EP1124865A1 - Procede de polymerisation d'une olefine a polymerisation cationique - Google Patents

Procede de polymerisation d'une olefine a polymerisation cationique

Info

Publication number
EP1124865A1
EP1124865A1 EP99928976A EP99928976A EP1124865A1 EP 1124865 A1 EP1124865 A1 EP 1124865A1 EP 99928976 A EP99928976 A EP 99928976A EP 99928976 A EP99928976 A EP 99928976A EP 1124865 A1 EP1124865 A1 EP 1124865A1
Authority
EP
European Patent Office
Prior art keywords
process defined
group
substituted
radicals
hydrocarbyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99928976A
Other languages
German (de)
English (en)
Inventor
Michael C. Baird
Arquimedes R. Ivic Centrode Quimica KARAM
Michelle A. Parent
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Inc
Original Assignee
Bayer Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Inc filed Critical Bayer Inc
Publication of EP1124865A1 publication Critical patent/EP1124865A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a process for polymerizing at least one cationically polymerizable olefin.
  • Cationic polymerization of olefins is known in the art.
  • Conventional, cationic polymerization is effected using a catalyst system comprising: (i) a Lewis acid, (ii) a tertiary alkyl initiator molecule containing a halogen, ester, ether, acid or alcohol group, and, optionally, (iii) an electron donor molecule such as ethyl acetate.
  • a catalyst system comprising: (i) a Lewis acid, (ii) a tertiary alkyl initiator molecule containing a halogen, ester, ether, acid or alcohol group, and, optionally, (iii) an electron donor molecule such as ethyl acetate.
  • Such catalysts systems have been used for the so-called “living” and “non-living” carbocationic polymerization of olefins.
  • Component (ii) of the catalyst system typically is a compound having the formula:
  • R 1 , R 2 and R 3 are a variety of alkyl or aromatic groups or combinations thereof, n is the number of initiator molecules and X is the functional group on which the Lewis acid effects a change to generate a carbocationic initiatiation site - i.e., X typically is a halogen, ester, ether, acid or alcohol group depending on the Lewis acid employed.
  • X typically is a halogen, ester, ether, acid or alcohol group depending on the Lewis acid employed.
  • One or two X groups per initiator molecule tends to lead to the production of substantially linear polymers, whereas three or more X groups per initiator molecule tends to lead to the production of substantially star polymers.
  • Catalyst systems based on halogens and/or alkyl-containing Lewis acids such as boron trichloride and titanium tetrachloride, use various combinations of the above components and typically have similar process characteristics .
  • Lewis acid concentrations it is conventional for Lewis acid concentrations to exceed the concentration of initiator sites by 16 to 40 times in order to achieve 100 percent conversion in 30 minutes (based upon a degree of polymerization equal to 890) at -75° to -80°C. Examples of the so-called "living " polymerization systems are taught in
  • ionizing compounds not containing an active proton is also known. See, for example, any one of:
  • Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anionic pre-cursors containing metallic oxidizing groups along with the anion groups - see, for example, published European patent application
  • United States patent 5,066,741 teaches the preparation of syndiotactic polystyrene or poly(vinyl aromatics) using non-coordinating anions in combination with cyclopentadienyl transition metal derivatives under coordination catalysis conditions.
  • United States patents 5,196,490 and 4,808,680 there is disclosed a similar procedure using an alumoxane. Jordan, in the Journal of the American Chemical Society (1986, 108,
  • the present invention provides a process for polymerizing a cationically polymerizable olefin comprising the step of polymerizing at least one cationically polymerizable olefin at a subatmospheric pressure in the presence of a cationic polymerization catalyst system.
  • the present invention provides a process for polymerizing an olefin monomer comprising isobutylene, the process comprising the step of polymerizing the olefin monomer at a subatmospheric pressure at a temperature higher than about -80 °C in the presence of a cationic polymerization catalyst system.
  • the present inventor has surprisingly and unexpectedly discovered that it is possible to produce useful polymers by polymerizing a cationically polymerizable olefin at a subatmospheric pressure.
  • This discovery is especially surprising and unexpected when applied to the polymerization of an olefin comprising isobutylene, optionally containing a diolefin such as isoprene.
  • the present process is applicable to the production of butyl rubber at temperatures higher than is conventional. This particular application of the process can result in significant savings in capital and operating expenses for a butyl rubber production facility.
  • the present process is directed to the polymerization of at least one cationically polymerizable monomer.
  • the present process may be used to polymerize a mixture of monomers comprising the cationically polymerizable monomer.
  • the mixture may comprise another cationically polymerizable monomer and/or another polymerizable monomer.
  • the cationically polymerizable olefin is selected from the group comprising an olefin, a styrenic olefin, a heteroatom olefin and mixtures thereof.
  • the olefin comprises a C 2 -C 30 olefin, more preferably a C 2 -
  • Non-limiting examples of a useful olefm may be selected from the group comprising ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, dodecyldocecene, 3-methylpentene-l, 3,5,5- trimethylhexene-1, isobutylene, 2-methyl-butene, 2-methyl-pentene, vinyl ether, vinyl carbazole and mixtures thereof.
  • the styrenic olefin is selected from the group comprising styrene, C,-C 60 alkyl substituted styrene and mixtures thereof.
  • Non-limiting examples of useful styrenic olefins may be selected from the group comprising styrene, oc-methyl styrene, p-chlorostyrene, p-methylstyrene and mixtures thereof.
  • the heteroatom olefin is selected from the group comprising alkyl vinyl ethers, alkyl, amines, alkenyl amines and aryl amines.
  • useful heteroatom olefins may be selected from the group comprising methyl vinyl ether, isobutylvinyl ether, butyl vinyl ether, vinyl carbazole and mixtures thereof.
  • a preferred monomer comprises a mixture of isobutylene and p-methyl styrene.
  • polymerization is conducted in the presence of the at least one cationically polymerizable olefin and a diene monomer.
  • the diene monomer may be conjugated or non-conjugated.
  • Diolefin monomers are well known in the art and the choice thereof for use in the present process is within the purview of a person skilled in the art.
  • the non-conjugated diolefin can be straight chain, branched chain or cyclic hydrocarbon dioolefins having from 6 to 15 carbon atoms.
  • Illustrative nonlimiting examples are straight chain acyclic diolefms such as 1 ,4-hexadiene and 1,6-octadiene, the branched chain acyclic diolefms such as 5- methylhexadiene- 1,4, 7-methy 1-octadiene- 1 , 6 and 7-methyl-octadiene- 1,7; single ring alicyclic diolefins such as 1,4-cyclohexadiene and 1,5- cyclooctadiene, and multi ring alicyclic fused and bridged ring dioolefins such as tetrahydroindene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5- vinylidene-2-norbornene and 5-isopropylidene-2-norbornene.
  • the conjugated diolefin is preferably selected from the group comprising 2,3-dimethyl- but
  • butyl rubber as used throughout this specification is intended to denote polymers prepared by reacting a major portion, e.g. , from about 70 to 99.5 parts by weight, usually 85 to 99.5 parts by weight of an isomonoolefin, such as isobutylene, with a minor portion, e.g. , about 30 to 0.5 parts by weight, usually 15 to 0.5 parts by weight, of a multiolefin, e.g., a conjugated diolefin, such as isoprene or butadiene, for each 100 weight parts of these monomers reacted.
  • a multiolefin e.g., a conjugated diolefin, such as isoprene or butadiene
  • the isoolefin in general, is a C 4 to C 8 compound , e.g., isobutylene, 2-methyl- 1-butene, 3 -methyl- 1-butene, 2-methyl-2-butene and 4-methyl-l-pentene.
  • the preferred monomer mixture for use in the production of butyl rubber comprises isobutylene and isoprene.
  • an additional olefinic termonomer such as styrene, ⁇ -methylstyrence, p-methylstyrene, chlorostyrene, pentadiene and the like may be incorporated in the butyl rubber polymer. See, for example, any one of:
  • the present process is conducted at subatmospheric pressure.
  • the pressure at which the present process is conducted is less than about 100 kPa, more preferably less than about 90 kPa, even more preferably in the range of from about 0.00001 to about 50 kPa, even more preferably in the range of from about 0.0001 to about 40 kPa, even more preferably in the range of from about 0.0001 to about 30 kPa, most preferably in the range of from about 0.0001 to about 15 kPa.
  • the present process comprises the use of a cationic polymerization system.
  • the cationic polymerization system comprises a reactive cation and a compatible non-coordinating anion.
  • the reactive cation may be any cation that can react with an olefin to create a carbocationic polymerization site.
  • compatible non-coordinating anion and “NCA” are used interchangeably throughout this specification and are intended to encompass an anion which either does not coordinate the cation or which is only weakly coordinated to the cation thereby remaining sufficiently labile to be displaced by an olefin monomer.
  • compatible non-coordinating anion specifically refers to an anion which, when functioning as a stabilizing anion in the cationic polymerization system used in the present process, does not irreversibly transfer an anionic substituent or fragment thereof to the cation thereby forming a neutral byproduct or other neutral compound.
  • Compatible non-coordinating anions are anions which are not degraded to neutrality when the initially formed complex decomposes.
  • Non-limiting examples of such compatible non-coordinating anions may be selected from the group comprising alkyltris(pentafluorophenyl) boron (RB(pfp) j ), tetraperfluorophenylboron (B(pfp) 4 ), tetraperflouro- phenylaluminum, carboranes, halogenated carboranes and the like.
  • R,, R 2 , and R 3 are a variety of substituted or unsubstituted alkyl or aromatic groups or combinations thereof
  • n is the number of initiator molecules and is preferably greater than or equal to 1 , even more preferably between 1 and 30, and
  • X is the functional group on which the Lewis acid affects a change to bring about the carbocationic initiating site. This group is typically a halogen, ester, ether, alcohol or acid group depending on the Lewis acid employed.
  • the preferred cationic polymerization system comprises: (i) a reactive cation, and (ii) a non-coordinating anion.
  • a preferred class of compatible non-coordinating anions includes chemically stable, non-nucleophilic substituted anionic complexes.
  • any metal or metalloid compound may be used that is capable of forming an anionic complex which is resistant to irreversibly transferring a substituent or fragment to the cation to neutralize the cation to produce a neutral molecule.
  • any metal or metalloid capable of forming a coordination complex which is stable in water may also be used or contained in a composition comprising the anion. Suitable metals include, but are not limited to, boron, phosphorus, silicon and the like.
  • the non-coordinating anion has the formula:
  • M' is a metal or metalloid
  • Qi to Q n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals , halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q to Q n may be a halide radical; m is an integer representing the formal valence charge of M; n is the total number of ligands Q; and d is an integer greater than or equal to 1.
  • Non-limiting examples of a metal useful as M may be selected from the group comprising aluminum, gold and platinum.
  • Non-limiting examples of a metalloid useful as M may be selected from the group comprising boron, phosphorus and silicon.
  • Q 3 and Q 4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals , halocarbyl and substituted-halocarbyl radicals , hydrocarbyl- and fialocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the proviso that Q 3 and Q 4 will not be halide at the same time.
  • Non-limiting examples of boron components which may be used as NCA's may be selected from the group comprising: tetra-valent boron compounds such as tetra(phenyl)boron, tetra(p-tolyl)boron, tetra(o-tolyl)boron, tetra(pentafluorophenyl)boron, tetra(o,p-dimethylphenyl)boron, tetra(m,m- dimethylphenyl)boron, (p-tri-fluoromethylphenyl)boron and mixtures thereof.
  • tetra-valent boron compounds such as tetra(phenyl)boron, tetra(p-tolyl)boron, tetra(o-tolyl)boron, tetra(pentafluorophenyl)boron, tetra(o,p-dimethylphenyl)boron, tetra(m,m-
  • Another preferred class of NCA's is the class comprising those NCA comprising a plurality of boron atoms, including boranes and carboranes.
  • Non- limiting examples of carborane NCA's may be selected from the group comprising: dodecaborate, decachlorodecaborate, dodecachlorododecaborate, 1-carbadecaborate, 1-carbaundecaborate, 1-trimethylsilyl-l-carbadecaborate and mixtures thereof.
  • Non-limiting examples of borane and carborane complexes and salts of borane and carborane anions may be selected from the group comprising decaborane(14) , 7 ,8-dicarbadecaborane(13) , 2,7- dicarbaundecaborane( 13) , undecahydrido-7 , 8-dimethyl-7 , 8- dicarbaundecaborane, 6-carbadecaborate(12), 7-carbaundecaborate, 7,8- dicarbaundecaborate.
  • NCA's comprising metallaborane anions are also useful.
  • Non- limiting examples of such NCA's may be selected from the group comprising bis(nonahydrido-l,3-dicarbanonaborato)cobaltate(III), bis(undecahydrido-7,8- dicarbaundecaborato)ferrate(III), bis(undecahydrido-7,8-dicarbaundecaborato) cobaltate(III), bis(undecahydrido-7,8-dicarbaborato) nikelate(III), bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III), bis(tribromooctahydrido-7 , 8-dicarbaundecaborato)cobaltate(III) , bis(undecahydridodicarbadodecaborato)cobaltate(III), bis(undecahydrido-7- carbaundecaborato) cobaltate(III) and mixtures
  • NCA compositions most preferred for use in the cationic polymerization system are those containing a tris-perfluorophenyl boron, tetrapentafluorphenyl boron anion and/or two or more tripentafluorophenyl boron anion groups covalently bonded to a central atomic molecular or polymeric complex or particle.
  • the other component in the preferred cationic polymerization catalyst system comprises one or more reactive cations that are selected from different classes of cations and cation sources. Some preferred classes are:
  • preferred cyclopentadienyl metal derivatives may be selected from the group comprising compounds that are a mono-, bis- or tris-cyclopentadienyl derivative of a transition metal selected from Groups 4, 5 or 6 of the Periodic Table of Elements.
  • Preferred compositions include mono- cyclopentadienyl (Mono-Cp) or bis-cyclopentadienyl (Bis-Cp) Group 4 transition metal compositions, particularly zirconium, titanium and/or hafnium compositions.
  • Preferred cyclopentadienyl derivatives are transition metal complexes selected from the group comprising:
  • (A-Cp) is either (Cp)(Cp*) or Cp-A'-Cp*;
  • Cp and Cp* are the same or different cyclopentadienyl rings substituted with from 0 to 5 substituent groups S, each substituent group S being, independently , a radical group selected from the group comprising hydrocarbyl , substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl- substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C 4 to C 20 ring system to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
  • R is a substituent on one of the cyclopentadienyl radicals which is also bonded to the metal atom;
  • A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings or (C 5 H 5 . y . x S x ) and JR'( z .,. y ) groups;
  • M is a Group 4,5, or 6 transition metal; y is 0 or 1 ; (C 5 H 5 . y . x S x ) is a cyclopentadienyl ring substituted with from 0 to 5 S radicals; x is from 0 to 5;
  • JR'( z .,_ y ) is a heteroatom ligand in which J is a Group 15 element with a coordination number of three or a Group 16 element with a coordination number of 2, preferably nitrogen, phosphorus, oxygen or sulfur; R" is a hydrocarbyl group;
  • X and X 1 are independently a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, and hydrocarbyl- and halocarbyl-substituted organometalloid radical, substituted pnictogen radical, or substituted chalcogen radicals; and
  • L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.
  • Other cyclopentadienyl compounds that may be used in the cationic polymerization catalyst system are described in:
  • a preferred group of reactive cations comprises carbocationic compounds having the formula:
  • R 1 , R 2 and R 3 are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R 1 , R 2 and R 3 may be hydrogen.
  • none of R 1 , R 2 and R 3 are H.
  • R 1 , R 2 and R 3 are independently a C x to C 20 aromatic or aliphatic group.
  • suitable aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
  • Non-limiting examples of suitable aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
  • a preferred group of reactive cations comprises substituted silylium cationic compounds having the formula:
  • R 1 , R 2 and R 3 are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, with the proviso that only one of R 1 , R 2 and R 3 may be hydrogen.
  • none of R 1 , R 2 and R 3 are H.
  • R 1 , R 2 and R 3 are, independently, a C x to C 20 aromatic or aliphatic group. More preferably, R 1 , R 2 and R 3 are independently a C, to C g alkyl group.
  • Non- limiting examples of useful aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
  • Non-limiting examples of useful aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
  • a particularly preferred group of reactive substituted silylium cations may be selected from the group comprising trimethylsilylium, triethylsilylium and benzyldimethylsilylium. Such cations may be prepared by the exchange of the hydride group of the R !
  • the source for the cation may be any compound that will produce a proton when combined with the non-coordinating anion or a composition containing a non-coordinating anion.
  • Protons may be generated from the reaction of a stable carbocation salt which contains a non- coordinating, non-nucleophilic anion with water, alcohol or phenol to produce the proton and the corresponding by-product.
  • reaction may be preferred in the event that the reaction of the carbocation salt is faster with the protonated additive as compared with its reaction with the olefin.
  • Other proton generating reactants include thiols, carboxylic acids, and the like. Similar chemistries may be realized with silylium type catalysts.
  • an aliphatic or aromatic alcohol may be added to inhibit the polymerization.
  • Another method to generate a proton comprises combining a Group 1 or Group 2 metal cation, preferably lithium, with water, preferably in a wet, non-protic organic solvent, in the presence of a Lewis base that does not interfere with polymerization.
  • a wet solvent is defined to be a hydrocarbon solvent partially or fully saturated with water. It has been observed that when a Lewis base, such as isobutylene, is present with the Group 1 or 2 metal cation and the water, a proton is generated.
  • the non- coordinating anion is also present in the "wet" solvent such that active catalyst is generated when the Group 1 or 2 metal cation is added.
  • Another preferred source for the cation is substituted germanium, tin or lead cations.
  • Preferred non-limiting examples of such cations include substances having the formula:
  • R 1 , R 2 and R 3 are independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group, and M is germanium, tin or lead with the proviso that only one of R 1 , R 2 and R 3 may be hydrogen.
  • M is germanium, tin or lead with the proviso that only one of R 1 , R 2 and R 3 may be hydrogen.
  • none of R 1 , R 2 and R 3 are H.
  • R 1 , R 2 and R 3 are, independently, a C, to C 20 aromatic or aliphatic group.
  • Non-limiting examples of useful aromatic groups may be selected from the group comprising phenyl, toluyl, xylyl and biphenyl.
  • Non-limiting examples of useful aliphatic groups may be selected from the group comprising methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl and 3,5,5-trimethylhexyl.
  • a further preferred non-coordinating anion comprises a compound selected from the group comprising:
  • d is an integer greater than or equal to 1 ;
  • Z is selected from the group comprising: OR “ , SR “ , SeR “ , NR 2 , PR 2 , AsR 2 “ , SbR 2 “ , F, Cl “ , Br ' and I “ ;
  • R is selected from the group comprising hydrogen, C C 40 alkyl, C r C 40 cycloalkyl, C 5 -C 40 aryl, halogen substituted derivatives thereof and heteratom substituted derivatives thereof;
  • M' and M" may be the same or different and each has the formula
  • M is a metal or metalloid
  • Q, to Q n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals , halocarbyl and substituted-halocarbyl radicals and hydrocarbyl and halocarbyl-substituted organometalloid radicals and any one, with the proviso that not more than one of Q ⁇ to Q n may be a halide radical; and n is an integer representing the formal valence charge of M.
  • M is selected from the group comprising B, Al, Ga and In.
  • the preferred non-coordinating anion is a tetra-valent boron compound.
  • Non-limiting examples of such compounds may be selected from the group comprising tri(phenyl)boron, tri(p-tolyl)boron, tri(o-tolyl)boron, tri(pentafluorophenyl)boron, tri(o,p-dimethylphenyl)boron, tri(m,m- dimethylphenyl)boron and (p-tri-fluoromethylphenyl)boron.
  • a particularly preferred type of cationic polymerization catalyst system is disclosed in United States patent 5,448,001.
  • the coinitiator (BRR'R) disclosed in the '001 patent as the sole component of the cationic polymerization system in the present process.
  • This approach is particularly well suited for the production of isobutylene-based polymers such as isobutylene homopolymer and the like.
  • the present process is particularly well suited for the production of butyl rubber and other isobutylene-based polymers. Specifically, it has been discovered that such rubbers and polymers having desirable physical properties may be produced at higher temperatures than conventionally used.
  • the present process may be conducted at a temperature higher than about -80° C, preferably at a temperature in the range of from about -80 °C to about 25 °C, more preferably at a temperature in the range of from about -40 °C to about 25 °C, even more preferably at a temperature in the range of from about -30 °C to about 25 °C, even more preferably at a temperature in the range of from about -20°C to about 25°C, most preferably at a temperature in the range of from about 0°C to about 25 °C.
  • Embodiments of the present invention will be described with reference to the following Examples which are provided for illustrative purposes only and should note be used to limit the scope of or construe the invention.
  • the diene monomers (isoprene (IP) or 2, 3 -dimethyl- 1,3 -butadiene, (DMBD)) were dried over molecular sieves and then distilled.
  • the system was evacuated to 10 "1 to 10 "2 torr, and the IB was melted and distilled at a temperature in the range of from about -10°C to about -6.5°C (the boiling point of IB being -6.4 °C at one atmosphere pressure) into the glass polymerization vessel; 6 mL of solvent (toluene) was added to the condenser which was attached to the reactor; and the solution of IB was brought to the desired temperature (usually approximately -30°C). Solutions of Cp*TiMe 3 (Cp* ⁇ ⁇ 5 -pentamethylcyclopentadienyl; Me ⁇ methyl; usually 14 mg, 0.06 mmol; recrystallized from pentane) and B(C 6 F 5 ) 3
  • an amount of diene equivalent to ⁇ 1 % (mole) of the amount of IB was added to the reaction vessel prior to the addition of initiator and co-initiator.
  • Solutions of olefin(s) and initiator system were generally stirred as long as possible under a static vacuum and at the predetermined temperature (by "static vacuum", it is meant that the system was closed at this point and the pressure essentially was the vapour pressure of PIB at the reaction temperature).
  • Copious amounts of polymeric materials generally began to precipitate after about 2 minutes, and reactions were terminated after 10-30 min by the addition of 5-10 mL methanol.
  • the precipitated polymeric materials were purified of inorganic residues by dissolving in pentane or hexane and passing through a short silica column. Solvents were removed under reduced pressure and the solid, white polymers were dried at 60°C-90°C for at least two days. Control reactions were also run using just Cp*TiMe 3 or B(C 6 F 5 ) 3 .
  • Example 2 As will be apparent to those of skill in the art, a vacuum was not applied during polymerization in Examples 1 and 3. Accordingly, Examples 1 and 3 are provided for comparative purposes only and are not encompassed by the present invention.
  • Table 1 support the conclusion that conducting the polymerization of isobutylene at subatmospheric pressure (Example 2) results in the production of a polymer having a higher Mw when compared to conducting the polymerization of isobutylene at atmospheric pressure (Example 1).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un procédé de polymérisation d'une oléfine à polymérisation cationique telle qu'un mélange d'isoprène et d'isobutylène, afin de produire du butyle. Le procédé est conduit sous pression réduite en présence d'un système conventionnel de catalyseur de polymérisation cationique. Un catalyseur de polymérisation cationique préféré comprend Cp*TiMe3 et B(C6H5)3. En conduisant le procédé de cette manière, sous pression réduite, on peut obtenir, à température plus élevée, comparativement aux moyens habituels, un polymère avec des caractéristiques de poids moléculaire recherchées, ce qui permet d'abaisser les coûts de production et en capital de l'installation de production de ce polymère.
EP99928976A 1998-07-17 1999-07-16 Procede de polymerisation d'une olefine a polymerisation cationique Withdrawn EP1124865A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US9327698P 1998-07-17 1998-07-17
US93276P 1998-07-17
PCT/CA1999/000644 WO2000004061A1 (fr) 1998-07-17 1999-07-16 Procede de polymerisation d'une olefine a polymerisation cationique

Publications (1)

Publication Number Publication Date
EP1124865A1 true EP1124865A1 (fr) 2001-08-22

Family

ID=22238075

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99928976A Withdrawn EP1124865A1 (fr) 1998-07-17 1999-07-16 Procede de polymerisation d'une olefine a polymerisation cationique

Country Status (7)

Country Link
EP (1) EP1124865A1 (fr)
JP (1) JP2002520453A (fr)
CN (1) CN1309670A (fr)
AU (1) AU4597799A (fr)
CA (1) CA2337003A1 (fr)
HK (1) HK1039951A1 (fr)
WO (1) WO2000004061A1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2332203A1 (fr) * 2001-01-24 2002-07-24 Bayer Inc. Procede de production de polymeres d'isobutylene de poids moleculaire eleve
CA2360611C (fr) * 2001-10-30 2010-08-17 Bayer Inc. Initiateur exempt de metaux de transition pour la preparation de polymeres a base d'isobutylene
CA2368724C (fr) 2002-01-21 2011-06-14 Bayer Inc. Procede de preparation de polymeres a base d'isobutylene
US7425601B2 (en) 2002-12-20 2008-09-16 Exxonmobil Chemical Patents Inc. Polymers with new sequence distributions
CA2510856C (fr) * 2002-12-20 2013-01-08 Exxonmobil Chemical Patents Inc. Procedes de polymerisation faisant intervenir un ou des hydrofluorocarbures (hfc)
WO2004058827A1 (fr) * 2002-12-20 2004-07-15 Exxonmobil Chemical Patents Inc. Procedes de polymerisation
CA2510860C (fr) * 2002-12-20 2012-10-09 Exxonmobil Chemical Patents Inc. Procede de polymerisation pour lequel on utilise des hydrofluorocarbures comme diluants
US7332554B2 (en) 2002-12-20 2008-02-19 Exxonmobil Chemical Patents Inc. Polymers with new sequence distributions
US7202317B2 (en) 2003-04-17 2007-04-10 The University Of Akron Polymerization of i-butene in hydrocarbon media using bis(borane) co-initiators
US7196149B2 (en) 2003-04-17 2007-03-27 The University Of Akron Polymerization of i-butane in hydrocarbon media using bis(borane) co-initiators
CA2441079C (fr) 2003-09-16 2012-04-24 Bayer Inc. Procede de fabrication de butylcaoutchouc
CA2581050C (fr) 2004-06-15 2012-01-10 Exxonmobil Chemical Patents Inc. Compositions elastomeriques, barrieres pneumatiques, et leurs procedes de fabrication
WO2006009553A1 (fr) 2004-06-23 2006-01-26 Exxonmobil Chemical Patents Inc. Procedes de separation de composants de melanges
WO2006011868A1 (fr) 2004-06-25 2006-02-02 Exxonmobil Chemical Patents Inc. Procede de polymerisation mettant en oeuvre des hydrocarbures fluores
CA2578679A1 (fr) 2006-03-14 2007-09-14 Lanxess Inc. Procede de polymerisation au moyen d'amorceurs a base d'halogenure de zinc
US7629397B2 (en) 2006-06-23 2009-12-08 Exxonmobil Chemical Patents Inc. Phase separation process utilizing a hydrofluorocarbon
US8148450B2 (en) 2006-06-23 2012-04-03 Exxonmobil Chemical Patents Inc. Process to produce a hydrocarbon rubber cement utilizing a hydrofluorocarbon diluent
US7402636B1 (en) 2007-03-23 2008-07-22 Exxonmobil Chemical Patents Inc Method and apparatus for decreasing polymer deposition
US7981991B2 (en) 2007-04-20 2011-07-19 Exxonmobil Chemical Patents Inc. Separation of polymer slurries
CN103588918B (zh) * 2013-11-07 2016-03-30 济南开发区星火科学技术研究院 一种丁基橡胶的制备方法
KR102156110B1 (ko) * 2018-04-05 2020-09-15 주식회사 엘지화학 양이온성 금속 복합체 및 보레이트계 벌키 음이온을 갖는 유기금속 촉매, 이의 제조 방법 및 이를 이용한 올리고머 또는 폴리머의 제조 방법
CN113527556B (zh) * 2021-01-12 2022-05-24 福州大学 催化制备乙烯基醚聚合物的方法
CN119039495B (zh) * 2023-05-29 2025-10-10 浙江理工大学 用于乙烯基醚立体选择性阳离子聚合的催化体系

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL85097A (en) * 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
US5391629A (en) * 1987-01-30 1995-02-21 Exxon Chemical Patents Inc. Block copolymers from ionic catalysts
PL276385A1 (en) * 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
US5066741A (en) * 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
US5635573A (en) * 1992-12-01 1997-06-03 Exxon Chemical Patents Inc. Method for preparing alpha-olefin/cycloolefin copolymers
US6008307A (en) * 1994-04-28 1999-12-28 Exxon Chemical Patents Inc Process for producing olefin polymers using cationic catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0004061A1 *

Also Published As

Publication number Publication date
JP2002520453A (ja) 2002-07-09
WO2000004061A1 (fr) 2000-01-27
CA2337003A1 (fr) 2000-01-27
CN1309670A (zh) 2001-08-22
HK1039951A1 (zh) 2002-05-17
AU4597799A (en) 2000-02-07

Similar Documents

Publication Publication Date Title
EP1124865A1 (fr) Procede de polymerisation d'une olefine a polymerisation cationique
EP0548274B1 (fr) Catalyseur ionique pour la production de poly-alpha-olefines a tacticite controlee
EP0468537B1 (fr) Catalyseurs, méthode de préparation de ces catalyseurs et procédé d'utilisation
US6444606B1 (en) Supported catalyst system, method for the production and use thereof in olefin polymerization
KR101514378B1 (ko) 1-부텐 에틸렌 공중합체
US6265493B1 (en) Polyolefin graft copolymers derived from linear copolymers of alpha-olefins and divinylbenzene having narrow molecular weight and composition distributions and process for preparing same
JP5793820B2 (ja) 分枝ビニル末端ポリマー及びその製造方法
JP4291693B2 (ja) １−ブテンを重合する方法および１−ブテンポリマー
US6008307A (en) Process for producing olefin polymers using cationic catalysts
EP0631589A1 (fr) CATALYSEUR IONIQUE UTILISE POUR PRODUIRE DES POLY-$g(a)-OLEFINES A TACTICITE CONTROLEE
HU208326B (en) Process for producing polymerization catalyst compositions and for polymerizing olefins, diolefins and monomers having acetylene bond by using the catalyst compositions
CA2178077A1 (fr) Procede de (co)polymerisation d'olefines
WO2001070395A2 (fr) Catalyseurs
US20080275201A1 (en) Process for making high molecular weight Isobutylene polymers
JP3332051B2 (ja) 重合用触媒及び該触媒系を用いる重合体の製造方法
ES2210762T3 (es) Procedimiento para producir polipropileno isotactico en fase condensada, mediante la utilizacion de titanocenos.
US6252019B1 (en) Process for polymerizing tactioselective polyolefins in condensed phase using hafnocenes
CA2360611C (fr) Initiateur exempt de metaux de transition pour la preparation de polymeres a base d'isobutylene
JP2014511910A (ja) ビニル末端高級オレフィンコポリマーおよびその生成方法
RU2316559C2 (ru) Соединения, каталитическая композиция, способы гомо- или сополимеризации
McAdon et al. Catalyst activator
Burger et al. Olefin Polymerization with Single Component Organoscandium and Organoyttrium Catalysts
MXPA96005175A (en) Catiónic catalysts and process for using such catalysts
MXPA00009934A (en) Propylene copolymers containing styrene units

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20030404