Propylene copolymers for adhesive applications

• US 20100029851A9
• Filed: 09/29/2006
• Published: 02/04/2010
• 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: Henning, David Aaron, Brant, Patrick, Sims, Charles L., Jiang, Peijun, Johnsrud, David R.
• Granted Patent: US 8,618,219 B2
• Time in Patent Office: Days
• US Class Current: 525/191
• CPC Class Codes: C08F 10/06 Propene
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 2500/09 Long chain branches
• CPC Class Codes: C08F 2500/11 Melt tension or melt strength
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 2500/21 Rubbery or elastomeric properties
• CPC Class Codes: C08L 23/142 at least partially crystalline copolymers of propene with other olefins
• CPC Class Codes: C08L 2666/06 Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
• CPC Class Codes: C09J 123/142 at least partially crystalline copolymers of propene with other olefins

Abstract

Disclosed herein is an in-reactor produced multi-component copolymer comprises a semi-crystalline component having a crystallinity of 20% or more, and an amorphous component having a crystallinity of 5% or less. The copolymer comprises at least 80 wt % of units derived from propylene and from about 1 to about 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin. The copolymer has a viscosity at 190° C. of at least 530 mPa sec and a heat of fusion between about 10 and about 70 J/g. An adhesive containing the copolymer exhibits a good balance of adhesive properties and mechanical strength.

Claims

1. An in-reactor produced multi-component copolymer comprising a semi-crystalline component having a crystallinity of 20% or more, and an amorphous component having a crystallinity of 5% or less, wherein the copolymer comprises at least 80 wt % of units derived from propylene and from about 1 to about 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin, and wherein the copolymer has a viscosity at 190°

C. of at least 530 mPa sec and a heat of fusion between about 10 and about 70 J/g.

2. The copolymer of claim 1 further having a viscosity at 190°

C. of between 600 and 25,000 mPa sec.

3. The copolymer of claim 1 further having a heat of fusion between about 10 and about 60 J/g.

4. The copolymer of claim 1 further having a heat of fusion between about 20 and about 50 J/g.

5. The copolymer of claim 1 wherein the ratio of the weight averaged molecular weight of the copolymer to the number averaged molecular weight of the copolymer is at least 4.

6. The copolymer of claim 1 wherein the ratio of the weight averaged molecular weight of the copolymer to the number averaged molecular weight of the copolymer is between about 4 and about 9.

7. The copolymer of claim 1 wherein the weight ratio of semi-crystalline component to the amorphous component is from about 90:

10 to about 30;

70.

8. The copolymer of claim 1 and further comprising a polypropylene homopolymer component.

9. The copolymer of claim 1 wherein the copolymer comprises about 1 wt % to about 15 wt % of units derived from said at least one C₆ to C₁₂ alpha-olefin.

10. The copolymer of claim 1 wherein the copolymer comprises about 2 wt % to about 12 wt % of units derived from said at least one C₆ to C₁₂ alpha-olefin.

11. The copolymer of claim 1 wherein the copolymer comprises about 3 wt % to about 10 wt % of units derived from said at least one C₆ to C₁₂ alpha-olefin.

12. The copolymer of claim 1 wherein said at least one alpha-olefin has 6 to 10 carbon atoms.

13. The copolymer of claim 1 wherein said at least one alpha-olefin has 6 to 8 carbon atoms.

14. The copolymer of claim 1 wherein said at least one alpha-olefin comprises hexene-1.

15. A process for producing a multi-component copolymer comprising at least 80 wt % of units derived from propylene and up to 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin, the process comprising:

(a) polymerizing propylene and one or more C₆ to C₁₂ alpha-olefins in a first reaction zone in the presence of a first catalyst system to produce a first polymer product, wherein the first catalyst system comprises a first polymerization catalyst capable of producing a semi-crystalline poly-alpha-olefin having a crystallinity of 20% or more, and a second polymerization catalyst capable of producing an amorphous poly-alpha-olefin having a crystallinity of 5% or less; and

(b) contacting the first polymer product under polymerization conditions with a second catalyst system in a second reaction zone separate from the first reaction zone.

16. The process of claim 15 wherein the second catalyst system is the same as the first catalyst system.

17. The process of claim 15 wherein additional propylene is supplied to said second reaction zone.

18. The process of claim 17 wherein the amount of propylene supplied to the first reaction zone is between about 30% and about 90% of the total propylene supplied to the first and second reaction zones.

19. The process of claim 17 wherein the molar ratio of propylene to said one or more C₆ to C₁₂ alpha-olefins in said first reaction zone is different from that in said second reaction zone.

20. The process of claim 15 wherein said at least one alpha-olefin has 6 to 10 carbon atoms.

21. The process of claim 15 wherein said at least one alpha-olefin has 6 to 8 carbon atoms.

22. The process of claim 15 wherein said at least one alpha-olefin comprises hexene-1.

23. A process for preparing a copolymer comprising at least 80 wt % of units derived from propylene and up to 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin, the process comprising:

(a) polymerizing propylene and one or more C₆ to C₁₂ alpha-olefins in a first reaction zone in the presence of a first catalyst system capable of producing a semi-crystalline copolymer having a crystallinity of 20% or more; and

(b) contacting the semi-crystalline copolymer product with propylene in a second reaction zone separate from the first reaction zone and in the presence of a second catalyst system to produce said copolymer, the second catalyst system comprising a first polymerization catalyst capable of producing a crystalline poly-alpha-olefin having a crystallinity of 20% or more, and a second polymerization catalyst capable of producing an amorphous poly-alpha-olefin having a crystallinity of 5% or less.

24. The process of claim 23 wherein said at least one alpha-olefin has 6 to 10 carbon atoms.

25. The process of claim 23 wherein said at least one alpha-olefin has 6 to 8 carbon atoms.

26. The process of claim 23 wherein said at least one alpha-olefin comprises hexene-1.

27. The process of claim 23 wherein the molar ratio of propylene to said one or more C₆ to C₁₂ alpha-olefins in said second reaction zone is different from that in said first reaction zone.

28. A process for preparing a copolymer comprising at least 80 wt % of units derived from propylene and up to 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin, the process comprising:

(a) polymerizing propylene in a first reaction zone in the presence of a first catalyst system to produce a first polymer product; and

(b) contacting the first polymer product with propylene and one or more C₆ to C₁₂ alpha-olefins in a second reaction zone separate from the first reaction zone and in the presence of a second catalyst system to produce said copolymer, the second catalyst system comprising a first polymerization catalyst capable of producing a crystalline poly-alpha-olefin having a crystallinity of 20% or more, and a second polymerization catalyst capable of producing an amorphous poly-alpha-olefin having a crystallinity of 5% or less.

29. The process of claim 28 wherein the first catalyst system is the same as the second catalyst system.

30. The process of claim 28 wherein the molar ratio of propylene to said one or more C₆ to C₁₂ alpha-olefins in said second reaction zone is different from that in said first reaction zone.

31. The process of claim 28 wherein said at least one alpha-olefin has 6 to 10 carbon atoms.

32. The process of claim 28 wherein said at least one alpha-olefin has 6 to 8 carbon atoms.

33. The process of claim 28 wherein said at least one alpha-olefin comprises hexene-1.

34. An adhesive composition comprising an in-reactor produced multi-component copolymer comprising a semi-crystalline component having a crystallinity of 20% or more, and an amorphous component having a crystallinity of 5% or less, wherein the copolymer comprises at least 80 wt % of units derived from propylene and from about 1 to about 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin, wherein the copolymer has a viscosity at 190°

C. of at least 530 mPa sec and a heat of fusion between about 10 and about 70 J/g, and wherein the adhesive composition has the following properties;

(a) at least 50% fiber tear at −

18°

C. used Inland paper board as a substrate;

(b) at least 50% fiber tear at 20°

C. used Inland paper board as a substrate;

(c) a viscosity of less than 1,200 mPa sec at 190°

C.;

(d) a set time of less than 3 seconds; and

(g) a toughness of 3.4 megajoule/m or more.

35. An adhesive composition comprising an in-reactor produced multi-component copolymer comprising a semi-crystalline component having a crystallinity of 20% or more, and an amorphous component having a crystallinity of 5% or less, wherein the copolymer comprises at least 80 wt % of units derived from propylene and from about 1 to about 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin, wherein the copolymer has a viscosity at 190°

C. of at least 530 mPa sec and a heat of fusion between about 10 and about 70 J/g, and wherein the adhesive composition has the following properties;

(a) a viscosity of less than 25,000 mPa sec at 190°

C.;

(b) a Dot T-Peel adhesion of 10 Newton or more for adhesion between a fiber board and a fabric substrate;

(c) a set time of 10 seconds or less;

(d) an open time of 3 seconds or longer;

(i) a toughness of 7 megajoule/m³ or more, preferably 14 megajoule/m³ or more; and

(j) an elongation of 400% or more.

36. An adhesive, composition comprising an in-reactor produced multi-component copolymer comprising a semi-crystalline component having a crystallinity of 20% or more, and an amorphous component having a crystallinity of 5% or less, wherein the copolymer comprises at least 80 wt % of units derived from propylene and from about 1 to about 20 wt % of units derived from at least one C₆ to C₁₂ alpha-olefin, wherein the copolymer has a viscosity at 190°

C. of at least 530 mPa sec and a heat of fusion between about 10 and about 70 J/g, and wherein the adhesive composition has the following properties;

(a) a viscosity of 25,000 mPa sec. or less sec at 190°

C.;

(b) a Dot T-Peel adhesion of 10 Newton or more for adhesion between two polyethylene terephthalate films at room temperature (25°

C.);

(c) a Dot T-Peel adhesion of 10 Newton or more for adhesion between two polyethylene terephthalate films at 40°

C.;

(d) a toughness of 7 megajoule/m³ or more, preferably 14 megajoule/m³ or more; and

(g) an elongation of 400% or more.