CN1085992C - 热塑性纤维的氟代酯熔体添加剂 - Google Patents
热塑性纤维的氟代酯熔体添加剂 Download PDFInfo
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Abstract
一种对低表面张力流体有排斥性的组合物，其中包含一种按如下制备的材料：形成一种混合物，使其含有从聚链烯烃、聚酰胺、聚酯、聚丙烯酸酯及其掺合物和共聚物组成的一组中选择的一种聚合物，和一种含氟化合物，包括下式的一种碳氟/碳氢酯：Rf-O-C(O)-R1或Rf-C(O)-O-R1，式中Rf选自下列组成的一组：1)F(CF2)x-(CH2)m，式中x是约4～约20，且m是约0～约6；和2)F(CF2)x-SO2N(R2)-R3，式中x是约4～约20的一个正整数，R2是一个有约1～约4个碳原子的烷基，R3是一个有约1～约12个碳原子的亚烷基；而R1是一个有约12～约76个碳原子的脂肪族烃基；其先决条件是，所述含氟化合物不是硬脂酸全氟烷基乙酯；和熔融挤出该混合物。
Description
发明领域
本发明涉及通过向聚合物熔体中添加某些氟代酯类，从而赋予热塑性聚合物、尤其纤维、织物、非织造布、薄膜和模塑制品以优异的对低表面张力流体的排斥性的方法。
发明背景
热塑性聚合物纤维经常用含氟化合物处理，以期影响该纤维的表面特征，例如改善斥水性或赋予防沾污性或干抗污性。最经常的是，通过喷雾、浸轧或发泡，向由这些纤维制成的织物局部地施用含氟化学品分散液，然后通过一个干燥步骤脱水。
例如，已知有一种方法，可用于通过局部地施用从n为约3～14且m为1～3的通式CnF2n+1(CH2)mOH的全氟烷基脂族醇以及含有3～30个碳而且可以含有其它取代基的一元或多元羧酸衍生的各种各样氟代酯的水分散液，而使一种织物纤维获得干抗污性和不燃性传导特征。这些氟代酯，除其它外，还包括一种相当于“ZONYL”FTS的硬脂酸全氟烷基乙酯，以及从十二碳烷二酸或十三碳烷二酸制成的全氟烷基乙基二酯。
人们充分认识到，如果这种局部施用代之以在该纤维挤出之前向聚合物熔体中加进一种含氟化学添加剂，就可以简化热塑性聚合物纤维和织物的制造工艺，而且可以消除显著的基本投资。在寻找适用而有效的含氟化学添加剂方面一直存在困难。
热塑性聚合物，除其它外，还包括聚链烯烃、聚酯、聚酰胺和聚丙烯酸酯。聚链烯烃，尤其聚丙烯，经常用于一次性非织造防护服装，尤其在医疗/外科领域，其部分原因是聚链烯烃的固有斥水性。然而，聚链烯烃对于医疗领域中经常遇到的其它较低表面张力流体如血液和异丙醇来说不是固有良好的排斥剂。为了弥补这种缺陷，可向这些织物局部地施用含氟化学品分散液。
对适合于掺入聚链烯烃熔体中的添加剂的要求，除该添加剂低浓度时排斥低表面张力流体的能力外，还包括令人满意的热稳定性和耐加工条件的低挥发性。较好的是，该化合物将能迁移到纤维的表面，从而最大限度减少为达到足够排斥性所需要的添加剂数量。虽然这种迁移往往会因该纤维的挤出后加热而增强，但更好的是这种迁移无需这一加热步骤也能发生。对聚合物纤维中移动性的这种要求又倾向于限制该含氟化学品分子的大小，并有效地把高分子量聚合物含氟化学添加剂排除在考虑之外。
把含氟化学添加剂掺入到聚链烯烃纤维熔体中的一般概念是已知的，但在寻找适用的有效添加剂方面的困难限制了这个概念的应用。过去为评估此类含氟化学添加剂而做的许多努力一直以改善该聚链烯烃的其它性能为宗旨，而且没有公开其改善对低表面张力流体的排斥性的方法。
非织造复合结构是已知的，部分地由两个或多个熔体挤出非织造层组成，其中至少一层包括一种添加剂，使得无需任何种类的成形后处理而由于该添加剂向表面优势迁移的结果就能赋予该表面至少一种不同于该聚合物本身表面特征的特征。这种含添加剂层的实例包括用商业上可得含氟化学添加剂改性的聚丙烯，其中包括以上定义的“ZONYL”FTS。
美国专利5,178,931和美国专利5,178,932分别公开了部分地由三个熔体挤出非织造层组成的特定非织造层压和复合结构，其中第二层包括一种无需任何种类的成形后处理而由于添加剂向表面优势迁移的结果就能赋予斥醇性的添加剂，而且在这种情况下第一层和第三层中至少一层已经通过局部施用一种药剂进行处理，以便使其特征有某种改变。这种含添加剂的第二层的实例包括商业上可得的含氟化学品，其中包括“ZONYL”FTS。
抗污聚合物组合物是已知的，它是通过有非聚合物含氟化学品均匀分散在聚合物中的熔体挤出制备的。所用的聚合物包括聚丙烯、聚乙烯、聚酰胺和聚酯，而所用的含氟化学品是一种硬脂酯全氟烷酯，尤其“ZONYL”FTS。
此外，一种聚合物组合物是已知的，其中包含一种混合物，由选自聚丙烯、聚乙烯、聚酰胺和聚酯这一组的一种聚合物与一种含有一个氟代疏油、疏水烷基基团任选地通过一个连接片断连接到一个非氟代亲油烷基、芳基、芳烷基或烷芳基片断上的含氟化学品组成，且可以是作为混合物挤出的熔体。以上含氟化学品的更具体描述没有公开，但在适用的很多化合物中间，有其亲油有机基团含有2～35个碳原子的酯类。其实例是“ZONYL”FTS，或“ZONYL”BA与硬脂酸甲酯和棕榈酸甲酯进行酯交换制成的产物。
已知有一种汽车涂膜，其中含有一种具有一个含氟有机基团的可溶于有机溶剂的蜡质烃。这种成分是由一种高分子量醇与一种具有含氟基团的羧酸进行酯化和偶联而得到的一种产物，或是由一种高分子量脂肪酸与一种具有含氟基团的醇进行酯化和偶联而得到的一种产物。作为所包括的高分子量醇的实例，是那些碳链平均长度可多达50个碳者。作为所包括的高分子量脂肪酸的实例，是那些碳链长度可多达31个碳者(蜂蜡酸)。这些产品只作为汽车上蜡剂进行过测试。
Kao公司的日本专利申请3-41160公开了一种热塑性树脂组合物，其中含有式Rf-R1-OCO-R2的一种含全氟烷基的长链脂肪酯，式中Rf是一个有5～16个碳的全氟烷基，R1是一个有1～4个碳的亚烷基，而R2是一个有21～50个碳的不饱和烷基或饱和烷基。一个实例是C8F17C2H4OH与C27H55COOH反应产生这种酯。树脂包括聚乙烯和聚丙烯。这种添加剂的好处是用水与该树脂的模塑制品的接触角显示的。关于所形成聚合物对低表面张力流体的排斥性的试验尚未见报道。
总而言之，虽然先有技术公开了为改变所挤出纤维的表面特征而含有在熔融阶段掺入的含氟化学添加剂的聚烯烃纤维的许多实例，但这多数是为了耐沾污与着色、斥水性或其它目的。以赋予聚烯烃织物以斥醇性为宗旨的那些参考文献采用了“ZONYL”FTS。目前存在着实现对低表面张力流体的优异排斥性和优异产品效率这样一种需要。本发明的氟代化合物满足了这种需要。
发明概述
本发明包含用来赋予热塑性聚合物制品以低表面张力流体排斥性的组合物和方法。本发明对低表面张力流体有排斥性的组合物包含一种按以下制备的材料：
形成一种混合物，其中含有从聚烯烃、聚酰胺、聚酯、聚丙烯酸酯、及其掺合物和共聚物组成的一组中选择的一种聚合物，和一种含氟化合物，包括下式的一种碳氟/碳氢酯：
Rf-O-C(O)-R1或Rf-C(O)-O-R1式中Rf选自如下组成的一组：
1)F(CF2)x-(CH2)m，式中x是约4～约20，且m是约0～约6，和
2)F(CF2)x-SO2N(R2)-R3，式中x是约4～约20的一个正整数，R2是一个有1～约4个碳原子的烷基，且R3是一个有1～约12个碳原子的亚烷基，
R1是一个有约12～约76个碳原子的脂族烃；其前提是，所述含氟化合物不是硬脂酸全氟烷基乙酯；
和熔融挤出该混合物。
本发明进一步包含呈长丝、纤维、非织造布或纤维网、薄膜或模塑物品等形式的上述组合物。
本发明进一步包含一种用于赋予热塑性聚合物物品以低表面张力流体排斥性的方法，包括：在物品成形前形成一种混合物，其中含有如以上定义的一种聚合物和有效量的一种含氟化合物，包括一种碳氟/碳氢酯，以及熔融挤出该混合物。这样的物品包括长丝、纤维、非织造纤维网或织物、薄膜或模塑物品。
发明详细描述
对低表面张力流体的优异排斥性，是通过在物品成形前向一种聚合物中添加某些单体氟代酯化合物和熔融挤出所形成的混合物，而赋予热塑性聚合物物品，尤其纤维、织物、长丝、非织造布、薄膜和模塑物品的。无论采用或不采用为促进该添加剂向物品表面移动而对该物品进行的挤出后加热步骤，都可以使用这种方法，因为本发明的酯类化合物就其本质而言倾向于集中到表面上。
“低表面张力流体”这一术语在此用来指表面张力小于50达因/cm(50×10-7牛顿米)的流体。此类流体的实例包括醇类、血液和某些体液。
本发明的组合物包含一种通过熔融挤出一种混合物制备的材料，该混合物含有从聚链烯烃、聚酰胺、聚酯、聚丙烯酸酯及其掺合物和共聚物组成的一组中选择的一种聚合物，和除硬脂酸全氟烷基乙酯外的一种含氟化合物，包括下式的一种碳氟/碳氢酯：
Rf-O-C(O)-R1或Rf-C(O)-O-R1
其中，上式中的Rf是F(CF2)x-(CH2)m，式中x的优选平均值为约7～10、范围为约4～约20，而m的值为0～6。
Rf特别好的是一种组合物，其中链长分布如下：
x＝6或以下 0-10％(重量)
x＝8 45-75％(重量)
x＝10 20-40％(重量)
x＝12 1-20％(重量)
x＝14或以上 0-5％(重量)这种组合物范围，当m＝2且x的平均值为约9时，在下文中简称为Telomer BN。式Rf-OH中Rf的这种定义简称为Telomer BN醇。
替而代之，Rf也可以是结构为F(CF2)x-SO2N(R2)-R3的一种氟代磺酰胺，式中x是一个约4～约20、较好4～10(包括上下限)的正整数，R2是一个有1～4个碳原子的烷基，而R3是一个有1～12个碳原子的亚烷基。较好的是，R2是CH3且R3是-CH2CH2-、-(CH2)3-或-(CH2)4-。
替代Rf结构的氟烷基部分是一个链上有至少三个全氟代连接的碳原子的氟代、较好饱和的一价非芳香族的脂族基团。该基团上的这个链是直链、支化链或(当足够大时)环状链，并任选地插入了只与碳原子连接的二价氧原子、六价硫原子或三价氮原子。较好的是全氟代脂族基团，但该基团中也可以有氢原子或氯原子作为取代基存在，只要该基团中每两个碳原子存在着不多于一个其中任意一种原子即可。
R1是一个碳链长度约12～约76个碳、较好约24-约50个碳的脂族烃。对应于R1-OH的醇类可购自Petrolite公司聚合物分公司总部(6910 E.14th Street，Tulsa，Oklahoma，USA 74112)，商标为“UNILIN”。“UNILIN”醇类是全饱和长链线性醇类。“UNILIN”350、425、550和700的近似R1范围分别是12～50、14～58、16-56和14～66。“UNILIN”350、425、550和700的平均链长分别是约24、32、40和48。这些醇用于本发明是较好的。对应于R1-COOH的酸类可购自Petrolite公司聚合物分公司总部(6910 E.14th Street，Tulsa，Oklahoma，USA 74112)，商标为“UNICID”。“UNICID”350、425、550和700的平均链长范围分别为24-29、29-37、37-45和40-48。这些酸用于本发明是较好的。更具体地说，“UNILIN”和“UNICID”的碳链长度是如表A中所说明的。
表 A
GC数据**UNILIN 文献平均值* ％醇 范围 平均值350 C24-26 C12-46 C24-26425 C30-32 85.0 C14-58 C30-32550 C40-42 79.5 C16-56 C38700 C48-50 83.6 C14-66 C50
GC数据**UNICID 文献平均值* ％酸 范围 平均值350 C24-29 79.0 C12-50 C28-30425 C29-37550 C37-45 80.0 C16-62 C42-44700 C40-48 C16-76
*文献平均值
**气相色谱数据
有各种方法可以用来制备以上化合物，而本发明的方法不限于某一特定制备方法。例如，以上化合物是通过使一种适当脂肪醇与该适当碳氟酸反应生成一种酸酯，或通过使一种适当脂肪酸与该适当碳氟醇反应，而方便地制备的。熟悉本门技术的人员遵循类似的方法，就能容易地制备这些组中的其它化合物。
可用于本发明中的酯类通过将其添加到片状、粒状、粉末状或其它适当形式的聚合物中并将该混合物碾轧、搅拌或配合，而与热塑性聚合物混合，得到一种均匀混合物，然后进行熔融挤压。替而代之，还可以把这些酯类添加到一种聚合物熔体中，形成一种混合物，然后进行熔融挤压。热塑性聚合物是一种聚链烯烃、聚酯、聚酰胺或聚丙烯酸酯。热塑性聚合物较好是一种聚链烯烃，一种或多种聚链烯烃的混合物或共混物，聚链烯烃共聚物，多种聚链烯烃共聚物的混合物，或至少一种聚链烯烃与至少一种聚链烯烃共聚物的混合物。热塑性聚合物更好的是一种聚链烯烃聚合物或共聚物，其中聚合物单元或共聚物单元是乙烯、丙烯或丁烯或其混合物。因此，聚链烯烃较好的是聚丙烯、聚乙烯、聚丁烯或者其共混物或共聚物。
要添加到热塑性聚合物中的氟代化合物数量，较好的是在该聚合物重量的0.1～约5％之间。这一范围以上的数量是可以使用的，但相对于所收到的效益而言是昂贵的，不必要的。然后使该共混物熔融，用已知方法挤压成纤维、长丝、非织造纤维网或织物、薄膜或模塑物品。这种纤维、长丝、从其制备的非织造织物或纤维网、薄膜或模塑物品的氟含量，是约200μg/g～约25,000μg/g。
用挤压来形成各种类型的非织造织物。具体地说，用挤压来形成一种平均直径为约0.1～10微米、较好在约3～5微米范围内的连续且无规沉积微纤维的熔喷非织造纤维网。这种熔融挤压是通过模具以每分钟每孔至少0.1～5克的树脂流量进行的，使这些微纤维无规地沉积在一种移动支撑体上而形成该纤维网。
在上述熔喷工艺中，把聚合物和本发明的一种化合物进料到一台挤压机中，在此使之熔融和通过一个含有一排微小喷丝孔的模具。当该聚合物从该模具喷出时，使之接触两股集束高速热空气流，后者使该聚合物细化，变成直径为0.1～10微米的微细不连续纤维的一股气流。可用的聚合物通过量或流量范围为每分钟每孔0.1～5克。典型的气体流量范围为每分钟每平方英寸气体出口面积2.5～100磅(1.72×105～6.89×105Pa)。空气温度范围为约400°F(204℃)～750°F(399℃)。然后，冷却空气使该纤维骤冷，并使它们在一个置于该股纤维气流前方6～12英寸(15.2～30.5cm)处的移动筛网上沉积成为一种无规交织的纤维网。
熔喷工艺在下列文章中有更详细的描述：V.A.Wente，“超细热塑性纤维”，Industrial and Engineering Chemistry，Vol.48(8)，pp1342-1346(1956)；R.R.Buntin和D.T.Lohkamp，“熔喷一新型非织造产品的一步法纤维网工艺”，Journal of the TechnicalAssociation of the Pulp and Paper Industry，Vol.56(4)，pp 74-77(1973)；以及R.R.Buntin的美国专利3,972,759。这些资料的公开内容均列为本文参考文献。
由微细交织纤维无规配列组成的熔喷非织造纤维网的独特性质包括非常大的表面积，非常小的孔径，中等强度和轻质织物结构。这些性质使该非织造纤维网特别适合于作为医用织物这样的应用，其中，遮断性以及透气性和悬垂性是重要的。
挤压法也用来形成聚合物薄膜。在薄膜应用中，一种成膜聚合物当由一个或多个旋转螺杆通过挤压机输送，然后被迫诸如通过一个狭缝或平板模具挤出时，同时被熔融和混合，其中，用熟悉本门技术的人员已知的各种各样技术使该薄膜骤冷。该薄膜任选地在骤冷之前，通过使该薄膜在高温拉伸或展幅，进行取向。
模塑物品是通过把来自如以上描述的熔体挤压机的熔融聚合物压入或注射到一个会使该聚合物固化的模具中来生产的。典型的熔体成形技术包括注射模塑、吹塑、压缩模塑和挤塑，而且是熟悉本门技术的人员众所周知的。然后使该模塑物品脱模，并任选地进行热处理，以使该聚合物添加剂能迁移到该物品的表面。
可以进行一个任选的加热或退火步骤，但不要求如此。聚合物熔融挤出而成的纤维、长丝、非织造纤维网或织物、薄膜或模塑的物品被加热到约25℃～约150℃的温度。这种加热在一些情况下可以提高该含氟化学添加剂赋予斥醇性的有效性。
本发明的组合物可用于各种纤维、长丝、非织造纤维网或织物、薄膜和模塑物品。实例包括织物和地毯中使用的纤维，医疗/外科领域中使用的防护服中所用的非织造织物，和很多类型的模塑塑料物品。本发明的方法可用于赋予各种热塑性聚合物物品例如长丝、纤维、非织造纤维网或织物、薄膜和模塑制品以低表面张力流体排斥性。
实例1
Rf-O-C(O)-R1的合成，式中Rf是其x的平均值为9、m＝2的式F(CF2)x(CH2)m的脂族碳氟烃基团，且式中R1的平均值为32个碳原子。
一个250mL烧瓶装配一个机械搅拌器、温度控制器、迪安-斯达克榻分水器、水冷凝器、氮气导入管和加热罩。向该烧瓶中加入79.1g(0.15mol)F(CF2)nCH2CH2OH，其中n＝6-18，平均n＝9，和89.4g(0.15mol)“UNICID”425酸(C29-C37脂族酸，购自Petrolite公司(6910 E.14th Street，Tulsa，Oklahoma，USA 74112)，酸值＝94mgKOH/g)。混合物加热并保持在120℃。当混合物均匀时，添加0.3g亚磷酸和0.12g硼酸。使温度上升到140-145℃，并保持约87小时且连续脱水。当反应混合物的气相色谱分析显示全部Telomer BN醇业已反应时，该混合物稍微冷却、出料，得到44.65g(87％)产品。红外分析证实了以上结构。该产物是一种褐色固体，用差示扫描量热法(DSC)测定的熔点为66.65℃。分析实测的百分含氟率为32.4％，相比之下，理论分析值为33.4％。
实例2-15
这些实例是用实例1的程序制备的。表2列出了用来制备氟代酯的酸，和该醇的碳氟原子分布。这些实例全部用来像实例16中所述那样制备熔喷非织造纤维网和进行斥醇性测试。
实例16
步骤1：聚合物掺合物的制备
实例1-16中产生的含氟化学添加剂与一种聚烯烃一起的均匀混合物，是通过使其合并并将该混合物碾轧约24小时来制备的。比较例A-D使用了单酯“ZONYL”FTS，并以类似方式制备。具体地说，对于实例4的化合物，16.1g(1.2％重量)实例4的微细粉碎化合物和1,349gEscorene PD 3746G(Exxon Chemical Americas，P.O.Box 3273，Houston，Texas 77001)聚丙烯树脂(熔体流动速率约1000)的均匀混合物，是通过使该混合物碾轧24小时制备的。该混合物中的氟浓度计算值为3300μgF/g。非织造纤维网中的实际氟浓度是2930μgF/g。指定为A～D的比较例是用同样方法制备的。
步骤2：熔喷纤维网成形
熔喷非织造纤维网是从以上混合物、用6英寸(15cm)熔喷试验装置以每分钟每孔约0.4克的聚合物进料速度制备的。把聚合物共混物进料到有温度范围为175～250℃的三个套筒加热区的挤压机中。模具温度是200℃～260℃，模具处的空气温度从200℃到270℃不等。模具前端间隙是0.060英寸(0.15cm)，初级空气压力是2.6psi(17.9×103Pa)。纤维网是在涂了“特氟隆”的转鼓上以每分钟每孔0.4克的产率形成，并收集在以30英尺/分钟(914cm/分钟)运转的卷绕辊上，形成单位重量为1.0盎司/平方码(34克/平方米)的织物。
步骤3：排斥性测试
熔喷纤维网的斥水性能是用异丙醇/水试验测定的，用百分异丙醇等级表示。1～2分钟后抵御了100％异丙醇/0％水溶液(最低表面张力流体)穿透的纤维网定义为最高级别100。1～2分钟后只抵御了100％水/0％异丙醇溶液的纤维网定义为最低级别0。表1列出了本测试中使用的、对应于其它异丙醇/水混合物的级别。一种给定织物的级别对应于1～2分钟后不使该织物润湿的最低表面张力流体(最大％异丙醇/水溶液)。
表 1
百分率异丙醇等级
等级 ％异丙醇/％水(体积比)
100 100/0
90 90/10
80 80/20
70 70/30
60 60/40
50 50/50
40 40/60
30 30/70
20 20/80
为了评估半成品排斥性，该纤维网在离开熔喷工艺线之后立即、然后在2天后和约一周后评定等级。表2总结了含有实例1～15的酯类的聚丙烯熔喷纤维网和含有购自杜邦公司(E.I.du Pont deNemours and Company，Wilmington，Delaware)有不同氟浓度水平的“ZONYL”FTS的比较例A-D的百分率异丙醇数据。该表中也包括一个聚丙烯对照样品(PP对照)。
表2中的结果显示，本发明组合物有优于比较样品和对照样品的明显优点，这些优点既立即显示出来，也随时间推移而显示出来。本发明组合物的一个相关优点是在含氟化学添加剂较低时有较好的性能。
表 2
聚丙烯熔喷纤维网的异丙醇排斥性
μg/g氟 异丙醇排斥性实例 分布1 酸 目标/实际 刚制成 2天 1周 加热21 BN “UNICID”350 1500/1480 40 -- 90-100 30a2 BL “UNICID”350 1700/1480 40 -- 80 30a3 BN “UNICID”425 3300/2930 90 90-100 90-100 90b4 BN “UNICID”425 3300/3120 40 80 90 90b5 BN “UNICID”550 3300/2720 100 100 100 100b6 BN “UNICID”550 3300/2790 40 60 90 90b7 BN “UNICID”550 1980/1910 70-80 100a8 BL “UNICID”550 1980/1570 60 -- -- 92a9 BN “UNICID”700 3300/3210 100 100 100 100c10 BN “UNICID”700 4500/2760 40 40 100b11 BN “UNICID”700 1980/1780 50-60 80 90 70c12 BN 硬脂酸 3300/2940 70 80-90 90-100 80b13 BN 硬脂酸 3300/3510 30 60 80 70b14 M “UNICID”550 1980/1550 40 50 80 50a15 M 硬脂酸 1980/1610 30 40 30aA B 硬脂酸 3300/3050 70 80-90 90 80bB B 硬脂酸 3300/3010 30 60 80 60-70bC B 硬脂酸 2875/2426 40 80 80 80bD B 硬脂酸 2423/1910 30 70 70-80 80-90b对照 20 20 201 碳氟原子分布：BL＝C4F9-C8F17；B＝C4F9-C18F37；BN＝C8F17-C12F25；M＝C8F17SO2N(CH2H5)-(CH2)2-OH2 退火工艺：a.纤维网加工后很快在176F(80℃)退火15秒b.纤维网加工后约1周在140F(60℃)退火25小时c.纤维网加工后很快在180F(82.20℃)退火1分钟
Claims (9)
1.一种对表面张力小于5.0×10-7牛顿米的流体有排斥性的组合物，该组合物包含一种按以下制备的材料：
形成一种混合物，其中含有从聚链烯烃、聚酰胺、聚酯、聚丙烯酸酯、及其掺合物和共聚物组成的一组中选择的一种聚合物，和一种下式的含氟化合物的酯化合物：
Rf-O-C(O)-R1或Rf-C(O)-O-R1式中Rf选自如下组成的一组：
1)F(CF2)x-(CH2)m，式中x是4～20，且m是0～6，和
2)F(CF2)x-SO2N(R2)-R3，式中x是4～20的一个正整数，R2是一个有1～4个碳原子的烷基，且R3是一个有1～12个碳原子的亚烷基，
R1是平均碳原子数为30-50的脂族直链烃；其前提是，
和熔融挤出该混合物。
2.权利要求1的组合物，其中该聚合物选自下列组成的一组：聚链烯烃、多种聚链烯烃的混合物、聚链烯烃共聚物、多种聚链烯烃共聚物的混合物，和至少一种聚链烯烃与至少一种聚链烯烃共聚物的混合物。
3.权利要求1的组合物，其中Rf是F(CF2)x(CH2)m，式中x是8～12，且平均值为9，而m是2。
4.权利要求1的组合物，其中含氟化合物的存在量是该聚合物重量的0.1％～5％。
5.权利要求1的组合物，其氟含量为200μg/g～25,000μg/g。
6.权利要求1的组合物，呈一种选自下列一组的形式：挤出的长丝、纤维、非织造纤维网、非织造织物、薄膜和模制品。
7.使一种热塑性聚合物物品对表面张力小于5.0×10-7牛顿米的流体具有排斥性的方法，该方法包括在物品成形前形成一种混合物，其中含有一种聚合物和0.1％-5％重量的一种下式的含氟化合物的酯化合物：
Rf-O-C(O)-R1或Rf-C(O)-O-R1式中Rf选自下列组成的一组：
1)F(CF2)x-(CH2)m，式中x是4～20，且m是0～6；和
2)F(CF2)x-SO2N(R2)-R3，式中x是4～20的一个正整数，R2是一个有1～4个碳原子的烷基，而R3是一个有1～12个碳原子的亚烷基；和
R1是平均碳原子数为30-50的脂肪族直链烃；
和熔融挤出该混合物。
8.权利要求7的方法，进一步包括将所形成的物品加热到25℃～150℃的温度。
9.权利要求7的方法，其中成形后的物品的氟含量为200μg/g～25,000μg/g。
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| TW376397B (en) | 1999-12-11 |
| EP0868475A1 (en) | 1998-10-07 |
| CN1205723A (zh) | 1999-01-20 |
| WO1997022659A1 (en) | 1997-06-26 |
| JP2000502382A (ja) | 2000-02-29 |
| US5898046A (en) | 1999-04-27 |
| CA2240548A1 (en) | 1997-06-26 |
| AU721468B2 (en) | 2000-07-06 |
| KR20000064504A (ko) | 2000-11-06 |
| KR100451334B1 (ko) | 2004-11-16 |
| US6063474A (en) | 2000-05-16 |
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