Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the present invention relates to ethylene copolymers. This invention particularly relates to fluorine-containing ethylene copolymers and products made therefrom. Description of the Related Art
• Fluoropolymer compositions are widely used for surface modification, as agents to impart desirable surface properties to various types of surfaces.
• fluoropolymer compositions can impart or enhance the water and oil repellency of certain surfaces, including fabrics and upholstery.
• surface treatment using fluoropolymers can involve complex processing steps to ensure that the fluoropolymer is applied and bonded to the surface being treated. The process can be difficult and expensive. Organic solvent vapors can be released to the atmosphere during the processing. Surface treatment can involve high temperature curing of the fluoropolymer to the substrate surface.
• fluorochemicals or fluoropolymers can be dissolved or dispersed either in organic solvents or in water.
• fluorinated copolymers mainly comprising perfluoroalkyl methacrylate, and vinyl copolymers are disclosed in U.S. Pat. No. 3,277,039.
• U.S. Pat. No. 2,803,615 discloses acrylate/methacrylate esters of N-alkyl or N-alkanol perfluoroalkanesulfona ides used to impart grease and oil repellency.
• Fluorochemical compositions for treating textile fibers and fabrics comprising an aqueous solution or dispersion of a fluorochemical acrylate and a polyalkoxylated polyurethane having pendant perfluoroalkyl groups is described in U.S. Pat. No. 5,350,557.
• U.S. Pat. No. 5,536,304 describes a composition for imparting water and oil repellency comprising a fluoroaliphatic radical containing agent, and a cyclic carboxylic acid anhydride-containing polysiloxane.
• Fluorochemicals can be melt-blended with thermoplastic polymers, and thereby impart water and oil repellency to the polymer by migrating to the polymer surface as described in, for example, U.S. Pat.
• thermoplastic compositions comprising fluoroaliphatic radical containing aminoalcohols and a thermoplastic synthetic organic polymer.
• Ethylene copolymers are useful polymeric materials in many applications. Ethylene copolymers can find use in applications such as packaging, laminate films, and adhesives for example.
• Conventional polyolefins such as polypropylene, polyethylene, and conventional ethylene copolymers have high surface tension relative to fluoropolymers such as polytetrafluoroethylene, for example.
• fluoropolymers such as polytetrafluoroethylene, for example.
• articles made from polyolefins must be treated to attain a satisfactory level of repellency.
• treatment of polyolefins with fluorochemicals or fluoropolymers is, in general, much more difficult than treating other thermoplastic polymers.
• Copolymers of ethylene and fluorine-containing monomers are known.
• Tefzel® manufactured by E.I DuPont de Nemours and Company
• Copolymers of this type are very different from conventional polyethylene copolymers in many aspects.
• fluorine- containing ethylene copolymers are typically melt- processable only at much higher temperature than conventional ethylene polymers and ethylene copolymers, and the properties of fluorine-containing ethylene copolymers differ form conventional ethylene copolymers.
• Copolymers of this type are not amenable to manufacture or processing under the type of conditions used to manufacture and process conventional ethylene copolymers.
• Ethylene/fluoromonomer copolymers of this type are not compatible in systems that currently use polyethylene copolymers.
• known conventional ethylene/tetrafluoroethylene copolymers have no adhesion to polyethylene.
• the present invention is a fluorine containing ethylene copolymer obtained by the copolymerization of ethylene with suitable fluorine- containing comonomer compounds, comprising: from about 0.5 wt% to about 40 wt% of a fluorine-containing comonomer compound and from about 30 wt% to about 99.5 wt% ethylene.
• the present invention is a melt- processable ethylene copolymer blend
• a fluorine containing ethylene copolymer obtained by the copolymerization of ethylene with suitable fluorine- containing comonomer compounds wherein the fluorine- containing comonomer compound is present at a concentration of up to 40% by weight, based on the total weight of the ethylene copolymer, and wherein the blend comprises from about 5 to about 95%, by weight, fluorine-containing ethylene copolymer based on the total weight of the blend.
• the present invention is an article of manufacture, including a molded part, a blown film, a woven or a non-woven fiber, or a multilayer composite film, comprising a fluorine containing ethylene copolymer obtained by the copolymerization of ethylene with at least one suitable fluorine-containing comonomer compound, wherein the fluorine-containing comonomer compound is present at a concentration of up to 40% by weight, based on the total weight of the ethylene copolymer.
• the present invention is a fluorine-containing ethylene copolymer.
• Ethylene copolymers of the present invention include up to about 40% by weight, based on the total weight of the copolymer (wt%) , of a suitable fluorine-containing monomer.
• the fluorine-containing comonomer is from about 2 to about 30 wt% of the copolymer. More preferably, the fluorine-containing comonomer is from about 10 to about 25 wt% of the copolymer.
• the copolymer comprises from about 30 wt% to about 99.5 wt% ethylene comonomer.
• the copolymer comprises from about 40 wt% to about 95 wt% ethylene comonomer, more preferably from about 50 wt% to about 90 wt% ethylene comonomer, and most preferably from about 70 wt% to about 90 wt% ethylene comonomer.
• the copolymer can optionally comprise other comonomers.
• a copolymer, as the term is used herein, is a polymer obtained by the polymerization of at least two comonomers.
• a comonomer is any monomer that is polymerized in the presence of at least one other monomer to produce a copolymer of the present invention.
• a copolymer can be the product of polymerization of two, three, four, or five comonomers, or more. Where the concentration of all but one of the comonomers is specified, the concentration of the remaining comonomer can be deduced by subtraction of the known constituents from 100 wt%, that is, the total wt% of the copolymer.
• Cf is a fluorinated aliphatic group having at least 4 carbon atoms wherein the aliphatic group can be: straight chain or branched; acyclic or cyclic; and can include heteroatoms such as nitrogen, oxygen, and/or sulfur. It is preferable that Cf is a perfluorinated aliphatic group of the formula C n F 2n + ⁇ , wherein n is an integer from 3 to 20;
• L is a linking group that connects the fluorinated aliphatic group with the
• L can contain from 1 to 10 carbon atoms, and can optionally include oxygen, nitrogen, or sulfur-containing groups, or combinations thereof; L can be straight-chain or branched, cyclic alkylene, arylene, arylalkylene, sulfonyl, sulfoxy, sulfonamide, carboxyamino, carbonyloxy, urethanylene, or combinations thereof.
• Mixtures or physical combinations of comonomers described by the general formulas above are contemplated to be within the scope of the present invention.
• non- acrylic fluoroalkyl monomers can be used in the practice of the present invention, particularly when using transition metal catalysts.
• Copolymers of the present invention can be prepared by conventional methods for polymerization or copolymerization of polyethylene polymers and copolymers.
• copolymers of the present invention can be prepared by copolymerization of ethylene with fluorine containing comonomers described herein by high pressure free radical polymerization or, alternatively, by using low pressure transition metal catalysis. Using high pressure free radical polymerization is preferred herein.
• Conventional methods for preparing ethylene copolymers are described in patented literature and reference textbooks. For example, an ethylene copolymerization process is described in U.S. Pat. No. 4,351,931.
• Copolymers of the present invention are melt- processable polymers and can be processed by methods used with conventional ethylene copolymers.
• copolymers of the present invention can be molded, extruded, blown, or spun to yield molded parts, fibers, or films, for example, in the same manner as conventional polyethylene polymers and copolymers.
• polymers of the present invention have low surface tension.
• Copolymers and copolymer blends of the present invention have surface tensions of less than those of conventional polyethylene and/or polypropylene polymers and copolymers.
• Copolymers (including blends) of the present invention have surface tensions of less than about 32 dyne/cm.
• the surface tension is less than about 28 dyne/cm, and more preferably less than about 24 dyne/cm.
• the present invention is a terpolymer comprising in addition to the above comonomers, from about 0.5 wt% to about 5 wt% of a terpolymer X, wherein X is a reactive functional comonomer.
• X can be glycidyl methacrylate, aleic anhydride, or a half-ester of maleic anhydride and/or derivatives thereof.
• the terpolymer includes from about 1 wt% to about 4.5 wt% of X, more preferably from about 1.5 wt% to about 4 wt% of X. Most preferably the terpolymer comprises from about 2 wt% to about 4 wt% of X.
• the present invention is a terpolymer comprising, in addition to the ethylene and fluoroalkyl comonomers described hereinabove, from about 0.5 wt% to about 50 wt% of a terpolymer Y, wherein Y is a vinyl acetate or an acrylate comonomer, such as methyl acrylate and butyl acrylate.
• Y is included in an amount of from about 2 wt% to about 45 wt%, and more preferably from about 5 wt% to about 40 wt%. Most preferably, Y is included in an amount of from about 5 wt% to about 35 wt%.
• Y is a vinyl acetate monomer.
• the present invention is a terpolymer comprising, in addition to the ethylene and fluoroalkyl comonomers described hereinabove, from about 1.0 to about 20 wt% of a terpolymer Z, wherein Z is acrylic acid or methacrylic acid comonomer.
• Z is included in an amount of from about 1.5 wt% to about 18 wt%, and more preferably from about 2.5 wt% to about 17 wt%.
• Z is included in an amount of from about 3 wt% to about 15 wt%.
• the present invention is a fluorine-containing ethylene copolymer comprising, in addition to at least 40 wt% ethylene and from 0.5 wt% to about 40 wt% fluoroalkyl comonomer, any combination of at least two comonomers selected from the group consisting of X, Y, and Z in a total amount of from about 0.5 wt% to about 59.5 wt%.
• the two comonomers are present in a total amount of from about 2 wt% to about 50 wt%, more preferably in an amount of from about 5 wt% to about 45 wt%, and most preferably in an amount of from about 7 wt% to about 40 wt%.
• the combination includes Y.
• the present invention is a composite film that includes at least one layer of an ethylene/fluoroalkyl copolymer of the present invention.
• a composite film of the present invention can be obtained in the same manner as composite films comprising conventional polyethylene polymer or copolymer layers with other polymer layers.
• U. S. Pat. No. 3,589,976 describes a process suitable for making the composite films of polystyrene polyolefins made by a coextrusion process.
• Composite films of the present invention can include laminate composite films, with or without adhesive layers.
• the present invention is a composite fiber that includes at least one component of an ethylene/fluoroalkyl copolymer of the present invention.
• a composite fiber of the present invention can be obtained in the same manner as composite fibers comprising conventional polymers.
• 3,329,557 describes a preparation of composite fibers of nylon and poly (ethylene terephalate) for making antistatic filaments.
• Copolymers of the present invention can be used alone or in blends with other polymers, for example, thermoplastic materials and thermoplastic elastomers.
• Polymers suitable for blending with copolymers of the present invention include, for example: polyamides, polyethylene terephthalate, polyurethane, polystyrene, polyethylene, ethylene copolymers, and polypropylene.
• Blends of the present invention include from about 1 wt% to about 99 wt% of the fluorine containing ethylene copolymer of the present invention.
• blends of the present invention comprise from about 5 wt% to about 95 wt% of the fluorine-containing ethylene copolymer, more preferably from about 10 wt% to about 90 wt% , and most preferably from about 20 wt% to about 80 wt%.
• Copolymers can be used in a process for making films or in a process for making woven or non- woven fibers, for example.
• EXAMPLES The following examples are merely illustrations of the present invention, and not intended to limit the scope of the present invention in any way. Testing
• MI Melt Index
• IC Chromatography IC Chromatography
• compositions of ethylene/perfluoroalkyl (meth) acrylate copolymers were measured and calculated by fluorine content alone.
• Compositions that include vinyl acetate and methyl acrylate were measured by a combination of fluorine content analysis and infrared spectroscopy (IR) .
• Ethylene copolymers listed in Table 1 were prepared according to the following procedures. Ethylene was copolymerized in the presence of fluoroalkyl (meth) acrylate monomers. The free radical polymerizations were carried out at high pressure (27,000 psi) and a temperatures ranging from 160°C to 250°C, in the presence of a peroxide free radical initiator.
• Example CI is not an example of the present invention, and is a copolymer of ethylene and methacrylic acid, prepared under the same conditions as the examples of the present invention.
• Example 1 is a terpolymer of ethylene, methacrylic acid, and Zonyl® TA-N
• Examples 2-6, Example 9 and Examples 11-19 are copolymers of ethylene and either Zonyl® TA-N or Zonyl® TM.
• Examples 7 and 8 are terpolymers of ethylene, vinyl acetate, and Zonyl® TM.
• Example 10 is a terpolymer of ethylene, methyl acrylate and Zonyl® TM. It is an amorphous polymer without a melting point.
• the blends of fluorine-containing copolymers, Examples 20-26, are listed in Table 2. The blends were prepared in a 30 mm twin screw extruder.
• Example C2 is not an example of this invention, and is a low density polyethylene with a MI of 4.4 and a melting point of 115 °C.
• Examples 20-21 and Examples 23-24 are blends of LDPE described in C2, and either Zonyl® TM or Zonyl® TA-N.
• Example 22 is a blend of PP and Zonyl® TM.
• the PP is a polypropylene with a MI of 1.5 and a melting point of 166 °C.
• Examples 25-26 are blends of HDPE and Zonyl® TA-N.
• the HDPE is a high-density polyethylene with a MI of 0.6 and a melting point of 139 °C.
• Zonyl® TA-N and Zonyl® TM are both available from E.I. DuPont de Nemours and Company.
• Zonyl® TM is a perfluoroalkylethyl methacrylate of the general formula:

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2002
  • 2002-03-07 CA CA002438317A patent/CA2438317A1/en not_active Abandoned
  • 2002-03-07 WO PCT/US2002/007058 patent/WO2002072648A2/en not_active Ceased
  • 2002-03-07 EP EP02709804A patent/EP1366092B1/en not_active Expired - Lifetime
  • 2002-03-07 DE DE60211315T patent/DE60211315T2/de not_active Expired - Fee Related
  • 2002-03-07 JP JP2002571556A patent/JP2004527610A/ja not_active Withdrawn
  • 2002-03-07 US US10/469,293 patent/US6953830B2/en not_active Expired - Fee Related

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