Tackifiers and a process to obtain tackifiers

• US 5,652,308 A
• Filed: 07/21/1995
• Issued: 07/29/1997
• Est. Priority Date: 07/22/1994
• Status: Expired due to Term

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Sims, Charles Lewis, Robertson, Martha Hetzel, Montagna, Angelo Anthony, Farley, James McLeod, Merrill, Natalie Ann, Pannell, Richard Byron
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US08/505,421
• Time in Patent Office: 739 Days
• Field of Search: 526/126, 526/127, 526/134, 526/160, 526/281, 526/282, 526/283, 526/308, 526/931, 526/935, 525/88, 525/97, 525/210, 525/211, 525/216, 524/553, 524/554, 156/334
• US Class Current: 525/211
• 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 210/06 Propene
• CPC Class Codes: C08F 232/00 Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08F 2500/02 Low molecular weight, e.g. <100,000 Da.
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/06 Comonomer distribution, e.g. normal, reverse or narrow
• CPC Class Codes: C08F 2500/25 Cycloolefine
• 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 4/65925 two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C09J 11/08 Macromolecular additives
• CPC Class Codes: C09J 201/00 Adhesives based on unspecified macromolecular compounds
• CPC Class Codes: Y10S 526/931 Pressure sensitive adhesive
• CPC Class Codes: Y10S 526/935 Hot melt adhesive

Abstract

Novel tackifier resins having a M_n of 5,000 or less and a T_g of 0° C. or above are produced by combining a metallocene catalyst with an alpha-olefin and a cyclic monomer. New adhesives are produced by blending the novel tackifier with a base polymer.

Claims

1. A method for producing a tackifier resin, said method comprising copolymerizing at least one alpha-olefin and at least one cyclic olefin in the presence of a metallocene catalyst system under conditions suitable for the production of a copolymer having a M_n of 5000 or below and a T_g of 0°

C. or above.

2. The method of claim 1 wherein the conditions are suitable for production of a copolymer having a M_n in the range of from 200 to 2000.

3. The method of claim 1 wherein the conditions are suitable for production of a copolymer having a T_g of greater than 30°

C.

4. The method of claim 1 wherein the conditions are suitable for production of a copolymer containing about 20 to about 95 mole % of the cyclic olefin.

5. The method of claim 1 wherein the conditions are suitable for production of a copolymer having a M_w /M_n of 3 or less.

6. The method of claim 1 wherein the metallocene catalyst system comprises a metallocene transition metal compound and an activator.

7. The method of claim 2 wherein the metallocene catalyst system comprises a cyclopentadienyl transition metal compound selected from the group consisting of:

dimethylsilanyl bis(methylcyclopentadienyl)zirconium dichloride;

dimethylsilanyl bis(cyclopentadienyl)zirconium dichloride;

bis(methylcyclopentadienyl)zirconium dichloride;

bis(cyclopentadienyl)zirconium dichloride;

dimethylsilanyl bis(tetrahydroindenyl)zirconium dichloride;

rac-dimethylsilyl-bis(tetrahydroindenyl)zirconium dimethyl;

dimethylsilanyl bis(methylcyclopentadienyl)zirconium dimethyl;

dimethylsilanyl bis(cyclopentadienyl)zirconium dimethyl;

bis(methylcyclopentadienyl)zirconium dimethyl;

bis(cyclopentadienyl)zirconium dimethyl;

dimethylsilanyl[(tetramethylcyclopentadienyl)(dodecyl-amino)]titanium dichloride; and

cyclopentadienyl (t-butoxy)zirconium dichloride.

8. The method of claim 1 wherein the metallocene catalyst system comprises an activator of methylalumoxane or dimethylanilinium tetrakis(pentafluorophenyl) boron.

9. The method of claim 1 wherein the alpha-olefin contains from 3 to 8 carbon atoms.

10. The method of claim 1 wherein the cyclic olefin is selected from the olefins represented by the following formulae:

##STR1## wherein each R^a through R^s is independently hydrogen, halogen, hydrocarbyl, or halohydrocarbyl;

ac and dc are integers of 2 or more, and bc and cc are integers of 0 or more.

11. The method of claim 1 wherein the cyclic olefin is a trimer or a dimer of a cyclic olefin.

12. The method of claim 1 wherein the alpha-olefin is propylene and the cyclic olefin is dicyclopentadiene, 5-ethylidene-2-norbornene, or norbornene.

13. The method of claim 1 further comprising the step of hydrogenating the tackifier resin.

14. A tackifier resin consisting essentially of at least one alpha-olefin and from about 20 to about 95 mole % of at least one cyclic olefin, said alpha-olefin and cyclic olefin copolymerized in the presence of a metallocene catalyst system under conditions suitable for the production of a copolymer having a T_g of 0°

C. or more and a M_n of 5000 or less.

15. The tackifier resin of claim 14 wherein the tackifier produced has an M_n in the range of from 200 to 2000.

16. The tackifier resin of claim 14 wherein the tackifier produced has a T_g of greater than 30°

C.

17. The tackifier resin of claim 14 wherein the tackifier produced has a T_g of 35°

C. or more.

18. The tackifier resin of claim 14 wherein the tackifier resin produced has a M_w /M_n of 3 or less.

19. The tackifier resin of claim 14 wherein the alpha-olefin contains from 3 to 8 carbon atoms.

20. The tackifier resin of claim 14 wherein the cyclic olefin is selected from the olefins represented by the following formulae:

##STR2## wherein each R^a through R^s is independently hydrogen, halogen, hydrocarbyl, or halohydrocarbyl;

ac and dc are integers of 2 or more, and bc and cc are integers of 0 or more.

21. The tackifier resin of claim 14 wherein the cyclic olefin is a trimer or a dimer of a cyclic olefin.

22. The tackifier resin of claim 14 wherein the alpha-olefin is propylene and the cyclic olefin is dicyclopentadiene, 5-ethylidene-2-norbornene, or norbornene.

23. The tackifier resin of claim 14, said tackifier resin having been hydrogenated.

24. The tackifier resin of claim 14 further having a Saybolt color of 15 or more.

25. An adhesive comprising a base polymer and a tackifier resin said tackifier resin consisting essentially of at least one alpha-olefin and from about 20 to about 95 mole % of at least one cyclic olefin, said alpha-olefin and cyclic olefin copolymerized in the presence of a metallocene catalyst system under conditions suitable for the production of a copolymer having a T_g of 0°

C. or more and a M_n of 5000 or less.

26. The adhesive of claim 25, wherein the base polymer is selected from the group consisting of:

polyethylene, ethylene alpha-olefin copolymers, polypropylene, ethylene-vinyl acetate, polyvinyl chloride, natural rubber, nitrile rubber, polychloroprene rubber, polyisoprene, polyisobutylene and its copolymers, ethylene-propylene rubber, ethylene-propylene-diene termonomer rubber, butyl rubber, polystyrene, polybutadiene and styrenic block copolymers.

27. The adhesive of claim 25 wherein the alpha-olefin contains from 3 to 8 carbon atoms and the cyclic olefin is selected from the olefins represented by the following formulae:

##STR3## wherein each R^a through R^s is independently hydrogen, halogen, hydrocarbyl, or halohydrocarbyl;

ac and dc are integers of 2 or more, and bc and cc are integers of 0 or more.

28. The adhesive of claim 25 further comprising additive, said additive comprising at least one member selected from the group consisting of an oil, a plasticizer, a wax, and a stabilizer.

29. The adhesive of claim 25 wherein the alpha-olefin is propylene and the cyclic olefin is dicyclopentadiene, norbornene, or 5-ethylidene-2-norbornene.

30. An article of manufacture comprising the adhesive of claim 25.