Chromium(iii) silicate catalysts suitable for pe synthesis

Patent metadata

Field	Value
Publication number	US-2016168283-A1
Application number	US-201414905666-A
Country	US
Kind code	A1
Filing date	Jul 17, 2014
Priority date	Jul 18, 2013
Publication date	Jun 16, 2016
Grant date	—

Abstract

Molecular precursor chromium compounds and chromium on silica catalyst precursors suitable for sure in producing chromium on silica catalysts are disclosed. The molecular precursor compounds can be chromium(II) and/or chromium(III) and/or chromium (IV) compounds wherein all ligands are easily removable, in particular ligands selected from the group consisting of anionic ligands of the type —O—CR 3 R 4 —CH—R 1 —R 2 or —O—Si—(O—CR 3 R 4 —CH—R 1 R 2 ) 3 wherein R1, R2, R3 and R4 may be the same or different and may be any group that does not affect decomposition of the ligand via elimination of beta-hydrogen from —CR 3 R 4 —CH—R 1 R 2 , amide anionic ligands of the type —N—Si—R 5 R 6 R 7 and/or —N—C—R 5 R 6 R 7 , wherein R 5 , R 6 and R 7 can be the same or different and are preferably selected from hydrogen, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, tert-butyl groups or aromatic groups; as well as coordinating solvents. These molecular precursors can be grafted to silica and—if need be—either before or after heat treatment during which the ligands are removed, oxidized to Cr(III). The chromium on silica catalyst is characterized by the absence of any organic ligands.

First claim

1 .- 18 . (canceled)

19 . Use of a molecular precursor chromium compound for producing a chromium (III) on silica catalyst, said molecular precursor compound being a chromium(II) and/or a chromium(III) and/or a chromium (IV) compound wherein all ligands are easily removable, in particular ligands selected from the group consisting of anionic ligands of the type —O—CR 3 R 4 —CH—R 1 R 2 or —O—Si—(O—CR 3 R 4 —CHR 1 R 2 ) 3 wherein R1, R2, R3 and R4 may be the same or different and may be any group that does not affect decomposition of the ligand via elimination of beta-hydrogen from —CR 3 R 4 —CH—R 1 R 2 , and amide anionic ligands of the type —N—(Si—R 5 R 6 R 7 ) 2 and/or —N—(C—R 5 R 6 R 7 ) 2 wherein R 5 , R 6 and R 7 can be the same or different and are preferably selected from hydrogen, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, tert-butyl groups or aromatic groups; as well as coordinating solvents, in particular a monomeric or dimeric molecular precursor chromium compound.

20 . The use of claim 19 wherein R 1 to R 4 are independently from each other selected from the group consisting of hydrogen, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, tert-butyl groups, and aryl groups, preferably R 1 to R 4 are independently from each other selected from the group consisting of hydrogen, methyl and phenyl, most preferred R 1 and R 2 are hydrogen, and R 3 and R 4 are methyl.

21 . The use of claim 19 , wherein at least one of the anionic ligands is selected from the group consisting of tri-tert-butoxysilanolate (—OSi(O t Bu) 3 ) and hexamethyldisilazide (—N(SiMe 3 ) 2 ).

22 . The use of claim 19 , wherein the molecular precursor chromium compound is a dimer wherein all ligands are —O—CR 3 R 4 —CH—R 1 R 2 and/or —O—Si—(O—CR 3 R 4 —CHR 1 R 2 ) 3 .

23 . The use of claim 19 , wherein the molecular precursor chromium compound is selected from Cr(N(Si(CH 3 ) 3 ) 2 ) 3 , [Cr(OSi(O t Bu) 3 ) 2 ] 2 , Cr(O t Bu) 4 , Cr(OSi(O t Bu) 3 ) 3 *2thf, and C 48 H 108 Cr 2 O 17 Si 4 (5), in particular C 48 H 108 Cr 2 O 17 Si 4 (5) and [Cr(OSi(O t Bu) 3 ) 2 ] 2 .

24 . A molecular precursor chromium compound as defined in claim 19 that is suitable for use in producing a chromium on silica catalyst, with the proviso that the molecular precursor chromium compound is not
Cr(N(Si(CH 3 ) 3 ) 2 ) 3 , Cr(OSi(OtBu) 3 ) 3 *2thf, Cr(O t Bu) 4 , Cr(O t Bu) 3 (O—Si(O t Bu) 3 ), Cr(O t Bu) 2 (O—Si(O t Bu) 3 ) 2 ,Cr(HNEt 2 ) 2 (O—Si(O t Bu) 3 ) 2 , and Cr(HNEt 2 ) 2 (O—Si(O t Bu) 3 ) 3 .

25 . A chromium on silica catalyst precursor, wherein at least one ligand of the molecular precursor compound, is replaced by a surface O—Si—O group (≡SiO), said compound being a chromium(II) and/or a chromium(III) and/or a chromium (IV) compound wherein all ligands are easily removable, in particular ligands selected from the group consisting of anionic ligands of the type —O—CR 3 R 4 —CH—R 1 R 2 or —O—Si—(O—CR 3 R 4 —CHR 1 R 2 ) 3 wherein R1, R2, R3 and R4 may be the same or different and may be any group that does not affect decomposition of the ligand via elimination of beta-hydrogen from —CR 3 R 4 —CH—R 1 R 2 , and amide anionic ligands of the type —N—(Si—R 5 R 6 R 7 ) 2 and/or —N—(C—R 5 R 6 R 7 ) 2 wherein R 5 , R 6 and R 7 can be the same or different and are preferably selected from hydrogen, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, tert-butyl groups or aromatic groups; as well as coordinating solvents, in particular a monomeric or dimeric molecular precursor chromium compound.

26 . The chromium on silica catalyst precursor of claim 25 , that is a Cr(II) or Cr(III) or Cr(IV) compound comprising ligands and being attached to the silica surface via at least one Si—O bond, in particular [(≡SiO)Cr 2 (OSi(O t Bu) 3 ) 3 ] or C 48 H 108 Cr 2 O 17 Si 4 grafted on silica (6) or[(≡SiO)Cr(OSi(O t Bu) 3 ) 2 (thf)].

27 . The chromium on silica catalyst precursor of claim 25 , that is a Cr(II) compound attached to the silica surface via Si—O bonds, wherein all ligands have been removed or replaced by a surface O—Si—O group (≡SiO), in particular [(≡SiO) 4 Cr 2 ].

28 . A chromium on silica catalyst that is a Cr(III) or Cr(IV) compound attached to the silica surface via Si—O bonds, wherein all ligands have been either removed or replaced by a surface O—Si—O group (≡SiO), in particular such a Cr(III) compound, especially [(≡SiO) 6 Cr 2 ] or [(≡SiO) 3 Cr].

29 . A method for producing a molecular precursor chromium compound, in particular a molecular precursor chromium compound suitable for being used for producing a chromium (III) on silica catalyst, said method comprising treating a Cr(II) or Cr(III) or Cr(IV) starting compound, in particular Cr(HMDS) 2 *2thf or Cr(HMDS) 3 or CrCl 3 *3thf or CrCl 3 or CrCl 2 *2thf or CrCl 2 , with one or more ligand precursor(s) like protonated ligands and/or one or more metal salts of the ligand, wherein the ligand(s) are easily removable under conditions that allow coordination of the one or more ligands, in particular ligands selected from the group consisting of anionic ligands of the type —O—CR 3 R 4 —CH—R 1 R 2 or —O—Si—(O—CR 3 R 4 —CHR 1 R 2 ) 3 wherein R1, R2, R3 and R4 may be the same or different and may be any group that does not affect decomposition of the ligand via elimination of beta-hydrogen from —CR 3 R 4 —CH—R 1 R 2 , and amide anionic ligands of the type —N—(Si—R 5 R 6 R 7 ) 2 and/or —N—(C—R 5 R 6 R 7 ) 2 wherein R 5 , R 6 and R 7 can be the same or different and are preferably selected from hydrogen, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, tert-butyl groups or aromatic groups; as well as coordinating solvents, in particular a monomeric or dimeric molecular precursor chromium compound and in particular by reacting a slurry of the Cr(II) or Cr(III) or Cr(IV) starting compound in a non coordinating solvent at temperatures of −40 to 150° C., preferentially at temperatures comprised between 15 and 40° C.

30 . A method for producing a chromium on silica catalyst precursor of claim 26 comprising treating silica with a molecular precursor chromium compound said molecular precursor compound being a chromium(II) and/or a chromium(III) and/or a chromium (IV) compound wherein all ligands are easily removable, in particular ligands selected from the group consisting of anionic ligands of the type —O—CR 3 R 4 —CH—R 1 R 2 or —O—Si—(O—CR 3 R 4 —CHR 1 R 2 ) 3 wherein R1, R2, R3 and R4 may be the same or different and may be any group that does not affect decomposition of the ligand via elimination of beta-hydrogen from —CR 3 R 4 —CH—R 1 R 2 , and amide anionic ligands of the type —N—(Si—R 5 R 6 R 7 ) 2 and/or —N—(C—R 5 R 6 R 7 ) 2 wherein R 5 , R 6 and R 7 can be the same or different and are preferably selected from hydrogen, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, tert-butyl groups or aromatic groups; as well as coordinating solvents, in particular a monomeric or dimeric molecular precursor chromium compound especially a Cr(II) and/or a Cr(III) molecular precursor chromium compound.

31 . A method for producing a chromium on silica catalyst precursor of claim 27 , comprising treating a chromium on silica catalyst precursor wherein at least one ligand of the molecular precursor compound, is replaced by a surface —O—Si—O— group (≡SiO), said compound being a chromium(II) and/or a chromium(III) and/or a chromium (IV) compound wherein all ligands are easily removable, in particular ligands selected from the group consisting of anionic ligands of the type —O—CR 3 R 4 —CH—R 1 R 2 or —O—Si—(O—CR 3 R 4 —CHR 1 R 2 ) 3 wherein R1, R2, R3 and R4

Assignees

• Eth Zuerich

Inventors

• Copéret Christophe
• Conley Matthew
• Delley Murielle

Classifications

• C08F10/02 Primary

  Ethene · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• C07F13/005

  Compounds without a metal-carbon linkage · CPC title

• C08F2410/03

  Multinuclear procatalyst, i.e. containing two or more metals, being different or not · CPC title