CN102575029A - 具有改善的拒油性的聚酯膜 - Google Patents
具有改善的拒油性的聚酯膜 Download PDFInfo
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- CN102575029A CN102575029A CN2010800470030A CN201080047003A CN102575029A CN 102575029 A CN102575029 A CN 102575029A CN 2010800470030 A CN2010800470030 A CN 2010800470030A CN 201080047003 A CN201080047003 A CN 201080047003A CN 102575029 A CN102575029 A CN 102575029A
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- reaction flask
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Images
Classifications
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- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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Abstract
本发明提供了由共聚酯制成的膜,与常规的共聚酯相比,其具有改善的拒油性。所述共聚酯衍生自某些全氟化单体。
Description
发明领域
本发明涉及由衍生自全氟化单体的共聚酯制得的膜。所述聚酯膜表现出改善的拒油性。
发明背景
氟化材料具有许多用途。具体地讲,它们用于聚合物相关产业中,并且更具体地讲,用于纤维相关产业中,以赋予防垢性和抗油性。一般来讲,这些材料作为局部处理物施用,但是由于材料因磨损和清洗而损耗,因此它们的有效性随着时间的推移而降低。
需要提供一般具有改善以及持久的拒垢性和拒油性的聚合材料。通过将氟化芳族二酯掺入到聚合物主链中,可获得更持久的拒垢性和拒油性。
发明概述
本发明的一个方面是由包含全氟化单体的共聚酯形成的膜,其中全氟化单体的量为所述共聚酯的约0-100重量%,并且其中由所述共聚酯形成的膜表现出超过60度的己烷接触角、以及超过110度的水接触角。
所述共聚酯能够由式I、II或II表示:
其中,对于(I)和(II),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为Cl或Br;
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10;
每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;
每个q独立地为0-10;
m为1-10,000;并且
w为1-10,000;
并且其中,对于(III),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为H、Cl或Br,前提条件是仅一个Z能够为H;并且
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10,每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;
每个q独立地为0-10;
m为1-10,000;并且
w为1-10,000。
附图简述
图1a为聚(对苯二甲酸三亚甲基酯)均聚物表面上己烷珠的摄影图示。
图1b为聚(对苯二甲酸三亚甲基酯)均聚物表面上水珠的摄影图示。
图2a为聚(对苯二甲酸三亚甲基酯)与全氟化单体共聚物表面上己烷珠的摄影图示。
图2b为聚(对苯二甲酸三亚甲基酯)与全氟化单体共聚物表面上水珠的摄影图示。
图3a为聚(对苯二甲酸三亚甲基酯)与全氟化单体共聚物表面上己烷珠的摄影图示。
图3b为聚(对苯二甲酸三亚甲基酯)与全氟化单体共聚物表面上水珠的摄影图示。
图4a为聚(对苯二甲酸三亚甲基酯)与全氟化单体共聚物表面上己烷珠的摄影图示。
图4b为聚(对苯二甲酸三亚甲基酯)与全氟化单体共聚物表面上水珠的摄影图示。
图5为1,3-丙二醇与5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧基)间苯二甲酸二甲酯以及对苯二甲酸二甲酯的共聚物的1H-NMR和19F-NMR扫描图示。
发明详述
已发现本文公开的新型共聚酯表现出使它们适用于多种最终用途的特性,包括膜和模塑制品、以及纤维和由所述纤维制造的材料。所述共聚酯包含任选卤化的1,1,2-三氟芳族酯作为聚合单元,例如2-卤代-1,1,2-三氟芳族酯。该共聚酯还适用于纤维纺丝。
通过在溶剂(任选卤代的)和催化剂的存在下,将羟基芳族二酯加入到全氟化乙烯基化合物如全氟化乙烯基醚中,制得氟化芳族二酯。
虽然能够使用任何羟基芳族二酯,但是尤其有用的是2-羟基对苯二甲酸1,4-二甲酯、2-5-二羟基对苯二甲酸1,4-二乙酯、2-羟基-对苯二甲酸1,4-二甲氧酯、5-羟基间苯二甲酸二甲酯、4-羟基间苯二甲酸二甲酯、4,6-二羟基间苯二甲酸二甲酯、2-羟基间苯二甲酸二甲酯、2,5-二羟基间苯二甲酸二甲酯、2,4-二羟基间苯二甲酸二甲酯、2,3-二羟基间苯二甲酸二甲酯、3-羟基邻苯二甲酸二甲酯、4-羟基邻苯二甲酸二甲酯、3,4-二羟基邻苯二甲酸二甲酯、4,5-二羟基邻苯二甲酸二甲酯、3,6-二羟基邻苯二甲酸二甲酯、4,8-二羟基萘-1,5-二甲酸二甲酯、3,7-二羟基萘-1,5-二甲酸二甲酯和2,6-二羟基萘-1,5-二甲酸二甲酯。
多种全氟化乙烯基化合物可用于本文公开的合成反应中,如1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2-三氟乙烯氧基)丙-2-基氧基)丙烷、七氟丙基三氟乙烯基醚、全氟乙烯、全氟丙-1-烯、全氟丁-1-烯、全氟戊-1-烯、全氟己-1-烯、全氟庚-1-烯、全氟辛-1-烯、全氟壬-1-烯和全氟癸-1-烯。
一般来讲,在卤化溶剂如四氯甲烷、四溴甲烷、六氯乙烷和六溴乙烷的存在下,混合如上所公开的羟基芳族二酯和全氟化乙烯基化合物。
本文所公开的反应由碱催化。可使用多种碱性催化剂,即能够使苯酚去质子的任何催化剂。非限制性实例包括甲醇钠、氢化钙、钠金属、甲醇钾和叔丁醇钾。尤其有用的是叔丁醇钾。
在溶剂和催化剂的存在下混合羟基芳族二酯和全氟化乙烯基化合物,直至反应完成。一般来讲,反应在约-70℃至反应混合物回流温度,优选约室温(25℃)至反应混合物回流温度范围内的温度下进行。反应混合物可保持在回流温度下,直至达到所期望的反应进程。反应时间随反应温度和反应混合物组分而变化,并且易于由技术人员采用多种技术确定,包括但不限于核磁共振光谱、薄层色谱和气相色谱。然后任选用酸(例如10%HCl)淬灭反应混合物,并且在真空浓缩后,用溶剂(例如二氯甲烷)淋洗。反应混合物中可制得多于一种的全氟化芳族二酯,然后经由技术人员已知的任何方法分离,包括蒸馏或柱层析。
所得的2-卤代-1,1,2-三氟芳族酯可由下式中的一个表示:
其中,对于(A)和(B),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为H、Cl或Br;
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10;
每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;
并且每个q独立地为0-10;
并且其中,对于(C),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为H、Cl或Br,前提条件是仅一个Z能够为H;
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10;每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;并且
每个q独立地为0-10。
如上式中所示,取代基能够连结至苯环任何位点,因此使得可能具有如上定义的邻位、间位和对位取代基。
为制得包含全氟化醚芳族二酯的共聚酯,可将其它芳族二酯加入到反应中,包括芳族二元羧酸以及它们的二甲基酯。一种可加入的尤其可用的二酯是对苯二甲酸二甲酯。一些非限制性代表性的芳族二元羧酸是间苯二甲酸、对苯二甲酸、2,6-萘二甲酸、4,4’-磺酰基二苯甲酸、4-磺基邻苯二甲酸和联苯-4,4’-二甲酸。还可通过例如在催化剂的存在下,将二元羧酸加入到二醇(例如1,3-丙二醇)中,合成这些二元羧酸的二酯形式。一般来讲,在反应中使用基于钛(IV)的酯交换催化剂(例如丁醇钛(IV)和异丙醇钛(IV)),但是也可使用其它催化剂(例如基于锑、锌和锡的催化剂)。所述混合物在高温下搅拌并且反应,直至反应完成,然后任选经由地技术人员已知的方法例如真空蒸馏、沉淀、或拆解容器,分离出所形成的聚酯。
当制得包含1,1,2-三氟(全氟化醚)乙氧基二酯的共聚酯时,所述产物可由以下通式中的一个表示:
其中,对于(I)和(II),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为H、Cl或Br;
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10;
每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;
每个q独立地为0-10;
m为1-10,000;并且
w为1-10,000;
并且其中,对于(III),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为H、Cl或Br,前提条件是仅一个Z能够为H;
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10;每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;
每个q独立地为0-10;
m为1-10,000;并且
w为1-10,000。
可以上文公开的类似方式,通过混合全氟化芳族二元羧酸、第二芳族二元羧酸和二醇,从而形成共聚酯。
如上式中所示,取代基能够连结至苯环任何位点,因此使得可能具有如上定义的邻位、间位和对位取代基。
用于制备本文公开材料的1,3-丙二醇可以通过多种熟知化学途径中的任何一种或通过生物化学转化途径而获得。优选的途径公开于例如US20050069997A1中。
优选地,1,3-丙二醇以生化方式由可再生来源(“生物衍生的”1,3-丙二醇)获得。
尤其优选的1,3-丙二醇源是经由使用可再生生物源的发酵方法获得。作为得自可再生资源的原料的例证性实例,已经公开了获得1,3-丙二醇(PDO)的生化途径,所述途径利用由生物的并且可再生的资源如玉米原料制得的原料。例如,能够将甘油转化为1,3-丙二醇的细菌菌株存在于菌种克雷伯氏菌属(Klebsiella)、柠檬酸细菌属(Citrobacter)、梭菌属(Clostridium)和乳酸杆菌属(Lactobacillus)中。US5821092特别公开了一种使用重组生物体由甘油生物制备1,3-丙二醇的方法。所述方法引入了对1,2-丙二醇具有特异性的异源pdu二醇脱水酶基因转化的大肠杆菌。转化过的大肠杆菌在作为碳源的甘油存在下生长,并且从生长培养基中分离出1,3-丙二醇。由于细菌和酵母都能够将葡萄糖(如玉米糖)或其它碳水化合物转化为甘油,因此公开于这些公布中的方法提供了快速、廉价并且环保的1,3-丙二醇单体源。
生物衍生的1,3-丙二醇,例如通过上文公开和参考的方法制备的那种,包含由植物所吸收的来自大气二氧化碳的碳,其构成了制备1,3-丙二醇的原料。优选用于本文所公开方法中的生物衍生的1,3-丙二醇仅包含可再生的碳,而不包含基于化石燃料或基于石油的碳。因此,衍生自生物1,3-丙二醇的PO3G对环境的影响较小,这是因为组合物中所用的1,3-丙二醇没有耗减化石燃料,并且降解后将碳释放回到大气中以被植物再次利用。因此,在一些实施方案中,与包含石油基二醇的类似组合物相比,本文公开的组合物的特征在于更加自然,并且具有较小的环境影响。
如本文所公开的,可经由合成途径对聚酯主链进行修饰,以使得聚合物本性疏油,或提供增强的疏水性。更具体地讲,已经制得对苯二甲酸二甲酯(DMT)、全氟醚对苯二甲酸二甲酯、或全氟醚间苯二甲酸二甲酯与1,3-丙二醇(PDO)的共聚物,并且用于形成共聚物。一般来讲,可引入两种不同的全氟醚侧链长度,使得每个重复单元具有10或16个氟原子。
相应的共聚物结构可由光谱(1H-NMR、19F-NMR)和热分析表征,所述热分析一般仅显示熔融微量扰动,以及与纯聚(对苯二甲酸三亚甲基酯)相比的玻璃化转变温度。通常获得具有约0.9-1.0本征粘度(IV)的共聚酯。
可采用本领域技术人员已知的由热塑性聚合物形成膜的方法,使用所述共聚物来形成膜或薄片。通常,对具有约250微米或更高厚度的此类制品,使用术语“薄片”,而对于具有小于约250微米厚度的制品,使用术语“膜”。形成膜的方法一般归属于三大类:溶液流铸(适于制备涂层)、熔融浇铸和压塑。
溶液流铸通常用于不能进行熔融-挤出或对热极度敏感的聚合物,但是能够被用于多种聚合物,包括共聚酯如本文公开的那些。在膜溶液流铸中,将聚合物与任选添加剂如抗氧化剂、阻燃剂和/或颜料一起溶于溶剂中。通常,将均匀的聚合物溶液过滤并且脱气,接着形成凝胶膜并且干燥。接着将所述溶液沉积在表面上。通过蒸发和凝聚,由所述溶液形成凝胶膜。适宜表面的实例为金属、玻璃、或另一种聚合物,这取决于表面的粘合性能和所期望的最终用途。流铸后,通过例如加热移除膜中的溶剂。所述膜可保留在表面上,或剥离形成自立式膜,这取决于旨在的最终用途。凝胶膜干燥形成自承膜的速率部分取决于溶剂扩散速率;因此,溶液流铸最适于相对薄的膜。溶液流铸膜的特征包括低残余定向、所有方向的均匀特性和光滑的表面。
熔融浇铸通常用于由熔融聚合物形成连续膜。将通常为粒料、薄片、或粉末形式的聚合物加入到熔融挤出机(单螺杆或双螺杆)中,其中所述聚合物熔融形成连续熔融流,然后在螺杆连续旋转产生的压力下,将所述熔融流加入到膜模头中。所述模头具有选定的厚度,一般为约25-100微米,但是可以薄得多,例如约10微米。可将如上所述的任选添加剂与所述聚合物一起共进料到挤出机中。膜宽度可变,例如在商业操作中可窄至约25cm,或宽至6英尺。作为另外一种选择,模头可使膜形成连续中空圆柱,其直径可高达若干英尺。加工条件影响膜的特性。根据聚合物,膜散热速率决定膜结晶程度和形态,以及残余定向度。影响膜特性的另一个因素是膜散热处的温度。如果需要高质量表面或均匀的热传递,则可采用针扎步骤。针扎定义为将熔融膜强制施用于浇铸表面。针扎可经由气刀、真空箱、轧辊或强静电场来实施。针扎在保持整个膜均一特性的同时,仍可达到高产率。针扎力可预防气体被捕获在膜与浇铸表面之间。针扎方法的选择取决于操作速率与膜品质。
压塑通常以较小规模实施,例如实验室规模而不是商业规模。将熔融聚合物放入到具有所期望长度、宽度和厚度(例如4英寸×4英寸×150微米厚)的框架内,然后使其经历加热,并且使用例如水压机加压。在聚合物以足够的时间填充框架然后冷却后,从所述框架中取出膜,并且经受测试。
已显示,氟的掺入显著降低了所得的共聚物的总表面能。熔融挤压并且纺丝的样本已显出,氟化的低能组分富集于气-固界面,与纯聚酯(通常为聚(对苯二甲酸三亚甲基酯))相比,这使得拒水性和拒油性均提高。通常,纯聚(对苯二甲酸三亚甲基酯)完全润湿十六烷(C16-类脂)液滴,并且表现出超过60°的水接触角。包含一种或多种全氟化单体的聚酯(例如相对于对苯二甲酸二甲酯具有10重量%的全氟化单体总载量的基于F16-异-全氟醚-聚(对苯二甲酸三亚甲基酯)的共聚物)具有超过60°的十六烷接触角,以及超过110°的水接触角,如图1a和2a所示。当移除加入的十六烷液滴时,其完全去湿,因此证明该新型表面的疏油性。由包含一种或多种全氟化单体的聚酯(如相对于对苯二甲酸二甲酯具有10重量%的全氟化单体总载量的基于F16-对-全氟醚-聚(对苯二甲酸三亚甲基酯)的共聚物)制得的膜具有超过50°的十六烷接触角,和超过105°的水接触角,如图3所示。由包含一种或多种全氟化单体的聚酯(如相对于对苯二甲酸二甲酯具有10重量%的全氟化单体总载量的基于F10-异-全氟醚-聚(对苯二甲酸三亚甲基酯)的共聚物)制得的膜具有超过35°的十六烷接触角,和超过90°的水接触角,如图4所示。
因此,已示出,将全氟化单体加入到聚(对苯二甲酸三亚甲基酯)中,即使仅包含有限的氟含量,也显著改善了所得的共聚物的拒油性,此外增强了疏水性。
使用整合的DROPimage Advanced v2.3软件系统,在Rame’-HartInstrument Co.测角器Rame’-Hart 100-25-A型仪器上记录静态接触角。对水或十六烷,使用微注射器分配体系,并且使用4μL体积的分配液体。
使用单色Al X射线源(100μm,100W,17.5kV),在Ulvac-PHIQuantera SXM光度计上实施化学分析电子能谱(ESCA)(还被称为X射线光电子能谱(XPS))。为进行分析,首先以广泛全谱扫描方式检查样本表面(~1350μm×200μm),以确定表面上存在哪种元素。采用55eV传递能和0.2eV步长,获得高分辨率精细光谱采集,以测定检出元素的化学态和它们的原子浓度。通常以45°出射角分析碳、氧和氟(对于碳电子,逸出深度为)。采用PHI MultiPak软件进行数据分析。
实施例
化学品与试剂均按收到的原样用于下列实施例中:
得自Sigma-Aldrich(Milwaukee,WI):
●对苯二甲酸二甲酯
●叔丁醇钾
●二甲基甲酰胺
●二氯甲烷
●四氯甲烷(四氯化碳)
●四溴甲烷(四溴化碳)
●盐酸(HCl)
●无水硫酸钠
●2-羟基对苯二甲酸1,4-二甲酯
得自DuPont Tate & Lyle(Loudon,TN):
●1,3-丙二醇
得自SynQuest Labs.(Alachua,FL):
●七氟丙基三氟乙烯基醚
制备2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对 苯二甲酸二甲酯;
在干箱操作手套箱中,将2-羟基对苯二甲酸1,4-二甲酯(30.25g,0.144mol)加入到烘箱干燥的500mL多颈反应烧瓶中,所述烧瓶配备搅拌棒和均压(PE)加料漏斗。然后加入四氢呋喃(THF,288mL),从而形成混合物。搅拌所述混合物,直至获得均匀的溶液。加入叔丁醇钾(4.435g,0.040mol),从而获得非均质性混合物。经由PE漏斗,加入1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2三氟乙烯氧基)丙-2-基氧基)丙烷(155.52g,0.36mol),获得反应混合物。将反应混合物在室温(大约25℃)下搅拌~40小时。通过加入5mL 10%HCl,淬灭反应混合物。由反应混合物形成材料。将反应烧瓶中的材料减压浓缩。然后将材料溶于二氯甲烷(~300mL)中,然后用10%HCl(2×75mL)洗涤,接着用水(~75mL)洗涤,获得有机相和水相。然后在无水硫酸钠上干燥分离出的有机相。然后过滤出硫酸钠,并且将所得的材料减压浓缩,接着真空分馏。收集介于1.4-1.1托下134-136℃(84.55g,收率91.4%)与1.1托下136-138℃(3.35g)(合并收率:95.04%)之间沸腾的馏分。这些样品的NMR(核磁共振)示出为2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯。
制备5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间 苯二甲酸二甲酯;
在干箱操作手套箱中,将四氢呋喃(THF,1000mL)和5-羟基间苯二甲酸二甲酯(42.00g,0.20mol)加入到烘箱干燥的圆底反应烧瓶中,所述烧瓶配备搅拌器和加料漏斗;然后加入叔丁醇钾(6.16g,0.055mol)。然后经由加料漏斗加入1,1,1,2,2,3,3-七氟-3-(1,1,1,2,3,3-六氟-3-(1,2,2三氟乙烯氧基)丙-2-基氧基)丙烷(216g,0.50mol),从而形成反应。将反应在室温下搅拌。24小时后,通过加入80mL 10%HCl来终止反应。将反应减压浓缩,用二氯甲烷稀释,用10%HCl(2×100mL)洗涤,然后用水(2×100mL)洗涤,从而形成有机相和粗产物。将有机相在无水硫酸钠上干燥并且减压浓缩。粗产物经由柱层析纯化,获得86.07g(67.32%收率)5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-(全氟丙氧基)丙氧基)乙氧基)间苯二甲酸二甲酯。
实施例1:1,3-丙二醇与5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基) 丙氧基)乙氧基)间苯二甲酸二甲酯以及对苯二甲酸二甲酯的共聚。
向预干燥的500mL三颈圆底反应烧瓶中加入对苯二甲酸二甲酯(DMT,130g,0.66mol)、5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧基)间苯二甲酸二甲酯(相对DMT的重量%)、以及1,3-丙二醇(90.4g,1.19mol,相对于DMT为1.8eq)。将塔顶搅拌器和蒸馏冷凝器连结至反应烧瓶。将反应烧瓶中的反应物以50转/分钟(rpm)的速率搅拌,将所得的反应混合物保持在氮气(g)(N2)吹扫气氛下,并且将冷凝器保持在23℃下。通过将反应烧瓶排空至100托并且用N2气体回填,将反应烧瓶内容物脱气三次。第一次排空后加入TyzorTPT催化剂[对于理论聚合物产率50ppm Ti,δTYZOR=0.96g/mL]。将反应烧瓶浸入到设至160℃的预热金属浴中。使反应烧瓶内的固体在160℃下完全熔融20分钟,之后使搅拌速率缓慢增加至180rpm。使反应烧瓶的温度增加至210℃并且在该温度下保持90分钟以将大部分形成的甲醇蒸馏至蒸馏烧瓶中。将反应烧瓶的温度增加至250℃,之后关闭氮气吹扫并且开始施加梯度真空,并且在约60分钟后,真空值达到50-60毫托。当真空稳定时,将搅拌器的搅拌速率增加至225rpm并且将反应保持最多3-4小时。监测搅拌器的扭矩(在180rpm下的读数),并且通常在当扭矩值达到~100N/cm2时停止反应。通过移除热源停止聚合。停止塔顶搅拌器,并且在关闭真空之前从反应烧瓶底部提起,并且用N2气体吹扫体系。将反应烧瓶中形成的产物冷却至环境温度并且取下反应容器,并且用锤小心地击碎玻璃后回收产物。分离出的聚合物产物包含1,3-丙二醇与5-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧基)间苯二甲酸二甲酯以及对苯二甲酸二甲酯的共聚物,使用Wiley研磨将所述产物冷冻研磨(使用液氮)成灰白色粉末。总收率为~80-90%。1H-NMR(CDCl3/TFA-d,700MHz):δ8.60(ArH,s,主链),8.25-7.90(ArH-,m,主链),7.65(ArH,s,环状二聚体),6.10(-CF2-CFH-O-,d,侧链),4.75-4.45(COO-CH 2-,m,主链),3.95(HO-CH 2-R,t,端基),3.82(-CH 2-O-CH 2-,t,主链DPG),2.45-2.05(-CH2-,m,主链)。F19-NMR的实施例示于图5中。
当压成膜时,纯聚(对苯二甲酸三亚甲基酯)完全润湿十六烷(C16-类脂)液滴,并且还具有约60°的水接触角。由包含一种或多种全氟化单体的聚酯如基于F16-异-全氟醚-聚(对苯二甲酸三亚甲基酯)的共聚物(对苯二甲酸二甲酯载量为10重量%,氟化单体总含量为2.9摩尔%)制得的膜具有超过60°的十六烷接触角,以及超过110°的水接触角,如图1和2中所示。
ESCA/XPS数据示于下表1中。
表1:
实施例 | F(原子%) | C(原子%) | O(原子%) |
聚(对苯二甲酸三亚甲基酯) | / | 73.3 | 26.7 |
(比较) | |||
实施例1氟化共聚物 | 13 | 63 | 23 |
实施例2:1,3-丙二醇与2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基) 丙氧基)乙氧基)对苯二甲酸二甲酯以及对苯二甲酸二甲酯的共聚。
向预干燥的500mL三颈圆底反应烧瓶中加入对苯二甲酸二甲酯(DMT,130g,0.66mol)、2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯(相对DMT的重量%)、以及1,3-丙二醇(90.4g,1.19mol,相对于DMT为1.8eq)。将塔顶搅拌器和蒸馏冷凝器连结至反应烧瓶。将反应烧瓶中的反应物以50转/分钟(rpm)的速率搅拌,将反应烧瓶中的反应物质保持在氮气(g)(N2)吹扫气氛下,并且将冷凝器保持在23℃下。通过将烧瓶排空至100托并且用N2气体回填将反应烧瓶内容物脱气三次。第一次排空后加入TyzorTPT催化剂[对于理论聚合物产率50ppmTi,δTYZOR=0.96g/mL]。将反应烧瓶浸入到设至160℃的预热金属浴中。使反应烧瓶内的固体在160℃下完全熔融20分钟,之后使搅拌速率缓慢增加至180rpm。使反应烧瓶温度增加至210℃并且在该温度下保持90分钟以将大部分形成的甲醇蒸馏至蒸馏烧瓶中。将反应烧瓶的温度增加至250℃,之后关闭氮气吹扫并且开始施加梯度真空,并且在约60分钟后,真空值达到50-60毫托。当真空稳定时,将搅拌速率增加至225rpm并且将反应保持最多3-4小时。监测搅拌器的扭矩(在180rpm下的读数),并且通常在当扭矩值达到~100N/cm2时停止反应。通过移除热源停止聚合。关闭塔顶搅拌器,并且在关闭真空之前从反应容器底部提起,并且用N2气体吹扫体系。将反应烧瓶中形成的产物冷却至环境温度并且移除反应烧瓶,并且用锤小心地击碎玻璃后回收产物。分离出的聚合物产物包含1,3-丙二醇与2-(1,1,2-三氟-2-(1,1,2,3,3,3-六氟-2-全氟丙氧基)丙氧基)乙氧基)对苯二甲酸二甲酯以及对苯二甲酸二甲酯的共聚物,使用Wiley研磨将所述产物冷冻研磨(使用液氮)成灰白色粉末。总收率为~80-90%。1H-NMR(CDCl3/TFA-d,700MHz):δ8.25-7.90(ArH-,m,主链),7.65(ArH,s,环状二聚体),6.18(-CF2-CFH-O-,d,侧链),4.75-4.45(COO-CH 2-,m,主链),3.97(HO-CH 2-R,t宽峰,端基),3.82(-CH 2-O-CH 2-,t,主链DPG),2.45-2.05(-CH2-,m,主链)。
当压成膜时,当将一滴己烷和水放置在材料(对苯二甲酸二甲酯载量为10重量%)上时,所述材料分别表现出~50°和~109°的接触角,如图3a和3b中所示。
ESCA/XPS数据示于下表2中。
表2:
实施例 | F(原子%) | C(原子%) | O(原子%) |
聚(对苯二甲酸三亚甲基酯) | / | 73.3 | 26.7 |
(比较) | |||
实施例2氟化共聚物 | 12 | 63 | 24 |
实施例3:1,3-丙二醇与5-(1,1,2-三氟-2-(全氟丙氧基)乙氧基)间苯二甲 酸二甲酯以及对苯二甲酸二甲酯的共聚。
向预干燥的500mL三颈圆底反应烧瓶中充入对苯二甲酸二甲酯(DMT,130g,0.66mol)、5-(1,1,2-三氟-2-(全氟丙氧基)乙氧基)间苯二甲酸二甲酯(相对DMT的重量%)、以及1,3-丙二醇(90.4g,1.19mol,相对于DMT为1.8eq)。将塔顶搅拌器和蒸馏冷凝器连结至反应烧瓶。反应物形成反应混合物并且使其在反应烧瓶中以50转/分钟(rpm)的速率搅拌,并且将反应混合物保持在氮气(g)(N2)吹扫气氛下,并且将冷凝器保持在23℃下。通过将反应烧瓶排空至100托并且用N2气体回填,将反应烧瓶内容物脱气三次。第一次排空后将TyzorTPT催化剂[对于理论聚合物产率50ppmTi,δTYZOR=0.96g/mL]加入到反应烧瓶中。将反应烧瓶浸入到设在160℃的预热金属浴中。使反应烧瓶中的固体在160℃下完全熔融20分钟,之后使搅拌速率缓慢增加至180rpm。使反应烧瓶的温度增加至210℃并且保持90分钟,以将大部分形成的甲醇蒸馏至蒸馏烧瓶中。将反应烧瓶的温度增加至250℃,之后关闭氮气吹扫并且开始施加梯度真空,在约60分钟后,真空值达到50-60毫托。当真空稳定时,将搅拌速率增加至225rpm并且将反应保持最多3-4小时。监测搅拌器的扭矩(在180rpm下的读数),并且通常在当扭矩值达到~100N/cm2时停止反应。通过移除热源来停止聚合。停止塔顶搅拌器并且在关闭真空之前从反应烧瓶的底部提起,并且用N2气体吹扫体系。将反应烧瓶中形成的产物冷却至环境温度并且移除反应烧瓶,并且用锤小心地击碎玻璃后回收产物。分离出的聚合物产物包含1,3-丙二醇与5-(1,1,2-三氟-2-(全氟丙氧基)乙氧基)间苯二甲酸二甲酯以及对苯二甲酸二甲酯的共聚物,使用Wiley研磨将所述产物冷冻研磨(使用液氮)成灰白色粉末。总收率为~80-90%。1H-NMR(CDCl3/TFA-d,700MHz):δ8.60(ArH,s,主链),8.25-7.90(ArH-,m,主链),7.65(ArH,s,环状二聚体),6.10(-CF2-CFH-O-,d,侧链),4.75-4.45(COO-CH 2-,m,主链),3.95(HO-CH 2-R,t,端基),3.82(-CH 2-O-CH 2-,t,主链DPG),2.45-2.05(-CH2-,m,主链)。
当压成膜时,当将一滴己烷和水放置在材料(对苯二甲酸二甲酯载量为10重量%)上时,所述材料分别表现出~35°和~93°的接触角,如图4a和4b中所示。
ESCA/XPS数据示于下表3中。
表3
实施例 | F(原子%) | C(原子%) | O(原子%) |
聚(对苯二甲酸三亚甲基酯) | / | 73.3 | 26.7 |
(比较) | |||
实施例3氟化共聚物 | 9.1 | 67 | 24 |
Claims (2)
1.由包含全氟化单体的共聚酯形成的膜,其中所述全氟化单体的量为所述共聚酯的0-100重量%,其中所述膜表现出超过60度的己烷接触角、以及超过110度的水接触角。
2.权利要求1的膜,其中所述聚酯由式(I)、(II)、或(III)表示
其中,对于(I)和(II),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为H、Cl或Br;
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10;
每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;
每个q独立地为0-10;
m为1-10,000;并且
w为1-10,000;
并且其中,对于(III),
每个R独立地为H、C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个R1独立地为C1-C10烷基、C5-C15芳基、或C6-C20芳烷基;
每个X独立地为O或CF2;
每个Y独立地为O或CF2;
每个Z独立地为H、Cl或Br,前提条件是仅一个Z能够为H;并且
每个Rf1独立地为(CF2)n,其中每个n独立地为0-10,每个Rf2独立地为(CF2)p,其中每个p独立地为0-10,
前提条件是当p为0时,Y为CF2;
每个q独立地为0-10;
m为1-10,000;并且
w为1-10,000。
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