Activated catalyst components for olefin polymerization
An activated solid catalyst component is disclosed formed from a magnesium compound, a titanium compound, an organosilicon compound, a supportive electron donor, and at least one internal electron donor. The solid catalyst component is activated to include titanium and carbon bonds by reaction with an activation agent, such as an aluminum compound. In one embodiment, small amounts of polymer are polymerized with the catalyst component during activation. The activated catalyst component is stable and, when formed, can later be used to produce various polyolefin polymers. The activated catalyst component has controlled reaction kinetics so that the catalyst does not overheat and degrade during initial polymerization.
1. An activated and non-phthalate solid catalyst component for olefin polymerization comprising a reaction product of:
(a) a halide-containing magnesium compound;
(b) a titanium compound containing titanium in an oxidation state of at least +3 and +2;
(c) an organosilicon compound containing Si—O groups;
(d) an alkylaluminum compound;
(e) a supportive electron donor comprising a monobenzoate, the supportive electron donor being present in the catalyst component in an amount from about 0.01% to about 5% by weight;
(f) at least one internal electron donor, the at least one internal electron donor being present in the catalyst component in an amount from about 1% to about 15% by weight; and
(g) a polymer formed from an alpha-olefin having the formula: CH 2 ═CHR 1 , wherein R 1 comprises hydrogen, or a C 1 to C 7 alkyl group, and being present in the catalyst component in an amount from about 0.3 g to about 200 g of polymer per gram of catalyst component.
2. The activated solid catalyst component of claim 1 , wherein the at least one internal electron donor comprises an aryl diester.
3. The activated solid catalyst component of claim 1 , wherein the alpha-olefin comprises ethylene or propylene.
4. The activated solid catalyst component of claim 1 , wherein the halide-containing magnesium compound comprises magnesium chloride.
5. The activated solid catalyst component of claim 1 , wherein the olefin polymer is present in an amount less than or equal to about 20 g of polymer per gram of activated solid catalyst component.
6. The activated solid catalyst component of claim 1 , wherein the organosilicon compound is a silane, siloxane or polysiloxane having the following chemical structure:
R n Si(OR′) 4 - n
wherein:
each R is H, alkyl, or aryl;
each R′ is H, alkyl, aryl, or a SiR n ′(OR′) 3-n ; and
n is 0, 1, 2, or 3.
7. The activated solid catalyst component of claim 1 , wherein the internal electron donor is represented by the following formula:
wherein:
each of R 15 through R 20 are independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and
q is an integer from 0 to 12.
8. The activated solid catalyst component of claim 1 , wherein the internal electron donor is represented by one of the following formulas:
where R 1 -R 4 , are the same or different and each R 1 -R 4 is selected from the group consisting of hydrogen, a substituted hydrocarboyl group having 1 to 20 carbon atoms, an a unsubstituted hydrocarboyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom and combinations thereof and at least one of R 1 -R 4 is not hydrogen; and
E 1 and E 2 are the same or different and each E 1 and E 2 is selected from the group consisting of a substituted hydrocarboyl group having 1 to 20 carbon atoms, an a unsubstituted hydrocarboyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom and combinations thereof
wherein X 1 and X 2 are each O, S, an alkyl group, or NR 5 and wherein R 5 is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen; or
wherein:
each of R 1 through R 6 are independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; or
wherein each of R 7 through R 14 are independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl groups.
9. The activated solid catalyst component of claim 1 , wherein the supportive electron donor has the following formula:
wherein R′ comprises an alkyl group, a cyclic group, an aryl group having from 1 to 20 carbon atoms, a heteroatom or a combination thereof, and wherein R″ is hydrogen, an alkyl group, a cyclic group, an aryl group having from 1 to 20 carbon atoms, or a heteroatom.
10. The activated solid catalyst component of claim 1 , wherein the catalyst component has an average particle size of from about 5 microns to about 300 microns.
11. The activated solid catalyst component of claim 1 further comprising an organic phosphorus compound comprising a phosphate acid ester.
12. The activated solid catalyst component of claim 1 further comprising an activity limiting agent comprising a C 4 to C 30 aliphatic acid ester, a diether, or a poly(alkene glycol) ester of a C 4 to C 30 aliphatic acid.
13. The activated solid catalyst component of claim 1 , wherein the supportive electron donor is present in the catalyst component in an amount from about 0.01% to by weight to about 3% by weight and the at least one internal electron donor is present in the catalyst component in an amount from about 3% by weight to about 10% by weight.
14. The activated solid catalyst component of claim 9 , wherein the supportive electron donor comprises ethylbenzoate.
15. The activated solid catalyst component of claim 1 , wherein a solid catalyst component is formed and then fed to a polymerization reactor for forming the activated solid catalyst having the polymer associated therewith.
16. A process for producing an activated solid catalyst component comprising:
a. forming a catalyst precursor component by reacting a magnesium alkoxide Mg(OR) n X 2-n , or magnesium alcholate MgX 2 mR′OH with Ti(OR″) g X 4-g wherein X is Br, Cl, or I; and n is 1 or 2; m is 0.5-10; g is 0, 1, 2, 3, or 4; and R, R′, R″ are independently C 1 -C 10 alkyl, the catalyst precursor further containing a supportive electron donor and an internal electron donor
b. reacting the product obtained from (a) with a trialkyl aluminum compound in the presence of an organosilicon compound having the following formula R 2n Si(OR 3 ) 4-n , wherein R 2 is H, alkyl, or aryl; each R 3 is alkyl, or aryl; n is 0, 1, 2 or 3,
c. reacting the product obtained in (b) with an olefin having the formula CH 2 ═CHR′ wherein R′═H, or a C 1 -C 7 alkyl group and polymerizing the olefin to form a polymer coating on the solid catalyst component particles, the olefin polymer being present in an amount of less than 200 g per 1 g of the activated solid catalyst component,
d. isolating the activated solid catalyst component.
17. The process of claim 16 , wherein an activity limiting agent is further added in step b) and the activity limited agent comprises a C 4 to C 30 aliphatic acid ester, a diether, or a poly(alkene glycol) ester of a C 4 to C 30 aliphatic acid.
18. The process of claim 16 , wherein the internal electron donor is represented by one of the following formulas:
where R 1 -R 4 , E 1 , and E 2 are the same or different and each R 1 -R 4 , E 1 , and E 2 is selected from the group consisting of hydrogen, a substituted hydrocarboyl group having 1 to 20 carbon atoms, an a unsubstituted hydrocarboyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom and combinations thereof and at least one of R 2 -R 4 is not hydrogen; E 1 and E 2 are the same or different and each E 1 and E 2 is selected from the group consisting of a substituted hydrocarboyl group having 1 to 20 carbon atoms, an a unsubstituted hydrocarboyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom and combinations thereof;
and wherein X 1 and X 2 are each O, S, an alkyl group, or NR 5 and wherein R 5 is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen; or
wherein:
each of R 1 through R 14 are independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and
q is an integer from 0 to 12,
and wherein the supportive electron donor has the following formula:
wherein R′ comprises an alkyl group, a cyclic group, an aryl group having from 1 to 20 carbon atoms, a heteroatom or a combination thereof, and
wherein R″ comprises one or more substituted groups, each substituted group can comprise independently hydrogen, an alkyl group, a cyclic group, an aryl group having from 1 to 20 carbon atoms, a heteroatom, or a combination thereof.
19. A process for producing olefin polymers comprising:
polymerizing an olefin in the presence of an activated solid catalyst component in a gas phase polymerization reactor, the activated solid catalyst component comprising:
(a) a halide-containing magnesium compound;
(b) a titanium compound wherein titanium has as oxidation state of at least +3 and +2;
(c) an organosilicon compound containing Si—O groups;
(d) an alkyl-aluminum compound;
(e) a supportive electron donor comprising a mono benzoate, the supportive electron donor being present in the catalyst component in an amount from about 0.01% to about 5% by weight;
(f) at least one internal electron donor, the internal electron donor comprising an aryl diester, the at least one internal electron donor being present in the catalyst component in an amount from about 1% to about 15% by weight; and
(g) a polymer formed from an alpha-olefin having the formula: CH 2 ═CHR 1 , wherein R 1 comprises hydrogen, or a C 1 to C 7 alkyl group, the alpha-olefin polymer forming a coating on the catalyst particles and being present in the catalyst component in an amount from about 0.3 g to about 200 g of polymer per gram of catalyst particles;
wherein the activated solid catalyst component is prepared outside of the polymerization reactor and fed to the reactor.
20. The process of claim 19 , wherein the olefin is polymerized in a fluidized bed.