Mutliple catalyst system for olefin polymerization and polymers produced therefrom

• US 7,294,681 B2
• Filed: 10/15/2003
• Issued: 11/13/2007
• Est. Priority Date: 10/15/2002
• Status: Expired due to Term

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Abhari, Ramin, Canich, Jo Ann Marie, Jiang, Peijun, Johnsrud, David Raymond, Sims, Charles Lewis, Garcia-Franco, Cesar Alberto, Dekmezian, Armenag Hagop
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US10/687,508
• Publication Number:
  US 20040138392A1
• Time in Patent Office: 1,490 Days
• Field of Search: 525/240, 525/245, 525/247, 526/113, 526/116, 526/114, 526/160, 526/165, 526/348.2, 526/336, 526/337, 526/943
• US Class Current: 526/348.2
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 236/20 unconjugated
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/05 Bimodal or multimodal molecular weight distribution
• CPC Class Codes: C08F 2500/09 Long chain branches
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/15 Isotactic
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 4/63904 in combination with another component of C08F4/62
• CPC Class Codes: C08F 4/65904 in combination with another component of C08F4/64
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• 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 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 57/02 Copolymers of mineral oil hydrocarbons
• CPC Class Codes: C09J 123/10 : Homopolymers or copolymers of propene
• CPC Class Codes: C09J 123/12 : Polypropene
• CPC Class Codes: C09J 2301/302 : the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• CPC Class Codes: C09J 2301/312 : parameters being the characterizing feature
• CPC Class Codes: C09J 2301/416 : use of irradiation
• CPC Class Codes: C09J 2401/006 : in the substrate
• CPC Class Codes: C09J 2421/00 : Presence of unspecified rubber
• CPC Class Codes: C09J 2423/006 : in the substrate
• CPC Class Codes: C09J 2423/046 : in the substrate
• CPC Class Codes: C09J 2423/106 : in the substrate
• CPC Class Codes: C09J 2427/006 : in the substrate
• CPC Class Codes: C09J 2433/00 : Presence of (meth)acrylic polymer
• CPC Class Codes: C09J 5/00 : Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• CPC Class Codes: C09J 7/20 : characterised by their carriers
• CPC Class Codes: Y10S 526/943 : Polymerization with metallocene catalysts

Abstract

This invention relates to a polymer of one or more C3 to C40 olefins, optionally one or more diolefins, and less than 15 mole % of ethylene, and polymerization processes for producing the same.

Claims

1. A branched olefin polymer prepared from a continuous process comprising the steps of:

1) selecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 5% or less under selected polymerization conditions;

2) selecting a second catalyst component capable of producing polymer having an Mw of 100,000 or less and a crystallinity of 20% or more at the selected polymerization conditions;

3) contacting the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins;

4) at a temperature of greater than 100°

C.; and

5) at a residence time of 120 minutes or less;

6) wherein the ratio of the first catalyst to the second catalyst is from 1;

1 to 50;

1;

7) wherein the activity of the catalyst components is at least 50 kilograms of polymer per gram of the catalyst compounds; and

wherein at least 80% of the olefins are converted to polymer,

wherein the polymer has the following properties;

a) a Dot T-Peel of 1 Newton or more on Kraft paper;

b) an Mw of 10,000 to 100,000;

c) a branching index (g′

) of 0.4-0.98 measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 60,000, or

 

a branching index (g′

) of 0.4-0.95 measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 100,000; and

d) amorphous polymer segments and semi-crystalline polymer segments.

2. The polymer product of claim 1 where the polymer is a homopolypropylene or a copolymer of propylene and up to 5 mole % ethylene having:

a) an isotactic run length of 1 to 30,

b) a percent of r dyad of greater than 20%, and

c) a heat of fusion of between 1 and 70 J/g.

3. The polymer product of claim 1 wherein the olefin comprises propylene.

4. The polymer product of claim 1 wherein the first catalyst component comprises a non-stereospecific metallocene catalyst compound.

5. The polymer product of claim 1 wherein the first catalyst component comprises a stereospecific metallocene catalyst compound.

6. The polymer product of claim 1 wherein the second catalyst component comprises a stereospecific metallocene catalyst compound.

7. The polymer product of claim 1 wherein the second catalyst component comprises one or more of the racemic versions of:

dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dimethyl, dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dichloride, dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dimethyl, dimethylsilylbis(indenyl)hafnium dimethyl, dimethylsilylbis(indenyl)hafnium dichloride, dimethylsilylbis(indenyl)ziconium dimethyl, dimethylsilylbis(indenyl)zirconium dichloride,

the racemic isomers of;

dimethylsilanediylbis(2-methylindenyl)metal dichloride;

dimethylsilanediylbis(indenyl)metal dichloride;

dimethylsilanediylbis(indenyl)metal dimethyl;

dimethylsilanediylbis(tetrahydroindenyl)metal dichloride;

dimethylsilanediylbis(tetrahydroindenyl)metal dimethyl;

dimethylsilanediylbis(indenyl)metal diethyl; and

dibenzylsilanediylbis(indenyl)metal dimethyl;

wherein the metal is chosen from Zr, Hf, or Ti.

8. The polymer product of claim 1 wherein the activator comprises an alumoxane.

9. The polymer product of claim 1 wherein the activator comprises an ionizing compound.

10. The polymer product of claim 1 wherein the activator comprises a non-coordinating anion.

11. The polymer product of claim 1 wherein the first catalyst component is capable of polymerizing macromonomers having reactive termini;

and the second component is capable of producing macromonomers having reactive tennini.

12. The polymer product of claim 1 wherein the monomers comprise propylene and butene.

13. The polymer product of claim 1 further comprising contacting the catalyst components in the presence of one or more activators with a diolefin.

14. The polymer product of claim 13 wherein the diolefin comprises one or more C4 to C40 diolefins.

15. The polymer product of claim 13 wherein the diolefin is selected from the group consisting of 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, polybutadiones having an Mw less than 1000 g/mol, and combinations thereof.

16. The polymer product of claim 1 further comprising contacting the catalyst components in the presence of one or more activators with one or more dienes selected from the group consisting of 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, polybutadienes having an Mw less than 1000 g/mol, and combinations thereof.

17. The polymer product of claim 1 wherein the reaction zone is a gas phase reactor.

18. The polymer product of claim 1 wherein the reaction zone is a solution phase reactor.

19. The polymer product of claim 1 wherein the reaction zone is a slurry phase reactor.

20. The polymer product of claim 1 wherein the olefin comprises propylene and the reaction zone is a solution phase reactor.