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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/42—Introducing metal atoms or metal-containing groups
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • 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
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

• This invention relates to functionalization of vinyl terminated polyolefins by hydros ilylation reactions with a metallocene.
• U.S. Patent No. 4,1 10,377 discloses secondary aliphatic amines alkylated with alpha-olefins, such as ethylene, propylene, hexene, and undecene.
• alpha-olefins such as ethylene, propylene, hexene, and undecene.
• alpha-olefins such as ethylene, propylene, hexene, and undecene.
• alpha-olefins such as ethylene, propylene, hexene, and undecene.
• alpha-olefins such as ethylene, propylene, hexene, and undecene.
• hydroaminoalkylation of olefins using various catalysts see J.
• USSN 12/488,093, filed June 19, 2009 discloses a process to functionalize propylene homo- or co-oligomer comprising contacting an alkene metathesis catalyst with a heteroatom containing alkene and a propylene homo- or co-oligomer having terminal unsaturation.
• End-functionalized polyolefins that feature a chemically reactive or polar end group are of interest for use in a broad range of applications as compatibilizers, tie-layer modifiers, surfactants, and surface modifiers.
• transition metal catalysts such as metallocenes
• hydrosilane groups are both a commercially economical and an "atom-economical" route to end functionalized polyolefins.
• a novel method for their production by the reaction of vinyl-terminated polyolefins with difunctional hydrosilanes in the presence of a metallocene catalyst is useful for a range of vinyl terminated polyolefins, including isotactic polypropylene (iPP), atactic polypropylene (aPP), ethylene propylene copolymer (EP), and polyethylene (PE).
• iPP isotactic polypropylene
• aPP atactic polypropylene
• EP ethylene propylene copolymer
• PE polyethylene
• This invention relates to a process to functionalize polyolefins (as used herein, polyolefin is defined to include both polymers and oligomers) comprising contacting a metallocene catalyst with a difunctional hydrosilane, and one or more vinyl terminated polyolefins.
• This invention further relates to diblock hydrosilane-functionalized polyolefins, preferably represented by the formula:
• each PO and PO* independently, is a substituted or unsubstituted hydrocarbyl group having from 20 to about 10,000 carbon atoms;
• L is a bond, an oxygen atom, a Q to a C20 substituted or unsubstituted hydrocarbyl group, a Ci to a C20 substituted or unsubstituted hydrocarbyl ether group, or an R 3 -SiH2-SiH2- 4 group, wherein each R 3 and R 4 , independently is a Q to a C20 substituted or unsubstituted hydrocarbyl group or a C j to a C20 substituted or unsubstituted hydrocarbyl ether group, wherein R 3 and R 4 can, optionally, be tethered to each other to form a cyclic ring.
• hydros ilylated product can be further converted to other moieties such as an -Si(R*)2-OEt that would be useful to modify inorganic oxides such as silica.
• Figure 1 is a 13 C NMR of the product from the synthesis of a block polymer using a metallocene catalyst and 1, 10 disiladecane.
• oligomer is defined to have an Mn of from 100 to 25,000 g/mol as measured by NMR.
• a polymer has an Mn of more than 25,000 g/mol.
• a propylene oligomer or polymer is an oligomer or polymer having at least 50 mol% of propylene, respectively.
• Mn is number average molecular weight (measured by l R NMR unless stated otherwise)
• Mw is weight average molecular weight (measured by Gel Permeation Chromatography)
• Mz is z average molecular weight (measured by Gel Permeation Chromatography)
• wt% is weight percent
• mol% is mole percent.
• Mw Measured by Gel Permeation Chromatography
• Mn measured by l R NMR
• all molecular weight units e.g., Mw, Mn, Mz
• alkene is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
• a polymer or copolymer (or oligomer or co-oligomer) is referred to as comprising an olefin, including, but not limited to ethylene, propylene, and butene
• the olefin present in such polymer or copolymer (or oligomer or co-oligomer) is the polymerized form of the olefin.
• a copolymer when a copolymer is said to have an "ethylene" content of 35-55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35-55 wt%, based upon the weight of the copolymer.
• a "polymer” has two or more of the same or different mer units.
• “homopolymer” is a polymer having mer units that are the same.
• a “copolymer” is a polymer having two or more mer units that are different from each other.
• a “terpolymer” is a polymer having three mer units that are different from each other.
• a “polymer” has two or more of the same or different mer units.
• a “homo-oligomer” is an oligomer having mer units that are the same.
• a “co-oligomer” is an oligomer having two or more mer units that are different from each other.
• the term “different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.
• copolymer or co-oligomer includes terpolymers or "ter-oligomers” and the like.
• the term “different” as used to refer to polyolefins indicates that the mer units of the polyolefins differ from each other by at least one atom, the mer units of the polyolefins differ isomerically, the polyolefins differ in Mn, Mw, Mz, tacticity, Mw/Mn, g'vis, vinyl, vinylidene, vinylene, or internal unsaturation content, amount of comonomer (when the comonomer is the same or different in the polyolefins), density, melting point, heat of fusion, and the like.
• the definition of copolymer or co-oligomer, as used herein includes terpolymers or "ter-oligomers” and the like.
• a "higher" alpha-olefin is an alpha-olefin having at least 4 carbon atoms.
• Ethylene shall be considered an alpha-olefin.
• Me is methyl
• Ph is phenyl
• Et is ethyl
• Pr is propyl
• iPr is isopropyl
• n-Pr normal propyl
• Bu is butyl
• iBu is isobutyl
• tBu is tertiary butyl
• nBu normal butyl
• TMS is trimethylsilyl
• TIBAL is triisobutylaluminum
• TNOAL is triisobutyl n-octylaluminum
• MAO is methylalumoxane
• pMe is para-methyl
• Ar* is 2,6-diisopropylaryl
• Bz is benzyl
• THF is tetrahydrofuran
• RT room temperature
• tol is toluene.
• Bromine number is determined by ASTM D 1 159. ICPES (Inductively Coupled Plasma Emission Spectrometry), which is described in J. W. Olesik, "Inductively Coupled Plasma Emission Spectrometry
• this invention relates to a process to functionalize polyolefins comprising contacting a metallocene catalyst with a difunctional hydros ilylating agent, optionally in the presence of a base, and one or more vinyl terminated polyolefins, wherein:
• the metallocene is represented by the formula: TnCp2M3 ⁇ 4 T is a bradging group;
• n 0 or 1 ;
• each Cp is, independently, a substituted or unsubstituted cyclopentadienyl ring
• M is Zr, Ti, or Hf
• each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof;
• difunctional hydrosilylation agent is represented by the formula:
• L is a bond, an oxygen atom, a C to a C20 substituted or unsubstituted hydrocarbyl group, a Ci to a C20 substituted or unsubstituted hydrocarbyl ether group, or an R 3 -SiH 2 -SiH 2 - 4 group, wherein each R 3 and R 4 , independently is a Q to a C20 substituted or unsubstituted hydrocarbyl group or a Ci to a C20 substituted or unsubstituted hydrocarbyl ether group, wherein R 3 and R 4 can, optionally, be tethered to each other to form a cyclic ring;
• R 1 and R 2 are, independently, a substituted or unsubstituted Q to a C20 hydrocarbyl group
• the vinyl terminated polyolefin is substituted or unsubstituted hydrocarbyl group having from
• This invention relates to a process to functionalize polyolefins (as used herein, polyolefin is defined to include both polymers and oligomers) comprising contacting a metallocene catalyst with a difunctional hydrosilylating agent, optionally in the presence of a reducing agent (such as a base), and one or more vinyl terminated polyolefins.
• a metallocene catalyst with a difunctional hydrosilylating agent, optionally in the presence of a reducing agent (such as a base), and one or more vinyl terminated polyolefins.
• the reactants are typically combined in a reaction vessel at a temperature of - 50°C to 300°C (preferably 25°C, 150°C). Likewise the reactants are typically combined at a pressure of 0 to 1,000 MPa (preferably 0.5 to 500 MPa, preferably 1 to 250 MPa) for a residence time of 0.5 seconds to 10 hours (preferably 1 second to 5 hours, preferably 1 minute to 1 hour).
• metallocene 0.0005 to 0.01 moles of metallocene are charged to the reactor per mole of polyolefin charged.
• the process is typically a solution process, although it may be a bulk or high pressure process. Homogeneous processes are preferred. (A homogeneous process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where reactant concentration in all feeds to the reactor is 70 vol% or more.) Alternately no solvent or diluent is present or added in the reaction medium (except for the small amounts used as the carrier for the catalyst or other additives, or amounts typically found with the reactants; e.g., propane in propylene).
• Suitable diluents/solvents for the process include non-coordinating, inert liquids.
• Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorinated C4 0 alkanes, chlorobenzene, and aromatic; and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
• the feed concentration for the process is 60 vol% solvent or less, preferably 40 vol% or less, preferably 20 vol% or less.
• the process may be batch, semi-batch or continuous.
• continuous means a system that operates without interruption or cessation.
• a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
• Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruder, pipe or pump.
• This invention further relates to a process, preferably an in-line process, preferably a continuous process, to produce functionalized polyolefin, comprising introducing monomer and catalyst system into a reactor, obtaining a reactor effluent containing vinyl terminated polyolefin, optionally removing (such as flashing off) solvent, unused monomer and/or other volatiles, obtaining vinyl terminated polyolefin (such as those described herein), introducing vinyl terminated polyolefin, metallocene catalyst (as described herein) and difunctional hydros ilane (as described herein) into a reaction zone (such as a reactor, an extruder, a pipe and/or a pump) and obtaining functionalized polyolefin (such as those described herein).
• a reaction zone such as a reactor, an extruder, a pipe and/or a pump
• a metallocene catalyst is defined as an organometallic compound with at least one ⁇ -bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two ⁇ -bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties. This includes other ⁇ -bound moieties such as indenyls or fluorenyls or derivatives thereof.
• Useful metallocenes include those represented by the formula:
• each Cp is, independently, a substituted cyclopentadienyl ring (preferably selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms) or an unsubstituted cyclopentadienyl ring and the Cp groups may be bridged by a bridging group T (preferably represented by the formula R-2 a J, where J is C, Si or Ge, and each R a is, independently, hydrogen, halogen, Q to C20 hydrocarbyl or a Q to C20 substituted hydrocarbyl, and two R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system);
• a bridging group T preferably represented by the formula R-2 a J, where J is C, Si or Ge, and each R a is, independently, hydrogen, halogen, Q to C20 hydrocarbyl or a Q to C20 substituted hydrocarbyl, and two R a can form a cyclic structure including aromatic
• n 0 or 1, indicating the presence or absence of a bridge, T;
• M is Zr, Ti, or Hf, preferably Zr;
• each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof.
• n is 0.
• at least 1 position on the Cp ring is H, preferably at least 2 positions on the Cp ring are hydrogen, preferably at least 3, preferably at least 4, preferably 5 positions are H, or if the Cp is an indene, at least 1 position on the Cp ring is H, preferably at least 2, at least 3, at least 4, at least 5, at least 6, or 7 of the positions on the indene are hydrogen.
• n is 0, and at least 1 position on the Cp ring is hydrogen, preferably at least 2 positions on the Cp ring are H, preferably at least 3, preferably at least 4, preferably 5 positions are H, or if the Cp is an indene, preferably at least 1 position is H, preferably at least 2 positions are H, preferably at least 3, at least 4, at least 5, at least 6, or 7 of the positions on the indene are hydrogen.
• n is optionally 0 and at least 2 positions on the Cp ring are hydrogen, preferably at least 3, preferably at least 4, preferably 5, or if the Cp is an indene, preferably at least 2, at least 3, at least 4, at least 5, at least 6, or 7 of the positions in the indene are hydrogen, provided that if any positions on the Cp or indene are substituted that the substituent on the Cp or indene is a small group, such as a Ci to Ci Q hydrocarbyl, preferably a C ⁇ to C ⁇ alkyl, preferably a Q to C 4 alkyl, such as methyl, ethyl, propyl, or butyl.
• a Ci to Ci Q hydrocarbyl preferably a C ⁇ to C ⁇ alkyl, preferably a Q to C 4 alkyl, such as methyl, ethyl, propyl, or butyl.
• the substituent groups on the Cp do not form a substituted or unsubstituted fluorene.
• the Cp is not a substituted or unsubstituted indene.
• the substituent groups on the Cp do not form a substituted or unsubstituted fluorene or a substituted or unsubstituted indene.
• the metallocene is one or more of any precursor that can be reduced to a [Cp2ZrII] species; generally halides C ⁇ CXi, Cp2ZrBr 2 , etc, Cp2HfCl2, CP2 1CI2, mixed halides, dimers [Cp2ZrCl]2Cl, with any halide.
• reductants such as nBuLi, t-BuLi, EtMgCl, Na, Li, Mg, K, LiH, LiBEt 3 H, NaBH 4 , LiAlH 4 , sec-BuLi, (nBu)2Mg, MeLi, R*ZnX*, wherein X* is a leaving group such as a halide and R* is a hydrocarbyl group.
• the metallocene can be bridged or unbridged.
• the metallocene can be a bridged or unbridged substituted metallocene such as T n (CpMe) 2 MX 2 , T n (CpPrMe) 2 MX 2 , T n (CpBuMe) 2 MX 2 , T n (Cpn- Pr) 2 MX 2 , T n (Cpt-Butyl) 2 MX 2 , T n (CpSiMe 3 ) 2 MX 2 , T n (Indenyl)(Cp)MX 2 , T n (Fluorenyl)(Cp)MX 2 , wherein M, T, X and n are as a defined above, preferably n is 0.
• Suitable T groups include, for example, M ⁇ Si, CR*2, Et2Si, CH2CH2 and the like wherein R* is a hydrocarbyl group.
• a "catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material, where the system can polymerize monomers to polymer.
• catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
• the metallocene catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably.
• An "anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
• a “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
• the difunctional hydrosilylation agent is represented by the formula:
• L is a bond, an oxygen atom, a Q to a C20 substituted or unsubstituted hydrocarbyl group, a Q to a C20 substituted or unsubstituted hydrocarbyl ether group, or an R 3 -SiH 2 -SiH 2 -R 4 group, wherein each R 3 and R 4 , independently is a Q to a C20 substituted or unsubstituted hydrocarbyl group or a C j to a C20 substituted or unsubstituted hydrocarbyl ether group, wherein R 3 and R 4 can, optionally, be tethered to each other to form a cyclic ring;
• R 1 and R 2 are, independently, a substituted or unsubstituted to a C20 hydrocarbyl group.
• Hydrosilylation reagents further include: wherein x is a number from 1 to 40. It should be understood that excess vinyl containing PO may be used during the reaction to cause difunctionalization to occur.
• the difunctional hydrosilylation agents is one or more of 1, 10 disiladecane, SiH 3 (CH 2 ) 2 SiH 3 , SiH 3 (CH 2 ) 6 SiH 3 , SiH 3 (CH 2 ) 16 SiH 3 , SiH 3 (CH 2 ) 4 SiH 3 SiH 3 (CH 2 ) 8 SiH 3 , SiH 3 (CH 2 ) 3 SiH 3 , SiH 3 (CH 2 ) 10 SiH 3 , SiH 3 (CH 2 )SiH 3 , SiH 3 (CH 2 ) 3 SiH 3 ortho, meta, or para-SiH 3 (C 6 H 4 ) 2 SiH 3 , SiMeH 2 (CH 2 ) 2 SiMeH 2 , SiMeH 2 (CH 2 ) 1 _ 18 SiMeH 2 ,
• a strong reducing agent such as n-butyl lithium can be used to help facilitate the hydrosilylation process when X is a halide in the metallocene.
• suitable reducing agents include, for example, t-BuLi, EtMgCl, Na, Li, Mg, K, LiH, LiBEt 3 H, NaBH 4 , L1AIH4, sec- BuLi, (nBu)2Mg, MeLi, R*ZnX*, wherein X* is a leaving group such as a halide and R* is a hydrocarbyl group.
• Allyl chain ends (also referred to as “vinyl termination”, “allylic vinyl end group”, “vinyl chain ends” or “vinyl content”) is defined to be a polyolefin (polymer or oligomer) having at least one terminus represented by formula I: allylic vinyl end group
• ⁇ represents the polyolefin chain.
• allyl chain end is represented by the formula II:
• the amount of allyl chain ends is determined using NMR at 120°C using deuterated tetrachloroethane as the solvent on a 500 MHz machine, and in selected cases confirmed by 13 C NMR.
• Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a Bruker AM 300 spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon) for vinyl terminated propylene polymers in J. American Chemical Soc, 114, 1992, 1025- 1032 that are useful herein.
• Isobutyl chain end is defined to be a polyolefin containing at least 1 mol% propylene and having at least one termin represented by the formula:
• M represents the polyolefin chain.
• isobutyl chain end is represented by one of the following formulae:
• M represents the polyolefin chain
• the percentage of isobutyl end groups is determined using 13 C NMR (as described in the example section) and the chemical shift assignments in Resconi et al, J. Am. Chem. Soc, 1992, 1 14, 1025-1032 for 100% propylene polymers (and polymers) and set forth in Figure 2 for E-P polymers (and polymers) of USSN 12/143,663, filed June 20, 2008.
• the "isobutyl chain end to allylic vinyl group ratio" is defined to be the ratio of the percentage of isobutyl chain ends to the percentage of allyl chain ends.
• This invention can be practiced with any vinyl containing materials, preferably with vinyl terminated polymers or oligomers, such as vinyl terminated ethylene homo- and copolymers or homo-or co-oligomers, and vinyl terminated propylene homo- and copolymers or homo-or co-oligomers.
• Useful vinyl terminated polyolefins include homo-and copolymers or homo-or co-oligomers of heteroatom containing monomers, as well as polymers or oligomers of olefin monomers only.
• the term vinyl terminated polyolefins includes vinyl terminated polymers and vinyl terminated copolymers, vinyl terminated homo-oligomers and vinyl terminated co-oligomers.
• Preferred vinyl terminated polyolefins include vinyl terminated isotactic polypropylene (preferably having a melting point of 100°C or more, preferably 150°C or more), vinyl terminated polyethylene (preferably having a melting point of 100°C or more, preferably 115°C or more).
• any vinyl terminated polyolefin described herein has at least 75% allyl chain ends (relative to total unsaturations), preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%.
• any vinyl terminated polyolefin described herein has an Mn of 200 g/mol or more, alternately from 200 to 60,000 g/mol, preferably from 200 to 50,000 g/mol, preferably from 200 to 40,000 g/mol, preferably from 500 to 30,000 g/mol, preferably from 1,000 to 10,000 g/mol.
• the vinyl terminated polyolefin used herein comprises at least 10 mol% (alternately at least 20 mol%, alternately at least 40 mol%, alternately at least 60 mol%) of a C 4 or greater olefin (such as butene, pentene, octene, nonene, decene, undecene, dodecene, preferably C 5 to C 4 Q alpha olefin such as pentene, octene, nonene, decene, undecene, dodecene) and has: 1) at least 30% allyl chain ends (relative to total unsaturations), preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%; and 2) an Mn of from 200 to 60,000 g/mol, preferably from 200 to
• the vinyl terminated polyolefin is a homopolymer, copolymer, homo-oligomer or co-oligomer comprising one or more C2 to C 4 Q olefins, preferably C2 to C 4 Q alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, 1 -nonene, 1 -decene, 1 -undecene, 1 -dodecene, and/or 4-methylpentene-l .
• the vinyl terminated polyolefin used herein has an Mn of from 200 to 60,000 g/mol, preferably from 500 to 30,000 g/mol, preferably from 1,000 to 20,000 g/mol and is a homopolymer, copolymer, homo-oligomer or co-oligomer comprising two or more C2 to C 4 o olefins, preferably two or more or C3 to C20 alpha olefins, preferably two or more of ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and/or dodecene and has at least 30% allyl chain ends (relative to total unsaturations), preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%.
• the vinyl terminated polyolefin is a polymer or oligomer having an Mn of from 200 to 21,000 g/mol (preferably 500 to 15,000, preferably
• the vinyl terminated polyolefin is a polymer or an oligomer having an Mn of from 500 to 21,000 g/mol (preferably 700 to
• alpha olefins selected from the group consisting of C2 to C40 alpha olefins, preferably C3 to C20 alpha olefins, preferably two or more alpha olefins selected from the group consisting ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene and has at least 30% allyl chain ends (relative to total unsaturations), preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%.
• the vinyl terminated polyolefin is an ethylene polymer or oligomer, e.g. a homo-polymer of ethylene, copolymer of ethylene, homo-oligomer of ethylene or co- oligomer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C3 to C40 alpha olefin comonomers, preferably selected from the group consisting of propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• ethylene polymer or oligomer e.g. a homo-polymer of ethylene, copolymer of ethylene, homo-oligomer of ethylene or co- oligomer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C3 to C
• the vinyl terminated polyolefin is a propylene polymer or oligomer, e.g., a homopolymer of propylene, copolymer of propylene, homo-oligomer of propylene or co-oligomer of propylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C2 and C 4 to C 4Q alpha olefin comonomers, preferably selected from the group consisting of ethylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• the vinyl terminated polyolefin is a copolymer or co-oligomer of ethylene and/or propylene and a C 4 to C 4Q alpha-olefin, such as butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene and has at least 30% allyl chain ends (relative to total unsaturations), preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%.
• the vinyl terminated polyolefin is a copolymer or co-oligomer of ethylene and/or propylene and two or more C 4 to C 4Q alphaolefins, such as butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• the vinyl terminated polyolefin has at least 30% allyl chain ends, relative to total unsaturations (preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%) and the vinyl terminated polyolefin is a copolymer or co- oligomer of:
• ethylene and two or more C 4 to C 4Q alpha olefins such as butene, pentene, hexene, octene, nonene, decene, undecene, dodecene; or
• propylene and two or more C 4 to C 4Q alpha olefins such as butene, pentene, hexene, octene, nonene, decene, undecene, dodecene; or
• ethylene and propylene and two or more C 4 to C 4 Q alphaolefins such as butene, pentene, hexene, octene, nonene, decene, undecene, dodecene; or
• propylene and two or more alpha olefins selected from butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• the vinyl terminated polyolefin is a polymer or oligomer having an Mn of greater than 1,000 g/mol (preferably from 2,000 to 60,000, preferably 5,000 to 50,000) comprising one or more alpha olefins selected from the group consisting of C2 to C 4 Q alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, and 4-methyl-pentene-l .
• the vinyl terminated polyolefin is an ethylene polymer or oligomer, e.g., a homo-polymer of ethylene, copolymer of ethylene, homo-oligomer of ethylene or co-oligomer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C3 to C 4 Q alpha olefin comonomers, preferably selected from the group consisting of propylene, butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, and 4- methyl-pentene- 1.
• ethylene polymer or oligomer e.g., a homo-polymer of ethylene, copolymer of ethylene, homo-oligomer of ethylene or co-oligomer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20
• the vinyl terminated polyolefin is propylene polymer, e.g., a homopolymer of propylene, a copolymer of propylene, a homo-oligomer of propylene or co- oligomer of propylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C2 to C 4 Q alpha olefins comonomers, preferably selected from the group consisting of ethylene, butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, and 4-methyl-pentene-l having at least 30% allyl chain ends, relative to total unsaturations (preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95
• the vinyl terminated polyolefin useful herein may be one or more vinyl terminated polyolefins having an Mn (measured by !fi NMR) of 200 g/mol or more, (preferably 300 to 60,000 g/mol, preferably 400 to 50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000 g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000 g/mol); and comprising: (i) from about 20 to about 99.9 mol% (preferably from about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol%, or from about 50 to about 95 mol%) of at least one
• C 5 to C 4 o olefin (preferably C 5 to C30 a-olefins, more preferably C5-C20 a-olefins, preferably, Cs-C ⁇ a-olefins, preferably pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5- cyclooctadiene, 1 -hydroxy-4-cyclooctene, 1 -acetoxy-4-cyclo
• the vinyl terminated polyolefins useful herein may be one or more vinyl terminated polyolefins having an Mn (measured by NMR) of 200 g/mol or more (preferably 300 to 60,000 g/mol, 400 to 50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000 g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to 10,000 g/mol) and comprises: (i) from about 80 to 99.9 mol% (preferably 85 to 99.9 mol%, more preferably 90 to 99.9 mol%) of at least one C 4 olefin (preferably 1-butene); and (ii) from about 0.1 to 20 mol% of propylene, preferably 0.1 to 15 mol%, more preferably 0.1 to 10 mol%; wherein the vinyl terminated polyolefins has at least 40% allyl chain ends relative to total unsaturations, preferably at least 50%, at least 60%, at least
• the invention relates to a composition
• a composition comprising vinyl terminated polyolefins polymers having an Mn of at least 200 g/mol, (preferably 200 to 100,000 g/mol, preferably 200 to 75,000 g/mol, preferably 200 to 60,000 g/mol, preferably 300 to 60,000 g/mol, or preferably 750 to 30,000 g/mol) (measured by l R NMR) comprising of one or more (preferably two or more, three or more, four or more, and the like) C 4 to C 4 Q (preferably C 4 to C30, C 4 to C20, or C 4 to C ⁇ , preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecen
• these higher olefin vinyl terminated polymers may comprise ethylene derived units, preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, or preferably at least 90 mol% ethylene).
• ethylene derived units preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, or preferably at least 90 mol% ethylene).
• the vinyl terminated polyolefin useful herein is a branched polyolefin having an Mn of 7,500 to 60,000 g/mol (and optionally a Tm of greater than 60°C (preferably greater than 100°C), and/or, optionally, a AHf of greater than 7 J/g
• alpha olefins preferably ethylene and/or propylene and optionally a C 4 to alpha olefin
• said branched polyolefin having: (i) 50 mol% or greater allyl chain ends, relative to total unsaturated chain ends (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more); (ii) a g'(vis) of 0.90 or less (preferably 0.85 or less, preferably 0.80 or less); (iii), optionally, an allyl chain end to internal vinylidene ratio of greater than 5: 1 (preferably greater than 10: 1); (iv) optionally, an allyl chain end to vinylidene chain end ratio of greater than greater than 10: 1 (preferably greater than 15: 1).
• the vinyl terminated polyolefin useful herein is a branched polyolefin having an Mn of 60,000 g/mol or more (and optionally a Tm of greater than 60°C (preferably greater than 100°C), and/or, optionally, a AHf of greater than 7 J/g (preferably greater than 50 J/g)) comprising one or more alpha olefins (preferably ethylene and/or propylene and optionally a C 4 to CIQ alpha olefin), and having: (i) 50 mol% or greater allyl chain ends, relative to total unsaturated chain ends (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more); (ii) a g'(vis) of 0.90 or less (preferably 0.85 or less, preferably 0.80 or less); (iii) a bromine number which, upon complete hydrogenation, decreases by at least 50%
• the vinyl terminated polyolefin useful herein is a branched polyolefin having an Mn of less than 7,500 g/mol, preferably from 100 to 7,000 g/mol, preferably form 400 to 6,500 g/mol (and optionally a Tm of greater than 60°C (preferably greater than 100°C), and/or, optionally, a AHf of greater than 7 J/g (preferably greater than 50 J/g)) comprising one or more alpha olefins (preferably ethylene and/or propylene and optionally a C 4 to Cio alpha olefin), and having: (i) 50 mol% or greater allyl chain ends, relative to total unsaturated chain ends (preferably 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more); (ii) a ratio of percentage of saturated chain ends to percentage of allyl chain ends of 1.2 to 2.0 (preferably a ratio of percentage of saturated chain ends
• C 4 to Qo alpha olefin monomers useful in the branched polymers described above include butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, and isomers thereof.
• the vinyl terminated polyolefin consist essentially of propylene, functional group and optionally ethylene.
• C 4 olefins are substantially absent from the vinyl terminated polyolefin.
• C 4 _2o olefins are substantially absent from the vinyl terminated polyolefin.
• isobutylene is substantially absent from the vinyl terminated polyolefin.
• substantially absent is meant that the monomer is present in the polyolefin at 1 wt% or less, preferably at 0.5 wt% or less, preferably at 0 wt%.
• the vinyl terminated polyolefin has a branching index, g' vjs (as determined by GPC), of 0.98 or less, alternately 0.96 or less, alternately 0.95 or less, alternately 0.93 or less, alternately 0.90 or less, alternately 0.85 or less, alternately 0.80 or less, alternately 0.75 or less, alternately 0.70 or less, alternately 0.65 or less, alternately 0.60 or less, alternately 0.55 or less.
• g' vjs as determined by GPC
• the vinyl terminated polyolefin preferably has a glass transition temperature (Tg) of less than 0°C or less (as determined by differential scanning
• the vinyl terminated polyolefin has a melting point (DSC first melt) of from 30°C to 200°C, alternately 40°C to 180°C, alternately 50°C to 100°C.
• the polymers described herein have no detectable melting point by DSC following storage at ambient temperature (23 °C) for at least 48 hours.
• the vinyl terminated polyolefins described herein are a liquid at 25°C.
• the vinyl terminated polymers described herein have a viscosity at 60°C of greater than 1,000 cP, greater than 12,000 cP, or greater than 100,000 cP. In other embodiments, the vinyl terminated polymers have a viscosity of less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP. Viscosity is measured using a Brookfield Digital Viscometer.
• any of the vinyl terminated polyolefins described or useful herein have 3-alkyl vinyl end groups (where the alkyl is a CI to C38 alkyl), also referred to as a "3-alkyl chain ends" or a "3-alkyl vinyl termination", represented by the formula:
• R b is a CI to C38 alkyl group, preferably a CI to C20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, and the like.
• the amount of 3-alkyl chain ends is determined using 13 C NMR as set out below.
• any of the vinyl terminated polyolefins described or useful herein have at least 5% 3-alkyl chain ends (preferably at least 10% 3-alkyl chain ends, at least 20% 3-alkyl chain ends, at least 30% 3-alkyl chain ends; at least 40% 3-alkyl chain ends, at least 50% 3-alkyl chain ends, at least 60% 3-alkyl chain ends, at least 70% 3-alkyl chain ends; at least 80%3-alkyl chain ends, at least 90% 3-alkyl chain ends; at least 95% 3- alkyl chain ends, relative to total unsaturation.
• 3-alkyl chain ends preferably at least 10% 3-alkyl chain ends, at least 20% 3-alkyl chain ends, at least 30% 3-alkyl chain ends; at least 40% 3-alkyl chain ends, at least 50% 3-alkyl chain ends, at least 60% 3-alkyl chain ends, at least 70% 3-alkyl chain ends; at least 80%3-alkyl chain ends, at least 90% 3-alkyl chain ends; at least 95% 3- alkyl chain ends, relative
• any of the vinyl terminated polyolefins described or useful herein have at least 5% of 3-alkyl + allyl chain ends, (e.g all 3-alkyl chain ends plus all allyl chain ends), preferably at least 10% 3-alkyl + allyl chain ends, at least 20% 3-alkyl + allyl chain ends, at least 30% 3-alkyl + allyl chain ends; at least 40% 3-alkyl + allyl chain ends, at least 50% 3-alkyl + allyl chain ends, at least 60% 3-alkyl + allyl chain ends, at least 70% 3-alkyl + allyl chain ends; at least 80%3-alkyl + allyl chain ends, at least 90% 3-alkyl + allyl chain ends; at least 95% 3-alkyl + allyl chain ends, relative to total unsaturation.
• 3-alkyl + allyl chain ends e.g all 3-alkyl chain ends plus all allyl chain ends
• the vinyl terminated polyolefin comprises one or more of:
• a propylene polymer (or oligomer), comprising more than 90 mol% propylene and less than 10 mol% ethylene, wherein the polymer has: at least 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol (as measured by ⁇ NMR), an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, and less than 1400 ppm aluminum; and/or
• a propylene polymer (or oligomer), comprising at least 50 mol% propylene and from 10 to 50 mol% ethylene, wherein the polymer has: at least 90% allyl chain ends, Mn of about 150 to about 10,000 g/mol (as measured by !fi NMR), and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.3: 1.0, wherein monomers having four or more carbon atoms are present at from 0 to 3 mol%; and/or
• a propylene polymer (or oligomer), comprising at least 50 mol% propylene, from 0.1 to 45 mol% ethylene, and from 0.1 to 5 mol% C 4 to olefin, wherein the polymer has: at least 87%o allyl chain ends (alternately at least 90%), an Mn of about 150 to about 10,000 g/mol, (as measured by !fi NMR), and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0; and/or
• a propylene polymer (or oligomer), comprising at least 50 mol% propylene, from 0.1 to 45 mol% ethylene, and from 0.1 to 5 mol% diene, wherein the polymer has: at least 90% allyl chain ends, an Mn of about 150 to about 10,000 g/mol (as measured by l R NMR), and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0; and/or
• vinyl terminated polyolefins useful in this invention include propylene polymers or oligomers, comprising propylene and less than 0.5 wt% comonomer, preferably 0 wt% comonomer, wherein the polymer or oligomer has:
• Mn a number average molecular weight (Mn) of about 500 to about 20,000 g/mol, as measured by X H NMR (preferably 500 to 15,000, preferably 700 to 10,000, preferably 800 to 8,000 g/mol, preferably 900 to 7,000, preferably 1,000 to 6,000, preferably 1,000 to 5,000);
• Vinyl terminated olefin polyolefins useful in this invention also include propylene copolymers (or co-oligomers) having an Mn of 300 to 30,000 g/mol as measured by ⁇ NMR (preferably 400 to 20,000, preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to 10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol), comprising 10 to 90 mol% propylene (preferably 15 to 85 mol%, preferably 20 to 80 mol%, preferably 30 to 75 mol%, preferably 50 to 90 mol%) and 10 to 90 mol% (preferably 85 to 15 mol%, preferably 20 to 80 mol%, preferably 25 to 70 mol%, preferably 10 to 50 mol%) of one or more alpha- olefin comonomers (preferably ethylene, butene, hexene, or octene, preferably ethylene), wherein the polymer has at least X% allyl chain ends (
• X is 80% or more, preferably 85% or more, preferably 90% or more, preferably 95% or more.
• the polymer has at least 80% isobutyl chain ends (based upon the sum of isobutyl and n- propyl saturated chain ends), preferably at least 85% isobutyl chain ends, preferably at least
• Vinyl terminated olefin polyolefins useful in this invention also include propylene polymers (or oligomers), comprising more than 90 mol% propylene (preferably 95 to 99 mol%, preferably 98 to 9 mol%) and less than 10 mol% ethylene (preferably 1 to 4 mol%, preferably 1 to 2 mol%),wherein the polymer has:
• Mn number average molecular weight of about 400 to about 30,000 g/mol, as measured by 3 ⁇ 4 NMR (preferably 500 to 20,000, preferably 600 to 15,000, preferably 700 to 10,000, preferably 800 to 9,000, preferably 900 to 8,000, preferably 1,000 to 6,000);
• Vinyl terminated olefin polyolefins useful in this invention also include propylene polymers (or oligomers), comprising: at least 50 (preferably 60 to 90, preferably 70 to 90) mol% propylene and from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol% ethylene, wherein the polymer has:
• At least 90% allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
• Vinyl terminated olefin polyolefins useful in this invention also include propylene polymers (or oligomers), comprising:
• mol% propylene from 0.1 to 45 (alternately at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% C 4 to olefin (such as butene, hexene or octene, preferably butene), wherein the polymer has:
• At least 90% allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%
• Mn number average molecular weight
• Vinyl terminated olefin polyolefins useful in this invention also include propylene polymers (or oligomers), comprising:
• mol% propylene preferably at least 60, preferably at least 70 to 99.5, preferably at least 80 to 99, preferably at least 90 to 98.5
• mol% propylene from 0.1 to 45 (alternately at least 35, preferably 0.5 to 30, preferably 1 to 20, preferably 1.5 to 10) mol% ethylene, and from 0.1 to 5 (preferably 0.5 to 3, preferably 0.5 to 1) mol% diene (such as C 4 to (3 ⁇ 4 alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the polymer has:
• diene such as C 4 to (3 ⁇ 4 alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene
• At least 90% allyl chain ends preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%;
• Mn a number average molecular weight (Mn) of about 150 to about 20,000 g/mol, as measured by l K NMR (preferably 200 to 15,000, preferably 250 to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750 to 9,000); and
• Any of the vinyl terminated polyolefins described herein preferably have less than 1400 ppm aluminum, preferably less than 1 ,000 ppm aluminum, preferably less than 500 ppm aluminum, preferably less than 100 ppm aluminum, preferably less than 50 ppm aluminum, preferably less than 20 ppm aluminum, preferably less than 5 ppm aluminum.
• the vinyl terminated polyolefin (preferably a propylene polymer or oligomer) comprises less than 3 wt% of functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen, and carboxyl, preferably less than 2 wt%, more preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.1 wt%, more preferably 0 wt%, based upon the weight of the vinyl terminated polyolefin.
• functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen, and carboxyl, preferably less than 2 wt%, more preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.1 wt%, more preferably 0
• the vinyl terminated polyolefin is a polymer (or oligomer) having an M n as determined by l K NMR of 150 to 25,000 g/mole, 200 to 20,000 g/mol, preferably 250 to 15,000 g/mol, preferably 300 to 15,000 g/mol, preferably 400 to 12,000 g/mol, preferably 750 to 10,000 g/mol.
• a desirable molecular weight range can be any combination of any upper molecular weight limit with any lower molecular weight limit described above.
• the vinyl terminated polyolefin contains less than 80 wt% of C 4 olefin(s) (such as isobutylene n-butene, 2-butene, isobutylene, and butadiene), based upon the weight of the vinyl terminated polyolefin, preferably less than 10 wt%, preferably 5 wt%, preferably less than 4 wt%, preferably less than 3 wt%, preferably less than 2 wt%, preferably less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.25 wt% of C 4 olefin(s) based upon the weight of the vinyl terminated polyolefin.
• C 4 olefin(s) such as isobutylene n-butene, 2-butene, isobutylene, and butadiene
• the vinyl terminated polyolefin contains less than 20 wt% of C 4 or more olefin(s), (such as C 4 to C30 olefins, typically such as C 4 to olefins, typically such as C 4 , Cg, (3 ⁇ 4, olefins, etc.), based upon the weight of the vinyl terminated polyolefin, preferably less than 10 wt%, preferably 5 wt%, preferably less than 4 wt%, preferably less than 3 wt%, preferably less than 2 wt%, preferably less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.25 wt% of C 4 olefin(s) based upon the weight of the vinyl terminated polyolefin, as determined by 13 C NMR.
• olefin(s) such as C 4 to C30 olefins, typically such as C 4 to olefins, typically such as C 4
• any vinyl terminated polyolefin composition described herein comprises less than 20 wt% dimer and trimer (preferably less than 10 wt%, preferably less than 5 wt%, more preferably less than 2 wt%, based upon the weight of the vinyl terminated polyolefin composition), as measured by Gas Chromatography. Products are analyzed by gas chromatography (Agilent 6890N with auto-injector) using helium as a carrier gas at 38 cm/sec. A column having a length of 60 m (J & W Scientific DB-1, 60 m x 0.25 mm ID.
• x 1.0 ⁇ film thickness packed with a flame ionization detector (FID), an Injector temperature of 250°C, and a Detector temperature of 250°C are used.
• FID flame ionization detector
• the sample was injected into the column in an oven at 70°C, then heated to 275°C over 22 minutes (ramp rate 10°C/min to 100°C, 30°C/min to 275°C, hold).
• An internal standard usually the monomer, is used to derive the amount of dimer or trimer product that is obtained. Yields of dimer and trimer product are calculated from the data recorded on the spectrometer. The amount of dimer or trimer product is calculated from the area under the relevant peak on the GC trace, relative to the internal standard.
• any vinyl terminated polyolefin described herein contains less than 25 ppm hafnium, preferably less than 10 ppm hafnium, preferably less than 5 ppm hafnium based on the yield of polymer produced and the mass of catalyst employed.
• any vinyl terminated polyolefins described herein may have a melting point (DSC first melt) of from 60°C to 165°C, alternately 50°C to 120°C.
• the vinyl terminated polyolefins described herein have no detectable melting point by DSC following storage at ambient temperature (23 °C) for at least 48 hours.
• T m and Tg are measured using Differential Scanning Calorimetry (DSC) using commercially available equipment such as a TA Instruments 2920 DSC.
• DSC Differential Scanning Calorimetry
• the sample is equilibrated at 25°C, then it is cooled at a cooling rate of 10°C/min to -80°C.
• the sample is held at -80°C for 5 min and then heated at a heating rate of 10°C/min to 25°C.
• the glass transition temperature is measured from the heating cycle.
• the sample is equilibrated at 25°C, then heated at a heating rate of 10°C/min to 150°C.
• the endothermic melting transition if present, is analyzed for onset of transition and peak temperature.
• the melting temperatures reported are the peak melting temperatures from the first heat unless otherwise specified.
• the melting point is defined to be the peak melting temperature (i.e., associated with the largest endothermic calorimetric response in that range of temperatures) from the DSC melting trace.
• Particularly useful vinyl terminated polyolefins may be isotactic, highly isotactic, syndiotactic, or highly syndiotactic propylene polymer, particularly isotactic polypropylene.
• isotactic is defined as having at least 10% isotactic pentads, preferably having at least 40% isotactic pentads of methyl groups derived from propylene according to analysis by 13 C-NMR.
• “highly isotactic” is defined as having at least 60% isotactic pentads according to analysis by 13 C-NMR.
• the polyolefin (preferably polypropylene) has at least 85% isotacticity.
• “syndiotactic” is defined as having at least 10% syndiotactic pentads, preferably at least 40%, according to analysis by 13 C-NMR.
• “highly syndiotactic” is defined as having at least 60% syndiotactic pentads according to analysis by 13 C-NMR.
• the polyolefin (preferably polypropylene) has at least 85% syndiotacticity.
• the polyolefins described herein have an Mw (measured as described below) of 1,000 to about 60,000 g/mol, alternately 2000 to 25,000 g/mol, alternately 3,000 to 20,000 g/mol and/or an Mz of about 1700 to about 150,000 g/mol, alternately 800 to 100,000 g/mol.
• Mw, Mn, Mz, number of carbon atoms, and g' vjs are determined by Gel Permeation Chromatography (GPC) using a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer.
• GPC Gel Permeation Chromatography
• Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous agitation for about 2 hours. All quantities are measured gravimetrically.
• the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 145°C.
• the injection concentration is from 0.75 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
• Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample.
• the LS laser is turned on 1 to 1.5 hours before running the samples.
• the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, I DR1 , using the following equation:
• KDRI is a constant determined by calibrating the DRI
• (dn/dc) is the refractive index increment for the system.
• (dn/dc) 0.104 for propylene polymers, 0.098 for butene polymers and 0.1 otherwise.
• concentration is expressed in g/cm 3
• molecular weight is expressed in g/mole
• intrinsic viscosity is expressed in dL/g.
• the LS detector is a Wyatt Technology High Temperature mini-DAW .
• the molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971): AR ° (e) ⁇ ⁇ ( ⁇ ) + 2AL °
• AR(Q) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
• c is the polymer concentration determined from the DRI analysis
• (dn/dc) 0.104 for propylene polymers, 0.098 for butene polymers and 0.1 otherwise
• ⁇ ( ⁇ ) is the form factor for a monodisperse random coil
• K 0 is the optical constant for the system:
• A is Avogadro's number
• (dn/dc) is the refractive index increment for the system.
• a high temperature Viscotek Corporation viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity.
• One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
• the specific viscosity, r ⁇ s for the solution flowing through the viscometer is calculated from their outputs.
• the intrinsic viscosity, [ ⁇ ] at each point in the chromatogram is calculated from the following equation:
• the branching index (g' v is) 1S calculated using the output of the SEC-DRI-LS-VIS method as follows.
• ] aV g, of the sample is calculated by: where the summations are over the chromatographic slices, i, between the integration limits.
• the branching index (g' v i s ) is calculated using the output of the SEC-DRI-LS-VIS method as follows.
• the branching index g' vjs is defined as:
• M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis. See Macromolecules, 2001, 34, 6812-6820 and Macromolecules, 2005, 38, 7181-7183, for further guidance on selecting a linear standard having similar molecular weight and comonomer content and determining k coefficients and a exponents.
• the vinyl terminated polyolefins described above are typically prepared in a homogeneous process, preferably a bulk process, as described in USSN 12/143,663, filed on June 20, 2008, which is incorporated by reference herein.
• Vinyl terminated polyolefins may also be produced using the processes (and catalyst compounds and/or activators) disclosed in concurrently filed USSN 13/072,280, filed March 25, 2011 entitled “Novel Catalysts and Methods of use Thereof to Produce Vinyl Terminated Polymers" and USSN 13/072,279, filed March 25, 201 1, entitled "Enhanced Catalyst Performance for Production of Vinyl Terminated Propylene and Ethylene/Propylene Macromers".
• Useful vinyl terminated polyolefins can also be produced using the processes disclosed in concurrently filed USSN 13/072,288, filed March 25, 2011, entitled “Vinyl Terminated Higher Olefin Polymers and Methods to Produce Thereof, and concurrently filed USSN 13/072,249, filed March 25, 2011, entitled “Vinyl Terminated Higher Olefin Copolymers and Methods to Produce Thereof, and concurrently filed USSN 61/467,681, filed March 25, 201 1, entitled "Branched Vinyl Terminated Polymers and Methods for Production Thereof.
• one, two, three, or more C2 to C40 alpha olefins such as ethylene, propylene, butene, pentene, hexene, octene, decene and dodecene (preferably ethylene and/or propylene and optional comonomers (such as one, two, three or more of ethylene, butene, hexene, octene, decene, and dodecene) can be polymerized/polymerized by reacting a catalyst system (comprising metallocene compound(s), and one or more activators) with the olefins.
• a catalyst system comprising metallocene compound(s), and one or more activators
• additives may also be used, as desired, such as scavengers and/or hydrogen.
• Any conventional suspension, homogeneous bulk, solution, slurry, or high- pressure polymerization process can be used. Such processes can be run in a batch, semi- batch, or continuous mode. Such processes and modes are well known in the art. Homogeneous polymerization processes are preferred. A bulk homogeneous process is particularly preferred. Alternately no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene).
• the process is a slurry process.
• slurry polymerization process means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
• the butene source may be a mixed butene stream comprising various isomers of butene.
• the 1 -butene monomers are expected to be preferentially consumed by the polymerization process.
• Use of such mixed butene streams will provide an economic benefit, as these mixed streams are often waste streams from refining processes, for example C 4 raffinate streams, and can therefore be substantially less expensive than pure 1 -butene.
• Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
• examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof such as can be found commercially (Isopars); perhalogenated hydrocarbons, such as perfluorinated C4 0 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
• straight and branched-chain hydrocarbons such as isobutane
• Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene, 4-methyl-l-pentene, 1-octene, and 1-decene. Mixtures of the foregoing are also suitable.
• aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
• the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt%, preferably at 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents.
• the feed concentration for the polymerization is 60 vol% solvent or less, preferably 40 vol% or less, preferably 20 vol% or less.
• the polymerization is run in a bulk process.
• Suitable additives to the polymerization process can include one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.
• scavenger such as trialkyl aluminum
• the scavenger is present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1.
• hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172.4 kPa), more preferably 0.1 to 10 psig (0.7 to 68.95 kPa). It has been found that in the present systems, hydrogen can be used to provide increased activity without significantly impairing the catalyst's ability to produce allylic chain ends.
• the catalyst activity (calculated as g/mmolcatalyst/hr) is at least 20% higher than the same reaction without hydrogen present, preferably at least 50% higher, preferably at least 100% higher.
• Catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcat ⁇ hr "1 . Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor. Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP/molcat).
• the productivity at least 4500 g/mmol/hour, preferably 5000 or more g/mmol/hour, preferably 10,000 or more g/mmol/hr, preferably 50,000 or more g/mmol/hr.
• the productivity is at least 80,000 g/mmol/hr, preferably at least 150,000 g/mmol/hr, preferably at least 200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr.
• the activity of the catalyst is at least 50 g/mmol/hour, preferably 500 or more g/mmol/hour, preferably 5000 or more g/mmol/hr, preferably 50,000 or more g/mmol/hr.
• the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, preferably 20% or more, preferably 30% or more, preferably 50% or more, preferably 80% or more.
• Preferred polymerizations can be run at typical temperatures and/or pressures, such as from 25°C to 150°C, preferably 40°C to 120°C, preferably 45°C to 80°C, and preferably from 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa.
• the residence time of the reaction is up to 60 minutes, preferably between 5 to 50 minutes, preferably between 10 to 40 minutes.
• alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1 : 1.
• an alumoxane is used to produce the vinyl terminated polymers then, the alumoxane has been treated to remove free alkyl aluminum compounds, particularly trimethyl aluminum.
• the activator used herein to produce the vinyl terminated polymer is a bulky activator as defined herein and is discrete.
• the polymerization 1) is conducted at temperatures of 0 to 300°C (preferably 25 to 150°C, preferably 40 to 120°C, preferably 45 to 80°C), and 2) is conducted at pressure of atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa), and 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptan
• the scavenger is present at zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1); and 8) optionally hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)).
• the catalyst system used in the polymerization comprises no more than one catalyst compound.
• reaction zone also referred to as a "polymerization zone” is a vessel where polymerization takes place, for example a batch reactor.
• each reactor is considered as a separate polymerization zone.
• each polymerization stage is considered as a separate polymerization zone.
• the polymerization occurs in one reaction zone. Room temperature is 23 °C unless otherwise noted.
• Catalyst compounds useful herein to produce the vinyl terminated polyolefins include one or more metallocene compound(s) represented by the formulae:
• Hf is hafnium
• each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof, preferably methyl, ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide, (alternately two X's may form a part of a fused ring or a ring system);
• each Q is, independently carbon or a heteroatom, preferably C, N, P, S (preferably at least one Q is a heteroatom, alternately at least two Q's are the same or different heteroatoms, alternately at least three Q's are the same or different heteroatoms, alternately at least four Q's are the same or different heteroatoms);
• each R 1 is, independently, hydrogen or a to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, R 1 may be the same or different as R 2 ;
• each R 2 is, independently, hydrogen or a to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided that at least one of R 1 or R 2 is not hydrogen, preferably both of R 1 and R 2 are not hydrogen, preferably R 1 and/or R 2 are not branched; each R 3 is, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, preferably a substituted or unsubstituted Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that at least three R 3 groups are not hydrogen (alternately four R 3 groups are not hydrogen
• each R 4 is, independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group, a heteroatom or heteroatom containing group, preferably a substituted or unsubstituted hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, preferably a substituted or unsubstituted Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl), phenyl, silyl, substituted silyl, (such as CH2S1 , where R' is a Ci to hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);
• R 5 is hydrogen or a to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl;
• R 6 is hydrogen or a to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl;
• each R 7 is, independently, hydrogen, or a to Cg alkyl group, preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, provided however that at least seven R 7 groups are not hydrogen, alternately at least eight R 7 groups are not hydrogen, alternately all R 7 groups are not hydrogen, (preferably the R 7 groups at the 3 and 4 positions on each Cp ring of Formula IV are not hydrogen);
• N is nitrogen
• R2 a T is a bridge, preferably T is Si or Ge, preferably Si, and each R a , is independently, hydrogen, halogen or a to C20 hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system; and further provided that any two adjacent R groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated.
• At least one R 4 group is not hydrogen, alternately at least two R 4 groups are not hydrogen, alternately at least three R 4 groups are not hydrogen, alternately at least four R 4 groups are not hydrogen, alternately all R 4 groups are not hydrogen.
• Catalyst compounds that are particularly useful in this invention include one or more of:
• the "dimethyl" after the transition metal in the list of catalyst compounds above is replaced with a dihalide (such as dichloride, dibromide, or difluoride) or a bisphenoxide, particularly for use with an alumoxane activator.
• a dihalide such as dichloride, dibromide, or difluoride
• a bisphenoxide particularly for use with an alumoxane activator.
• Preferred activators useful with the above include:
• dimethylaniliniumtetrakis(heptafluoronaphthyl) borate trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammonium tetrakis(perfluorobiphenyl)borate, tripropylammonium tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium
• the vinyl terminated polyolefins useful here in may produced using the catalyst compound represented by the formula:
• each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system) (preferably each X is independently selected from halides and to C 5 alkyl groups, preferably each X is a methyl group); each R 8 is, independently, a Q to alkyl group (preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof, preferably each R 8 is a methyl group); each R 9 is, independently, a Q to CIQ alkyl group (preferably methyl, ethyl, propyl
• Catalyst compounds that are particularly useful in this invention include one or more of:
• the "dimethyl" after the transition metal in the list of catalyst compounds above is replaced with a dihalide (such as dichloride or difluoride) or a bisphenoxide, particularly for use with an alumoxane activator.
• a dihalide such as dichloride or difluoride
• a bisphenoxide particularly for use with an alumoxane activator.
• the catalyst compound is rac-dimethylsilylbis(2- methyl,3-propylindenyl)hafniumdimethyl or dichloride, or rac-dimethylsilylbis(2-methyl,3- propylindenyl)zirconiumdimethyl or dichloride.
• Preferred activators useful with the above include:
• Preferred combinations of catalyst and activator include:
• the vinyl terminated polyolefins useful here in may be produced using the catalyst com ound represented by the formula:
• each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof; each R 15 and R 17 are, independently, a to Cg alkyl group (preferably a Q to Cg linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl); and each R , R ⁇ , R20 ; R21 ; R22 ; R23 ; R24 ; R25 ; R26 ; R27 ; and R 28 ⁇ ⁇ independently, hydrogen, or a substituted or unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms (preferably 1 to
• R 24 -R28 groups are not hydrogen (alternately four of R 24 -R 28 groups are not hydrogen, alternately five of R 24 -R 28 groups are not hydrogen). In a preferred embodiment, all five groups of R 24 -R 28 are methyl. In a preferred embodiment, four of the R 24 -R 28 groups are not hydrogen and at least one of the R24 .
• R28 groups is a C 2 to Cg substituted or unsubstituted hydrocarbyl (preferably at least two, three, four or five of R 24 -R 28 groups are a C 2 to Cg substituted or unsubstituted hydrocarbyl).
• R 15 and R 17 are methyl groups
• R 16 is a hydrogen
• R 18 -R 23 are all hydrogens
• R 24 -R 28 are all methyl groups
• each X is a methyl group.
• Catalyst compounds that are particularly useful in this invention include:
• the "dimethyl" (Me 2 ) after the transition metal in the list of catalyst compounds above is replaced with a dihalide (such as dichloride or difluoride) or a bisphenoxide, particularly for use with an alumoxane activator.
• a dihalide such as dichloride or difluoride
• a bisphenoxide particularly for use with an alumoxane activator.
• the branched polymers described herein may be produced as described in concurrently filed USSN 61/467,681, filed March 25, 201 1, entitled "Branched Vinyl Terminated Polymers and Methods for Production Thereof.
• substituted means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom or a heteroatom containing group.
• methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group and ethyl alcohol is an ethyl group substituted with an -OH group.
• activator is used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.
• Non-limiting activators include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
• Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract one reactive, ⁇ -bound, metal ligand making the metal complex cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.
• alumoxane activators are utilized as an activator in the catalyst composition.
• Alumoxanes are generally polymeric compounds containing -Al(Ri)-
• alumoxanes examples include methylalumoxane
• MAO modified methylalumoxane
• MMAO modified methylalumoxane
• ethylalumoxane ethylalumoxane
• isobutylalumoxane ethylalumoxane
• Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
• alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Patent No. 5,041,584).
• MMAO modified methyl alumoxane
• the activator is an alumoxane (modified or unmodified)
• some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst precursor (per metal catalytic site).
• the minimum activator-to-catalyst-precursor is a 1 : 1 molar ratio. Alternate preferred ranges include up to 500: 1, alternately up to 200: 1, alternately up to 100: 1 alternately from 1 : 1 to 50: 1.
• alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1 : 1.
• an alumoxane is used to produce the VTM's then, the alumoxane has been treated to remove free alkyl aluminum compounds, particularly trimethyl aluminum.
• the activator used herein to produce the vinyl terminated polyolefin is bulky as defined herein and is discrete.
• Aluminum alkyl or organoaluminum compounds which may be utilized as co- activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.
• an ionizing or stoichiometric activator neutral or ionic non-coordinating anion (as defined in USSN 12/143,663, filed on June 20, 2008) such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459), or combination thereof.
• an ionizing or stoichiometric activator neutral or ionic non-coordinating anion
• the activator is N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetrakis(perfluorophenyl)borate
• the activator is a bulky activator represented by the formula:
• each Ri is, independently, a halide, preferably a fluoride
• each R2 is, independently, a halide, a to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Q to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R2 is a fluoride or a perfluorinated phenyl group);
• each R3 is a halide, to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R3 is a fluoride or a perfluorinated aromatic hydrocarbyl group); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2 and R3 form a perfluorinated phenyl ring);
• L is an neutral Lewis base
• (L-H) + is a Bronsted acid
• d is 1, 2, or 3;
• anion has a molecular weight of greater than 1020 g/mole
• Molecular volume is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.
• Molecular volume may be calculated as reported in "A Simple "Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962 to 964.
• V s is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V s is decreased by 7.5% per fused ring.
• Exemplary bulky activators useful in catalyst systems herein include: trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6- trimethylanilinium) tetrakis
• the typical activator-to-catalyst-precursor ratio is a 1 : 1 molar ratio for non- alumoxane activators.
• Alternate preferred ranges include from 0.1 : 1 to 100: 1, alternately from 0.5: 1 to 200: 1, alternately from 1 : 1 to 500: 1 alternately from 1 : 1 to 1,000: 1.
• a particularly useful range is from 0.5: 1 to 10: 1, preferably 1 : 1 to 5: 1. Support Materials
• the catalyst system to produce the vinyl terminated polyolefins may comprise an inert support material.
• the supported material is a porous support material, for example, talc, and inorganic oxides.
• Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material and the like, or mixtures thereof.
• the support material is an inorganic oxide in a finely divided form.
• Suitable inorganic oxide materials for use in metallocene catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides such as silica, alumina and mixtures thereof.
• Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like.
• Other suitable support materials can be employed, for example, finely divided functionalized polyolefins such as finely divided polyethylene.
• Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania and the like.
• Preferred support materials include AI2O 3 , Zr02, S1O2, and combinations thereof, more preferably S1O2, AI2O 3 , or S1O2/AI2O 3 .
• the support material most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m 2 /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ . More preferably, the surface area of the support material is in the range of from about 50 to about 500 m 2 /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ .
• the surface area of the support material is in the range is from about 100 to about 400 m 2 /g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 ⁇ .
• the average pore size of the support material useful in the invention is in the range of from 10 to 1,000 A , preferably 50 to about 500 A , and most preferably 75 to about 350 A .
• the support material should be dry, that is, free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100°C to about 1,000°C, preferably at least about 600° C. When the support material is silica, it is heated to at least 200°C, preferably about 200°C to about 850°C, and most preferably at about 600°C; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours.
• the calcined support material must have at least some reactive hydroxyl (OH) groups to produce the catalyst system of this invention.
• the calcined support material is then contacted with at least one polymerization catalyst comprising at least one metallocene compound and an activator.
• the support material having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a metallocene compound and an activator.
• the slurry of the support material in the solvent is prepared by introducing the support material into the solvent, and heating the mixture to about 0° to about 70°C, preferably to about 25° to about 60°C, preferably at room temperature.
• Contact times typically range from about 0.5 hours to about 24 hours, from about 0.5 hours to about 8 hours, or from about 0.5 hours to about 4 hours.
• Suitable non-polar solvents are materials in which all of the reactants used herein, i.e., the activator, and the metallocene compound, are at least partially soluble and which are liquid at reaction temperatures.
• Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene and ethylbenzene, may also be employed.
• the support material is contacted with a solution of a metallocene compound and an activator, such that the reactive groups on the support material are titrated, to form a supported polymerization catalyst.
• the period of time for contact between the metallocene compound, the activator, and the support material is as long as is necessary to titrate the reactive groups on the support material.
• titrate is meant to react with available reactive groups on the surface of the support material, thereby reducing the surface hydroxyl groups by at least 80%, at least 90%, at least 95%, or at least 98%.
• the surface reactive group concentration may be determined based on the calcining temperature and the type of support material used.
• the support material calcining temperature affects the number of surface reactive groups on the support material available to react with the metallocene compound and an activator: the higher the drying temperature, the lower the number of sites.
• the support material is silica which, prior to the use thereof in the first catalyst system synthesis step, is dehydrated by fluidizing it with nitrogen and heating at about 600°C for about 16 hours, a surface hydroxyl group concentration of about 0.7 millimoles per gram (mmols/gm) is typically achieved.
• mmols/gm millimoles per gram
• the exact molar ratio of the activator to the surface reactive groups on the carrier will vary. Preferably, this is determined on a case-by-case basis to assure that only so much of the activator is added to the solution as will be deposited onto the support material without leaving excess of the activator in the solution.
• the amount of the activator which will be deposited onto the support material without leaving excess in the solution can be determined in any conventional manner, e.g., by adding the activator to the slurry of the carrier in the solvent, while stirring the slurry, until the activator is detected as a solution in the solvent by any technique known in the art, such as by l H NMR.
• the amount of the activator added to the slurry is such that the molar ratio of B to the hydroxyl groups (OH) on the silica is about 0.5: 1 to about 4: 1, preferably about 0.8: 1 to about 3: 1, more preferably about 0.9: 1 to about 2: 1 and most preferably about 1 : 1.
• the amount of boron on the silica may be determined by using ICPES (Inductively Coupled Plasma Emission Spectrometry), which is described in J. W. Olesik, "Inductively Coupled Plasma- Optical Emission Spectroscopy," in the Encyclopedia of Materials Characterization, C. R. Brundle, C. A. Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp. 633-644.
• ICPES Inductively Coupled Plasma Emission Spectrometry
• a vinyl terminated polyolefin can be produced by the method disclosed in Macromol. Chem. Phys., 2010, 21 1, 1472-1481.
• Preferred diblock hydrosilane-functionalized polyolefins prepared herein are preferably represented by the formula:
• each PO and PO* independently, is a substituted or unsubstituted hydrocarbyl group having from 20 to about 10,000 carbon atoms;
• L is a bond, an oxygen atom, a Q to a C20 substituted or unsubstituted hydrocarbyl group, or a Ci to a C20 substituted or unsubstituted hydrocarbyl ether group.
• the hydrosilane-functionalized polyolefin has a Mn of from 500 to 60,000 g/mol, preferably 500 to 50,000 g/mol, preferably from 1,000 to 30,000 g/mol, preferably from 1,500 to 20,000 g/mol.
• the "polyolefin" portion of the hydrosilane-functionalized polyolefin is a homopolymer, homo-oligomer, copolymer or co-oligomer comprising one or more C2 to C40 olefins, preferably C2 to C40 alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• the "polyolefin" portion of the hydrosilane-functionalized polyolefin is any of the vinyl terminated polyolefins described above, except that the allyl chain ends have been consumed in the hydrosilation reaction.
• the diblock hydrosilane-functionalized polyolefin is an oligomer having an Mn of from 500 to 21,000 g/mol (preferably 700 to 21,000, preferably 800 to 20,000 g/mol) comprising one or more alpha-olefins selected from the group consisting of C2 to C40 alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene and dodecene.
• the oligomer portion of the diblock hydrosilane-functionalized polyolefin is an ethylene oligomer, e.g., a homo- oligomer of ethylene or co-oligomer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C2 to C40 alpha-olefin comonomers, preferably selected from the group consisting of propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• ethylene oligomer e.g., a homo- oligomer of ethylene or co-oligomer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C2 to C40 alpha-olefin comonomers, preferably selected from the group consisting of propy
• the oligomer portion of the diblock hydrosilane-functionalized polyolefin is a propylene oligomer, e.g., a homo-oligomer of propylene or co-oligomer of propylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C2 to C40 alpha-olefin comonomers, preferably selected from the group consisting of ethylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• the diblock hydrosilane-functionalized polyolefin is a polymer having an Mn of greater than 21,000 g/mol (preferably from 25,000 to 100,000, preferably 25,000 to 50,000 g/mol) comprising one or more alpha-olefins selected from the group consisting of C2 to C40 alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• the polymer portion of the diblock hydrosilane-functionalized polyolefin is an ethylene polymer, e.g., a homopolymer of ethylene or co-polymer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C3 to C40 alpha-olefin comonomers, preferably selected from the group consisting of propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• ethylene polymer e.g., a homopolymer of ethylene or co-polymer of ethylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C3 to C40 alpha-olefin comonomers, preferably selected from the group consisting of propylene, butene, pentene,
• the polymer portion of the diblock hydrosilane-functionalized polyolefin is propylene polymer, e.g., a homopolymer of propylene or a co-polymer of propylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C2 to C40 alpha-olefins comonomers, preferably selected from the group consisting of ethylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.
• propylene polymer e.g., a homopolymer of propylene or a co-polymer of propylene and up to 50 mol% (preferably from 0.5 to 25 mol%, preferably from 1 to 20 mol%) of one or more C2 to C40 alpha-olefins comonomers, preferably selected from the group consisting of ethylene
• the diblock hydrosilane-functionalized polyolefins consist essentially of propylene, functional group, and optionally ethylene.
• C 4 olefins such as isobutylene, butadiene, n-butene
• C4.20 olefins are substantially absent from the diblock hydrosilane-functionalized polyolefins.
• isobutylene is substantially absent from the diblock hydrosilane-functionalized polyolefins.
• substantially absent is meant that the monomer is present in the polyolefin at 1 wt% or less, preferably at 0.5 wt% or less, preferably at 0 wt%.
• the diblock hydrosilane-functionalized polyolefins produced herein have a melting point (DSC, second melt) of 100°C or more, preferably 120°C or more, preferably 130°C or more.
• the diblock hydrosilane-functionalized polyolefin produced herein is an diblock hydrosilane- functionalized propylene polymer having a melting point (DSC, second melt) of 145°C or more, preferably 150°C or more, preferably 155°C or more.
• the diblock hydrosilane-functionalized polyolefin produced herein is an diblock hydrosilane-functionalized ethylene polymer having a melting point (DSC, second melt) of 100°C or more, preferably 110°C or more, preferably 125°C or more.
• DSC melting point
• the diblock hydrosilane-functionalized polyolefins may be characterized by any degree of tacticity, including isotacticity or syndiotacticity, and/or may be atactic.
• the diblock hydrosilane-functionalized polyolefin has more than 50% meso dyads as measured by 13 C-NMR, preferably more than 60%.
• the hydro-silane functionalized polyolefin has more than 50% racemic dyads as measured by 13 C-NMR, preferably more than 60%>.
• Particularly useful diblock hydrosilane-functionalized polyolefins may be isotactic, highly isotactic, syndiotactic, or highly syndiotactic propylene polymer, particularly isotactic polypropylene.
• isotactic is defined as having at least 10% isotactic pentads, preferably having at least 40% isotactic pentads of methyl groups derived from propylene according to analysis by 13 C-NMR.
• “highly isotactic” is defined as having at least 60% isotactic pentads according to analysis by 13 C-NMR.
• the diblock hydrosilane-functionalized polyolefin (preferably polypropylene) has at least 85% isotacticity.
• “syndiotactic” is defined as having at least 10% syndiotactic pentads, preferably at least 40%, according to analysis by 13 C-NMR.
• “highly syndiotactic” is defined as having at least 60% syndiotactic pentads according to analysis by 13 C-NMR.
• the diblock hydrosilane functionalized polyolefin (preferably polypropylene) has at least 85% syndiotacticity.
• the diblock hydrosilane-functionalized polyolefins described herein have less than 10% allyl chain ends, preferably less than 8%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%, preferably less than 1% (relative to total unsaturations as measured by 1H NMR, using the protocol described in USSN 12/143,663, filed on June 20, 2008). No hydrogen or chain transfer/termination agent should be used during functionalization, derivatization or stripping (of unreacted monomer) for measurement of unsaturations.
• the number of functional groups is present at 0.60 to 1.2, alternately 0.75 to 1.1 functional groups per chain (preferably assuming that Mn has not altered by more than 15% as compared to the Mn of the polyolefin prior to functionalization and optional derivatization).
• Number of functional groups per chain F/Mn, (comparison of Mn of vinyl macromer to Mn of PO-SiH by GPC where F is SiH) as determined by l H NMR as follows.
• the instrument used is a 400 MHz Varian pulsed Fourier transform NMR spectrometer equipped with a variable temperature proton detection probe operating at 120°C.
• the sample is dissolved in 1, 1,2,2- tetrachloroethane-d2 (TCE-d2) or CDCI3 and transferred into a 5 mm glass NMR tube.
• TCE-d2 1, 1,2,2- tetrachloroethane-d2
• CDCI3 CDCI3
• Chemical shifts are determined relative to the residual TCE-d ⁇ signal which is set to 5.98 ppm and residual CHCI3, which is set at 7.24 ppm.
• VRA is the normalized integrated signal intensity for the vinyls with shifts between from about 4.9 to 5.1 ppm.
• VDRA is the normalized integrated signal intensity for the vinylidene resonances between from about 4.65 to 4.85 ppm and the vinylene resonances at from about 5.15 to 5.6 ppm.
• IA is the normalized integrated signal intensities for the aliphatic region of interest between from about 0 to 2.1 ppm (IA).
• the number of vinyl groups/ 1,000 Carbons (VI) is determined from the formula: (VRA * 1,000)/(IA +VRA + VDRA).
• VE vinylidene & vinylene groups/ 1,000 carbons
• VRA, VDRA and IA are the normalized integrated signal intensities in the chemical shift regions defined above.
• Percent functionalization of the oligomer (F * 100)/(F+VI +VE).
• the number of vinyl groups/1,000 carbons (VI*) and number of vinylidene groups/1,000 carbons (VE*) for the functionalized polyolefin are determined from the ⁇ FTNMR spectra of the functionalized oligomer in the same manner as VI and VE for the unfunctionalized oligomer.
• the percent functionalization of the polyolefin is 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more.
• Preferred functional groups include acyl groups derived from monounsaturated mono-or dicarboxylic acids and their derivatives, e.g., esters and salts.
• the diblock hydrosilane-functionalized polyolefin produced herein has a branching index, g' vjs (as determined by GPC), of 0.98 or less, alternately 0.96 or less, alternately 0.95 or less, alternately 0.93 or less, alternately 0.90 or less, alternately 0.85 or less, alternately 0.80 or less, alternately 0.75 or less, alternately 0.70 or less, alternately 0.65 or less, alternately 0.60 or less, alternately 0.55 or less.
• g' vjs as determined by GPC
• the functionalized vinyl terminated polyolefins described herein may be further derivatized as described in U.S. Patent No. 6,022,929.
• the Si-H bond can be converted to a halide; PO-Si-X by reaction with AIX 3 or organic RX 4 (PO is a polyalpha olefin, X is preferably a halide, such as CI).
• PO is a polyalpha olefin, X is preferably a halide, such as CI).
• the PO-Si-H could be transformed into a radical [PO-Si]- by a variety of reactants (see Organosilanes in Radical Chemistry, Wiley, 2004) and further derivatized into silyl-halides, siloxanes, or silazanes.
• the PO-silanes or derivatized versions themselves may be polymerized to polysilanes; -Si(PO)-Si(PO)-Si(PO)- (See Silicon Chemistry: From the Atom to Extended Systems, Wiley-VCH, 2007). Less substituted PO- S1H2- themselves may act as hydrosilation reagents with unsaturated molecules as alkynes, ketones, alkenes, etc with suitable hydrosilation catalysts as H ⁇ PtCl ⁇ .
• the diblock hydrosilane-functionalized (and optionally derivatized) polyolefins produced by this invention may be blended with up to 99 wt% (typically 80 wt% to 98 wt% and ideally about 2 wt% to about 5 wt%) of one or more other polymers, including but not limited to, thermoplastic polymer(s) and/or elastomer(s).
• thermoplastic polymer(s) is meant a polymer that can be melted by heat and then cooled without appreciable change in properties.
• Thermoplastic polymers typically include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene resins, polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrile resins, styrene maleic anhydride, polyimides, aromatic polyketones, or mixtures of two or more of the above.
• Preferred polyolefins include, but are not limited to, polymers comprising one or more linear, branched or cyclic C2 to C40 olefins, preferably polymers comprising propylene copolymerized with one or more C3 to C40 olefins, preferably a C3 to C20 alpha-olefin, more preferably C3 to C ⁇ alpha-olefins. More preferred polyolefins include, but are not limited to, polymers comprising ethylene including but not limited to ethylene copolymerized with a C3 to C40 olefin, preferably a C3 to C20 alpha-olefin, more preferably propylene and/or butene.
• elastomers all natural and synthetic rubbers, including those defined in ASTM D1566.
• the diblock hydrosilane-functionalized (and optionally derivatized) polyolefins produced herein may further be combined with one or more of polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935 g/cm 3 ) linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/cm 3 ), very low density polyethylene (density 0.90 to less than 0.915 g/cm 3 ), medium density polyethylene (density 0.935 to less than 0.945 g/cm 3 ), high density polyethylene (density 0.945 to 0.98 g/cm 3 ), ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene- 1, isotactic polybutene
• Tackifiers may be blended with the diblock hydrosilane-functionalized (and optionally derivatized) polyolefins produced herein and/or with blends of the diblock hydrosilane-functionalized (and optionally derivatized) polyolefins produced by this invention (as described above).
• tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.
• the tackifier is hydrogenated.
• the tackifier has a softening point (Ring and Ball, as measured by ASTM E-28) of 80°C to 140°C, preferably 100°C to 130°C.
• the tackifier if present, is typically present at about 1 wt% to about 50 wt%, based upon the weight of the blend, more preferably 10 wt% to 40 wt%, even more preferably 20 wt% to 40 wt%.
• the diblock hydrosilane-functionalized (and optionally derivatized) polyolefins of this invention, and/or blends thereof further comprise typical additives known in the art, such as fillers, cavitating agents, antioxidants, surfactants, adjuvants, plasticizers, block, antiblock, color masterbatches, pigments, dyes, processing aids, UV stabilizers, neutralizers, lubricants, waxes, and/or nucleating agents.
• the additives may be present in the typically effective amounts well known in the art, such as 0.001 wt% to 10 wt%.
• Preferred fillers, cavitating agents and/or nucleating agents include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay, and the like.
• Preferred antioxidants include phenolic antioxidants, such as Irganox 1010, Irganox, 1076 both available from Ciba-Geigy.
• Preferred oils include paraffinic or naphthenic oils, such as Primol 352, or Primol 876 available from ExxonMobil Chemical France, S.A. in Paris, France. More preferred oils include aliphatic naphthenic oils, white oils, or the like.
• the diblock hydrosilane-functionalized (and optionally derivatized) polyolefins produced herein are combined with polymers (elastomeric and/or thermoplastic) having functional groups such as unsaturated molecules- vinyl bonds, ketones or aldehydes under conditions such that they react. Reaction may be confirmed by an at least 20% (preferably at least 50%, preferably at least 100%) increase in Mw as compared to the Mw of the diblock hydrosilane-functionalized polyolefin prior to reaction. Such reaction conditions may be increased heat (for example, above the Tm of the diblock hydrosilane- functionalized polyolefin), increased shear (such as from a reactive extruder), presence or absence of solvent.
• polymers elastomeric and/or thermoplastic having functional groups such as unsaturated molecules- vinyl bonds, ketones or aldehydes under conditions such that they react. Reaction may be confirmed by an at least 20% (preferably at least 50%, preferably at least 100%) increase in Mw as compared to the Mw of the
• Conditions useful for reaction include temperatures from 150°C to 240°C and where the PO-Si-H species can be added to a stream comprising polymer and other species via a side arm extruder, gravimetric feeder, or liquids pump.
• Useful polymers having functional groups that can be reacted with the diblock hydrosilane-functionalized polyolefins produced herein include polyesters, polyvinyl acetates, nylons (polyamides), polybutadiene, nitrile rubber, and hydroxylated nitrile rubber.
• the hydrosilane-functionalized (and optionally derivatized) polyolefin of this invention may be blended with up to 99 wt% (preferably up to 25 wt%, preferably up to 20 wt%, preferably up to 15 wt%, preferably up to 10 wt%, preferably up to 5 wt%), based upon the weight of the composition, of one or more additional polymers.
• Suitable polymers include:
• Copolymers of ethylene and one or more polar monomers preferably selected from vinyl acetate, methyl acrylate, n-butyl acrylate, acrylic acid, and vinyl alcohol (i.e., EVA, EMA, EnBA, EAA, and EVOH); ethylene homopolymers and copolymers synthesized using a high-pressure free radical process, including LDPE; copolymers of ethylene and C3 to C40 olefins (preferably propylene and/or butene) with a density of greater than 0.91 g/cm 3 to less than 0.94 g/cm 3 ), including LLDPE; and high density PE (0.94 to 0.98 g/cm 3 ).
• comonomer selected from ethylene and C 4 to C12 olefins (preferably selected from ethylene, butene, and hexene; preferably ethylene);
• a metallocene-type catalyst preferably made using a metallocene-type catalyst; and having one or more of the following properties:
• M w of 20 to 5,000 kg/mol (preferably 30 to 2,000 kg/mol, preferably 40 to 1,000 kg/mol, preferably 50 to 500 kg/mol, preferably 60 to 400 kg/mol); and/or
• molecular weight distribution index (M w /M n ) of 1.5 to 10 (preferably 1.7 to 5, preferably 1.8 to 3);
• GPC-determined g' index value of 0.9 or greater (preferably 0.95 or greater, preferably 0.99 or greater);
• melt flow rate of at least 0.2 dg/min (preferably 1-500 dg/min, preferably 2-300 dg/min);
• H f heat of fusion (H f ) of 0.5 J/g or more (preferably 1 J/g or more, preferably 2.5 J/g or more, preferably 5 J/g or more) but less than or equal to 75 J/g (preferably less than or equal to 50 J/g, preferably less than or equal to 35 J/g, preferably less than or equal to 25 J/g); and/or
• DSC-determined crystallinity of from 1 to 30 wt% (preferably 2 to 25 wt%, preferably 2 to 20 wt%, preferably 3 to 15 wt%); and/or
• T c crystallization temperature of 90°C or less (preferably 60°C or less); and/or j) greater than 80% of the propylene residues (exclusive of any other monomer such as ethylene) arranged as 1,2 insertions with the same stereochemical orientation of the pendant methyl groups, either meso or racemic, as determined by 13 C-NMR; and/or
• 13 C-NMR-determined mm triad tacticity index of 75% or greater (preferably 80% or greater, preferably 82% or greater, preferably 85% or greater, preferably 90% or greater).
• Useful low-crystallinity propylene/olefin copolymers are available from ExxonMobil Chemical; suitable examples include VistamaxxTM 6100, VistamaxxTM 6200 and VistamaxxTM 3000. Other useful low-crystallinity propylene/olefin copolymers are described in WO 03/040095, WO 03/040201, WO 03/040233, and WO 03/040442, all to Dow Chemical, which disclose propylene-ethylene copolymers made with non-metallocene catalyst compounds.
• Olefin block copolymers including those described in WO 2005/090425, WO 2005/090426, and WO 2005/090427.
• maleated polyolefins that have been post-reactor functionalized with maleic anhydride (so-called maleated polyolefins), including maleated ethylene polymers, maleated EP Rubbers, and maleated propylene polymers.
• the amount of free acid groups present in the maleated polyolefin is less than about 1,000 ppm (preferably less than about 500 ppm, preferably less than about 100 ppm), and the amount of phosphite present in the maleated polyolefin is less than 100 ppm.
• SBCs Styrenic Block Copolymers
• Polycarbonates such as poly(bisphenol-a carbonate); polyamide resins, such as nylon 6 ( 6), nylon 66 ( 66), nylon 46 (N46), nylon 1 1 (Ni l), nylon 12 ( 12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer ( 6/66), nylon 6/66/610 (N6/66/610), nylon MXD6 (MXD6), nylon 6T (N6T), nylon 6/6T copolymer, nylon 66/PP copolymer, and nylon 66/PPS copolymer; polyester resins, such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET/PEI copolymer, polyacrylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxalkylene diimide diacid/polybutyrate terephthalate copolymer, and other aromatic polyesters; n
• EP Rubbers including copolymers of ethylene and propylene, and optionally one or more diene monomer(s), where the ethylene content is from 35 to 85 mol%, the total diene content is 0 to 5 mol%, and the balance is propylene with a minimum propylene content of 15 mol%.
• the EP Rubbers have a density of less than 0.86 g/cc.
• the diblock hydrosilane-functionalized polyolefins of this invention may be used in any known thermoplastic or elastomer application.
• examples include uses in molded parts, films, tapes, sheets, tubing, hose, sheeting, wire and cable coating, adhesives, shoe soles, bumpers, gaskets, bellows, films, fibers, elastic fibers, nonwovens, spun bonds, corrosion protection coatings, and sealants.
• Preferred uses include additives for lubricants and/or fuels.
• This invention further relates to:
• each PO and PO* independently, is a substituted or unsubstituted hydrocarbyl group having from 20 to about 10,000 carbon atoms;
• L is a bond, an oxygen atom, a Q to a C20 substituted or unsubstituted hydrocarbyl group, a
• Ci to a C20 substituted or unsubstituted hydrocarbyl ether group, or an R 3 -SiH 2 -SiH 2 -R 4 group, wherein each R 3 and R 4 , independently is a to a C20 substituted or unsubstituted hydrocarbyl group or a C j to a C20 substituted or unsubstituted hydrocarbyl ether group, wherein R 3 and R 4 can, optionally, be tethered to each other to form a cyclic ring.
• a process to produce the diblock hydrosilane-functionalized polyolefin of paragraphs 1 to 9 or a process to functionalize polyolefins comprising contacting a metallocene, a difunctional hydrosilylation reagent, optionally a reducing agent and one or more vinyl terminated polyolefins, wherein the metallocene is represented by the formula:
• each Cp is, independently, a substituted or unsubstituted cyclopentadienyl ring
• T is a bridging group
• n 0 or 1 ;
• M is Zr, Ti, or Hf
• each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof;
• difunctional hydrosilylation agent is represented by the formula:
• L is a bond, an oxygen atom, a Q to a C20 substituted or unsubstituted hydrocarbyl group, a Q to a C20 substituted or unsubstituted hydrocarbyl ether group, or an R 3 -SiH 2 -SiH 2 - 4 group, wherein each R 3 and R 4 , independently is a Ci to a C 2 o substituted or unsubstituted hydrocarbyl group or a C j to a C 2 Q substituted or unsubstituted hydrocarbyl ether group, wherein R 3 and R 4 can, optionally, be tethered to each other to form a cyclic ring;
• R 1 and R 2 are, independently, a substituted or unsubstituted to a C 2 Q hydrocarbyl group
• the vinyl terminated polyolefin is substituted or unsubstituted hydrocarbyl group having from 20 to about 10,000 carbon atoms.
• n is 0 and at least one position on the Cp ring is hydrogen, alternately at least two positions on the Cp ring are hydrogen, alternately at least three positions on the Cp ring are hydrogen, alternately at least four positions on the Cp ring are hydrogen, alternately five positions on the Cp ring are hydrogen.
• n is 0 and the Cp ring is an indene and at least one position on the indene is hydrogen, alternately at least two positions on the indene are hydrogen, alternately at least three positions on the indene are hydrogen, alternately at least four positions on the indene are hydrogen, alternately at least five positions on the indene are hydrogen, alternately at least six positions on the indene are hydrogen, alternately seven positions on the indene are hydrogen.
• the metallocene is one or more of T n (CpMe) 2 MX 2 , T n (CpPrMe) 2 MX 2 , T n (CpBuMe) 2 MX 2 , T n (Cpn-Pr) 2 MX 2 , T n (Cpt- Bu) 2 MX 2 , T n (CpSiMe 3 ) 2 MX 2 , T n (Indenyl)(Cp)MX 2 , T n (Fluorenyl)(Cp)MX 2 , wherein: each Cp is, independently, a substituted or unsubstituted cyclopentadienyl ring;
• T is a bridging group
• n 0 or 1 ;
• M is Zr, Ti, or Hf
• each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or a combination thereof; and
• Pr is propyl
• Me is methyl
• Bu is butyl
• n-Pr is n-propyl
• n is one and T is Me 2 Si, CR* 2 , Et 2 Si, or CH 2 CH 2 , wherein R* is a hydrocarbyl group, Me is methyl, and Et is ethyl.
• x is a number from 1 to 40.
• the reducing agent is present and is one or more of n-BuLi, t-BuLi, EtMgCl, Na, Li, Mg, K, LiH, LiBEt 3 H, NaBH 4 , LiAlH 4 , sec-BuLi, (nBu) 2 Mg, MeLi, and R*ZnX*, wherein X* is a leaving group, R* is a hydrocarbyl group, Bu is butyl, Et is ethyl, Me is methyl.
• the vinyl terminated polyolefin comprises propylene and at least 10 mol% of a C 4 or greater olefin and has: 1) at least 30% allyl chain ends (relative to total unsaturations); and 2) an Mn of from 200 to 60,000 g/mol, preferably from 200 to 50,000 g/mol, preferably from 500 to 40,000 g/mol.
• !fi NMR data was collected at either room temperature or 120°C (for purposes of the claims, 120°C shall be used) in a 5 mm probe using a Varian spectrometer with a hydrogen frequency of at least 400 MHz. Data was recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 120 transients. Spectral signals were integrated and the number of unsaturation types per 1,000 carbons was calculated by multiplying the different groups by 1,000 and dividing the result by the total number of carbons.
• M n of the macromer is determined by !fi NMR spectroscopy by comparison of integrals of the aliphatic region to the olefin region as determined using the protocol described in the Experimental section of USSN 12/143,663, filed on June 20, 2008.
• aPP is atactic polypropylene
• iPP is isotactic polypropylene
• EP is ethylene-propylene copolymer
• TCE 1, 1,2,2-tetrachloroethane
• h hours
• min minutes.
• the vinyl-terminated polyolefins listed in Table 1 were prepared according to procedures described in WO 2009/155471 (USSN 12/143,663, filed on June 20, 2008).
• Macromer A was made in a batch reactor.
• a 2 L stainless autoclave was charged with 0.5 ml of 1.0 M triisobutylaluminum (Aldrich) and 800 ml of isohexanes.
• Propylene 200 ml was added and the reactor was heated to 85°C.
• a catalyst solution was prepared by combining rac-C2H2(4,7-dimethylindenyl) 2 hafnium dimethyl (Boulder Scientific, 15 mg) and [PhNHMe2)[B(C 1 oF 7 )4] (Albemarle, 33 mg) in 15 ml toluene. The catalyst solution was stirred at room temperature for 30 minutes.
• Catalyst solution (3.0 ml of original solution) was put in a catalyst tube and injected into the reactor with high pressure nitrogen. The polymerization was allowed to proceed for 40 minutes and the reactor cooled to room temperature. After the pressure was vented the reactor contents were filtered and dried in vacuo (70°C, 4 hrs). The yield was 70 g.
• Macromer B was made was made in a batch reactor. A 2 L stainless autoclave was charged with 0.5 ml of 1.0 M triisobutylaluminum (Aldrich) and 400 mis of isohexanes.
• Catalyst solution A Biscyclopentadienylzirconium dichloride (0.062 g, 0.2 mmol) was slurried in hexane (5 mis) and cooled to 0°C. Two equivalents of n-butyl lithium ( 0.3 ml, 0.4 mmol, 1.6 M in hexanes) was added and the solution was warmed to room temperature.
• Macromer A (16.0 g) and Macromer B (5.0 g) were slurried in toluene (150 mis) and heated to 120°C (external set point) with stirring until the solution became transparent.
• 1, 10-disiladecane (0.28 g, 1.6 mmol) was added to the macromer solution followed by catalyst solution A. The reaction immediately turned an orange color. After one hour an aliquot was taken and volatiles removed for NMR analysis (130 mg). The NMR spectrum indicated that some vinyls groups remained. An aliquot at 3 hrs (102 mg) indicated that all vinyl groups had reacted.
• the hydrosilylation product was also characterized by 13 C NMR.
• the ratio of the integration of the signal at 14.3 ppm (C ⁇ methyl) to the integration from 23 to 18 ppm of (C3 methyls from both the iPP and aPP) was 1 to 21.4.
• Subtracting out the integration due to the aPP methyls from the isotactic methyls [21.4 (1)(80.6)/19.4] gives an integration value of 17.7 due to Macromer A methyls.
• the experimentally calculated ratio of Macromer A methyls to Macromer B methyls is 17.2 to 5.2.
• the number of methyls in one macromer of A is 333 (Mn/42) and the number of methyls in one macromer of B is 99 (Mn/(.806X42) + Mn(.194X74)).
• the molar ratio of the hydrosilation product determined by 13 C NMR shows that equivalent molar amounts of macromers A and B are present in the isolated product.
• compositions, an element or a group of elements are preceded with the transitional phrase "comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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  • 2012-03-05 WO PCT/US2012/027677 patent/WO2012134716A2/en active Application Filing
  • 2012-03-05 CN CN201280014778.7A patent/CN103443133B/zh not_active Expired - Fee Related
  • 2012-03-05 EP EP12764614.9A patent/EP2688919A4/de not_active Withdrawn

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