CN109312031A - 含氟聚合物 - Google Patents

含氟聚合物 Download PDF

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CN109312031A
CN109312031A CN201780034801.1A CN201780034801A CN109312031A CN 109312031 A CN109312031 A CN 109312031A CN 201780034801 A CN201780034801 A CN 201780034801A CN 109312031 A CN109312031 A CN 109312031A
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方海波
R·弗里德里西
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Merck Patent GmbH
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Abstract

本发明涉及新的含氟聚合物，包含所述聚合物的组合物，所述聚合物在涂料中，尤其在防水和防污涂料中的用途，和用含有所述聚合物的涂料涂覆的产物。

Description

含氟聚合物
本发明涉及新的含氟聚合物，包含所述聚合物的组合物，所述聚合物在涂料中，尤其在防污涂料中的用途，和用含有聚合物的涂料涂覆的产品。
防污涂料对于许多技术应用而言是至关重要的部分。经常使用氟化材料，因为它们具有同时提供防油性和防水性的独特特性。户外装备，技术防护服如消防服、防弹衣或防弹服，仅是这些应用的一些实例。
对于防污涂料，经常使用基于C6化学的全氟化单体。在全世界的监管部门，这些氟化材料引起环境方面的担忧。由于全氟化部分的链长，这种类型的化合物潜在地是生物累积的、持久的和有毒的。具有2-5个碳原子的较短的全氟化烷基链已知是毒性和生物累积性较小的，但表现出不充分的效能。
一直存在对用于涂料的可选氟化材料的需求。
现在已经发现新的聚合物，它们适用于功能涂料用于改进在环氧、丙烯酸系和PUR涂料中以及在服装或皮革上的耐沾污性，并且它们在它们的生态毒理学性能状况方面是有益的。
本发明涉及如下聚合物，其包含衍生自至少一种式(I)或(II)的单体的单体单元
(Rf1-CHF-CF2-O-CHR1)m1-L1-(X1)n1 (I)
(Rf2-CHF-CF2-S-CHR2)m2-L2-(X2)n2 (II)
其中
Rf1和Rf2彼此独立地是全氟化的、优选含杂原子的烷基基团，
R1和R2彼此独立地是H或烷基基团，
L1和L2彼此独立地是单键或二价有机基团，
X1和X2彼此独立地是烯属不饱和基团，
m1和m2彼此独立地为≥1，和
n1和n2彼此独立地为≥1。
所述新的聚合物可以包含一种或多种式(I)的单体，或者一种或多种式(II)的单体，或者一种或多种式(I)的单体和一种或多种式(II)的单体的组合。
优选地，Rf1和Rf2彼此独立地选自如下基团：
CF3-(CF2)0-3-、
CF3-(CF2)0-3-O-、
CF3-(CF2)0-3-O-(CF2)1-3-、
CF3-(CF2)0-3-O-(CF2)1-3-O-、
CF3-(CF2)0-3-O-(CF2)1-3-O-CF2-、
CF3-(CF2)0-3-O-(CF2-O)1-8-和
CF3-(CF2)0-3-O-(CF2-O)1-8-CF2-。
在本发明的尤其优选的变体中，Rf1和Rf2彼此独立地选自如下基团：
CF3-(CF2)1-2-、
CF3-(CF2)1-2-O-、
CF3-O-(CF2)1-3-、
CF3-O-(CF2)1-2-O-、
CF3-(CF2)1-2-O-CF2-、
CF3-O-(CF2)1-2-O-CF2-、
CF3-O-(CF2-O)1-8-和
CF3-O-(CF2-O)1-8-CF2-。
优选地，R1和R2彼此独立地选自H和C1-C3烷基。
优选地，L1和L2彼此独立地选自单键和饱和的、支化或非支化的、任选含有杂原子(尤其是O和/或S原子)和/或官能基团的有机基团，尤其是亚烷基基团。
优选地，X1和X2彼此独立地是丙烯酸酯或甲基丙烯酸酯基团。
优选地，m1和m2彼此独立地是1-3，特别是1-2。
优选地，n1和n2彼此独立地是1-3，特别是1。
优选如下聚合物，该聚合物包含衍生自至少一种式(I)和/或(II)的单体的单体单元，其中一个或多个变量具有所述优选的含义。尤其优选如下聚合物，该聚合物包含衍生自至少一种式(I)和/或(II)的单体的单体单元，其中所有变量同时具有所述优选的含义。
特别优选如下的式(I)和(II)的化合物，其中：
Rf1和Rf2彼此独立地选自
CF3-(CF2)1-2-、CF3-(CF2)1-2-O-、CF3-O-(CF2)1-3-、CF3-O-(CF2)1-3-O-、CF3-(CF2)1-2-O-CF2-、CF3-O-(CF2)1-2-O-CF2-、CF3-O-(CF2-O)1-8-和CF3-O-(CF2-O)1-8-CF2-，
R1和R2彼此独立地是H或CH3，
L1和L2彼此独立地是单键或C1-C4亚烷基基团，该基团任选是支化的和/或包含杂原子，尤其是O或S，和/或官能基团，
X1和X2彼此独立地是丙烯酸酯或甲基丙烯酸酯基团，和
m＝1或2，和n＝1。
尤其优选的是如下聚合物，该聚合物包含衍生自至少一种选自下式(Ia)至(Id)(尤其是(Ia)至(Ic))和/或(IIa)至(IIc)的单体的单体单元。
其中，
Rf是全氟化的、任选含有杂原子的烷基基团，和
R’和R”彼此独立地是H或烷基基团。
特别优选的是如下聚合物，该聚合物包含衍生自至少一种选自式(Ia)至(Ic)和/或(IIa)至(IIc)的单体的单体单元，其中
Rf是
CF3-(CF2)1-2-、
CF3-(CF2)1-2-O-、
CF3-O-(CF2)1-3-、
CF3-O-(CF2)1-2-O-、
CF3-(CF2)1-2-O-CF2-、
CF3-O-(CF2)1-2-O-CF2-、
CF3-O-(CF2-O)1-8-或
CF3-O-(CF2-O)1-8-CF2-，和
R’和R”彼此独立地是H或甲基。
在本发明尤其优选的变体中，所述聚合物包含衍生自至少一种选自式(Ia)至(Ic)和/或(IIa)至(IIc)的单体的单体单元，其中Rf是
CF3-(CF2)1-2-、
CF3-(CF2)1-2-O-、
CF3-O-(CF2)1-3-或
CF3-O-(CF2)1-2-O-，和
R’和R”彼此独立地是H或甲基。
优选地，所述聚合物包含衍生自至少一种选自式(Ia)至(Ic)和/或(IIa)至(IIc)的单体的单体单元，其中Rf是CF3-CF2-CF2-O-、CF3-CF2-O-或
CF3-O-，和
R’和R”彼此独立地是H或甲基。
特别优选如下聚合物，该聚合物包含衍生自选自如下单体的至少一种单体的单体单元：
式(I)和(II)的化合物可以通过简单的、标准的方法步骤制备。例如，式(I)的化合物可以通过相应的醇与酸或酸酐的反应，通过本领域技术人员已知的方法制备。
式(II)的化合物可以通过相应的全氟烯烃与相应的硫代化合物的反应制备。
必要的起始材料是可商购的，可通过已知的方法由可商购产品制备，或者可以通过已知的合成类似地制备，
根据式(I)和(II)的化合物和它们的制备方法描述在WO2016/096129中。
所述新的聚合物可以仅包含衍生自至少一种式(I)和/或(II)的官能共聚单体的单体单元。
在本发明的变体中，所述新的聚合物可以包含衍生自至少一种式(I)和/或(II)的官能共聚单体和至少一种官能共聚单体和/或至少一种非官能共聚单体的单体单元。这样的共聚物可以由式(III)表示
其中
R1＝氟化的基团
R2＝官能基团
R3＝非官能基团
n、m、o＝各自单体的总数
R’＝H、CH3
所述官能共聚单体优选选自包含-OH、环氧基、-Si(OMe)3、-Si(OEt)3、-CO2H或叔氨基基团的单体。尤其优选的官能共聚单体选自如下单体，其中R”’＝H或甲基：
所述非官能共聚单体优选选自包含直链或支化烷基基团或聚醚基团的单体或选自苯乙烯类的单体。尤其优选的非官能共聚单体选自如下单体，其中R””＝H或甲基：
在本发明的一个优选变体中，所述聚合物包含衍生自至少一种式(I)和/或(II)的单体、至少一种官能共聚单体和至少一种非官能共聚单体的单体单元。
所述聚合物可以包含所述三种类型的单体(氟化的基团：Rf-G，官能基团：F-G，和非官能基团：nF-G)，其每种的量在1-99％之间，在最终聚合物中得到总量100％(％＝重量％)。
优选的组合是
表1
Rf-G 20-80％ 50-98％
F-G 2-20％ 2-50％
nF-G 20-80％ 0％
总计 100％ 100％
平衡所述共聚物的组成对于在最终组合物或涂层中的所述聚合物的最终性能是关键的。
所述聚合自身可以通过标准方法完成，即通过在溶液中、本体中或乳液中的自由基聚合完成。合适的引发剂是例如偶氮二(异丁腈)(AIBN)和2-2'-偶氮双(2,4-二甲基戊腈)(Vazo)。合适的溶剂是例如乙酸异丙酯，1,4-二噁烷，四氢呋喃和甲苯。
聚合方法对于本领域技术人员而言是已知的。
常规的工艺参数例示在实验部分中。所述聚合物可以被分离或者在分散体或溶液中使用。优选地，所述聚合在与随后的涂料分散体使用的相同的溶剂中进行。如果所述溶剂是不合适的，在聚合之后可以进行溶剂更换。优选地，所述聚合作为自由基聚合在惰性气氛下、采用如AIBN的热活化引发剂进行。
根据本发明的聚合物可以原样用作涂料或用作常规涂料的添加剂。
根据本发明的聚合物，其包含式(I)和/或(II)的化合物，优选式(Ia)至(Ic)和/或(IIa)至(IIc)的化合物，特别以它们优选的变体形式，可以具有与现有技术聚合物相比改进的环境性质，因为它们不发生化学或生物降解而形成长链PFCA或PFAS。
优选的使用领域例如是根据本发明的聚合物作为添加剂用于如下方面的用途：用于表面涂布的制剂，例如油漆(paint)、漆(lacquer)、防护涂料、在电子或半导体应用中的特殊涂料(例如光致抗蚀剂、顶部抗反射涂料、底部抗反射涂料)中或在光学应用中的特殊涂料(例如感光涂料(photographic coatings)、光学元件的涂料)，用于农用化学品中，用于上光剂和蜡中，例如用于家具，地板覆盖材料和机动车的那些，特别是用于地板蜡中，用于灭火组合物、润滑剂中，或用于光刻方法中，特别是用于浸没光刻法中，例如在显影剂溶液、漂洗溶液、浸没油中和/或在光致抗蚀剂自身中，尤其用于制备印刷电路或者在用于相应制剂的添加剂制剂中。
为了使用，通常将根据本发明的聚合物相应地引入到设计的制剂中。通常的使用浓度是基于整个组合物计，0.01-30.0重量％，优选0.01-10.0重量％的根据本发明的聚合物。本发明同样涉及包含根据本发明的聚合物的相应组合物。这样的组合物优选包含适合于各自应用的溶剂，以及任选的另外的活性物质和/或任选的添加剂。优选的组合物是油漆和涂料制剂，灭火剂，润滑剂，洗涤剂和去垢剂和除冰剂或显影剂溶液、漂洗溶液、浸没油和用于光刻方法的光致抗蚀剂，特别用于浸没光刻方法的那些，和特别用于制造印刷电路，农用化学品，地板蜡，化妆产品，化妆产品或用于织物整理或玻璃处理的疏水化剂。此处优选的组合物是油漆和涂料制剂和印刷油墨。
另外，本发明还涉及水基表面涂料配制剂，其包含根据本发明的聚合物，所述根据本发明的聚合物是单独的或与添加剂混合的。优选使用基于如下合成膜形成物的表面涂料配制剂：缩聚树脂，例如醇酸树脂、饱和/不饱和聚酯、聚酰胺/酰亚胺、有机硅树脂；酚醛树脂；脲树脂和三聚氰胺树脂，聚加成树脂，例如聚氨酯和环氧树脂，聚合树脂，例如聚烯烃，聚乙烯基化合物和聚丙烯酸酯。
另外，根据本发明的聚合物还适合在基于天然产物和改性的天然产物的表面涂料中使用。优选基于油、多糖，例如淀粉和纤维素的表面涂料，以及基于天然树脂，例如环状低聚萜烯，聚萜烯和/或虫胶的表面涂料。
根据本发明的聚合物可以用于物理固化性(热塑性塑料)和交联性(弹性体和热固性塑料)水性表面涂层体系二者。根据本发明的聚合物优选改进了经涂覆的表面的防水和/或防污性。
本发明涉及待根据本发明使用的聚合物的此处提及的所有用途。用于所述目的的聚合物的各自用途对于本领域技术人员而言是已知的，并且因此待根据本发明使用的聚合物的使用不存在问题。
本发明特别涉及根据本发明的聚合物和它们的上述优选实施方案作为功能涂料和在功能涂料中的用途，例如用于改进涂料配制剂的防水和/或防污性，所述涂料配制剂例如环氧、丙烯酸系和PUR涂料。
除了包含式(I)和/或(II)的化合物的单体单元的聚合物外，根据本发明的涂料配制剂还可以包含溶剂、添加剂、助剂和填料，以及非氟化的聚合物。
包含一种或多种根据本发明的聚合物的溶液或分散体可作为用于常规涂料的添加剂应用，但将所述溶液或分散体自身作为薄层旋涂在基底上也可能是有益的。合适的基底例如是玻璃、陶瓷、金属、纺织品、服装或皮革。
所述聚合物和包含这样的聚合物的涂料可以关于它们的生态毒理学性能状况方面是有益的，并且同时显示出良好的防水和防污性。另外，根据本发明的聚合物和涂料可以显示出良好的可加工性和/或贮存稳定性。
明确提及的所有的申请和公开出版物的全部公开内容通过引用也属于本申请的公开内容。从权利要求书和实施例中还可得到本发明的其它特征、优点和变体。下面的实施例更详细地解释本发明，而不限制保护范围。
实施例
缩写
MTBE 叔丁基甲基醚
DI水 去离子水
RT 室温
wt 重量百分比
实施例1：2-甲基丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙基硫烷基)乙基酯的合成
实施例1a：
将77.30g全氟丙基乙烯基醚、52.21g 2-巯基乙醇、40ml乙腈和12g碳酸钾在压力反应器中加热至100℃持续18小时。向反应混合物中添加25ml水和25ml MTBE并进行相分离。水相用2×25mL MTBE萃取，并将合并的有机相用70mL水和70mL饱和NaCl溶液洗涤。使萃取物经硫酸钠干燥，并移除溶剂和将原料蒸馏(在0.1毫巴下沸点45-49℃)。产物：63.40g＝63％
1H-NMR:6.8ppm(dt,1H,-CFH)；3.6ppm(t,2H,-CH2O-)；3.1ppm(t,2H,-SCH2)；
实施例1b：
将10g得自实施例1b的醇与0.5g甲苯-4-磺酸一水合物一起溶解在60ml甲苯中。然后在搅拌下缓慢添加4.5g甲基丙烯酸酐，并将反应混合物在110℃下搅拌24小时。将混合物冷却到RT，添加25mL水和25mL MTBE并进行相分离。随后用2×25mL MTBE洗涤水相。将合并的有机相经硫酸钠干燥、过滤和将溶剂在旋转蒸发仪中蒸馏除去。
产物：11.30g＝94％
1H-NMR:7.1ppm(m,1H,-CFH)；6.1ppm(m,1H,＝CH)；5.7ppm(m,1H,＝CH)；4.3ppm(t,2H,-CH2O-)；3.2ppm(t,2H,-SCH2)；1.9ppm(s,3H,-CH3)
实施例2：2-甲基丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙氧基)乙酯的合成
在氩气下将41.4g(126.2mmol)2-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-乙醇，(0.1当量)TEMPO和16.6g(164mmol，1.3当量)三乙胺首先引入至具有220mL MTBE的三颈圆底烧瓶，并在冰冷却下冷却至0℃。逐滴加入14.5g(138mmol，1.3当量)甲基丙烯酰氯。将混合物在冰冷却下搅拌过夜，然后在回流下搅拌18小时。通过用水和MTBE进行溶剂萃取来纯化产物。分离各相，将水相用75ml MTBE萃取两次。将合并的有机相用100mL水和100mL饱和NaCl溶液洗涤，经硫酸钠干燥并真空除去溶剂。产物：53克
1H-NMR(DMSO,60MHz):
实施例3：2-甲基-丙烯酸2-{3-[2,3-双-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-丙氧基]-丙基硫烷基}-乙酯的合成
在氩气下将4.7g(6.3mmol)2-{3-[2,3-双-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-丙氧基]-丙基硫烷基}-乙醇和0.84g(8.3mmol，1.3当量)三乙胺首先引入具有30mL MTBE的三颈圆底烧瓶中，并在冰冷却下冷却至0℃。逐滴加入1.2g(11.4mmol，1.8当量)甲基丙烯酰氯。将混合物在冰冷却下搅拌过夜，然后在回流下搅拌18小时。通过用水和MTBE进行溶剂萃取来纯化产物。分离各相，将水相用75ml MTBE萃取两次。将合并的有机相用100mL水和100mL饱和NaCl溶液洗涤，经硫酸钠干燥并真空除去溶剂。产物：5.1克
1H-NMR(DMSO,60MHz):
实施例4：2-甲基-丙烯酸2,3-双-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-丙酯的合成
首先将10g(16mmol)2,3-双-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-丙-1-醇和0.55g(3mmol，0.2当量)4-甲基苯磺酸一水合物引入35毫升甲苯中。逐滴加入2.72克(18毫摩尔，1.1当量)甲基丙烯酸酐。将混合物在回流下搅拌24小时。向反应混合物中加入25mL水和25mL MTBE，并分离各相。用25ml MTBE洗涤水相两次。将合并的有机相用25mL水洗涤，经硫酸钠干燥并过滤。真空除去溶剂。产物：9.9g
1H-NMR(DMSO,60MHz):
实施例5：丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙基硫烷基)-乙酯的合成
将50.0g(145mmol)2-(1,1,2-三氟-2-七氟丙氧基-乙基硫烷基)-乙醇，12.1g(168mmol，1.15当量)丙烯酸和4.5g(0.2当量)4-甲基苯磺酸一水合物引入300mL甲苯中。并在回流下搅拌24小时。
通过用水和MTBE进行溶剂萃取来纯化产物。
分离各相，将水相用75ml MTBE萃取两次。将合并的有机相用100mL水和100mL饱和NaCl溶液洗涤，经硫酸钠干燥并真空除去溶剂。产物：36.9g
1H-NMR(DMSO,60MHz):
实施例6：丙烯酸2-{3-[2,3-双-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-丙氧基]-丙基硫烷基}-乙酯的合成
将10.7g(14mmol)2-{3-[2,3-双-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-丙氧基]-丙基硫烷基}-乙醇，1.09g(15mmol，1.15当量)丙烯酸和0.6g(0.22当量)4-甲基苯磺酸一水合物引入30mL甲苯中，并在回流下搅拌24小时。
通过用水和MTBE进行溶剂萃取来纯化产物。
分离各相，将水相用75ml MTBE萃取两次。将合并的有机相用100mL水和100mL饱和NaCl溶液洗涤，经硫酸钠干燥并真空除去溶剂。产物：5.4克
1H-NMR(DMSO,60MHz):
实施例7：用于共聚的通用程序A：
将配备有气体入口、冷凝器和隔膜的50ml三颈玻璃圆底烧瓶装填19.35g单体和溶剂预混物。通过交替抽真空和输入氮气产生惰性气氛。
在小瓶中，通过注射器，在惰性气氛下，穿过所述隔膜添加在0.4g乙酸异丙酯中的0.04g VazoTM52(Chemour)，并将混合物加热至高达60℃持续24小时。
额外添加在0.2g乙酸异丙酯中的0.01VazoTM52，并将混合物在惰性气氛下，在60℃下搅拌另外12小时。
通过蒸馏移除溶剂。
实施例7a：
为了改进处理操作，制备如下材料的20g预混物：
2.16g 2-甲基-丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙基硫烷基)-乙基酯
2.16g甲基丙烯酸正丁酯
0.48g甲基丙烯酸2,3-环氧丙基酯
14.55g乙酸异丙酯
实施例7b：
制备如下材料的20g预混物：
2.32g 2-甲基-丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙基硫烷基)-乙基酯
2.16g甲基丙烯酸正丁酯
0.48g甲基丙烯酸2-羟基乙基酯
14.39g乙酸异丙酯
实施例7c：
制备如下材料的20g预混物：
2.16g 2-甲基-丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙基硫烷基)-乙基酯
2.16g甲基丙烯酸正丁酯
0.48g甲基丙烯酰氧基丙基三甲氧基硅烷
14.39g乙酸异丙酯
实施例8：应用测试
在不同的浓度下或作为没有树脂的经稀释的溶液(玻璃涂层)的相应涂料体系中，通过接触角测量测试所述聚合物的排斥效果。所用的装置是液滴形状分析仪(得自Kruess,德国的DSA100)，测试液体是DI水。
实施例8a：
表2：2K PUR涂料配制剂：
制备基础涂料：
在250ml烧瓶中，添加组分1-6，并用磁力搅拌器混合12小时。
采用所述基础涂料、固化剂和得自实施例9b的聚合物，制备如下混合物：
表3
将所述组分用磁力搅拌器混合45分钟。
为了涂层施加，使用如下设备：
-byko-卡纸/遮盖力卡纸(Opacity Chart)(byk-Gardner GmbH AG-5305)黑/白刮涂卡纸(Black/White Drawdown chart)
-刮片(Erichsen,型号360,30μm)
-自动涂膜机(byk-Gardner GmbH)
-真空烘箱
制备涂层：
-将漆以30μm的湿膜厚度施加
-使所述卡纸流平15分钟
-固化条件，在130℃和250毫巴下30分钟。
实施例8a的结果：
图1显示了在有和没有聚合物添加剂的情况下在2K-PUR涂层上水滴的接触角测量的结果。在经涂覆的基底的不同区域上重复测量5次。从这5次测量中，评价平均值(黑条的高度)和平均偏差(黑条顶部的误差线(bracket))。
所述空白测量显示出纯涂层的接触角(水排斥性)，所述样品测量揭示了由于存在以1％、5％和10％浓度的氟化添加剂导致的排斥性的改进。所述接触角从83.14°增加到98.33°。
实施例8b：
表4：环氧涂料配制剂：
制备基础涂料：
将组分1-4用抹刀混合。将化合物5在使用之前加热到40℃持续1小时。然后将环氧化物5添加到1-4中，并在Speedmixer中在2800UPM下混合2分钟。添加固化剂6并用Speedmixer在2800UPM下混合30秒。
表5
为了涂层施加，使用如下设备：
-小铝碗5×5×0.5cm
-通风炉
制备涂层：
-将所述树脂倾倒到所述铝碗中
-使所述卡纸流平60分钟
-固化条件，在100℃下60分钟
实施例8b的结果：
图2显示了在有和没有聚合物添加剂的情况下在环氧涂层上水滴的接触角测量的结果。在经涂覆的基底的不同区域上重复测量5次。从这5次测量中，评价平均值(黑条的高度)和平均偏差(黑条顶部的误差线)。
所述空白测量显示出纯涂层的接触角(水排斥性)，所述样品测量揭示了由于存在1％、5％和10％浓度的氟化添加剂导致的排斥性的改进。所述接触角在低至1％的聚合物添加的情况下从82.77°增加到102.41°。更多的添加剂不进一步改进所述排斥性(对于2％和10％分别为101.38°和99.77°)。
实施例8c：
没有树脂的经稀释溶液的玻璃涂层：
用乙酸正丁酯稀释实施例7c的聚合物残余物以产生0.5重量％的分散体。
制备涂层：
在穿过50μm过滤器进行过滤后，将所述材料施加到(用丙酮清洁的)玻璃基底上。使溶剂在室温下干燥45分钟，并在100℃下另外固化60分钟。
实施例8c的结果：
图3显示了在有和没有聚合物添加剂的情况下在经清洁的载玻片上水滴的接触角测量的结果。在经涂覆的基底的不同区域上重复测量5次。从这5次测量，评价平均值(黑条的高度)和平均偏差(黑条顶部的误差线)。
所述空白测量显示了纯玻璃的接触角(水排斥性)，所述样品测量揭示了由于存在所述氟化添加剂导致的排斥性的改进(因为所述聚合物在没有另外的涂料体系的情况下施加，因此所述材料可以视为100％添加剂)。所述接触角从43.82°增加至94.29°。
实施例9：用于共聚合的通用方法B：
将单体(62.50wt％氟-MA，20.83wt％甲基丙烯酸十八烷基酯，2.08wt％甲基丙烯酸2-羟甲基酯，12.50wt％甲基丙烯酸异冰片酯)和乙酸异丙酯首先引入干燥的三颈圆底烧瓶中。通过交替抽真空和输入氩气产生惰性气氛。对应于总组合物的0.2重量％，逐滴加入VazoTM52在乙酸异丙酯(50重量％)中的溶液。将组合物加热并搅拌过夜。另外，对应于总组合物的0.1重量％，逐滴加入VazoTM52在乙酸异丙酯(5重量％)中的溶液，并将组合物再次加热并搅拌过夜。随后，在真空中除去溶剂。
实施例10：均聚
实施例10a
将乙酸异丙酯中的丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-乙酯引入干燥的三颈圆底烧瓶中，通过交替抽真空和输入氩气产生惰性气氛。对应于总组合物的0.2重量％，逐滴加入VazoTM52在乙酸异丙酯(50重量％)中的溶液。将组合物加热并搅拌过夜。另外，对应于总组合物的0.1重量％，逐滴加入VazoTM52在乙酸异丙酯(5重量％)中的溶液，并将组合物再次加热并搅拌过夜。随后，在真空中除去溶剂。
实施例10b
将乙酸异丙酯中的甲基丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙氧基)-乙酯引入干燥的三颈圆底烧瓶中，通过交替抽真空和输入氩气产生惰性气氛。对应于总组合物的0.2重量％，逐滴加入VazoTM52在乙酸异丙酯(50重量％)中的溶液。将组合物加热并搅拌过夜。另外，对应于总组合物的0.1重量％，逐滴加入VazoTM52在乙酸异丙酯(5重量％)中的溶液，并将组合物再次加热并搅拌过夜。随后，在真空中除去溶剂。
实施例10c
将乙酸异丙酯中的丙烯酸2-(1,1,2-三氟-2-七氟丙氧基-乙基硫烷基)-乙酯引入干燥的三颈圆底烧瓶中，通过交替抽真空和输入氩气产生惰性气氛。对应于总组合物的0.2重量％，逐滴加入VazoTM52在乙酸异丙酯(50重量％)中的溶液。将组合物加热并搅拌过夜。另外，对应于总组合物的0.1重量％，逐滴加入VazoTM52在乙酸异丙酯(5重量％)中的溶液，并将组合物再次加热并搅拌过夜。随后，在真空中除去溶剂。
实施例11：防油性试验
防油性测试是评估聚合物在织物上的防油和防水效果(DWR效果)的方法。基于AATCC测试方法118-2013，将具有不同表面张力的标准测试溶剂滴放置在用聚合物处理的表面上。将织物(棉和聚酯)预先铺在DWR溶液中并干燥。如织物尺寸，溶液体积，溶液浓度和干燥时间等参数是可重复的和相同的条件。表6显示了测试溶剂和防护等级。防油性等级是编号最高的测试液体，其不润湿织物表面。这种非润湿标准必须在30秒内保持。当织物未通过矿物油测试液时，指定为零级。
分级示例(模式(pattern)AATCC测试方法118-2013)：A＝通过；澄清良好圆形(well-rounded)的滴B＝边界通过(borderline pass)；圆形的滴，部分变暗C＝失败；芯吸(wicking)明显和/或完全润湿D＝完全润湿
表6
防油性纺织品的特定要求,No.FTTS-FA-01[在线]，可获自:[http://www.ftts.org.tw/images/fa012E.pdf][2016年8月6日咨询]
表7:测试结果

Claims (24)

1.聚合物，其包含衍生自至少一种式(I)或(II)的单体的单体单元
(Rf1-CHF-CF2-O-CHR1)m1-L1-(X1)n1 (I)
(Rf2-CHF-CF2-S-CHR2)m2-L2-(X2)n2 (II)
其中
Rf1和Rf2彼此独立地是全氟化的、任选含杂原子的烷基基团，
R1和R2彼此独立地是H或烷基基团，
L1和L2彼此独立地是单键或二价有机基团，
X1和X2彼此独立地是烯属不饱和基团，
m1和m2彼此独立地为≥1，和
n1和n2彼此独立地为≥1。
2.根据权利要求1的聚合物，其特征在于Rf1和Rf2彼此独立地选自如下基团：
CF3-(CF2)0-3-、
CF3-(CF2)0-3-O-、
CF3-(CF2)0-3-O-(CF2)1-3-、
CF3-(CF2)0-3-O-(CF2)1-3-O-、
CF3-(CF2)0-3-O-(CF2)1-3-O-CF2-、
CF3-(CF2)0-3-O-(CF2-O)1-8-和
CF3-(CF2)0-3-O-(CF2-O)1-8-CF2-。
3.根据权利要求1至2的一项或多项的聚合物，其特征在于Rf1和Rf2彼此独立地选自如下基团：
CF3-(CF2)1-2-、
CF3-(CF2)1-2-O-、
CF3-O-(CF2)1-3-、
CF3-O-(CF2)1-2-O-、
CF3-(CF2)1-2-O-CF2-、
CF3-O-(CF2)1-2-O-CF2-、
CF3-O-(CF2-O)1-8-和
CF3-O-(CF2-O)1-8-CF2-。
4.根据权利要求1至3的一项或多项的聚合物，其特征在于R1和R2彼此独立地选自H或C1-C3烷基。
5.根据权利要求1至4的一项或多项的聚合物，其特征在于L1和L2彼此独立地选自单键和饱和的、支化或未支化的、任选含有杂原子和/或官能基团的亚烷基基团。
6.根据权利要求1至5的一项或多项的聚合物，其特征在于X1和X2彼此独立地是丙烯酸酯或甲基丙烯酸酯基团。
7.根据权利要求1至6的一项或多项的聚合物，其特征在于m1和m2彼此独立地等于1-3。
8.根据权利要求1至7的一项或多项的聚合物，其特征在于n1和n2彼此独立地等于1-3。
9.根据权利要求1至8的一项或多项的聚合物，其特征在于
Rf1和Rf2彼此独立地选自
CF3-(CF2)1-2-、
CF3-(CF2)1-2-O-、
CF3-O-(CF2)1-3-、
CF3-O-(CF2)1-3-O-、
CF3-(CF2)1-2-O-CF2-、
CF3-O-(CF2)1-2-O-CF2-、
CF3-O-(CF2-O)1-8-和
CF3-O-(CF2-O)1-8-CF2-，
R1和R2彼此独立地是H或CH3，
L1和L2彼此独立地是单键或C1-C4亚烷基基团，其任选是支化的和/或包含杂原子，尤其是O，和/或官能基团，
X1和X2彼此独立地是丙烯酸酯或甲基丙烯酸酯基团，
m1和m2彼此独立地等于1或2，和
n1和n2彼此独立地等于1。
10.根据权利要求1至9的一项或多项的聚合物，其特征在于所述单体选自下式(Ia)至(Ic)和/或(IIa)至(IIc)：
其中，
Rf是全氟化的、任选含有杂原子的烷基基团，和
R’和R”彼此独立地是H或烷基基团。
11.根据权利要求10的聚合物，其特征在于
Rf是CF3-CF2-CF2-O-、CF3-CF2-O-或CF3-O-，和
R’和R”彼此独立地是H或甲基。
12.根据权利要求1至11的一项或多项的聚合物，其特征在于其包含至少一种官能和/或非官能的共聚单体。
13.根据权利要求1至12的一项或多项的聚合物，其特征在于其包含至少一种官能共聚单体，该官能共聚单体选自包含OH、环氧基、-Si(OMe)3、-Si(OEt)3、-CO2H或叔氨基基团的共聚单体。
14.根据权利要求1至13的一项或多项的聚合物，其特征在于其包含至少一种非官能单体，该非官能单体选自包含直链或支化烷基基团或聚醚基团的共聚单体或选自苯乙烯类的单体。
15.通过使用至少一种根据权利要求1至14的一项或多项的聚合物制造功能涂料和/或表面改性物的方法，尤其用于防污涂料的方法。
16.处理基底的方法，该方法包括使基底与如下组合物接触和干燥在所述基底上的所述组合物，所述组合物包含至少一种根据权利要求1至14的一项或多项的聚合物、任选的成膜粘结剂、任选的溶剂和任选的添加剂。
17.根据权利要求16的方法形成的经涂覆的基底。
18.根据权利要求1至14的一项或多项的聚合物用于制备功能涂料和/或表面改性物的用途。
19.根据权利要求1至14的一项或多项的聚合物用于油漆、涂料、印刷油墨、防护涂料、在电子或光学应用中的特殊涂料、光致抗蚀剂、顶部抗反射涂料或底部抗反射涂料、化妆产品、农用化学品、地板蜡、感光涂料或光学元件涂料中的用途。
20.一种组合物，其包含至少一种根据权利要求1至14的一项或多项的聚合物、任选的成膜粘结剂、任选的溶剂和任选的添加剂。
21.根据权利要求20的组合物，其特征在于所述组合物是油漆组合物、涂料组合物、灭火组合物、润滑剂、除冰剂组合物、光致抗蚀剂组合物、光刻组合物、化妆产品、农用化学品、地板蜡或用于织物整理或玻璃处理的疏水化组合物。
22.通过固化根据权利要求20的组合物制造的膜。
23.一种产物，其具有包含至少一种根据权利要求1至14的一项或多项的聚合物的涂层。
24.制备聚合物的方法，该方法包括：
(a)在包含至少一种引发剂、任选的至少一种溶剂和任选的至少共聚单体的组合物中，聚合式(I)或(II)的单体的至少一种单体
(Rf1-CHF-CF2-O-CHR1)m1-L1-(X1)n1 (I)
(Rf2-CHF-CF2-S-CHR2)m2-L2-(X2)n2 (II)
其中
Rf1和Rf2彼此独立地是全氟化的、任选含杂原子的烷基基团，
R1和R2彼此独立地是H或烷基基团，
L1和L2彼此独立地是单键或二价有机基团，
X1和X2彼此独立地是烯属不饱和基团，
m1和m2彼此独立地为≥1，和
n1和n2彼此独立地为≥1，和
(b)任选分离所述聚合物。
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