Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • 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
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • 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
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene
• • 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
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/14—Monomers containing five or more carbon atoms

Definitions

• This invention relates to polymerizable compositions comprising alpha-olefin hydrocarbon monomers and a method for their polymerization, wherein the method is tolerant of both oxygen and water Catalysts for the polymerization include organometallic complexes of Group VIII metals (CAS version of the Periodic Table), preferably Pd or Ni Methods for polymerizing the polymerizable composition in open air and in the presence of water to provide novel polymers are desc ⁇ bed
• 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) polyme ⁇ zations 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 acryiate esters
• ZN Ziegler-Natta
• REP ring-opening metathesis polymerizations
• GTP group-transfer polymerizations
• cationic and anionic polymerizations of activated olefins such as styrene or acryiate esters
• metallocene catalysts have received considerable attention for polyme ⁇ z
• European Patent Application No 454231 describes a polymerization catalyst and a method of polymerizing ethylene, other olefins, and alkynes using 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
• a preferred cationic portion has the formula
• V is a two-electron donor ligand and L" L" are chelating ligands wherein each L" is a neutral two-electron donor ligand, and M is nickel or palladium
• All olefin polymerizations were conducted with ethylene, were carried out under dry, oxygen-free nitrogen atmospheres and all solvents were thoroughly dried under nitrogen by distillation from, e.g., sodium/benzophenone High polymer (M w > 90,000) was not disclosed Johnson et al., (J. Am. Chem.
• R 1 is H or methyl, or the two R s taken together are 1,8- naphthalene-diyl, i.e ,
• U S Patent No 5,296,566 describes certain organometallic catalysts for ROMP of ring-strained cyclic olefins that are stable towards oxygen and water However, these catalysts are ineffective for polymerization of linear alpha-olefin monomers
• Japanese Patent Application No JP 0725932 describes Group VIII catalysts (such as Ni) which polymerize ethylene
• U S Patent No 4,724,273 describes the use of nickel catalysts to polymerize alpha-olefins, yielding polymers with methyl branching points
• U S Patent No 5,030,606 describes nickel- containing catalysts which are useful for producing copolymers of ethylene and polar or non-polar comonomers
• European Patent Application No 603,557 describes catalytic compositions prepared by contacting an organonickel compound with a cyclicazacarbyl compound which can be used to convert one or more olefins to oligomerization and/or polymerization products Only ethylene is exemplified. Summary of the Invention
• the present invention describes a polymerizable composition
• a polymerizable composition comprising one or more alpha-olefin hydrocarbon monomers, an effective amount of an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Ni or Pd, and a polydentate ligand providing steric bulk sufficient to permit formation of high polymer, and at least one of water and air
• the invention describes a method of polymerizing a composition, the composition comprising at least one alpha-olefin monomer, as catalyst an effective amount of the above-mentioned organometallic catalyst comprising a Group VIII metal, preferably Ni or Pd, and at least one of water and air
• the present invention provides an alpha-olefin polymer comprising a plurality of C 3 or larger alpha-olefin units wherein the polymer M w is greater than 90,000, preferably greater than 100,000, and the polymer has an average number of branch points less than one per alpha-olefin unit
• the present invention provides a mixture comprising an alpha-olefin polymer comprising at least one of 1) a plurality of C 3 or larger alpha-olefin units wherein the polymer has an average number of branch points less than one per monomer unit, and 2) a plurality of C 2 alpha-olefin units wherein the polymer has an average number of branch points greater than 0 01, preferably greater than 0 05, per alpha-olefin unit, the mixture further comprising water in an amount sufficient to form a second phase
• the polymer M w is greater than 90,000, and most preferably greater than 100,000
• the present invention provides crosslinked alpha- olefin polymers
• a method employing high-energy irradiation of the polymer, preferably by electron beam irradiation, is used
• a method employing ultraviolet (UV) irradiation is used, preferably further comprising the addition of UV-activated crosslinking agents
• the present invention provides improved one-part catalysts which are organometallic salts useful for the polymerization of alpha-olefin monomers in the presence of at least one of water and air
• two-part catalysts comprising a neutral organometallic compound and a cocatalyst, useful for the polymerization of alpha- olefins, optionally in the presence of one or both of air and water, and methods of preparation thereof, are also provided
• the present invention provides an improved method of preparing an organometallic catalyst wherein a neutral organometallic compound is reacted with a salt of a non-coordinating counterion to give an organometallic salt as catalyst and a halide salt as by-product Variations of the method involve different process conditions, to give one-part and two-part catalysts Different variations may be preferred in specific applications In this invention
• 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 which can be acyclic or cyclic and preferably is an acyclic alpha-olefin,
• 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 CH unit in the polymer, bonded to three other carbon atoms, e g ,
• alpha-olefin unit means a group of carbon atoms in a polymer derived by polymerization from a single alpha-olefin molecule
• high polymer means a polymer having a weight average molecular weight (M w ) greater than 90,000, 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, a bidentate ligand having steric bulk sufficient to permit formation of high polymers, and a metal to R bond, wherein R is H, 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
• Me means methyl (CH 3 -)
• Et means ethyl (CH,CH 2 -)
• i-Pr means isopropyl
• gel fraction means the fraction of polymer that is insoluble in an appropriate solvent, e.g., toluene, particularly after crosslinking
• polymerization reactions of the invention proceed in the presence of air and/or water at useful rates and produce in high yields high polymers that have useful properties Water may occur naturally in the monomer, especially in liquid monomer The polymerization reaction can even be carried out successfully in systems in which water is present or added in amounts sufficient to form a second (aqueous) phase It is advantageous to be able to eliminate the costs and process steps associated with drying and deoxygenating monomers and solvents
• ZN nor metallocene catalysts containing Periodic Groups IIIB, IVB, or VB metals are active in the presence of oxygen or water
• Cocatalysts such as alkylaluminum compounds, methylaluminoxane, alkyl zinc compounds and the like, are also sensitive to air and moisture and are not useful under the conditions in this invention and organometallic catalyst
• polymers having different properties can be produced. Certain of these polymers may be preferred for specific applications.
• the polymers of the invention find use as functional and decorative coatings, as molded or extruded articles, and as binders.
• a distinct aqueous phase is present in the polymerizable composition such as in aqueous emulsion or suspension polymerizations and provides processing advantages such as reduction or elimination of organic solvents. Also, it provides a thermal sink to aid in process temperature control.
• a distinct aqueous phase is present in addition to the polymer and this mixture provides processing advantages such as lower overall viscosity.
• compositions comprising two or more monomers and copolymers produced from such compositions are also within the scope of the present invention.
• the present invention describes a polymerizable composition
• a polymerizable composition comprising an alpha-olefin hydrocarbon monomer, an effective amount of an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Ni or Pd, and a polydentate ligand having steric bulk sufficient to permit formation of high polymer, and at least one of water and air (oxygen).
• an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Ni or Pd
• a polydentate ligand having steric bulk sufficient to permit formation of high polymer, and at least one of water and air (oxygen).
• Alpha-olefin hydrocarbon monomers useful in the invention include substituted and unsubstituted, including acyclic, branched, and cyclic alpha-olefins, 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, 1- hexadecene, 1 -octadecene, 1 -eicosene, and the like, and cyclic alpha-olefins such as cyclopentene, and combinations thereof.
• acyclic alpha-olefins such as ethylene, propene, 1 -butene, 1- pentene, 1-hexene, 1-heptene, 1 -octene, 1-decene, 1-dodecene, 1 -tetradecene, 1- hexadecene
• alpha-olefins include propene, 1 -butene, 1-hexene, 1 -octene, and other alpha-olefins up to about C 20 .
• liquid monomers are preferred, and higher boiling alpha-olefins, e.g., 1 -octene to about 1 -hexadecene, are particularly preferred
• Copolymers may be random or blocky (block copolymers), depending on polymerization kinetics and processes
• Useful comonomers can include other alpha-olefins, alkyl acrylates and methacrylates, and acrylic and methacrylic acids and salts thereof
• Organometallic catalysts useful in the invention comprise metals of Periodic Group VIII, ligands providing steric bulk sufficient to permit formation of high 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
• 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 in the invention can be one-part or two-part.
• One-part catalysts are organometallic salts of a Group VIII metal and a polydentate ligand having steric bulk sufficient to permit formation of high polymer, and an anion selected from the group consisting of B(C6F 5 ) 4 ft PF 6 ft SbF 6 ⁇ , AsF 6 ft BF 4 ft B ⁇ 3,5-C 6 H 3 (CF 3 ) 3 ⁇ 4 ⁇ (R f SO 2 ) 2 CHft (R f SO 2 ) 3 Cft (R f SO 2 ) 2 Nft and R f SO 3 " , wherein Rf 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 is to be added to the reaction mixture immediately before polymerization is to begin.
• Such catalysts can be useful in batch reactions used to prepare polymer.
• One-part catalysts can be isolated and are essentially pure compounds.
• One-part catalysts are preferably cationic complexes, and further comprise non-coordinating counterions.
• Preparation of one-part Group VIII metal complexes useful as catalysts in polymerizable compositions of the invention have been described in the previously- mentioned European Patent Application No. 454,23 1, and the article by Johnson et al. (J. Am. Chem. Soc, 1995, 117. 6414-6415), wherein these catalysts were disclosed to be useful in inert atmospheres.
• the catalysts were characterized as complexes having a cationic portion of the formula
• 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.
• a preferred cationic portion has the formula (L') 2 M-R + wherein the two L 1 groups are joined through chemical bonds and each L 1 is a two- electron donor ligand as defined above, and M and R are as previously defined.
• Johnson et al. J. Am. Chem. Soc, 1995, 117. 6414-6415
• catalysts comprising nickel or palladium and ligand groups chosen to provide steric bulk sufficient to permit formation of high polymer.
• preferred Pd(II)- and Ni(II)-based catalysts for olefin polymerizations are cationic metal methyl complexes of the general formula
• R 2 can be -CH 3 , t-butyl, or -CH 2 (CF 2 ) 6 CF 3 , as reported by Johnson et al. (J. Am. Chem. Soc, 1996, H8, 267-268 and supplementary material) to be useful in inert atmospheres.
• the present invention provides new compositions of matter useful as one-part catalysts.
• One preferred counterion is which is safer to prepare than B(3,5-C ⁇ H 3 (CF 3 ) 2 ) " , as judged by the number of reported explosions, and is commercially available from Boulder Scientific Company, Mead, CO, and provides better control over polymer molecular weight.
• Multiple reports have appeared concerning the hazards associated with the preparation of trifluoromethyl-substituted tetraarylborate compounds, including the explosion of intermediate aryl magnesium compounds (see I C. Appleby, Chemistry and Industry, 1971, 120, and E. Hauptman, R. M. Waymouth, J W. Ziller, J.
• each R f is independently selected from the group consisting of highly fluorinated or perfluorinated alkyl or fluorinated aryl radicals.
• Compounds of Formulas XHa, Xllb and XIIc may also be cyclic, when a combination of any two Rf groups are linked to form a bridge
• the R f 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, 1 or 2 of which can be heteroatoms.
• the alkyl radical Rf 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 at least half replaced with fluorine that are not replaced with fluorine be replaced with bromine and/or chlorine.
• At least two out of three hydrogens on the alkyl group be replaced with fluorine, still more preferred that at least three of four hydrogen atoms be replaced with fluorine and most preferred that all hydrogen atoms be replaced with fluorine to form a perfluorinated alkyl group.
• the fluorinated aryl radicals of Formulas XHa through Xlld 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 8 F 17 SO 2 ) 3 C ⁇ , (CF SO 2 ) 3 C ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (C 4 F 9 SO 2 ) ?
• F in the ring means the ring carbon atoms are perfluorinated, and the like. More preferred anions are those described by Formulas Xllb and XIIc wherein Rf is a perfluoroalkyl radical having 1 -4 carbon atoms.
• Anions of this type, and representative syntheses, are described in, e.g., U S Patent Nos 4,505,997, 5,021,308, 4,387,222, 5,072,040, 5, 162, 177, and 5,273,840, inco ⁇ orated herein by reference, and in Turowsky and Seppelt, Inorg. Chem., l9SS, 27, 2135-2137.
• Such counterions may be preferred with certain metals and ligands, or in some processes
• Other useful fluorinated non-coordinating counterions include PF 6 " , SbF 6 ⁇ AsF 6 " , and BF 4 '
• 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
• the present invention provides improved one-part catalysts useful for the polymerization of alpha-olefin monomers These catalysts are designed with the advantages of improved counterions and ethers, and are new compositions of matter Preferred compositions can be of the formula
• Q can be selected from B(CeF5) 4 , anions as shown in Formulas XHa through Xlld, PF 6 , 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 Xlla through Xlld
• 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 or Ni 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.
• Preferred neutral compounds can be of the general formula
• Ar, R and R 1 are as defined above, and X represents a halogen atom, preferably chlorine or bromine, most preferably chlorine.
• silver salts are preferred and can have the formulae
• ne 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 integer 1, 2, or 3
• the less expensive alkali metal salts Periodic Group IA
• Particular counterions may be preferred under specific reaction conditions For example, in two-part systems comprising a second aqueous phase, B(C6F 5 ) 4 is preferred
• 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 ⁇ - (toluene), Li + ⁇ B(C 6 F 5 )4 ⁇ ft Na + ⁇ B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ⁇ -, Li + ⁇ N(SO 2 CF 3 ) 2 ⁇ Lf ⁇ B(C 6 F 5 ) 4 ⁇ -(Et 2 O) 2 , Li + ⁇ N(SO 2 CF 3 )(SO 2 C4F 9 ) ⁇ -, Li + ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ " , Li + ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ -(hydrate), Li + ⁇ N(SO 2 C4F
• One- and two-part catalysts can be present in the invention mixture in the range of 0 0001 to about 3 weight percent, preferably 0 001 to 1 weight percent.
• the present invention provides an improved method of preparation of organometallic catalyst
• a neutral organometallic compound is reacted with a salt of a non-coordinating counterion preferably comprising fluorine (F) to give an organometallic catalyst and a halide salt as by-product
• a salt of a non-coordinating counterion preferably comprising fluorine (F)
• F fluorine
• there is at least one mole of A + Q " per mole of neutral organometallic compound In some cases, excess A + Q ' may be preferred since A * Q " may function as a surfactant in the reaction mixture
• the reaction is conducted in an ether solvent, or mixture of solvents containing an ether at or near room temperature (20° to 25°C)
• the one-part catalyst is isolated from the reaction mixture by removal of solvent
• filtration to remove and recover AgCI by-product and further purification by methods such as solvent extraction (for example, dissolution of catalyst in an organic solvent such as CH 2 C1 2 , optional filtration, washing of this solution with a portion of water, and removal of organic solvent) or recrystallization are apparent to those skilled in the art and are within the scope of this invention.
• One-part Pd catalysts have been prepared according to this method with various counterions, including ⁇ N(SO 2 C 4 F 9 ) 2 ⁇ “ , ⁇ CH(SO 2 CF 3 ) 2 ⁇ (SO 3 CF 3 ) ⁇ (SbF 6 ) ⁇ (BF 4 ) ' , and (PF 6 ) " .
• This method is particularly preferred for counterions wherein the corresponding silver salt is readily available. It is also a useful method for rapid synthesis when water-sensitive counterions are used
• a fourth variation of the method provides two-part catalysts
• a neutral organometallic compound as defined in the third variation is used in combination with a cocatalyst comprising a silver salt of a non-coordinating counterion
• the advantages of two-part catalysts have been previously described
• a fifth variation of this 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
• Such 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 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 Additives, adjuvants and
• Monomers or comonomers containing organic functional groups can also be useful in the invention Such monomers may be useful to modify polymer properties
• a second (aqueous) phase which can provide process advantages such as lower overall viscosity, higher polymer molecular weight or yield, temperature control, reduction or elimination of organic solvents, and is preferred in certain applications.
• the aqueous phase may be continuous, discontinuous, or cocontinuous with the organic phase.
• Polymerizable compositions may further comprise surfactants. Surfactants are preferred when a second aqueous phase is present. Ionic surfactants are preferred.
• Suitable surfactants include sodium and ammonium sulfonates
• 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 In particular, polyether groups and halides, such as are found in polyether sulfonate or tetraalkylammonium halide surfactants, should be avoided
• Surfactants can be present in the composition in the range of about 0.01 to 5 weight percent
• the present invention also is directed toward a method of polymerizing a composition comprising at least one alpha-olefin monomer, an effective amount of an organometallic complex of a Group VIII metal, preferably Ni or Pd, as a catalyst, and at least one of water and air
• polymerizations of the invention have been demonstrated to take place both in open air and in the presence of water
• the above-mentioned one- or two-part palladium catalyst is mixed with the alpha-olefin monomer (for example, 1 -octene) in a container and polymerization is allowed to proceed
• organic solvents may be used to dissolve or disperse catalysts and may be present in amounts from about 0 5 to 99 percent by weight
• method (A) the neutral organometallic compound and cocatalyst salt can be mixed together and added to the monomer
• method (B) the monomer can be mixed with neutral organometallic compound and the cocatalyst salt subsequently added to that mixture
• method (C) two separate monomer streams, one containing neutral organometallic compound and one containing cocatalyst salt can be mixed.
• reaction temperature is -78° to +35° C, more preferably -40° to +25° C, and most preferably -10° to +20° C
• Temperatures above about 40° C may deactivate the catalyst, and good thermal control may be preferred since the polymerization of alpha-olefin monomers is exothermic
• a second aqueous phase as a heat sink to aid in the control of reaction temperature
• Polymerizations can be conducted at pressures greater than atmospheric, particularly in cases where one or more of the monomers is a gas
• liquid monomers may be preferred
• catalyst and monomer can be mixed and coated onto a substrate, and the mixture allowed to polymerize without protection from the ambient atmosphere
• monomers with boiling points greater than about 100°C such as 1 -octene and higher alpha-olefin monomers Variations in "temperature, concentration and the like may be employed See European Patent Application No 694,575
• Water can be present in the polymerizable composition and during polymerization in the range of 0 001 up to 99 weight percent of the total composition
• Water may be present in minor amounts when care is not taken to dry the monomer or optional organic solvents
• water is soluble in 1-hexene to the extent of approximately 480 parts per million at room temperature, and such concentration is within the scope of the present invention, since water at that concentration is known to deactivate ZN and metallocene catalysts
• Monomers are often supplied with varying amounts of water, from 0.001 weight percent up to the maximum solubility of water in the monomer, depending on temperature, specific monomer, ambient humidity, storage conditions, and the like.
• Optional solvents similarly contain varying amounts of water
• Oxygen can be present in an amount of 0.001 to about 2 weight percent or more of the total composition.
• Monomers and solvents may contain varying amounts of oxygen from the atmosphere depending on temperature, specific monomer or solvent, storage conditions, and the like.
• Oxygen can also be present in atmospheric amounts in environments surrounding the polymerizable mixture, such as headspace in a reaction vessel It is advantageous to avoid the expense and process steps of drying and deoxygenating monomer and solvent
• 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
• the polymer structure will vary as the monomer or monomers used in the polymerizable composition vary.
• a polymer made from 1 -octene, that is, n is 8 has a structure consisting essentially of ⁇ -CH 2 -CH(n-hexyl)- ⁇ and ⁇ -(CH 2 ) g - ⁇ y , wherein x is in the range 0.45 to 0.70, and (x + y) is in the range 0.90 to 0 98
• a polymer made from 1-hexene, that is, n is 6, has a structure consisting essentially of ⁇ -CH 2 -CH(n-butyl)- ⁇ x and ⁇ -(CH 2 ) 6 - ⁇ , wherein x is in the range 0.50 to 0.75, and (x + y) is in the range 0 90 to 0.98
• Polymer structure can affect polymer properties,
• a high polymer (M w over 90,000, preferably over 100,000, up to about 10,000,000, preferably up to about 2,000,000) is highly desirable, resulting in 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.
• a crosslinked polymer provides 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 beams, gamma radiation, or ultraviolet irradiation, occurring after polymerization
• Thermal means or actinic radiation including high energy sources such as electron beams, gamma radiation, or ultraviolet irradiation, occurring after polymerization
• Crosslinked polymers are within the scope of this invention
• Polyolefins prepared using organometallic catalysts described above, especially those comprising Ni or Pd 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.
• polyethylene can be crosslinked to produce a useful material upon irradiation without significant polymer degradation whereas polypropylene degrades much faster than it crosslinks, and polyolefins prepared via traditional Ziegler-Natta polymerizations are only modestly affected by irradiation
• treatment of polyolefins of the present invention with electron beams produces crosslinked polymers as indicated by the presence of a polymer gel fraction
• 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
• electron-beam crosslinking can be carried out after fabrication or other processing of the polyolefin by, e.g., extrusion, solvent casting, coating, molding, and the like, to give crosslinked shaped articles such as fibers, tubes, blocks, profiles, films, and the like
• Other useful high-energy sources are known, and are within the scope of the present invention
• Polymers of the present invention 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 s-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)
• Other useful additives will be apparent to those skilled in the art and are within the scope of this invention
• Crosslinking by ultraviolet irradiation is preferred in certain processes and product constructions, wherein it is necessary to process an uncrosslinked polymer, as in a solution or an extrusion process, prior to crosslink
• Alpha-olefin polymers of the present invention are useful as molded or extruded articles, as functional or decorative coatings, and as binders
• Example 1 Ag(toluene) 3 B(C6F 5 ) , referred to as Ag-A Ag(toluene) 3 B(C 6 F 5 ) 4 was prepared as follows, and is referred to as Ag-A throughout these examples. Under a nitrogen atmosphere, using dry, oxygen-free solvents, a solution of 200 mL hexane, 50 mL diethyl ether, and 17.29 g BrCeFs was cooled to -78°C. Thirty mL of 2.5 M n-BuLi in hexane was added all at once with stirring. The reaction was stirred for 30 minutes, during which time an orange precipitate formed. (CAUTION!
• Sample 2-B 0 75 g of catalyst solution was mixed with 4 8 g C 8 in air
• Sample 2-C 1 5 g of catalyst solution was placed in a vial, and solvent was removed The resulting solids were mixed with 5 0 g C 8 in air
• Samples 2-A and 2-B became viscous within 15 minutes, forming polymer at similar rates
• Sample 2-C became viscous and hot (due to the polymerization exotherm) within ten minutes
• This example illustrates the polymerization of propylene (C 3 ) in air
• the monomer is a gas at ambient temperature and pressure, so the polymerization was conducted in a high pressure reactor
• Catalyst was prepared from 260 mg Pd-A and 441 mg Ag-A in 6 49 g diethyl ether Ether was removed, and the resulting solids were mixed with 26 g CH 2 C1 in air The catalyst solution was placed in the reactor, which was then cooled to below -24°C, evacuated (so as to maximize the amount of C 3 that could be charged to the reactor) and filled with 150 g C 3 The reactor was shaken and allowed to warm at room temperature over a period of about four hours, then left for an additional 20 hours Excess C 3 was vented, and 30 g of polymer was recovered from the reactor.
• This example illustrates a polymerizable composition comprising alpha- olefin monomer, catalysts, and water in an amount sufficient to form a second, aqueous phase
• Catalyst was prepared from 84 mg Pd-A and 132 mg Ag-A in 5 mL diethyl ether. Ether was removed, and the resulting solids mixed with 3.66 g CH 2 C1 2 in air 271 g deionized water, 121 g 1 -octene and 1.32 g sodium heptadecyl sulfate (Tergitol 7TM, Union Carbide, New York, New York) were placed in a flask, and stirred with a magnetic stir bar. A milky mixture resulted.
• Samples 5-A, 5-B, and 5-C were generally performed as described in the previous examples
• Pd-A and Ag-A were mixed in diethyl ether, ether was removed, solvent (CH 2 C1 2 unless otherwise indicated) was used to dissolve the resulting solids in air, and this solution was mixed with monomer and other additives, as indicated.
• Samples 5-D, 5-E, and 5-1 employed one part catalyst Pd-B, dissolved in CH 2 C1 2 and added to monomer
• Sample 5-F also employed a one-part catalyst dissolved in CH 2 C1 2 except that a second, aqueous phase, was present
• Samples 5-G and 5-H were prepared in a manner similar to 5-D, using a one-part catalyst and, instead of solvent, vigorous mixing, with phosphite additives added after polymerization had occurred
• a temperature "r t " indicates room temperature (about 23 °C)
• W618F is Weston 618F (distearylpenterythritol diphosphite)
• Sample 5-B contained Irganox 1010TM (Ciba Geigy Corp , Ardsley, NY), a hindered-phenol-type stabilizer throughout the polymerization This sample was compared to 5-A, and no significant differences in polymerization rate were observed Polymer yields at about 2 days were 62% for 5-A and 63% for 5-B Sample 5-C, Polymer Analyses M w 1 04 x 10 5 , M n 4 23 x IO 4
• This example illustrates one method of preparing a two-part catalyst
• a neutral organometallic compound was used in combination with a cocatalyst comprising a silver salt of a non-coordinating counterion
• two-part catalysts were prepared by weighing equimolar amounts of Pd-A and Ag-A into a container and adding a solvent, typically an ether such as diethyl ether or THF. This was performed either under inert atmosphere to prevent adsorption of water by the silver salt (which might result in inaccuracies in weighing), or in air. Within minutes, the color of the mixture changed, and a precipitate (presumably AgCI) formed.
• a solvent typically an ether such as diethyl ether or THF
• the solution could be handled in air and added to monomer at this point, or ether or THF solvent (which affect polymerization rates) could be substantially removed to yield a yellow-brown solid which could be suspended in monomer or used in a different solvent Variations in order of addition, stoichiometry, amounts and kinds of solvent, atmosphere (e.g , pure oxygen or air of high or low humidity) and the like are within the scope of this invention.
• it may be desired to mix Pd-A and Ag-A after dissolution in the monomer, or after cooling, or to add each reagent to different portions or different phases of a polymerizable composition
• two-part catalysts may be preferred to control the onset of polymerization.
• a one-part catalyst was prepared by reacting the silver salt of a non-coordinating counterion with a neutral organometallic compound.
• One part catalyst Pd-B was prepared from equimolar amounts of Pd-A and
• Pd catalysts containing the following counterions were prepared: and ⁇ NSO 2 (CF 2 ) 2 SO 2 ⁇ -.
• This example shows that a neutral organometallic catalyst can be prepared without the necessity of isolating an intermediate silver salt of the counterion.
• a neutral organometallic catalyst can be prepared directly from a lithium salt of a noncoordinating anion without the need to use a silver salt. Although reaction time is longer, the method requires few steps and uses less expensive and less hazardous reagents.
• Examples 10 and 1 1 show that alpha-olefin polymerization can take place in a simple, rapid, one-pot procedure without the need to isolate the catalyst or to use relatively expensive silver salts
• a large volume of water was used as a sink for the heat of polymerization, and the reaction was carried out at a sufficiently low temperature that good polymer yield and molecular weight were achieved
• Example 12 Polymerization of Monomers to give Polymers, Employing Variations in Monomer and Catalyst
• catalyst was mixed with monomer and optional solvent as indicated Polymerization was conducted at the temperature and for the time indicated All procedures were conducted in air and with no attempt to remove water from monomer or solvent
• the amounts by weight of monomer to CH 2 C1 2 are A-l, 1 to 1; A-2, 3 to 1, A-4, 7 7 to 1, A-5, 1 to 2, A-6, 3 8 to 1, A-7, 5 portions of each comonomer to 1 portion of CH 2 C1 2 ; and A-8, 5 to 1 Reaction mixture was homogeneous initially, and polymer precipitated in some cases depending on monomer, temperature and extent of reaction
• one-part catalyst was dissolved in CH 2 CI 2 in a pressure vessel and gaseous monomer was added, but the exact amount of monomer charged was not recorded
• reaction times are shown as unknown, reaction progress was not carefully monitored and reaction times were greater than 100 hours, but not known with certainty
• reaction mixture contained one-part catalyst, 4 portions by weight of ethyl acetate, and 1 portion by weight of monomer. Reaction mixture was initially homogeneous, but polymer soon began to precipitate from solution
• D contained one-part catalyst and monomer, with no solvent Reaction mixture formed a solution and polymer precipitated from the solution as it formed Reaction progress was not carefully monitored and reaction times were greater than 100 hours, but not known with certainty.
• D* contained one-part catalyst and 1 portion by weight of each of two comonomers
• Example 14 Post-Polymerization Crosslinking by UV Irradiation Polyhexene was prepared by adding 100 0 gm of 1-hexene (cooled to 0°C) to
• Example 15 Preparation of a molded article.
• This example shows the use of one-part catalysts with varying non- coordinating counterions
• the catalyst was mixed in the amount specified with 10 g CH 2 C1 2 and 10 g 1 -octene. Mixing and polymerization occurred at 0°C. No attempt was made to remove or exclude water or air.
• Reaction progress was monitored by removing an aliquot from each sample at the times indicated, and drying each aliquot to determine the amount of non-volatile polymer present, from which the weight yield of polymer at that time was calculated. The molecular weight of the polymers formed after 24 hr of reaction time was measured.

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