Catalyst for the polymerisation of olefins, process for its production and use

Patent metadata

Field	Value
Publication number	US-9701770-B2
Application number	US-201314391827-A
Country	US
Kind code	B2
Filing date	Apr 16, 2013
Priority date	Apr 19, 2012
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

Silica supported catalyst composition useful in olefin polymerization, having a SiO 2 content not more than 70 weight %, a transition metal (M) content between 2.5 and 9.1 weight %, a magnesium content between 0.5 and 3.3 weight %, an aluminium content between 0.3 and 5 weight % and a chlorine content between 5 and 30 weight %. The silica support has, prior to addition of catalytically active ingredients, a residual surface hydroxyl content between 0.6 and 2 mmole/g of silica, and the molar ratio of transition metal (M) to magnesium is between 0.3 and 2.5.

First claim

The invention claimed is:

1. Silica supported catalyst composition which is useful in olefin polymerization, said composition comprising:
a SiO 2 content not more than 70 weight %;
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %;
and wherein
the said silica support has, prior to addition of catalytically active ingredients, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica, and
the molar ratio of transition metal (M) to magnesium is comprised between 0.3 and 2.5.

2. Catalyst composition which is useful in olefin polymerization comprising:
a SiO 2 content not more than 70 weight %,
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %;
wherein said composition is obtained by a preparation process comprising
in a first stage, the formation of a Mg-M liquid complex (M is a transition metal) in the absence of halogen containing compound by reacting at least one organic oxygen-comprising compound of magnesium with at least one organic oxygen-comprising compound of a transition metal,
in a second stage, the impregnation of a silica support by means of the said Mg-M liquid complex, and
in a subsequent stage, the precipitation of the said Mg-M liquid complex on the silica by means of an halogenated organoaluminium compound,
wherein
during the first stage reaction, the molar amount of the transition metal M added per mole of magnesium is comprised between 0.06 and 4, and
the said silica support has, prior to the Mg-M liquid complex impregnation, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica.

3. Catalyst composition according to claim 2 wherein the silicon dioxide content of the catalyst composition is more than 40 weight %.

4. Process for polymerizing olefins comprising contacting olefins with the catalyst composition according to claim 2 together with a co-catalyst in a continuous slurry phase or a continuous gas phase process for the polymerisation of olefins wherein the co-catalyst is chosen from organometallic compounds of a metal from Groups 1, 2, 12, 13, and 14.

5. Catalyst composition which is useful in olefin polymerization characterised by
a SiO 2 content not more than 70 weight %,
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %;
wherein said composition is obtained by a preparation process comprising
in a first stage, the formation of a Mg-M liquid complex (M is a transition metal) by reacting at least one organic oxygen-comprising compound of magnesium with at least one organic oxygen-comprising compound of a transition metal, wherein the organic oxygen-comprising compounds of magnesium only comprise magnesium-oxygen-organic radical bonds per magnesium atom, to the exclusion of any other bond and wherein the organic oxygen-comprising compounds of a transition metal only comprise transition metal-oxygen-organic radical bonds per transition metal atom, to the exclusion of any other bond,
in a second stage, the impregnation of a silica support by means of the said Mg-M liquid complex, and
in a subsequent stage, the precipitation of the said Mg-M liquid complex on the silica by means of an halogenated organoaluminium compound,
wherein
during the first stage reaction, the molar amount of the transition metal M added per mole of magnesium is comprised between 0.06 and 4, and
the said silica support has, prior to the Mg-M liquid complex impregnation, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica.

6. Catalyst composition according to claim 5 wherein the silicon dioxide content of the catalyst composition is more than 40 weight %.

7. Process for polymerizing olefins comprising contacting olefins with the catalyst composition according to claim 5 together with a co-catalyst in a continuous slurry phase or a continuous gas phase process for the polymerisation of olefins wherein the co-catalyst is chosen from organometallic compounds of a metal from Groups 1, 2, 12, 13, and 14.

8. Gas phase process for the (co-)polymerisation of olefins, comprising contacting olefins with a silica supported polymerisation catalyst having the following characteristics:
a SiO 2 content not more than 70 weight,
a transition metal (M) content comprised between 3 and 9.1 weight %;
a magnesium content comprised between 0.5 and 3.3 weight %;
an aluminium content comprised between 0.3 and 5 weight % and
a chlorine content comprised between 5 and 30 weight %
wherein
the said silica support has, prior to addition of catalytically active ingredients, a residual surface hydroxyl content comprised between 0.6 and 2 mmole/g of silica, and
the molar ratio of transition metal (M) to magnesium is comprised between 0.3 and 2.5, and
wherein the productivity is greater than 10000 g of polymer per g of catalyst, space time yield is greater than 100 kg/m 3 /h and the partial pressure of hydrocarbon condensable under reaction conditions is greater than 2 bar.

9. Catalyst composition according to claim 3 wherein the silicon dioxide content of the catalyst composition is more than 50 weight %.

10. Catalyst composition according to claim 6 wherein the silicon dioxide content of the catalyst composition is more than 50 weight %.

11. The process according to claim 4 wherein the co-catalyst is chosen from one or more trialkylaluminiums.

12. The process according to claim 7 wherein the co-catalyst is chosen from one or more trialkylaluminiums.

13. The catalyst composition according to claim 2 wherein the complex impregnation (second stage) is performed on a silica which has been subjected to a thermal treatment step at a temperature of at least 200° C. for up to 24 hours.

14. The catalyst composition according to claim 13 wherein the thermal treatment step is at a temperature 250° C. to 350° C. for 4 to 10 hours.

15. The catalyst composition according to claim 2 wherein the organic oxygen-comprising compound of magnesium is a magnesium dialkoxide.

16. The catalyst composition according to claim 2 wherein the organic oxygen-comprising compound of a transition metal is a titanium tetraalkoxide, a zirconium tetraalkoxide, or a mixture thereof.

17. The catalyst composition according to claim 2 wherein during the impregnation stage, the amount of liquid complex impregnated in the inorganic support is selected such that the impregnated silica support comprises
a magnesium content comprised between 1 mmole and 2 mmole of magnesium per g of silica support, and
a titanium content comprised between 2 mmole and 4 mmole of titanium per g of silica support.

18. The catalyst composition according to claim 2 wherein the halogenated organoaluminium compound used in the precipitation stage is chosen from organoaluminium compounds corresponding to the general formula A1 RnX3-n, in which R is a hydrocarbon-comprising radical comprising up to 20 carbon atoms, X is a halogen and n is less than or equal to 2.

19. The catalyst composition according to claim 5

Assignees

• Ineos Europe Ag

Inventors

• Bini Fabien
• Fiasse Paul
• Girardot Luc
• Koch Benoit

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F210/08

  Butenes · CPC title

• C08F4/025

  Metal oxides · CPC title

• C08F4/6555

  and magnesium or compounds thereof · CPC title