CN1249104C - 氟聚合物的水分散体 - Google Patents

氟聚合物的水分散体 Download PDF

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CN1249104C
CN1249104C CNB998142409A CN99814240A CN1249104C CN 1249104 C CN1249104 C CN 1249104C CN B998142409 A CNB998142409 A CN B998142409A CN 99814240 A CN99814240 A CN 99814240A CN 1249104 C CN1249104 C CN 1249104C
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H·布拉戴尔
K·辛特泽
G·罗尔
W·施沃特菲格
R·A·舒尔兹巴赫
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Abstract

向分散体中添加非离子型乳化剂，接着与阴离子交换材料接触而除去含氟乳化剂并使分散体与阴离子交换材料分离，就能从氟聚合物分散体中除去含氟乳化剂。所得到的分散体可经过浓缩并且可用于涂料。

Description

氟聚合物的水分散体
本发明涉及基本上不含含氟乳化剂的氟聚合物的水分散体、制备这类分散体的工艺及其用途。“基本上不含”指的是含量小于100ppm，优选小于50ppm，特别是小于25ppm并且尤其是小于5ppm。
聚氟乙烯分散体在涂料行业有着广泛的用途，因为这类涂料在比如防粘性、高耐候性和耐火性方面有着独特的性能。它们主要用于涂刷厨房用具、化学设备和玻璃织物。在这些应用当中，施用的是固含量相当高的分散体，比如最高可达70wt.％。这些浓缩的分散体大多利用胶体化学的方法借助非离子型乳化剂如烷芳基聚乙氧基醇和烷基聚乙氧基醇实现稳定。
主要有两种不同的制备氟聚合物的聚合反应工艺，即形成聚合物颗粒的悬浮聚合反应以及形成胶态水分散体的被称为乳液聚合反应的工艺。本发明涉及乳液聚合反应、所得到的分散体及其用途。
制造这类分散体一般包含两个工艺步骤，聚合和浓缩。
通过水乳液聚合反应得到首先是无法进行熔体加工的均聚物，比如PTFE，其次是“改性型”聚合物，比如四氟乙烯(TFE)超过约99mol％而共聚单体的量极低的聚合物从而产物保持其“无法熔体加工”特性，再者是低分子量的“微粉”分散体，它可进行熔体加工，而第四种则是共聚物，比如氟代热塑性塑料或氟代弹性体。氟代热塑性塑料包括主要由TFE和赋予产品熔体加工性能所必需的量，比如1～50mol％，优选1～10mol％的一种或多种共聚单体而构成的共聚物。除了TFE以外，常见的氟单体是偏氟乙烯(VDF)，其它氟代烯烃如一氯三氟乙烯(CTFE)，特别是2～8个碳原子的全氟代烯烃如六氟丙烯(HFP)，氟代醚，特别是烷基链段带1～6个碳原子的全氟乙烯基烷基醚如全氟(正丙基乙烯基)醚(PPVE)。共聚单体也可以是非氟代烯烃，比如乙烯或丙烯。所得到的可熔体加工或不可熔体加工的聚合物分散体其固含量一般是15～30wt.％。为了满足涂料应用对上述高固含量的要求并且也有利于贮存和运输，必须通过浓缩来提高固含量。于此可用的方法例是加热浓缩法(US-A 3 316 201)、滗析法(US-A-3 037 953)和超滤法(US-A-4 369 266)。
已知的乳液聚合反应大都如EP-B-30 663所述，在压力5～30bar和温度5～100℃的条件下进行。制备PTFE分散体的聚合反应工艺基本上与制备称为膏产品(US-A-3 142 665)的树脂细粉的已知工艺相同。制备共聚物比如氟代热塑性塑料分散体的聚合反应工艺，与这些材料在制备熔体丸粒形式时的工艺相同。
在所有这些乳液聚合反应中，所需要的是一种不因发生链转移反应而干扰聚合反应的乳化剂。这类乳化剂称为非调聚型乳化剂(US-A-2 559 752)。主要采用铵盐和/或碱金属盐形式的全氟辛酸(PFOA比如PFOA，CAS No.335-67-1)。但是，下文在使用PFOA一词时并不排除其它类型的氟代乳化剂。乳化剂的含量一般是0.02～1wt.％，基于聚合物。
有时采用其它类型的氟代乳化剂。比如EP-A-822 175描述了含CH2-的氟代羧酸盐在TFE乳液聚合反应中的应用。WO-A-97/08214描述了2-全氟己基乙磺酸或其盐在TFE聚合反应中的应用。
US-A-2 559 752描述了其它类型的氟代乳化剂，但因为其挥发性很差都没获得广泛应用。这些物质会使终产品在加工温度较高时发生变色。
PFOA的一个最大优势是其高的挥发性。PFOA是高效乳化剂并且由于它在聚合反应过程中呈现惰性因而在实际中是必不可少的。但是PFOA无法经生物降解而且近来也被划归为对环境有害。
但是，已知PFOA可从废气(EP 731 081)中除去，并且还描述了从废水中除去PFOA的适宜工艺(US-A-4 282 162以及1998年6月2日提交的尚未公开的德国专利申请198 24 614.5和198 24615.3)。
在上述旨在提高浓度的各种方法中，即使是超滤或者借助非离子型乳化剂100倍过量的滗析法进行清除，还是有很大一部分的PFOA残留在聚合物分散体中。
比如在US-A-4 369 266的超滤法中，约30％的PFOA初始含量残留在成品分散体中。在特殊情况下，PFOA的残留量可降低到低于10％，但一般而言工艺的成本较高；为了得到这种降低效果，需要向要浓缩的分散体中添加水和非离子型乳化剂。因而工艺时间过长而不可接受。
在这类分散体的后续应用当中，PFOA比如可随着清洗设备时不可避免产生的废水而流散到环境中以及以气溶胶的形式散逸到大气中。后一种排放形式在生产涂料时更加明显，因为PFOA及其铵盐的挥发性很高。除此之外，PFOA及其盐在常用的煅烧温度350～450℃下可通过脱羧基反应发生分解而生成能加重全球变暖效应(“温室效应”)的氟代烃。
本发明提供了基本上不含PFOA的高固含量分散体。在本发明中，“基本上不含”指的是含量小于100ppm，优选小于50ppm，特别是小于25ppm并且尤其小于5ppm。这些数值是基于整个分散体的，并非基于固体份。通过阴离子交换法，即通过向氟聚合物分散体中添加非离子型乳化剂并使该稳定化的分散体与碱性阴离子交换材料接触的方法从氟聚合物分散体如PTFE-、氟代热塑性塑料-或氟代弹性体分散体中除去氟代乳化剂如PFOA，就能实现此目的。该工艺可在不使离子交换床因胶乳粒子的凝聚而堵塞或团凝的情况下进行。所得到的分散体可选再加以浓缩。
相应地，本发明还提供了一种从氟聚合物水分散体中除去含氟乳化剂的方法，其包含向分散体中添加有效量的非离子型乳化剂以稳定分散体，稳定化的分散体与有效量的阴离子交换树脂接触和使分散体与阴离子交换树脂分离，其中分离后的分散体基本上不含氟乳化剂。
对于本发明，分散体的固含量通常是10-70wt.％。
于本发明有用的氟聚合物分散体包括一种或多种氟代单体如TFE、VDF或CTFE或其它2～8个碳原子的氟代烯烃、2～8个碳原子的全氟烯烃如HFP，氟代醚，特别是烷基带1～6个碳原子的全氟乙烯基-烷基醚如全氟-(正丙基-乙烯基)醚和全氟-(甲基-乙烯基)醚的均聚物和共聚物的分散体。因此，本发明的氟聚合物可以是四氟乙烯聚合物，其中可以含有例如90-100mol％的四氟乙烯。有用的共聚单体也包括非氟代烯烃，比如乙烯和丙烯。本发明旨在函盖这类分散体，而不管所得到的氟聚合物能否熔体加工。
胶乳粒子的直径一般为亚微级，小于400nm并优选40～400nm。通过已知的“微乳液聚合反应”可得到更细的粒子尺寸。胶乳粒子通过胶体化学方法而经阴离子稳定化。通过阴离子端基，大多情况下是COOH基团和阴离子乳化剂如PFOA来达到阴离子稳定化状态。这类经阴离子稳定化的分散体在阴离子交换床上会快速凝聚并因此而阻塞离子交换床。原因是双电层在离子交换点处遭到破坏。因此认为以阴离子交换材料处理经阴离子稳定化的分散体在技术上是不可行的，特别是在浓度较高时。
甚至是在浓度为聚合物粗分散体，即聚合后的分散体1/1000的情况下，也能观察到离子交换床遭受损害或发生凝聚的现象。
在对有用的离子交换材料进行选择时，这一观察结果很有帮助，即与阴离子交换材料的抗衡离子相对应的酸的pKa值必须比聚合物阴离子端基的pKa值高。优选阴离子交换材料有一个与pKa值至少为3的酸相对应的抗衡离子。
相反，即使是称为“FEP”的TFE与HFP的共聚物以及称为“PFA”的TFE与PPVE的共聚物的分散体，如果阴离子交换材料是SO4 2-或Cl-形式，经过长时间之后也可观察到凝聚现象。这两种共聚物都有强酸性的端基。对这类端基的生成机理所作的说明见“ModernFluoropolymers”，John Scheirs(Editor)，John Wiley&Sons，Chichester(1997)，pp.227-288，244。在加工TFE-乙烯或VDF共聚物分散体时，离子交换床在这些条件下几乎会立即发生阻塞或团凝。
因此开始时，阴离子交换过程在基本碱性的条件下进行。优选将离子交换树脂转变成OH-形式，但也可采用弱酸阴离子如氟或草酸根。这些阴离子一般存在于分散体中并且由聚合反应配方而来。
所用的阴离子交换材料其具体的碱度并不严格限制。由于观察到的效率较高因而在分离PFOA时优选强碱性树脂。从分散体中去除PFOA的效率取决于离子交换条件。弱碱性离子交换树脂出现PFOA流穿现象的时间也较早。流率较高时也是如此。
流率没有严格的限制，可采用标准流率。流动可以是上行或下行的。
离子交换工艺也可通过在容器中缓慢搅拌分散体与离子交换树脂的方法而以按批量工艺的形式进行。处理结束后经过滤分离出分散体。采用本发明能使批量工艺中的凝聚现象降至最低。
非离子型乳化剂在“Nonionic Surfactants”M.J.Schick(editor)，Marcel Dekker，Inc.，New York 1967中有详述。
非离子型乳化剂的选择也没有严格限制。烷基芳基聚乙氧基醇、烷基聚乙氧基醇或其它任何非离子型乳化剂都可采用。这是一大优势，因为从商品分散体中除去PFOA能保持待施分散体的配方基本不变。
采用非离子型表面活性剂例如烷基芳基聚乙氧基醇如TritonTMX100型或者是烷基聚乙氧基醇如GENAPOLTM X 080型时，在PFOA分离效率、流率或离子交换床有否阻塞方面没观察到什么区别。
优选用聚合反应的粗分散体进行PFOA分离。这类分散体的固含量一般为15～30wt.％。向其中添加足量的非离子型乳化剂以便在后续加工，比如浓缩过程中使分散体获得稳定性。足量的非离子型乳化剂一般指的是O.5～15wt.％，并优选1～5wt.％。这些百分数基于分散体的固体份。除去PFOA之后，分散体可借助普通工艺如超滤法或热浓缩法进行浓缩。最终产品中非离子型乳化剂的浓度最好不比同类市售产品的要高。工艺中没有了PFOA并不对浓缩工艺造成任何损害，就是说热浓缩和超滤过程中所形成的凝聚物并不比有PFOA的时候要多。
固含量最高为70wt.％的事先经过浓缩的分散体也可经由阴离子交换法而除去PFOA。但由于这类分散体的粘度和密度较大，该工艺在实施时有一定的困难。此时，离子交换处理优选按上流法进行，以避免因离子交换床的漂浮而造成的困难。高粘度一般不允许高流率。对于这类高固含量的分散体而言，批量工艺显得更为适宜。
PFOA的除去是这样进行的，在中等搅拌条件下一般向分散体中添加1～5wt.％的非离子型乳化剂并使分散体流过阴离子交换材料。阴离子交换材料可采用与待交换分散体所用相同的非离子型乳化剂溶液进行预处理。优选将阴离子交换树脂转变成OH-形式。使阴离子交换树脂与NaOH溶液接触即可实现之。
分散体一般无需调整pH值就可用于离子交换工艺，但也可通过添加碱，比如氨水或氢氧化钠水溶液，来增加pH值以提高分散体的胶体稳定性。7～9范围之内的pH值就足够了。增加pH值对去除PFOA的效率影响不大。可能是由于PFOA不仅被交换而且也被强烈地吸收在离子交换树脂上。
离子交换过的分散体随后进行浓缩，优选采用热浓缩法或超滤法。这些工艺不会造成任何损害。本发明的分散体在实际加工性能或应用性能上更不会有什么变化。
非离子型乳化剂存在下的阴离子交换工艺，在不阻塞离子交换床的情况下，可成功地用于除去任何聚合反应工艺中所用的任何其它阴离子乳化剂。
此工艺也可用于任何类型的氟聚合物粗分散体，比如PFA、FEP、THV(THV是TFE、HFP和VDF的三元共聚物)、ET(ET是TFE和乙烯的共聚物)、TFE/P(TFE与丙烯的共聚物)，VDF和HFP的共聚物，以及包含其它氟代烯烃或乙烯醚的均聚物或共聚物的分散体。这些聚合物在上述的“Modern Fluoropolymers”中有详细说明。
US-A 5 463 021所公开的整理工艺着重描述了作为一个整理步骤经由离子交换工艺对THV粗分散体所作的处理。但这是一个阳离子交换工艺，目的是除去由作为聚合反应引发剂的高锰酸盐而来的锰离子。在阳离子交换过程中，起稳定作用的双电层没受影响，因为胶乳粒子是经阴离子稳定化的。
本发明就以下的实施例作以进一步的说明。
实验数据
所有百分数都是质量百分数，除非另有说明。
PFOA的测定
阴离子交换过的分散体中PFOA的含量可采用“Encyclopedia ofIndustrial Chemistry Analysis”，Vol.1 pp.339-340，IntersciencePublishers，New York，NY，1971和EP-A 194 690所述的方法进行定量分析。另一个可用的方法是将PFOA转化成甲基酯并经由带内标的气相色谱分析该酯的含量。后一种方法对PFOA的检出下限是5ppm。以下实施例中采用了后一种方法。
阴离子交换
采用标准设备。柱尺寸是5×50cm。以容量为1.2meq/ml的AMBERLITETM IRA 402作为强碱性阴离子交换树脂(AMBERLITE是Rohm&Haas的商标)。床体积一般是400ml。NaOH溶液将离子交换材料转变成OH-形式。交换材料事先以5％的非离子型乳化剂溶液进行处理。离子交换在室温下进行。试验在表1所给的各种流率下进行。非离子型乳化剂以10wt.％溶液的形式向分散体中添加。含量的变化情况见表1。这些值基于聚合物含量。如果在不阻塞床并且没有PFOA流穿的情况下，所用的离子交换树脂至少有5％的理论容量为含PFOA的分散体所消耗，那么该工艺在技术上就实现了可行性。
采用以下的非离子型表面活性剂：
NIS 1：辛基苯氧基聚乙氧基乙醇(商品名TRITONTM X 100，TRITON是Union Carbide Corp的商标)。
NIS 2：长链醇的乙氧化物(商品名GENAPOLTM X 080，GENAPOL是Hoechst AG的商标)。
实施例1～7
所有的试验都采用OH-形式的AMBERLITE IRA 402。以非离子型表面活性剂水溶液对阴离子交换树脂所作的不同的预处理见表1。
据EP-B 30 663法由TFE经均聚反应制得氟聚合物分散体。所用的粗分散体其固含量约20％，而平均粒径约为200～240nm。pH值是7。向粗分散体中所添加的非离子型乳化剂的量及其类型按表1进行变化。
分散体中PFOA的含量约为0.13wt.％(相应于3.14mmol/kg分散体)。这相当于2.7ml离子交换树脂/1kg粗分散体。实施例3表明消耗掉了离子交换树脂400ml总体积中的54ml。因此对所有的实施例而言，所提供的离子交换容量过量了5倍之多。
表1中的试验数据提供了不同的流率。在给定的测试当中，未观察到流率有什么改变。这说明离子交换床不存在阻塞现象。试验的持续时间最长为连续67h，而没有流穿现象。所有的实施例都得到PFOA含量小于5ppm的分散体，这是所用方法的分析检出下限。
实施例8
向含有201与实施例1～7所用分散体相同但经超滤法浓缩过的(固含量：52.5％，PFOA含量：0.065％，NIS 1含量：5％，基于聚合物含量)分散体的搅拌容器中缓慢添加800ml的AMBERLITE IRA 402(OH-形式，以5％的NIS 1溶液预处理)。在室温下中速搅拌8h之后，过滤出阴离子交换材料并分析分散体的PFOA含量，结果小于5ppmPFOA。
实施例9
采用与实施例1～7相同的步骤纯化PFA粗分散体。采用了400ml的AMBERLITE IRA 402(OH-形式，以1％的NIS 2溶液预处理)。以基于分散体固含量计5wt.％的NIS 2来稳定PFA分散体(1500ml，固含量20％)。该分散体包含0.066wt.％的PFOA并且pH值为4。分散体以100ml/h的流率流过阴离子交换床。相应于持续时间为15h。未观察到床的阻塞现象并且所得到的分散体其PFOA含量＜5ppm。
实施例10
采用经5wt.％的NIS 2稳定过的FEP粗分散体(固含量20wt.％，PFOA含量0.08wt.％)重复实施例9。该离子交换工艺得到PFOA含量＜5ppm的FEP分散体。没观察到床阻塞的现象。
实施例11
重复实施例9，但采用固含量20％而平均粒径为80nm的THV分散体。在分散体进行阴离子交换之前，US-A 5 43 021所述的阳离子交换树脂处理之。该阴离子交换工艺得到PFOA含量＜5ppm的THV分散体并且没观察到床阻塞的现象。
表1
  实施例序号   1   2   3   4   5   6   7
离子交换树脂，ml 400ml 400ml 400ml   4根平行柱，每个400ml   4根平行柱，每个400ml 400ml 400ml
  经水溶液预处理离子交换树脂   1wt.％NIS 1   5wt.％NIS 1   3wt.％NIS 1   5wt.％NIS 1   5wt.％NIS 2   5wt.％NIS 2   1wt.％NIS 2
  粗分散体：
  固含量   22.7％   22.6％   22.7％   22.7％   22.5％   23％   22.8％
  PFOA含量   0.132％   0.130％   0.132％   0.136％   0.138％   0.138％   0.136％
  粗分散体
  稳定以*)   1％NIS 1   3％NIS 1   4％NIS 1   5％NIS 1   5％NIS 2   4％NIS 2   1％NIS 2
  流通总量   5kg   19kg   20kg   40kg   50kg   18kg   8kg
  流率   0.5l/h   0.6l/h   0.3l/h   0.6l/h   0.6l/h   0.6l/h   0.5l/h
  持续时间   10h   35h   67h   17h   21h   30h   16h
  阻塞 是/否   否   否   否   否   否   否   否
  离子交换过的分散体
  PFOA含量   ＜5ppm   ＜5ppm   ＜5ppm   ＜5ppm   ＜5ppm   ＜5ppm   ＜5ppm
  *)基于分散体固含量

Claims (8)

1.一种从氟聚合物水分散体中除去含氟乳化剂的方法，其包含向分散体中添加有效量的非离子型乳化剂以稳定分散体，稳定化的分散体与有效量的阴离子交换树脂接触和使分散体与阴离子交换树脂分离，其中分离后的分散体含有少于100ppm的含氟乳化剂。
2.权利要求1的方法，其中分散体的固含量是10～70wt.％。
3.权利要求1的方法，其中稳定化的分散体与阴离子交换树脂在碱性环境中接触。
4.权利要求2的方法，其中添加了0.5～15wt.％的非离子型乳化剂，基于分散体固含量的重量计。
5.权利要求4的方法，其中非离子型乳化剂的加入量为1～5％，基于固含量计。
6.权利要求1的方法，其中阴离子交换树脂具有一个与pKa值至少是3的酸相应的抗衡离子。
7.权利要求1的方法，其中采用的是OH-形式的阴离子交换树脂。
8.权利要求1的方法，其中对分离的分散体进行浓缩。
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