Granted Patent B2

US 8,933,180 · App. 13/829,284 · Granted Jan 13, 2015

Abstract

Claims (234)

1. A solid catalyst component for use in olefinic polymerization comprising:

titanium,

magnesium,

halogen and

an internal electron donor compound, wherein said internal electron donor compound comprises at least one 9-(alkoxymethyl)-9H-fluorene compound represented by chemical formula (I):

wherein

R 1 is C 1 -C 20 linear or branched alkyl, C 5 -C 20 cycloalkyl, C 5 -C 20 cycloalkenyl, C 5 -C 20 cyclodialkenyl, phenyl, C 7 -C 18 alkylaryl, or C 7 -C 18 arylalkyl;

R 2 is —(C═O)—O—R 11 or —O—(C═O)—R 12 ;

R 3 -R 10 are independently hydrogen, halogen, C 1 -C 6 linear or branched alkyl, C 6 -C 10 cycloalkyl, phenyl, C 7 -C 10 alkylaryl, or C 7 -C 18 arylalkyl;

R 11 is C 1 -C 20 linear or branched alkyl, C 5 -C 20 cycloalkyl, C 5 -C 20 cycloalkenyl, C 5 -C 20 cyclodialkenyl, phenyl, C 7 -C 18 alkylaryl, or C 7 -C 18 arylalkyl; and

R 12 is C 6 -C 12 aryl.

2. The solid catalyst component according to claim 1 , wherein the magnesium is a magnesium compound and the titanium is a titanium compound.

3. The solid catalyst component according to claim 2 wherein said titanium compound has at least one titanium-halogen bond, said magnesium compound is magnesium halide, and the internal electron donor compound is supported on said magnesium halide.

4. The solid catalyst component according to claim 2 wherein said titanium compound has at least one titanium-halogen bond, said magnesium compound is magnesium halide, and the internal electron donor compound is supported on said magnesium dichloride.

5. The solid catalyst component according to claim 3 , wherein the titanium compound is TiCl 4 or TiCl 3 .

6. The solid catalyst component according to claim 4 , wherein the titanium compound is TiCl 4 or TiCl 3 .

7. The solid catalyst component according to claim 2 , wherein the magnesium compound is a magnesium halide, an alkoxy magnesium halide, an aryloxy magnesium halide, an aryloxy magnesium, or a carboxylic acid salt of magnesium; and

the titanium compound has a general formula: TiX n (OR) 4-n , wherein R is a hydrocarbon radical having 1 to about 20 carbon atoms, X is a halogen, and n is from 1 to 4.

8. The solid catalyst component according to claim 1 , wherein the at least one 9-(alkoxymethyl)-9H-fluorene compound of the formula (I) is selected from the group consisting of

octyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

7-methyloctyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylhexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate; and

9-(methoxymethyl)-9H-fluorene-9-yl benzoate.

9. The solid catalyst component according to claim 1 , wherein the at least one 9-(alkoxymethyl)-9H-fluorene compound of the formula (I) is selected from the group consisting of

methyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

ethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

propyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

butyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

pentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

hexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

heptyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

octyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

nonyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

decyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

undecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

dodecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

tridecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

tetradecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

pentadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

hexadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

heptadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

octadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

nonadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

icosyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

henicosyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

isopropyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

isobutyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

isopentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

4-methylpentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

5-methylhexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

6-methylheptyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

7-methyloctyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

8-methylnonyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

9-methyldecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

10-methylundecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

11-methyldodecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

12-methyltridecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

13-methyltetradecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

14-methylpentadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

15-methylhexadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

16-methylheptadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

17-methyloctadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

18-methylnonadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

19-methylicosyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylbutyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylpentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylhexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylheptyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyloctyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

2-ethylnonyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyldecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylundecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyldodecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyltridecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyltetradecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylpentadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylhexadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylheptadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate; and

2-ethyloctadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate.

10. The solid catalyst component according to claim 1 , wherein the at least one 9-(alkoxymethyl)-9H-fluorene compound of the formula (I) is selected from the group consisting of

methyl 9-(methoxymethyl)-4-methyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-methyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-2-methyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-methyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-2-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-chloro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-chloro-9H-fluorene-9-carboxylate;

methyl 9-methoxymethyl)-2-chloro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-chloro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-fluoro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-fluoro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-2-fluoro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-fluoro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-phenyl-9H-fluorene-9-carboxylate:

methyl 9-(methoxymethyl)-3-phenyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-2-phenyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-phenyl-9H-fluorene-9-carboxylate;

methyl 4-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 3-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 2-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 1-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(ethoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(propoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(butoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(isobutoxymethyl)-9H-fluorene-9-carboxylate;

cyclohexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

cyclohexylmethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-cyclohexylethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

phenyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

benzyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate; and

phenethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate.

11. The solid catalyst component according to claim 1 having a surface area, by B.E.T. method, between about 10 and about 1,000 m 2 /g.

12. A catalyst system for use in olefinic polymerization comprising:

said solid catalyst component according to claim 1 ;

an organoaluminum compound; and

an organosilicon compound or an alkyl benzoate compound.

13. The catalyst system according to claim 12 , wherein the organoaluminum compound is an alkyl-aluminum compound.

14. The catalyst system according to claim 13 , wherein the alkyl-aluminum compound is a trialkyl aluminum compound.

15. The catalyst system according to claim 14 , wherein the trialkyl aluminum compound is selected from the group consisting of triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum.

16. A method of making a solid catalyst component for a catalyst system comprising: contacting a magnesium compound and a titanium compound with an internal electron compound,

wherein said internal electron compound comprises at least one 9-(alkoxymethyl)-9H-fluorene compound represented by chemical formula (I):

wherein

R 1 is C 1 -C 20 linear or branched alkyl, C 5 -C 20 cycloalkyl, C 5 -C 20 cycloalkenyl, C 5 -C 20 cyclodialkenyl, phenyl, C 7 -C 18 alkylaryl, or C 7 -C 18 arylalkyl;

R 2 is —(C═O)—O—R 11 or —O—(C═O)—R 12 ;

R 3 -R 10 are independently hydrogen, halogen, C 1 -C 6 linear or branched alkyl, C 6 -C 1 cycloalkyl, phenyl, C 7 -C 10 alkylaryl, or C 7 -C 18 arylalkyl;

R 11 is C 1 -C 20 linear or branched alkyl, C 5 -C 20 cycloalkyl, C 5 -C 20 cycloalkenyl, C 5 -C 20 cyclodialkenyl, phenyl, C 7 -C 18 alkylaryl, or C 7 -C 18 arylalkyl; and

R 12 is C 6 -C 12 aryl.

17. The method according to claim 16 , further comprising contacting the magnesium compound and the titanium compound with a second internal electron donor compound,

wherein the at least one 9-(alkoxymethyl)-9H-fluorene compound of the formula (l) is selected from the group consisting of

9-(methoxymethyl)-9H-fluorene-9-carboxylate:

7-methyloctyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate:

2-ethylhexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate; and

9-(methoxymethyl)-9H-fluorene-9-yl benzoate.

18. The method according to claim 16 further comprising contacting the magnesium compound and the titanium compound with a second internal electron donor compound,

wherein the at least one 9-(alkoxymethyl)-9H-fluorene compound of the formula (I) is selected from the group consisting of

methyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

ethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

propyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

butyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

pentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

hexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

heptyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

octyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

nonyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

decyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

undecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

dodecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

tridecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

tetradecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

pentadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

hexadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

heptadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

octadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

nonadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

icosyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

henicosyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

methyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

isopropyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

isobutyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

isopentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

4-methyl pentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

5-methylhexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

6-methylheptyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

7-methyloctyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

8-methylnonyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

9-methyldecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

10-methylundecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

11-methyldodecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

12-methyltridecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

13-methyltetradecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

14-methylpentadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

15-methylhexadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

16-methylheptadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

7-methyloctadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

18-methylnonadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

19-methylicosyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylbutyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

2-ethylpentyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylhexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyl heptyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate:

2-ethyloctyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylnonyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyldecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylundecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyldodecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyltridecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyltetradecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylpentadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylhexadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethylheptadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-ethyloctadecyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-methyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-methyl-9H-fluorene-9-carboxylate:

methyl 9-(methoxymethyl)-2-methyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-methyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-2-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-bromo-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-chloro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-chloro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-2-chloro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-chloro-9H-fluorene-9-carboxylate:

methyl 9-(methoxymethyl)-4-fluoro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-fluoro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-2-fluoro-9H-fluorene-9-carboxylate:

methyl 9-(methoxymethyl)-1-fluoro-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-4-phenyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-3-phenyl-9H-fluorene-9-carboxylate:

methyl 9-(methoxymethyl)-2-phenyl-9H-fluorene-9-carboxylate;

methyl 9-(methoxymethyl)-1-phenyl-9H-fluorene-9-carboxylate:

methyl 4-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 3-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate:

methyl 2-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate:

methyl 1-cyclohexyl-9-(methoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(ethoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(propoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(butoxymethyl)-9H-fluorene-9-carboxylate;

methyl 9-(isobutoxymethyl)-9H-fluorene-9-carboxylate;

cyclohexyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

cyclohexylmethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

2-cyclohexylethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

phenyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate;

benzyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate; and

phenethyl 9-(methoxymethyl)-9H-fluorene-9-carboxylate.

19. A process for polymerizing or copolymerizing an olefin monomer, comprising the steps of:

providing the catalyst system according to claim 16 ;

polymerizing or copolymerizing the olefin monomer in the presence of the catalyst system to form a polymer or a copolymer; and

recovering the polymer or copolymer.

20. The process according to claim 19 , wherein the olefin monomer is selected from the group consisting of ethylene, propylene, 1-butylene, methyl-1-pentent, 1-hexene, and 1-octene.

Assignments (9)