Chromium complex and catalyst therefrom

Patent metadata

Field	Value
Publication number	US-10207262-B2
Application number	US-201615557886-A
Country	US
Kind code	B2
Filing date	Mar 10, 2016
Priority date	Mar 13, 2015
Publication date	Feb 19, 2019
Grant date	Feb 19, 2019

Abstract

The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

First claim

What is claimed is:

1. A catalyst system comprising a) a source of chromium selected from the group consisting of CrCl 3 (THF) 3 (trichlorotris(tetrahydrofuran)chromium), CrBr 3 (THF) 3 , CrI 3 (THF) 3 , CrCl 3 , CrBr 3 , CrI 3 , CrCl 2 , CrCl 2 (THF) 2 , Cr(acac) 3 (chromium (III) acetylacetonate), Cr(acetate) 3 (chromium (III) acetate), Cr(2-ethylhexanoate) 3 (chromium (III) 2-ethylhexanoate), (THF) 3 CrMeCl 2 , (Mes) 3 Cr(THF), ((TFA) 2 Cr(OEt) 2 ) 2 , (THF) 3 CrPh 3 , Cr(NMe 3 ) 2 Cl 3 , Cr(neopentyl) 3 (THF) 3 , Cr(CH 2 —C 6 H 4 -o-NMe 2 ) 3 , Cr(TFA) 3 , Cr(CH(SiMe 3 ) 2 ) 3 , Cr(Mes) 2 (THF) 3 , Cr(Mes) 2 (THF)Cr(Mes) 2 (THF) 2 , Cr(Mes)Cl(THF) 2 , Cr(Mes)Cl(THF) 0.5 , Cr(p-tolyl)Cl 2 (THF) 3 , Cr(diisopropylamide) 3 , Cr(picolinate) 3 , Cr(NO 3 ) 3 , Cr(hexafluoroacetylacetonato) 3 , (THF) 3 Cr(η 2 -2,2″biphenyl)Br, Cr(CO) 6 , Cr(CO) 3 (THF) 3 , Cr(CO) 3 (NCCH 3 ) 3 , (benzene)Cr(CO) 3 , (toluene)Cr(CO) 3 chromium (III) acetylacetonate, chromium (III) acetate and mixtures thereof; b) one or more activators selected from the group consisting of neutral Lewis acids, Group 13 metal and metalloid compounds; polymeric alumozanes; oligomeric alumoxanes; aluminates; and, c) at least one phosphacycle-containing ligating compound of the formula:

wherein:
R 5 attached to N is independently C 1-40 substituted or unsubstitued alkyl, C 1-40 substituted or unsubstituted aryl;
each R 5 attached to the phenyl group is independently halogen, C 1-40 substituted or unsubstituted alkyl, C 1-40 substituted or unsubstituted aryl; n is an integer from 0 to 5; and each X″ is independently hydrogen, halogen, C 1-4 aldyl or substituted alkyl, C 6-10 aryl or substituted aryl, cyano or nitro.

2. The catalyst system as in claim 1 comprising a phosphacycle-containing ligating compound-chromium complex.

3. The catalyst system of claim 1 comprising an isolated phosphacycle-containing ligating compound-chromium complex.

4. The catalyst system of claim 1 comprising an in situ-formed phosphacycle-containing ligating compound-chromium complex.

5. The catalyst system of claim 1 , wherein the source of chromium is selected from the group consisting of trichlorotris(tetrahydrofuran)chromium, chromium (III) acetylacetonate, chromium (III) 2-ethylhexanoate, and chromium (III) acetate.

6. The catalyst system of claim 1 , wherein the source of chromium and the ligating compound are contacted in proportions to provide Cr:ligating compound ratios from 1000:1 to 1:1000.

7. The catalyst system of claim 1 , wherein at least one activator is selected from the group consisting of (hydrocarbyl) aluminum compounds, (hydrocarbyl)gallium compounds, (hydrocarbyl)boron compounds, (hydrocarbyl)zinc compounds, Bronsted acid salts, salts of a cationic oxidizing agent and a non-coordinating, compatible anion, carbenium salts, and silylium salt.

8. The catalyst system of claim 1 , wherein the activator is an alkylaluminoxane.

9. The catalyst system of claim 1 , wherein the source of chromium and the aluminoxane are combined in proportions to provide chromium:activator molar ratios from 1:1 to 1:10,000.

10. The catalyst system of claims 1 - 9 wherein the phosphacycle-containing ligating compound is selected from the group consisting of:

Assignees

• Dow Global Technologies Llc

Inventors

• Klosin Jerzy
• Milbrandt Kara A
• Boelter Scott D
• Wilson David R
• Rosen Mari S
• Welsh Dean M
• Margl Peter M
• Koh Kyoung Moo
• Pearson David M
• Huacuja Rafael

Classifications

• C07C2/36 Primary

  as phosphines, arsines, stilbines or bismuthines · CPC title

• B01J2531/62

  Chromium · CPC title

• C07F9/65846

  the phosphorus atom being part of a six-membered ring which may be condensed with another ring system · CPC title

• C07F9/65848

  Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring · CPC title

• B01J31/188

  Amide derivatives thereof · CPC title