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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
  • B05D7/57—Three layers or more the last layer being a clear coat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0209—Multistage baking
• • 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
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/08—Butenes
  • C08F210/10—Isobutene
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  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
• • C—CHEMISTRY; METALLURGY
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  • 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
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
• • 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
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
  • C08F291/04—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to halogen-containing macromolecules
• • 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
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
  • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
  • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
  • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
  • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
  • C08G18/8074—Lactams
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C09D123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C09D123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
  • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
  • B05D3/065—After-treatment
  • B05D3/067—Curing or cross-linking the coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/53—Base coat plus clear coat type
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2150/00—Compositions for coatings
  • C08G2150/20—Compositions for powder coatings

Definitions

• the present invention relates generally to fluoropolymers and thermosetting compositions containing fluoropolymers . More specifically, the present invention is directed to fluoropolymers containing functional groups and thermosetting compositions that contain functional fluoropolymers .
• Coatings derived from compositions containing fluoropolymers typically provide good chemical resistance, weather resistance, and heat resistance. Due to these properties, interest in using fluoropolymer-based paints has •increased in various areas.
• fluoropolymer-containing paints are used as weather resistant paints in the areas of architecture, automobile, and chemical engineering.
• the fluoropolymers used in such paints typically include a- fluorocarbon monomer, such as chlorotrifluoroethylene, tetrafluoroethylene, or vinylidene fluoride, and another monomer, such as a vinyl ester or a vinyl ether, usually added to increase the solubility of the resulting fluoropolymer .
• U.S. Patent No. 4,345,057 to Yamabe et al. discloses a fluoropolymer having improved curing properties. Coatings using the fluoropolymer reportedly have a glossy finish, good chemical resistance, and good weatherability. '; '
• the durability of a coating will depend- on obtaining an optimum balance of ' physical properties, ' such as the hardness and flexibility of a coating film.- Generally speaking, obtaining this optimum balance has been an elusive goal .
• Functional fluoropolymers are typically random cop ' olymers that include functional group-containing acrylic and/or methacrylic monomers. Such a functional fluoropolymer will contain a mixture of polymer molecules having varying individual functional equivalent weights and polymer chain ' structures. In such a copolymer,. the functional groups are located randomly along the polymer chain. Moreover, the number of functional groups is not divided equally among the polymer molecules, such that some polymer molecules may ' . actually be free of functionality.
• thermosetting composition the formation of a three-dimensional ' crosslinked network is dependent on. the functional equivalent weight as well as the architecture .of the individual polymer molecules that comprise it.
• Polymer • molecules having little or no reactive functionality (or having functional groups that are unlikely to participate in crosslinking reactions due to their locations along the .polymer chain) will contribute little or nothing to the formation of the three-dimensional- crosslinked network, • resulting in decreased crosslink density and less than optimum
• thermosetting compositions that are low cost, have a predictable polymer architecture and provide an optimum balance of film hardness and 1 flexibility in ' a durable coating.
• the present invention is directed to ⁇ a composition , ' that includes a fluorine-containing copolymer containing at ' least- 30 ol % of residues having the following alternating - structural unit:
• DM represents a residue from a donor monomer having the following structure (I):
• R 1 is linear or branched C x to C alkyl
• R 2 is selected from methyl, linear, cyclic or branched C x to C 2 o alkyl, alkenyl, aryl, alkaryl, and aralkyl
• AM represents an acceptor monomer.
• the copolymer contains . at least 5 wt.% fluorine .
• the present invention is also directed to a composition that includes the copolymer described above, -where the composition contains co-reactive functional groups. . non-limiting example of such a composition is a thermosetting composition.
• the present invention is also directed to a- substrate, ' where at least a portion of the substrate is coated ' with the thermosetting composition. '
• the present invention is -further directed to a thermosetting composition that . includes- the copolymer described above,, containing reactive functional groups and at least one other component • that, contains functional, groups that are reactive with the functional groups of the copolymer.
• the present invention is additionally directed to a substrate, where at least a portion of- the substrate is coated with the thermosetting composition.
• the present invention is still further directed to a multi-component composite 1 coating composition that includes a base coat deposited from a pigmented film-forming composition and a substantially pigment free top coat applied over ' at least a portion of the base coat.
• the base coat and/or the top coat include one of the thermosetting compositions described above.
• the present invention is also directed to substrates where at least a portion of the substrate is coated with the multi-component composite coating composition.
• copolymer composition is meant to include a synthesized copolymer, as well- as residues from initiators, catalysts, and ' other elements attendant to the synthesis of the . copolymer, but not covalently incorporated thereto. Such residues and other elements considered as part ' of the copolymer composition are typically mixed or co-mingled with the copolymer such that they tend to remain with the copolymer when it is transferred between •- vessels or between solvent or dispersion media.
• substantially- free is meant to indicate that a material is present as an incidental' impurity. In other words, the.
• donor monomer refers to monomers that have a polymerizable, ethylenically unsaturated ' group that has relatively high electron density in the ethylenic double bond
• acceptor monomer refers to monomers that have a polymerizable, ethylenically unsaturated group that has- relatively low electron density in the ethylenic double bond.
• a positive value for e indicates that a .monomer has - a relatively low electron density and is an acceptor monomer, as is the case for maleic anhydride, which has an e. value of 3.69.
• -A low or negative value for e indicates that a monomer has' a relatively high electron density and is a donor monomer, as is the case for vinyl ethyl ether, which has an e value of -1.80.
• a strong acceptor monomer is meant to ⁇ include those monomers with an.e value greater than 2.0.
• the term "mild .acceptor monomer" is meant to include those monomers with an e.
• the term “strong donor monomer” is meant to include those monomers with an e value of less- than -1.5
• the term “mild donor monomer” is meant to include those monomers with an e value of less than- 0.5 to those with an e value of -1.-5.
• fluorinated is used to describe a material, typically a . polymer or copolymer, ' that contains fluorine atoms. '
• the present invention is directed to a composition that includes a fluorine-containing copolymer.
• the copolymer - includes at least 30 mol.%, in many cases at least 40 mol %, typically at least 50 mol %, in some cases at least 60 mol %, and in other cases at least 75 mol % of residues of the copolymer derived from alternating sequences of donor monomer - acceptor monomer pairs having the alternating monomer residue units of structure: . * .
• the copolymer may be a 100% alternating copolymer of DM and AM. More particularly, at least 15 mol % of the copolymer comprises a donor monomer, which is an isobutylene-type monomer, having - the following structure (I) :
• R 1 is linear or branched Ci to C 4 alkyl
• .R 2 is one or more of methyl, linear, cyclic, or branched C ⁇ to C 2 o alkyl, alkenyl, aryl, alkaryl, and aralkyl. Further, at least 15 mol % of the copolymer includes an -acceptor monomer.
• the - group R 2 may . include one or more functional groups selected from epoxy,- -carboxylic acid, hydroxy, thiol, isocyanate, capped isocyanate, amide, amine, aceto acetate, methylol, methylol ether, oxazoline carbamate, and beta-hydroxyalkylamide-.
• the copolymer .contains - at least 5 wt.% fluorine, in some cases at least 10 wt.% fluorine . and in other cases at least 15 wt.% ' fluorine, and up. to 50 wt.% fluorine, in some . cases up to 40 wt.% fluorine, . in- other cases up to 35 wt.% fluorine and in some situations up to 30 wt.% fluorine.
• the copolymer may contain fluorine in any range of values inclusive of those stated above.
• the copolymer incorporates a substantial portion - ' of alternating residues of a mild donor monomer as described by structure I and a mild acceptor monomer.
• The. acceptor monomer will include vinyl monomers having fluoro and/or chloro substituents and may include acrylic acceptor monomers.
• the present composition includes the aforementioned structural unit -[DM-AM]- in the fluorine- containing copolymer, in which the structural unit may " specifically include the following structural units (II) :
• R and R are as defined above; R is a group that includes one or both of chlorine and fluorine; and R 4 and R 5 are independently selected from H, Cl, and F.
• R is a group that includes one or both of chlorine and fluorine; and R 4 and R 5 are independently selected from H, Cl, and F.
• Any suitable donor monomer may be used in the present invention.
• Suitable donor monomers that may be used include strong donor monomers and mild donor monomers .
• the present invention is particularly useful. for preparing alternating copolymers where a mild donor molecule is. used.
• the present copolymers will include a mild donor monomer described by structure I, such as isobutylene and diisobutylene, dipentene,' isoprenol and 1-octene-, .and may additionally include other suitable mild donor monomers.
• the mild donor monomer of structure I is present in the copolymer composition at a level of at least 15 mol %, in some cases at least 25 mol %, ' typically at least 30 mol % and in some cases at least 35 mol %.
• the mild donor monomer of structure I is present in the copolymer composition at a level of up to 50 mol %, in some cases up to 47.5 mol %, typically up to ' 45 mol %, . and, in some cases, up to 40 mol %.
• ⁇ the mild donor monomer of structure I used is determined by the properties that. are to be incorporated into the copolymer ' composition. Residues from the mild donor monomer ' of structure I may be present in the copolymer composition in any range of values inclusive of those stated above.
• Suitable other donor monomers that may be used in the present invention include, but are not limited to, ethylene,. butene, styrene, substituted styrenes, methyl styrene, substituted styrenes, vinyl ethers, vinyl esters ' , vinyl pyridines, divinyl benzene, vinyl naphthalene, and divinyl- naphthalene.
• Vinyl esters include vinyl esters of carboxylic acids, which include, but are. not limited to, vinyl acetate, vinyl butyrate, vinyl 3, 4-dimethoxybenzoate,- and •vinyl benzoate.
• the use of other donor monomers is optional; when other donor monomers -are- present, they are present at a- level of at least 0.01 mol % of the copolymer composition, often at least 0.1 mol %, typically at least 1 mol %, and, in some cases, at least 2 mol %.
• the other donor monomers may be present at up to 25 mol %, in some cases up to 20 mol %, typically up to 10 mol %, and, in some cases, -up to 5 mol %.
• the level of other donor monomers used is determined by the properties that are to.be incorporated into the- copolymer composition. Residues from the other donor monomers may be present in the copolymer composition in any range of values inclusive of those stated above.
• the copolymer composition includes acceptor monomers as part of the alternating donor .monomer - acceptor monomer units along the copolymer chain.
• Suitable acceptor monomers include strong acceptor • monomers and mild acceptor monomers.
• a non-limiting class of suitable acceptor monomers are those described by the structure (III) :
• R 4 is selected from the group consisting of H, poly (ethylene oxide), poly (propylene oxide), linear or branched Cx to C 2 o alkyl, alkylol, aryl and aralkyl, linear or branched Qi to C 20 fluoroalkyl, fluoroaryl and fluoroaralkyl, - a siloxane radical, a polysiloxane radical, an alkyl ' siloxane radical, an ethoxylated trimethylsilyl siloxane radical, and a propoxylated trimethylsilyl siloxane.
• a class of mild acceptor monomers that may be included in the present copolymer composition are acrylic acceptor monomers. Suitable acrylic acceptor -monomers include those described by structure (IV) :
• R 3 is selected from the group consisting of H,. linear or branched Ci to C 20 alkyl, and linear or branched ' Ci to C 20 ' alkylol;
• R 4' is selected from the group . consisting of H, poly (ethylene oxide), poly (propylene oxide), linear, cyclic, or branched C ' ⁇ to C 20 alkyl, alkylol, aryl and - aralkyl, linear or branched Ci- to C 2 o.
• R s is a divalent linear or branched Ci to C 20 ' alkyl linking group.
• acrylic acceptor monomers • are those described by structure IV, ' where Y includes at least one functional group of epoxy, carboxylic acid, : hydroxy, thiol, isocyanate, capped isocyanate, amide, amine, aceto acetate, methylol, methylol ether, oxazoline carbamate, and/or beta-hydroxyalkylamide. - 5 ,
• acceptor monomers include, but - are not limited to, chlorotrifluoroethylene, tetrafluoroethylene, trifluproethylene, difluoroethylene, vinyl fluoride, hexafluoropropylene, and mixtures thereof, and : optionally further selected from acrylic acid, acrylic acid esters, acryla ide, N-alkyl substituted acrylamide ' s , acrylonitrile, ' hydroxyethyl acrylate, hydroxyprppyl acrylate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylat , isobutyl acrylate, isobornyl acrylate, dimethylaminoethyl acrylate, .acrylamide, perfluoro methyl ethyl acrylate, perfluoro ethyl ethyl acrylate, perfluoro butyl ethyl acrylate, trifluoromethyl benzyl acrylate,
• the acrylic acceptor monomers are present in the copolymer composition at a level of at least 15 mol %, in . some cases at least 25 mol ' %, typically at least 30 mol %, and, ' in some cases,- at least 35 mol %.
• the acrylic acceptor, monomers of structure III are present in the copolymer ' composition at a level of up to 50 mol %, in some cases up to 47.5 mol %, typically up to 45 -mol % ' , and,- . in some cases, up to 40 mol .% .
• the level and type of acceptor monomers used is determined by the properties that are ' to be incorporated into the copolymer composition. Residues from the acceptor monomers may be present in the copolymer composition in any range of values inclusive of those stated above.. [0034] Suitable other mild acceptor monomers that may be
• • used in the present invention include, but are. not limited to, acrylonitrile, methacryl ' onitrile, crotonic acid, .vinyl alkyl sulfonates, and acrolein.
• the use of other mild acceptor monomers is optional; when other mild acceptor monomers are. present, they are present at a level of at. least 0.01 mol % of the copolymer. composition, often at least 0.1 mol %,' typically at least 1 mol %, and, in some cases, at least 2 mol %.
• the other acceptor monomers may be present at up to 35 mol %, in some cases up to 25 mol %, typically up to 15 mol %, and, in some cases, up to 10 mol %.
• the level of other acceptor monomers used is determined by the properties that are to be incorporated into the copolymer composition. Residues from .
• the other acceptor monomers may be present in the copolymer composition in any range- of values inclusive of those stated above .
• the present copolymer has a molecular weight of at least 250, in many cases.at least 500, ' typically at least 1,000, and, in some cases, ' at least 2,000.
• the present copolymer may have a molecular weight of up to 1,000,000, in many cases up o 500,000, typically up to 10.0,000, ' and, in ' .some cases, up to 50,000.
• Certain applications will require that the molecular weight of the present copolymer • ot exceed 30,000, in some cases not exceed 25,000, in other cases not exceed 20,000, and,, in certain instances, not exceed 16,000.
• the molecular weight 'of the copolymer is selected based on .
• the polydispersity index (PDI) of the present copolymer is not always critical.
• the polydispersity index of the copolymer. is usually less than 4, in many cases less than - 3.5, typically less than 3, and, in some cases, less than 2.5.
• polydispersity index is determined from the following equation: (weight average, molecular weight (Mw) /number average molecular weight (Mn) ) .
• a monodisperse polymer has a PDI of 1.0.
• Mn and Mw. are determined from gel permeation chromatography using polystyrene standards.
• the copolymer. composition of the present invention may have all of the incorporated monomer residues in an alternating architecture.
• a non-limiting example of a . copolymer segment having 100% alternating architecture of • diisobutylene (DIIB) and hexafluoropropylene (HFP) is shown by structure V: (V) -HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-DIIB-HFP-
• the present copolymer will contain alternating segments and random segments as shown by structure VI, a copolymer, of DIIB, HFP, and other monomers, M:
• Structure VI shows an embodiment of the present invention where the copolymer may- include alternating segments as shown in the boxes and random segments .as shown by the underlined segments.
• the random segment ' s of the copolymer may contain donor, or acceptor monomer residues that have not been incorporated into the copolymer composition by way of an alternating architecture.
• the random segments of the copolymer composition may further include residues from other ethylenically unsaturated monomers.
• ⁇ all references to--polymer segments derived from alternating sequences of donor monomer - acceptor monomer pairs are meant to include segments of monomer residues such as those shown by the boxes in structure VI.
• the other ethylenically unsaturated monomers include .any suitable monomer not traditionally categorized as being an acceptor monomer or a donor monomer.. ' ⁇ [0042]
• the other ethylenically unsaturated monomers, residue of monomer M of structure VI, is derived from at least one ethylenically unsaturated, radically polymerizable monomer.
• ethylenically unsaturated, radically polymerizable monomer are meant to include vinyl monomers, allylic monomers, olefins, and other ethylenically unsaturated monomers that are radically polymerizable and not classified ' as donor monomers or acceptor monomers .
• Classes of vinyl monomers from which M may be derived include, but are not limited to, monomer residues derived from monomers of t a VII:
• R 11 , R 12 , and R 14 are independently selected from the group consisting of H, CF 3 , straight or branched ' alkyl of 1 to 20 carbon atoms, aryl, unsaturated straight or branched alkenyl or alkynyl of 2 t ⁇ 10 carbon atoms, unsaturated straight or branched alkenyl of 2 to 6 carbon atoms substituted with a halogen, C 3 -C 8 cycloalkyl, heterocyclyl and phenyl;
• R 13 is selected from the group ..consisting of H, Ci ⁇ -Cg -linear, cyclic, or branched alkyl, COOR 18 , ' wherein R 18 is selected from the group consisting of H, an alkali metal, a Ci to C 6 alkyl group, glycidyl, and aryl.
• methacrylate .propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, and 3, 3, 5-trimethylcyclohexyl methacrylate, as well as functional ' methacrylates, such as hydroxyalkyl methacrylates, oxirane functional methacrylates, and carboxylic ' acid functional methacrylates.
• functional ' methacrylates such as hydroxyalkyl methacrylates, oxirane functional methacrylates, and carboxylic ' acid functional methacrylates.
• Residue of monomer M may also be selected from monomers having more than one methacrylate group, for example, methacrylic anhydride and diethyleneglycol bis (methacrylate) .
• methacrylic anhydride for example, methacrylic anhydride and diethyleneglycol bis (methacrylate) .
• allylic . monomer (s) what is meant is monomers containing substituted and/or unsubstituted allylic functionality, i.e., one or more ' radicals represented by the following general formula VIII,
• allylic monomers include, but are not limited to, (meth)allyl alcohol; .(meth)allyl ethers, such as methyl (meth) allyl ' ether; allyl esters of carboxylic acids, such as ⁇ (meth) allyl acetate, (meth) allyl butyrate, (meth) allyl . 3, 4-dimethoxybenzoate, and (meth) allyl benzoate.
• the present alternating copolymer is prepared by a method including the steps of (a) providing a, donor monomer composition comprising one or more donor ' monomers of structure I; (b) mixing an ethylenically unsaturated monomer composition comprising one or more acceptor monomers with, (a) to form a total monomer composition; and (c) polymerizing the total monomer composition in the presence ' of a free radical initiator.
• the monomer of structure I is present at a molar excess based on the amount of acceptor monomer.
• any amount of excess monomer of structure I may be used in the present invention in order to encourage the formation of the desired alternating- architecture.
• the excess amount of monomer- of structure I may ' be at least 10 mol %, in some cases up to 25 mol %, typically up to 50 mol %, and, in some cases, up to 100 mol % based on the amount of acrylic acceptor monomer.
• the process may not be economical on a commercial scale.
• the level ' of the monomer used is determined by the -properties that are to be incorporated into the copolymer composition.
• the ethylenically unsaturated monomer composition . . of the present method may include other donor monomers as • described above, as well as other monomers designated by M and described above.
• the use of other mild acceptor monomers is optional in the presen method. When other mild acceptor monomers are present, they are present a a level of at least 0.01 mol . % of the copolymer composition, .often at least 0.1 mol %, typically at least 1 mol %, and, in some cases, at least 2.mol % of the total monomer composition.
• the other acceptor monomers may be present at up to 35 mol %, in some . cases up. to 25 mol %, typically up to 15 mol %, and, in some cases, up to 10 mol % of the total monomer composition.
• the - level of other acceptor monomers used herein is determined by the properties that are to be incorporated into the copolymer composition. Residues from the other acceptor monomers may be present in the copolymer composition in any range of values . inclusive of those stated above.
• the use of other monomers, -M is optional ' in the present method.
• they are present at a level of at least 0.01 mol % of the copolymer' composition, often at least 0.1 mol %, typically at least 1 mol %, and, in some cases, at least 2 mol-%.
• the other, monomers may be present at up to 35 ' mol %, in some cases up to 25 mol %, typically up to- 15 mol %, and, in some cases, up to 10 mol %.
• the - level of other monomers used herein is determined by the properties that .are to be incorporated into , the copolymer composition.
• Residues from the other monomers, M may be present in the copolymer composition in any range of • values inclusive of those stated above.
• an excess of monomer of structure I is used, and the unreacted monomer of structure I is removed from the resulting copolymer composition by evaporation.- -The removal o.f unreacted monomer is typically facilitated by the application of a vacuum to the reaction vessel.
• any. suitable free radical' initiator may be used -in the present invention.
• suitable free , radical initiators include, but are not limited to, thermal free radical initiators, photo-initiators, and redox initiators.
• suitable thermal free radical initiators include, but are not limited to, peroxide compounds, azo compounds, and persulfate compounds.
• Suitable peroxide compound ' initiators include, but are not limited to, hydrogen peroxide, methyl ethyl ketone peroxides, benzoyl peroxides, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide,, diacyl peroxides, decanoyl peroxides, lauroyl peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, and mixtures thereof.
• Suitable azo compounds include, but are not limited to, 4-4' -azobis (4-cyanovaleric acid), 1-1' -azobiscyclohexanecarbonitrile) , ' 2-2' -azobisisobutyronitrile, 2-2' -azobis (2- methylpropionamidine) dihydrochloride, 2-2' -azobis (2- methylbutyronitrile) , 2-2' -azobis (propionitrile) , 2-2' -azobis (2, 4-dimethylvaleronitril.e) , 2-2' -azobis (valeronitrile) , 2,2' -azobis [2-methyl-N- (2- hydroxyethyl)propionamide]', 4,.4' -azobis (4-cyanopentanoic acid), 2, 2 '-azobis (N,N' -dimethyleneisobutyramidine) , ' 2,2 ' -azobis (2-amidinopropane)
• the ethylenically unsaturated monomer composition and the free radical polymerization initiator are separately and ⁇ simultaneously added to and mixed with the donor monomer composition.
• the ethylenically unsaturated monomer composition and the free ' radical polymerization initiator may be added to the donor monomer composition over a period of at least 15 minutes, in some cases at least 20, minutes, typically at least 30 minutes, and, in some cases ' , at least 1 hour.
• the ethylenically unsaturated monomer composition and the free radical polymerization initiator may further be added to the donor monomer composition o er a period of up to 24 hours, in ' some case up to 18 hours, typically up to 12 hours, and, in some cases, up to 8 hours.
• the time- for adding the ethylenically unsaturated monomer must be sufficient to maintai -a suitable excess of donor monomer of structure I over unreacted acrylic acceptor monomer to encourage the formation of donor monomer - acceptor monomer alternating segments.
• the addition time is not so long as to render the process economically unfeasible on a commercial scale.
• the addition time may vary. in any range o values inclusive of those stated above. .
• the present polymerization method can be run at any suitable temperature.
• Suitable temperature for the present method may be ambient, at least ' 50°C, in many cases at least 60°C, typically at least 75°C, and, in some cases, at least 100°C.
• Suitable' temperature for the present method may further be described as being up to 300°C, in many cases up to 275°C, typically up to 250°C, and, in some cases, up to 225°C.
• the temperature is typically high enough to encourage good reactivity from the monomers and initiators employed. However, the volatility of ⁇ the monomers and corresponding partial pressures create . a • practical upper limit on ' temperature determined by the pressure rating of the reaction vessel.
• the polymerization temperature may vary in any range of values inclusive of those stated above.
• the present polymerization method can be run at any suitable pressure.
• a suitable pressure for the present- method may be ambient, at least 1 psi, in many cases at least 5 psi,- typically at least 15 " psi, and, in some cases, at least 20 psi.
• Suitable pressures , for the present method may further be described as ' being- up to 200 psi, in' many cases up to - 175 psi, typically up to 150 psi, and, in. some cases, up to 125 psi.
• the pressure is typically high enough to maintain the monomers and . initiators in a liquid phase.
• the pressures employed have a practical upper limit based on the pressure rating of the reaction vessel employed.
• the pressure during polymerization temperature may vary in any range of values
• copolymer that results from the present method ' may be utilized as a starting material for the preparation of other polymers by using functional group transformations by methods known in the art.
• Functional groups that can be introduced by these methods are epoxy, carboxylic acid, • hydroxy, thiol, isocyanate, capped isocyanate, amide, amine, aceto acetate, methylol, methylol ether, oxazoline carbamate, and beta-hydroxyalkylamide .
• a copolymer of the present method comprising methyl acrylate will contain carbomethoxy groups .
• the carbomethoxy groups can be hydrolyzed to carboxyl groups or transesterified with an alcohol to form the corresponding ester of the alcohol.
• ammonia the aforementioned methyl acrylate copolymer can be converted to an amide or, ' using a primary or secondary amine, can.be converted to the corresponding N-substituted amide.
• a diamine such as ethylene diamine, one can convert the aforementioned copolymer of the present method to an N-aminoethylamide- or, with ethanolamine, to an N-hydroxyethylamide .
• the N-aminoethylamide f ⁇ nctionality can be further converted to an oxazoline by dehydration.
• the N-aminoethylamide can be further reacted with a carbonate such as ' propylene carbonate to produce the corresponding urethane functional copolymer.
• These transformations can be carried out to convert all of the carbomethoxy groups or can be carried out in part, leaving some of the . carbomethoxy groups intact. - -
• Epoxy groups can be introduced -into the copolymer- ' of the present method directly by using glycidyl acrylate in ' • the copolymer preparation or indirectly by functional ' group ' - transformation.
• One example of an indirect method is to oxidize residual unsaturati ⁇ n in-, the copolymer to epoxy groups using a peracid such as peroxyacetic acid.
• the resulting epoxy-functional copolymer can be further reacted with the appropriate. active hydrogen containing reagents to form alcohols, amines, or sulfides.
• Hydroxyl groups can be introduced directly using a hydroxyl-functional monomer such as hydroxyethyl acrylate in the copolymer of the present, method, or they can be introduced by functional group transformation.
• a hydroxyl-functional monomer such as hydroxyethyl acrylate in the copolymer of the present, method
• they can be introduced by functional group transformation.
• an epoxy By treating the carboxyl-functional copolymer described above with an epoxy, one can produce a hydroxyl functional polymer.
• Suitable epoxies include, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, and glycidyl neodecanoate.
• the above-described hydroxyl functional copolymers can be further reacted to form other copolymers. .
• a copolymer containing hydroxyethyl groups can be treated with a carbamylating agent, such as methyl carbamate, to produce the corresponding carbamate functional copolymer.
• carbamylating agent such as methyl carbamate
• the hydroxyl groups can also be converted to acetoacetate esters .
• Isocyanate functional copolymers ' can also be produced. Copolymers of .the present method, ' which contain 2 or more hydroxyl groups , can be treated with a diisocyanate such as isophoronediisocyanate to produce isocyanate- functiona-1 polymers. Primary amine functional copolymers, described above, can be phosgenated to produce isocyanate ' functionality.
• the composition - contains co-reactive functional groups .
• the composition is a ' thermosetting composition.
• the composition includes the above described alternating ⁇ copolymer and at least one other component.
• The. copolymer contains reactive functional groups and the other component contains functional groups that are reactive with the functional groups of the copolymer.
• the functional groups of the copolymer are one or more selected from epoxy,. carboxylic acid, hydroxy, thiol, isocyanate, capped isocyanate, amide, amine, aceto acetate, methylol, methylol ether, oxazoline carbamate, and beta-hydroxyalkylamide
• the functional groups, of the other component are selected from epoxy, carboxylic acid, hydroxy, thiol, amide, amine, ' oxazoline, ' aceto acetate, methylol,. methylol ether, .isocyanate, capped isocyanate, beta hydroxyalkamide and carbamate.
• the functional group equivalent weight of the copolymer is from 100 to 5,000 grams/equivalent and the functional group equivalent weight of the other material is from 50 to ' 5,000 grams/equivalent..
• the thermosetting composition may include additional fluorinated polymers.
• the additional fluorinated, polymers may include functional groups selected from epoxy, carboxylic acid, hydroxy, thiol, isocyanate-, capped isocyanate, amide, amine, aceto acetate, methylol, methylol ether, oxazoline carbamate, and beta-hydroxyalkylamide, which are reactive with the functional groups of the other component described above.
• the -additional fluorinated polymers may be those described in U.S. Patent No. 4,34-5,057 to Yamabe et al., which is herein incorporated by reference.
• the additional fluorinated polymers that may be used are the LUMIFLON polymers available from Asahi Glass Company, Ltd., Tokyo, Japan.
• the additional fluorinated ⁇ polymers may include one or more curable fluorocopolymers that include from 40 to 60 mol % of fluoroolefin units, from 5 to 45 mol % of cyclohexyl vinyl ether units, from' 5 to 45 mol % o ' f- alkyl vinyl ether units, and from 3 to 15, mol % of hydroxyalkyl vinyl ether units.
• any suitable fluoroolefin ' monomers may be used to make the additional curable fluorocopolymers.
• Suitable fluoroolefins that may be used include, but are not limited to, chlorotrifluoroethylene, tetrafluoroethylene, trifluoroethylene, difluoroethylene . , hexafluoropropylene and vinyl, fluoride. [0069] .
• the molar or equivalent ratio of functional groups in the present alternating copolymer and, optionally, the additional curable fluorocopolymers with the functional groups in the at least one other component is from 0.7:1 to 2:1.
• a particular embodiment of the present invention is directed to a liquid thermosetting composition that includes an ungelled copolymer composition that includes the present fluorine-containing copolymer containing functional groups and, optionally, the additional curable fluorocopolymers with functional groups and a' crosslinking agent having at least two functional groups that are - reactive with the functional groups of the copolymer as the at least one other component.
• the functional groups in the fluorinated copolymer are any suitable functional groups as indicated above.
• The- crosslinking agent will have suitable functional groups that will react with the ' functional groups in the copolymer.
• Suitable functional groups for the crosslinking agent include, but are not limited to, epoxy, carboxylic acid, hydroxy, thiol, amide, amine, oxazoline, - aceto -acetate, methylol, methylol ether, isocyanate, capped isocyanate, beta hydroxyalkamide, and carbamate.
• the equivalent ratio of functional • groups of the cros.slinking agent to functional equivalents in the fluorinated functional copolymer is typically within the range of 1:3 to 3:1.
• the crosslinking agent is present in the liquid thermosetting composition in an amount of. from 1 to 45 percent by weight, based, on total weight of resin solids, and the fluorinated. functional copolymer is present in an amount . of from 55 to 99 -percent by weight, based on total weight of • resin solids.
• a non-limiting example of the present liquid thermosetting composition is one where the functional group of the fluorinated copolymer is hydroxy and the functional group - of the crosslinking agent is a capped polyisocyanate, where the capping group of the capped polyisocyanate crosslinking agent is one or more of hydroxy functional compounds,- lH-azoles, lactams, ketoximes, and mixtures thereof.
• the capping group may be phenol, p-hydroxy methylbenzoate, 1H-1,2, 4-triazole, 1H-2, 5-dimethyl pyrazole, 2-propanone oxime, 2-butanone oxime, cyclohexanone oxime, e-caprolactam, or mixtures thereof.
• the polyisocyanate of- the capped polyisocyanate crosslinking agent is one or more of 1 , 6-hexamethylene diisocyanate, cyclohexane diisocyanate, ⁇ , ⁇ ' -xylylene diisocyanate, ⁇ , ⁇ , ' , ⁇ ' -tetramethylxylylene diisocyanate, l-i.socyanato-3, 3, 5-trimethyl-5- isocyanatomethylcyclohexane, diis ⁇ cyanato-dicyclohexylmethane, dimers of the polyisocyanates, or trimers of the polyisocyanates .
• the fluorinated copolymer When the fluorinated copolymer has hydroxy - functionality,- it will typically have a hydroxy equivalent weight of from 100 to 10,000 grams/equivalent . ' The equivalent ratio of isocyanate equivalents in the capped polyisocyanate crosslinking agent to hydroxy equivalents in the hydroxy functional fluorinated copolymer is typically within the range of 1:3 to 3:1. In this, embodiment, the capped polyisocyanate • • crosslinking agent is present in the liquid thermosetting composition in an amount of from 1 to 45 percent by weight, based on total weight of resin solids, and the hydroxy functional fluorinated copolymer is present in an amount of from 55 to 99 percent by weight, based on total weight of. resin solids.
• the present liquid thermosetting composition is one where the fluorinated copolymer has epoxy -functional- groups and the crosslinking agent is a. carboxylic acid functional compound having from- 4 • to 20 carbon atoms.
• the carboxylic acid crosslinking agent may be one or more of. dodecanedioic acid, azelaic acid, adipic acid, 1, 6-hexanedioic acid, succinic acid, pimelic acid, sebacic acid, maleic acid, citric acid, itaconic -acid, or aconitic acid.
• a further non-limiting example of the present liquid thermosetting composition is one where the fluorinated copolymer has carboxylic acid functional groups and the crosslinking agent is a beta-hydroxyalkylamide compound.
• the liquid thermosetting composition may further include a second polycarboxylic acid functional material selected from the group consisting of C 4 to C 2 o aliphatic carboxylic acids, polymeric polyanhydrides, polyesters, polyurethanes, and mixtures thereof.
• the beta-hydroxyalkylamide may be represented by the following structure IX:
• E is a chemical bond or monovalent or polyvalent organic radical derived from saturated, unsaturated, or aromatic hydrocarbon radicals including ' substituted hydrocarbon radicals containin from 2 to.20 carbon atoms ' ; m is 1 of 2; n is from ' 0 to 2; and m+n is at least 2.
• the liquid thermosetting composition of the present invention is preferably used as a film-forming, (coating) composition and may contain adjunct ingredients conventionally used in such compositions.
• Optional ingredients such as, for example, plasticizers, -surfactants, thixotropic agents/ anti-gassing agents, organic cosolvents, flow controllers, anti-oxidahts, UV light absorbers and similar additives conventional in the art, may be included in the composition. These ingredients are typically present at up to about.40% by weight based on the total weigh of resin solids.
• the liquid thermosetting composition of the present invention may be waterborne, but is usually solventborne.
• Suitable solvent carriers include the various esters, ethers, and aromatic solvents, including mixtures thereof, that are known in the art of coating formulation.
• the composition typically has a total solids content of about 40 to about 80 percent by weight.
• the liquid thermosetting compositions of the present invention will often have a VOC content of less than 4 percent by weight, typically less than 3.5 percent by weight and many times less. than 3 percent by weight.
• the liquid thermosetting composition of the present invention may contain color pigments conventionally- used in surface coatings and may be used as a monocoat, that ' is, a pigmented coating.
• Suitable color pigments include, for example, inorganic pigments such as .titanium dioxide, iron ox ' ides, chromium oxide, lead chromate, 'and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. ' Mixtures of the. above mentioned - pigments may also be used.
• Suitable metallic pigments • include, in particular, aluminum flakes, copper bronze flakes, and metal oxide coated mica,' nickel flakes, tin flakes, and mixtures thereof.
• the pigment is. incorporated into the coating composition in amounts up to. about 80 percent by-- ⁇ weight based on the total weight of coating solids.
• the metallic pigment is employed in amounts of about 0.5 to about
• the present thermosetting composition is a co-reactable solid, particulate mixture, or powder of a reactant having at least two functional groups and a composition including the present fluorine-containing copolymer having functional groups, and, optionally, the additional curable fluorocopolymers with the functional groups.
• the reactant may have functional groups selected from epoxy, carboxylic acid, hydroxy, thiol, amide, amine, oxazoline-, aceto acetate, methylol, methylol ether, ' isocyanate, ' capped isocyanate, beta hydroxyalkamide, and carbamate.
• the functional' groups of the fluorine-containing copolymer are those indicated above.
• the fluorine-containing functional copolymer ' typically has a functional group equivalent weight of from 100 to 5,000 grams/equivalent and the equivalent ratio of reactant •
• - functional groups to functional copolymer functional groups is within the range of 1:3 to -3:1.
• the reactant is present in an amount of from 1 to 45 percent by weight, based
• the functional groups of the fluorinated--copolymer are hydroxy functional groups and the reactant is a capped polyisocyanate crosslinking agent.
• the capping group of the capped polyisocyanate crosslinking agent is one or more of hydroxy functional compounds, lH-azoles, lactams, and .ketoximes .
• the capping group is one or more of phenol, p-hydroxy methylbenzoate, 1H-1,2, 4-triazole, 1H-2, 5-dimethyl pyrazole, 2-propanone oxime, 2-butanone oxime, cyclohexanone oxime, and e-caprolactam.
• the polyisocyanate of the capped polyisocyanate crosslinking agent is one or more of 1, 6-hexamethylene diisocyanate, cyclohexane diisocyanate, ⁇ , ⁇ ' -xylylene diisocyanate, ⁇ , ⁇ , ⁇ ' , ⁇ ' -tetramethylxylylene diisocyanate,' l-isocyanato-3, 3, 5-trimethyl-5- isocyanatomethylcycl ' ohexane, 2, 4, 4-trimethyl hexamethylene ⁇ diisocyanate, 2, 2, 4-trimethyl hexamethylene diisocyanate, • diisocy ' anato-dicyclohexylmethane, dimers of said polyisocyanates, and trimers of the polyisocyanates.
• the fluorinated hydroxy functional copolymer typically has a hydroxy equivalent weight of from 100 to " 10,000 grams/equivalent and the equivalent ratio of isocyanate equivalents in the capped polyisocyanate crosslinking agent to hydroxy equivalents in the hydroxy functional copolymer- is within the range of 1:3 to 3:1.
• the capped polyisocyanate crosslinking agent is present in an amount of from 1 to 45 percent by weight, based on total weight of resin solids
• the hydroxy functional copolymer is -present in an amount of. from 55 to 99 percent by weight, based on total weight of resin solids.
• the functional groups of the fluorinated copolymer are epoxy functional groups and the reactant is a carboxylic functional reactant having from 4 to 20 carbon atoms.
• the carboxylic acid reactant is typically one or more . of dodecanedioic; acid, azelaic acid, adipic- acid, . 1, 6-hexanedioic acid, succinic acid, pimelic acid, sebacic acid, maleic acid, citric acid, itaconic acid, and aconitic acid.
• the functional groups of the fluorinated copolymer are carboxylic functional groups and the reactant is a beta-hydroxyalkylamide.
• the powder thermosetting composition may further include a second polycarboxylic acid, typically one or more of C to C 20 aliphatic carboxylic acids, polymeric polyanhydrides, polyesters, polyurethanes, and mixtures thereof.
• the beta-hydroxyalkylamide is typically one represented by structure IX as detailed above.
• the powder thermosetting composition of the present invention may also include one or more cure catalysts for catalyzing the reaction between the crosslinking agent and the functional copolymer.
• Classes of useful catalysts include metal compounds, in particular, organic tin compounds, and tertiary amines.
• organic tin compounds include,- but are not limited to, tin (II) salts- of carboxylic acids, e.g., tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate and tin (II) laurate; tin (IV) compounds, e.g., dibutyltin oxide, dibutyltin dichlofide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin .diacetate.
• tin (II) salts- of carboxylic acids e.g., tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate and tin (II) laurate
• Suitable tertiary amine catalysts include, but are not limited to, diazabicyclo [2.2.2] octane and 1, 5-diazabicyclo [4, 3, 0]non-5-ene.
• Preferred catalysts include tin (II) octanoate and dibutyltin (IV) dilaurate.
• the powder thermosetting composition of the present invention may also include pigments and fillers.
• pigments include, but are not limited to, inorganic pigments, e.g., titanium dioxide -and iron oxides; organic pigments, e.g., phthalocyanines, anthraquinones, quinacridones, and thioindigos; and carbon blacks-.
• Examples of- fillers include, but are . not limited to, silica, e.g., precipitated silicas, ' clay, and barium sulfate.
• pigments and fillers are typically present in amounts of from 0.1 percent to 70 . percent by weight, based • on total weight of the thermosetting composition. More often, the thermosetting composition- of the present invention is used as a clear composition being substantially free of pigments • and fillers .
• the powder thermosetting composition of the present ⁇ invention may optionally contain additives-- such as waxes for flow and wetting, flow control agents, e.g., poly (2-ethylhexyl) acrylate, degassing additives such as benzoin, adjuvant resin to modify and optimize coating' properties, ant ' ioxidants, and ultraviolet (UV) light • absorbers .
• additives-- such as waxes for flow and wetting, flow control agents, e.g., poly (2-ethylhexyl) acrylate, degassing additives such as benzoin, adjuvant resin to modify and optimize coating' properties, ant ' ioxidants, and ultraviolet (UV) light • absorbers .
• flow control agents e.g., poly (2-ethylhexyl) acrylate
• degassing additives such as benzoin
• adjuvant resin to modify and optimize coating' properties e.g., ant ' ioxidants,
• the powder thermosetting composition of the present invention is typically prepared by first dry blending the hydroxy functional polymer, the crosslinking agent, and additives, such as flow control agents, degassing agents and catalysts, in a blender, ' .e.g. , a Henshel blade blender.
• the blender is operated for a period of time sufficient to result in a homogenous dry blend of the materials charged thereto.
• the homogenous dry blend is then melt blended in an extruder, e.g., a twin screw co-rotating extruder, operated within a temperature range .of 80°C to 140°C, e.g., from 100°C to 125°C.
• the extrudate of the thermosetting composition of the present invention is cooled and, when used as a powder coating composition, is typically milled to an average particle size, of from, for example, 15 to' 30 microns.
• the present invention is also directed to a method of coating a substrate, which- includes the steps of: (A) applying a thermosetting ' composition to the substrate; '
• thermosetting composition coalescing the thermosetting composition to form a substantially continuous film
• thermosetting composition is typically, the liquid thermosetting composition or powder thermosetting composition described above.
• the thermosetting composition includes the copolymer composition of the present invention, which includes a functional fluorinated copolymer as previously described and . a crosslinkin agent having at least two functional groups that are reactive with the functional groups of the functional copolymer.
• thermosetting compositions described above can , be applied to various substrates to which they adhere, including wood; metals such as ferrous substrates and aluminum substrates; glass; plastic, and sheet molding ' compound based plastics.
• compositions can be applied by conventional means including brushing, dipping, flow coating, spraying, and the like, but they are most often, applied by spraying.
• the usual . spray techniques, and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used.
• - Substrates that may be coated by the -method of the present invention include, for example, wood, metal,- glass, and plastic.
• thermosetting composition of the present invention may be applied to the substrate by any appropriate means that are known to those of ordinary skill in the art.
• the ' thermosetting composition may be in the form of a dry powder or, alternatively, a liquid medium ' ..
• the thermosetting composition is • typically electrostatically applied.
• ' .Electrostatic spray application generally involves drawing the thermosetting composition from a fluidized bed and propelling it through a corona field.
• the particles of the thermosetting - composition become charged as they pass 'through the corona field and are attracted to and deposited upon the electrically conductive substrate, .which is grounded. As the charged particles begin to build up, the substrate becomes insulated, thus limiting further particle deposition.
• the substrate is typically preheated prior to application of the thermosetting composition.
• the preheated temperature of the substrate is equal to or greater than that of the melting point of the thermosetting composition, but less than its cure temperature.
• thermosetting composition With spray application over preheated substrates, film builds of the thermosetting composition in excess of 6 mils (150 microns) can be achieved, e.g., 10 to 20 mils (254 to 508 microns).
• the thermosetting composition is a liquid
• the composition is allowed to coalesce to form a substantially continuous film on the substrate.
• the film thickness will be about 0.01 to about 5 mils (about 0.254 to about 127 microns), preferably about 0.1 to about 2 mils (about 2.54 to about 50.8 microns) in thickness.
• the film is' formed on the surface of the substrate by driving solvent, ' i.e., organic solvent and/or water,, out of the film by heating or by an air drying period.
• the heating will only be for a short period of time, sufficient to- ensure that any subsequently applied coatings can be applied to the film without dissolving the composition.
• Suitable drying conditions will depend on the particular composition but, in general, a drying time of from about 1 to 5 minutes at a temperature, of about 68-250°F (20-121°C) will be adequate. More than one coat of the. composition may be applied to develop the • optimum appearance, Between coats, the previously applied coat may be flashed, that is, exposed to ambient conditions for about 1 to 20 minutes. [0106] After application to the substrate, the thermosetting composition is then coalesced to form a substantially continuous film.
• Coalescing of the applied composition is generally achieved through the application of heat at a temperature equal to or greater than that of the melting point of the composition, but less than its cure temperature. In -the- case of preheated substrates, the application and coalescing steps can be achieved in essentially one step. ⁇
• thermosetting composition is next cured by the application of heat.
• cured is meant a three-dimensional crosslink network formed by covalent bond formation, e.g., between the free isocyanate groups, of the crosslinking agent and the hydroxy groups .of the polymer.
• the temperature at which the thermosetting composition of the present invention cures is variable and depends in part on the type and amount of catalyst used.
• the thermosetting composition has a .cure temperature within the range of 130°C to 160°C, e.g., from 140°C to 150°C. - [0108]
• a.cure temperature within the range of 130°C to 160°C, e.g., from 140°C to 150°C. -
• multi-component composite coating composition that includes a base coat layer deposited from a pigmented film-forming composition; and a substantially pigment free top coat applied over at least a portion of the base coat.
• Either the base coat or .the top coat or both coats may include the liquid thermosetting composition or the powder thermosetting composition described above.
• the multi- component composite coating composition as described herein is commonly ' referred to as a color-plus-clear coating composition. .
• the pigmented film-forming composition from which the base coat is deposited can be any of the compositions useful in coatings applications, ' particularly automotive applications in which color-plus-clear coating compositions are extensively used.
• Pigmented film-forming compositions conventionally comprise a resinous binder and a pigment to act as a colorant.
• Particularly useful resinous binders are ⁇ acrylic polymers, polyesters including alkyds, polyufethanes, and the copolymer composition of the present invention.
• the resinous binders for the pigmented film-forming base coat composition can be organic solvent-based materials, such as those described in U.S. Patent No. 4,220,679, note column 2, line 24 through column . 4, line 40.
• water- ⁇ based coating compositions such as those described in U.S. Patent Nos. 4,403,003, 4,147,679, and 5, 071, 904 ' can be used as the binder in the pigmented film-forming composition.
• the pigmented film-forming base coat composition is colored and may also contain metallic pigments. Examples ' of suitable pigments can be found in U.S. Patent Nos. 4,220,679, 4,403,003, 4,147,679, and 5,071,904.
• Ingredients that may be optionally present in the pigmented film-forming base coat composition are those which are well known in the art of formulating surface coatings and include surfactants-, flow control agents, thixotropic agents, fillers, anti-gassing agents, organic co-solvents, . catalysts, and other customary auxiliaries. Examples of these optional materials and suitable amounts are described in the aforementioned. U.S. Patent Nos . 4,220,679, 4,403,003, . 4,147,679, and ' 5,071,904.
• the pigmented film-forming base coat composition- can be applied to the substrate by any of the conventional coating techniques, such as brushing, spraying, dipping, or flowing, but are most often applied by. spraying.
• the usual spray techniques and equipment for air spraying, airless -.spraying, and electrostatic spraying employing either manual or automatic methods can be used.
• the pigmented film-forming composition is applied in " an amount sufficient to provide a base coat having a film thickness typically of 0.1 to 5 mils (2.5 to 125 microns) and preferably 0.1 to 2 mils (2.5 to 50 microns) .
• the base coat can be cured or alternatively dried.
• organic solvent and/or water is driven out of the base coat film by heating or the passage of air over its surface. Suitable drying conditions will depend on the particular base coat composition used and on the ambient humidity in-' the case of certain water-based compositions. - In general, drying of the deposited .base coat is • performed over a period of from 1 to 15 minutes and at a temperature of 21°C to 93°C.
• the substantially pigment free top coat is applied over the deposited base coat by any of the methods by which coatings are known to be applied.
• the substantially pigment free top coat is - applied by electrostatic spray application as described previously herein.
• the two coatings can be co-cured to form the multi- component composite coating composition of the present invention.
• Both the base- coat and top coat are heated together to conjointly cure the two layers.
• curing conditions of 130°C to 160°C for a- period of 20 to 30 minutes are employed.
• the substantially pigment free top coat typically has a thickness within the .range of 0.5 to.6 mils - (13 to 150 microns), e.g., from 1 to 3 mils (25 to- 75 microns)
• Example 1-3 demonstrate the - synthesis of the present fluorinated alternating copolymer. ' The following ingredients were used in the polymerizations: - • •
• Example 4-6 Coating- compositions were prepared using the following ingredients:
• ExxonMobil Chemicals [0120] The resins were charged to a paint can and the ' various pigments were added in the order indicated with . mixing. The mixture was then added to a mixing mill and milled with a- zircoa- media until a Hegman grind of 7+ was obtained. This formed component one of a two-component composition.- Component two was prepared by adding the rest of the ingredients • in the order indicated to a. second vessel and mixing to form a homogeneous mixture. The two components were kept separate until immediately before application. [0121] The coating compositions were applied to. oth a galvanized steel substrate and an aluminum substrate as shown in the table below. The coatings were cured at the temperature and time indicated in the table.
• The. T-bend test was evaluated for loss of adhesion and for cracking after the coated panel was bent to varying degrees.
• the first number indicates the diameter of the bend is so many times the thickness of the steel panel. For example, a "3" indicates that the diameter- of the bend was three times the thickness of the steel panel before loss of adhesion was indicated.
• ' Loss of adhesion was -determined by pressing a ' piece of adhesive tape down onto the film surface and then quickly ripping the tape from the film.
• the second, number was a subjective number related to cracking. The , rating was assigned on a scale of 1 to 9. A score of 9 indicated no cracking and no film removal with -the tape, while a score of 0 indicated severe cracking and complete film removal by the tape.
• the pencil hardness is a measure of the resistance of the coating to a pencil indentor.
• the pencil, hardness ⁇ scale begins with 4B, which- indicates a relatively soft
• the scale reads as follows: 4B, 3B, 2B, B, HB, F, H, 2H, 3H up to 10H..
• the coating was indented with pencils of increasing hardness until. the pencil scratched or etched the surface.
• the reverse impact resistance was determined by subjecting the cured coatings to 60 inch-pounds of reverse

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