Multiple catalyst system for olefin polymerization and polymers produced therefrom

• US 8,071,687 B2
• Filed: 08/02/2007
• Issued: 12/06/2011
• 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: Jiang, Peijun, Dekmezian, Armenag Hagop, Canich, Jo Ann Marie, Sims, Charles Lewis, Abhari, Ramin, Garcia-Franco, Cesar Alberto, Johnsrud, David Raymond
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US11/888,870
• Publication Number:
  US 20090069475A1
• Time in Patent Office: 1,587 Days
• Field of Search: 525/240, 525/247, 524/570, 524/582, 526/248, 526/351
• US Class Current: 525/240
• 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 an adhesive comprising a polymer composition comprising at least 50 mol % of one or more C3 to C40 olefins where the polymer composition has (a) a Dot T-Peel of 1 Newton or more on Kraft paper; (b) an Mw of at least 7000 to 80,000; (c) a branching index (g′) of from 0.4 to 0.90 measured at the Mz of the polymer composition; (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 composition, where the heptane insoluble fraction has branching index g′ of 0.9 or less as measured at the Mz of the polymer composition.

Claims

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

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

b) an Mw of at least 7000 to 80,000;

c) a branching index (g′

) of from 0.4 to 0.90 measured at the Mz of the polymer composition;

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 composition, where the heptane insoluble fraction has branching index g′

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

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

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

b) a branching index of 0.4 to 0.8;

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 wherein the polymer composition 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 composition comprises propylene and less than 15 mole % of ethylene.

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

sec or less at 190°

C.

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

sec or less at 190°

C.

7. The adhesive of claim 1 wherein the polymer composition has a melt viscosity of between 250 and 6000 mPa·

sec at 190°

C.

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

sec at 190°

C.

9. The adhesive of claim 4 wherein the polymer composition 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, wherein the adhesive comprises less than 5% hydrocarbon resin.

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

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

22. The adhesive of claim 1 wherein the polymer composition 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 composition; and

an Mw of 100,000 or less.

23. The adhesive of claim 1 wherein the polymer composition 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 composition 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 composition 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; and

e) a peak melting point between 60 and 190°

C., and

f) a viscosity of 8000 mPa·

sec or less at 190°

C.; and

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

h) a Shore A Hardness (as measured by ASTM

     2240) of 70 or less; and

i) A Shear Adhesion Fail Temperature 40 to 150°

C.; and

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

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

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

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

29. The adhesive of claim 1 wherein the polymer composition has been contacted with an unsaturated acid or anhydride.

30. The adhesive of claim 29 wherein the unsaturated acid or anhydride is an unsaturated organic compound containing at least one double bond and at least one carbonyl group.

31. The adhesive of claim 29 wherein the unsaturated acid or anhydride is selected from the group consisting of carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic.

32. The adhesive of claim 30 wherein the organic compound contains an ethylenic unsaturation conjugated with a carbonyl group (—

C═

O).

33. The adhesive of claim 29 wherein the unsaturated acid or anhydride is selected from the group consisting of carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic.

34. The adhesive of claim 29 wherein the unsaturated acid or anhydride is selected from the group consisting of maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha.methyl crotonic, and cinnamic acids as well as their anhydrides, esters and salt derivatives.

35. The adhesive of claim 29 wherein the unsaturated acid or anhydride is maleic anhydride.

38. A pellet comprising the adhesive of claim 29.

39. The adhesive of claim 29 further comprising a functionalized wax.

40. The adhesive of claim 29 further comprising a wax.

41. The adhesive of claim 29 adhesive further comprising a hydrocarbon resin.

43. The adhesive of claim 34 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.

47. The adhesive of claim 29 wherein the polymer composition is a copolymer of propylene and hexene.

48. The adhesive of claim 29 wherein the polymer composition 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 composition 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; and

e) a peak melting point between 60 and 190°

C.; and

f) a viscosity of 8000 mPa·

sec or less at 190°

C.; and

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

h) a Shore A Hardness (as measured by ASTM

     2240) of 70 or less; and

i) A Shear Adhesion Fail Temperature 40 to 150°

C.; and

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

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

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

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

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

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

b) an Mw of at least 7000 to 80,000;

c) a branching index (g′

) of from 0.4 to 0.90 measured at the Mz of the polymer composition;

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 composition, where the heptane insoluble fraction has branching index g′

of 0.9 or less as measured at the Mz of the polymer composition, where the polymer composition is functionalized.

28. The adhesive of claim 27 wherein polymer composition is functionalized with functional groups of maleic acid or maleic anhydride.

36. A pellet comprising the adhesive of claim 27.

37. A pellet comprising the adhesive of claim 28.

42. The adhesive of claim 27 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.

44. The adhesive of claim 27 wherein the polymer composition 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 composition; and

an Mw of 100,000 or less.

45. The adhesive of claim 27 wherein the polymer composition is a copolymer of propylene and hexene.

46. The adhesive of claim 28 wherein the polymer composition is a copolymer of propylene and hexene.