Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C9/00—Aliphatic saturated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound

Definitions

• a process to produce polymacromonomers comprises contacting a vinyl-terminated macromonomer having a number average molecular weight (Mn) of 125 (preferably 160) Da or more and at least 30% (preferably at least 40%, at least 50%, preferably at least 60%, preferably at least 70%) vinyl termination (as measured by l H NMR) relative to total unsaturations, and up to 40 wt% of C2 to comonomer, with a catalyst system capable of oligomerizing vinyl-terminated macromonomer, optionally, in the presence of a reversible chain transfer agent selected from an aluminum containing compound, a zinc containing compound, or a combination thereof, under polymerization conditions at a temperature from 20°C to 180°C and a reaction time of 1 min to 24 hours to produce a polymacromonomer having a degree of polymerization greater than 10, a branching index g' (vis) less than 0.9, a Tg from -10°C to 40°C and an Mn
• the hydrocarbyl radical is independently selected from methyl, ethyl, ethenyl, and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, dec
• ethylene content of 35 wt% to 55 wt%
• the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
• A is Avogadro's number
• (dn/dc) is the refractive index increment for the system.
• 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);
• g'(vis) of greater than 0.95 (preferably greater than 0.96, preferably greater than 0.98, preferably greater than 0.98, and, optionally, preferably less than or equal to 1.0).
• Useful stoichiometric (or non-alumoxane) activator-to-catalyst ratios range from 0.5: 1 to 10: 1, preferably 1 : 1 to 5: 1, although ranges of 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 1000: 1 may be used.
• the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds, and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl, or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups. Most preferably, the neutral stoichiometric activator is tris perfluorophenyl boron or tris perfluoronaphthyl boron.
• the ionic stoichiometric activators are represented by the following formula (1):
• the boron anion component has a molecular weight of greater than 1020 g/mol; and wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic A, alternately greater than 300 cubic A, or alternately greater than 500 cubic A.
• the weight ratio of macromonomer to catalyst compound entering the reactor is 10: 1 to 20,000: 1, or 100: 1 to 15000: 1, or 500: 1 to 10000: 1, or 50: 1 to 15000: 1, or 1000: 1 to 10000: 1. In embodiments, the ratio of macromonomer to catalyst compound is greater than 500: 1 or greater than 1000: 1. In embodiments, the ratio of macromonomer to catalyst compound is less than 1000: 1 or less than 500: 1.
• the polymacromonomer can comprise macromonomers that differ in total comonomer content by at least 2 wt%, or by at least 5 wt%, or by at least 10 wt%, or by at least 15 wt%, or by at least 20 wt%.
• a process to produce polymacromonomers comprising contacting (1) a vinyl- terminated macromonomer (VTM) having an Mn of 125 Da or more, at least 70% vinyl termination (as measured by NMR) relative to total unsaturations, and preferably an MWD of less than 1.5, (preferably less than 1.4, preferably from 1.01 to 1.4, preferably from 1.01 to 1.3, preferably from 1.01 to 1.2, preferably from 1.01 to 1.1); and (2) up to 40 wt% of (3 ⁇ 4 to Cig comonomer; with (3) a catalyst system capable of oligomerizing vinyl-terminated macromonomer, in the presence of a chain transfer agent, under polymerization conditions at a temperature from 20°C to 180°C and a reaction time of 1 min to 24 hours to produce a polymacromonomer having a degree of polymerization greater than 10, and an Mn of greater than or equal to about 5000 Da.
• VTM vinyl- terminated macromonomer
• NMR as measured by NMR
• Ad- is a non-coordinating anion having the charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar 3 C+), where Ar is aryl radical, an aryl radical substituted with a heteroatom, an aryl radical substituted with one or more Q to C40 hydrocarbyl radicals, an aryl radical substituted with one or more functional groups comprising elements from Groups 13 to 17 of the periodic table of the elements, or a combination thereof.
• polymacromonomer of any one of embodiments 40 to 54 wherein the polymacromonomer comprises a flow activation energy greater than 12 kcal/mol, or greater than 15 kcal/mol.
• the polymacromonomer of any one of embodiments 40 to 55 comprising a bimodal MWD.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

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• 2013
  • 2013-01-29 EP EP13751938.5A patent/EP2817343A4/fr not_active Withdrawn
  • 2013-01-29 WO PCT/US2013/023613 patent/WO2013126187A1/fr not_active Ceased
  • 2013-01-29 JP JP2014558749A patent/JP2015513583A/ja active Pending
  • 2013-01-29 CN CN201380010287.XA patent/CN104169312A/zh active Pending

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