CN101155837B - 从含氟聚合物水分散体移除含氟表面活性剂的方法中监测柱穿透 - Google Patents
从含氟聚合物水分散体移除含氟表面活性剂的方法中监测柱穿透 Download PDFInfo
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Abstract
本发明涉及一种降低稳定化包含含氟表面活性剂的含氟聚合物水分散体的含氟表面活性剂含量的方法,所述方法是通过使分散体通过第一阴离子交换树脂固定床以降低含氟表面活性剂含量。第一固定床具有在离子交换树脂饱和时移动通过所述柱的工作区。所述方法包括在分散体离开固定床时监测分散体的性质,以确定工作区的穿透,从而指示固定床的饱和。所监测的性质选自pH和电导率。
Description
发明领域
本发明涉及一种用阴离子交换树脂从含氟聚合物水分散体移除含氟表面活性剂的方法。
发明背景
含氟表面活性剂一般在含氟聚合物的分散聚合中用作聚合助剂,含氟表面活性剂充当非调聚型分散剂。例如,含氟表面活性剂的此用途的一个早期说明发现于美国专利2,559,752(Berry)。由于环境问题,由于含氟表面活性剂昂贵,现在已经为了将其从废水和含氟聚合物水分散体回收开发了多种方法。
从含氟聚合物分散体移除含氟表面活性剂的一种方法公开于美国专利4,369,266(Kuhls等人),其包括加入稳定表面活性剂,随后通过超过滤浓缩。此专利教授可通过含水渗出物移除高比率的含氟表面活性剂。已知也可通过吸附于离子交换树脂上移除含氟表面活性剂,如美国专利3,882,153(Seki等人)和美国专利4,282,162(Kuhls)所教授。Kuhls教授了在聚合物从分散体凝聚后在水相中溶解的或待浓缩的含水聚合物分散体中的氟化乳化剂的回收。US 2003/0125421A1(Bladel等人)也教授通过与阴离子交换剂接触从含氟聚合物分散体移除含氟乳化剂。
用阴离子交换树脂从含氟聚合物分散体移除含氟表面活性剂的已知方法利用强碱性阴离子交换树脂或弱碱性阴离子交换树脂。虽然可使用弱碱性树脂,因为它们能够更容易地再生,但在需要将含氟表面活性剂降低到极低量以及为了高度利用树脂时,强碱性树脂是优选的。强碱性离子交换树脂也具有对介质的pH敏感性较差的优点。
为了实际工业制备具有低含氟表面活性剂含量的含氟聚合物分散体,已知可使含氟聚合物分散体通过固定床,如阴离子交换树脂柱。然而需要制备均匀分散体产物,即具有标准低含量的减少表面活性剂的分散体。含氟表面活性剂浓度分析常规离线进行,而且完成测定需要大约8个小时。这种时间拖延不是确定可接受产品是否正被制备的实用方式。当固定床饱和使得离子交换部位不再充分吸收足够的含氟表面活性剂,并因此产生具有高的、不可接受含氟表面活性剂含量的分散体时,可能产生具有高的含氟表面活性剂含量的不可接受的产物。
在固定床(如柱)中有以分散体流动方向渐进通过柱的工作区(质量传递区),使得含氟表面活性剂被吸收在此工作区中的离子交换树脂。具体地讲,具有初始含氟表面活性剂含量的含氟聚合物分散体进入工作区,而离开所述区时具有降低的含氟表面活性剂含量。具有降低的含氟表面活性剂含量的含氟聚合物分散体通过其余不饱和柱,并且离开该柱。工作区渐进通过柱,直到柱完全饱和。在柱完全饱和使工作区完全移动通过该柱并且不再有被离子交换树脂充分吸收的点被称为穿透。
因此,需要一种降低稳定化含氟聚合物分散体的含氟表面活性剂含量以在柱末端检测工作区穿透(即柱饱和)的方法。
发明概述
本发明涉及一种降低稳定化包含含氟表面活性剂的含氟聚合物水分散体的含氟表面活性剂含量的方法,所述方法是通过使分散体通过第一阴离子交换树脂固定床,以降低含氟表面活性剂含量。第一固定床具有在离子交换树脂饱和时移动通过所述柱的工作区。所述方法包括在分散体离开固定床时监测分散体的性质,以确定工作区的穿透,从而指示固定床的饱和。所监测的性质选自pH和电导率。
在一个优选的实施方案中,所述方法利用第二固定床,其中在监控指示第一固定床饱和时将稳定化包含含氟表面活性剂的含氟聚合物水分散体通到第二固定床。
所述方法优选将含氟表面活性剂含量降低到不大于约300ppm的预定水平,更优选不大于约100ppm的预定水平,最优选不大于50ppm的预定水平。
发明详述
如上讨论,稳定化包含含氟表面活性剂的含氟聚合物水分散体的含氟表面活性剂含量可通过使分散体通过阴离子交换树脂固定床得以降低。根据本发明,可通过监测分散体的性质确定第一阴离子交换树脂固定床的饱和,所述性质选自pH和电导率。在一个优选的实施方案中,在柱中包含固定床。
本发明认识到,随着工作区(以上定义)移动通过第一固定床且该固定床变得饱和,在工作区达到柱末端即发生穿透时,分散体的pH和电导率发生变化。通过监测pH或电导率变化,可确定工作区穿透,表明含氟表面活性剂的浓度升高。在此转变中,pH降低,而电导率增加。pH和电导率的变化会很急剧,由此可精确地确定通过柱的分散体的窄范围体积内的穿透。例如,在氢氧离子型强碱性阴离子交换柱中,柱以含氟表面活性剂(如全氟辛酸铵)饱和使氢氧根离子的释放缓慢或实质上停止,导致pH的可测降低,例如1个pH单位,而电导率增加,例如100μS。在此变化发生期间的分散体体积可能很小。
监测优选在线进行,并且可指示何时停止处理过程,或优选指示何时将稳定化包含含氟表面活性剂的含氟聚合物水分散体流转向第二不饱和阴离子交换树脂固定床。
以下将更充分地描述,根据本发明,稳定化包含含氟表面活性剂的含氟聚合物水分散体通过第一阴离子交换树脂固定床以降低含氟表面活性剂含量使含氟表面活性剂含量降低到不大于约300ppm的预定水平,更优选不大于约100ppm的预定水平,尤其不大于约50ppm的预定水平。
含氟聚合物
用于根据本发明处理的稳定化包含含氟表面活性剂的含氟聚合物水分散体用分散聚合(也被称为乳液聚合)制备。含氟聚合物水分散体为一种稳定化包含含氟表面活性剂的含氟聚合物水分散体,这意味其包含足够非离子表面活性剂,以便在含氟表面活性剂含量降低时防止分散体凝聚。以后更详细解释,根据何时利用本发明的方法,非离子表面活性剂可能已经存在,即如果在浓缩的分散体中进行,或者为了稳定可能在根据本发明处理之前加入。浓缩后,可将含氟聚合物水分散体用作涂料或浸渍组合物,并用于制备流延薄膜。
含氟聚合物分散体包含由单体制备的聚合物微粒,其中至少一种单体包含氟。本发明所用的水分散体的微粒的含氟聚合物独立地选自三氟乙烯、六氟丙烯、一氯三氟乙烯、二氯二氟乙烯、四氟乙烯、全氟烷基乙烯单体、全氟(烷基乙烯基醚)单体、偏二氟乙烯和氟乙烯的聚合物和共聚物。
在分散体的含氟聚合物组分为不可熔融加工的聚四氟乙烯(PTFE)(包括改性的PTFE)时,本发明尤其有用。聚四氟乙烯(PTFE)是指没有任何显著共聚单体存在的自身聚合的四氟乙烯。改性的PTFE是指TFE与不使所得聚合物的熔点实质降低到低于PTFE的熔点的低浓度共聚单体的共聚物。此共聚单体的浓度优选低于1%重量,更优选低于0.5%重量。改性的PTFE包含在烘烤(熔融)期间改善薄膜形成能力的少量共聚单体改性剂,如全氟烯烃,尤其是六氟丙烯(HFP)或全氟(烷基乙烯基)醚(PAVE),其中烷基包含1至5个碳原子,并且全氟(乙基乙烯基)醚(PEVE)和全氟(丙基乙烯基)醚(PPVE)是优选的。其中还包括三氟氯乙烯(CTFE)、全氟丁基乙烯(PFBE)或将大侧基引入分子的其它单体。PTFE一般具有至少1×109Pa·s的熔体蠕变粘度。这种高熔体粘度表明PTFE在熔融态不流动,因此不可熔融加工。PTFE和改性的PTFE通常以分散体形式售出,并且在装运容器中运输,可很容易地用本发明的方法降低此分散体的含氟表面活性剂含量。
分散体的含氟聚合物组分可熔融加工。可熔融加工是指聚合物可在熔融态加工(即,从熔体制成显示具有足够强度和韧度以用于预期用途的成形的制品,如薄膜、纤维和管等)。这种可熔融加工的含氟聚合物的实例包括四氟乙烯(TFE)和至少一种氟化的可共聚单体(共聚单体)的共聚物,可共聚单体以使共聚物的熔点降低到实质低于TFE均聚物、聚四氟乙烯(PTFE)的熔点的足够量存在于聚合物中,例如降低到不高于315℃的熔融温度。此类含氟聚合物包括聚三氟氯乙烯、四氟乙烯(TFE)或三氟氯乙烯(CTFE)的共聚物。与TFE使用的优选共聚单体为具有3至8个碳原子的全氟烯烃,如六氟丙烯(HFP)和/或全氟(烷基乙烯基醚)(PAVE),其中线形或支化的烷基包含1至5个碳原子。优选的PAVE单体为其中烷基包含1、2、3或4个碳原子的单体,并且共聚物可用数种PAVE单体制备。优选的TFE共聚物包括FEP(TFE/HFP共聚物)、PFA(TFE/PAVE共聚物)、TFE/HFP/PAVE,其中PAVE为PEVE和/或PPVE和MFA(TFE/PMVE/PAVE,其中PAVE的烷基具有至少两个碳原子)。可通过一定量共聚单体结合到共聚物提供通常具有约1-100g/10min熔体流动速率的共聚物(根据ASTM D-1238在为特定共聚物标准的温度测定),从而制备可熔融加工的共聚物。由如美国专利4,380,618所述修改的ASTM D-1238方法在372℃测定,熔体粘度通常为102Pa·s至约106Pa·s,优选103Pa·s至约105Pa·s。其它可熔融加工的含氟聚合物为乙烯或丙烯与TFE或CTFE尤其是ETFE、ECTFE和PCTFE的共聚物。其它有用的聚合物为聚偏二氟乙烯(PVDF)、偏二氟乙烯的共聚物以及聚氟乙烯(PVF)和氟乙烯共聚物的成膜聚合物。
含氟表面活性剂
在包含含氟表面活性剂的分散体中,要在本发明方法中减少的含氟表面活性剂为可溶于水并且包含离子性亲水基团和疏水部分的非调聚型可离子化分散剂。疏水部分优选为含至少4个碳原子的脂族氟烷基,其中除了最多一个并且是最接近增溶基团的那一个碳原子以外的所有碳原子携带至少两个氟原子,此外末端碳原子还携带选自氢或氟的原子。这些含氟表面活性剂用作分散的聚合助剂,并且由于它们不链转移,不会导致形成具有不合乎需要短链长度的聚合物。宽范围的适合含氟表面活性剂公开于授予Berry的专利2,559,752中。含氟表面活性剂优选为具有6-10个碳原子的全氟化羧酸,并且通常以盐形式使用。适合含氟表面活性剂为全氟羧酸铵,例如全氟羊脂酸铵或全氟辛酸铵。含氟表面活性剂通常相对于生成的聚合物的量以0.02至1%重量的量存在。
离子交换树脂
所用的阴离子交换树脂可为强碱性或弱碱性。适合的弱碱性阴离子交换树脂包含伯胺基、仲胺基或叔胺基。适合的强碱性阴离子交换树脂包含季铵基。虽然可使用弱碱性树脂,因为它们能够更容易地再生,但在需要将含氟表面活性剂减少到极低量和为了高度利用树脂时,强碱性树脂是优选的。强碱性离子交换树脂也具有对介质的pH敏感性较差的优点。强碱阴离子交换树脂具有缔合的反离子,并且通常可以氯离子形式或氢氧根离子形式得到,但如果需要,可很容易地将其转化成其它形式。具有氢氧根离子、氯离子、硫酸根离子和硝酸根离子的阴离子交换树脂可用于移除含氟表面活性剂,但氢氧根离子形式的阴离子交换树脂可优选防止引入不合乎需要的阴离子,并且在阴离子交换期间增加pH,因为在运输前高pH(即大于9)对产物抑制细菌生长合乎需要。具有季铵基与三甲胺部分的适合市售强碱阴离子交换树脂的实例包括DOWEX550A、US FilterA464-OH、SYBRON M-500-OH、S YBRON ASB1-OH、PUROLITEA-500-OH、Itochu TSA 1200、AMBERLITEIR 402。具有季铵基与二甲基乙醇胺部分的适合市售强碱阴离子交换树脂的实例包括USFilter A244-OH、AMBERLITE410、DOWEXMARATHON A2和DOWEXUPCORE Mono A2。
本发明方法所用的阴离子交换树脂优选为单分散性。阴离子交换树脂粒更优选具有一种数均粒径分布,其中95%的粒具有在数均粒径的±100μm内的粒径。
单分散阴离子交换树脂具有提供通过床的适合压降的粒径。极大的粒易碎,并且倾向于破裂。很小的阴离子交换树脂粒容易使颗粒填充紧密,使床内通道转折弯曲。这可能导致床内高剪切条件和高压降。优选的阴离子交换树脂具有约450至约800μm的数均粒径,更优选阴离子交换树脂粒具有约550至约700μm的数均粒径。
非离子表面活性剂
根据Marks等人的美国专利3,037,953和Holmes的美国专利3,704,272的教授,芳族醇乙氧基化物可作为非离子表面活性剂用于在离子交换处理前使包含含氟表面活性剂的含氟聚合物水分散体稳定化,也用于此分散体的浓缩。然而,由于芳族化合物的某些可能的环境影响问题,优选的非离子表面活性剂为脂族醇乙氧基化物。适合的非离子表面活性剂包括在浓缩期间提供所需浊点且在分散体中提供所需性质(例如,低烧尽温度,分散稳定性等)的任何种类脂族醇乙氧基化物或其混合物。这些非离子表面活性剂组合物有很多描述于Marks等人的美国专利3,037,953和Miura等人的美国专利6,153,688。尤其优选的非离子表面活性剂为下式的化合物或化合物的混合物:
R(OCH2CH2)nOH
其中R为具有8-18个碳原子的支化烷基、支化烯基、环烷基或环烯基烃基,n为5至18的平均值,如Cavanaugh的EP 1472307A1所公开。
方法
优选聚合物PTFE的水分散聚合的一般方法是将TFE蒸气送入包含含氟表面活性剂、石蜡和去离子水的加热的反应器中。如果需要降低PTFE的分子量,也可以加入链转移剂。加入自由基引发剂溶液,并且在聚合进行时,加入另外的TFE以保持压力。反应放热由使冷却水循环通过反应器夹套移除。数小时后,停止进料,将反应器排气,用氮气吹扫,并且将容器中的粗分散体转移到冷却容器中。除去石蜡,将分散体分离,并用非离子表面活性剂稳定化。稳定化的分散体优选包含基于分散体中含氟聚合物固体重量2-11%重量的非离子表面活性剂。
如此制备的含氟聚合物分散体将含一定量铁离子,铁离子来自聚合和处理中所用的金属设备,或来自于加入铁化合物如催化剂等,或由于在水自身中存在。在本发明的方法中,优选在使包含含氟表面活性剂的含氟聚合物水分散体与氢氧化物形式阴离子交换树脂接触之前,将有效量的适合螯合剂加入稳定化的包含含氟表面活性剂的含氟聚合物水分散体中。以此方式,形成强力结合的铁络合物,并且防止泡沫形成。
可熔融加工的TFE共聚物的分散聚合类似,不同之处在于将一种或多种共聚单体在开始加入所述批中和/或在聚合期间引入。此外,为了预期目的,还用调聚剂(如烃)控制分子量以取得所需聚合物的熔体流动。
阴离子交换过程可利用使稳定化的分散体通过阴离子交换树脂固定床来进行,优选通过包含阴离子交换树脂固定床的柱。由于树脂保持在固定床中,可向上或向下流动通过所述床,并且不需要单独的分离步骤。
在稳定化分散体进入固定床前,测定要监测的性质的值,即稳定化分散体的pH和/或电导率,如使用在线pH计和/或电导率仪。在分散体离开固定床时,再次测定pH和/或电导率的值。pH降低和/或电导率增加为柱工作区穿透的标志。由于此监测优选在线进行,所以可指示何时阴离子交换处理不再产生具有所需低含量表面活性剂的稳定化分散体,固定床饱和且需要更换。在本发明的一个优选实施方案中,在指示第一固定床饱和时,使稳定化包含含氟表面活性剂的含氟聚合物水分散体流转向第二不饱和阴离子交换树脂固定床。
如果需要,可从阴离子交换树脂回收含氟表面活性剂,或者可将具有含氟表面活性剂的树脂以环境可接受的方法处理掉,例如焚化。如果需要回收含氟表面活性剂,则可通过洗脱方法从树脂移除含氟表面活性剂。洗脱吸附在阴离子交换树脂上的含氟表面活性剂可很容易地用稀无机酸与有机溶剂的混合物(例如,HCl/乙醇)进行,如Kuhls在美国专利4,282,162中说明,或者用强无机酸进行,如硫酸和硝酸,将所吸附的氟化羧酸转移到洗脱液。洗脱液中高浓度的含氟表面活性剂可容易地以纯酸形式或盐形式由普通方法回收,如酸沉积、盐析或其它浓缩形式等。
在离子交换处理后,将具有降低的含氟表面活性剂含量的含氟聚合物水分散体转移到分散体浓缩操作。在分散体浓缩操作中,分散体借助于非离子表面活性剂浓缩,如Marks等人的美国专利3,037,953和Holmes的美国专利3,704,272所教授,以使固体从名义35%重量提高到约60%重量。Miura等人的美国专利6,153,688公开了一种类似方法。在为了离子交换处理将分散体分离时(除蜡后),所选择的非离子表面活性剂通常是为了稳定作用选择的表面活性剂。
如上所述,使稳定化的分散体与阴离子交换树脂接触在浓缩前进行。这可能是有利的,因为低固体分散体具有较低粘度并且便于处理。本发明的方法也可以对已浓缩的稳定化分散体进行。可将用于PTFE分散体的相同阴离子交换处理和分散体浓缩操作用于TFE共聚物分散体。
实施例
以下说明关于浓缩前稳定化PTFE水分散体的本发明的方法。分散体具有约42%重量的含氟聚合物固体含量,包含约4%重量非离子表面活性剂,Tergitol TMN-100X,购自Dow Chemical Corporation。分散体包含约1800ppm全氟辛酸铵,其电导率为600μS,pH为4。
使稳定化分散体通过在约8英尺长14英寸直径柱中容纳的市售氢氧化物形式强碱阴离子交换树脂(Dowex 550A)的固定床,所述强碱阴离子交换树脂具有季铵基与三甲胺部分。在柱饱和前的正常操作中,稳定化的分散体通过工作区,并且离开所述柱。在约250加仑稳定化分散体通过柱后,分散体在离开柱时的电导率为200μS,pH为10。电导率用电导率仪在线测定。pH用pH计在线测定。含氟表面活性剂含量离线测定,经测定为19ppm,标志着柱处于良好操作条件,且未耗尽。在约6000加仑流动通过柱后,检测离开柱的分散体,电导率急剧增加到300μS,pH急剧降低到9。这些变化为饱和柱工作区穿透的标志,需要停止使用该柱。然后使液流转向类似于以上所述柱的含不饱和阴离子交换树脂的第二固定床。
为了确定第一柱饱和,在使表面活性剂转向第二柱之前离线测定稳定化表面活性剂的含氟表面活性剂含量,经测定为约200ppm,证明工作区的穿透,即柱饱和。
Claims (8)
1.一种降低包含含氟表面活性剂的含氟聚合物水分散体的含氟表面活性剂含量的方法,所述包含含氟表面活性剂的含氟聚合物水分散体是以足够非离子表面活性剂稳定化的,从而在含氟表面活性剂的含量降低时,防止分散体凝聚,
所述方法包括:
使所述稳定化包含含氟表面活性剂的含氟聚合物水分散体通过第一阴离子交换树脂固定床以降低含氟表面活性剂含量,所述第一固定床具有工作区,其该工作区中,所述含氟表面活性剂被吸收在所述阴离子交换树脂,并且所述工作区在所述离子交换树脂饱和时移动通过所述固定床;并且
在所述分散体离开所述第一固定床时监测所述分散体的性质,以便确定所述工作区的穿透,在所述穿透中,工作区完全移动通过所述第一固定床,从而指示所述第一固定床的饱和,
所述性质选自pH和电导率。
2.权利要求1的方法,所述方法进一步包括在所述监测确定所述第一固定床饱和时使所述分散体通过第二固定床。
3.权利要求1的方法,其中所述固定床被容纳在柱中。
4.权利要求1的方法,其中所述阴离子交换树脂包含聚合物基体和包括季铵基的官能团。
5.权利要求1的方法,其中所述阴离子交换树脂包括阴离子交换树脂粒,所述粒为单分散性。
6.权利要求1的方法,其中所述使稳定化包含含氟表面活性剂的含氟聚合物水分散体通过第一阴离子交换树脂固定床以降低含氟表面活性剂含量使含氟表面活性剂含量降低到不大于300ppm的预定水平。
7.权利要求1的方法,其中所述使稳定化包含含氟表面活性剂的含氟聚合物水分散体通过第一阴离子交换树脂固定床以降低含氟表面活性剂含量使含氟表面活性剂含量降低到不大于100ppm的预定水平。
8.权利要求1的方法,其中所述使稳定化包含含氟表面活性剂的含氟聚合物水分散体通过第一阴离子交换树脂固定床以降低含氟表面活性剂含量使含氟表面活性剂含量降低到不大于50ppm的预定水平。
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US65160505P | 2005-02-10 | 2005-02-10 | |
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PCT/US2006/006982 WO2006086793A1 (en) | 2005-02-10 | 2006-02-10 | Monitoring column breakthrough in a process for removing fluorosurfactant from aqueous fluoropolymer dispersions |
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CN2006800110077A Expired - Fee Related CN101155837B (zh) | 2005-02-10 | 2006-02-10 | 从含氟聚合物水分散体移除含氟表面活性剂的方法中监测柱穿透 |
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