CN105492549A - 具有短全氟链的抗水和抗油含氟聚合物 - Google Patents

具有短全氟链的抗水和抗油含氟聚合物 Download PDF

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CN105492549A
CN105492549A CN201380076312.4A CN201380076312A CN105492549A CN 105492549 A CN105492549 A CN 105492549A CN 201380076312 A CN201380076312 A CN 201380076312A CN 105492549 A CN105492549 A CN 105492549A
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hfo
nano particle
textile fabric
water resistant
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S·冯
林云
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Honeywell International Inc
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Abstract

公开了用于纺织织物的抗水抗油涂层，其具有低表面能部分和纳米部分，所述低表面能部分具有Rf为4或更少的聚烯烃，所述纳米部分具有纳米颗粒。也公开了涂覆的织物、以及制备涂覆的织物的方法。

Description

具有短全氟链的抗水和抗油含氟聚合物
发明领域
本发明涉及具有抗水和抗油性质的氟化聚合物。更具体地，本发明涉及具有此类氟化聚合物的纺织织物涂层。
发明背景
多年来，向制品(例如纤维产品，PET合成纤维)表面赋予抗水/抗油性的流行和通常的方法为将基材浸入具有基于具有带有至少8个碳原子的聚氟烷基的单体的结构单元的共聚物乳液中。参见，例如，U.S.专利5,334,903号(Raiford等)，U.S.专利4,321,404号(Williams等)，U.S.专利5,144,056号(Anton等)和U.S.专利5,446,118号(Shen等)。
然而，如所论述的，特别是如U.S.专利5,688,884号(Baker等)中论述的，美国环境保护局(theUnitedStatesEnviromentalProtectionAgency，EPA)已发现具有至少8个碳原子的全氟烷基(Rf基团)的化合物分解缓慢、可能会生物积累于活性有机体内并潜在地对环境造成重大影响。相应地，已经进行了研究以确定具有基于具有带有少于8个碳原子的Rf基团的单体的结构单元的聚合物或共聚物作为抗水/抗油组合物是否会有效。
例如，Takao等(U.S.专利申请公开2012/0259045号)公开了使用丙烯酸全氟烷基乙基酯/偏二氯乙烯/(甲基)丙烯酸烷基酯共聚物乳液，在由乳液制剂施加于尼龙和聚酯布料(cloth)之后其赋予基材抗油和抗水性。Takao等所用的丙烯酸全氟烷基乙基酯单体的化学式为如下：
CF3(CF2)5-C2H4-OC(O)CH＝CH2
Gregg等(U.S.专利申请公开2007/0173149号)公开了另一种氟代丙烯酸酯，其具有带有少于6个的碳原子的Rf基团，其甚至短于Takeo等所用的单体。例如，Gregg等所用的一种单体的化学结构为如下：
CF3(CF2)3SO2N(CH3)(CH2)m-OC(O)NH-(C6H4-CH2-C6H4)-HNC(O)O-(CH2)n(O)COC＝CH2
(m＝2-8，n＝2-30)
同样如Gregg等所说明的，预期的是具有比6个碳或8个碳全氟化基团更低级的Rf基团使得化合物毒性更低和更少的生物积累，同时保持良好的抗水/抗油能力。
相应地，需要研发更为环保的含氟聚合物，例如具有更低级的Rf基团和具有相对良好的疏水和疏油性质。
发明概述
本发明通过提供具有比4Rf基团低级的含氟聚合物来解决该需求，所述含氟聚合物可用于抗水和抗油涂层，并可在涂覆溶液中用于制品例如由天然和/或合成纤维(包括但不限于棉、纤维素、毛线、丝绸、聚酰胺、聚酯、聚烯烃、聚丙烯腈、纸以及皮革)制得的织造纺织织物和非织造纺织织物之上。
根据本发明的第一方面，提供用于纺织织物的抗水抗油涂层，该涂层具有含有聚烯烃的低能部分、和含有纳米颗粒、改变纺织织物形态的纳米部分。优选地，聚烯烃包含至少一种下式代表的含氟聚合物：
其中R1、R2、R3各自选自H、Cl和F，m为整数，和聚合物具有1000至100,000的分子量。优选地，该聚合物可在引发剂的存在下在反应溶液中合成。
根据本发明的第二方面，提供具有根据第一方面的涂层的纺织织物。
根据本发明的第三方面，提供一种用第一方面的涂层涂覆纺织织物的方法。
附图简要说明
已选择具体的实施例用以阐述和描述的目的，并示于构成说明书的一部分的附图中。
图1为在织物上制备抗水抗油涂层的方法流程图。
发明详述
图1为阐述了在织物上形成疏水和疏油涂层的方法的流程图。根据该方法，抗水/抗油涂层通过在引发剂的存在下并在适合的反应条件下使通式为CF3CR1＝CR2R3的氟碳化合物聚合形成。所得聚合物由下式所代表：
其中R1、R2、R3各自选自H、Cl和F，和聚合物具有1000至100,000的分子量。
形成聚合物之后，可加入酸以沉淀聚合物。然后可将沉淀的聚合物过滤、干燥并与常见有机溶剂合并以形成关键组分(即组分A)。多种可商购的氢氟烯烃或(HFO)可用以制备含氟聚合物。适合的HFO可具有通式CF3CR1＝CR2R3，其中R1、R2、R3各自选自H、Cl和F。适合的HFO包括四氟丙烯化合物和五氟丙烯化合物。优选的四氟丙烯化合物为2，3，3，3-四氟-1-丙烯(HFO-1234yf)，其形成具有下式的聚合物：
其它适合的四氟丙烯化合物包括HFO-1234ze、HFO-1233zd和HFO-1234zf。适合的五氟丙烯化合物包括HFO-1225。任意前述化合物的立体异构体也可以为适合的。
聚合优选在一种或多种自由基引发剂的存在下进行。适合的引发剂包括偶氮二异丁腈、2，2′-偶氮双(2-甲基丙酰胺)二盐酸盐、脂族过酸酯例如四丁基过氧化氢、过硫酸盐例如过硫酸钠、过硫酸钾、过硫酸铵和过硫酸铁，及前述的组合。过硫酸盐引发剂可特别适用于本发明。引发剂可基于单体的总重量少于10wt％，更特别地少于5wt％和甚至更特别地少于1.0wt％。
根据本发明优选的合成1234yf均聚物的方法为乳液聚合。该方法的一个益处在于不使用氯氟碳(chlorofluorocarbon)或常见溶剂。该方法为环境友好的。其它常见的替代方法，例如溶液聚合和本体聚合也可使用。
可于1234yf均聚物制备期间使用的表面活性剂包括，但不限于，含氟表面活性剂和烃表面活性剂(例如辛基磺酸钠、十二烷基磺酸钠、癸基磺酸钠、辛酸钠、硬脂酸钠和壬基酚聚(环氧乙烷))。优选地，使用氟表面活性剂或全氟化羧酸，例如具体实施例中的全氟辛酸铵。
根据本发明制备的1234yf均聚物通过NMR方法和元素确认。如下表1所示，1234yf均聚物在某些常见有机溶剂，例如乙酸乙酯和甲乙酮中具有良好的溶解度。相应地，含氟聚合物可以溶液形式用于涂覆织物。优选地，涂覆溶液为0.5-95wt％的含氟聚合物，和甚至更优选地为0.5-5.0wt％的含氟聚合物。
表1：均-1234yf溶解度测试结果
溶剂 溶解度
氯仿 不溶
乙二醇 不溶
丙二醇 不溶
石油醚 不溶
乙醇 不溶
甲醇 不溶
异丙醇 不溶
异丁醇 不溶
乙酸乙酯 可溶
丙酮 可溶
甲乙酮 可溶
四氢呋喃 可溶
优选的用于本发明的纳米颗粒包括二氧化硅、氧化锌、二氧化钛、氧化铝及前述的组合。以下实施例2提供了用于制备纳米颗粒的通常程序。该纳米颗粒分配溶液(即组分B)优选用于在制备上面的低表面能含氟聚合物层涂层之前在纺织织物上形成底层。
优选的纺织织物包括，但不限于，多种由天然或合成纤维(包括棉、纤维素、毛线、丝绸、聚酰胺、聚酯、聚烯烃、聚丙烯腈和人造丝)制备的织造纺织织物和非织造纺织织物。
实施例
实施例1
2，3，3，3-四氟-1-丙烯聚合物(均-1234yf)的聚合
向1000mL高压釜加入450mL去离子水、6g全氟辛酸铵、1.2g过硫酸铵、3.36gNa2HPO4和2.22gNaH2PO4·2H2O。三次氮气脱氧循环之后，将混合物溶液冷却至0℃，将360g2，3，3，3-四氟丙烯单体经由泵、经5分钟的时间装入高压反应器，期间在200rpm下搅拌反应器内容物。单体进料步骤之后，将反应器保持在400rpm和70℃。48小时之后，停止聚合并从高压釜释放多余气体。使聚合胶乳凝结于25％HCl中并用蒸馏水洗涤聚合产物和在50℃下干燥过夜。最终，获得237.15g白色聚合物，产率为66％。产物为无定形含氟弹性体，其具有54℃的玻璃化转变温度(如通过差示扫描量热法(DSC)所确定的)。发现氟含量是66.5％。
实施例2
二氧化硅纳米颗粒溶液的制备
向250mL配有磁力搅拌器的圆底烧瓶加入10mL去离子水、25mL乙醇和35mL原硅酸四乙酯。在室温、400rpm搅拌速度下反应10分钟之后，向反应溶液缓慢加入几滴碱和/或酸。2小时之后，形成二氧化硅纳米颗粒溶液并可直接使用。
实施例3
织物上抗水抗油涂层的制备
用丁酮稀释一定量的均-1234yf固体以致聚合物含量为0.5-5％，作为组分A，以上所制备的二氧化硅纳米颗粒溶液用作组分B。所选的用于测试的织物包括蓝色尼龙、PET、聚烯烃非织造物和未染色的棉织物。测试之前，聚烯烃织物于室温下干燥24小时并随后在38℃下热处理10秒。尼龙织物在使用前空气干燥24小时。首先将织物浸入组分B体系中3分钟，随后分别在80℃下固化3分钟和在150℃下固化3分钟。形成第一纳米层之后，随后将织物浸入组分A中，并于150℃下干燥3分钟以制得疏水和疏油涂层的层。该两层涂层赋予了织物良好的抗水和抗油性。
实施例4
平均粒度
用已通过50μιη过滤器的蒸馏水将二氧化硅纳米颗粒溶液稀释为0.05质量％以获得样品。样品的平均粒度通过动态光散射方法经由粒度测量系统测量。发现平均粒度是180nm。
实施例5
抗水性喷淋测试
对于测试布料，根据喷淋测试方法(AATCC标准测试方法No.22)评价抗水性。测试期间，将250ml水在27度角度下以狭窄物流的方式倾倒至铺展于6英寸(15.2cm)直径塑料箍之上的织物样品上，自悬于织物样品之上6英寸的漏斗泄出。移除过量水之后，通过参考公开的标准，在视觉上对织物进行打分。等级100表示无水渗透或表面粘附；等级90表示轻微的不规则的粘连或润湿，且更低值表示更大的润湿。等级0表示完全润湿。抗水性评分测试结果分别是PET为95，尼龙为95和棉织物为90，表明了非常好的抗水性，其导致织物上的水呈珠状。
实施例6
抗油性测试
通过AATCC标准测试方法No.118的变型来测试经处理的织物样品的抗油性。将一系列有机液体(如下表2中所确认的)逐滴引至织物样品。于最低编号的测试液体(抗油性等级1号)开始，将一滴(0.05mL体积)置于三个位置中的每个上，所述三个位置的间距为至少5mm。观察液滴30秒。该时段结束时，如果三滴中的两滴在形状上仍然为球形至半球形，且液滴周围无芯吸(wicking)，则将三滴下一最高编号的液体置于相邻位置并类似地观察30秒。继续该程序，直至测试液体之一导致三滴中的两滴无法维持球形至半球形，或者发生润湿或芯吸。织物的抗油性等级为三滴中的两滴于30秒内维持球形至半球形、并且无芯吸的最高编号测试液体。
表2：
a正十六烷中Vol％
经由测试，发现抗油性等级是PET为4，尼龙为4和棉织物为3，表明织物具有良好的抗油等级。

Claims (15)

1.用于纺织织物的抗水抗油涂层，包含：
低表面能部分，其包含Rf为4或更少的聚烯烃；和
纳米部分，其包含纳米颗粒。
2.权利要求1的抗水抗油涂层，其中所述聚烯烃包括下式的聚合物
其中R1，、R2、R3各自选自H、Cl和F，且所述聚合物具有1000至100,000的分子量。
3.权利要求2的抗水抗油涂层，其中所述聚烯烃选自四氟丙烯和五氟丙烯化合物。
4.权利要求3的抗水抗油涂层，其中所述四氟丙烯和五氟丙烯化合物选自HFO-1234yf、HFO-1234ze、HFO-1233zd、HFO-1234zf、HFO-1225，其立体异构体，及其组合。
5.权利要求1的抗水抗油涂层，其中所述纳米颗粒包括选自二氧化硅、氧化锌、二氧化钛、氧化铝及其组合的纳米颗粒。
6.权利要求5的抗水抗油涂层，其中所述纳米颗粒基本上由选自二氧化硅、氧化锌、二氧化钛、氧化铝及其组合的纳米颗粒组成。
7.涂覆有权利要求1的抗水抗油涂层的纺织织物，其中抗水抗油涂层至少包括：
第一层和第二层，第一层与所述纺织织物相邻并包含所述纳米部分，
第二层包含所述低表面能部分，
其中所述第一层位于所述纺织织物和所述第二层之间。
8.根据权利要求1的纺织织物，其中所述纺织织物选自棉、纤维素、毛线、丝绸、聚酰胺、聚酯、聚烯烃、聚丙烯腈和人造丝。
9.用根据权利要求1的抗水抗油涂层涂覆纺织织物的方法，包括步骤：
用包含所述纳米颗粒的溶液涂覆至少一部分的纺织织物；和
用包含Rf为4或更少的聚烯烃的溶液涂覆所述部分。
10.根据权利要求9的方法，进一步包括制备包含聚烯烃的溶液的步骤。
11.根据权利要求10的方法，其中制备溶液包括步骤：
具有下式的含氟聚合物聚合
其中R1、R2、R3各自选自H、Cl和F，含氟聚合物具有1000至100,000的分子量；
使含氟聚合物沉淀；和
将沉淀的含氟聚合物溶解于至少一种溶剂中。
12.根据权利要求11的方法，其中所述含氟聚合物选自四氟丙烯和五氟丙烯化合物。
13.根据权利要求12的方法，其中所述四氟丙烯和五氟丙烯化合物选自HFO-1234yf、HFO-1234ze、HFO-1233zd、HFO-1234zf、HFO-1225，其立体异构体，及其组合。
14.根据权利要求13的方法，其中所述纳米颗粒包括选自二氧化硅、氧化锌、二氧化钛、氧化铝及其组合的纳米颗粒。
15.根据权利要求14的方法，其中所述纳米颗粒基本上由选自二氧化硅、氧化锌、二氧化钛、氧化铝及其组合的纳米颗粒组成。
CN201380076312.4A 2013-05-08 2013-05-08 具有短全氟链的抗水和抗油含氟聚合物 Pending CN105492549A (zh)

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