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WO1997048740A1 - Microspheres en polyolefine - Google Patents

Microspheres en polyolefine Download PDF

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Publication number
WO1997048740A1
WO1997048740A1 PCT/US1997/009269 US9709269W WO9748740A1 WO 1997048740 A1 WO1997048740 A1 WO 1997048740A1 US 9709269 W US9709269 W US 9709269W WO 9748740 A1 WO9748740 A1 WO 9748740A1
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WO
WIPO (PCT)
Prior art keywords
microspheres
alpha
polymer
olefin
catalyst
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PCT/US1997/009269
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English (en)
Inventor
Katherine A. Brown
Michael R. Kesti
Edward G. Stewart
Joseph M. Mcgrath
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Minnesota Mining And Manufacturing Company
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Filing date
Publication date
Priority claimed from US08/667,153 external-priority patent/US6368708B1/en
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to AU32907/97A priority Critical patent/AU3290797A/en
Publication of WO1997048740A1 publication Critical patent/WO1997048740A1/fr

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    • 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
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • This invention relates to polyolefin microspheres and methods of preparation therefor.
  • microsphere adhesives are prepared via suspension polymerization of one or more free-radically polymerizable monomers, usually acrylate or methacrylate monomers, in the presence of surfactants and/or suspension stabilizers. Suspension polymerization is particularly advantageous, since microspheres result directly from the polymerization process as opposed to post-polymerization suspension of an already-formed polymer.
  • Microsphere adhesives described to date comprise homopolymers or copolymers of acrylate or methacrylate monomers, presumably due to the ease with which such monomers can be suspension polymerized in aqueous systems.
  • the preparation of acrylate-based microsphere adhesives is described in, for instance, U. S. Patent Nos. 3,691,140, 4,166,152, and 5,053,436. Microsphere adhesives prepared from alpha-olefins have not been described.
  • Non-free radical polymerizations of ethylenically-unsaturated monomers are well known. Typically, these polymerizations use catalysts instead of initiators to effect polymerizations. Examples of such catalyzed polymerizations include Ziegler-Natta (ZN) polymerizations of alpha-olefins, ring-opening metathesis polymerizations (ROMP) of cyclic olefins, group-transfer polymerizations (GTP), and cationic and anionic polymerizations of activated olefins such as styrene or acrylate. More recently, metailocene catalysts have received considerable attention for polymerization of alpha-olefins.
  • ZN Ziegler-Natta
  • REP ring-opening metathesis polymerizations
  • GTP group-transfer polymerizations
  • cationic and anionic polymerizations of activated olefins such as styrene or acryl
  • ZN and metailocene catalysts for alpha-olefin polymerizations are susceptible to deactivation by adventitious oxygen and water, requiring that such deactivating materials be rigorously excluded from all reagents as well as the reaction vessel.
  • a polymerization catalyst whose cationic portion has the formula
  • LM-R + wherein M is a Group VIII metal, L is a ligand or ligands stabilizing the Group VIII metal, and R is H, a hydrocarbyl radical or a substituted hydrocarbyl radical, and a substituted tetraphenylborate anion as the counterion has been described in, e.g. European Patent Application No. 454231.
  • a preferred cationic portion has the formula
  • L' is a two-electron donor ligand and L" L" are chelating ligands wherein each L" is a neutral two-electron donor ligand, M is nickel or palladium and L is a two-electron donor ligand or the two L ligands together are a chelating ligand.
  • the present invention provides microspheres comprising a polymer including one or more of, 1) a plurality of C 3 or larger alpha-olefin units wherein the C 3 or larger alpha-olefin units are incorporated into the polymer so as to give an average number of less than one branch point per C 3 or larger alpha-olefin unit, 2) a plurality of C 2 alpha-olefin units wherein the C 2 alpha-olefin units are inco ⁇ orated so as to give an average number of branch points greater than 0.01 per C 2 alpha- olefin unit, preferably greater than 0.05, and more preferably greater that 0 10 per C 2 alpha-olefin unit, and 3) cyclopentene or substituted cyclopentene, said microspheres preferably having an average diameter in the range of 1 to 300 micrometers.
  • microspheres of the invention are prepared as the polymerization product of cyclopentene or one or more alpha-olefin hydrocarbon monomers having 2 to 30 carbon atoms, the polymerization being carried out in the presence of an effective amount of an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Pd, the catalyst further comprising a polydentate ligand providing steric bulk sufficient to permit formation of polymer, and at least one liquid reaction medium in which the polymer microspheres are essentially insoluble.
  • organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Pd
  • the catalyst further comprising a polydentate ligand providing steric bulk sufficient to permit formation of polymer, and at least one liquid reaction medium in which the polymer microspheres are essentially insoluble.
  • the invention describes a method of producing the microspheres, comprising admixing, in any order, alpha-olefin monomer(s) and cyclopentene, catalyst, and at least one liquid reaction medium in which the resultant polymer is insoluble, and allowing polymerization of the monomer(s) to take place
  • One variation of the method comprises dispersing into an aqueous medium, in any order, one or more of C 2 to C 3 o alpha-olefin monomers and cyclopentene, a polymerization organometallic catalyst comprising a Group VIII metal with which is complexed a polydentate ligand having steric bulk sufficient to permit formation of polymer, and optionally a surfactant or suspension stabilizer, and allowing the monomer(s) to polymerize, to produce polymer microspheres
  • a second variation of the method comprises admixing one or more of C 2 to C 30 alpha-olefin monomers and cyclopentene, a polymerization organometallic
  • the polymer M w of the microspheres is greater than 5000, preferably greater than 90,000, and most preferably greater than 100,000 up to about 5,000,000, preferably 2,000,000
  • the present invention provides microspheres comprising crosslinked polymers.
  • a method employing high- energy irradiation of the polymer, preferably by electron beam irradiation, is used in another embodiment, a method employing ultraviolet (UV) irradiation is used, the polymerized composition preferably further comprising UV-activated crosslinking agents.
  • UV ultraviolet
  • the present invention provides films, fibers, articles and coatings comprising microspheres comprising a polymer including one or more of 1) a plurality of C 3 or larger alpha-olefin units wherein the C 3 or larger alpha- olefin units are incorporated into the polymer so as to give an average number of less than one branch point per C 3 or larger alpha-olefin unit, 2) a plurality of C 2 alpha-olefin units wherein the C 2 alpha-olefin units are incorporated so as to give an average number of branch points greater than 0 01 per C 2 alpha-olefin unit, preferably greater than 0 05, and more preferably greater that 0 10 per C 2 alpha- olefin unit, and 3) cyclopentene or substituted cyclopentene, said microspheres preferably having an average diameter in the range of 1 to 300 micrometers Films, fibers, articles and coatings comprising the microspheres can be prepared by methods known in the art,
  • late metal means a metal of Group VIII (CAS version of the Periodic Table);
  • polymerization product means a polymer derived from an alpha-olefin monomer or cyclopentene by polymerization, and containing from 0 to 3 percent by weight of late metal;
  • alpha-olefin and “alpha-olefin hydrocarbon” are equivalent and mean a hydrocarbon containing a double bond in the 1 -position, more particularly, ethylene or a 1-olefin containing three or more carbon atoms wherein the carbon atoms numbered 3 or higher can be acyclic or cyclic, preferably acyclic, the term “alpha- olefin” and “alpha-olefin hydrocarbon” includes ethylene as used by those skilled in the art (see EP 0 765 888 A2 at page 5, lines 57-58, and page 6, lines 35-38);
  • alpha-olefin polymer means a polymer formed from at least one alpha olefin monomer which, not considering end groups, contains an average of two bonds connecting each monomer unit to other monomer units,
  • branch point means a C unit in the polymer backbone, bonded to three other carbon atoms, e.g ,
  • cyclopentene means unsubstituted and substituted cyclopentene wherein the substitutent is a linear, branched, or cyclic hydrocarbyl group having up to 10 carbon atoms
  • stereo bulk means a size large enough and a location in the ligand sufficient to physically block access to non-polymerizing sites on the metal
  • alpha-olefin unit means a group of carbon atoms in a polymer derived from polymerization of a single alpha-olefin molecule
  • cyclopentene unit means a group of carbon atoms in a polymer derived from polymerization of cyclopentene
  • high polymer means a species having a weight average molecular weight (M w ) greater than 5,000, preferably greater than 90,000, more preferably greater than 100,000, "poly” means two or more,
  • organometallic catalyst means a catalyst comprising a Group VIII metal, preferably one of Pd and Ni, more preferably Pd, a bidentate ligand having steric bulk sufficient to permit formation of polymers, and a metal to R bond, wherein R is Ff, a hydrocarbyl radical, or a hydrocarbyl radical substituted by at least one alkyl, haloalkyl or aryl group, each group having up to 20 carbon atoms,
  • group means a chemical species that allows for substitution or which may be substituted by conventional substituents that do not interfere with the desired product
  • insoluble means less than five parts polymer dissolves in one hundred parts by weight of solvent at about 23° C,
  • Me means methyl (CH 3 -)
  • i-Pr means isopropyl
  • gel fraction means the fraction by weight of polymer that is insoluble in an appropriate solvent, e.g., toluene, particularly after crosslinking
  • “hollow” means containing at least one void or cavity
  • “cavity” means a space within the walls of a droplet or microsphere that is suspended or dispersed in the polymerization reaction medium, the space containing a portion of the reaction medium, "void” means a space completely within the walls of polymerized microsphere,
  • droplet means the liquid stage of a microsphere prior to completion of polymerization; and “solid” means free of voids and/or cavities, not hollow
  • microspheres comprising a polymer including one or more of 1) a plurality of C 3 or larger alpha-olefin units wherein the C 3 or larger alpha-olefin units are inco ⁇ orated into the polymer so as to give an average number of less than one branch point per C 3 or larger alpha- olefin unit, 2) a plurality of C 2 alpha-olefin units wherein the C 2 alpha-olefin units are incorporated so as to give an average number of branch points greater than 0 01 per C 2 alpha-olefin unit, preferably greater than 0 05, and more preferably greater that 0.10 per C 2 alpha-olefin unit, and 3) cyclopentene or substituted cyclopentene
  • polymerization of alpha-olefin monomers to give polyolefins having this branching pattern have been previously described, polyolefins in the shape of microspheres having diameters of from about 1 to about 300
  • Microspheres comprising copolymers which are prepared from two or more alpha-olefin hydrocarbon monomers are also within the scope of the present invention Also included are microspheres comprising copolymers prepared from at least one alpha-olefin hydrocarbon monomer and at least one non-alpha-olefin monomer, which can be cyclopentene or substituted cyclopentene, or which can be an acrylate or methacrylate.
  • microspheres comprising a polymer including one or more of 1 ) a plurality of C 3 or larger alpha-olefin units wherein the C 3 or larger alpha-olefin units are incorporated into the polymer so as to give an average number of less than one branch point per C 3 or larger alpha-olefin unit, 2) a plurality of C 2 alpha-olefin units wherein the C 2 alpha-olefin units are incorporated so as to give an average number of branch points greater than 0.01 per C 2 alpha- olefin unit, preferably greater than 0.05, and more preferably greater that 0.10 per C 2 alpha-olefin unit, and 3) cyclopentene or substituted cyclopentene, said microspheres having an average diameter in the range of 1 to 300 micrometers.
  • Microspheres of the invention are prepared from one or more of alpha-olefin hydrocarbon monomers and cyclopentene, an effective amount of an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Pd, that is complexed with a polydentate ligand having steric bulk sufficient to permit formation of polymer, in the presence of at least one liquid reaction medium in which the polymer microspheres are essentially insoluble.
  • an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Pd
  • Microspheres of the invention can be prepared from alpha-olefin hydrocarbon monomers which include substituted and unsubstituted, including acyclic, branched, and cyclic substituents, wherein substituents on the olefin do not interfere with the polymerization process.
  • Alpha-olefins preferred for polymerizations of the invention can have from 2 to about 30 carbon atoms, and include acyclic alpha-olefins such as ethylene, propene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, I -hexadecene, 1 -octadecene, 1-eicosene, and the like.
  • Other useful monomers include cyclopentene and substituted cyclopentenes, and combinations with alpha-olefins.
  • alpha-olefins include ethylene, propene, 1-butene, 1-hexene, 1- octene, and other alpha-olefins up to about C 2 o.
  • liquid monomers are preferred, and higher boiling alpha-olefins, e.g., 1-hexene to about 1- eicosene, are particularly preferred.
  • Microspheres of the invention can be prepared from more than one monomer in the polymerizable composition, and microspheres comprising copolymers of two or more different alpha-olefin monomers or cyclopentene, in any proportion, are within the scope of this invention.
  • Copolymers may be random or blocky (block copolymers), depending on polymerization kinetics and processes.
  • Other useful comonomers which are non-alpha-olefin monomers can include alkyl acrylates and methacrylates, and acrylic and methacrylic acids and salts thereof, providing the comonomers do not comprise more than about 10 mole percent of the total monomer composition, preferably not more than about 5 mole percent.
  • microspheres of the invention can be prepared by admixing, in any order, monomers which are alpha-olefin monomer(s) or cyclopentene, catalyst (described below), and at least one fluid, preferably a liquid, and allowing the monomer(s) to polymerize.
  • the liquid can be any liquid in which the polymer is insoluble.
  • One preferred liquid is water, which preferably can be used in an amount above the solubility limit of the monomer(s) such that a second (aqueous) phase, preferably a continuous aqueous phase, is formed.
  • Aqueous media can be present in at least 25 percent by weight, based on the total volume of the polymerizing reaction mixture, preferably 50 percent by weight, and most preferably 60 percent by weight.
  • Water can be present in an amount up to about 99 percent by weight, based on the total weight of the polymerizable composition, preferably up to about 90 percent by weight, and more preferably up to about 80 percent by weight.
  • Monomer(s) form a suspension in the aqueous phase, preferably through the use of one or more surfactants or through high-shear stirring.
  • suspension polymerization is commonly used to describe polymerizations of water-insoluble monomer(s) suspended as discontinuous droplets in a continuous aqueous phase wherein the polymerization reaction proceeds predominantly within the monomer droplet.
  • an organic liquid such as dichloromethane, can be used as an aid in dissolution of catalyst in the alpha-olefin or cyclopentene monomer(s).
  • catalyst, monomer(s) and organic liquid can be added to the polymerization reaction mixture in any order.
  • Water can be desirable as a second phase in the preparation of microspheres of the invention because of its low toxicity and environmental impact, low cost, and large heat capacity. Microspheres may be easily handled in water as 'low- viscosity liquids' during synthesis, processing, and coating procedures.
  • Preferred liquids include organic solvents that dissolve hydrocarbon alpha- olefin monomer(s) or cyclopentene but in which polymer microspheres are essentially insoluble
  • organic solvents are used as the polymerization reaction medium, monomer(s), catalyst, optionally surfactant or suspension stabilizer, and solvent are mixed to form a solution, polymerization is allowed to occur, and the resulting polymer phase separates as microspheres as it is formed.
  • the term "dispersion polymerization” is commonly used to describe this type of polymerization.
  • Solvents useful in polymerizations that yield microspheres of the invention include esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, halogenated solvents such as dichloromethane (which is preferred for polymerization of dodecene and hydrocarbon monomers having more than 12 carbon atoms), and ethers such as methyl t-butyl ether Ethyl acetate is particularly preferred when it is desired to remove catalyst from the polymer microspheres.
  • esters such as ethyl acetate
  • ketones such as acetone or methyl ethyl ketone
  • halogenated solvents such as dichloromethane (which is preferred for polymerization of dodecene and hydrocarbon monomers having more than 12 carbon atoms)
  • ethers such as methyl t-butyl ether Ethyl acetate is particularly preferred when it is desired to remove catalyst from the polymer microspheres.
  • Palladium-containing compounds are formed in and remain soluble in ethyl acetate after polymerization takes place.
  • the solubility of palladium compounds in ethyl acetate provides a means of removing palladium residues from microspheres Facile removal of palladium compounds is advantageous, since it provides microspheres that are free of contaminants as well as providing a means of recovering and recycling palladium.
  • Other Lewis base solvents such as alcohol or isopropyl alcohol may similarly enable removal and recovery of palladium
  • organic solvents can be present as at least 25 percent by weight of the total reaction mixture, preferably 50 percent by weight, and most preferably 60 percent by weight and up to 99 weight of the total composition. Microspheres are particularly suitable for production of polymers which are free of contamination.
  • washing of microspheres is more effective. Washing may be accomplished by adding the same or other liquids, that is, aqueous media or the same or other organic liquids, to microspheres that have or have not been separated from the liquids in which they were formed. Suitable liquids and the order and process washing are apparent to those skilled in the art. Removal of other contaminants, such as residual monomer, salts, organic liquids or water, are also easily accomplished from polymer microspheres
  • microspheres wherein the weight ratio of metal M to polymer is less than the weight ratio of metal M to monomers used to make the microspheres, and microspheres wherein the weight ratio of ligand L to polymer is less than the weight ratio of ligand L to monomers used to make the microspheres
  • the neutral organometallic compound and cocatalyst salt (as described below) can be mixed together and added to the monomer, or the monomer can be mixed with neutral organometallic compound and the cocatalyst salt subsequently added to that mixture, or two separate monomer streams, one containing neutral organometallic compound and one containing cocatalyst salt can be mixed.
  • Such process variability allows for the control of the onset of polymerization.
  • Other process advantages such as solubilizing the organometallic compound or cocatalyst salt may also be achieved.
  • Advantages of further variations in the order of mixing are apparent to those skilled in the art, and are within the scope of this invention.
  • a plurality of dispersions and suspensions of microspheres can be mixed to achieve useful properties.
  • Polymerizations can be conducted at various temperatures.
  • the reaction temperature is -78° to +35° C, more preferably -40° to +25° C, and most preferably -10° to +20° C.
  • a minimum reaction temperature is preferred.
  • Temperatures above about 40° C may deactivate the catalyst, and good thermal control may be preferred since the polymerization of alpha-olefin monomers and cyclopentene is exothermic. It may be particularly advantageous to employ a second aqueous phase as a heat sink to aid in the control of reaction temperature.
  • Polymerizations can be conducted at atmospheric pressure or pressures greater than atmospheric, particularly in cases where one or more of the monomers is a gas. However, to avoid the expense of pressurized reaction vessels, liquid monomers may be preferred
  • surfactants and/or suspension stabilizers can be added to the aqueous phase prior to or after addition of a mixture of monomer and catalyst, or in any other useful sequence.
  • process conditions such as stirring rate, amount of surfactant, and other additives, polymer particles of different properties, including particle size, may be formed. Agglomeration of polymer may occur, again depending on variables such as monomer, reaction temperature, and additives, and is desirable in some processes (for example, where polymer is to be separated from the water) and undesirable in others (for example, where polymer is to be coated from the aqueous mixture).
  • Organometallic catalysts useful for preparation of microspheres of the invention comprise metals of Periodic Group VIII, ligands providing steric bulk sufficient to permit formation of polymers, and a metal to R bond, wherein R is H, a hydrocarbyl radical, or a hydrocarbyl radical substituted by at least one of alkyl, haloalkyl or aryl groups.
  • Periodic Group VIII metals include Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt, and preferred metals are Co, Ni and Pd. Ni and Pd are especially preferred, and Pd is most preferred.
  • Ligands (L) can be selected so that, when they are coordinated to the metal atom, they are of sufficient size so as to block steric access to certain coordination sites on the metal atom. Without wishing to be bound by theory, it is believed that blocking certain sites will reduce or eliminate processes which result in displacement of the polymer chain from the metal, which prematurely terminates polymerization and results in lower polymer molecular weights. Thus, steric bulk in the ligand permits the formation of high polymer.
  • Preferred catalysts comprise ligands that are chelating.
  • Chelating means that a ligand molecule contains two or more atoms or groups of atoms that are able to form coordinate links to a central metal atom
  • Preferred chelating atoms or groups of atoms are two-electron donors, preferably containing nitrogen, more preferably containing an imine
  • a chelating ligand comprises two imine groups. Imine groups bearing a substituted or unsubstituted group on the nitrogen are preferred, more preferably such groups are polysubstituted aryl, and most preferably they are 2,6-disubstituted aryl. Substitutents on the aryl ring include alkyl, haloalkyl, and aryl, preferably alkyl, more preferably methyl or isopropyl, and most preferably isopropyl. Catalysts also comprise an atom or group R, defined below, which preferably is H or methyl, most preferably methyl.
  • Organometallic catalysts useful for preparation of microspheres of the invention can be one-part or two-part.
  • One-part catalysts are organometallic salts, preferably comprising a cationic portion comprising a Group VIII metal that is complexed with a polydentate ligand having steric bulk sufficient to permit formation of polymer, and a non-coordinating counterion, preferably an anion selected from the group consisting of B(C 6 Fs)4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , AsF 6 " , BF 4 " , B ⁇ 3,5- C 6 H 3 (CF 3 ) 2 ⁇ 4 ⁇ (RfSO 2 ) 2 CFT, (R f SO 2 ) 3 C ⁇ , (R f SO 2 ) 2 N " , and R f SO 3 ⁇ , wherein R f is as defined below, which, when added to monomer, can immediately begin to form polymer, such that no additional reagents or further reactions are necessary to generate an active polymerization catalyst.
  • Such catalysts are advantageous in certain processes, particularly when it is desired that a catalyst
  • M is a Group VIII metal
  • L is a two-electron donor ligand or ligands, as defined above, stabilizing the Group VIII metal
  • R is H, a hydrocarbyl radical or a substituted hydrocarbyl radical, wherein the substituting groups can be alkyl (1 to 10 carbon atoms), aryl (5 to 20 carbon atoms), or halogen substituted alkyl.
  • M is exemplified as cobalt and a substituted tetraphenylborate anion is described as the counterion.
  • Tetraarylborate with (CF 3 ) substituents is preferred in the reference and B ⁇ 3,5-C 6 H 3 (CF 3 ) 2 ⁇ 4 " .is exemplified.
  • a preferred cationic portion has the formula
  • R 2 can be -CH 3 , t-butyl, or -CH 2 (CF 2 ) (i CF 1 , as reported by Johnson et al (J. Am. Chem. Soc, 1996, 1 18. 267-268 and supplementary material) to be useful in inert atmospheres
  • Counterions can be preferred to provide improved catalysts for preparing microspheres of the invention
  • One preferred counterion is B(C6F 5 ) 4 " , which is commercially available from Boulder Scientific Company, Mead, CO, and provides better control over polymer molecular weight
  • the counterion B ⁇ FsV is particularly preferred for the preparation of microspheres in an aqueous medium
  • Other anions useful as the anionic portion of the catalysts of the present invention may be generally classified as fluorinated (including highly fluorinated and perfluorinated) alkyl- or arylsulfonyl-containtng compounds, as represented by Formulas la through Id
  • each R r is independently selected from the group consisting of highly fluorinated or perfluorinated alkyl or fluorinated aryl radicals
  • each R r is independently selected from the group consisting of highly fluorinated or perfluorinated alkyl or fluorinated aryl radicals
  • Compounds of Formulas la, lb and Ic may also be cyclic, when a combination of any two Rf groups are linked to form a bridge
  • the Rf alkyl chains may contain from 1-20 carbon atoms, with 1-12 carbon atoms preferred.
  • the R f alkyl chains may be straight, branched, or cyclic and preferably are straight.
  • Heteroatoms or radicals such as divalent non-peroxidic oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the skeletal chain
  • Rf is or contains a cyclic structure, such structure preferably has 5 or 6 ring members, I or 2 of which can be heteroatoms
  • the alkyl radical R f is also free of ethylenic or other carbon-carbon unsaturation e.g., it is a saturated aliphatic, cycloaliphatic or heterocyclic radical
  • “highly fluorinated” is meant that the degree of fluorination on the chain is sufficient to provide the chain with properties similar to those of a perfluorinated chain More particularly, a highly fluorinated alkyl group will have more than half the total number of hydrogen atoms on the chain replaced with fluorine atoms Although hydrogen atoms may remain on the chain, it is preferred that all hydrogen atoms be replaced with fluorine to form a perfluoroalkyl group, and that any hydrogen atoms beyond
  • the fluorinated aryl radicals of Formulas la through Id may contain from 6 to 22 ring carbon atoms, preferably 6 ring carbon atoms, where at least one, and preferably at least two, ring carbon atoms of each aryl radical is substituted with a fluorine atom or a highly fluorinated or perfluorinated alkyl radical as defined above, e.g., CF 3
  • Examples of anions useful in the practice of the present invention include (C 2 F 5 SO 2 ) 2 N ⁇ (C 4 F 9 SO 2 ) 2 N ⁇ (C s F 17 SO 2 ) 3 C ⁇ (CF,SO 2 ) 3 C ⁇ , (CF 3 SO 2 ) 2 N ⁇ (C 4 F 9 SO 2 ) 3 C ⁇ , (CF 3 SO 2 ) 2 (C 4 F 9 SO 2 )CT (CF 3 SO 2 )(C4F 9 SO 2 )N ⁇ , ⁇ (CF 3 ) 2 NC 2 F 4 SO 2 ⁇ 2 N , (CF 3 ) 2 NC 2 F 4 SO 2 C (SO 2 CF 3 ) 2 , (3,5-bis(CF 3 )C 6 H 3 )SO 2 N ⁇ SO 2 CF 3 , C 6 F s SO 2 C ⁇ (SO 2 CF 3 ) 2 , C 6 F 5 SO 2 N ⁇ SO 2 CF 3 , CF 3 SO 3 ⁇ , C 8 F I7
  • F in the ring means the ring carbon atoms are perfluorinated. More preferred anions are those described by Formulas lb and Ic wherein Rf is a perfluoroalkyl radical having 1-4 carbon atoms. Particularly preferred anions for use in polymerizations carried out in organic solvents are those described by Formula ic.
  • diethyl ether can be useful but it is preferable to avoid its use because it can be dangerous to store and handle due to its extreme flammability and tendency to form explosive peroxides.
  • Alternative useful ethers are organic compounds containing one ether-type oxygen atom and include tetrahydrofuran and methyl t-butyl ether. Methyl t-butyl ether is particularly preferred.
  • Preferred catalysts can be of the formula
  • Id PF ⁇ , SbF 6 , AsF 6 , and BF 4 .
  • Particularly preferred are compounds wherein ether is methyl t-butyl ether and Q is selected from B(C6F 5 ) 4 and anions as shown in Formulas la through Id.
  • Examples of preferred one-part catalysts include:
  • Two-part catalysts comprise two reagents, a neutral organometallic compound and a cocatalyst salt, that react upon mixing optionally in the presence of monomer to yield an active catalyst.
  • Two-part catalysts are particularly advantageous when partial mixing of monomer and an organometallic compound is desired (such as to achieve good solubility or suspension) but when it is also desired to initiate polymerization at a later time, for instance, when the second reagent is added. Process advantages resulting from the ability to control the time at which polymerization begins are significant.
  • Two-part catalysts may also allow for the in situ generation of active catalytic compounds which cannot be isolated, and may also be preferred for those situations where the added time and expense of isolating a one-part catalyst are not warranted.
  • Two-part catalysts preferably comprise a neutral organometallic Pd compound which includes a ligand or ligands as previously defined, a moiety R which is H, hydrocarbyl radical, or substituted hydrocarbyl radical, and a halogen atom (preferably chlorine), and a cocatalyst.
  • a + Q wherein A is selected from silver, thallium, and metals of Periodic Group IA, and Q is selected from B(3,5-C6H 3 (CF 3 ) 2 ) 4 , B(C ⁇ F5) 4 , anions as shown in Formulas la through Id, PF 6 , SbF 6 , AsF 6 , and BF 4 , and solvates and hydrates thereof
  • silver salts are preferred and can have the formulae Ag ⁇ B(C 6 F 5 ) 4 ⁇ (arene) p and Ag ⁇ B(C 6 H 3 (CF 3 ) 2 ) 4 ⁇ (arene) p wherein arene can be an aromatic hydrocarbon group having 6 to 18 carbon atoms that can be substituted by up to 6 alkyl or aryl groups each having up to 12 carbon atoms, preferably arene can be benzene, toluene, ortho-, meta-, or para-xylene, and mesitylene, and p can be an
  • Examples of preferred cocatalyst salts include: Ag + ⁇ B(C 6 F 5 ) 4 ⁇ -(toluene) 3 , Ag + ⁇ B(C 6 F 5 ) 4 ⁇ -(xylene) 3 , Ag + ⁇ B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 r (toluene), Li + ⁇ B(C 6 F 5 ) 4 ⁇ - , Na + ⁇ B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ⁇ Li + ⁇ N(SO 2 CF 3 ) 2 ⁇ Li + ⁇ B(C 6 F 5 ) 4 ⁇ (Et 2 O) 2 , Lf ⁇ N(SO 2 CF 3 )(SO 2 C 4 F 9 ) ⁇ Li + ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ Li + ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ -(hydrate), Li + ⁇ N(SO 2 C 4 F 9 ) 2 ⁇
  • a neutral organometallic compound is reacted with a salt of a non-coordinating counterion preferably comprising fluorine to give an organometallic catalyst and a halide salt as by-product.
  • a salt of a non-coordinating counterion preferably comprising fluorine
  • excess A + Q " may be preferred since A + Q " may function as a surfactant in the reaction mixture.
  • an alkali metal salt of a non-coordinating anion can be dissolved in water and treated with a molar equivalent of AgNO 3 at or near room temperature (20° to 25°C) Within minutes, a reaction occurs. While not wishing to be bound by theory, the reaction product is believed to be the silver salt of the non-coordinating anion, stabilized by one or more water (solvent) molecules.
  • the organic layer can be separated from solid AgCl (which may be recovered and recycled) and the aqueous layer, and removal of solvent produces clean one-part Pd catalyst in good yield.
  • This method is preferred because it provides for rapid synthesis of one- part catalyst in good yield, and does not require the preparation and isolation of the silver salt of a non-coordinating counterion
  • This procedure can be used to prepare one-part Pd catalysts containing the following counterions: ⁇ C(SO 2 CF 3 ) 3 ⁇ " , ⁇ B(C 6 F 5 ) 4 ⁇ -, (B ⁇ 3,5-C 6 H 3 (CF 3 ) 2 ⁇ 4 ⁇ (SO 3 C 4 F 9 ), N(SO 2 CF 3 ) 2 ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ and NSO 2 (CF 2 ) 2 SO 2 -.
  • a preferred method provides two-part catalysts useful in two-phase systems.
  • This variation of a two-part catalyst comprises a neutral organometallic compound as described above and a cocatalyst of a Group IA metal in a two phase system.
  • a catalyst system may be preferred because the second (preferably aqueous) phase provides a heat sink which moderates polymerization exotherms
  • This variation also avoids the expense and environmental hazards of silver- containing reagents. In the presence of an aqueous phase, these two-part catalysts rapidly initiate polymerization.
  • Adjuvants optionally useful in any of the methods of catalyst synthesis of the invention include solvents such as methylene chloride, and the like
  • One and two-part catalysts can be present in the range of 0.0001 to 20 weight percent, preferably 0.001 to 5 weight percent, most preferably 0.01 to 2 weight percent of the weight of cyclopentene or alpha-olefin monomer.
  • Microspheres may contain metal-containing residues, either as elemental metal or as inorganic or organometallic compounds, in the amount of 0 to 3 percent by weight of metal Additional processing steps, such as washing with solvent, may be employed to remove metal residues from microspheres Some or all of the metal residues may also be present in the aqueous or organic solvent phase, with or without the use of additional processing steps.
  • One- and two-part catalysts described herein can be used to prepare high polymer
  • use of appropriate variations in reaction conditions such as low conversions of monomer to polymer, short reaction times, or higher catalyst to monomer ratios can lead to polymers of lower molecular weight
  • it is preferred to control of molecular weight by choice of catalyst to monomer ratio, and higher ratios (that is, more catalyst relative to monomer) result in lower molecular weights.
  • Variations in ligand structure can also lead to lower polymer molecular weight
  • Such catalysts, methods and polymers are also useful and within the scope of the invention.
  • Additives, adjuvants and fillers as are known in the art can be added to the polymerizable composition for preparing the microspheres, providing they do not interfere with the intended polymerization process or adversely affect the chemical and physical properties of the resultant microspheres.
  • Additives, adjuvants and fillers can include, but are not limited to, tackifiers, inorganic oxides, pigments, dyes, or other polymers.
  • Adjuvants may be present in the composition in the range of 0.1 to 90 weight percent Adjuvants may be supplied and used as suspensions
  • Relatively acidic organic compounds such as, e.g., phenols and carboxylic acids, can be present in the polymerizable compositions which provide microspheres of the invention without deleterious effect on the subsequent polymerization reaction
  • a hindered phenol- type antioxidant such as Irganox 1010TM (commercially available from Ciba Specialty Chemicals Inc., Basel, Switzerland)
  • Hindered phenol-type antioxidants useful in the invention are well known to those skilled in the art, and are described in Jesse Edenbaum, Plastics Additives and Modifiers Handbook.
  • antioxidants containing phosphorus for example, as phosphine or phosphite, are also known as additives in polymers These secondary antioxidants halt polymerization They can therefore be useful for stopping polymerization and they may also provide other benefits, for example, lighter color, but they are not usefully added to monomer prior to polymerization Sulfur containing compounds such as thiols are also useful in halting polymerization, as are strong oxidants such as bleach (sodium hypochlorite).
  • Monomers or comonomers containing organic functional groups can also be useful to prepare microspheres in the invention.
  • Such monomers may be useful to modify polymer properties (e.g., to increase modulus) or improve microsphere suspension stability, and may be present in amounts up to about 10 mole percent of total monomer content, more preferably up to about 5 mole percent.
  • microspheres of the invention comprise greater than 90 mole percent cyclopentene or hydrocarbon alpha-olefin polymers, and most preferably 95 mole percent cyclopentene or hydrocarbon alpha-olefin polymers.
  • Hydrocarbon polymer microspheres exhibit advantageous properties over those prepared, for instance, from acrylate ester monomers, such as decreased sensitivity to moisture, low corrosivity and low susceptibility to corrosion, low cost, good thermal and oxidative stability (particularly as compared to unsaturated polymers, such as those derived from dienes) and low dielectric constant.
  • Polymerizable compositions may further comprise surfactants, emulsifiers, or suspension stabilizers, or the polymerizations may be carried out under particular process conditions, that induce the formation of and substantially prevent the agglomeration of the resulting microsphere particles.
  • Surfactants are preferred when a second aqueous phase is present.
  • Ionic surfactants are preferred Suitable surfactants include sodium, lithium, and ammonium sulfates and sulfonates.
  • Specific examples of suitable surfactants include sodium heptadecyl sulfate, sodium lauryl sulfate, and ammonium lauryl sulfate
  • Certain surfactants contain groups which reduce catalyst activity, and these should be avoided in the practice of this invention.
  • polyether groups and halides such as are found in polyether sulfonate or tetraalkylammonium halide surfactants, should be avoided.
  • Surfactants, emulsifiers, and stabilizers can each be present in the composition in the range of about 0.01 to 5 weight percent.
  • Polymerizable compositions may also comprise suspension stabilizers in place of or in combination with surfactants.
  • stabilizers and “stabilization” mean the use of a method for producing polymer dispersions that are stable towards aggregation processes This meaning is quite different from usage in other branches of polymer science, wherein “stability” and “stabilizers” can often be used to refer to processes and additives which confer on treated polymers an enhanced resistance towards thermal and/or photolytic degradation processes
  • Preferable suspension stabilizers are those that effectively provide sufficient stabilization of the final polymerized droplets and reduce agglomeration within a suspension polymerization process
  • Useful polymeric suspension stabilizers include those salts of poly(acrylic acid) having an M w greater than about 5000, including ammonium, sodium, lithium and potassium salts, carboxy-modified poly(acrylamides) such as CYANAMERTM A-370 (commercially available from American Cyanamid Co., Parsippany, NJ), copolymers of acrylic acid and dimethylaminoethyl methacrylate, polymeric quaternary amines such as GAFQUATTM 755, a quatemized poly(vinylpyrrolidone) (commercially available from General Aniline and Film Corp (GAF), Wayne, NJ) or RJRTM-400S, a quaternized-amine substituted cellulosic, and cellulosics and carboxy-modified cellulosics such as sodium carboxymethyl cellulose,
  • Microspheres of the invention can be solid, hollow, or a combination thereof They may be spherical, or in other shapes, that is, microparticles Other shapes include ovoids, other geometric shapes, and irregular structures, particularly including agglomerates
  • the present invention provides microspheres comprising a polymer including one or more of 1) a plurality of C 3 or larger alpha-olefin units wherein the C 3 or larger alpha-olefin units are incorporated into the polymer so as to give an average number of less than one branch point per C 3 or larger alpha-olefin unit, 2) a plurality of C 2 alpha-olefin units wherein the C 2 alpha-olefin units are inco ⁇ orated so as to give an average number of branch points greater than 0.01 per C 2 alpha- olefin unit, preferably greater than 0.05, and more preferably greater that 0.10 per C 2 alpha-olefin unit, and 3) cyclopentene or substituted cyclopentene.
  • C 3 and higher alpha-olefin polymers obtained using catalysts of the invention consist essentially of two types of repeating units: ⁇ -CH 2 -CHR 4 - ⁇ X and ⁇ -(CH 2 ) n - ⁇ y wherein n is the number of carbon atoms in the C 3 or higher alpha- olefin monomer used to make the polymer and R 4 is ⁇ CH 3 (CH 2 ) (n .
  • the number of branched units ⁇ -CH 2 -CHR 4 - ⁇ is less than the total number of monomer units in the polymer, that is x has a value from 0.01 to 0 99, preferably 0.20 to 0.95, more preferably 0.40 to 0.90, and (x + y) has a value of 0.90 to 1.00.
  • polymer structure will vary as the monomer or monomers used in the polymerizable composition vary
  • a polymer made from 1-octene that is, n equals 8
  • a polymer made from 1 -hexene that is, n equals 6
  • Polymers made from C 2 alpha-olefin monomer (ethylene) contain essentially two types of repeating units ⁇ -
  • Cyclopentene appears to be incorporated into the polymer backbone through carbons 1 and 3.
  • variations in polymerizable composition such as the kind and amount of optional solvent or aqueous phase or the catalyst selected and polymerization method can affect the polymer structure
  • Polymer structure can affect polymer properties, such as crystallinity or modulus, which, in turn, affects microsphere properties, including stickiness, tack, hardness, waxiness, slipperiness, or elasticity.
  • the polymerizable hydrocarbon alpha-olefin monomer used to prepare microspheres of the invention is ethylene, branching of greater than 10 mole percent is preferred.
  • High polymers are easily handled in microsphere form (as suspensions, dispersions or dried powders) and can lead to improved product performance.
  • High polymers can be obtained by, for instance, an appropriate choice of catalyst-to-monomer ratio.
  • high polymers can be obtained by continuing the polymerization reaction essentially to completion, that is, consumption of substantially all available monomer.
  • Low molecular weight polymeric microspheres (M w of from about 5000 to about 90,000) can also be useful, and can be advantageously processed as aqueous suspensions, organic dispersions, or as powders.
  • microspheres comprising crosslinked polymer provide better product performance.
  • Crosslinking may be accomplished during the polymerization reaction by copolymerization with a polyfunctional monomer, or may be effected by chemical reactions brought about by thermal means or actinic radiation, including high energy sources such as electron beam, gamma radiation, or ultraviolet irradiation, occurring after polymerization
  • Polymer gel fractions can be in the range of 1 to 100 percent, preferably 5 to 100 percent.
  • Microspheres comprising a polymer including one or more of 1) a plurality of C 3 or larger alpha-olefin units wherein the C 3 or larger alpha-olefin units are incorporated into the polymer so as to give an average number of less than one branch point per C 3 or larger alpha-olefin unit, 2) a plurality of C 2 alpha- olefin units wherein the C 2 alpha-olefin units are incorporated so as to give an average number of branch points greater than 0.01 per C 2 alpha-olefin unit, preferably greater than 0.05, and more preferably greater that 0.10 per C 2 alpha- olefin unit, and 3) cyclopentene or substituted cyclopentene, can be crosslinked via irradiation with electron beams at dosages preferably in the range of 20 MRad or less, more preferably 10 MRad or less.
  • the crosslinked polyolefins are free of added chemical crosslinking agents that might otherwise impair the chemical or physical properties of the polymer or be disadvantageous in subsequent use, for example, due to color or leaching.
  • Other useful high-energy sources are known, including high energy radiation, and are within the scope of the present invention.
  • Microspheres comprising a polymer including one or more of 1) a plurality of C 3 or larger alpha-olefin units wherein the C 3 or larger alpha-olefin units are incorporated into the polymer so as to give an average number of less than one branch point per C 3 or larger alpha-olefin unit, 2) a plurality of C 2 alpha- olefin units wherein the C 2 alpha-olefin units are incorporated so as to give an average number of branch points greater than 0.01 per C 2 alpha-olefin unit, preferably greater than 0.05, and more preferably greater that 0.10 per C 2 alpha- olefin unit, and 3) cyclopentene or substituted cyclopentene, can also be crosslinked by ultraviolet irradiation.
  • additives that absorb ultraviolet light and subsequently react to give radicals by homolytic cleavage and/or hydrogen abstraction are mixed with the polymer prior to irradiation.
  • Typical additives include trihalomethyl-substituted .v-triazines (such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine), aryl alkyl ketones (such as acetophenone, benzoin ethers, and ketals of benzil), and diaryl ketones (such as benzophenone and anthraquinone).
  • trihalomethyl-substituted .v-triazines such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine
  • aryl alkyl ketones such as acetophenone, benzoin ethers, and ketals of benzil
  • diaryl ketones such as benzo
  • Microspheres are useful as a form of polymer due to the convenience with which they can be handled as a fluid suspension, recovered by centrifugation or agglomeration, or handled as free-flowing powders when removed from liquid.
  • One particular embodiment of the invention provides powder coatings prepared from the microspheres. A general description of powder coating may be found in Encyclopedia of Polvmer Science and Engineering. Vol. 3, "Coating Methods," pages 552-615 (subsection on "Powder Coating," pages 575-601), Wiley-lnterscience Publishers (New York, 1985) Powder coating can be accomplished by a variety of means, including the use of fluidized beds, flame guns, electrostatic sprays, plasma sprays, hot flocking, etc. These methods are all generically fusion-coating processes.
  • the applied powder is fused to form a continuous coating.
  • Powder coating is inherently solvent-free, powder overspray is generally collectable and potentially recyclable, and coatings in a range of thicknesses are attainable It is advantageous to directly prepare the powders used in these processes, particularly when it would otherwise be necessary to cryogrind thermoplastics with low glass transition temperatures.
  • Adjuvants such as fillers, flow agents, pigments, etc can be included in powder coating as is known to those skilled in the art
  • Microspheres of the invention find use as powders or as suspensions in fluid media Because of their ease of handling they may be processed further into, e.g., films, fibers, solutions, pellets, and beads, articles or coatings
  • Coatings comprising microspheres of the invention on a substrate can be continuous or discontinuous Discontinuous coatings can be used, for example, as repositionable adhesives
  • Continuous coatings or films can be obtained by coating microspheres of the invention as a dispersion or suspension in an amount sufficient to completely cover the coated substrate Alternatively, continuous coatings can be prepared by solvent-coating a solution of dissolved microspheres of the invention or by extruding previously isolated solid microspheres Continuous coatings may be useful as pressure-sensitive adhesives Free-standing films prepared from microspheres of the invention may be useful as adhesive films
  • Fibers can also be prepared from polymeric microspheres by means such as solvent casting or extrusion Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples,
  • Peel adhesion is the force required to remove an adhesive-coated flexible sheet material from a test panel measured at a specific angle and rate of removal. In the examples, the force is expressed in grams per width of adhesive-coated sheet.
  • Adhesion to Polyester Poly(ethyleneterephthalate), PET
  • Adhesion to polyester film was measured by application of a 3.2 cm-wide strip of polyester film to the surface of an adhesive-coated sample fixed on a horizontal test plate. A 2 kg hard rubber roller was used to apply the strip. The free end of the polyester film was attached to an adhesion tester load cell such that the angle of removal was 90° relative to the horizontal test plate. The polyester film strip was peeled from the adhesive at a constant rate of 31 cm per minute. A load cell reading in grams per 3.2 cm was recorded. The test was repeated and the data was reported as the average of the number of trials.
  • a dhesion to Bond Paper Poly(ethyleneterephthalate), PET
  • Peel adhesion is the force required to remove a coated sheet from a bond paper substrate at a specific angle and rate of removal. In the examples, this force is expressed in grams per 2.54 cm width of coated sheet.
  • a strip, 2.54 cm wide, of coated sheet was applied to the horizontal surface of white bond paper (20 pound standard weight, 75 g/m 2 , commercially available from Georgia Pacific Papers, Atlanta, GA).
  • a 2 kg hard rubber roller was used to firmly apply the strip to the bond paper
  • the free end of the coated sheet was attached to an adhesion tester load cell such that the angle of removal was 90 degrees
  • the test plate was then clamped in the jaws of a tensile testing machine that was capable of moving the test plate away from the load cell at a constant rate of 31 cm per minute
  • a load cell reading in grams per 2 54 cm of coated sheet was recorded The test was repeated and the data was reported as the average of the number of trials
  • the compound was prepared according to the procedure described in R Rulke, J M Ernsting, A L Spek, C Elsevier, P W N M van Meeuwen, K Vrieze Inorg. Chem., 1993, 32, 5769-5778 All procedures were conducted in a dry nitrogen atmosphere
  • reaction solution When the reaction solution was a pale yellow, it was filtered once more, and solvent was removed. There was obtained 63.94 g white (l,5-cyclooctadiene)Pd(Me)Cl. This compound was preferably handled in an inert atmosphere.
  • This neutral organometallic compound was prepared according to the procedure described in L. K.Johnson, C. M. Killian, M Brookhart J. Am. Chem. Soc, 1995, 1 17. 6414-6415 and supplementary material.
  • 31.64 g (l,5-cyclooctadiene)Pd(Me)Cl (synthesis B, above) was placed in 375 mL of dry deoxygenated diethyl ether. The (l,5-cyclooctadiene)Pd(Me)Cl was not completely dissolved.
  • Pd catalysts containing the following counterions were prepared: ⁇ C(SO 2 CF 3 ) 3 ⁇ ⁇ B(C 6 H 5 ) 4 ⁇ -, ⁇ B(C 6 F 5 ) 4 ⁇ ⁇ B ⁇ 3,5-C 6 H 3 (CF 3 ) 2 ⁇ 4 ⁇ (SOsC ⁇ V, ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ and ⁇ NSO 2 (CF 2 ) 2 SO 2 ⁇ -.
  • Example 2 Microspheres Coated on a Substrate
  • a portion of the microsphere suspension from Example 1 was coated on polyester film (ScotchTM 8050 film, 3M Company, St Paul, MN) at a wet thickness of 0.1 mm, and dried in an oven at 150°C for several minutes. Microscopic examination showed that the dried coating contained spheres of about 20 to 75 micrometer diameter.
  • Example 3 Repositionable adhesive A portion of the microsphere suspension from Example 1 was coated at a wet thickness of 0.1 mm onto approximately half of a 5 x 10.8 cm piece of paper (yellow Post-ItTM paper, 3M Company, St. Paul MN; the paper was cut to remove the adhesive that was present in the product as commercially supplied). The sample was dried in an oven at 150° C for several minutes. The sample was then placed, coating side down, on a piece of white bond paper. Adhesion was sufficient that the larger piece of white paper could be handled (such as held vertically) while the yellow sample remained adhered to the white paper. The yellow sample was then easily peeled from the white paper and could be reapplied.
  • Example 1 A 15.444 g sample of the microsphere adhesive of Example 1, suspended in water, was mixed with 0.606 g Shellflex 371 Oil (Shell Chemical Company, Houston TX). Portions of the unmodified microsphere sample (Example 1) and the oil-treated sample were coated onto pink Post-ItTM paper (3M Company, St. Paul, MN) using a No. 40 wire-wrapped rod, and dried and examined as in Example 3. Both samples showed adhesion to paper, and could be removed and repositioned. The oil-treated sample showed qualitatively higher levels of adhesion; i.e., it was more difficult remove than the unmodified adhesive. Example 5, Preparation of microspheres
  • Example 5 The creamy suspension from Example 5 was coated through a 0 025 mm orifice onto polyester film (ScotchTM 8050 film, 3M Company, St Paul, MN) The coated samples were dried in a forced air oven at 66° C for 15 min The samples were evaluated for peel adhesion to polyester (average of 4 replicates) and bond paper (average of 3 replicates) in the manner described in Test Methods, above, peel adhesion values were found to be 13 g/3.18 cm and 1 1 g/2 54 cm, respectively Samples were removed cleanly from the polyester and bond paper
  • Example 7 Preparation of microspheres in an aqueous medium (See Table 1)
  • DDSNa is dodecylsulfate, sodium salt.
  • Wingtack PlusTM is a resin available from Goodyear Tire and Rubber Co., Akron Ohio. It was dissolved in alpha-olefin monomer and this solution was added to other materials in the sample.
  • ALS is ammonium lauryl sulfate; the weight indicated is the weight used of a gel of ALS in water, 29% solids, supplied as Stepanol AM-VTM (Stepan Co., Northfield, IL).
  • Colloidal silica is Nalco 1130TM, 30% in water (Nalco Chemical Co., Naperville, IL).
  • cyclopentene can be used instead of the monomers of Table 1 .
  • MEK means methyl ethyl ketone
  • Sample 9- A 97 mg Pd catalyst, 0 122 g benzophenone, 19 2 g ethyl acetate, and 10.26 g 1-octene
  • Sample 9-B 97 mg Pd catalyst, 0 096 g 2-(3,4-dimethoxyphenyl)-4,6- bis(trichloromethyl)-l,3,5-t ⁇ azine (the preparation of which is described in German
  • Patent 1,200,314) 17 566 g ethyl acetate, and 10 02 g 1-decene
  • microspheres in Samples 9-A and 9-B were separated from ethyl acetate by filtration, and dried under vacuum A portion of each dried sample, about 3 g, was placed in a layer in a pan of area about 20 cm 2 , and then irradiated under a medium pressure mercury arc lamp (14 mW/cm 2 ) for 1 1 min, stirring the solid microspheres once An attempt was then made to prepare solutions of the samples so as to measure the fraction of polymer gel (crosslinked polymer) in unirradiated (9-A-un and 9-B-un) and irradiated (9-A-ir and 9-B-ir) microsphere samples: about 1 g of each sample was placed in 20 ml of toluene, which was gently agitated for about 72 hr.
  • Sample 9-C The microspheres in Sample 9-C were similarly irradiated as an aqueous suspension in an open beaker with sample surface area 7 9 cm 2 , with constant stirring, for 11 min When examined under the microscope, microspheres were observed of size range 15-150 micron in both Samples (9-C-un and 9-C-ir) Water was removed and the microspheres were dried under vacuum. An attempt was then made, as described above, to prepare toluene solutions of these samples and filter them. Sample 9-C-un filtered slowly, but Sample 9-C-ir did not pass through the filter, because swollen gelled microspheres clogged the filter.
  • liquids were transferred by evacuating vessels and/or using a positive pressure of N 2 gas to effect transfer and to re-pressurize.
  • a steel can In a steel can were placed several steel balls, 100 gm of the above-made poly(l-octene) microspheres, and 0.5 g of Cab-o-SilTM TS-610 silane-treated amorphous fumed silica (Cabot Corp., Tuscola, IL) The closed can was rolled to effect mixing. The resulting mixture was placed in the fluidized bed powder supply container of an electrostatic spray gun (Nordson Corp., Amherst, OH). The powder settings were 0.28 MPa, 0.03 MPa, and 0.17 MPa, and the gun electrode was set at 80 kV. A 15.6 cm x 30.8 cm rectangular piece of aluminum was placed at one end of an electrostatic spray booth in which the electrostatic spray gun was mounted.
  • the conveyor belt speed control of the spray booth was set at 30 (DC motor speed control; « 4.6 m/min; spray booth also from Nordson Corp., Amherst, OH).
  • the powder was applied to the aluminum plate as it moved past the fixed gun, and then the coated piece of aluminum passed through a Thermation oven, model # 109964 (18 kW, two-zone infrared oven; BH Electronics, Burnsville, MN) - speed 13, short wave IR @ 140V, medium wave IR @ MOV This resulted in a fused, translucent coating of 1 9 g of poly( 1 -octene) on the piece of aluminum
  • Sample 12- A was prepared by mixing 2300 g ethyl acetate, 1 29 g catalyst, and 600 g 1-hexene at 0° C The microspheres so formed were collected by filtration Sample 12-B was prepared from 605 g ethyl acetate, 0 945 g catalyst, and 160 g 1-hexene at 10° C Comparative sample 12-C was prepared by mixing 1001 g methylene chloride, 1000 g 1-hexene, and 2 23 g catalyst and maintaining the reaction at 0° C Solvent was removed from the product in a vacuum oven Use of methylene chloride as solvent did not yield microspheres, as the 1-hexene polymer formed under these conditions was soluble in the solvent for most or all of the reaction time Comparative sample 12-D was prepared from 100 g 1-hexene, 100 g methylene chloride, and 0 571 g catalyst at 10° C

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Abstract

L'invention concerne des microsphères en polymère comprenant un ou plusieurs des éléments suivants: 1) une pluralité d'unités en alpha-oléfine de type C3 ou supérieur, intégrées au polymère selon un nombre moyen de points d'embranchement inférieur à un par unité, 2) une pluralité d'unités en alpha-oléfine C2, intégrées selon un nombre moyen de points d'embranchement supérieur à 0,01 par unité, et 3) cyclopentène ou cyclopentène substitué. Le diamètre moyen des microsphères est compris entre 1 et 300 microns. Facultativement, le polymère peut être réticulé. On peut préparer les microsphères par polymérisation en suspension ou dispersion dans des milieux de réaction aqueux ou organiques. La fabrication de revêtements en poudre est possible à partir des microsphères.
PCT/US1997/009269 1996-06-20 1997-06-02 Microspheres en polyolefine WO1997048740A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000006296A3 (fr) * 1998-07-28 2001-04-12 Aventis Res & Tech Gmbh & Co Microparticules fabriquees a partir de copolymeres de cyclo-olefines et leur utilisation pour la liberation controlee de constituants actifs
US6245871B1 (en) 1997-04-18 2001-06-12 Eastman Chemical Company Group 8-10 transition metal olefin polymerization catalysts
WO2001044325A1 (fr) * 1999-12-17 2001-06-21 Basf Aktiengesellschaft Procede de polymerisation en emulsion d'olefines
US6350837B1 (en) 2000-06-09 2002-02-26 Eastman Chemical Company Copolymerization of norbornene and functional norbornene monomers
WO2003020779A1 (fr) * 2001-08-31 2003-03-13 Kaneka Corporation Copolymere greffe de polyolefine produit avec un catalyseur de polymerisation de coordination a base d'un complexe de metal de transition apparaissant dans une periode ulterieure et procede pour preparer ce copolymere
WO2002064638A3 (fr) * 2001-02-14 2003-03-20 Basf Ag Procede de polymerisation en emulsion d'olefines
US6545108B1 (en) 1999-02-22 2003-04-08 Eastman Chemical Company Catalysts containing N-pyrrolyl substituted nitrogen donors
US6559091B1 (en) 1999-02-22 2003-05-06 Eastman Chemical Company Catalysts containing N-pyrrolyl substituted nitrogen donors
US6579823B2 (en) 2000-02-18 2003-06-17 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US6605677B2 (en) 2000-02-18 2003-08-12 Eastman Chemical Company Olefin polymerization processes using supported catalysts
US6620896B1 (en) 1999-02-23 2003-09-16 Eastman Chemical Company Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom
WO2002083749A3 (fr) * 2001-04-12 2003-09-25 Basf Ag Procede de production, par catalyse a l'aide de metaux de transition, de dispersions aqueuses contenant des polyolefines ou des polymeres aromatiques vinyliques
US6706891B2 (en) 2000-11-06 2004-03-16 Eastman Chemical Company Process for the preparation of ligands for olefin polymerization catalysts
US7056996B2 (en) 2000-02-18 2006-06-06 E. I. Du Pont De Nemours And Company Productivity catalysts and microstructure control

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0304671A1 (fr) * 1987-08-07 1989-03-01 Hoechst Aktiengesellschaft Procédé de préparation d'un polymère d'une oléfine
EP0371635A2 (fr) * 1988-11-30 1990-06-06 Minnesota Mining And Manufacturing Company Microsphères creuses en polymères d'acrylate
EP0454231A2 (fr) * 1990-04-20 1991-10-30 The University Of North Carolina At Chapel Hill Catalyseurs à base de métaux à transition tardive pour polymérisation d'oléfines
EP0504418A1 (fr) * 1990-10-05 1992-09-23 Idemitsu Kosan Company Limited Procede de production de polymere de cycloolefine et de copolymere de cycloolefine et composition et moulage prepares a partir de ces composes
US5480952A (en) * 1995-03-06 1996-01-02 Northwestern University Zirconium and hafnium-catalyzed polymerization of methylenecyclopropane
WO1996011963A2 (fr) * 1994-10-18 1996-04-25 Eastman Chemical Company Catalyseurs et synthese de polyolefines amorphes de poids moleculaire eleve et leur recuperation
WO1996023010A2 (fr) * 1995-01-24 1996-08-01 E.I. Du Pont De Nemours And Company POLYMERES D'OLEFINES ET DE α-OLEFINES ET PROCEDES DE POLYMERISATION

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0304671A1 (fr) * 1987-08-07 1989-03-01 Hoechst Aktiengesellschaft Procédé de préparation d'un polymère d'une oléfine
EP0371635A2 (fr) * 1988-11-30 1990-06-06 Minnesota Mining And Manufacturing Company Microsphères creuses en polymères d'acrylate
EP0454231A2 (fr) * 1990-04-20 1991-10-30 The University Of North Carolina At Chapel Hill Catalyseurs à base de métaux à transition tardive pour polymérisation d'oléfines
EP0504418A1 (fr) * 1990-10-05 1992-09-23 Idemitsu Kosan Company Limited Procede de production de polymere de cycloolefine et de copolymere de cycloolefine et composition et moulage prepares a partir de ces composes
WO1996011963A2 (fr) * 1994-10-18 1996-04-25 Eastman Chemical Company Catalyseurs et synthese de polyolefines amorphes de poids moleculaire eleve et leur recuperation
WO1996023010A2 (fr) * 1995-01-24 1996-08-01 E.I. Du Pont De Nemours And Company POLYMERES D'OLEFINES ET DE α-OLEFINES ET PROCEDES DE POLYMERISATION
US5480952A (en) * 1995-03-06 1996-01-02 Northwestern University Zirconium and hafnium-catalyzed polymerization of methylenecyclopropane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
L.K. JOHNSON ET AL.: "Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II)- Catalysts", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 118, no. 1, 10 January 1996 (1996-01-10), WASHINGTON, XP002025460 *
L.K. JOHNSON ET AL.: "New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and alpha-Olefins", JOURNAL OF THE AMERICAN SOCIETY, vol. 117, no. 23, 14 June 1995 (1995-06-14), WASHINGTON, XP002025459 *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6245871B1 (en) 1997-04-18 2001-06-12 Eastman Chemical Company Group 8-10 transition metal olefin polymerization catalysts
US6656869B2 (en) 1997-04-18 2003-12-02 Eastman Chemical Company Group 8-10 transition metal olefin polymerization catalysts
AU758139B2 (en) * 1998-07-28 2003-03-13 Aventis Cropscience Gmbh Microparticles produced from cyclic olefin copolymers and their use for the controlled release of active agents
AU758139C (en) * 1998-07-28 2003-12-11 Aventis Cropscience Gmbh Microparticles produced from cyclic olefin copolymers and their use for the controlled release of active agents
WO2000006296A3 (fr) * 1998-07-28 2001-04-12 Aventis Res & Tech Gmbh & Co Microparticules fabriquees a partir de copolymeres de cyclo-olefines et leur utilisation pour la liberation controlee de constituants actifs
US6825356B2 (en) 1999-02-22 2004-11-30 Eastman Chemical Company Catalysts containing N-pyrrolyl substituted nitrogen donors
US6545108B1 (en) 1999-02-22 2003-04-08 Eastman Chemical Company Catalysts containing N-pyrrolyl substituted nitrogen donors
US6559091B1 (en) 1999-02-22 2003-05-06 Eastman Chemical Company Catalysts containing N-pyrrolyl substituted nitrogen donors
US6620896B1 (en) 1999-02-23 2003-09-16 Eastman Chemical Company Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom
WO2001044325A1 (fr) * 1999-12-17 2001-06-21 Basf Aktiengesellschaft Procede de polymerisation en emulsion d'olefines
US7129292B1 (en) 1999-12-17 2006-10-31 Basf Aktiengesellschaft Method for the emulsion polymerization of olefins
US6579823B2 (en) 2000-02-18 2003-06-17 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US6605677B2 (en) 2000-02-18 2003-08-12 Eastman Chemical Company Olefin polymerization processes using supported catalysts
US6844446B2 (en) 2000-02-18 2005-01-18 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US6946532B2 (en) 2000-02-18 2005-09-20 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US7056996B2 (en) 2000-02-18 2006-06-06 E. I. Du Pont De Nemours And Company Productivity catalysts and microstructure control
US6538085B2 (en) 2000-06-09 2003-03-25 Eastman Kodak Company Copolymerization of norbornene and functional norbornene monomers
US6350837B1 (en) 2000-06-09 2002-02-26 Eastman Chemical Company Copolymerization of norbornene and functional norbornene monomers
US6706891B2 (en) 2000-11-06 2004-03-16 Eastman Chemical Company Process for the preparation of ligands for olefin polymerization catalysts
WO2002064638A3 (fr) * 2001-02-14 2003-03-20 Basf Ag Procede de polymerisation en emulsion d'olefines
WO2002083749A3 (fr) * 2001-04-12 2003-09-25 Basf Ag Procede de production, par catalyse a l'aide de metaux de transition, de dispersions aqueuses contenant des polyolefines ou des polymeres aromatiques vinyliques
WO2003020779A1 (fr) * 2001-08-31 2003-03-13 Kaneka Corporation Copolymere greffe de polyolefine produit avec un catalyseur de polymerisation de coordination a base d'un complexe de metal de transition apparaissant dans une periode ulterieure et procede pour preparer ce copolymere
US7335703B2 (en) 2001-08-31 2008-02-26 Kaneka Corporation Polyolefin graft copolymer prepared in the presence of coordination polymerization catalyst based on late transition metal complex and method for making the same

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