CN113748144B - 低聚六氟环氧丙烷衍生物 - Google Patents

低聚六氟环氧丙烷衍生物 Download PDF

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CN113748144B
CN113748144B CN202080029587.2A CN202080029587A CN113748144B CN 113748144 B CN113748144 B CN 113748144B CN 202080029587 A CN202080029587 A CN 202080029587A CN 113748144 B CN113748144 B CN 113748144B
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D·内斯
S·鲁特洛夫
J·格茨
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Abstract

一种式(I)的化合物，
Figure DDA0003308430140000011
其中n选自3至8且R为氢或C1‑C8烷基，还涉及该化合物的制备方法和该化合物的用途。

Description

低聚六氟环氧丙烷衍生物
技术领域
本发明涉及基于六氟环氧丙烷(HFPO)的新型低聚化合物、含有这些化合物的组合物、表面已用这些化合物改性的基材以及这些化合物的制备方法和用途。
背景技术
在现有技术中，已知抗粘添加剂，其可以以小于1％的质量百分比在UV-NIL(NIL表示纳米压印光刻)压花表面产生莲花效应(lotus effect)(参见“The Lowest SurfaceFree Energy Based on-CF3 Alignment”,Takashi Nishino,Masashi Meguro,KatsuhikoNakamae,Motonori Matsushita and Yasukiyo Ueda Langmuir 1999,15,4321-4323)。除了压花表面的结构或粗糙度之外，莲花效应是基于高比例的CF3基团，其表面能比-CF2基团低得多。
一种高表面活性产品是丙烯酸酯官能化的抗粘添加剂低聚-HFPO-2-羟乙基甲基丙烯酸酯(以下也称为“HFPO甲基丙烯酸酯”)：
Figure BDA0003308430070000011
该分子的特殊表面活性归因于具有CF3侧基的全氟聚醚链的支化结构。HFPO甲基丙烯酸酯可通过将HFPO醇的-CH2-OH醇基团氧化成羧酸基团并随后与甲基丙烯酸2-羟乙酯酯化来制备。
本发明解决的问题
本发明的一个目的是提供一种高效的抗粘添加剂和包含该抗粘添加剂的组合物(UV-NIL压花清漆)。
另一个目的是提供一种制造不粘添加剂的简单方法及其用途。
发明内容
本发明问题通过提供根据本发明的化合物、组合物、聚合物、涂覆基材、方法和用途来解决。
根据本发明的这些目的在权利要求中进行定义。
本发明优点
根据本发明的化合物具有低表面能并且可以以多种方式用作抗粘添加剂(例如用于基于(甲基)丙烯酸酯的UV-NIL压花清漆)。以这种方式，根据本发明的化合物可以显著降低压花印模
Figure BDA0003308430070000012
与压花清漆分离过程中的粘附力或脱模力，并且还赋予UV-NIL压花表面防污或自清洁性能，同时在合适的结构上产生莲花效应。
根据本发明的化合物可以以比HFPO甲基丙烯酸酯更简单的方式和更高的产率制备。
将低聚HFPO醇直接加成到(甲基)丙烯酸2-异氰基乙酯以得到相应的低聚氨基甲酸酯(甲基)丙烯酸酯比HFPO甲基丙烯酸酯的多步合成更简单，并且可以以更高的产率进行。
可用于合成本发明化合物的起始化合物制备简单且成本低廉。
附图说明
图1示意性地示出了根据本发明的化合物的氨基甲酸酯基团之间氢键的形成。
图2示出了在惰性气体下已被UV固化的实施例1的压花清漆层上的水和二碘甲烷接触角(KW)作为PFPE-UA-3浓度的函数。
图3示出了在惰性气体下已被UV固化的实施例1的压花清漆层上的表面能作为PFPE-UA-3浓度的函数。
γ：总表面能；d：分散部分；p：极性部分。
图4示出了作为PFPE-UA-3浓度的函数的实施例2的压花清漆层上的水和二碘甲烷接触角。
图5示出了作为PFPE-UA-3浓度的函数的实施例2的压花清漆层上的表面能。
γ：总表面能；d：分散部分；p：极性部分。
本发明具体实施方式
本发明提供了式(I)的化合物：
Figure BDA0003308430070000021
其中，n选自3至8，R为氢或C1-C8烷基。优选地，R是氢或甲基。
可聚合碳-碳双键可优选在光和/或热的作用下和/或通过化学手段有机聚合。它是在光化辐射的作用下可以光化学聚合的基团，特别是可UV聚合的基团。
聚合作用反应通常是聚合反应，其中反应性双键或环在热、光、电离辐射或化学(通过氧化还原反应)(加成聚合)的作用下转化为聚合物。有机聚合优选通过(甲基)丙烯酸基团发生。
除了或替代C＝C双键的聚合反应(加聚)，包含这些双键的化合物与二胺或更高级胺或二硫醇或更高级硫醇通过迈克尔加成反应(分别为硫醇-烯反应或与胺的类似反应)也是可能的。
根据本发明的化合物具有高度的CF3残基。
在式(I)的结构中，所有CF3残基排列成在每种情况下插入-CF2-O-基团。
在氨基甲酸酯基团和相邻的CF3残基之间存在类似于-CF2-O基团的-CH2-O基团。
由于这种排列，根据本发明的化合物具有非常规则的结构，这使得能够形成有序且非常密集组装的氟表面活性剂层结构。该结构通过在根据本发明的化合物的氨基甲酸酯基团之间形成氢键的可能性而得到加强(参见图1)。
总体来说，这使得根据本发明的化合物大大缩小了表面，从而大大降低了压花清漆(例如基于丙烯酸酯基的)的粘附能，因此能够赋予其显著的荷花效应。
根据本发明的化合物可通过醇与异氰酸酯的反应获得。与现有技术的化合物HFPO甲基丙烯酸酯的不同在于制备工艺。
HFPO甲基丙烯酸酯可通过将HFPO醇的-CH2-OH醇基团氧化为羧酸基团并随后与甲基丙烯酸2-羟乙酯进行酯化来制备。
例如，根据本发明的化合物是低聚氨基甲酸酯丙烯酸酯并且可以例如通过使低聚HFPO醇与丙烯酸2-异氰基乙酯(AOI)加成反应形成氨基甲酸酯丙烯酸酯来制备。
这致使本发明与HFPO甲基丙烯酸酯之间具有以下结构差异：
本发明化合物：...-CH2-O-CO-NH-CH2-...
HFPO甲基丙烯酸酯：...-CO-O-CH2-...
用作起始化合物的低聚物具有仅源自环氧丙烷的单元，因此它可以以简单的方式制备。
在根据本发明的化合物中作为头基(head group)存在的氨基甲酸酯基团由于额外的N原子而具有极性，并且由于N原子上的H原子可以另外形成H桥键。这致使聚合物表面上更高度有序和更密集组装的氟表面活性剂单层，从而实现更低的表面能(参见图1)。
在根据本发明的实施例中，制备了具有不同HFPO-UA-3含量的UV固化压花清漆层，然后测量位于这些层上的水和二碘甲烷液滴的接触角并由此确定表面能。在这个过程中测量和计算的值证明了优异的表面活性，至少等于HFPO甲基丙烯酸酯的表面活性。其表面活性在M.Leitgeb,D.Nees et al.,ACS Nano 10(5),4926(2016)中有描述(其中以PFPE-A1表示)。
根据本发明的组合物包含根据本发明的化合物和聚合物起始材料(startingmaterial)。所述聚合物起始材料包含具有至少一个反应性基团的单体和/或低聚物，所述反应性基团可在聚合作用下与根据本发明的化合物中的碳-碳双键反应。在最简单的示例中，这也是具有碳-碳双键的基团。含双键基团的示例是具有可进行迈克尔加成的双键的基团，例如苯乙烯基、降冰片烯基或(甲基)丙烯酸衍生物；然而，它们也可以是乙烯基或烯丙基。(甲基)丙烯酸基衍生物或(甲基)丙烯酸的衍生物特别是指(甲基)丙烯酸酯和(甲基)丙烯酰胺。附加地或作为替换，所述聚合物起始材料还可包含含有二胺或更高级胺或二硫醇或更高级硫醇的残基，其可通过迈克尔加成反应进行反应(分别为硫醇-烯反应或与胺的类似反应)。在任何情况下，所述聚合物起始材料的可聚合基团必须选择成允许在将本发明化合物引入聚合物的情况下进行聚合。
根据本发明的组合物包含0.001-10％、优选0.001-1.0％的量的根据本发明的化合物和50-99.999％的量的聚合物起始材料。其余组分可以是例如优选量为5-40％的反应性稀释剂和光引发剂。除非另有说明，本发明中的百分比均以重量计。优选的组合物包含0.01-3％的本发明化合物、50-80％的聚合物起始材料、5-30％的活性稀释剂和0.1-3％的光引发剂，这些组分的总量为本发明组合物总量的至少90％，优选至少95％。
在根据本发明的组合物聚合之后形成根据本发明的聚合物。所述聚合物可以是任何形式，例如作为膜的固体形式或在外墙涂料或喷雾中的液体形式。
本发明的化合物可以以本发明的组合物的形式用于涂覆基材。所述基材可以是任何物体，该物体表面将被提供有所需的抗粘性能。因此，所述基材例如是微结构中的基材或载体，其具有压花清漆或用于压印这种清漆的印模(Stempel)。然而，所述基材也可以是任何表面，例如玻璃表面，其表面将要被制成防污或自清洁性的。所述基材的其他例子是光伏、照明或光学领域的表面，也可以是要制成具有自清洁或防污性能的纺织品、遮阳篷、防水油布和帆布。
该种涂层使得根据本发明的经涂覆基材具有所需的表面特性，特别是抗粘性能和改变的表面能。
根据本发明的经涂覆基材可以是例如涂覆有根据本发明的聚合物作为压花清漆的基材，或涂覆有根据本发明的聚合物作为抗粘涂层的用于纳米压印光刻的工作印模，或其中压花结构或压花浮雕包含根据本发明的所述聚合物。这种印模可包括聚合物基材膜(例如PET)，其具有至少在其表面上的包含本发明所述聚合物的结构化表面层。所述结构化表面层可以是可通过将丙烯酸酯与根据本发明的化合物一起UV固化而获得的聚合物。
为了进行纳米压印光刻工艺，如果压印清漆和压印表面都包含根据本发明的化合物，则是特别有利的。
在根据本发明的经涂覆基材中，基材和根据本发明的聚合物之间的键可原则上基于共价键或非共价键。
如果例如希望允许本发明的聚合物层是可移除的，则优选非共价键。这种情况可能是例如要替换该层。根据本发明的这种聚合物的一个示例是热塑性的。
然而，共价键也可能是优选的。这些可以通过使用合适的粘合剂将本发明的聚合物粘合到基材上而形成。然而，它们也可以由具有与在本发明化合物聚合期间与本发明化合物的反应性基团反应并因此结合到聚合物中的残基的键的基材形成，或可以由具有与在本发明的组合物聚合期间与本发明化合物和/或其他可聚合组分的反应性基团反应并因此结合到聚合物中的残基的键的基材形成。在这种情况下，可以通过将根据本发明的组合物施加到未涂覆的基材上然后聚合来制备根据本发明的经涂覆基材。
根据本发明的化合物可以用作在UV-NIL压花清漆中的抗粘添加剂并降低在压印工艺中对工作印模(例如由镍、石英或聚合物制成)的粘附力，和/或可以被用来作为用于UV纳米压印光刻的工作印模中的抗粘添加剂并降低在压印工艺中对压印清漆的粘附力。
所述抗粘添加剂可以永久降低UV-NIL压花清漆表面的表面能，从而实现防水和防污，并在必要时在合适的微纳米结构上产生莲花效应，即自清洁功能。莲花效应可以通过利用例如酒精清洁脏污的表面可逆地再生。
本发明的化合物尤其适用于所有UV压花清漆配方，例如用于具有许多不同结构(鲨鱼皮、蛾眼、衍射光栅)的UV-NIL压花表面。
具体的应用是功能性表面，例如抗反射涂层(蛾眼效应)以及光伏的防尘或自清洁涂层、减少流动摩擦的涂层(鲨鱼皮效应)、照明、光学、建筑玻璃等。
本发明化合物的制备
在下文中，参考优选实施方案描述根据本发明的化合物的制备。
根据本发明的化合物可通过醇与异氰酸酯的反应获得。
带有支链CF3侧基的3-HFPO至6-HFPO(低聚物)醇是可商购的。其示例包括：
1H,1H-全氟-2,5,8-三甲基-3,6,9-三氧杂十二烷-1-醇:
2-{1,1,2,3,3,3-六氟-2-[1,1,2,3,3,3-六氟-2-(七氟丙氧基)丙氧基]丙氧基}-2,3,3,3-四氟丙烷-1-醇(CAS 14620-81-6)
Figure BDA0003308430070000041
1H,1H-全氟(2,5,8,11-四甲基-3,6,9,12-四氧杂十五烷-1-醇)：
2,4,4,5,7,7,8,10,10,11,13,13,14,14,15,15,15-十七氟-2,5,8,11-四(三氟甲基)-3,6,9,12-四氧杂十五烷-1-醇(CAS 141977-66-4)
Figure BDA0003308430070000051
1H,1H-全氟(2,5,8,11,14-五甲基-3,6,9,12,15-五氧杂十八烷-1-醇)(CAS27617-34-1)。
被表示为CAS 14620-81-6和CAS 141977-66-4的多元醇是优选的。
这些化合物与丙烯酸2-异氰基乙酯(H2C＝CH-CO-O-CH2-CH2-N＝C＝O；CAS 13641-96-8)连接，以优异的收率得到相应的低聚-HFPO氨基甲酸酯丙烯酸酯。
根据本发明的此类化合物的优选示例是式(I)的低聚-HFPO氨基甲酸酯丙烯酸酯，其中R可为H且n可为3或4。
示例
参考下文示例对本发明进行进一步阐释。
示例1
在N2惰性气体下固化压花清漆层(75％E8402、23％nOA、2％TPO-L)。使用不同浓度的PFPE-UA-3作为抗粘添加剂。化合物PFPE-UA-3是根据本发明的式(I)化合物，其中n为3且R为H。E8402(Ebecryl 8402)是来自Allnex的脂肪族氨基甲酸酯丙烯酸酯，用作压花清漆基料。使用的反应性稀释剂是丙烯酸正辛酯(nOA)。TPO-L是光引发剂(2,4,6-三甲基苯甲酰基)苯基次膦酸乙酯。
图2示出了在低于1％的极低浓度的PFPE-UA-3下，水和二碘甲烷的接触角显著增加。
图3示出了即使在低浓度的PFPE-UA-3下，表面能也显著降低，这主要是由于表面能分散部分的降低。
在本发明中，表面能通过Owens、Wendt、Rabel和Kaelble的方法(OWRK)测定(D.H.Kaelble,Dispersion-Polar Surface Tension Properties of OrganicSolids.In:J.Adhesion 2(1970),pp.66-81；D.Owens；R.Wendt,Estimation of theSurface Free Energy of Polymers.In:J.Appl.Polym.Sci 13(1969),pp.1741-1747；W.Rabel,Einige Aspekte der Benetzungstheorie und ihre Anwendung auf dieUntersuchung und
Figure BDA0003308430070000053
der />
Figure BDA0003308430070000054
von Polymeren.In:Farbeund Lack 77,10(1971),pp.997-1005)。OWRK方法是根据与几种液体的接触角计算固体表面自由能的标准方法。表面自由能分为极性部分和分散部分。
示例2
压花清漆层(75％E8402、23％nOA、2％TPO-L)在涂覆FPS的镍片上固化。使用不同浓度的PFPE-UA-3作为抗粘添加剂。
FPS为1H,1H,2H,2H全氟辛基膦酸：
Figure BDA0003308430070000052
这种化合物在镍(FPS-SAM-Nickel)上形成自组装单层(SAM)并用于镍印模的抗粘涂层。
图4示出了在低于1％的极低浓度的PFPE-UA-3下，接触角显著增加。
图5示出了即使在低浓度的PFPE-UA-3下，表面能也显著降低。

Claims (4)

1.一种纳米压印光刻工艺，包括用印模压印清漆层，其中所述清漆层是包含式(I)的化合物和可与可聚合碳－碳双键反应的聚合物起始材料的组合物，并且所述印模具有包含一聚合物的结构化表面层，所述聚合物通过将包含式(I)的化合物和可与可聚合碳－碳双键反应的聚合物起始材料的组合物进行聚合反应而得到，
Figure QLYQS_1
其中，n选自3至8，R为氢或
Figure QLYQS_2
烷基。
2.根据权利要求1所述的纳米压印光刻工艺，其中n为3或4，R为氢或甲基。
3.根据权利要求1或2所述的纳米压印光刻工艺，所述组合物包含0.001－10重量％的量的所述化合物和50－99.999 重量％的量的所述聚合物起始材料。
4.根据权利要求1或2所述的纳米压印光刻工艺，所述组合物包含0.001－1.0重量％的量的所述化合物。
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