CN101484316A - 挠性多层偏氟乙烯管 - Google Patents

挠性多层偏氟乙烯管 Download PDF

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CN101484316A
CN101484316A CNA2007800253395A CN200780025339A CN101484316A CN 101484316 A CN101484316 A CN 101484316A CN A2007800253395 A CNA2007800253395 A CN A2007800253395A CN 200780025339 A CN200780025339 A CN 200780025339A CN 101484316 A CN101484316 A CN 101484316A
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layer
pvdf
sandwich construction
kynar
elastic layer
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S·哲拉法迪
G·S·奥布里恩
W·J·哈策尔
J·J·亨利
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Arkema Inc
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Arkema Inc
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Abstract

本发明涉及具有偏氟乙烯接触层的坚韧的挠性多层管或其它结构。这种管特别适用于高纯度接触应用，以及需要耐化学性的接触应用。所述偏氟乙烯层是可熔融加工的，可以是均聚物、共聚物或三元共聚物。

Description

挠性多层偏氟乙烯管
发明领域
本发明涉及具有偏氟乙烯均聚物或共聚物作为接触层的坚韧的挠性多层管或其它结构。这种管特别适用于高纯度接触应用和/或需要极佳耐化学性的化学接触应用。所述偏氟乙烯层是可熔融加工的，可以是均聚物、共聚物、三元共聚物、混合物或合金。
发明背景
坚韧的挠性管用于许多商业和工业应用中。这种管可以长时间夹紧，或者压缩上千次，但是仍然迅速恢复到其初始形状。所述管在使用时不能丧失挠性，而且不会产生裂纹或破裂。
许多应用和制造方法需要不仅具有韧性和挠性而且还具有化学和生物惰性的管子。这类管子的内表面必须对从其中通过的流体(液体或气体)没有活性，具有极佳的阻挡性质，应该几乎不含或完全不含可萃取物。
目前用于生物制药应用的管技术包括例如硅酮(silicone)、热塑性聚烯烃(TPO)、热塑性聚乙烯(TPE)和膨胀PTFE复合管。
所述管的一种应用是用于蠕动泵。蠕动泵是用于转移流体的非接触正排量泵。通过以下方式产生流体的转移：连续压缩管壁，产生压力使流体转移。该应用需要管具有极佳的记忆和回复性质。对于这些应用，需要具有良好阻挡性质的高纯度耐化学性管。蠕动泵可用于转移化学材料和生物制药材料，其中流体不会接触泵。
聚偏氟乙烯(PVDF)以其高耐化学性和惰性而著称。不幸的是，PVDF不具有承受严酷的蠕动泵循环所需的高挠性和恢复能力。
令人惊奇的是，已经发现一种多层管满足蠕动泵应用的要求，这种多层管具有作为流体接触层的PVDF薄层以及一层或多层挠性聚合物外层。目前，在市场上还没有能够在接触层纯度、耐化学性、阻挡性以及整体结构的挠性和恢复性(或返回原状)的综合性能方面能够比得上本发明管的产品。
发明概述
本发明涉及一种多层挠性结构，该结构包括聚偏氟乙烯接触层和弹性层，其中聚偏氟乙烯层直接或间接粘附在弹性层上。
发明详述
本发明涉及一种挠性多层结构，该结构包括薄聚偏氟乙烯接触层和弹性聚合物非接触层。
文中所用的术语“挠性”指多层结构在反复多次变形后能够恢复其原始形状的能力。该结构必须是可变形的，并且能够恢复到其原始形状。
PDVF接触层提供极佳的耐化学性和防渗透性，含极低的可萃取物性或完全不含可萃取物。就可萃取物而言，PVDF是最纯的可商购聚合物之一。PVDF也是对于全部化学物质具有极佳耐化学性的半结晶含氟聚合物。另外，PVDF对于H2O、CO2、O2、CO和烃类燃料以及许多其它化合物具有极佳的防渗透性。
本发明的聚偏氟乙烯聚合物包括：通过偏氟乙烯(VDF)聚合制得的均聚物，以及偏氟乙烯的共聚物、三元共聚物和更高级聚合物，其中偏氟乙烯单元在聚合物的所有单体单元的总重量中占70重量％以上，更优选占75重量％以上。偏氟乙烯的共聚物、三元共聚物和更高级聚合物可以通过使偏氟乙烯与一种或多种选自下组的单体反应制得：偏氟乙烯，三氟乙烯，四氟乙烯，一种或多种部分或完全氟化的α-烯烃，诸如3，3，3-三氟-1-丙烯、1，2，3，3，3-五氟丙烯、3，3，3，4，4-五氟丁烯和六氟丙烯，部分氟化的烯烃六氟异丁烯，全氟化的乙烯基醚，诸如全氟甲基乙烯基醚、全氟乙基乙烯基醚、全氟正丙基乙烯基醚和全氟-2-丙氧基丙基乙烯基醚，氟化的间二氧杂环戊烯，诸如全氟(1，3-二氧杂环戊烯)和全氟(2，2-二甲基-1，3-二氧杂环戊烯)，烯丙基类(allylic)，部分氟化的烯丙基类或氟化烯丙基类单体，诸如2-羟乙基烯丙基醚或3-烯丙氧基丙二醇，以及乙烯或丙烯。优选的是与偏氟乙烯、三氟乙烯、四氟乙烯(TFE)和六氟丙烯(HFP)形成的共聚物或三元共聚物。
优选的共聚物包含约71-99重量％的VDF以及对应的约1-29％的TFE；约71-99重量％的VDF以及对应的约1-29％的HFP(如美国专利第3,178,399号中揭示的)；和约71-99重量％的VDF以及对应的约1-29重量％的氯三氟乙烯(CTFE)。
优选的三元共聚物是VDF、HFP和TFE的三元共聚物，以及VDF、三氟乙烯和TFE的三元共聚物。特别优选的三元共聚物含有至少71重量％的VDF以及其他单体，其他单体可为不同比例，但总量占三元共聚物的29重量％。
最优选的PVDF共聚物包括包含2-30重量％HFP的那些共聚物，例如KYNAR FLEX 2800，2750和2500树脂(阿科玛股份有限公司(ArkemaInc.))。
聚偏氟乙烯也可以是官能化的PVDF，通过共聚时官能化或聚合后官能化而生成，例如来自阿科玛股份有限公司的Kynar ADX。Kynar ADX可以是混合或纯的接枝聚合物。在接触层中使用官能化的PVDF的做法可以用于最高纯度不是主要问题的工业应用中。但是，在需要高纯度的生物制药或其它应用中，官能化的PVDF不能用于直接表面接触，这是因为一些官能化单体会从PVDF中渗出。
因此，马来酸酐接枝的PVDF之类的官能化PVDF可以用于只要求耐化学性的应用中，但是该物质不是生物制药应用中最佳的候选者。
PVDF也可以是PVDF与以下物质的混合物或合金：其它PVDF共聚物或与PVDF相容的聚合物，例如聚甲基丙烯酸甲酯和聚甲基丙烯酸甲酯共聚物；以及THV(四氟乙烯、六氟乙烯和偏氟乙烯的氟化三元共聚物)。在混合物或合金的情况中，全部组成中至少50重量％是PVDF。
PVDF接触层是厚度为3-500微米、优选15-150微米、最优选25-75微米的薄层。PVDF层的厚度和组成将取决于使用该结构的应用。
文中使用的术语“多层”结构或管是指具有两层或更多层的结构，其中接触层(管的内层)是PVDF。该结构可以由2、3、4、5、6或更多层粘附在一起形成。粘结层(tie layers)和粘合层可以作为所述结构的一部分，或者在没有粘结层或粘合剂的情况下使不同的层粘附在一起。
聚偏氟乙烯通常不具有足够的挠性使其在连续变形后能够恢复到原始形状。因此，本发明的结构必需是多层结构，包括PVDF接触层和至少一个弹性层，以弥补PVDF接触材料在弹性回复方面的缺陷。因此，整个多层结构具有挠性和恢复性，使得该结构可以经历上百甚至上千次变形到恢复的循环。
弹性聚合物是那些在负荷除去后能够恢复其原始形状的材料。最常用于本发明的弹性层的弹性聚合物是那些容易熔融加工的材料。弹性层也可以是能够施加于PVDF层，然后在二次操作中固化的层。可用的弹性体的例子包括但不限于：弹性聚酰胺TPE(热塑性弹性体)，例如PEBAX(阿科玛股份有限公司)；热塑性硫化橡胶(vulcanates)(TPV)，例如SANTOPRENE(聚丙烯-EPDM TPV，由高级弹性体系统公司(Advanced Elastomer Systems)生产)；热塑性烯烃(TPO)，例如Engage(乙烯-丙烯聚烯烃弹性体，由陶氏化学公司(Dow Chemical)生产)；热塑性硫化橡胶(TPV)，其含有接枝或反应的官能团，包括马来酸酐或缩水甘油基(glycidal)甲基丙烯酸酯，例如SANTOPRENE；基于聚酰胺(PA基)或基于热塑性聚酯弹性体的热塑性硫化橡胶(例如HYTREL，杜邦公司(Dupont)生产)；丙烯酸酯橡胶，例如SEBS(苯乙烯-乙烯-丁烯-苯乙烯共聚物，壳牌公司(Shell)生产)；热塑性聚氨酯(基于聚酯或聚醚的TPU)；聚酯类TPE，例如HYTREL；含氟弹性体(来自杜邦公司的VITON，来自阿科玛股份有限公司的Kynar Ultraflex)，硅酮，氯丁橡胶(Neoprene)，腈橡胶，丁基橡胶，聚酰胺，聚烯烃，例如聚乙烯和聚丙烯，氯化乙烯基(chlorinated vinyls)，例如PVC和挠性化的PVC，其中挠性化的PVC通常是被增塑的。
形成包含PVDF的多层结构的一个困难是只有很少的材料能够很好地粘附在PVDF上，因此形成具有恢复性质的多层结构是富有挑战性的。在一个实施方式中，马来酸酐官能PVDF，例如来自阿科玛股份有限公司的KYNAR ADX，可以直接粘附在PVDF接触层上，然后可以粘附到许多弹性化合物上。
使PVDF粘附到弹性体上的另一种方法是使用粘结层。单层或多层粘结层在本领域是已知的，可以根据弹性层进行选择，包括但不限于以下材料中的一种或多种：KYNAR ADX，LOTADER(官能化的聚乙烯，来自阿科玛股份有限公司)，OREVAC(官能化的PE，来自阿科玛股份有限公司)，热塑性聚氨酯(TPU)，CPE(氯化聚乙烯)，官能粘结层(TPO-热塑性烯烃)，聚酰胺，特别是胺封端的聚酰胺，含氟聚合物，聚烯烃，聚甲基丙烯酸甲酯和其它丙烯酸类。在某些情况中，也可以将这些材料混合制得优良的粘结层。例如，将TPU和Pebax混合，可以得到用于Kynar和Pebax结构的极佳的高温粘结层。另一个例子是混合Engage与Lotader，产生具有足够的官能度以粘附到Kynar ADX上的挠性粘结层。另外，混合Kynar和PMMA以提高PMMA的性质，可以得到更坚固的整体结构。
弹性层的厚度随最终应用的尺寸要求而变化。通常，弹性层的厚度为250-1500微米。为了使结构获得最佳的恢复性，弹性层通常比结构中的PVDF层厚，但是这两层的厚度也可以相同，或者弹性层的厚度略薄一些。
当本发明的多层结构用作挠性管时，该挠性管可以为任何尺寸。蠕动泵应用中使用的管的尺寸通常约为1/8英寸至两英寸。
在本发明的范围内，可以具有PVDF层-与接触层的组成相同或不同-作为多层结构的外层，以及一个或多个中间弹性层。具有外层PVDF层便于焊接其它PVDF组分，例如PVDF袋，可以用于生物制药应用中。外层上的PVDF可以是纯PVDF或用DBS(癸二酸二丁酯)之类的增塑剂增塑的PVDF。加入增塑剂可以降低PVDF的劲度，提供更好的恢复性。
在本发明的一个实施方式中，PVDF均聚物或共聚物接触层的两层结构可以被作为挠性层的挠性PVDF(例如来自阿科玛股份有限公司的KYNARFLEX)包围。这种结构具有能够再循环和再利用的优点，因为该结构完全由聚偏氟乙烯聚合物制得。
可以向所述多层结构中增加其它层以提供特定性质，例如提供阻挡层、色彩、透明度、更低的价格和增强的物理性质。在一个实施方式中，聚乙烯醇层作为阻挡层加入。
一些可用于本发明的结构如下所述。本领域技术人员根据所提供的列表和信息可以想象出许多类似的结构。如以下所列，第一列材料(PVDF)是与生物制药或化学试剂接触的层，可以是PVDF均聚物、共聚物、三元共聚物、官能化的均聚物或官能化的共聚物。
-PVDF/KYNAR ADX/粘结层/弹性体
-PVDF/KYNAR ADX/LOTADER/PEBAX
-PVDF/KYNAR ADX/TPU/PEB AX
-KYNAR ADX/TPU/PEBAX
-PVDF/KYNAR ADX/聚酰胺(优选是胺封端的)/PEBAX
-PVDF/KYNAR ADX/TPU/EVOH/TPU
-PVDF/TPU/EVOH/TPU
-PVDF/KYNAR ADX/LOTADER/PEBAX/LOTADER/KYNARADX/PVDF
-KYNAR ADX/LOTADER/PEBAX
-PVDF/KYNAR ADX/LOTADER/TPO
-KYNAR ADX/LOTADER/TPO
-PVDF/TPU/PEBAX
-KYNAR/橡胶
-KYNAR ADX/橡胶
-KYNAR/KYNAR ADX/橡胶
-KYNAR/KYNAR ULTRAFLEX
-KYNAR/KYNAR ULTRAFLEX/TPU
-KYNAR/KYNAR ADX/硅酮
-KYNAR 2500/KYNAR ADX与KYNAR 2500/LOTADER/PEBAX混合
-KYNAR 2500/KYNAR ADX与KYNAR2500/LOTADER/ENGAGE混合
-KYNAR/KYNAR ADX/EVOH/OREVAC/聚乙烯
-KYNAR/KYNAR ADX/EVOH/尼龙
-KYNAR/PMMA/PVC
-KYNAR/TPU/PVC
-KYNAR/KYNAR ADX/TPU+PVC
在内层和外层上都具有PVDF的结构包括但不限于：
-PVDF/KYNAR ADX/LOTADER/PEBAX/LOTADER/KYNARADX/PVDF
-PVDF/KYNAR ADX/LOTADER/TPO/LOTADER/KYNARADX/PVDF
-PVDF/TPU/PEBAX/TPU/PVDF
-PVDF/TPU/PVDF
-PVDF/RUBBER/PVDF
-PVDF/KYNAR ULTRAFLEX/PVDF
-PVDF/KYNAR ULTRAFLEX/TPU/PVDF
-PVDF/硅酮/PVDF
本发明的多层结构可通过本领域已知的方法形成，例如共挤出或层压法。优选的方法是多挤出方法，其中2-7个层被挤出。
本发明的多层结构优选用作挠性管。包括PVDF接触层的多层管将挠性、耐久性、纯度、耐高温性、防渗透性、抗张强度和耐化学性结合在单个结构中。这种结构具有表面张力低的表面，因此对蛋白质胆固醇(cholestrol)和类脂具有低粘附性。
多层结构也可以成膜，用于制造各种最终制品。本领域技术人员可以想象本发明具有挠性、耐久性、惰性的材料的许多应用。一些可能的应用包括容器、管和袋，使得仅仅使用一种流体接触材料的系统成为可能。因为该挠性结构具有极佳的耐化学性和惰性，可以使用根据本发明制造的膜制备多种化学物质，特别是用于生物、生物医药和生物制药(biopharma)接触应用。本发明的其它应用可以包括气体取样袋—包括用于汽车排放应用的气体取样袋，用于辊筒的耐化学性衬垫，用于温室的遮盖，等等。
在一个实施方式中，本发明的多层挠性结构可以是一件个人防护服，它是本质上与管相反的结构，具有暴露于环境的PVDF接触层和挠性内层。这种结构可以用作耐生物和化学性质的防护服、防护靴、防护手套或其它外衣。通过使用PEBAX作为与皮肤接触的层，个人防护结构可以具有一定的透气性。使用PEBAX/粘结/PVD(使用吸水的粘结层)可以将化学或生物试剂隔离在外，并且使人体感觉舒适。这种防护外套具有便于移动的挠性，并且具有PVDF层提供的耐久性、坚韧性和耐受性。
实施例
通过共挤出形成多层管，然后在一定时间内通过一系列蠕动泵测试来进行测试，以检查管子能承受的循环的次数。还在以下一个或多个ASTM测试中检测了管：拉伸性质(D412)；伸长率(D412)；硬度(D2240)；伸长率为100％、200％时的模量(D412)；抗撕裂性能(D624)；以及比重(D792)。
实施例1
制备包括PEBAX 4033/LOTADER AX8900/KYNAR 2750的三层管。层厚度为650微米/75微米/150-170微米。管的外径为8毫米。该管表现出良好的挠性和回弹性。
实施例2
制备包括PEBAX 4033/LOTADER AX8900/KYNAR ADX/KYNAR2750的四层管。层厚度为790-830微米/150微米/94-75微米/330-380微米。管的外径为8毫米。
实施例3(对比例)
用KYNAR 2500制备管，含有13％ DBS增塑剂，或不含有增塑剂。管的外径为3/8＂，管的厚度为35密耳。由Kynar 2500制得的包含增塑剂的管比不含增塑剂的管具有高得多的挠性。
实施例4(对比例)
制备包括Santoprene 101-64/LOTADER AX8840/ADX 2285-03/KYNAR 2750的四层管。层厚度为790-830微米/150微米/94-75微米/330-380微米。管的外径为8毫米。
实施例5
类似于实施例4所述的四层管，不同之处在于将Engage 7086混入Lotader AX 8840中以提高管的整体挠性和粘合性。
实施例6
通过多层模具和挤出法制备以下结构的直径分别为6.2毫米和8.2毫米的两个四层管。
 
Pebax 3533 SN01 AX 8840 KF2500-20g+KF2500-20(50％+50％)          KF 2500-20
Pebax Lotader 接枝Kynarflex+Kynarflex Kynarflex
700微米 50微米 80微米 80微米
所述管在层与层之间具有良好的粘合性，并且具有用于蠕动管应用的足够的挠性和弹性。
实施例7：
通过多层模头(head)和挤出法制备以下结构的直径为8.2毫米的四层管。
 
Engage 7256 AX 8840 ADX 1280-03 KF 2500-20
聚烯烃弹性体 Lotader 接枝Kynar Kynarflex
700微米 50微米 80微米 80微米
所述管在层与层之间具有良好的粘合性，并且具有用于蠕动管应用的足够的挠性和弹性。
实施例8-14：
可以制备具有以下本发明结构的管：
-KYNAR 2800/KYNAR ADX/LOTADER/PEBAX 2533，厚度5密耳/5密耳/3密耳/35密耳
-KYNAR 2800/KYNAR ADX/LOTADER/TPO，厚度5密耳/5密耳/3密耳/35密耳
-KYNAR 2800/KYNAR ADX/LOTADER/TPU，厚度5密耳/5密耳/3密耳/35密耳
-KYNAR 2800/KYNAR ULTRAFLEX
-KYNAR2800/增塑的KYNAR ULTRAFLEX或KYNAR 2500
-在内侧和外侧都有KYNAR 2800并且在内侧有KYNAR ULTRAFLEX或KYNAR 2500的对称结构。
-内侧上的KYNAR 2800可以用任何其它级别的KYNAR代替，例如KYNAR 2500或KYNAR 740。

Claims (20)

1.一种多层挠性结构，其包括：
a)聚偏氟乙烯聚合物(PVDF)接触层；和
b)一个或多个弹性层，
其中所述聚偏氟乙烯层可以直接或间接地粘附在所述弹性层上。
2.如权利要求1所述的多层结构，其特征在于，所述PVDF接触层包含官能化的聚偏氟乙烯聚合物。
3.如权利要求1所述的多层结构，其特征在于，所述PVDF接触层不含添加的官能度、增塑剂、着色剂、添加剂或加工助剂。
4.如权利要求1所述的多层结构，其特征在于，所述聚偏氟乙烯层的厚度为3-500微米。
5.如权利要求1所述的多层结构，其特征在于，所述弹性层的厚度为250-1500微米。
6.如权利要求1所述的多层结构，其特征在于，所述PVDF层是包含70-99重量％PVDF单元的共聚物或三元共聚物。
7.如权利要求1所述的多层结构，其特征在于，所述结构还包括一个或多个在所述PVDF层和所述弹性层之间的粘结层。
8.如权利要求7所述的多层结构，其特征在于，所述结构包括一个或多个由选自下组的材料形成的粘结层：官能化的PVDF、官能化的聚乙烯、热塑性聚氨酯、氯化聚乙烯、热塑性聚烯烃、聚甲基丙烯酸甲酯、聚酰胺、官能聚酰胺和它们的混合物。
9.如权利要求1所述的多层结构，其特征在于，所述弹性体选自下组：弹性聚酰胺、含有接枝或反应的官能团的热塑性聚烯烃、聚烯烃弹性体、乙烯/丙烯共聚物、橡胶、苯乙烯-乙烯-丁烯-苯乙烯聚合物、热塑性聚氨酯、含氟弹性体、硅酮、硅橡胶、氯丁橡胶、共聚酯嵌段热塑性聚乙烯、腈橡胶、丁基橡胶、聚酰胺热塑性硫化橡胶、聚烯烃和氯化乙烯基。
10.如权利要求1所述的多层结构，其特征在于，所述弹性层包含弹性聚酰胺。
11.如权利要求1所述的多层结构，其特征在于，所述结构还包括夹在所述PVDF层和所述弹性层之间的乙烯乙烯基醇层。
12.如权利要求1所述的多层结构，其特征在于，所述结构是管、膜或袋。
13.如权利要求12所述的多层结构，其特征在于，所述管用于与蠕动泵连接。
14.如权利要求1所述的多层结构，其特征在于，所述PVDF接触层直接接触化学或生物制药流体。
15.如权利要求1所述的多层结构，其特征在于，所述结构是一件个人防护设备，其中PVDF层在暴露于环境的外表面上，弹性层在内表面上。
16.如权利要求1所述的多层结构，其特征在于，所述结构包括聚醚-嵌段-酰胺作为弹性层、PVDF接触层、在所述PVDF层与聚乙烯-嵌段-聚酰胺层之间的至少一个粘结层。
17.如权利要求16所述的多层结构，其特征在于，所述粘结层是：
a)单层，其包含热塑性聚氨酯(TPU)或与聚醚-嵌段-聚酰胺混合的TPU；或
b)双层，包括作为第一层的TPU、胺封端的聚酰胺或官能化的聚乙烯；以及作为第二层的官能化的PVDF。
18.如权利要求1所述的多层结构，其特征在于，所述结构包括TPU作为弹性层，以及任选的夹在所述TPU和PVDF之间的粘结层。
19.如权利要求1所述的多层结构，其特征在于，所述结构包括：基于烯烃的热塑性硫化橡胶作为弹性层，在所述弹性层旁边的由乙烯-丙烯聚烯烃弹性体的混合物组成的粘结层，在乙烯-丙烯聚烯烃弹性体和PVDF层之间的官能化的PVDF层，以及PVDF接触层。
20.如权利要求1所述的多层结构，其特征在于，所述弹性层是挠性聚偏氯乙烯。
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JP5378208B2 (ja) 2013-12-25
EP2054228A4 (en) 2012-05-16
WO2008005744A2 (en) 2008-01-10
US20090202759A1 (en) 2009-08-13
WO2008005744A3 (en) 2008-02-21
CN105690873A (zh) 2016-06-22
US9056447B2 (en) 2015-06-16

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