Catalyst composition and process for oligomerization of ethylene

Abstract

A catalyst composition including: (a) a chromium compound; (b) a ligand of the general structure (A) R 1 R 2 P—N(R 3 )—P(R 4 )—NR 5 R 6 or (B) R 1 R 2 P—N(R 3 )—P(XR 7 )R 8 or R 1 R 2 P—N(R 3 )—P(XR 7 ) 2 , with X═O or S, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently C 1 -C 10 -alkyl, C 6 -C 20 -aryl, C 3 -C 10 -cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; and (c) an activator or co-catalyst; and a process for tri- and/or tetramerization.

1 . A catalyst composition comprising:
 (a) a chromium compound;   (b) a ligand of the general structure
 (A) R 1 R 2 P—N(R 3 )—P(R 4 )—NR 5 R 6  or 
 (B) R 1 R 2 P—N(R 3 )—P(XR 7 )R 8  or R 1 R 2 P—N(R 3 )—P(XR 7 ) 2 , with X═O or S, wherein R 1 , R 2 , R 3 , R 4 , R 7  and R 8  are independently C 1 -C 10 -alkyl, C 6 -C 20 -aryl, C 3 -C 10 -cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; and 
   (c) an activator or co-catalyst;
 wherein at least one of R 5  or R 6  is not OEt. 
   
     
     
         2 - 11 . (canceled) 
     
     
         12 . A process for tri- and/or tetramerization of ethylene, comprising subjecting a catalyst composition to a gas phase of ethylene in a reactor and conducting an oligomerization; wherein the catalyst composition comprises (a) a chromium compound;
 (b) a ligand of the general structure
 (A) R 1 R 2 P—N(R 3 )—P(R 4 )—NR 5 R 6  or 
 (B) R 1 R 2 P—N(R 3 )—P(XR 7 )R 8  or R 1 R 2 P—N(R 3 )—P(XR 7 ) 2 , with X═O or S, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  are independently C 1 -C 10 -alkyl, C 6 -C 20 -aryl, C 3 -C 10 -cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; 
   (c) and an activator or co-catalyst.   
     
     
         13 . A process according to  claim 12 , wherein the oligomerization is carried out at a pressure of 1 to 200 bar. 
     
     
         14 . A process according to  claim 12 , wherein the oligomerization is carried out at a temperature of from 10 to 200° C. 
     
     
         15 . A process according to  claim 12 , wherein the mean residence time is from 10 minutes to 20 hours. 
     
     
         16 . The catalyst composition according to  claim 1 , wherein the ligand is Ph 2 P—N(i-Pr)—P[S(i-Pr)] 2 , Ph 2 P—N(i-Pr)P(OCH 3 ) 2 , or a combination thereof. 
     
     
         17 . The catalyst composition according to  claim 1 , wherein the ligand is Ph 2 P—N(i-Pr)—P[S(i-Pr)] 2 . 
     
     
         18 . The catalyst composition according to  claim 1 , wherein the ligand is Ph 2 P—N(i-Pr)P(OCH 3 ) 2 . 
     
     
         19 . The catalyst composition according to  claim 1 , wherein the chromium compound is CrCl 3 (THF). 
     
     
         20 . A catalyst composition according to  claim 1 , wherein the chromium compound is Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacarbonyl, Cr(III)-2-ethylhexanoate, (benzene)tricarbonyl-chromium, or a combination comprising at least one of the foregoing. 
     
     
         21 . A catalyst composition according to  claim 1 , wherein the activator or co-catalyst is trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminumsesquichloride, diethylaluminum chloride, ethylaluminumdichloride, methylaluminoxane (MAO), or a combination comprising at least one of the foregoing. 
     
     
         22 . A catalyst composition according to  claim 1 , wherein the activator or co-catalyst is trimethylaluminum. 
     
     
         23 . A catalyst composition according to  claim 1 , wherein the activator or co-catalyst is triethylaluminum. 
     
     
         24 . A catalyst composition according to  claim 1 , wherein the activator or co-catalyst is triisopropylaluminum. 
     
     
         25 . A catalyst composition according to  claim 1 , wherein the activator or co-catalyst is triisobutylaluminum. 
     
     
         26 . A catalyst composition according to  claim 1 , wherein the activator or co-catalyst is methylaluminoxane (MAO). 
     
     
         27 . A method for preparing a catalyst composition, the process comprising combining
 (a) a chromium compound;   (b) a ligand of the general structure
 (A) R 1 R 2 P—N(R 3 )—P(R 4 )—NR 5 R 6  or 
 (B) R 1 R 2 P—N(R 3 )—P(XR 7 )R 8  or R 1 R 2 P—N(R 3 )—P(XR 7 ) 2 , with X═O or S, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  are independently C 1 -C 10 -alkyl, C 6 -C 20 -aryl, C 3 -C 10 -cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; 
   (c) and an activator or co-catalyst,
 to form the catalyst. 
   
     
     
         28 . A method according to  claim 27 , wherein the activator or co-catalyst is triisopropylaluminum. 
     
     
         29 . A method according to  claim 27 , wherein the activator or co-catalyst is triisobutylaluminum. 
     
     
         30 . A method according to  claim 27 , wherein the activator or co-catalyst is methylaluminoxane (MAO).