙基己基丁酰胺基三嗪酮中的至少一种。
进一步地，所述高分子型紫外线吸收剂是由含双键侧基的二苯甲酮类化合物、含双键侧基的苯并三唑类化合物中的至少一种与丙烯酸类共聚单体、丙烯酸酯类共聚单体、丙烯酰胺类共聚单体中的至少一种聚合形成。
优选地，所述二苯甲酮类化合物选自2-羟基-4-(3-甲基丙烯酸酯基-2-羟基丙氧基)二苯甲酮、2-羟基-4-(3-丙烯酸酯基-2-羟基丙氧基)二苯甲酮、4-丙烯酸酯基-2-羟基二苯甲酮、4-甲基丙烯酸酯基-2-羟基二苯甲酮、2-羟基-4-(2-苯乙烯基甲氧基)二苯甲酮、4-烯丙氧基-2-羟基-4’-甲基二苯甲酮、4-(2-羟基-3-烯丙基)丙氧基-2-羟基二苯甲酮、3,5-二丙烯酰胺基甲基-2,4-二羟基二苯甲酮、2-羟基-4-烯丙氧基二苯甲酮中的至少一种；更为优选地，所述二苯甲酮类化合物选自2-羟基-4-(3-甲基丙烯酸酯基-2-羟基丙氧基)二苯甲酮、2-羟基-4-(3-丙烯酸酯基-2-羟基丙氧基)二苯甲酮、4-丙烯酸酯基-2-羟基二苯甲酮、4-甲基丙烯酸酯基-2-羟基二苯甲酮中的至少一种。
优选地，所述苯并三唑类化合物选自2-(2-羟基-3-烯丙基-5-甲基苯基)苯并三唑、2-[2-羟基-5-(甲基丙烯酰氧基乙基)苯基]苯并三唑、2-[2-羟基-3-(丙烯酰氧基甲基)-5-甲基苯基]苯并三唑、2-(2-羟基-4-丙烯酰氧基苯基)苯并三唑、2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并三唑、2-(2-羟基-5-乙烯基苯基)苯并三唑、2-(2-羟基-5-甲基乙烯基苯基)苯并三唑中的至少一种；更为优选地，所述苯并三唑类化合物选自2-(2-羟基-3-烯丙基-5-甲基苯基)苯并三唑、2-[2-羟基-5-(甲基丙烯酰氧基乙基)苯基]苯并三唑、2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并三唑中的至少一种。
优选地，所述丙烯酸类共聚单体选自丙烯酸和/或甲基丙烯酸。
优选地，所述丙烯酸酯类共聚单体选自丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸异丁酯、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基丙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯中的至少一种；更为优选地，所述丙烯酸酯类共聚单体选自丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸-2-羟基乙酯中的至少一种。
优选地，所述丙烯酰胺类共聚单体选自丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-异丙基丙烯酰胺、N-叔丁基丙烯酰胺、N-羟甲基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺中的至少一种；更为优选地，所述丙烯酰胺类共聚单体选自丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-异丙基丙烯酰胺、N-叔丁基丙烯酰胺中的至少一种。
具体地，所述高分子型紫外线吸收剂通过以下步骤制备获得：
在反应容器(如烧瓶)中加入N,N-二甲基乙酰胺并加热至60～120℃，将二苯甲酮类化合物、苯并三唑类化合物中的至少一种与丙烯酸类共聚单体、丙烯酸酯类共聚单体、丙烯酰胺类共聚单体中的至少一种以及引发剂的混合物滴入反应容器中，保温反应2～8h后，将反应液倒入过量的甲醇中，析出，过滤得到析出固体，在40～80℃的真空干燥箱中干燥20～40小时得到淡黄色粉状高分子型紫外线吸收剂。
本发明的高分子型紫外线吸收剂中包含丙烯酸类单体和/或丙烯酸酯类单体和/或丙烯酸酰胺类单体，该三类单体与含氟树脂具有很好的相容性，且可通过分子链之间的相互缠结，进一步增强与含氟树脂分子之间的相互作用力，提高透明含氟聚合物薄膜的耐抽提性能。
三嗪类紫外线吸收剂本身与含氟树脂的相容性较差，但与丙烯酸酯类树脂的相容性较好。基于此，本发明通过在高分子型紫外线吸收剂中引入丙烯酸类单体和/或丙烯酸酯类单体和/或丙烯酸酰胺类单体，增加了三嗪类紫外线吸收剂与高分子型紫外线吸收剂的相容性，从而提高三嗪类紫外线吸收剂与含氟树脂的相容性。同时，本发明的三嗪类紫外线吸收剂包含较多含氧长侧基结构(酯基、醚基或羟基等)，可通过氢键、分子间作用力或化学键等作用与高分子型紫外线吸收剂形成强相互作用，进一步提高三嗪类紫外线吸收剂与含氟树脂的牢固性，有效地改善紫外线吸收剂在含氟树脂中的迁移渗出和挥发。
本发明的透明含氟聚合物薄膜含二苯甲酮、苯并三唑、三嗪类多种紫外线吸收基团，能吸收200～380nm波段的紫外线，实现紫外波段屏蔽全覆盖。
本发明的透明含氟聚合物薄膜还包括受阻胺类光稳定剂、成核剂和其他添加剂。
所述受阻胺类光稳定剂选用常用的受阻胺类光稳定剂即可，作为优选，所述受阻胺类光稳定剂选自N,N'-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺/2,4,6-三氯-1,3,5-三嗪/N-丁基-1-丁胺/N-丁基-2,2,6,6-四甲基-4-哌啶胺共聚物、1,5,8,12-四[4,6-双(N-丁基-N-1,2,2,6,6-五甲基-4-哌啶基氨基)-1,3,5-三嗪-2-基]-1,5,8,12-四氮杂十二烷、聚[[6-[(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亚氨基]-1,6-己二基[(2,2,6,6-四甲基-4-哌啶基)亚氨]]、2,4-二[N-丁基-(1-环己氧基-2,2,6,6-四甲基-4-哌啶基)氨]-6-(2-羟乙胺)-1,3,5-三嗪、双(2,2,6,6-四甲基-1-辛氧基-4-哌啶基)癸二酸酯、2,2,6,6-四甲基-1-{2-[((3,5,5-三甲基己酰基)氧基]乙基}哌啶-4-基3,5,5-三甲基己酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、聚丁二酸(4-羟乙基-2,2,6,6-四甲基-1-哌啶乙醇)酯中的至少一种。
所述成核剂选用常用的成核剂即可，作为优选，所述成核剂选自山梨醇缩醛类成核剂和/或取代芳基磷酸盐类成核剂。具体地，所述山梨醇缩醛类成核剂选自二对甲基苄叉山梨醇、二甲基二亚苄基山梨醇、双(4-氟-3-甲基亚苄基)山梨醇、双(3-氟-4-甲基亚苄基)山梨醇、双(4-氟-3-甲基亚苄基)木糖醇、2,4-单(4-氟-3-甲基亚苄基)山梨醇中的至少一种。所述取代芳基磷酸盐类成核剂选自2,2’-亚甲基双(2,4-二叔丁基苯氧基)磷酸钠和/或2,2’-亚甲基双(4,6-二叔丁基苯氧基)磷酸铝中的至少一种。
所述其他添加剂可选自阻燃剂、抗氧剂、热稳定剂、氧化锌、二氧化硅中的至少一种。
本发明的透明含氟聚合物薄膜通过以下步骤制备：
在25～60℃下，将100份含氟树脂、0.5～15份高分子型紫外线吸收剂、0.2～2.5份三嗪类紫外线吸收剂、0.1～6份受阻胺类光稳定剂和0.2～2份成核剂分散在0～250份潜溶剂中，混合均匀后得到制膜浆料，所得浆料经挤出机挤出和狭缝模头铸片，膜片经双向拉伸和脱挥热定型处理，最后制得厚度为20～80μm的透明含氟聚合物薄膜。
优选地，所述潜溶剂选自γ-丁内酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、碳酸丙烯酯、六甲基磷酰胺中的至少一种。
本发明还提供上述任一所述的透明含氟聚合物薄膜的应用，所述透明含氟聚合物薄膜可用作太阳能电池前板或背板膜、户外建筑或标牌保护用膜。
本发明还提供一种透明复合膜，所述复合透明膜由聚合物基底膜、粘合剂层和上述任一所述的透明含氟聚合物薄膜组成。
所述聚合物基底膜选自PET膜、PEN膜、PBT膜、PA膜、PI膜中的至少一种。
所述粘合剂选自环氧树脂、聚氨酯、丙烯酸酯或有机硅类胶黏剂中的至少一种。与现有技术相比，本发明具有的有益效果为：
1、本发明的透明含氟聚合物薄膜在保证高透明性的基础上，避免了紫外线吸收剂迁移渗出，具有持久的紫外屏蔽性能。
2、本发明的透明含氟聚合物薄膜实现紫外波段屏蔽全覆盖，具有宽紫外吸收范围和高紫外屏蔽性能。
3、本发明的复合膜有效解决了紫外湿热老化后紫外屏蔽效果和层间粘接力大幅降低的问题，具有优异的耐紫外老化性能。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
实施例1：
高分子型紫外线吸收剂的制备：
在装有搅拌器、温度计、滴液漏斗、氮气导入管以及冷却器的烧瓶中，加入200g N,N-二甲基乙酰胺并加热到120℃后，将含有4-甲基丙烯酸酯基-2-羟基二苯甲酮单体70g、甲基丙烯酸20g和N,N-二甲基丙烯酰胺10g以及偶氮二异丁腈3g的混合物逐滴加入到烧瓶中，保温反应6h后，将反应液倒入到过量的甲醇中，过滤得到析出固体。在40℃的真空干燥箱中干燥30小时后，得到淡黄色粉状固体95g，以标准聚苯乙烯为基准的GPC分析其重量平均分子量为450000，a：(c+e)＝7：3，记为高分子型紫外线吸收剂A，如下所示：
Figure BDA0002616438200000081
透明含氟聚合物薄膜的制备：
在50℃下，将2000g聚氟乙烯树脂、120g高分子型紫外线吸收剂A、10g三嗪类紫外线吸收剂
Figure BDA0002616438200000091
1600、100g光稳定剂
Figure BDA0002616438200000092
111和10g成核剂双(4-氟-3-甲基亚苄基)山梨醇分散在3600g N,N-二甲基乙酰胺中，混合均匀后得到制膜浆料，所得浆料经挤出机挤出和狭缝模头铸片，膜片经双向拉伸和脱挥热定型处理，最后制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
将聚氨酯类双组份胶黏剂调配混合预处理后，涂覆在PET基体膜上，将涂有胶黏剂的PET膜置于230℃下干燥1min，再将上述PVF薄膜和涂覆有胶黏剂的PET基体膜预热至80℃，在1.5MPa的压力下复合，然后将复合膜置于50℃下熟化48h，最后制得PVF膜和PET膜的透明复合膜。
实施例2：
高分子型紫外线吸收剂的制备：
在装有搅拌器、温度计、滴液漏斗、氮气导入管以及冷却器的烧瓶中，加入200g N,N-二甲基乙酰胺并加热到120℃后，将含有2-羟基-4-(3-甲基丙烯酸酯基-2-羟基丙氧基)二苯甲酮单体20g、甲基丙烯酸20g和甲基丙烯酸甲酯60g以及偶氮二异丁腈3g的混合物逐滴加入到烧瓶中，保温反应5h后，将反应液倒入到过量的甲醇中，过滤得到析出固体。在40℃的真空干燥箱中干燥30小时后，得到淡黄色粉状固体97g，以标准聚苯乙烯为基准的GPC分析其重量平均分子量为357000，a：(c+d)＝1：4，记为高分子型紫外线吸收剂B，如下所示：
Figure BDA0002616438200000101
透明含氟聚合物薄膜的制备：
在50℃下，将2000g聚氟乙烯树脂、120g高分子型紫外线吸收剂B、10g三嗪类紫外线吸收剂
Figure BDA0002616438200000102
1600和100g光稳定剂
Figure BDA0002616438200000103
111分散在3600g N,N-二甲基乙酰胺中，混合均匀后得到制膜浆料，所得浆料经挤出机挤出和狭缝模头铸片，膜片经双向拉伸和脱挥热定型处理，最后制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
本实施例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本实施例制备获得的透明PVF薄膜。
实施例3：
透明含氟聚合物薄膜的制备：
在50℃下，将2000g聚偏氟乙烯树脂、300g高分子型紫外线吸收剂B、5g三嗪类紫外线吸收剂
Figure BDA0002616438200000104
S、20g光稳定剂
Figure BDA0002616438200000105
783以及20g成核剂二甲基二亚苄基山梨醇在螺杆挤出机中混合造粒后，粒料经挤出机挤出和狭缝模头铸片，膜片再经纵向拉伸，最后制得厚度为30μm的透明PVDF薄膜。
透明复合膜的制备：
本实施例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本实施例制备获得的透明PVDF薄膜。
实施例4：
高分子型紫外线吸收剂C的制备：
在装有搅拌器、温度计、滴液漏斗、氮气导入管以及冷却器的烧瓶中，加入200g N,N-二甲基乙酰胺并加热到120℃后，将含有2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并三唑单体50g、甲基丙烯酸-2-羟基乙酯20g和N,N-二甲基丙烯酰胺30g以及偶氮二异丁腈3g的混合物逐滴加入到烧瓶中，保温反应4h后，将反应液倒入到过量的甲醇中，过滤得到析出固体。在40℃的真空干燥箱中干燥40小时后，得到淡黄色粉状固体94g，以标准聚苯乙烯为基准的GPC分析其重量平均分子量为204000，b：(d+e)＝1：1，记为高分子型紫外线吸收剂C，如下所示：
Figure BDA0002616438200000111
透明含氟聚合物薄膜的制备：
在50℃下，将2000g聚氟乙烯树脂、50g高分子型紫外线吸收剂C、50g三嗪类紫外线吸收剂
Figure BDA0002616438200000112
1600、60g光稳定剂
Figure BDA0002616438200000113
111和10g成核剂2,2’-亚甲基双(2,4-二叔丁基苯氧基)磷酸钠分散在3600g N,N-二甲基乙酰胺中，混合均匀后得到制膜浆料，所得浆料经挤出机挤出和狭缝模头铸片，膜片经双向拉伸和脱挥热定型处理，最后制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
本实施例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本实施例制备获得的透明PVF薄膜。
实施例5：
高分子型紫外线吸收剂D的制备：
在装有搅拌器、温度计、滴液漏斗、氮气导入管以及冷却器的烧瓶中，加入200g N,N-二甲基乙酰胺并加热到120℃后，将含有2-(2-羟基-3-烯丙基-5-甲基苯基)苯并三唑单体70g、甲基丙烯酸10g和甲基丙烯酸甲酯20g以及偶氮二异丁腈3g的混合物逐滴加入到烧瓶中，保温反应2h后，将反应液倒入到过量的甲醇中，过滤得到析出固体。在40℃的真空干燥箱中干燥40小时后，得到淡黄色粉状固体95g，以标准聚苯乙烯为基准的GPC分析其重量平均分子量为106000，b：(c+d)＝7：3，记为高分子型紫外线吸收剂D，如下所示：
Figure BDA0002616438200000121
透明含氟聚合物薄膜的制备：
在50℃下，将2000g聚氟乙烯树脂、120g高分子型紫外线吸收剂D、10g三嗪类紫外线吸收剂
Figure BDA0002616438200000131
S、100g光稳定剂
Figure BDA0002616438200000132
783和20g成核剂2,2’-亚甲基双(4,6-二叔丁基苯氧基)磷酸铝分散在3600g N,N-二甲基乙酰胺中，混合均匀后得到制膜浆料，所得浆料经挤出机挤出和狭缝模头铸片，膜片经双向拉伸和脱挥热定型处理，最后制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
本实施例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本实施例制备获得的透明PVF薄膜。
对比例1：
透明含氟聚合物薄膜的制备：
本对比例的操作同实施例1，区别仅在于：采用105.2g 4-甲基丙烯酸酯基-2-羟基二苯甲酮紫外线吸收剂代替实施例1中的高分子型紫外线吸收剂A，制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
本对比例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本对比例制备获得的透明PVF薄膜。
对比例2：
透明含氟聚合物薄膜的制备：
本对比例的操作同实施例5，区别仅在于：采用104.4g 2-(2-羟基-3-烯丙基-5-甲基苯基)苯并三唑紫外线吸收剂代替实施例5中的高分子型紫外线吸收剂D，制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
本对比例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本对比例制备获得的透明PVF薄膜。
对比例3：
透明含氟聚合物薄膜的制备：
在50℃下，将2000g聚氟乙烯树脂、120g高分子型紫外线吸收剂D、100g光稳定剂
Figure BDA0002616438200000141
783和20g成核剂2,2’-亚甲基双(4,6-二叔丁基苯氧基)磷酸铝分散在3600g N,N-二甲基乙酰胺中，混合均匀后得到制膜浆料，所得浆料经挤出机挤出和狭缝模头铸片，膜片经双向拉伸和脱挥热定型处理，最后制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
本对比例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本对比例制备获得的透明PVF薄膜。
对比例4：
透明含氟聚合物薄膜的制备：
在50℃下，将2000g聚氟乙烯树脂、10g三嗪类紫外线吸收剂
Figure BDA0002616438200000142
S、100g光稳定剂
Figure BDA0002616438200000143
783和20g成核剂2,2’-亚甲基双(4,6-二叔丁基苯氧基)磷酸铝分散在3600g N,N-二甲基乙酰胺中，混合均匀后得到制膜浆料，所得浆料经挤出机挤出和狭缝模头铸片，膜片经双向拉伸和脱挥热定型处理，最后制得厚度为30μm的透明PVF薄膜。
透明复合膜的制备：
按实施例1中同样的方法制备透明复合膜。
本对比例透明复合膜的制备同实施例1，区别仅在于：透明含氟聚合物薄膜采用本对比例制备获得的透明PVF薄膜。
对实施例1～5，对比例1～4制得的透明含氟聚合物薄膜及其复合膜进行性能测试，测试方法主要包括：
(1)根据标准GB/T 1040.3-2006进行力学性能测试；
(2)根据标准GB/T 3979进行黄色色差值Δb测试；
(3)根据标准GBT 2410-2008进行紫外线可见光透过率测试；
(4)根据标准ASTM D1003-13进行雾度测试；
(5)根据标准JEDEC-22-A102进行PCT高压加速湿热老化试验，条件为：试验箱环境温度121℃，相对湿度100％RH，压力2atm，累计运行时间96h；
(6)紫外湿热老化试验：试验箱环境温度85℃，相对湿度85％RH，紫外波长280～400nm，其中，波长280～320nm辐照量占总波段的3～10％，累计辐照量120kWh/m2，累计运行时间2000h。
(7)层间剥离强度测试：取长为200mm，宽为(10±1)mm的透明复合膜试样，沿试样长度方向将透明复合膜的一层剥开，将试样剥开的一侧夹入万能拉力机的上夹具，另一侧放入下夹具，夹紧试样并保持垂直，两层之间保持180°角，剥离速度为100mm/min，至少剥离100mm的长度。
实施例1～5和对比例1～4所制备的透明含氟聚合物薄膜的初始性能如表1所示，从测试结果对照表可以看出，实施例1～5的透明含氟聚合物薄膜的初始平均紫外屏蔽率高于98％，初始平均可见光透过率高于92％。由此可以看出，高分子型紫外线吸收剂的引入对薄膜力学性能和透明性基本没有影响，高分子型紫外线吸收剂与PVF基体有较好的相容性，而且相较于低分子型紫外线吸收剂，高分子型紫外线吸收剂制成的透明含氟聚合物薄膜具有更高的紫外屏蔽效果，说明加工过程中高分子型紫外线吸收剂具有更佳的防迁移效果。且与三嗪类紫外线吸收剂相互作用，不仅提高了三嗪类紫外线吸收剂与含氟树脂的相容性，还有效改善了紫外线吸收剂在含氟树脂中的迁移渗出和挥发。
表1初始性能对照表
Figure BDA0002616438200000161
对实施例1～5和对比例1～4所制备的透明含氟聚合物薄膜进行PCT高压加速湿热老化试验，试验结果如下表2所示。由表可知，实施例1～5的透明含氟聚合物薄膜在PCT高压加速湿热老化后，黄变值Δb≤2，力学性能保持率大于70％、平均紫外屏蔽率高于95％、平均可见光透射率高于90％，相较于对比例具有更高的紫外屏蔽保持率，而且力学性能保持率相当，说明高分子型紫外线吸收剂具有更好的抗迁移渗出效果，对可见光透过率影响较小。
表2 PCT高压加速湿热老化试验结果
Figure BDA0002616438200000162
对实施例1～5和对比例1～4所制备的透明含氟聚合物薄膜进行紫外湿热老化试验，结果如下表3所示。由表可知，实施例1～5的透明含氟聚合物薄膜在紫外湿热老化后，黄变值Δb≤2，力学性能保持率大于60％、平均紫外屏蔽率高于93％、平均可见光透射率高于90％，而且采用高分子型紫外线吸收剂的PVF薄膜具有更佳优异的力学性能和紫外屏蔽保持率，更进一步说明高分子型紫外线吸收剂具有更佳的稳定性和抗迁移渗出效果。
表3紫外湿热老化试验结果
Figure BDA0002616438200000171
对实施例1～5和对比例1～4所制备的透明复合膜进行层间剥离强度测试和紫外湿热老化试验，结果如下表4所示。由层间剥离强度测试结果可知，实施例1～5所制备的透明复合膜初始层间剥离强度高于对比例1～4的复合膜，对比例1～2采用低分子型紫外线吸收剂制备的PVF膜表面出现发粘现象，而且与PET膜复合后，其初始层间剥离强度要远远地低于采用高分子型紫外线吸收剂制备的复合膜，说明在PVF膜加工制备过程中，低分子型紫外线吸收剂易迁移析出到薄膜表面，影响其与PET膜之间的复合效果；
由紫外湿热老化试验结果看出，实施例1～5的透明复合膜在紫外湿热老化试验后，黄变值Δb≤3，平均紫外屏蔽率高于93％、平均可见光透射率高于90％。而对比例1～2利用低分子型紫外线吸收剂制备的复合膜紫外湿热老化后，层间剥离强度保持率低于实施例1～5的透明复合膜，更进一步说明低分子型紫外线吸收剂在紫外湿热老化过程中迁移析出更为严重，从而影响到复合膜层间粘接力。
表4复合膜紫外湿热老化试验结果
Figure BDA0002616438200000181

Claims (9)

1.一种透明含氟聚合物薄膜，其特征在于：所述透明含氟聚合物薄膜包括100份含氟树脂、0.5～15份高分子型紫外线吸收剂和0.2～2.5份三嗪类紫外线吸收剂，所述高分子型紫外线吸收剂如下式结构式(I)所示：
Figure FDA0004086933370000011
其中，
R独立地选自H、C1～C4烷基、卤代C1～C4烷基；
R1选自C1～C16烷基、C1～C16羟烷基、C1～C16烷基环氧基；
R2独立地选自H、C1～C16烷基、C1～C16羟烷基或含氮官能基团；
a、b、c、d、e均为自然数，a和b不同时为0，c、d和e不同时为0，且20≤a+b≤1500，20≤c+d+e≤1200，0.1≤(a+b)/(a+b+c+d+e)≤0.9；
所述三嗪类紫外线吸收剂选自2-[4-[2-羟基-3-十三烷氧基丙基]氧基]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[4-[2-羟基-3-十二烷氧基丙基]氧基]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-[3-(2-乙基己氧基)-2-羟基丙氧基]苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-二[2-羟基-4-(2-乙基己氧基)苯基]-6-(4-甲氧基苯基)-1,3,5-三嗪、2-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-辛氧基酚、2-(4,6-二苯基-1,3,5-三嗪-2)-5-正己烷氧基苯酚、2-[4,6-二(4-联苯基)-1,3,5-三嗪-2-基]-5-[(2-乙基己基)氧基]苯酚、4,4',4”-(1,3,5-三嗪-2,4,6-三亚氨基)三苯甲酸三(2-乙基己基)酯、二乙基己基丁酰胺基三嗪酮中的至少一种。
2.根据权利要求1所述的透明含氟聚合物薄膜，其特征在于：200≤a+b≤1200，200≤c+d+e≤1000，0.3≤(a+b)/(a+b+c+d+e)≤0.8。
3.根据权利要求1所述的透明含氟聚合物薄膜，其特征在于：所述高分子型紫外线吸收剂是由含双键侧基的二苯甲酮类化合物、含双键侧基的苯并三唑类化合物中的至少一种与丙烯酸类共聚单体、丙烯酸酯类共聚单体、丙烯酰胺类共聚单体中的至少一种聚合形成。
4.根据权利要求3所述的透明含氟聚合物薄膜，其特征在于：所述二苯甲酮类化合物选自2-羟基-4-(3-甲基丙烯酸酯基-2-羟基丙氧基)二苯甲酮、2-羟基-4-(3-丙烯酸酯基-2-羟基丙氧基)二苯甲酮、4-丙烯酸酯基-2-羟基二苯甲酮、4-甲基丙烯酸酯基-2-羟基二苯甲酮、2-羟基-4-(2-苯乙烯基甲氧基)二苯甲酮、4-烯丙氧基-2-羟基-4’-甲基二苯甲酮、2-羟基-4-烯丙氧基二苯甲酮中的至少一种；
所述苯并三唑类化合物选自2-[2-羟基-5-(甲基丙烯酰氧基乙基)苯基]苯并三唑、2-(2-羟基-4-丙烯酰氧基苯基)苯并三唑、2-(2-羟基-4-甲基丙烯酰氧基苯基)苯并三唑、2-(2-羟基-5-乙烯基苯基)苯并三唑、2-(2-羟基-5-甲基乙烯基苯基)苯并三唑中的至少一种；
所述丙烯酸类共聚单体选自丙烯酸和/或甲基丙烯酸；
所述丙烯酸酯类共聚单体选自丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸异丁酯、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基丙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯中的至少一种；
所述丙烯酰胺类共聚单体选自丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-异丙基丙烯酰胺、N-叔丁基丙烯酰胺、N-羟甲基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺中的至少一种。
5.根据权利要求1所述的透明含氟聚合物薄膜，其特征在于：所述含氟树脂选自聚氟乙烯、聚偏氟乙烯、聚三氟氯乙烯、乙烯-三氟氯乙烯共聚物、乙烯-四氟乙烯共聚物中的至少一种。
6.根据权利要求1-5任一所述的透明含氟聚合物薄膜，其特征在于：所述透明含氟聚合物薄膜还包括受阻胺类光稳定剂和成核剂。
7.权利要求1所述的透明含氟聚合物薄膜的应用，其特征在于：所述透明含氟聚合物薄膜用作太阳能电池前板或背板膜、户外建筑或标牌保护用膜。
8.一种透明复合膜，其特征在于：所述透明复合膜由聚合物基底膜、粘合剂层和权利要求1-5任一所述的透明含氟聚合物薄膜组成。
9.根据按照权利要求8所述的透明复合膜，其特征在于：所述聚合物基底膜选自PET膜、PEN膜、PBT膜、PA膜、PI膜中的至少一种；所述粘合剂层选自环氧树脂、聚氨酯、丙烯酸酯或有机硅类胶黏剂中的至少一种。
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