Multiple catalyst system for olefin polymerization and polymers produced therefrom

• US 20090069475A1
• Filed: 08/02/2007
• Published: 03/12/2009
• Est. Priority Date: 10/15/2002
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Abhari, Ramin, Garcia-Franco, Cesar Alberto, Dekmezian, Armenag Hagop, Canich, Jo Ann Marie, Jiang, Peijun, Johnsrud, David Raymond, Sims, Charles Lewis
• Granted Patent: US 8,071,687 B2
• Time in Patent Office: Days
• US Class Current: 524/274
• 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 comprising one or more C3 to C40 olefins, optionally one or more diolefins, and less than 15 mole % of ethylene, where the polymer has:

• • a) a Dot T-Peel of 1 Newton or more; and
  • b) a branching index (g′) of 0.95 or less measured at the Mz of the polymer;
  • c) an Mw of 100,000 or less.

This invention also relates a polymer comprising one or more C3 to C40 olefins where the polymer has:

• • a) a Dot T-Peel of 1 Newton or more on Kraft paper;
  • b) a branching index (g′) of 0.95 or less measured at the Mz of the polymer;
  • c) a Mw of 10,000 to 100,000; and
  • d) a heat of fusion of 1 to 70 J/g.

This invention also relates a polymer comprising one or more C3 to C40 olefins where the polymer has:

• • a) a Dot T-Peel of 1 Newton or more on Kraft paper;
  • b) a branching index (g′) of 0.98 or less measured at the Mz of the polymer;
  • c) a Mw of 10,000 to 60,000;
  • d) a heat of fusion of 1 to 50 J/g.

This invention also relates to a homopolypropylene or a copolymer of propylene and up to 5 mole % ethylene having:

• • a) an isotactic run length of 1 to 30 (isotactic run length “IRL” is defined to be the percent of mmmm pentad divided by 0.5×percent of mmmr pentad) as determined by Carbon 13 NMR, preferably 3 to 25, more preferably 4 to 20,
  • b) a percent of r dyad of greater than 20%, preferably from 20 to 70% as determined by Carbon 13 NMR, and
  • c) a heat of fusion of 70 J/g or less, preferably 60 J/g or less, more preferably between 1 and 55 J/g, more preferably between 4 and 50 J/g.

This invention further relates to a process to produce an olefin polymer comprising:

• • 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 at 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, at the selected polymerization conditions in a reaction zone;
  • 4) obtaining the polymer.

This invention further relates to a continuous process to produce a branched olefin polymer comprising:

• • 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, and, optionally one or more diolefins;
  • 4) at a temperature of greater than 100° C.;
  • 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 100 kilograms of polymer per gram of the catalyst components; and wherein at least 20% of the olefins are converted to polymer.

Claims

1. An adhesive comprising a polymer comprising at least 50 mol % of one or more C3 to C40 olefins where the polymer has:

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

d) a heat of fusion of 1 to 70 J/g; and

e) a heptane insoluble fraction of 70 weight % or less, based upon the weight of the polymer, where the heptane insoluble fraction has branching index g′

of 0.9 or less as measured at the Mz of the polymer.

2. The adhesive of claim 1 wherein the polymer has:

a) a Dot T-Peel of 2 Newton or more on Kraft paper;

b) a branching index (g′

) of from 0.4 to 0.98 measured at the Mz of the polymer;

c) a Mw of 10,000 to 60,000; and

d) a heat of fusion of 1 to 50 J/g.

3. The adhesive 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 50 J/g.

4. The adhesive of claim 1 wherein the polymer comprises propylene and less than 15 mole % of ethylene.

5. The adhesive of claim 1 wherein the polymer has a melt viscosity of 7000 mPa·

sec or less at 190°

C.

6. The adhesive of claim 1 wherein the polymer has a melt viscosity of 5000 mPa·

sec or less at 190°

C.

7. The adhesive of claim 1 wherein the polymer has a melt viscosity of

between 250 and 6000 mPa·

sec at 190°

C.

8. The adhesive of claim 1 wherein the polymer has a melt viscosity of between 500 and 3000 mPa·

sec at 190°

C.

9. The adhesive of claim 4 wherein the polymer has a Tg of 0°

C. or less.

10. A pellet comprising the adhesive of claim 1.

11. The adhesive of claim 1 further comprising a functionalized wax.

12. The adhesive of claim 1 further comprising a wax.

13. The adhesive of claim 1 adhesive further comprising a hydrocarbon resin.

14. The adhesive of claim 1 further comprising one or more hydrocarbon resins selected from the group consisting of aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene-phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.

15. The adhesive of claim 1 further comprising hydrocarbon resin present at 1 weight % to about 80 weight %.

16. The adhesive of claim 1 further comprising hydrocarbon resin present at 2 weight % to about 40 weight %.

17. The adhesive of claim 1 further comprising hydrocarbon resin present at 3 weight % to 30 weight %.

18. The adhesive of claim 1 further comprising hydrocarbon resin present at 1 weight % to about 80 weight % selected from the group consisting of:

C5/C6 terpene resins, styrene terpenes, alpha-methyl styrene terpene resins, C9 terpene resins, aromatic modified C5/C6, aromatic modified cyclic resins, aromatic modified dicyclopentadiene based resins, resins obtained from the cationic polymerization of compositions containing one or more of the following monomers;

C5 diolefins;

C5 olefins;

C6 olefins, C9 vinylaromatics;

cyclics; and

or terpenes;

resins obtained by the thermal polymerization of dicyclopentadiene, and/or the thermal polymerization of dimers or oligomers of cyclopentadiene and/or methylcyclopentadiene, optionally with vinylaromatics.

19. The adhesive of claim 1, where the adhesive comprises less than 5% hydrocarbon resin.

20. The adhesive of claim 1, where the adhesive comprises less than 3% hydrocarbon resin.

21. The adhesive of claim 1, where the adhesive comprises less than 1% hydrocarbon resin.

22. The adhesive of claim 1 wherein the polymer is a homopolymer of propylene and or a copolymer of propylene and one or more of butene, pentene, hexene, octene, nonene, and decene, wherein the copolymer comprises less than 50 mole % ethylene, and wherein the homopolymer or copolymer has a Dot T-Peel of 3 or more Newtons;

a viscosity of 8000 mPa·

sec or less at 190°

C.;

a branching index (g′

) of from 0.4 to 0.85 measured at the Mz of the polymer; and

an Mw of 100,000 or less.

23. The adhesive of claim 1 wherein the polymer is a copolymer of propylene and hexene.

24. The adhesive of claim 22 wherein the homopolymer or copolymer has a SAFT of 60 to 130°

C.

25. The adhesive of claim 22 wherein the homopolymer or copolymer has a set time of 2 seconds or less.

26. The adhesive of claim 1 wherein the polymer is a polymer of propylene, having from 0 to 5 mol % ethylene and from 0 to 40 mol % of a C5 to C12 olefin, and 0 to 10 mol % of a diene where the polymer has:

a) a Dot T-Peel of 1 Newton or more; and

b) an Mw of 100,000 or less; and

c) a Mz/Mn of 2-200; and

d) an Mw of 100,000 or less and a branching index of from 0.4 to 0.5, or an Mw of 75,000 or less and a branching index of from 0.4 to 0.6, or an Mw of 50,000 or less and a branching index of from 0.4 to 0.7, or an Mw of 30,000 or less and a branching index of from 0.4 to 0.98; and

d) a peak melting point between 60 and 190°

C., and

e) a viscosity of 8000 mPa·

sec or less at 190°

C.; and

f) a heat of fusion of 70 J/g or less; and

g) a Shore A Hardness (as measured by ASTM

     2240) of 70 or less; and

h) A Shear Adhesion Fail Temperature 40 to 150°

C.; and

i) a set time of 5 seconds or less; and

j) an Mw/Mn of 3 to 75; and

k) an Mz of 20,000 to 500,000; and

l) a melt index of 900 dg/min or less.

27. A continuous process to prepare an adhesive comprising:

1) combining monomer, solvent, catalyst and activator in a reactor system,

2) withdrawing polymer solution from the reactor system,

3) removing at least 10% solvent from the polymer solution,

4) quenching the reaction,

5) devolatilizing the polymer solution to form molten polymer,

6) combining the molten polymer and one or more additives in a static mixer,

7) removing the polymer combination from the static mixer, and

8) pelletizing or drumming the polymer combination.

51. The process of claim 27 wherein the polymer is pelletized.

28. A continuous process to make an adhesive comprisingselecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 20% 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 40% or more at the selected polymerization conditions;

3) contacting, in a solvent and in a reaction zone under the selected polymerization conditions, the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins, and, optionally one or more diolefins;

4) at a temperature of greater than 100°

C.;

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;

8) withdrawing polymer solution from the reaction zone;

9) removing at least 10% solvent from the polymer solution;

10) quenching the reaction;

11) devolatilizing the polymer solution to form molten polymer;

12) combining the molten polymer and one or more additives in a mixer;

13) removing the polymer combination from the mixer; and

14) pelletizing or drumming the polymer combination.

29. The process of claim 28 wherein:

a) the olefins comprise propylene and one or more of butene, pentene, hexene, heptene, octene;

nonene, decene, dodecene; and

b) the temperature is greater than 110°

C.; and

c) the residence time is 120 minutes or less; and

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

1 to 1;

10.

30. The process of claim 28 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, polybutadienes having an Mw less than 1000 g/mol, butadiene, pentadiene, hexadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, or combinations thereof.

31. The process of claim 28 wherein the olefin comprises propylene and one or more of butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methyl pentene-1, and 3,5,5-trimethyl-hexene-1.

33. The process of claim 28 wherein the additives comprise one or more hydrocarbon resins selected from the group consisting of aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.

34. The process of claim 28 wherein the polymer comprises at least 50 mol % of one or more C3 to C40 olefins and the polymer has:

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

d) a heat of fusion of 1 to 70 J/g; and

e) a heptane insoluble fraction of 70 weight % or less, based upon the weight of the polymer, where the heptane insoluble fraction has branching index g′

of 0.9 or less as measured at the Mz of the polymer.

35. The process of claim 34 wherein the polymer has:

a) a Dot T-Peel of 2 Newton or more on Kraft paper;

b) a branching index (g′

) of from 0.4 to 0.98 measured at the Mz of the polymer;

c) a Mw of 10,000 to 60,000; and

d) a heat of fusion of 1 to 50 J/g.

36. The process of claim 34 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 50 J/g.

37. The process of claim 34 wherein the polymer comprises propylene and less than 15 mole % of ethylene.

38. The process of claim 34 wherein the polymer has a melt viscosity of 7000 mPa·

sec or less at 190°

C.

39. The process of claim 34 wherein the polymer has a melt viscosity of 5000 mPa·

sec or less at 190°

C.

40. The process of claim 34 wherein the polymer has a melt viscosity of between 250 and 6000 mPa·

sec at 190°

C.

41. The process of claim 34 wherein the polymer has a melt viscosity of between 500 and 3000 mPa·

sec at 190°

C.

42. The process of claim 37 wherein the polymer has a Tg of 0°

C. or less.

43. The process of claim 37 wherein the polymer has a Tg of −

10°

C. or less.

44. The process of claim 34 wherein the polymer has an Mw of 10,000 to 75,000 and a branching index of from 0.4 to 0.6.

45. The process of claim 28 wherein the polymer is pelletized.

46. The process of claim 34 wherein the polymer is pelletized.

47. The process of claim 34 wherein the additives comprise hydrocarbon resin.

48. The process of claim 34 wherein the additives comprise one or more hydrocarbon resins selected from the group consisting of aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.

49. The process of claim 28 wherein the polymer is a copolymer of propylene and hexene.

50. The process of claim 48 wherein the polymer is a copolymer of propylene and hexene.

52. The process of claim 28 wherein the mixer is a static mixer.

32. The process of clam 28 wherein the additives comprise hydrocarbon resin.