CN1182445A - 在氟化液体中形成含氟聚合物分散液的表面活性剂 - Google Patents
在氟化液体中形成含氟聚合物分散液的表面活性剂 Download PDFInfo
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- NJCBUSHGCBERSK-UHFFFAOYSA-N perfluoropentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NJCBUSHGCBERSK-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/095—Carboxylic acids containing halogens
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/20—Carboxylic acid amides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/43—Compounds containing sulfur bound to nitrogen
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
一种均匀的不消耗臭氧的含氟聚合物分散液,包括含氟聚合物、惰性全氟化液体、极性溶剂和下列表面活性剂:a)全氟脂族酰氨基链烷醇;b)亲水性单体和式(Ⅱ)单体的聚合产物,其中p和q为1—4,x和y为0—4,m为1或2,n为3—10,X’是甲基或氢,g是0或1,Q是式(i)亚磺酰氨基,其中R1是氢或1—6个碳原子的烷基,极性溶剂是有机的时,亲水性单体量为反应混合物的5—25重量%,极性溶剂是水时,亲水性单体量为反应混合物的1—25重量%;c)通式(Ⅳ)的全氟化醚酸,其中z为1—10,s为0—4,t为0—4,v为0—5,w为0或1,Y是F或CF3。
Description
发明的领域
本发明涉及制备含氟聚合物分散液。更具体地说,本发明涉及制备连续相包括全氟化无氯液体的聚四氟乙烯稳定液体分散液。另一方面,本发明涉及用连续相包括惰性全氟液体的稳定含氟聚合物分散液制备含氟聚合物涂覆制品。再一个方面,本发明涉及制备全氟化液体和极性溶剂的乳液。
发明背景
聚四氟乙烯(有时称作PTFE)是一种容易获得并具有广泛用途的聚合物,它具有各种用途,如作为干润滑剂用于制造,例如医用硬件设备、作为剥离剂、和作为工业增稠剂等。可用任何已知的工业涂覆方法可将分散在适当溶剂体系中的聚四氟乙烯施涂在经挑选的物体或基材上。在这些施涂方法中,蘸涂、喷涂和旋转盘涂覆很适合于涂覆聚四氟乙烯。按照这些涂覆方法,通过将要用含氟聚合物涂覆的基材或物体直接浸入分散液中、将分散液喷雾到物体或基材上、或利用离心力将含氟聚合物分布在旋转平台上而将该物体或基材置于分散的含氟聚合物中。然后,通过例如环境蒸发或烘干除去用于形成分散液的一种或多种溶剂,留下平整的含氟聚合物涂层。这些涂层方法的详细描述可参见Stanley C.Zink,“涂覆方法(Coating Processes)”,6 Kirk-Othmer Encyclopedia of Chemical Technology386-426(3d ed.1979)(蘸涂和喷涂的详细方法)和美国专利No.4,587,139(描述旋转盘涂覆)。
一些适合于涂覆方法的分散液可市售获得。一般来说,这些分散液含有20-30重量%固态聚四氟乙烯(在一种或多种有机溶剂或水组成的液相溶剂体系中)。这种市售分散液有杜邦VydaxTM Fluorotelomer Dispersion(一种分散于水或异丙醇中的低分子量聚四氟乙烯)。为了用于涂覆应用,在使用前常用合适的溶剂将这些分散液稀释成含1-3重量%固体。
在蒙特利尔条约规定逐步淘汰氯氟碳(CFCs)以前,很多市售含氟聚合物分散液是分散在CFC-113(1,1,2-三氯三氟乙烷)中的,因为这种液体除了影响环境外,很适合于工艺条件;它具有高挥发性、完全惰性、既无毒也不易燃,与许多材料高度相容。例如,CFC-113的沸点为47℃。
目前市售的分散液,如杜邦公司的VydaxTM Fluorotelomer Dispersion系列,是分散在异丙醇或水中的,不适合于方便的工业应用。由于异丙醇和水均相对不易挥发(在标准压力下沸点分别为82℃和100℃),在这些液体中充分稀释的分散液因其挥发速度慢而可导致涂层不平整。另外,含异丙醇的分散液是易燃的,而含水的分散液会腐蚀铁金属基材。
作为将水基和异丙醇基PTFE分散液混入涂料应用中的问题的部分解决方案,一些制造商单独使用各种氢氯氟碳(HCFC)和将其与全氟碳(PFC)组合在一起作为预处理稀释剂用于异丙醇基和水基市售分散液。虽然HCFC具有挥发性高和对许多物质的溶解能力好的优点(例如,HCFC 141b沸点为32℃),但由于溶解能力高,它们常降解聚合物基材,而且因为含氯,会消耗同温层臭氧,所以蒙特利尔条约也规定了其逐步淘汰的时间。如HCFC那样,PFC具有高挥发性、无毒并不易燃烧。但与HCFC不同,PFC对于聚合物材料是惰性的,并且由于无氯,它们不会消耗同温层臭氧。因此,PFC能与HCFC组合在一起作为稀释剂用于降低HCFC对聚合物基材的侵蚀作用。但是由于这种组合仍使用HCFC,所以它们的使用只能降低而非消除臭氧的消耗作用。
发明的概述
简单地说,本发明的一个方面是提供一种均匀的不消耗臭氧的含氟聚合物分散液,它包括惰性的全氟化液体、极性溶剂和选自某些支链的和同时含有侧接的脂族和侧接的含氟脂族链的聚合物化合物的表面活性剂。本发明的另一方面是提供一种使用上述稳定的含氟聚合物分散液将含氟聚合物涂覆在物体或基材上的方法。本发明的再一方面是提供一种稳定的乳液,它包括全氟化液体、极性溶剂和选自某些支链的和同时含有侧接的脂族和侧接的含氟脂族链的聚合物化合物的表面活性剂。
含氟聚合物分散液的工业用户需要分散溶剂的性能适合于工艺条件,并且不消耗臭氧的含氟聚合物分散液体系。全氟化液体很适合于这种用途。全氟化液体整体上是挥发性的、化学惰性的、无毒的并且是不易燃的。另外,由于这些液体不含氯,它们不会消耗环境臭氧,并且由于它们与材料的相容性要好于氢氯氟碳,所以它们不会损坏下层基材。发明的详细描述
出于本发明的目的,要求分散液在组分元素混合在一起而未使用剧烈的混合方法(如高剪力混合和升温)时是稳定的,产生能至少在5-10秒,最好大于30秒内保持均匀的均匀混合物。但是,由于用于涂覆应用的含氟聚合物分散液通常是连续搅拌的,因此未搅拌的分散液分层所需的时间仅是分散液质量的相对标准,而非其实用性的绝对标准。符合其它质量标准,在搅拌下保持分散但未搅拌不能长时间保持稳定的分散液仍被认为是适用的并包括在本发明的范围之内。用于本发明目的的“不消耗臭氧”是指分散液中不含据目前所知能分解大气层臭氧的化合物或试剂。
本发明分散液包括四种基本组分:全氟化溶剂、极性溶剂(包括水和极性有机溶剂)、润滑的含氟聚合物(通常是聚四氟乙烯)和合适的表面活性剂。用于形成分散液的溶剂体系(包括全氟化液体和极性共溶剂)可由任何相对比例的溶剂组分制得。但是形成的溶剂体系的性能最好很适合于工业涂覆应用,即高挥发性、化学惰性、无毒和不易燃。因此,溶剂体系通常包括主要量的全氟化液体。最好的是溶剂体系包括大于90重量%的全氟化液体。但是,应该理解本发明不对具体的溶剂比例范围进行任何限制。含氟聚合物颗粒在分散液中的浓度一般约占体系总量的0.1-30重量%。在分散液中产生稳定和均匀的分散液所必须的表面活性剂的浓度随具体的体系的不同而不同,但是一般表面活性剂约为体系总量的0.01-5.0重量%。
可使用涂覆在经挑选的基材上能形成光滑涂层的任何含氟聚合物制备本发明含氟聚合物分散液。通常,这种聚合物是聚四氟乙烯的均聚物,它可根据例如美国专利2,559,752(Berry等)和3,526,614(Schindler等)所述方法制备。这两个专利描述了使用分散剂和水溶性聚合引发剂在水性介质中间断聚合全氟化碳单体,形成胶体分散状的浓聚合物分散液的方法。可使用含氟聚合物干粉或者含氟聚合物颗粒在极性溶剂(如水或异丙醇)中的浓分散液制备含氟聚合物分散液。含氟聚合物颗粒的分子量常约为2,000-100,000,浓分散液常含有约15-30重量%含氟聚合物固体颗粒。在极性溶剂中的浓含氟聚合物分散液还可含有少量表面活性剂。适用的自由流动含氟聚合物粉末是市售的TeflonTM Fluoroadditive,适用的在极性溶剂中的浓含氟聚合物分散液是市售的VydaxTM Fluorotelomer分散液,两者都购自E.I.du Pont de Nemours and Company。
适用于本发明的全氟化液体是那些能与适当的表面活性剂和极性共溶剂一起,产生稳定和均匀的含氟聚合物分散液,并且在工业涂覆条件下能从涂覆基材上容易地蒸发的物质。适用的全氟化液体常含有5-18个碳原子并且可任选地含有一个或多个悬链(caernary)杂原子,如二价氧或三价氮原子。在本文中术语“全氟化液体”是指所有(或基本上所有)氢原子都被氟原子取代的有机化合物。代表性的全氟化液体包括环状和非环状全氟烷烃、全氟胺、全氟醚、全氟环胺及其任何混合物。具体的代表性全氟化液体包括:全氟戊烷、全氟己烷、全氟庚烷、全氟辛烷、全氟甲基环己烷、全氟三丁胺、全氟三戊胺、全氟-N-甲基吗啉、全氟-N-乙基吗啉、全氟异丙基吗啉、全氟-N-甲基吡咯烷、全氟-1,2-二(三氟甲基)六氟环丁烷、全氟-2-丁基四氢呋喃、全氟三乙胺、全氟二丁醚及其混合物和其它全氟化液体。可用于本发明的市售全氟化液体包括:FluorinertTM FCTM-43 ElectronicFluid、FluorinertTM FCTM-72 Electronic Fluid、FluorinertTM FCTM-77 ElectronicFluid、FluorinertTM FCTM-84 Electronic Fluid、FluorinertTM FCTM-87 ElectronicFluid、Performance FluidTM PF-5060、Performance FluidTM PF-5070和PerformanceFluidTM PF-5052。某些这类液体描述在美国3M公司91年2月发表的产品公告98-0211-6086(212)NPI的FluorinertTM Electronic Fluid中。其它适用于本发明的全氟化液体包括以GaldenTM LS液体和FlutesTM PP液体为名称出售的全氟化液体。
存在于本发明溶剂体系中的极性共溶剂包括任何极性溶剂。这种极性溶剂包括水和含有1-10个碳原子的极性有机溶剂,例如低分子量醇类如甲醇、乙醇、丙醇或异丙醇,酮类,乙二醇醚类及其任何混合物。较好的适用于本发明的极性共溶剂是水和异丙醇。
美国专利5,089,152(Flynn等)(列于此引为参考)描述了一类适用于本发明的表面活性化合物,它是由全氟化脂族的、碳酰氨基和亚磺酰氨基链烷醇类化合物组成的。Flynn等所述的并用下式表示的全氟脂族酰氨基链烷醇是本发明合适的表面活性剂:其中Rf是含有3-20个碳原子的两价惰性全氟脂族基团,它的主链可以是直链的、支链的,并且如果其足够大,还可以是环状的,或它们任意的组合。该主链还可任选地包括一个或多个仅连接在碳原子上的悬链两价氧原子或三价氮原子,这种杂原子作为氟脂族基团的氟碳部分之间的化学稳定的连接基,不影响Rf基团的惰性。
R1是氢或具有1-6个碳原子的直链、支链或环状的低级烷基,或它们的任意组合。
R2是含有2-12个碳原子的脂族基团,它还含有至少一个羟基,其中的一个是端接的。R2的主链可以是直链的、支链的,并且如果其足够大,它还可以是环状的,或者它们的任意组合。该主链还可任选地包括一个或多个仅连接在碳原子上的悬链杂原子,如二价氧原子。
Z是羰基(CO)或磺酰基(SO2)。
其中,R1和R2如前面所定义。
特别适合于本发明的较好的这类表面活性剂包括下列化合物:
另一类合适的表面活性剂是由某些含氟丙烯酸酯化合物和合适的亲水性单体(如丙烯酸、N-乙烯基吡咯烷酮、甲基丙烯酸或其它亲水性单丙烯酸酯)反应形成的聚合产物。所选择的亲水性单体不应是与含氟丙烯酸酯化合物聚合后在聚合产物中产生大量交联的化合物,如含有多于一个丙烯酸酯官能团的亲水性单体。下列通式描述了含氟丙烯酸酯单体化合物:其中p和q是1-4的整数,x和y是0-4的整数,m可以是1或2,n是3-10的整数,X’可以是甲基或者是一个氢原子,g可以是0或1,Q是下式亚磺酰氨基(sulfonamido)组分基团:
其中R1与式I的定义相同,是氢或具有1-6个碳原子的低级烷基,它可以是直链的、支链的、环状的或它们的任意组合。含氟丙烯酸酯化合物单体中的其它碳链也可以是直链或支链的。形成的聚合物也可包括少量链转移剂或聚合引发剂。代表性的含亚磺酰氨基组分基团的含氟化合物单体包括C8F17SO2N(C2H5)C2H4O2CC(CH3)=CH2和C8F17SO2N(C4H9)CH2CH2O2CCH=CH2。较好的含氟丙烯酸酯单体是甲基丙烯酸1,1-二氢全氟辛酯(有时称之为FOMA)和丙烯酸1,1,2,2-四氢全氟十二烷酯。当所用的极性共溶剂是极性有机溶剂,如低分子量醇类、酮类和乙二醇醚时,组分单体以相当于亲水性单体为5-25重量%的重量比混合在一起。当所用的极性共溶剂是水时,组分单体以相当于亲水性单体为1-25重量%的重量比混合在一起。
对于最好的使用丙烯酸作为亲水性单体的情况,形成的聚合物表面活性剂产物如下式所示是由无规放置的侧接的全氟脂族基团和羧酸基团组成的:其中p、q、x、y、m、n、g、X’和Q如上面所定义。
美国专利5,223,593(McAllister等)、5,270,378(Johnson等)和5,380,644(Yonkoski等)描述了适用于制造这些聚合物表面活性剂的间断聚合方法。根据这些专利所述的方法,以要求的重量比将组分单体溶解在乙酸乙酯中形成可聚合的混合物。随后将混合物脱气、封闭在密闭的反应容器中并聚合之。聚合反应完成后回收得到的表面活性剂产物是固态的。本发明的表面活性剂可用相同的方法制得,但是由于聚合化合物不溶解于乙酸乙酯,因此必须将组分单体溶解于合适的全氟化液体中。
适用于本发明的第三类表面活性剂是下列通式的全氟化醚酸:其中z可以是1-10,s为0-4,t为0-4,v为0-5,w为0或1,Y可以是F或CF3。关于这类氟化酸的制备的详细描述,可参见例如Patricia M.Savu“氟化高级羧酸(Fluorinated Higher Carboxylic Acid)”11 Kirk-Othmer Encyclopedia ofChemical Technology 551-58(4th ed.1994)。这些表面活性剂是市售的,如购自美国杜邦公司的KrytoxTM 157 FSM Fluorinated Oil和购自Ausimont Corp.,Morristown,New Jersey的FomblinTM Monoacid。
形成稳定和均匀的分散液所必需的表面活性剂的浓度会随具体的表面活性剂和感兴趣的溶剂体系的不同而稍有不同,但是在各种情况下都约占体系总重量的0.01-5.0重量%。最低可能的表面活性剂的浓度是较好的,以降低总体系的成本并避免在含氟聚合物涂覆表面上残留大量的表面活性剂。可以在以任何相对浓度比例形成的全氟化液体和极性共溶剂的溶液体系中用本发明表面活性剂分散含氟聚合物。在体系中分散的含氟聚合物的量约为0.1-30重量%。
可以用相同于上面将含氟聚合物分散在全氟化液体和极性溶剂中的方法,用本发明表面活性剂形成全氟化液体和极性溶剂的均匀乳液。用于这种用途的较好的表面活性剂种类是含有至少5重量%亲水性单体的聚合物表面活性剂。可以用这类表面活性剂形成任何全氟化液体和极性溶剂相对浓度比的乳液。当这些组分溶剂以相等的体积浓度存在时,约0.5重量%聚合物表面活性剂就可形成均匀的乳液。
用全氟化液体将市售的分散在极性有机溶剂中的30重量%含氟聚合物分散液稀释至含氟聚合物约为1.5重量%,就可获得用于涂覆工艺中的较好的体系。形成的体系含有约1.5重量%含氟聚合物,95重量%全氟化液体和约3.5重量%极性共溶剂。对于这种体系,约0.5重量%聚合物表面活性剂或约3重量%全氟脂族酰氨基链烷醇或约2重量%全氟化醚酸就足以形成均匀的分散液。
可使用本发明分散液涂覆以施涂含氟聚合物作为润滑剂的代表性制品包括:医疗仪器如外科纤维切断机、剃刀片或外科刀片,照相设备如聚焦镜筒,拉链,乐器栓塞和磁带如录相和录音带。本发明含氟聚合物分散液还可用于施涂含氟聚合物,作为模塑剥离剂和作为剥离底涂层用于各种涂覆部件如电动机线圈。
下列实施例用于更好地理解本发明。这些实施例介绍并评价了许多前面通式所定义的适用的表面活性剂。这种列举不应认为是对适用于本发明的表面活性剂的汇编,不应认为这些实施例是对本发明范围的限制。实施例
在下列实施例和比较例中,定量地将市售PTFE浓分散液置于小玻璃瓶中,随后加入足以形成固体含量约1.5重量%的分散液的定量全氟-N-甲基吗啉。滴加纯的表面活性剂,或表面活性剂在相同或不同全氟惰性液体中的溶液并搅拌之。如果形成稳定的分散液,则用下面所述的方法评价该分散液,并计算出加入的表面活性剂的重量百分数并记录之。如果未形成稳定的分散液,则再滴加表面活性剂并重复上述步骤。
一旦制得稳定的分散液,以秒为单位记录含氟聚合物从溶剂体系中沉淀出来所需的时间。在某些实施例中,另外制得具有较高浓度表面活性剂的分散液,再记录在该较高的浓度下分散液波乳或失去其均匀性并分层所需的时间。还对分散液按下列等级评价其均匀性:
等级 | 等级描述 |
1.差 | PTFE结块-无用 |
2.一般 | 有些结块;在小玻璃瓶表面上有广泛的粒状或蜡状的涂层 |
3.好 | 均匀分散液;在小玻璃瓶上有一些粒状涂层 |
4.很好 | 均匀分散液;在小玻璃瓶上很少或无粒状涂层 |
出于本发明的目的,较好至少为等级2.5以形成均匀的分散液。
使用下列缩写代表各种表面活性剂:43MA/AA C4F9OCF(CF)3CH2O(CO)C(CH3)=CH2和丙烯酸的共聚
物,组分单体的重量百分数列于表中。C9/AA C9F19CH2CH2O(CO)CH=CH2和丙烯酸的共聚物,组分单
体的重量百分数列于表中。FOMA/AA C7F15CH2O(CO)C(CH3)=CH2和丙烯酸的共聚物,组分单
体的重量百分数列于表中。FOMA/AA1% 相同的共聚物,还含有1%巯基乙酸甲酯作为链转移剂。FOMA/NVP C7F15CH2O(CO)C(CH3)=CH2和N-乙烯基吡咯烷酮的共
聚物,组分单体的重量百分数列于表中。EtFOSEMA/CW-Acrl 根据美国专利3,787,351(Olson)的实施例2所述的方法制
得的C8F17SO2N(C2H5)C2H4O2CC(CH3)=CH2和
Carbowax-750 acrylate(30∶70)的共聚物。BuFOSEA/Pluronic 根据美国专利3,787,351(Olson)的实施例1所述的方法制acrylate 得的C8F17SO2N(C4H9)CH2CH2O2CCH=CH2和Pluronic-44
acrylate(30∶70)的共聚物。EtFOSEMA/ODMA 根据美国专利3,787,351(Olson)的实施例3所述的方法制
得的C8F17SO2N(C2H5)C2H4O2CC(CH3)=CH2和甲基丙烯
酸十八烷酯(50∶50)的共聚物。FomblinTM monoacid 购自Ausimont corporation of Morristown,New Jersey的聚
氧全氟链烷酸。KrytoxTM 157FS氟化油 购自美国杜邦公司的全氟化聚醚羧酸。
其它表面活性剂的结构列于表中。分散液中含氟聚合物的重量百分数的计算值以“重量%PTFE”表示。用于制备分散液的表面活性剂的最终重量百分数的计算值以“重量%表面活性剂”表示。“分层时间”是以秒为单位的分散液失去其均匀性并分层的时间。“n/a”是指未形成均匀的分散液或者分散液立即分层。
对于下列实施例和比较例,使用购自美国杜邦公司的VydaxTM AR/IPAFluorotelomer分散液。该产品是30重量%平均分子量为3700的PTFE在异丙醇中的的分散液。在下列实施例中,对用于本发明组合物中的不同浓度的表面活性剂进行试验,并如上所述对形成的分散液进行评价。结果列于表1。
表1
实施例 | 重量%PTFE | 表面活性剂 | 重量%表面活性剂 | 等级 | 分层时间(秒) |
C-1 | 1.5 | 无 | - | 1 | n/a |
12 | 1.571.49 | 43MA/AA 95/543MA/AA 95/5 | 0.230.57 | 3.54 | 75120 |
345 | 1.51.51.5 | C9/AA 90/10C9/AA 90/10C9/AA 90/10 | 0.31.202.40 | 2.522 | 202265 |
C-267 | 1.171.341.52 | C4F9OC2F4OCF2(CO)NHCH2CH2OHC4F9OC2F4OCF2(CO)NHCH2CH2OHC4F9OC2F4OCF2(CO)NHCH2CH2OH | 2.362.774.03 | 144 | n/a150150 |
89 | 1.51.44 | FOMA/AA 80/20FOMA/AA 80/20 | 0.320.96 | 33 | 120150 |
1011 | 1.491.44 | FOMA/AA 80/20 1%FOMA/AA 80/20 1% | 0.221.08 | 43.5 | 4560 |
121314 | 1.51.51.45 | FOMA/AA 87/13FOMA/AA 87/13FOMA/AA 87/13 | 0.120.250.37 | 444 | 60120180 |
15161718 | 1.591.481.491.48 | FOMA/AA 90/10FOMA/AA 90/10FOMA/AA 90/10FOMA/AA 90/10 | 0.110.190.210.42 | 4443.5 | 9012020420 |
1920 | 1.481.98 | FOMA/AA 95/5FOMA/AA 95/5 | 0.070.47 | 3.53.5 | 5575 |
C-3 | 1.50 | FOMA/AA 98/2 | 5.01 | 1 | n/a |
C-4 | 1.50 | FOMA/AA 99/1 | 1.90 | 1 | n/a |
2122 | 1.491.40 | FOMA/NVP 95/5FOMA/NVP 95/5 | 0.391.61 | 43.5 | 6060 |
232425 | 1.501.521.50 | C8F17SO2NC2H5(CH2CH2O)nH(n=1-4)C8F17SO2NC2H5(CH2CH2O)nH(n=1-4)C8F17SO2NC2H5(CH2CH2O)nH(n=1-4) | 1.832.894.69 | 2.533 | 102020 |
262728 | 1.581.501.50 | EtFOSEMA/CW-AcrlEtFOSEMA/CW-AcrlEtFOSEMA/CW-Acrl | 0.461.062.49 | 33.53.5 | 124040 |
C-5 | 1.55 | EtFOSEMA/ODMA | 1.18 | 1.5 | n/a |
C-6 | 1.55 | BuFOSEA/Pluronic acrylate | 1.5 | 1.5 | n/a |
C-7 | 1.56 | C8F17SO2N(C2H5)(CnH2nO)5.5CH3 | 2.19 | 1.5 | n/a |
29 | 1.45 | C8F17SO2N(C2H5)(CnH2nO)13H | 2.36 | 2 | n/a |
C-8C-93031 | 1.481.501.501.48 | C6F13OC2F4CO2HC6F13OC2F4CO2HC6F13OC2F4CO2HC6F13OC2F4CO2H | 0.671.392.772.78 | 1133.5 | n/an/a110180 |
3233 | 1.241.48 | FomblinTM monoacidFomblinTM monoacid | 3.313.27 | 3.53 | 8585 |
3435 | 1.171.48 | KrytoxTM157FS氟化油KrytoxTM157FS氟化油 | 4.441.86 | 3.53 | 6530 |
由表1的数据可见,可使用本发明方法制备适用的聚四氟乙烯、全氟化液体和异丙醇的分散液。当使用异丙醇作为极性溶剂时,聚合物表面活性剂必须含有至少5重量%亲水性单体。亲水性单体含量小于5重量%(比较例3和4)、不含亲水性单体(比较例5)或含有交联的聚合物表面活性剂(比较例6)的混合物不能形成适用的分散液。分层时间一般随表面活性剂浓度增加而增加,表明表面活性随分散液中表面活性剂的量的上升而增加。综合分散液的定性等级、分层时间和形成优质分散液所需的表面活性剂的量来看,较好的表面活性剂种类是含有5-20重量%AA单体,最好AA浓度为10-13重量%的FOMA/AA类。
对于下列实施例,使用购自美国杜邦公司的VydaxTM ARW Fluorotelomer分散液。该产品是20重量%平均分子量为3700的PTFE在水中的的分散液。在下列实施例中,对用于本发明组合物中的不同浓度的表面活性剂进行试验,并如上所述对形成的分散液进行评价。结果列于表2。
表2
实施例 | 重量%PTFE | 表面活性剂 | 重量%表面活性剂 | 等级 | 分层时间(秒) |
C-10 | 1.5 | 无 | - | 1 | n/a |
3637 | 1.591.49 | 43MA/AA 95/543MA/AA 95/5 | 0.090.5 | 33.5 | 75120 |
38 | 0.83 | C9/AA 90/10 | 1.58 | 3 | - |
3940 | 0.941.0 | C4F9OC2F4OCF2(CO)NHCH2CH2OHC4F9OC2F4OCF2(CO)NHCH2CH2OH | 0.050.14 | 44 | 12060 |
414243 | 1.51.451.36 | FOMA/AA 80/20FOMA/AA 80/20FOMA/AA 80/20 | 0.390.911.5 | 333 | 60100150 |
4445 | 1.471.37 | FOMA/AA 80/20 1%FOMA/AA 80/20 1% | 0.61.18 | 33.5 | 90180 |
4647 | 1.491.36 | FOMA/AA 87/13FOMA/AA 87/13 | 0.560.94 | 2.52.5 | 6075 |
484950 | 1.511.41.44 | FOMA/AA 90/10FOMA/AA 90/10FOMA/AA 90/10 | 0.040.550.77 | 33.53 | 9018090 |
515253 | 0.941.501.49 | FOMA/AA 98/2FOMA/AA 98/2FOMA/AA 98/2 | 0.580.501.84 | 322.5 | 1201428 |
5455 | 1.461.4 | FOMA/NVP 95/5FOMA/NVP 95/5 | 0.751.44 | 22 | 6060 |
56575859 | 1.491.501.501.50 | EtFOSEMA/CW-AcrlEtFOSEMA/CW-AcrlEtFOSEMA/CW-AcrlEtFOSEMA/CW-Acrl | 0.471.022.074.02 | 2.532.53 | 505545120 |
6061 | 0.950.92 | C8F17SO2NC2H5(CH2CH2O)nH(n=1-4)C8F17SO2NC2H5(CH2CH2O)nH(n=1-4) | 0.090.19 | 34 | 10180 |
626364 | 1.501.501.49 | C6F13OC2F4CO2HC6F13OC2F4CO2HC6F13OC2F4CO2H | 0.530.751.04 | 3.53.53.5 | 240240240 |
6566 | 1.481.50 | FomblinTM monoacidFomblinTM monoacid | 1.790.50 | 43 | 180120 |
6768 | 1.541.50 | KrytoxTM 157SMKrytoxTM 157SM | 1.260.53 | 44 | 175125 |
由表2的数据可见,可使用本发明方法制备适用的聚四氟乙烯、全氟化液体和水的分散液。当使用水作为极性溶剂时,聚合物表面活性剂可含有小于5重量%亲水性单体,尽管大于5重量%是较好的。与全氟化液体和水一起使用的较好的表面活性剂是碳酰氨基链烷醇。尽管该材料随活性剂用量的增加而缩短了分层时间,但是分散液等级不受影响。在浓度为0.05重量%时其效力是很可靠的。亚磺酰氨基链烷醇也显示出良好的性能,在低浓度时显示出效力。
对于下列实施例,使用购自美国杜邦公司的VydaxTM HD FluorotelomerDispersion。该产品是平均分子量为70,000-100,000的PTFE干粉。先以30重量%的浓度将VydaxTM HD Fluorotelomer Dispersion分散在异丙醇中,随后使用本发明组合物和方法将其进一步以约1.5重量%的浓度分散在全氟-N-甲基吗啉中。在下列实施例中,对用于本发明组合物中的不同浓度的表面活性剂进行试验,并如上所述对形成的分散液进行评价。结果列于表3。
表3
实施例 | 重量%PTFE | 表面活性剂 | 重量%表面活性剂 | 等级 | 分层时间(秒) |
6970 | 1.541.5 | 43MA/AA 95/543MA/AA 95/5 | 0.150.18 | 33.5 | 90180 |
717273 | 1.501.491.50 | C4F9OC2F4OCF2(CO)NHCH2CH2OHC4F9OC2F4OCF2(CO)NHCH2CH2OHC4F9OC2F4OCF2(CO)NHCH2CH2OH | 1.012.053.00 | 3.544 | 758090 |
7475 | 1.451.43 | FOMA/AA 80/20FOMA/AA 80/20 | 0.550.85 | 3.53.5 | 3045 |
7677 | 1.521.39 | FOMA/AA 80/20 1%FOMA/AA 80/20 1% | 0.151.46 | 3.53.5 | 18090 |
7879 | 1.481.48 | FOMA/AA 87/13FOMA/AA 87/13 | 0.140.31 | 3.53.5 | 120180 |
8081 | 1.51.43 | FOMA/NVP 95/5FOMA/NVP 95/5 | 0.351.28 | 3.53.5 | 9060 |
828384 | 1.021.471.3 | C8F17SO2NC2H5(CH2CH2O)2HC8F17SO2NC2H5(CH2CH2O)2HC8F17SO2NC2H5(CH2CH2O)2H | 0.230.671.1 | 3.53.53.5 | 603090 |
由表3的数据可见,在干粉中加入异丙醇作为极性溶剂可制得适用的聚四氟乙烯分散液。
在下列实施例中,并用本发明聚合物表面活性剂和方法制备全氟化液体和极性溶剂的适用的乳液,对其进行评价。在各个实施例中,向小玻璃瓶中分别加入3ml全氟-N-甲基吗啉和极性溶剂,随后定量地加入聚合物表面活性剂。对小玻璃瓶进行搅拌,以秒为单位记录生成的分散液失去均匀性并分层所需的时间。用于评价的表面活性剂是FOMA/AA,单体的重量比列于表4
表4
实施例 | 极性溶剂 | 表面活性剂 | 重量%表面活性剂 | 分层时间(秒) |
8586 | 异丙醇异丙醇 | FOMA/AA 90/10FOMA/AA 90/10 | 0.0460.146 | 3075 |
87 | 异丙醇 | FOMA/AA 95/5 | 0.598 | 240 |
8889 | 异丙醇异丙醇 | FOMA/AA 98/2FOMA/AA 98/2 | 0.430.57 | 140140 |
C-11C-12 | 异丙醇异丙醇 | FOMA/AA 99/1FOMA/AA 99/1 | 0.050.15 | 00 |
90 | 水 | FOMA/AA 90/10 | 0.34 | 15 |
91 | 水 | FOMA/AA 95/5 | 1.07 | 16 |
C-13C-14 | 水水 | FOMA/AA 98/2FOMA/AA 98/2 | 0.531.90 | 00 |
C-15C-16 | 水水 | FOMA/AA 99/1FOMA/AA 99/1 | 0.160.34 | 00 |
由表4的结果可见,当亲水性单体的含量至少为5重量%时,可使用具有亲水性单体的聚合物表面活性剂制得适用的乳液。当亲水性单体的含量小于5重量%时,乳液立即分层。
在下列实施例中,将聚四氟乙烯的重量百分数和表面活性剂的浓度保持恒定,改变全氟化液体和极性溶剂的浓度。在列于表5和表6的所有实施例中,所使用的全氟液体是全氟-N-甲基吗啉,在表5的实施例中极性溶剂为异丙醇,而表6的实施例使用的是水。
表5
实施例 | 重量%PTFE | 表面活性剂 | 重量%表面活性剂 | 重量%异丙醇 | 等级 | 分层时间(秒) |
9293949596979899100101102103 | 1.511.491.491.501.451.451.501.491.441.431.471.52 | 均为FOMA/AA90/10 | 0.010.040.030.030.120.110.110.120.330.300.320.33 | 3.637.1814.9230.03.57.8915.0329.753.476.9414.7730.50 | 3.5432.543.53.5343.53.53 | 9660757060152590>600600>600420 |
表6
实施例 | 重量%PTFE | 表面活性剂 | 重量%表面活性剂 | 重量%水 | 等级 | 分层时间(秒) |
104105106107108109110111112113114115 | 1.501.501.501.501.501.501.501.501.481.501.501.50 | 均为C4F9OC2F4OCF2(CO)NHCH2CH2OH | 0.070.070.070.070.140.130.120.130.300.310.300.30 | 6.5913.2226.5952.966.6113.2326.652.906.5013.3926.3252.94 | 4433.5443.53.5443.53.5 | 607025>60090100180>600120115110>600 |
由表5和表6的数据可见,使用各种浓度的全氟化液体和极性溶剂可制得适用的PTFE分散液。
在不偏离本发明范围和精神的情况下,本发明的各种改进和变化对本领域中的熟练技术任意来说是显而易见的。应该理解本发明不限于上述说明性的实例。
Claims (10)
1.一种均匀的不消耗臭氧的分散液,它包括润滑的含氟聚合物、惰性的全氟化液体、极性溶剂和有效量的选自下列化合物的表面活性剂:
a.全氟脂族酰氨基链烷醇;
b.由亲水性单体和下列通式的单体的混合物反应形成的聚合产物:其中p和q是1-4的整数,x和y是0-4的整数,m是1或2,n是3-10的整数,X’是甲基或者是一个氢原子,g是0或1,Q是下式亚磺酰氨基组分基团:其中R1是氢或具有1-6个碳原子的低级烷基,当所用的极性溶剂是极性有机溶剂时,亲水性单体的用量是反应混合物的5-25重量%,当所用的极性溶剂是水时,亲水性单体的用量是反应混合物的1-25重量%;以及
c.下列通式的全氟化醚酸:其中z为1-10,s为0-4,t为0-4,v为0-5,w为0或1,Y是F或CF3。
3.如权利要求2所述的液体组合物,其特征在于亲水性单体选自丙烯酸和N-乙烯基吡咯烷酮。
4.如权利要求1所述的液体组合物,其特征在于所述组合物含有0.1-30重量%含氟聚合物,50-99重量%惰性全氟化液体,1-49重量%极性溶剂和0.01-5重量%表面活性剂。
5.将含氟聚合物涂覆在物体或基材上的方法,它包括使用含润滑的含氟聚合物、惰性全氟化液体、极性溶剂和有效量的表面活性剂的均匀且不消耗臭氧的分散液将含氟聚合物施涂或涂覆在物体或基材上,随后干燥经涂覆的物体或基材;所述表面活性剂选自:
a.全氟脂族酰氨基链烷醇;
b.由亲水性单体和下列通式的单体的混合物反应形成的聚合产物:其中p和q是1-4的整数,x和y是0-4的整数,m是1或2,n是3-10的整数,X’是甲基或者是一个氢原子,g是0或1,Q是下式亚磺酰氨基组分基团:其中R1是氢或具有1-6个碳原子的低级烷基,当所用的极性溶剂是极性有机溶剂时,亲水性单体的用量是反应混合物的5-25重量%,当所用的极性溶剂是水时,亲水性单体的用量是反应混合物的1-25重量%;以及
6.如权利要求5所述的方法,其特征在于含氟聚合物是聚四氟乙烯,并且极性有机溶剂选自水和具有1-10个碳原子的低分子量醇。
7.均匀且不消耗臭氧的分散液,它包括惰性全氟化液体、极性溶剂和选自下列化合物的表面活性剂:
a.由亲水性单体和下列通式的单体的混合物反应形成的聚合产物:其中p和q是1-4的整数,x和y是0-4的整数,m是1或2,n是3-10的整数,X’是甲基或者是一个氢原子,g是0或1,Q是下式亚磺酰氨基组分基团:其中R1是氢或具有1-6个碳原子的低级烷基,当所用的极性溶剂是极性有机溶剂时,亲水性单体的用量是反应混合物的5-25重量%,当所用的极性溶剂是水时,亲水性单体的用量是反应混合物的1-25重量%;以及
8.如权利要求1或7所述的液体组合物,其特征在于极性有机溶剂选自水和具有1-10个碳原子的低分子量醇。
9.如权利要求7所述的液体组合物,其特征在于所述组合物含有50-99重量%惰性全氟化液体,1-49重量%极性溶剂和0.01-5重量%表面活性剂。
10.一种制品,它涂有包括润滑的含氟聚合物、惰性的全氟化液体、极性溶剂和有效量的表面活性剂的均匀且不消耗臭氧的分散液,所述表面活性剂选自:
a.全氟脂族酰氨基链烷醇;
b.由亲水性单体和下列通式的单体的混合物反应形成的聚合产物:其中p和q是1-4的整数,x和y是0-4的整数,m是1或2,n是3-10的整数,X’是甲基或者是一个氢原子,g是0或1,Q是下式亚磺酰氨基组分基团:其中R1是氢或具有1-6个碳原子的低级烷基,当所用的极性溶剂是极性有机溶剂时,亲水性单体的用量是反应混合物的5-25重量%,当所用的极性溶剂是水时,亲水性单体的用量是反应混合物的1-25重量%;以及
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CN106715485A (zh) * | 2014-09-11 | 2017-05-24 | 3M创新有限公司 | 包含氟化表面活性剂的组合物 |
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- 1996-03-14 CN CN96193513A patent/CN1182445A/zh active Pending
- 1996-03-14 KR KR1019970707616A patent/KR19990008092A/ko not_active Application Discontinuation
- 1996-03-14 EP EP96908823A patent/EP0822960A1/en not_active Ceased
- 1996-03-14 WO PCT/US1996/003535 patent/WO1996034052A1/en not_active Application Discontinuation
- 1996-03-14 JP JP8532501A patent/JPH11504360A/ja active Pending
- 1996-05-07 US US08/646,154 patent/US5660888A/en not_active Expired - Fee Related
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1997
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Cited By (5)
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CN101484515B (zh) * | 2006-07-04 | 2014-11-26 | 西巴控股有限公司 | 用多相聚合技术制造的光引发剂的水基浓缩产品形式 |
CN106715485A (zh) * | 2014-09-11 | 2017-05-24 | 3M创新有限公司 | 包含氟化表面活性剂的组合物 |
CN106715485B (zh) * | 2014-09-11 | 2019-11-12 | 3M创新有限公司 | 包含氟化表面活性剂的组合物 |
CN111349194A (zh) * | 2020-04-29 | 2020-06-30 | 中海石油(中国)有限公司 | 一种含氟聚乙烯吡咯烷酮天然气水合物抑制剂及其制备方法 |
CN111349194B (zh) * | 2020-04-29 | 2021-08-31 | 中海石油(中国)有限公司 | 一种含氟聚乙烯吡咯烷酮天然气水合物抑制剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
WO1996034052A1 (en) | 1996-10-31 |
JPH11504360A (ja) | 1999-04-20 |
EP0822960A1 (en) | 1998-02-11 |
US5660888A (en) | 1997-08-26 |
US5532310A (en) | 1996-07-02 |
KR19990008092A (ko) | 1999-01-25 |
US5844034A (en) | 1998-12-01 |
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