Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages

Definitions

• R 1 1 is selected from the group consisting of substituted 5 or 6 membered aromatic rings;
• RlO is -E*(Rl2)(Rl3)- ;
• p 1 or 2;
• This invention further relates to process to make the above complex, process to make intermediates for the above complex and methods to polymerize olefins using the above complex.
• aromatic also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.
• the pyridyldiamido transition metal complex is represented by the Formula (I) or (II) above and at least one of R 12 * and R 13 * is a group containing from 1 to 5 (preferably 1 to 4, preferably 1 to 3) carbons.
• the pyridyldiamido transition metal complex is represented by the Formula (I) or (II) and R 12 * and R 13 * are hydrogen, E is C, and E* is C or Si.
• the second step then involves reaction of this halo-methyl group containing species with an amine or protected amine or deprotonated protected amine to yield an amine-containing linker.
• This amine-containing linker is then coupled with a suitable pyridine containing species, such as 6-bromo-2- pyridinecarboxaldehyde.
• This coupling step typically uses a metal catalyst (e.g., Pd(PPh 3 ) 4 ) in less than 5 mol% loading.
• the new derivative which can be described as amine-linker-pyridine-aldehyde, is then reacted with a second amine to produce the imine derivative amine-linker-pyridine-imine in a condensation reaction.
• Z is (L-H) or a reducible Lewis acid
• L is a neutral Lewis base
• H is hydrogen
• the catalyst complexes described herein are generally deposited on the support at a loading level of 10-100 micromoles of complex per gram of solid support; alternately 20-80 micromoles of complex per gram of solid support; or 40-60 micromoles of complex per gram of support. But greater or lesser values may be used provided that the total amount of solid complex does not exceed the support's pore volume.
• R 1 is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups (preferably alkyl, aryl, heteroaryl, and silyl groups);
• R 6 ; R 7 R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and the pairs of positions, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 15 , and/or R 16 & R 15 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
• Z is -(R 14 *) P Q-J(R 15 *) Q - where Q or J is bonded to R 10 ;
• a pre-weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels.
• the reactor was then closed and propylene (typically 1 mL) was introduced to each vessel as a condensed gas liquid. If ethylene was added as a comonomer, it was added before the propylene as a gas to a pre-determined pressure (typically 10-80 psi) while the reactor vessels were heated to a set temperature (typically 40°C).
• solvent typically isohexane
• scavenger and/or co-catalyst and/or a chain transfer agent such as tri-n-octylaluminum in toluene (typically 100-1000 nmol) was added.
• R 12 H because, inter alia: (i) it produced higher molecular weight ethylene-polypropylene copolymer; (ii) it has higher activity; and (iii) it enabled the production of ethylene-propylene copolymers containing low (i.e., less than 35%) amounts of ethylene.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

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• 2012
  • 2012-01-25 WO PCT/US2012/022476 patent/WO2012134615A1/en active Application Filing
  • 2012-01-25 EP EP12764279.1A patent/EP2688895A4/de not_active Withdrawn
  • 2012-01-25 CN CN201280020007.9A patent/CN103492397B/zh not_active Expired - Fee Related

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