Olefin polymerization catalyst system comprising mesoporous organosilica support

• US 10,294,312 B2
• Filed: 12/11/2015
• Issued: 05/21/2019
• Est. Priority Date: 12/12/2014
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Holtcamp, Matthew W., Day, Gregory S., Sanders, David F., Calabro, David C., Li, Quanchang, Mertens, Machteld M. W.
• Primary Examiner(s): Lee, Rip A
• Application Number:
  US15/526,513
• Publication Number:
  US 20170327604A1
• Time in Patent Office: 1,257 Days
• CPC Class Codes: B01D 15/00 Separating processes involving the treatment of liquids with solid sorbents using liquid sorbents B01D11/00; ion exchange processes or materials, sorbent materials in general B01J, e.g. sorbents for chromatography B01J20/281; for investigating or analysing materials G01N30/00; Apparatus therefor
• CPC Class Codes: B01D 2253/20 Organic adsorbents
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/40 Nitrogen compounds
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 71/702 Polysilsesquioxanes or combination of silica with bridging organosilane groups
• CPC Class Codes: B01J 20/0229 Compounds of Fe
• CPC Class Codes: B01J 20/0237 Compounds of Cu
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/10 comprising silica or silicate
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/16 : Alumino-silicates B01J20/12 takes precedence
• CPC Class Codes: B01J 20/18 : Synthetic zeolitic molecular sieves
• CPC Class Codes: B01J 20/22 : comprising organic material
• CPC Class Codes: B01J 20/262 : obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G
• CPC Class Codes: B01J 20/264 : derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
• CPC Class Codes: B01J 20/28011 : Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/28057 : Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28061 : being in the range 100-500 m2/g
• CPC Class Codes: B01J 20/28064 : being in the range 500-1000 m2/g
• CPC Class Codes: B01J 20/28066 : being more than 1000 m2/g
• CPC Class Codes: B01J 20/28069 : Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/28071 : being less than 0.5 ml/g
• CPC Class Codes: B01J 20/28073 : being in the range 0.5-1.0 ml/g
• CPC Class Codes: B01J 20/28076 : being more than 1.0 ml/g
• CPC Class Codes: B01J 20/28078 : Pore diameter
• CPC Class Codes: B01J 20/28083 : being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 20/286 : Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/3042 : Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• CPC Class Codes: B01J 20/3204 : Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3212 : consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3236 : containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/3238 : containing any type of zeolite
• CPC Class Codes: B01J 20/3272 : Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 2220/86 : Sorbents applied to inner surfaces of columns or capillaries
• CPC Class Codes: B01J 23/44 : Palladium
• CPC Class Codes: B01J 31/0274 : containing silicon ligands in coordination complexes B01J31/1608
• CPC Class Codes: B01J 35/615 : 100-500 m2/g
• CPC Class Codes: B01J 35/617 : 500-1000 m2/g
• CPC Class Codes: B01J 35/618 : more than 1000 m2/g
• CPC Class Codes: B01J 35/647 : 2-50 nm
• CPC Class Codes: B01J 37/0213 : Preparation of the impregnating solution
• CPC Class Codes: B01J 37/0236 : Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: C01B 37/00 : Compounds having molecular sieve properties but not having base-exchange properties
• CPC Class Codes: C07D 251/30 : Only oxygen atoms
• CPC Class Codes: C07F 7/0807 : comprising Si as a ring atom
• CPC Class Codes: C07F 7/081 : comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
• CPC Class Codes: C08F 210/02 : Ethene
• CPC Class Codes: C08F 210/14 : Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 : Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 4/02 : Carriers therefor
• CPC Class Codes: C08F 4/027 : Polymers
• CPC Class Codes: C08F 4/64013 : NN
• CPC Class Codes: C08F 4/64048 : NO
• CPC Class Codes: C08F 4/64089 : NNN
• CPC Class Codes: C08F 4/64148 : NN(R)N
• CPC Class Codes: C08F 4/64158 : ONO
• CPC Class Codes: C08F 4/64189 : ONNO
• CPC Class Codes: C08F 4/64193 : OOOO
• CPC Class Codes: C08F 4/659 : Component covered by group C08F4/64 containing a transition metal-carbon bond C08F4/64003 - C08F4/64196 take precedence
• CPC Class Codes: C08F 4/65912 : in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 : supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/6592 : containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65925 : two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: C08F 4/65927 : two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: C08G 77/26 : nitrogen-containing groups
• CPC Class Codes: C08G 77/60 : in which all the silicon atoms are connected by linkages other than oxygen atoms
• CPC Class Codes: C10G 25/003 : Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 31/09 : by filtration
• CPC Class Codes: C10G 35/06 : characterised by the catalyst used
• CPC Class Codes: C10G 45/00 : Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 45/04 : characterised by the catalyst used
• CPC Class Codes: C10G 45/34 : characterised by the catalyst used
• CPC Class Codes: C10G 45/44 : Hydrogenation of the aromatic hydrocarbons
• CPC Class Codes: C10G 45/46 : characterised by the catalyst used
• CPC Class Codes: C10G 45/52 : containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 45/60 : characterised by the catalyst used
• CPC Class Codes: C10G 45/64 : containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/02 : characterised by the catalyst used
• CPC Class Codes: C10G 50/00 : Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C10K 1/32 : with selectively adsorptive solids, e.g. active carbon
• CPC Class Codes: C10M 101/02 : Petroleum fractions
• CPC Class Codes: C23C 16/56 : After-treatment
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

A catalyst system comprising a combination of: 1) an activator; 2) one or more metallocene catalyst compounds; 3) a support comprising an organosilica material, which may be a mesoporous organosilica material. The organosilica material may be a polymer of at least one monomer of Formula [Z¹OZ²SiCH₂]₃ (I), where Z¹ represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a silicon atom of another monomer and Z² represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₆ alkyl group, or an oxygen atom bonded to a silicon atom of another monomer. This invention further relates to processes to polymerize olefins comprising contacting one or more olefins with the above catalyst system.

Claims

1. A catalyst system comprising:

one or more olefin polymerization catalyst compounds;

a catalyst support comprising an organosilica material that is a polymer of at least one monomer of Formula [Z¹OZ²SiCH₂]₃ (I), wherein Z¹ represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a silicon atom of another monomer and Z² represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₆ alkyl group, or an oxygen atom bonded to a silicon atom of another monomer; and

an activator.

2. The catalyst system of claim 1, wherein olefin polymerization catalyst compound is a coordination polymerization catalyst compound.

3. The catalyst system of claim 1, wherein Z² represents a hydroxyl group, a C₁-C₄ alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer, and, optionally, Z¹ represents a hydrogen atom, methyl, ethyl or a bond to a silicon atom of another monomer.

4. The catalyst system of claim 1, wherein the polymer further comprises a second distinct monomer of Formula [Z¹OZ²SiCH₂]₃ (I).

5. The catalyst system of claim 1, wherein the organosilica material further comprises at least one monomer selected from the group consisting of:

a monomer of Formula Z³OZ⁴Z⁵Z⁶Si (II), wherein Z³ represents a hydrogen atom or a C₁-C₄ alkyl group, or a bond to a silicon atom of another monomer; and

Z⁴, Z⁵ and Z⁶ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;

a monomer of Formula Z⁷Z⁸Z⁹Si—

R¹—

SiZ⁷Z⁸Z⁹ (III), wherein Z⁷ represents a hydroxyl group, a C₁-C₄ alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer;

Z⁸ and Z⁹ each independently represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, or an oxygen bonded to a silicon atom of another monomer; and

R¹ is selected from the group consisting of a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, a nitrogen-containing C₂-C₁₀ alkylene group, an optionally substituted C₆-C₂₀ aralkylene and an optionally substituted C₄-C₂₀ heterocycloalkylene group;

a trivalent metal oxide monomer of Formula M¹(OZ¹⁰)₃ (IV), wherein M¹ represents a Group 13 metal and Z¹⁰ represents a hydrogen atom, a C₁-C₆ alkyl or a bond to a silicon atom of another monomer;

a trivalent metal oxide monomer of Formula (Z¹¹O)₂M²-O—

Si(OZ¹²)₃ (V), wherein M² represents a Group 13 metal and Z¹¹ and Z¹² each independently represent a hydrogen atom, a C₁-C₆ alkyl group, or a bond to a silicon atom of another monomer;

a cyclic polyurea monomer of Formula

6. The catalyst system of claim 1, wherein the catalyst support comprising an organosilica material has:

an average pore diameter between about 2 nm and about 50 nm;

a pore volume about 0.1 cm³/g to about 10 cm³/g; and

/or

a surface area of about 100 m²/g to about 2,500 m²/g.

7. The catalyst system of claim 1, wherein the catalyst support comprising the organosilica material has an X-Ray diffraction spectrum exhibiting substantially no peaks above 4 degrees 2θ

; and

/or is made using substantially no added structure directing agent or porogen.

8. The catalyst system of claim 1, wherein the olefin polymerization catalyst compound comprises one or more metallocene compounds represented by the formula:

T_yCp_mM⁶G_nX⁵_q

wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M⁶ is a Group 4 transition metal, G is a heteroatom group represented by the Formula JR*_z where J is N, P, O or S, and R* is a linear, branched or cyclic hydrocarbyl group having from one to twenty carbon atoms and z is 1 or 2, T is a bridging group, and y is 0 or 1, X⁵ is a leaving group, and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal.

9. The catalyst system of claim 8, wherein each Cp is a cyclopentadienyl, indenyl or fluorenyl group, which may be substituted or unsubstituted, each M⁶ is titanium, zirconium, or hafnium, and each X⁵ is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.

10. The catalyst system of claim 8, wherein y is 1, m is 1, n is 1, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

11. The catalyst system of claim 8, wherein the at least one metallocene compound comprises one or more of:

bis(tetrahydroindenyl)Hf Me₂;

bis(1-butyl,3-methylcyclopentadienyl)ZrCl₂;

bis-(n-butylcyclopentadienyl)ZrCl₂;

(Dimethylsilyl)₂O bis(indenyl)ZrCl₂;

dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)ZrCl₂;

dimethylsilylbis(tetrahydroindenyl)ZrCl₂;

dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl₂;

dimethylsilyl(3-neopentylcyclopentadienyl)(tetramethylcyclopentadienyl)HfCl₂;

tetramethyldisilylene bis(4-(3,5-di-tert-butylphenyl)-indenyl)ZrCl₂;

cyclopentadienyl(1,3-diphenylcyclopentadienyl)ZrCl₂;

bis(cyclopentadienyl)zirconium dichloride;

bis(pentamethyl cyclopentadienyl)zirconiurn dichloride;

bis(pentamethylcyclopentadienyl)zirconium dimethyl;

bis(pentamethylcyclopentadienyl)hafnium dichloride;

bis(pentanmethylcyclopentadienyl)zirconium dimethyl;

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride;

bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;

bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride;

bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dimethyl;

bis(indenyl)zirconium dichloride;

bis(indenyl)zirconium dimethyl;

bis(tetrahydro-1-indenyl)zirconium dichloride;

bis(tetrahydro-1-indenyl)zirconium dimethyl;

dimethylsilylbis(tetrahydroindenyl)zirconium dichloride;

dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl;

dimethylsilylbis(indenyl)zirconium dichloride;

dimethylsilyl(bisindenyl)zirconium dimethyl;

dimethylsilylbis(cyclopentadienyl)zirconium dichloride; and

dimethylsilylbis(cyclopentadienyl)zirconium dimethyl.

12. The catalyst system of claim 1, wherein the activator comprises an alkylalumoxane and/or a non-coordinating anion.

13. The catalyst system of claim 1, wherein the one or more olefin polymerization catalyst compounds comprises a Ziegler-Natta catalyst compound.

14. The catalyst system of claim 1, wherein the one or more olefin polymerization catalyst compounds comprises one or more metallocene compounds of:

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl;

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride;

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl;

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride;

μ

-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M⁷(R¹⁵)₂;

μ

-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M⁷(R¹⁵)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M⁷(R¹⁵)₂;

μ

-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M⁷(R¹⁵)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M⁷(R¹⁵)₂;

μ

-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M⁷(R¹⁵)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M⁷(R¹⁵)₂;

or μ

-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M⁷(R¹⁵)₂;

where M⁷ is selected from a group consisting of Ti, Zr, and Hf and R¹⁵ is selected from halogen or C₁-C₅ alkyl.

15. The catalyst system of claim 1, wherein the one or more olefin polymerization catalyst compounds comprises a first metallocene compound and a second metallocene compound independently selected from the group consisting of:

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and bis(1-Bu,3-Me-Cp) ZrCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂) bis(indenyl)ZrCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrMe₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and SiMe₂(3-neopentylCp)((Me₄Cp)HfCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and SiMe₂(3-neopentylcyclopentadienyl)(Me₄Cp)HfMe₂;

SiMe₂(Me₄Cp)(1-adamantylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂; and

SiMe₂(Me₄Cp)(1-t-butylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂.

16. The catalyst system of claim 12, wherein the activator comprises methylalumoxane, ethylalumoxane, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate or a mixture thereof.

17. A process to produce polymer comprising:

contacting, in the gas phase or slurry phase, one or more olefin monomers with the catalyst system of claim 1; and

ii) obtaining a polymer.

18. The process of claim 17, wherein the polymer is an ethylene polymer or a propylene polymer.

19. The process of claim 17, wherein the process occurs at a temperature of from about 0°

C. to about 300°

C., at a pressure of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.

20. The process of claim 17, wherein the one or more olefin monomers comprise ethylene and one or more comonomer selected from propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene or a mixture thereof.

21. The process of claim 17, wherein the 2) catalyst support comprising an organosilica material comprises a plurality of mesopores having an average pore diameter between about 2 nm and about 50 nm and the polymerization occurs within the mesopores.