Polymerization Process and Adhesives Therefrom

• US 20090239999A1
• Filed: 06/09/2009
• Published: 09/24/2009
• Est. Priority Date: 01/18/2008
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Canich, Jo Ann M., Jiang, Peijun
• Granted Patent: US 8,143,353 B2
• Time in Patent Office: Days
• US Class Current: 525/55
• CPC Class Codes: C08F 10/06 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 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• 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 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

This invention relates to a propylene polymer comprising a component having a crystallinity of 10% or less and a component having a crystallinity of 20% or more, said propylene polymer having:

• a) a melting point of X ° C. or more where X=−0.0038(Tp)²+0.36(Tp)+150, where Tp is the temperature of polymerization in ° C.;
• b) an Mw of 10,000 g/mol or more;
• c) a heat of fusion of from 1-70 J/g;
• d) Stereodefects per 10,000 monomer units of Y or less where Y=2.35(Tp)−100 (where Tp is the temperature of polymerization in ° C.) for the portion of the blend that is insoluble in hexane at 23° C.;
• e) a dot T-Peel on Kraft paper of 1 N or more; and
• f) a branching factor of 0.98 or less, where the branching factor is the ratio of g′ measured at Mz to g′ measured at Mw, and process to produce such polymers.

Claims

1. A propylene polymer comprising a component having a crystallinity of 10% or less and a component having a crystallinity of 20% or more, said propylene polymer having:

a) a melting point of X °

C. or more where X=−

0.0038(Tp)²+0.36(Tp)+150, where Tp is the temperature of polymerization in °

C.;

b) an Mw of 10,000 g/mol or more;

c) a heat of fusion of from 1-70 J/g;

d) Stereodefects per 10,000 monomer units of Y or less where Y=2.35(Tp)−

100 (where Tp is the temperature of polymerization in °

C.) for the portion of the blend that is insoluble in hexane at 23°

C.;

e) a dot T-Peel on Kraft paper of 1 N or more; and

f) a branching factor of 0.98 or less, where the branching factor is the ratio of g′

measured at Mz to g′

measured at Mw.

2. The polymer of claim 1 where the component having a crystallinity of 10% or less is present at at least 2 wt % and the component having a crystallinity of 20% or more is present at least 2 wt %.

3. The polymer of claim 1 wherein X=−

0.0038(Tp)²+0.36(Tp)+152.

4. The polymer of claim 1 wherein the branching factor is 0.95 or less.

5. The polymer of claim 1 wherein the polymer has a melting temperature of 135°

C. or higher.

6. An adhesive comprising the composition of claim 1.

7. The adhesive of claim 6 wherein the adhesive has a dot T-Peel of 5-10,000 N.

8. The adhesive of claim 6 further comprising tackifier.

9. The adhesive of claim 6 further comprising maleated polymer.

10. A process for producing a propylene polymer, the process comprising:

1) contacting a monomer composition comprising propylene with a polymerization catalyst system under homogeneous polymerization conditions and at a temperature of about 100°

C. to about 195°

C., wherein the polymerization catalyst system includes an activator and two catalyst compounds, where the first catalyst compound is capable of producing a polymer having a heat of fusion of 10 J/g or less at said homogeneous polymerization conditions and at a temperature of 100°

C.-195°

C., and the second catalyst compound is represented by the formula (A);

wherein

M is a transition metal selected from group 4 of the Periodic Table of the Elements;

each R¹ is, independently, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R¹ groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;

each R², R³, R⁵, R⁶ and R⁷ is independently, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;

Y is a bridging group comprising carbon, silicon or germanium; and

each X is, independently, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals;

or both X are joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms;

or

both together can be an olefin, diolefin or aryne ligand;

or both X may, independently, be a halogen, alkoxide, aryloxide, amide, phosphide or other univalent anionic ligand or both X can also be joined to form a anionic chelating ligand;

2) obtaining a propylene polymer comprising a component having a crystallinity of 5% or less and a component having a crystallinity of 20% or more, said polymer having;

a) a melting point of X °

C. or more where X=−

0.0038(Tp)²+0.36(Tp)+150, where Tp is the temperature of polymerization in °

C.;

b) an Mw of 10,000 g/mol or more;

c) a heat of fusion of from 1-70 J/g;

d) Stereodefects per 10,000 monomer units of Y or less where Y=2.35(Tp)−

100 (where Tp is the temperature of polymerization in °

C.) for the portion of the blend that is insoluble in hexane at 23°

C.;

e) a dot T-Peel on Kraft paper of 1 N or more; and

f) a branching factor of 0.98 or less, where branching factor is the ratio of g′

measured at Mz to g′

measured at Mw.

11. The process of claim 10 wherein the process is a continuous process.

12. The process of claim 10 wherein:

a) the first catalyst component produces a polymer having an Mw of 500,000 or less, and a crystallinity of 10% or less;

b) the second catalyst component produces a polymer having an Mw of 500,000 or less, and a crystallinity of 20% or more;

c) the temperature is from 110°

C.-195°

C. and the catalyst system and monomers are contacted for a residence time of 120 minutes or less;

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

1-100;

1, preferably 1;

1-50;

1, more preferably 1;

1-1;

20;

e) the activity of the first and second catalyst components together is at least 3 kilograms of polymer per gram of the catalyst mixture; and

f) at least 50% of the monomers are converted to polymer products having an Mw of 5,000 g/mol or more.

13. The process of claim 10 wherein the blend is pelletized.

14. The process of claim 10 wherein said temperature is from 110°

C. to about 180°

C.

15. The process of claim 10 wherein each R′

is hydrogen and each of R², R³, R⁵, R⁶ and R⁷ is, independently, hydrogen, or a hydrocarbyl group having 1-10 carbon atoms.

16. The process of claim 10 wherein R² is methyl.

17. The process of claim 10 wherein each R¹, R³, R⁵, R⁶, and R⁷ are hydrogen.

18. The process of claim 10 wherein said monomer consists essentially of propylene.

19. The process of claim 10 wherein the monomer composition comprises a further comonomer selected from the group consisting of ethylene, and C₄-C₂₀ α

-olefins, cyclic olefins and α

-olefinic diolefins.

20. The process of claim 10 wherein the second catalyst compound is selected from the group consisting of dimethylsilylene-bis[2-methyl-4-(carbazol-9-yl)inden-1-yl]zirconium dimethyl and dimethylsilylene-bis[2-methyl-4-(carbazol-9-yl)inden-1-yl]zirconium dichloride, or a combination thereof.

21. The process of claim 10 wherein the activator comprises a non-coordinating anion.

22. The process of claim 10 wherein:

the process further comprises;

     1) contacting, in a solvent, the catalyst components in the presence of one or more activators with one or more C₃-C₄₀ olefins, and, optionally one or more diolefins;

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

1-50;

1;

     3) withdrawing polymer solution from the reaction zone;

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

     5) devolatilizing the polymer solution to form molten polymer;

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

23. The process of claim 13 wherein the pellets are pourable free flowing pellets.

24. The process of claim 22 further comprising 7) pelletizing the molten polymer and one or more additives.

25. The process claim 24 wherein after aging of the pellets at 120°

F. for 7 days, the aged pourability value of a 500 gram sample of the pellets is 300 seconds or less.