CN102482442B - 用于生产用于含氟聚合物的多层高吸附性涂层的方法 - Google Patents
用于生产用于含氟聚合物的多层高吸附性涂层的方法 Download PDFInfo
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- CN102482442B CN102482442B CN201080014425.8A CN201080014425A CN102482442B CN 102482442 B CN102482442 B CN 102482442B CN 201080014425 A CN201080014425 A CN 201080014425A CN 102482442 B CN102482442 B CN 102482442B
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Abstract
本发明涉及一种通过原子转移自由基聚合和后续处理用涂层物质涂覆含氟聚合物的方法,其中使含氟聚合物与反应混合物接触,所述反应混合物包括选自由多链和多环的胺类组成的组中的至少一种配体、其中金属处于第一氧化态的至少一种金属盐、至少一种溶剂、以及单体形式的有机涂层物质。
Description
技术领域
本发明涉及一种通过原子转移自由基聚合和后续处理而用涂层物质涂覆含氟聚合物的方法。
背景技术
已知含氟聚合物具有非常好的耐化学品性,因此被用于制造暴露于腐蚀性化学品的产品中。另一方面,含氟化合物也具有一些在许多情况下与它们的应用相冲突或使其难以或不能制造的不期望特性。例如,粘附于塑料或甚至许多金属的能力较弱,使得必须使用粘结剂(adhesivizingagents),其导致附着力的一定改善。然而,当使用粘结剂时,特别是当将薄膜应用于基板时,经常发现粘结剂移动到FP中并且不利地影响其耐化学性。
1938年,合成PTFE(聚四氟乙烯,)的Dr RJ.Plunkett发现了含氟聚合物。在该发明后,由于含氟聚合物以下独特的特性,其被迅速引入大众市场。
-不粘
-高的熔化温度
-低摩擦
-在不同条件(化学、紫外光、辐射等)下的极端耐用性
-鲜见于塑料的一些含氟聚合物的特性
-压电性、铁电性、热电性
-等等
然而,使用含氟聚合物具有许多问题,例如其非常难以
-用其他材料涂覆含氟聚合物,
-将它们粘合至其他表面,和
-能与任何化学试剂功能化,这是因为它们的疏水性能。
虽然含氟聚合物被广泛使用,但是因为传统的含氟聚合物涂覆技术不能够以不改变含氟聚合物特性的方式在含氟聚合物与施加的层之间形成足够强的键,因此它们的应用领域被限制。
存在已知的用于生产用于含氟聚合物的多层高吸附性涂层的不同方法,例如:
-基础聚合物与各种树脂混合的方法,其中该聚合物的一些特性(导电性、耐用性等)将会受到损害;
-使用表面的机械、热或等离子体加工的方法,这些方法具有诸如弱键的缺点;有限的应用可能性;和
-正在开发中的利用表面化学处理的方法。
大多数方法将氟原子从表面除去,但这不能保证足够的亲水性。
文献US 4308359 B(DYNAMIT NOBEL AG)29.12.1981描述了一种聚偏氟乙烯的接枝聚合物,其中聚偏氟乙烯将按重量计至少0.5%和按重量计可达98%的烯键式不饱和化合物的聚合物接枝在其上,所述烯键式不饱和化合物的聚合物是通过以下来制备的:在固相中使聚偏氟乙烯与烯键式不饱和化合物的单体接触,并且以这样的使所述聚偏氟乙烯仍保持在固相中的量将所述单体和自由基形成催化剂分散到所述聚偏氟乙烯中,之后在用于所述烯键式不饱和化合物的聚合条件下使所述聚偏氟乙烯保持在固相中,并且在没有水和/或溶剂的情况下聚合所述烯键式不饱和化合物。在该文献中指出可用于自由基聚合的已知催化剂,例如如有机过氧化物或偶氮化合物,可以被用作根据所述方法的催化剂。过氧化物包括,例如,二月桂酰基过氧化物,过氧化苯甲酰,或过碳酸盐,如联十六烷基过碳酸盐或二异丙基过碳酸盐,或过酸酯如叔丁基过氧化苯甲酸酯。催化活性的偶氮化合物的一个实例是偶氮异丁酸二腈。
含氟聚合物由于其高的化学、物理和生物稳定性,以及其他特殊特性而被广泛应用。同时,含氟聚合物的表面是极端疏水的,这阻碍了任何添加剂与其吸附。传统上,由于将添加剂粘附至其内含物(形成了具有更多亲水性物质的化合物),含氟聚合物的浓度(稠度)被改变,这显著地恶化了聚合物特性;或改性含氟聚合物的表面(化学地;电晕效应等),这不能引入必要量的添加剂也不能控制添加剂的行为(性能)。
发明内容
根据本发明的目的,提供了一种通过原子转移自由基聚合来生产用于含氟聚合物的多层高吸附性涂层(覆盖物)的方法,因此提供了一种使用涂层物质来涂覆含氟聚合物的方法,包括使含氟聚合物与反应混合物接触,该反应混合物包括至少一种配体、至少一种溶剂、其中该金属处于第一氧化态的至少一种金属盐、引发剂和单体形式的涂层物质。
由本发明的作者开发的新涂覆方法由以下基本步骤构成:
-对含氟聚合物表面进行特殊化学改性
-涂覆必要的层
-涂覆必要的功能成分
所述新方法由三个步骤构成:
1)使用ATRP反应(原子转移自由基聚合),用短链亲水性单体(如苯乙烯)取代含氟聚合物的一些氟原子;
2)用无机单层(如SiO2、Al2O3、TiO2)覆盖要点(1)的表面;
3)使具有必要厚度的无定形吸附剂层沉淀于表面(SiO2、Al2O3、TiO2等)。
如果有必要,可以使用另一单层覆盖表面以保护不受外部影响。这样的方法使得能够保留最初含氟聚合物的特性并且使其与所述添加剂完全隔离;也能够保证稳定性和永久的表面覆盖且能够获得用于表面涂层的必要特性。该方法可以应用于用于生产智能颗粒的纳米电子学,用于生产智能胶囊的医药,用于生产稀少的能源等。
所述方法通过使用已知的方法,如原子转移自由基聚合(ATRP)来提供此。ATRP反应的进行需要环境的有机和无机物质的平行溶解能力。到目前为止,通常已经使用了不同离子和阴离子溶剂(如,苯甲醚和二氢呋喃)的混合物,该混合物是不稳定的、有毒、易燃的并且对不同添加剂非常敏感(包括气体形式的氧)。
所述新方法也可以使用液态盐或反应类似液态盐的共晶溶剂(低共溶溶剂)(如,氯化胆碱和甘油)环境进行ATRP反应,该环境是稳定的、无毒的且对添加剂不敏感。
该新方法的优点
所有已知的含氟聚合物可以基于本发明被功能化(官能化)。不需要向纯的基础聚合物中添加树脂和其他成分。该基础聚合物的所有特性仍保持不变。在接枝前,不需要机械、热或等离子体处理含氟聚合物表面。可以使用各种单体来形成功能层。可以对施加层(应用层)的厚度和结构进行严格控制。含氟聚合物和施加表面利用极端的强度粘合。ATRP反应可以直接从在基础聚合物中存在氟原子开始。
含氟聚合物表面的化学改性
在金属络合物中使用多链或多环胺作为配体,使用特定的反应引发剂或使用聚合物晶体结构缺陷用于引发该反应。预先处理的溶液(混合物)将被用于表面改性。该溶液将以一定的顺序辗压在碳氟化合物表面上。
当在含氟聚合物的表面上获得亲水层后,使用水解和溶胶-凝胶法对该层进行处理,从而利用另外的无机的、微晶的或无定形层涂覆该层。
根据本发明,通过原子转移自由基聚合,利用涂层物质涂覆含氟聚合物的典型方法因此包括使含氟聚合物与反应混合物接触,所述反应混合物包括:
-选自由多链的和多环胺类组成的组的至少一种配体,
-其中金属处于第一氧化态的至少一种金属盐,
-至少一种溶剂,以及
-单体形式的有机涂层物质。
单体形式的有机涂层物质是指能够形成聚合物链的有机物质。
根据本发明的实施方式,所述反应混合物进一步包括引发剂。引发剂可以选自由有机酸的卤化物组成的组,例如异丁酸溴化物或其他有机卤化物。根据另一实施方式,该反应的引发是由聚合物的晶体结构缺陷引起的,因此不需要引发剂。
通常,该涂层物质选自由苯乙烯、磺酸、甲基丙烯酸甲酯、乙烯亚胺或一些其他亲水单体或它们的混合物组成的组。该物质的涂覆层厚度可以为1nm至100μm。
该反应混合物也可以包括多于一种氧化态的金属盐,例如,Cu+/Cu2+、Fe2+/Fe3+等。该金属盐例如可以选自由CuBr、CuCl和FeCl2组成的组。
根据本发明的实施方式,所述配体选自由三(2-氨乙基)胺(TREN)、三[2-(二甲基氨基)乙基]胺(Me6TREN)、2,2′-联吡啶(bpy)、四氮杂环四癸烷(CYCLAM)以及它们的混合物组成的组。当然,也可以使用任何其他合适的配体。
通过这种方法涂覆的含氟聚合物可以是任何含氟聚合物。一些实例是聚乙烯撑(聚次亚乙烯)、聚四氟乙烯、聚氟乙烯以及它们的混合物。含氟聚合物可以是任何合适的形式,如块、薄膜或颗粒。当使用薄膜时,该薄膜的厚度可以为1μm到1mm。
根据本发明的实施方式,所述溶剂选自由有机溶剂、液态盐和其反应类似液态盐的共晶溶剂组成的组。合适溶剂的一些实例是四氢呋喃和丙酮腈(丙腈,acetonenitrile)的混合物、氯化胆碱、甘油以及它们的混合物。
根据本发明的所述方法还可以包括用无机层涂覆物质涂覆的含氟聚合物的另外的步骤。无机层可以是Al2O3、SiO2、或TiO2层,并且该涂层可以通过金属有机化合物例如Al(CH3)3的水解来制备。该无机氧化物层也可以是具有一个氧化铝分子厚度的单层。
该方法也可以进一步包括另外的步骤:利用水解或溶胶-凝胶法,用微晶的或无定形的金属氧化物涂覆物质涂覆的含氟聚合物或单层和物质涂覆的含氟聚合物。微晶金属氧化物层的厚度可以是0.1nm至100μm。
在本发明的方法中使用的反应溶液可以进一步包括至少一种抗氧化剂例如抗坏血酸。该反应溶液还可以包括至少一种液态盐,例如氯化胆碱和甘油的混合物。
通常,反应时间为为1秒钟至60分钟,并且反应温度为30℃至90℃。
本发明还涉及一种涂覆有可通过本发明的方法获得的涂层物质的含氟聚合物。
本发明进一步涉及一种涂覆有涂层物质的含氟聚合物,其中根据方案(1),涂层物质的链与基础聚合物的链化学键合。
方案(1)示出了涂覆有聚苯乙烯层的聚四氟乙烯(PTFF)。
在根据本发明的涂覆的含氟聚合物中,该涂层物质可以为任何亲水性聚合物。并且,该亲水聚合物涂层的厚度通常至少为五个苯乙烯分子。该含氟聚合物也可以被进一步功能化。
本发明还涉及根据本发明的涂覆的含氟聚合物,例如用于反应柱填料(填充物),微过滤器,电子传感器,扭转向列球(扭球)或电泳显示器,用于生物技术的膜,燃料电池膜或生物沉降器中的应用。
本发明还进一步涉及
-扭转向列球或电泳显示器,其包括可通过本发明的方法获得的涂覆的含氟聚合物颗粒,
-通过发明的方法已被改性变成离子导电的燃料电池或水解器的膜。
-反应柱填料,其中通过本发明的方法使催化剂附着(固定)。
-功能化的微过滤器,其通过本发明的方法在过滤过程中能够进行反应或测试。
-微型机器和致动器,其中通过本发明的方法形成移动部件(例如,纳米阀门,其中该电极连接至聚合物)。
实验部分
实例(样品)1
基于本发明使用不同的反应条件改性PVDF微粒。基于该反应条件(催化剂、引发剂和单体浓度、温度和时间)可以获得具有不同结构的亲水聚合物(如苯乙烯)层,所述反应条件决定反应中心的质量:
-无定形
-坯料(半成品,blank)
-该化学改性方法的多孔优势。
由于产生的键非常强,因此含氟聚合物可以牢固地连接于不同的物质以增加耐久性,减少摩擦,并增强这些材料的外观。
这种可能性能够在市场领域中的新应用中使用含氟聚合物,如:航天航空、军事、化工、船舶、汽车、建筑等,其中需要高耐久性。
在附图中示出了根据本发明的方法的涂覆的PVDF,其中Solef 1008PVDF的球形颗粒在二氢呋喃和苯甲醚的10ml混合物中的15mg CuCl、23mg TREN和100ml纯苯乙烯的溶液在保持温度在60℃下处理5分钟。获得具有2μm厚度的多孔聚苯乙烯层。之后,该颗粒在三甲基铝的10%溶液中处理5秒钟,并且此后该颗粒通过利用75℃温度在20分钟内热水解酸化的硫酸铝溶液用微晶氧化铝层涂覆。获得了具有1μm厚度的氧化铝涂层。
施加金属层
不同金属(Cu、Au、Pt、Al等)的化学或离子沉淀是可能的。在含氟聚合物表面可用于施加电极(包括微电极)或催化剂。
应用领域:压电微型机器、压电传感器、功能膜等。
施加无定形或微晶无机惰性层
应用领域:功能膜、用于柱的催化剂填料、燃料电池膜(用催化剂和离子导体功能化的FP)、微过滤器(结合微过滤器和功能测试材料)、沉降器膜和生物沉降器,所有一体测试仪膜等。
实例(样品)2
将无定形或微晶无机惰性层施加至功能化的含氟聚合物。可以使用氧化铝、硅石、TiO2和其他氧化物。表面改性的步骤为:
-用亲水性聚合物链取代F原子
-切断卤素原子
-用无机单层覆盖表面
-厚微晶无机层的沉淀
实例2描述了使用在含氟聚合物表面上获得吸附层的新方法的可能性。
该新方法使得能够在高附加值的应用中使用与其他材料结合的含氟聚合物,其中需要作为极端耐久性或低摩擦的特性;或保留纯含氟聚合物的独特性能是必要的。
应用领域:用于柱的填料、功能性膜、微过滤器和薄膜、色谱和其他分析器膜、燃料电池膜、生物沉降器、用于不同应用(包括电子纸显示器)的智能含氟聚合物颗粒,等等。
Claims (30)
1.一种用涂层物质涂覆含氟聚合物的方法,所述方法由三个步骤组成,其中
-最初通过原子转移自由基聚合用涂层物质涂覆含氟聚合物,包括使含氟聚合物与反应混合物接触,所述反应混合物包括:选自由多链和多环的胺类组成的组中的至少一种配体,至少一种金属盐,其中所述金属处于第一氧化态,至少一种溶剂,以及单体形式的有机涂层物质,之后
-用无机层涂覆物质涂覆的含氟聚合物,以及
-在第三步骤中,用微晶的或无定形的金属氧化物涂覆物质涂覆的含氟聚合物。
2.根据权利要求1所述的方法,其特征在于,所述反应混合物进一步包括引发剂。
3.根据权利要求1所述的方法,其特征在于,反应的引发是通过聚合物晶体结构缺陷引起的。
4.根据权利要求1所述的方法,其特征在于,有机涂层物质选自由苯乙烯、磺酸、甲基丙烯酸甲酯、乙烯亚胺或它们的混合物组成的组。
5.根据权利要求1所述的方法,其特征在于,所述反应混合物包括处于多于一种氧化态的金属盐。
6.根据权利要求1所述的方法,其特征在于,所述配体选自由三(2-氨乙基)胺、三[2-(二甲氨基)乙基]胺、2,2'-联吡啶、四氮杂环四癸烷以及它们的混合物组成的组。
7.根据权利要求1所述的方法,其特征在于,所述含氟聚合物选自由聚偏氟乙烯、聚四氟乙烯、聚氟乙烯以及它们的混合物组成的组。
8.根据权利要求1所述的方法,其特征在于,所述溶剂选自由有机溶剂、液态盐和反应类似于液态盐的共晶溶剂组成的组。
9.根据权利要求8所述的方法,其特征在于,所述溶剂选自由四氢呋喃和丙酮腈的混合物、氯化胆碱、甘油及其混合物组成的组。
10.根据权利要求1或5所述的方法,其特征在于,所述金属盐选自由CuBr、CuCl和FeCl2组成的组。
11.根据权利要求2所述的方法,其特征在于,所述引发剂选自由有机酸的卤化物组成的组。
12.根据权利要求11所述的方法,其特征在于,所述有机酸的卤化物为异丁酸溴化物。
13.根据权利要求1所述的方法,其特征在于,通过金属有机化合物的水解,用Al2O3、SiO2、或TiO2的无机层涂覆所述物质涂覆的含氟聚合物。
14.根据权利要求13所述的方法,其特征在于,所述无机层是具有一个氧化铝分子厚度的无机氧化物单层。
15.根据权利要求1所述的方法,其特征在于,通过利用水解或溶胶-凝胶法,用微晶的或无定形的金属氧化物涂覆物质涂覆的含氟聚合物和无机层。
16.根据权利要求15所述的方法,其特征在于,所述微晶金属氧化物层的厚度为0.1nm至100μm。
17.根据权利要求7所述的方法,其特征在于,所述含氟聚合物是颗粒的形式。
18.根据权利要求7所述的方法,其特征在于,所述含氟聚合物是薄膜形式,其中所述薄膜的厚度为1μm至1mm。
19.根据权利要求1所述的方法,其特征在于,所述物质涂覆层的厚度为1nm至100μm。
20.根据权利要求1所述的方法,其特征在于,所述反应混合物进一步包括至少一种抗氧化剂。
21.根据权利要求20所述的方法,其特征在于,所述抗氧化剂为抗坏血酸。
22.根据权利要求1或20所述的方法,其特征在于,所述反应混合物还包括至少一种液态盐。
23.根据权利要求22所述的方法,其特征在于,所述液态盐为氯化胆碱和甘油的混合物。
24.根据权利要求1所述的方法,其特征在于,聚合时间为1秒钟至60分钟。
25.根据权利要求1所述的方法,其特征在于,聚合温度为30℃至90℃。
26.一种涂覆有可通过权利要求1-25中任一项所述的方法获得的涂层物质的含氟聚合物。
27.根据权利要求26所述的涂覆有涂层物质的含氟聚合物,其中,涂层聚合物的链按照方案(1)与基础聚合物的链化学结合,
28.根据权利要求26或27所述的涂覆有涂层物质的含氟聚合物,其特征在于,所述涂层物质为任意亲水性聚合物,并且所述任意亲水性聚合物涂层的厚度为至少5个苯乙烯分子。
29.根据权利要求26或27所述的涂覆有涂层物质的含氟聚合物,其特征在于,所述含氟聚合物被进一步功能化。
30.根据权利要求1-25所述的涂覆有涂层物质的含氟聚合物在用于反应柱填料、电传感器和电泳显示器中的应用。
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US61/256,766 | 2009-10-30 | ||
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4308359A (en) * | 1975-12-31 | 1981-12-29 | Dynamit Nobel Ag | Method for the modification of polyvinylidene fluoride |
CN1743351A (zh) * | 2005-09-30 | 2006-03-08 | 天津工业大学 | 一种温敏型聚偏氟乙烯智能膜材的制备方法及其产品 |
Family Cites Families (4)
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US3376168A (en) * | 1962-08-02 | 1968-04-02 | Yardney International Corp | Metal-containing graft-polymerized product and method of making same |
US20020147282A1 (en) * | 2000-09-11 | 2002-10-10 | Mayes Anne M. | Graft copolymers, methods for grafting hydrophilic chains onto hydrophobic polymers, and articles thereof |
AUPR404801A0 (en) * | 2001-03-28 | 2001-04-26 | Polymerat Pty Ltd | A method of polymerization |
WO2007117493A2 (en) * | 2006-04-05 | 2007-10-18 | University Of Massachusetts | Graft copolymers and related methods of preparation |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4308359A (en) * | 1975-12-31 | 1981-12-29 | Dynamit Nobel Ag | Method for the modification of polyvinylidene fluoride |
CN1743351A (zh) * | 2005-09-30 | 2006-03-08 | 天津工业大学 | 一种温敏型聚偏氟乙烯智能膜材的制备方法及其产品 |
Non-Patent Citations (4)
Title |
---|
Graft Copolymers from Poly(vinylidene fluoride-co-chlorotrifluoroethylene) via Atom Transfer Radical Polymerization;Mingfu Zhang et al.;《Macromolecules》;20060408;第39卷(第10期);3531-3539 * |
Mingfu Zhang et al..Graft Copolymers from Poly(vinylidene fluoride-co-chlorotrifluoroethylene) via Atom Transfer Radical Polymerization.《Macromolecules》.2006,第39卷(第10期),3531-3539. |
Single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes;Yong Woo Kim et al.;《European Polymer Journal》;20071231;第44卷;932-939 * |
Yong Woo Kim et al..Single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes.《European Polymer Journal》.2007,第44卷932-939. |
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