|Publication number||USRE40516 E1|
|Application number||US 10/241,660|
|Publication date||23 Sep 2008|
|Filing date||11 Sep 2002|
|Priority date||27 Jun 1997|
|Also published as||CA2294509A1, DE69823353D1, DE69823353T2, EP0991519A1, EP0991519B1, EP1454953A1, US6117508, WO1999000249A1|
|Publication number||10241660, 241660, US RE40516 E1, US RE40516E1, US-E1-RE40516, USRE40516 E1, USRE40516E1|
|Inventors||Edward E. Parsonage, Thomas J. Blong|
|Original Assignee||3M Innovative Properties Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (62), Non-Patent Citations (10), Referenced by (5), Classifications (27), Legal Events (2)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Fluoropolymers, or fluorine-containing polymers, are a commercially important class of materials. Fluoropolymers include, for example, crosslinked fluorocarbon elastomers and semi-crystalline or glassy fluorocarbon plastics. Fluorocarbon plastics (or fluoroplastics) are generally of high thermal stability and are particularly useful at high temperatures. They also exhibit extreme toughness and flexibility at very low temperatures. Many of these fluoroplastics are almost totally insoluble in a wide variety of solvents and are generally chemically resistant. Some have extremely low dielectric loss and high dielectric strength and many have unique nonadhesive and low-friction properties. See, for example, F. W. Billmeyer, Textbook of Polymer Science, 3rd ed., pp. 398-403, John Wiley & Sons, New York (1984).
Fluorocarbon elastomers, particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers, such a hexafluoropropene, have particular utility in high temperature applications, such as seals, gaskets, and linings. See, for example, R. A. Brullo, “Fluoroelastomer Rubber for Automotive Applications,” Automotive Elastomer & Design, June 1985, “Fluoroelastomer Seal Up Automotive Further,” Materials Engineering, October, 1988, and W. M. Grootaert, et al., “Fluorocarbon Elastomers,” Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 8, pp. 990-1005 (4th ed., John Wiley & Sons, 1993).
Fluoroplastics, particularly polychlorotrifluoroethylene, polytetrafluoroethylene, copolymers of tetrafluoroethylene, hexafluoropropylene, perfluoropropyl vinyl ether and poly (vinylidene fluoride), have numerous electrical, mechanical, and chemical applications. Fluoroplastics are useful, for example, in wire coatings, electrical components, seals, solid and lined pipes, and piezoelectric detectors. See, for example, “Organic Fluorine Compounds,” Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 11, pp., 20, 21, 32, 33, 40, 41, 50, 52, 62, 70, 71 (John Wiley & Sons, 1980).
In the automotive industry, for example, increased concern with evaporative fuel standards has led to the need for fuel system components that have improved barrier properties. This helps reduce the permeation of fuel vapors through automotive elements such as fuel filter lines, fuel supply lines, fuel tanks, and other elements of an automobile fuel system. Multi-layer tubing and other articles containing a fluorinated layer have been used in such automotive elements to provide a chemically resistant permeation barrier. Multi-layer articles are also useful in a number of other industries including, for example, the chemical processing and/or handling industries, and the electrical and electronics industries. Such multi-layer articles can include one or more other layers that can add strength, rigidity, or other mechanical properties.
Multi-layer compositions comprising a fluorinated polymer layer and a polyamide or polyolefin layer are known. See, for example, U.S. Pat. No. 4,933,090 (Krevor) which discloses laminate tubular articles that can include layers of fluorocarbon elastomers, and International Publication No. WO 93/1493 (LaCourt) which discloses a laminar film structure that includes a polyimide and a fluoropolymer.
To be useful, these multi-layer articles should not delaminate during use. That is, the adhesive bond strength between the layers of the multi-layer article should be sufficient to prevent the layers from separating. A variety of methods have been employed to increase the bond strength between a layer comprising a fluoropolymer and a layer comprising a substantially non-fluorinated polymer. For example, a layer of adhesive can be added between the two layers. However, the adhesive used must not limit the performance of the multi-layer article.
As an alternative to, or in addition to, adhesives, surface treatment of one or both of the layers has been used to increase the adhesive bond strength between the layers. For example, layers comprising a fluoropolymer have been treated with a charged gaseous atmosphere followed by application of a layer of thermoplastic polyamide. Such surface treatments add additional steps and cost to the manufacturing process and are limited to non-coextrusion processes.
In another approach, the adhesion between a substantially non-fluorinated polymer and a fluoropolymer, wherein the fluoropolymer is derived from vinylidene fluoride (VDF), and optionally hexafluoropropylene (HFP), has been found to increase upon exposure of the fluoropolymer to an amine compound. An example includes providing a fluoropolymer comprising interpolymerized units derived from vinylidene fluoride, a layer of a melt-processable, substantially non-fluorinated polymer, and a melt-processable aliphatic di- or polyamine of less than 1,000 molecular weight. Unfortunately, fluoropolymer derived from VDF are relatively susceptible to chemical attack by basic materials, thus rendering them unacceptable in certain chemical applications.
In contrast, fluoropolymers derived from fluorinated monomers that include substantially no VDF are known to be more chemically inert than fluoropolymer derived from VDF monomers, and are more resistant to chemical attack. Thus, such fluoropolymers are ideal for use in composite applications (e.g., articles having multi-layers) where a more resistant barrier layer is desired, such as automotive hose applications. Such articles combine the chemical resistance of the fluoropolymer with the structural properties of a generally thicker and lower cost hydrocarbon material. Examples of such substantially non-VDF derived fluoropolymers include fluoropolymers derived from monomers of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), and optional non-fluorinated monomers. The chemical resistance provided by these fluoropolymers make such composite articles useful as automotive fuel lines, fuel tanks, other elements of automobile systems, as well as liners, tubing and containers in chemical processing and any other use where chemically resistant barriers are desired.
However, because of the improved chemical resistance of these substantially non-VDF derived fluoropolymers, they are also less likely to undergo adhesion-promoting reactions with amines. Although some degree of adhesion may be obtained on exposure of a substantially non-VDF containing fluoropolymer to an amine, many applications will benefit from, and may require, higher adhesion to a fluoropolymer that provides a chemically resistant barrier. Thus, poor adhesion between the non-VDF containing fluoropolymer and a hydrocarbon material makes formation of useful composite articles difficult.
What is yet needed is a composite article that includes a barrier comprising a substantially non-vinylidene fluoride containing polymer that adheres well to a substantially non-fluorinated polymeric substrate.
In accordance with the invention, one embodiment is a composite article comprising: a blend component that has first and second surfaces, and a substantially non-fluorinated polymer component adhered to the first surface of the blend component. The non-fluorinated polymer component has one or more pendant primary or secondary amine groups and provides an exposed surface. The blend component comprises (i) a vinylidene-fluoride containing fluoropolymer and (ii) a first substantially non-vinylidene fluoride containing fluoropolymer. As used herein, the term “blend” means that the polymers are mixed together. These polymers can be mixed by any conventional method, including solution mixing, melt-mixing or dispersion mixing.
It was found that this embodiment of the invention improved the adhesion between a non-VDF containing fluoropolymer component and the component consisting of a substantially non-fluorinated polymer.
In another embodiment of the invention, a composite article includes a second substantially non-fluorinated polymer component adhered to the exposed surface of the first substantially non-fluorinated polymer component.
In either of the embodiments above, the composite article may further include a component comprising a second substantially non-VDF containing fluoropolymer bonded to the second surface of the blend component.
In another embodiment of the invention, a multi-layer composite article includes in order, a first layer of a substantially non-VDF containing fluoropolymer; a second layer of a blend of a VDF containing fluoropolymer and a substantially non-vinylidene fluoride containing fluoropolymer, a third layer comprising a substantially non-fluorinated polymer having pendant amine groups, and a fourth layer comprising a substantially non-fluorinated polymer.
Another embodiment of the invention includes a method for adhering a fluorinated component to a substantially non-fluorinated component. The method comprises the steps of providing (A) the non-fluorinated polymer, (B) a blend of (i) a VDF containing fluoropolymer; and (ii) a first substantially non-VDF containing fluoropolymer and (C) a substantially non-fluorinated polymer having one or more pendant primary or secondary amine groups, and, sequentially or simultaneously,
This method provides composite articles (e.g., multi-layer articles) having improved adhesive bond strength between a fluorinated component and a substantially non-fluorinated component through the inclusion of a fluoropolymer blend component. The composite article of the invention can be a shaped article, such as a sheet or film, a hose, a tube, a wire coating, a cable jacket, and a container. The invention provides composite articles suitable for use in motor vehicles, for example, as fuel-line hoses, chemical handling and processing, wire and cable applications, sheets or films, blow-molded and extruded articles such as bottles, tubes, etc. The articles of the invention are especially useful where chemical resistance and barrier properties are important.
The FIGS are not intended to limit the present invention. Consequently, it is understood that the specific constructions are illustrative only. In these several views, similar reference numbers refer to the same elements.
The various embodiments of the invention utilize fluorinated polymers (also known as fluoropolymers). Fluoropolymers used in the invention include vinylidene fluoride containing fluoropolymers and substantially non-vinylidene fluoride containing fluoropolymers. Additionally, the fluoropolymers used in the invention include both fluoroplastics (also known as fluorothermoplastics) and fluoroelastomers.
Fluoroplastics are distinguished from fluoroelastomers or fluororubbers by their properties. Fluoroplastic materials are melt-processable and have either a melt point and are semi-crystalline, or have a glass transition temperature above ambient temperature. In contrast, fluoroelastomers or fluororubbers are generally amorphous and usually do not exhibit a melt point. While some fluoroelastomers may be melt-processable, a curing step is typically used in making finished articles of fluoroelastomers. The curing step generally results in a material with substantially reduced melt-processability. The terms fluoroelastomer and fluororubber are generally used interchangeably. See, for example, American Society for Testing and Materials (ASTM) D 1566 for elastomer and rubber definitions.
Vinylidene Fluoride Containing Fluoropolymers
As used herein the term “vinylidene fluoride containing fluoropolymer” includes fluoropolymers derived from vinylidene fluoride (“VF2” or “VDF”) and fluoropolymers derived from other monomers which, when polymerized, form monomer sequences similar to polymerized vinylidene fluoride. In general, these fluoropolymers will readily dehydrofluorinate when exposed to a base. As a result, such fluoropolymers undergo relatively facile reactions with amine components. These reactions can result in improved adhesion. These other such monomers include ethylenically unsaturated monomers which, when incorporated into fluoropolymers, can produce a similar (including an identical) polymeric microstructure as the polymerized VDF. These similarly formed polymers are also prone to dehydrofluorination and a subsequent adhesion promoting reaction with an amine. In general, the microstructure of a carbon bonded hydrogen atom between carbon bonded fluorine atoms creates an amine reactive site. The reactivity of a carbon bonded hydrogen is further enhanced when its carbon atom is adjacent to, or attached to a carbon atom possessing a carbon bonded —CF3 group (supplied by HFP or 2-hydropentafluoropropylene for instance) or another electron withdrawing group. Monomers suitable for forming such carbon-bonded-hydrogen reactive sites include, but are not limited to, VDF, 1-hydropentafluoropropene, 2-hydropentafluoropropene, and trifluoroethylene.
Preferably, these VDF-containing fluoropolymers are easily prone to dehydrofluorination and are also prone to a subsequent adhesion promoting reaction with an amine. The carbon-bonded-hydrogen sites produced upon copolymerization of these monomers, including VDF, can be predehydrofluorinated (prior to blend formation) to form double bonds within the backbone of the fluoropolymer. While not wishing to be bound by any particular theory, it is believed that preformation of these double bonds may accelerate the amine adhesion promoting reaction. This dehydrofluorination reaction may also be produced in situ, e.g., during processing. This in situ dehydrofluorination reaction may be aided by the use of an appropriate catalyst, preferably of the type discussed below. Such VDF-containing fluoropolymers comprises at least 3% by weight of interpolymerized units derived from VDF or other monomers with similar reactivity when polymerized. These VDF-containing fluoropolymers may be homopolymers or copolymers with other ethylenically unsaturated monomers. More preferably, the VDF-containing fluoropolymer is formed from (i) a fluorine-containing monomer selected from the group of vinylidene fluoride, trifluoroethylene, 1-hydropentafluoropropylene, 2-hydropentafluoropropylene, mixture thereof, and optionally (ii) at least one monomer copolymerizable therewith. In one preferred embodiment, the VDF-containing fluoropolymer comprises a hexafluoropropylene-vinylidene fluoride polymer.
Such VDF-containing fluoropolymers (homopolymers, copolymers, terpolymers, etc.) can be made by well-known conventional means, for example by, free-radical polymerization of VDF with or without other ethylenically unsaturated monomers. The preparation of colloidal, aqueous dispersions of such polymers and copolymers is described, for example, in U.S. Pat. No. 4,335,238 (Moore et al.). Customary processes for making such amine-reactive fluoropolymers can include copolymerizing fluorinated olefins in aqueous, colloidal dispersions, which is carried out in the presence of water-soluble initiators which produce free radicals, such as, for example, ammonium or alkali metal persulfates or alkali metal permanganates, and in the presence of emulsifiers, such as, in particular, the ammonium or alkali metal salts of perfluorooctanoic acid.
These VDF-containing fluoropolymers useful in this invention can optionally include other useful fluorine-containing monomers such as hexafluoropropene (HFP), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), 2-chloropentafluoro-propene, a fluorinated vinyl ether, including a perfluoroalkyl vinyl ether such as CF3OCF═CF2 or CF3 CF2 CF2OCF═CF2. Certain fluorine-containing di-olefins are also useful, such as, perfluorodiallyether and perfluoro-1,3-butadiene.
The VDF-containing fluoropolymers useful in this invention may also comprise interpolymerized units derived from fluorine-free, unsaturated olefin comonomers, e.g., ethylene, propylene or butadiene. Preferably, at least 50% by weight of all monomers in a polymerizable mixture are fluorine-containing. The VDF-containing fluorine-containing monomer may also be copolymerized with iodine- or bromine-containing unsaturated olefin monomer. These monomers, sometimes referred to as cure-site monomers, are useful to prepare a peroxide curable polymer. Suitable cure-site monomers include terminally unsaturated monoolefins of 2 to 4 carbon atoms such as bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, and 4-bromo-3,3,4,4-tetrafluoro-1-butene.
Useful commercially available VDF-containing fluoropolymer materials include, for example, THV 200, THV 400, THV 500G fluoropolymer (available from Dyneon LLC, St. Paul, Minn.), KYNAR 740 fluoropolymer (available from Atochem North America, Philadelphia, Pa), HYLAR 700 (available from Ausimont USA, Inc., Morristown, N.J.), and FLUOREL FC-2178 (available from Dyneon LLC).
Substantially Non-vinylidene Fluoride Containing Fluoropolymers
These fluoropolymers typically do not contain VDF monomer (or any other similar monomer) at a level such that, when polymerized, produces a microstructure which is readily susceptible to reaction with a base, as described above. Hence, these fluoropolymers are referred to herein as “substantially non-vinylidene fluoride (non-VDF) containing fluoropolymers.” By “substantially non-VDF containing,” it is meant that the fluoropolymer preferably is substantially free from interpolymerized units derived from VDF monomer, or other monomers which provide a microstructure similar to that described above. These fluoropolymers comprise less than 3%, preferably less than 1% by weight of interpolymerized units derived from VDF or other monomers which produce a microstructure similar to that described above.
Useful substantially non-VDF containing fluoropolymers include melt processable fluoroplastics formed from polymerizing one or more fluorine-containing monomers selected from the group of HFP, TFE, CTFE, and a fluorinated vinyl ether, and may optionally include one or more cure site monomers. Such cure site monomers are typically iodide- or bromide-containing unsaturated olefins. Preferably the cure site monomers are terminally unsaturated monoolefins that contain from 2 to 4 carbon atoms. Examples of useful cure site monomers include bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, 4-bromo-3,3,4,4-tetrafluorobutene-1, and mixture thereof. Particularly useful fluorine-containing monomers are HFP, TFE, and CTFE.
The fluorine-containing monomer used to make the non-VDF containing fluoropolymer may also be copolymerized with fluorine-free unsaturated olefin comonomers, e.g., ethylene, propylene or butadiene. Certain fluorine-containing diolefins are also useful, such as perfluorodiallyether and perfluoro-1,3-butadiene. Preferably at least 50% by weight of all monomers in a polymerizable mixture are fluorine-containing.
Additional examples of fluoroplastics useful in the invention are substantially non-VDF containing copolymers of substantially fluorinated and substantially non-fluorinated olefins. One of these substantially non-VDF containing copolymers is a terpolymer containing TFE, HFP and ethylene. For instance, a useful copolymer contains about 45 mol % to about 75 mol % of TFE units, about 10 mol % to about 30 mol % of HFP units, and about 10 mol % to about 40 mol % of ethylene units and has a melting point of about 140° C. to about 250° C.
Another example of a useful fluoroplastic in the present invention comprises interpolymerized units derived from TFE and allylic hydrogen-containing olefin monomer. International Publication No. WO 96/18665 (Greuel) describes fluoropolymers and preferred methods of producing interpolymerized units derived from TFE and polypropylene. The copolymers can generally contain, e.g., from about 2 weight percent to about 20 weight percent (preferably from about 5 weight percent to about 15 weight percent, more preferably from about 7 weight percent to about 12 weight percent) allylic hydrogen-containing olefin monomer. These semi-crystalline copolymers typically have melt temperatures so that they can be processed at temperatures below about 300° C., preferably from about 200° C. to about 250° C.
Examples of useful substantially non-VDF containing fluoropolymers of this type include poly(ethylene-co-tetrafluoroethylene), poly(tetrafluoroethylene-co-propylene), poly(chlorotrifluoroethylene-co-ethylene), and the terpolymer poly(ethylene-co-tetrafluoroethylene-co-hexafluoropropylene), as well as perfluorinated melt processable plastics, among others. Also, many useful substantially non-VDF containing fluoropolymer materials are commercially available, for example from Dyneon, LLC, St. Paul, Minn., under the trade designations X6810, and X6820, from Daikin America, Inc., Dacatur, Ala., under the trade designations NEOFLON EP-541, EP-521, and EP-610, from Asahi Glass Co., Tokyo, Japan, under the trade designations AFLON COP C55A, C55AX, C88A, and from DuPont, Wilmington, Del., under the trade designations TEFZEL 230 and 290.
Many ways to make such polymers (including copolymers, terpolymers, etc.) are known. Such methods include, but are not limited to, suspension free-radical polymerization or conventional emulsion, which typically involve polymerizing monomers in an aqueous medium in the presence of an inorganic free-radical initiator system and surfactant or suspending agent. In general, the desired olefinic monomers can be copolymerized in an aqueous colloidal dispersion in the presence of water-soluble initiators which produce free radicals such as, for example, ammonium or alkali metal persulfates or alkali metal permanganates, and in the presence of emulsifiers such as, in particular, ammonium or alkali metal salts of perfluorooctanoic acid. See, for example, U.S. Pat. No. 4,335,238.
The substantially non-VDF containing fluoropolymers are comprised of essentially fluorinated and essentially non-fluorinated olefins. They can be prepared using a fluorinated sulfinate as a reducing agent and a water soluble oxidizing agent capable of converting the sulfinate to a sulfonyl radical. Preferred oxidizing agents are sodium, potassium, and ammonium persulfates, perphosphates, perborates, and percarbonates. Particularly preferred oxidizing agents are sodium, potassium, and ammonium persulfates.
Aqueous emulsion and suspension polymerizations can be carried out in conventional steady-state conditions in which, for example, monomers, water, surfactants, buffers and catalysts are fed continuously to a stirred reactor under optimum pressure and temperature conditions while the resulting emulsion or suspension is removed continuously. An alternative technique is batch or semibatch polymerization by feeding the ingredients into to stirred reactor and allowing them to react at a set temperature for a specified length of time or by charging ingredients into the reactor and feeding the monomer into the reactor to maintain a constant pressure until a desired amount of polymer is formed.
The blend component used in the invention includes the VDF containing fluoropolymer and a substantially non-VDF containing fluoropolymer, each described above. The blend component includes the VDF-containing fluoropolymer in an amount from preferably about 5 wt. %, to about 75 wt. %, and more preferably about 10 wt. % to preferably about 50 wt. %. The blend component also includes the substantially non-VDF containing fluoropolymer in an amount from preferably about 25 wt. %, to about 95 wt. %, and more preferably about 50 wt. % to about 90 wt. %.
Blends of the VDF-containing fluoropolymer and the substantially non-VDF containing fluoropolymer may be formed by a variety of known techniques. These include melt mixing these fluoropolymers either by a batch mixing technique or a continuous extrusion process. Mixing and coating of fluoropolymer dispersions, followed by thermal annealing, may also be used to form the blend component. Of course, material selection and choice of process may be determined by the end use requirements as well as melt viscosity ratios between the components.
When employing the blend component in the composite article, increased adhesion is observed by a greater peel strength value between the blend component and the component including a substantially non-fluorinated polymer containing pendant amine groups when compared to a peel strength value between a component consisting of a substantially non-VDF containing fluoropolymer and a component consisting of a substantially non-fluorinated polymer having pendant amine groups. This is particularly significant in applications where long durability of a composite article is required, such as in automobile fuel line where a fuel hose is continually exposed to petrochemicals (e.g., fuel).
Substantially Non-Fluorinated Polymers
It is contemplated that the invention may also include a substantially non-fluorinated thermoplastic or elastomeric polymer component bonded to the component comprising a polymer having pendant amine groups. Typically, this is opposite the blend component. The substantially non-fluorinated polymer component can provide added structural integrity and reduced cost, among other things.
Useful substantially non-fluorinated materials can include any of a number of well known, substantially non-fluorinated polymers. As used herein the term “substantially non-fluorinated” refers to polymers and polymeric materials having fewer than 10 percent of their carbon-bonded hydrogen atoms replaced with fluorine atoms. Preferably, the substantially non-fluorinated polymer has fewer than 2 percent of its carbon-bonded hydrogen atoms replaced with fluorine atoms, and more preferably fewer than 1 percent of its carbon-bonded hydrogen atoms are replaced with fluorine atoms.
Preferred substantially non-fluorinated polymers include thermoplastic polymers such as polyamides, polyimides, polyurethanes, polyolefins, polystyrenes, polyesters, polycarbonates, polyketones, polyureas, polyacrylates and polymethacrylates. The particular substantially non-fluorinated polymer selected will depend upon the application or desired properties.
Polyamides useful as the substantially non-fluorinated polymer are generally commercially available. For example, polyamides such as any of the well-known nylons are available from a number of sources. Particularly preferred polyamides are nylon-6, nylon-6,6, nylon-11, or nylon-12. It should be noted that the selection of a particular polyamide material should be based upon the physical requirements of the particular application for the resulting article. For example, nylon-6 and nylon-6,6 offer higher heat resistant properties than nylon-11 or nylon-12, whereas nylon-11 and nylon-12 offer better chemical resistant properties. In addition to those polyamide materials, other nylon materials such as nylon-6,12, nylon-6,9, nylon-4, nylon-4,2, nylon-4,6, nylon-7, and nylon-8 may also be used. Ring containing polyamides, e.g., nylon-6, T and nylon-6,1, may also be used. Polyether containing polyamides, such as PEBAX polyamides (Atochem North America, Philadelphia, Pa.), may also be used.
Useful polyurethane polymers include aliphatic, cycloaliphatic, aromatic, and polycyclic polyurethanes. These polyurethanes are typically produced by reaction of a polyfunctional isocyanate with a polyol according to well known reaction mechanisms. Useful diisocyanates for employment in the production of a polyurethane include dicyclohexylmethane4,4′-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexyl diisocyanate, and diphenylmethane diisocyanate. Combinations of one or more polyfunctional isocyanates may also be used. Useful polyols include polypentyleneadipate glycol, polyetramethylene ether glycol, polyethylene glycol, polycaprolactone diol, poly-1,2-butylene oxide glycol, and combinations thereof. Chain extenders, such as butanediol or hexanediol, may also optionally be used in the reaction. Commercially available urethane polymers useful in the present invention include: PN-3429 from Morton International, Inc., Seabrook, N.H., and X-4107 from B.F. Goodrich Company, Cleveland, Ohio.
The polyolefin polymers useful as the substantially non-fluorinated polymer are generally homopolymers or copolymers of ethylene, propylene, acrylic monomers, or other ethylenically unsaturated monomers, for example, vinyl acetate and higher alpha-olefins. Such polymers and copolymers can be prepared by conventional free-radial polymerization or catalysis of such ethylenically unsaturated monomers. The degree of crystallinity of the hydrocarbon polymer or copolymer can vary. The polymer may, for example, be a semi-crystalline high density polyethylene or may be an elastomeric copolymer of ethylene and propylene. Carboxyl, anhydride, or imide functionalities may be incorporated into the hydrocarbon polymer within the present invention, by polymerizing or copolymerizing functional monomers, for example, acrylic acid or maleic anhydride, or by modifying a polymer after polymerization, for example, by grafting, by oxidation or by forming ionomers. These include, for example, acid modified ethylene vinyl acetates, acid modified ethylene acrylates, anhydride modified ethylene acrylates, anhydride modified ethylene vinyl acetates, anhydride modified polyethylenes, and anhydride modified polypropylenes. The carboxyl, anhydride, or imide functional polymers useful as the hydrocarbon polymer are generally commercially available. For example, anhydride modified polyethylenes are commercially available from DuPont, Wilmington, Del., under the trade designation BYNEL coextrudable adhesive resins.
Polyacrylates and polymethacrylates useful as the substantially non-fluorinated polymer include, for example, polymers of acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methylacrylic acid, methyl methacrylate, and ethyl acrylate, to name a few. As mentioned above, other useful substantially non-fluorinated polymers include polyesters, polycarbonates, polyketones, and polyureas. These materials are generally commercially available, for example, SELAR polyester (DuPont, Wilmington, Del.), LEXAN polycarbonates (General Electric, Pittsfield, Mass.), KADEL polyketone (Amoco, Chicago, Ill.), and SPECTRIM polyurea (Dow Chemical, Midland, Mich.),
Preferred substantially non-fluorinated elastomer polymers include acrylonitrile butadiene (NBR), butadiene rubber, chlorinated and chloro-suflonated polyethylene, chloroprene, EPM EPDM, epichiorohydrin (ECO), isobutylene isoprene, isoprene, polysulfide, polyurethane, silicone, PVC-NBR, styrene butadiene, and vinyl acetate ethylene. Examples of these compounds include Nipol 1052 NBR (Zeon, Louisville, Ky.), Hydrin 2000 ECO (Zeon, Louisville, Ky.), Hypalon 48 (Dupont, Wilmington, Del.), and Nordel 2760P EPDM (Dupont, Wilmington Del.).
Substantially Non-Fluorinated Polymers having Pendant Amine Groups
Useful substantially non-fluorinated polymers having pendant amine groups preferably include any of the substantially non-fluorinated polymers described above so long as a pendant amine group is provided. More preferably, these non-fluorinated polymers having pendant amine groups contain one or more primary amine groups. For example, aliphatic di-, or polyamines mixed and reacted with a substantially non-fluorinated polymeric material described above can be used in a composite article according to the invention. The term “di-, or polyamines” as used within this description refers to organic compound containing at least two amine groups. By “aliphatic” it is meant that the nitrogen atoms of at least two of the two or more amines in the compound are bonded directly to only hydrogen atoms or aliphatic carbon atoms rather than being bonded directly to aromatic moieties or functional groups (e.g., carboxyl). For example, as “aliphatic di-, or polyamine” is used within the present description, aniline and urea are not aliphatic di-, or polyamines. Secondary amines are more preferred than tertiary amines and primary amines are most preferred. These amines modify a substantially non-fluorinated polymer which makes up the component of the composite article to which the blend is adhered.
Primary-amine containing polymers are obtained, for example, by reacting carboxyl-containing hydrocarbon elastomers with diamines, for example, 2-methylpentanediamine and N-aminoethylpiperazine. Most preferred are alkylene polyamines or diamines that comprise at least two primary amines, such as hexamethylene diamine, dodecyl diamine, and 2,4,8,10-tetraoxaspiro[5,5]undecane-3,9-dipropanamine. Such polymers and copolymers can be prepared by free radical polymerization of ethylenically unsaturated monomers.
A particularly useful non-fluorinated polymer (polyamide) having pendant amine groups is commercially available under the trade designation GRILAMID FE4943, now known as GRILAMID XE3595 and GRILAMID FE5405, both available from EMS Chemie AG (Switzerland). Other materials which may be modified with the addition of pendant amine groups include polyimides, polyesters, polycarbonates, polyketones, and polyureas. These materials are generally commercially available, for example, SELAR polyester from DuPont (Wilmington, Del.), LEXAN polycarbonate (General Electric, Pittsfield, Mass.), KADEL polyketone (Amoco, Chicago, Ill.), and SPECTRIM polyurea (Dow Chemical, Midland, Mich.).
In addition to pendant amine functionality, other catalyst systems may be added to the amine functionalized substantially non-fluorinated polymer component to accelerate bonding to the fluoropolymer blend component. Certain catalysts may also be added to the blend component provided that they are not overly reactive with the blend component. These catalysts may include oregano-onium compounds used in conjunction with an acid acceptor.
Many of the oregano-onium compounds useful in this invention are described in the art and contain at least one heteroatom (i.e., a non-carbon atom such as N, P, S, O) bonded to organic or inorganic moieties. See, for example, U.S. Pat. No. 4,882,390 (Grootaert et al.); U.S. Pat. No. 3,655,727 (Patel et al.); U.S. Pat. No. 3,712,877 (Patel et al.); U.S. Pat. No. 3,857,807 (Kometani): U.S. Pat. No. 3,686,143 (Bowman); U.S. Pat. No. 3,933,732 (Schmiegel); U.S. Pat. No. 3,876,654 (Pattison); U.S. Pat. No. 4,233,421 (Worm); U.S. Pat. No. 4,259,463 (Moggi et al.); U.S. Pat. No. 4,673,715 (Caywood): U.S. Pat. No. 4,833,212 (Yamada et al.); U.S. Pat. No. 4,748,208 (Kasahara et al.); U.S. Pat. No. 4,501,858 (Moggi); U.S. Pat. No. 4,882,390; and also see West, A. C. and Holcomb, A. G. “Fluorinated Elastomers”, Kirk-Othmer; Encyclopedia of Chemical Technolog, Vol. 8, 3rd Ed., John Wiley & Sons, Inc., pp. 500-515 (1979). Mixtures of oregano-onium compounds are also useful in this invention.
Preferably, the oregano-onium compounds include quaternary oregano-onium compounds (such as those selected from the group consisting of ammonium, arsonium, phosphonium, stibonium, amino-phosphonium, phosphorane and immium compounds) and sulfonium compounds. Many of such compounds are described in U.S. Pat. No. 4,882,390 (Grootaert et al.).
Representative oregano-onium compounds useful in this invention include:
tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium chloride, tetraheptylammonium chloride, triphenylben-zylphosphonium chloride, tetrapentylammonium chloride, tributylallylphosphonium chloride, tributylbenzylphosphonium chloride, dibutyldiphyneylphosphonium chloride, tetrabutylphosphonium chloride and tributyl(2-methoxy)propylphosphonium chloride, phenyltrimethylammonium chloride, tetrapropylammonium bromide, tetraheptylammonium bromide, tetramethylphosphonium chloride, tetramethylammonium chloride, tetraphenylphosponium chloride, tetraphenylarsonium chloride, tetraphenylstibonium chloride, benzyltris (dimethylamino) phoisphonium chloride, bis (benzyldiphenylphosphine) iminium chloride compounds and mixtures thereof.
Acid acceptors can be inorganic or organic compounds. Organic acid acceptors include sodium stearate, magnesium oxalate, and benzotriazoate. However, acid acceptors are generally inorganic bases and include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, etc.
The catalysts may also include amine compounds other than the pendant amine used in the substantially non-fluorinated polymer having pendant amine groups. Representative classes of useful amine compounds include aliphatic, aryl and amidine amine compounds. Preferably the amine compound is a secondary or tertiary amine compound. Examples of these include 4-dimethyl amino pyridine, triisooctyl amine, 1,8-diazobicyclo(2,2,2)-octane, 1,5-diazobicyclo[4.3.0] non-5-ene, and 1,8-diazobicyclo[5.4.0]undec-7-ene, imidazole, benzotriazole, to name a few.
A useful class of amine compounds can be represented by the following formula:
The catalyst may be incorporated into either the blend component or the pendant amine-containing non-fluorinated polymer component. Preferably it is incorporated into the latter.
The composite articles in accordance with the invention may also include optional additives, such as those typically used in other thermoplastic applications. The optional additives are preferably selected from the group of a polymer, a pigment, a tackifier, a filler, electrically conductive materials (such as those described in U.S. Pat. No. 5,552,199), electrically insulative materials, a stabilizer, an antioxidant, a lubricant, a processing aid, an impact modifier, a viscosity modifier, and mixtures thereof.
Discussion of the Drawings
The present invention, and the orientation of the previously described components within those components, will be further understood by reference to the FIGURES.
Referring first to
First layer 12 comprises the blend component of the VDF-containing fluoropolymer and the substantially non-VDF containing fluoropolymer. The blend layer 12 is advantageous because it can provide a chemical barrier to the construction 10. Second layer 18 comprises the substantially non-fluorinated polymer having pendant amine groups.
Referring now to
Referring now to
In the constructions of
In any of these embodiments, the substantially non-VDF containing fluoropolymer used in the blend layer and the fluoropolymer used in the layer providing the barrier can be the same or different substantially non-VDF containing polymer, such as those described previously. Preferably, the non-VDF containing fluoropolymers are compatible with one another. Most preferably, they are the same or similar.
In any of the embodiments of the invention, the various layers are bonded to the adjacent layer or layers. Preferably they are intimately bonded to the adjacent layer or layers. As used herein, the term “intimately bonded” means that the components or layers are not easily physically separated without substantially destroying the composite or multi-layer article. Additionally, any of the embodiments contemplated by the invention can be provided in the form of a sheet or film regardless of the specific embodiment illustrated in the FIGS. Further, the order of the layer may be reversed in any of these embodiments. Determination of what comprises the inner and outer layers is influenced by where the barrier properties are desired.
Composite Article Formation
Methods known in the polymer art can be used to produce a composite article, such as a bonded multi-layer article, wherein the fluoropolymer blend component is in substantial, preferably intimate, contact with the substantially non-fluorinated polymeric material having pendant amine groups. For instance, the fluoropolymer blend component and the substantially non-fluorinated polymeric material having pendant amine groups can be formed by known methods into thin films or thicker sheets. These films or sheets can be laminated together under heat and/or pressure to form a bonded multilayer article. Alternatively, the fluoropolymer blend component and the substantially non-fluorinated polymer having pendant amine groups can be simultaneously co-extruded into a multi-layer article.
The formulation of the fluoropolymer blend component may also be accomplished during the formulation of the composite article. For instance, the non-vinylidene fluoride containing fluoropolymer and the VDF-containing fluoropolymer may be fed to and melt mixed by the same extruder being employed during the co-extrusion process.
In addition, all of these methods can be used to apply additional polymeric components or layers either before, during, or after the formation of the fluoropolymer blend component in contact with the component including the substantially non-fluorinated polymer having pendant amine groups. For instance, a component including a substantially non-vinylidene fluoride containing fluoropolymer can be applied to the fluoropolymer blend component and then a component including the substantially non-fluorinated polymer having pendant amine groups can be applied to the fluoropolymer blend layer opposite the component including a substantially non-vinylidene fluoride containing fluoropolymer. An optional component including a substantially non-fluorinated polymer can be applied adjacent to the component including the substantially non-fluorinated polymer having pendant amine groups opposite the blend component.
Conditions by which two or more components are brought together (e.g., sequential extrusion, co-extrusion or lamination, to name a few) may be sufficient to provide adequate adhesion between the components. However, it may be desirable to further treat the resulting composite article with, for example, heat and/or pressure to improve adhesion. One way to supply additional heat, for example, is to slow the rate of cooling after extrusion of the components. Also, additional heat or energy can be added during or after extrusion or lamination processes, wherein the temperatures may be higher than that required for merely processing the components. Further, the complete composite article may be held at an elevated temperature and/or pressure for an extended period of time, such as in an oven, an autoclave, a heated liquid path and the like. A combination of these methods can also be used.
The many advantages of a composite article in accordance with the invention are further illustrated in the following non-limiting examples in which all parts and percentages are given as parts and percentages by weight unless otherwise stated.
In the following Examples and Comparative Examples, various composites were prepared and the adhesion between the components, or layers, was evaluated.
The abbreviations for the materials used are defined according to the following schedule shown in Table 1.
a terpolymer of tetrafluoroethylene,
hexafluoropropylene, and vinylidene,
fluoride, commercially available from
Dyneon LLC, St. Paul, MN, under the
trade designation THV 50OG
an amine pendant polyamide 12,
commercially available from EMS Chemie
AG, Switzerland, under the trade
having pendant amine
designation GRILAMD FE 4943
polyamide 12, commercially available
from Huls America, Piscataway, NJ under
the trade designation Vestamid ™
a film made from perfluorinated ethylene-
propylene, commercially available from
a terpolymer of ethylene, tetrafluoroethylene
and hexafluoropropylene, commercially
available from Dyneon LLC, St. Paul,
MN, under the trade designation X6820
91% tetrafluoroethylene (TFE)-9%
(percent by weight);
Tm of 205° C.
POLYMER 2 was prepared by the method described in International Publication No. WO 96/18665 (Greuel). In particular, a 150 L vertically stirred polymerization reactor was charged with 120,000 g deionized water, 70 g KOH, 430 g K2HPO4, 694 g ammonium perfluorooctanoate, 1,023 g of a 20% solution of C4F9SO2Na in deionized water. The reactor was then alternately evacuated and purged with N2 until the level of 02 was less than about 50 ppm. The reactor was then evacuated, the temperature raised to about 71° C., and the agitation speed set about 210 rpm. Next, the reactor was charged with about 3929 g of TFE and about 79 g of propylene to give a pressure of about 15.2 bar (220 psig). The polymerization was initiated by feeding a 5% solution of (NH4)2S2O8 in deionized water to the reactor by means of a metering pump at approximately 25 g/minute until 1 equivalent of(NH4)2S2O8 was fed(about 3,200 g of solution). Upon the observation of a pressure drop, the running feed, which consisted of 91% TFE and 9% propylene, was started and continuously adjusted by the reactor's control system in order to maintain the desired pressure. The polymerization was halted by allowing agitation after 31,300 g of TFE and 3,080 g of propylene has been fed, 5 hours after start of running feed to give a calculated average reaction rate of 57 g/L-h. The reactor was then vented, cooled, and drained to isolate the latex. The resulting polymer was coagulated by adding HCl to the latex, granulated, washed six times with deionized water, and dried overnight in an oven at about 120° C.
In Example 1, 30 g of POLYMER 1 and 10 g of VDFP were blended using a RHEOMIX 600 internal bowl mixture equipped with roller blades, available from Haake Buchler Instruments Inc., set at a temperature of 230° C. and a mixer rotor setting of 50 rpm. The pellets of the two components were added to the mixing bowl and blended for ten minutes. The internal-bowl mixed compound, i.e., the blend, was then removed from the mixer and molded at 230° C. into a sheet approximately 0.0254 cm thick using a 0.0254 cm shim stock and a Wabash Hydraulic Press Co. heated platen press.
A composite was made with 1.25 cm by 5.0 cm samples of the blend sheet and a 2.54 cm by 7.62 cm by a 0.038 cm thick extruded sheet of POLYMER 1. A 1.25 cm by 5.0 cm by 0.0254 cm thick sheet of PA was placed on the other side of the blend sheet. Finally, a sheet of 2.54 cm×7.62 cm by 0.038 cm thick sheet of NF was placed next to the PA layer given a final structure of a layer of NF, a layer of PA, a layer of the blend, and finally a layer of POLYMER 1. Referring to
The adhesion between the layers was tested using ASTM D-1876, commonly known as a “T-peel” test. To facilitate testing via the T-peel test, a sheet of 0.00762 cm thick FEP film was placed between the POLYMER 1 layer 66 and the NF layer 68 along the edges of the shorter edges of the blend layer 62 and the amine modified polyamide layer 64 as the composite was pressed and heated. The FEP film did not adhere to either the POLYMER 1 layer 66and the NF layer 68 and was used only to create a POLYMER 1 “tab” and a NF “tab” to insert into the jaws of the test device.
Three identical composites were simultaneously heated under pressure using a Wabash Hydraulic Press Co. heated platen press at 230° C. and 686 kPa for 3 minutes. The samples were removed from the press and allowed to cool to room temperature. Peel strength or adhesion was measured on the samples in accordance with ASTM D 1876 (T-Peel test). An INSTRON Model 1125 tester, available from Instron Corp., set at a 100 mm/minute crosshead speed was used as the test drive. The peel strength was calculated as the average load measured during the peel test.
Comparative Example C1
In Comparative Example C1 a composite sample was prepared and tested as in Example 1, except that no PA layer was included between the blend layer and the NF layer.
Comparative Example C2
In Comparative Example C2 a composite sample was prepared and tested as in Example 1, except that no blend layer was used between the POLYMER 1 and the PA layer.
Examples 2 and 3 were done to evaluate a composite article of the invention where the dehydrofluorination of the VDF polymer included a catalyst.
In Example 2, 40 g of PA was further modified by the addition of 0.4 g of Dynamar™ FM 5166 catalyst, available from Dyncon LLC (St. Paul, Minn.), and 0.4 g calcium hydroxide powder using a RHEOMIX 600 internal blow mixer equipped with roller blades, available from Haake Buchler Instruments Inc., set at a temperature of 200° C. and a mixer rotor setting of 50 rpm. The PA pellets were first melted in the mixing bowl for approximately one minute followed by the phase transfer catalyst and calcium hydroxide, and the entire composition was mixed for an additional five minutes. The internal-bowl mixed catalyzed compound was then removed from the mixer and molded at 230° C. into a sheet approximately 0.0254 cm thick using a 0.0254 cm shim stock and a Wabash Hydraulic Press Co. heated platen press. After cooling, a composite was prepared and tested as in Example 1 except the PA layer was replaced by a 1.25 cm by 5.04 cm sheet of the above described internal-blow mixed catalyzed compound containing the phosphonium calcium hydroxide catalysts.
In Example 3, 40 g of PA was further modified by the addition of 0.2 g of 4-dimethyl amino pyridine (DMAP), available from Aldrich Chemical Co., Milwaukee, Wis., using a RHEOMIX 600 internal bowl mixer equipped with roller blades, available from Haake Buchler Instruments Inc., set at a temperature of 200° C. and a mixer rotor setting of 50 rpm. The PA pellets were first melted in the mixing bowl for approximately one minute followed by the DMAP, and the entire composition was mixed for an additional five minutes. The blend was then removed from the mixer and molded at 230° C. into a sheet approximately 0.0254 cm thick using a 0.0254 cm shim stock and a Wabash Hydraulic Press Co. heated platen press. After cooling, a composite was prepared and tested as in Example 1 except the PA layer was replaced by a 1.25 cm by 5.04 cm sheet of the above described internal-blow mixed catalyzed compound containing the DMAP catalyst.
In Example 4, samples were prepared and tested as in Example 1, except that the blend consisted of 36 g POLYMER 1 and 4 g VDFP.
In Example 5, samples were prepared and tested as in Example 1, except that the blend consisted of 20 g POLYMER 1 and 20 g VDFP.
In Example 6, samples were prepared and tested as in Example 1, except that the blend consisted of 10 g of POLYMER 1 and 30 g VDFP.
The tests results of Examples 1-6 and C1-C2 are set out in Table 2.
Peel Strength Value
NF layer cohesive failure
POLYMER 1/PA layers
In Example 7, 30 g of POLYMER 2 and 10 g of VDFP were blended using RHEOMIX 600 internal bowl mixer equipped with roller blades, available from Haake Buchler Instruments Inc., set at a temperature of 230° C. and a mixer rotor setting of 50 rpm. The pellets of the two components were added to the mixing bowl and blended for ten minutes. The blend was then removed from the mixer and molded at 230° C. into a sheet approximately 0.0254 cm thick using a 0.0254 cm shim stock and a Wabash Hydraulic Press Co. heated platen press.
A composite was made with 1.25 cm by 5.08 cm samples of the blend film and a 2.54 cm by 7.62 cm by 0.038 cm thick sheet of POLYMER 2. A 1.25 cm by 5.0 cm by 0.0254 cm thick sheet of PA, was placed on the other side of the blend sheet. Finally, a sheet of 2.54 cm×7.62 cm by 0.0381 cm thick NF was placed adjacent to the PA sheet, giving a final structure of a layer of NF, a layer of PA, a layer of blend, and finally the layer of POLYMER 2. This layered construction was similar to that shown in
Comparative Example 3
In Comparative Example 3, a sample was prepared as in Example 7, except that no POLYMER 2-VDFP fluoropolymer blend layer was used.
All Examples and Comparative Examples were tested as explained in Example 1 above. Results are reposted in Table 1. Peel Strength Values are shown and the layer interface which separated during testing is also reported.
The test results of Examples 7 and C3 are shown in Table 3.
Peel Strength Value
POLYMER 2/PA layers
It is evident from the above examples and comparative examples that a composition consisting of a blend of substantially non-VDF containing fluoropolymer and a VDF containing fluoropolymer may be used to give improved adhesion of the substantially non-VDF containing fluoropolymer to a pendant amine containing non-fluorinated polymeric material.
The complete disclosures of all patents, patent applications, and publications are incorporated herein by reference as if individually incorporated. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth herein.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2993875 *||27 Jun 1957||25 Jul 1961||Union Carbide Corp||Coloring polychlorotrifluoroethylene with a color masterbatch of a copolymer of trifluorochloroethylene and vinylidene fluoride and composition thereof|
|US3190178||29 Jun 1961||22 Jun 1965||Minnesota Mining & Mfg||Reflex-reflecting sheeting|
|US3348312||24 Oct 1966||24 Oct 1967||John Jones||Corner guide system|
|US3551025||28 Mar 1969||29 Dec 1970||Minnesota Mining & Mfg||Highly flexible reflex reflecting constructions|
|US3655727||16 Jan 1970||11 Apr 1972||Minnesota Mining & Mfg||Curing systems for vinylidine fluoride elastomers|
|US3686143||22 Mar 1971||22 Aug 1972||Du Pont||Guanidine and amidine accelerators for vulcanization of fluoroelastomers|
|US3712877||6 Jul 1971||23 Jan 1973||Minnesota Mining & Mfg||Curable vinylidene fluoride elastomers containing phosphonium curing agents|
|US3765932 *||24 Mar 1972||16 Oct 1973||Kureha Chemical Ind Co Ltd||Method for anti-corrosive coating|
|US3857807||6 Nov 1972||31 Dec 1974||Daikin Ind Ltd||Fluoroelastomer composition|
|US3876654||28 Feb 1972||8 Apr 1975||Du Pont||Fluoroelastomer composition|
|US3933732||14 May 1974||20 Jan 1976||E. I. Du Pont De Nemours And Company||Fluoroelastomer composition and curing process|
|US3960825 *||15 Oct 1973||1 Jun 1976||Pennwalt Corporation||High-modulus thermoplastic ethylene-tetrafluoroethylene hexafluoropropene terpolymers|
|US3962373 *||21 Oct 1974||8 Jun 1976||Allied Chemical Corporation||Compositions of 3,3,3-trifluoro-2-trifluoromethyl propene/vinylidene fluoride copolymer and polytetrafluoroethylene|
|US4017344 *||23 May 1975||12 Apr 1977||Harold Lorber||Magnetically enhanced coaxial cable with improved time delay characteristics|
|US4025159||17 Feb 1976||24 May 1977||Minnesota Mining And Manufacturing Company||Cellular retroreflective sheeting|
|US4233421||26 Feb 1979||11 Nov 1980||Minnesota Mining And Manufacturing Company||Fluoroelastomer composition containing sulfonium curing agents|
|US4252859 *||31 Oct 1978||24 Feb 1981||E. I. Du Pont De Nemours And Company||Fluoropolymer blend coating compositions containing copolymers of perfluorinated polyvinyl ether|
|US4259463||8 Dec 1978||31 Mar 1981||Montedison S.P.A.||Vulcanizable compositions based on copolymers of vinylidene fluoride and containing vulcanization accelerators which are aminophosphinic compounds|
|US4335238||6 Oct 1980||15 Jun 1982||E. I. Du Pont De Nemours And Company||Fluoropolymer hexafluoropropene, tetrafluorethene and 1,1-difluoroethene|
|US4347487 *||25 Nov 1980||31 Aug 1982||Raychem Corporation||High frequency attenuation cable|
|US4423192 *||16 Jun 1982||27 Dec 1983||Pcuk Produits Chimiques Ugine Kuhlmann||Lubricated thermoplastic compositions of polyvinylidene fluoride|
|US4501858||21 Mar 1984||26 Feb 1985||Montedison S.P.A.||Accelerators for vulcanizing vinylidene fluoride elastomeric copolymers|
|US4673715||27 Aug 1986||16 Jun 1987||E. I. Du Pont De Nemours And Company||Fluoroelastomer composition containing accelerator|
|US4711811 *||22 Oct 1986||8 Dec 1987||E. I. Du Pont De Nemours And Company||Thin wall cover on foamed insulation on wire|
|US4724092 *||7 Nov 1985||9 Feb 1988||Daikin Industries Ltd.||Fluorine-containing grease composition|
|US4748208||5 Jun 1987||31 May 1988||Asahi Kasei Kogyo Kabushiki Kaisha||Curable elastomer composition|
|US4749752 *||24 Mar 1986||7 Jun 1988||Shanghai Institute Of Organic Chemistry Academia Sinica||Fluoropolymer alloys|
|US4833212||4 Feb 1988||23 May 1989||Nippon Mektron Limited||Fluorine-containing elastomer composition|
|US4882390||15 Feb 1989||21 Nov 1989||Minnesota Mining And Manufacturing Company||Fluoroelastomer composition with organo-onium compounds|
|US4896943||13 May 1987||30 Jan 1990||Minnesota Mining And Manufacturing Company||Encapsulated-lens retroreflective sheeting having improved cover film|
|US4912171||17 Aug 1989||27 Mar 1990||Minnesota Mining And Manufacturing Company||Fluoroelastomer curing process with phosphonium compound|
|US4933060||4 Feb 1988||12 Jun 1990||The Standard Oil Company||Surface modification of fluoropolymers by reactive gas plasmas|
|US4933090||28 Dec 1988||12 Jun 1990||Calgon Corporation||Method for controlling silica/silicate deposition in aqueous systems using phosphonates and carboxylic/sulfonic polymers|
|US4935467 *||11 Mar 1988||19 Jun 1990||Raychem Corporation||Polymeric blends|
|US4960624||29 Apr 1988||2 Oct 1990||Sumitomo Electric Industries, Ltd.||Fluoroelastomer composition and heat shrinkable articles comprising same|
|US5047287||27 Dec 1988||10 Sep 1991||Toyoda Gosei Co., Ltd.||Diaphragm|
|US5066098||19 Feb 1991||19 Nov 1991||Minnesota Mining And Manufacturing Company||Cellular encapsulated-lens high whiteness retroreflective sheeting with flexible cover sheet|
|US5069964||22 Feb 1991||3 Dec 1991||Minnesota Mining And Manufacturing Company||Flexible, substrate-insular retroreflective sheeting|
|US5086123||28 Nov 1990||4 Feb 1992||Minnesota Mining And Manufacturing Company||Fluoroelastomer compositions containing fluoroaliphatic sulfonamides as curing agents|
|US5170011||25 Sep 1991||8 Dec 1992||Teleflex Incorporated||Hose assembly|
|US5262490||24 Aug 1992||16 Nov 1993||Minnesota Mining And Manufacturing Company||Fluoroelastomer composition with organo-onium compounds|
|US5284184||16 Oct 1992||8 Feb 1994||Itt Corporation||Corrugated multi-layer tubing having at least one fluoroplastic layer|
|US5383087||11 Jun 1992||17 Jan 1995||Itt Corporation||Multi-layer fuel and vapor tube|
|US5472783 *||29 Nov 1993||5 Dec 1995||Sermatech International, Inc.||Coated article|
|US5552199||2 Sep 1994||3 Sep 1996||Minnesota Mining And Manufacturing Company||Melt-processable electroconductive fluoroplastic|
|US5626930||22 Feb 1996||6 May 1997||Minnesota Mining And Manufacturing Company||Multi-layer compositions having a fluoroplastic layer|
|US5651121||18 Dec 1992||22 Jul 1997||Xerox Corporation||Using mask operand obtained from composite operand to perform logic operation in parallel with composite operand|
|US5658670||17 Aug 1995||19 Aug 1997||Minnesota Mining And Manufactury Company||Multi-layer compositions having a fluoropolymer layer|
|US5718957 *||9 Sep 1994||17 Feb 1998||Tokai Rubber Industries, Ltd.||Fuel hose|
|US5741855 *||10 Jun 1996||21 Apr 1998||Raychem Corporation||Compatibilized fluoroplastic blends|
|US5763068 *||21 Mar 1996||9 Jun 1998||Canon Kabushiki Kaisha||Fluororesin-coated member, production method therefor and heat fixing device using the coated member|
|US5798158 *||25 Oct 1995||25 Aug 1998||Toyoda Gosei Co., Ltd.||Layered molding including fluoroplastic layer crosslinked with rubber layer|
|US5942201 *||1 Feb 1993||24 Aug 1999||Kronos, Inc.||Process utilizing titanium dioxide as a catalyst for the hydrolysis of carbonyl sulfide|
|US6790912 *||11 Dec 2001||14 Sep 2004||3M Innovative Properties Company||Extrudable fluoropolymer blends|
|EP0185590A2||12 Dec 1985||25 Jun 1986||Shin-Etsu Chemical Co., Ltd.||A method for the preparation of a laminated film|
|EP0523644A1||15 Jul 1992||20 Jan 1993||Central Glass Company, Limited||Plastic laminate having polyamide resin surface layer and fluororesin surface layer|
|EP0551094A1||5 Jan 1993||14 Jul 1993||Pilot Industries, Inc.||Fluoropolymer composite tube and method of preparation|
|WO1993001493A1||1 Jul 1992||21 Jan 1993||Marposs Societa' Per Azioni||Apparatus for checking surface features of conical parts|
|WO1995011464A2||20 Oct 1994||27 Apr 1995||Minnesota Mining And Manufacturing Company||Ultra-flexible retroreflective cube corner composite sheetings and methods of manufacture|
|WO1995011466A1||20 Oct 1994||27 Apr 1995||Minnesota Mining And Manufacturing Company||Flexible cube-corner retroreflective sheeting|
|WO1995011943A1||27 Oct 1994||4 May 1995||Western Mining Corporation Limited||Pigment extenders|
|WO1996018665A1||6 Nov 1995||20 Jun 1996||Minnesota Mining And Manufacturing Company||Fluorine-containing polymers and preparation thereof|
|1||"Elastomers, Synthetic (Fluorinated)", Encyclopedia of Chemical Technology, 3rd Edition, vol. 8, 1979, pp. 500-515.|
|2||"Elastomers, Synthetic (Fluorocarbon)", Encyclopedia of Chemical Technology, 4th Edition, vol. 8, pp. 99-1005.|
|3||"Fluorine Compounds, Organic", Encyclopedia of Chemical Technology, 3rd Edition, vol. 11, 1980, pp. 20-21, 32-33, 40-41, 50, 52, 62, 70-71.|
|4||ASTM D 1556, Standard Terminology Relating to Rubber, pp. 306-316, Jan. 1996.|
|5||ASTM D 1876, Standard Test Method for Peel Resistance of Adhesives (T-Peel Test)<SUP>1</SUP>, Jan. 1995.|
|6||Billmeyer, Jr., "Fluorine-Containing Polymers", Textbook of Polymer Science, 3rd Edition, John Wiley & Sons, pp. 398-406, Jan. 1984.|
|7||Brullo, "Fluoroelastomer rubber for automotive", Automotive Elastomers & Design, Jun. 1985.|
|8||Brullo, "Fluoroelastomers Seals Up Automotive Future", ME , Oct. 1988, pp. 36-40.|
|9||*||Concise Encyclopedia of Polymer Science and Engineering, Kroschwitz (ed.), p. 1167, Oct. 1990.|
|10||*||Encyclopedia of Polymer Science and Engineering, vol. 1: Additives, Aug. 1985.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US8356638 *||25 Jun 2008||22 Jan 2013||Nissan Motor Co., Ltd.||Multi-layer hose|
|US8685493||1 Jun 2012||1 Apr 2014||E I Du Pont De Nemours And Company||Process for forming a non-stick surface on the interior surface of a pipe|
|US20090000685 *||25 Jun 2008||1 Jan 2009||Nissan Motor Co., Ltd.||Multi-layer hose|
|US20100043905 *||27 Oct 2009||25 Feb 2010||E. I. Du Pont De Nemours And Company||Lined Pipes for Conveying Chemicals|
|WO2014113202A1 *||26 Dec 2013||24 Jul 2014||Agc Chemicals Americas, Inc.||A layered tube for a hose assembly|
|U.S. Classification||428/36.91, 428/212, 525/199, 428/422, 525/200, 428/412, 428/421, 428/411.1|
|International Classification||B32B27/34, B32B27/28, C08L27/12, B32B27/00, B32B27/30, B32B27/38, B32B1/08|
|Cooperative Classification||Y10T428/3154, Y10T428/31507, Y10T428/31544, Y10T428/31504, Y10T428/24942, B32B1/08, Y10T428/1393, B32B27/30, B32B27/28|
|European Classification||B32B27/30, B32B1/08, B32B27/28|
|26 Jan 2007||AS||Assignment|
Owner name: 3M INNOVATIVE PROPERTIES COMPANY, MINNESOTA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DYNEON LLC;REEL/FRAME:018810/0159
Effective date: 20070125
|22 Sep 2011||FPAY||Fee payment|
Year of fee payment: 12