Olefin polymerization catalyst system comprising mesoporous organosilica support

1. A catalyst system comprising:

(1) one or more olefin polymerization catalyst compounds comprising a nitrogen linkage to a Group 3-12 transition metal or a Group 13 or 14 main group metal;

(2) a catalyst support comprising an organosilica material that is a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I), wherein Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer; and

(3) an optional activator.

2. The catalyst system of claim 1 , wherein Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer.

3. The catalyst system of claim 1 , wherein Z 1 represents a hydrogen atom, methyl, ethyl or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, methyl, ethyl, ethoxy, methoxy, or an oxygen bonded to a silicon atom of another monomer.

4. The catalyst system of claim 1 , wherein the polymer further comprises a second distinct monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I).

5. The catalyst system of claim 1 , wherein the organosilica material further comprises at least one monomer selected from the group consisting of:

a monomer of Formula Z 3 OZ 4 Z 5 Z 6 Si (II), wherein Z 3 represents a hydrogen atom or a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; and Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a nitrogen-containing C 1 -C 10 alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;

(ii) a monomer of Formula Z 7 Z 8 Z 9 Si—R 1 —SiZ 7 Z 8 Z 9 (III), wherein Z 7 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; Z 8 and Z 9 each independently represent a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkyl group, or an oxygen bonded to a silicon atom of another monomer; and R 1 is selected from the group consisting of a C 1 -C 8 alkylene group, a C 2 -C 8 alkenylene group, a C 2 -C 8 alkynylene group, a nitrogen-containing C 2 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkylene and an optionally substituted C 4 -C 20 heterocycloalkylene group;

(iii) a trivalent metal oxide monomer of Formula M 1 (OZ 10 ) 3 (IV), wherein M 1 represents a Group 13 metal and Z 10 represents a hydrogen atom, a C 1 -C 6 alkyl or a bond to a silicon atom of another monomer;

(iv) a trivalent metal oxide monomer of Formula (Z 11 O) 2 M 2 -O—Si(OZ 12 ) 3 (V), wherein M 2 represents a Group 13 metal and Z 11 and Z 12 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group, or a bond to a silicon atom of another monomer;

(v) a cyclic polyurea monomer of Formula

wherein each R 2 is a Z 13 OZ 14 Z 15 SiZ 16 group, wherein Z 13 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; Z 14 and Z 15 each independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; and Z 16 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and

(vi) combinations thereof.

6. The catalyst system of claim 1 , wherein the catalyst support comprising the organosilica material has:

(i) an average pore diameter between about 2 nm and about 50 nm;

(ii) a pore volume about 0.1 cm 3 /g to about 10 cm 3 /g; and/or

(iii) a surface area of about 100 m 2 /g to about 2,500 m 2 /g.

7. The catalyst system of claim 1 , wherein the catalyst support comprising the organosilica material has an X-Ray diffraction spectrum exhibiting substantially no peaks above 4 degrees 2θ, and/or is made using substantially no added structure directing agent or porogen.

8. The catalyst system of claim 1 , wherein the one or more olefin polymerization catalyst compounds comprise at least one catalyst compound selected from the group consisting of:

(A) a compound represented by Formula (VII):

wherein:

M* is a Group 4 metal;

each E′ group is independently selected from carbon, silicon, or germanium;

each X′ is an anionic leaving group;

L* is a neutral Lewis base;

R′ 1 and R′ 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;

R′ 2 , R′ 3 , R′ 4 , R′ 5 , R′ 6 , R′ 7 , R′ 8 , R′ 9 , R′ 10 , R′ 11 , and R′ 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;

n′ is 1 or 2;

m′ is 0, 1, or 2; and

two X′ groups may be joined together to form a dianionic group;

two L* groups may be joined together to form a bidentate Lewis base;

an X′ group may be joined to an L* group to form a monoanionic bidentate group;

R′ 7 and R′ 8 may be joined to form a ring; and

R′ 10 and R′ 11 may be joined to form a ring;

(B) a compound represented by Formula (VIII):

wherein:

M is a Group 3-12 transition metal or a Group 13 or 14 main group metal;

each X is independently an anionic leaving group;

n is the formal oxidation state of M;

m is the formal charge of the ligand comprising Y, Z, and L;

Y is a Group 15 element;

Z is a Group 15 element;

L is a Group 15 or 16 element;

R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom-containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, phosphorus, or a halogen, where R 1 and R 2 may also be interconnected to each other;

R 3 is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom-containing group;

R 4 and R 5 are independently an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system; and

R 6 and R 7 are independently absent, or hydrogen, halogen, heteroatom or a hydrocarbyl group; and

(C) a compound represented by Formula (IX),

wherein:

M comprises a transition metal from Group 7, 8 or 9 of the Periodic Table of Elements;

X is an atom or group covalently or ionically bonded to the transition metal M;

n is 1, 2, 3, 4, or 5; and

R 1 to R 7 are independently selected from the group consisting of hydrogen, halogens, hydrocarbyls, and substituted hydrocarbyls, provided that when any two or more of R 1 to R 7 are hydrocarbyl or substituted hydrocarbyl, two or more may be linked to form one or more cyclic substituents.

9. The catalyst system of claim 8 , wherein the one or more olefin polymerization catalyst compounds comprise a catalyst compound of Formula (VII), wherein M* is hafnium, each E′ group is carbon, each X′ is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, or alkylsulfonate, each L* is a an ether, amine, or thioether, each R′ 1 and R′ 13 is an aryl group, each R′ 7 and R′ 8 is joined to form a six-membered aromatic ring with the joined R′ 7 and R′ 8 group being —CH═CHCH═CH—, and R′ 10 and R′ 11 may be a five-membered ring with the joined R′ 10 R′ 11 group being —CH 2 CH 2 — or a six-membered ring with the joined R′ 10 R′ 11 group being —CH 2 CH 2 CH 2 —.

10. The catalyst system of claim 8 , wherein the one or more olefin polymerization catalyst compounds comprise a catalyst compound of Formula (VIII), wherein M is zirconium or hafnium, n is +3, +4, or +5, m is 0, −1, −2 or −3, L is nitrogen; Y is nitrogen or phosphorus, Z is nitrogen or phosphorus, R 1 and R 2 are a C 2 to C 20 alkylene, arylene or aralkylene group, R 3 is absent, a linear, cyclic or branched alkyl C 1 to C 20 group, or hydrogen, R 4 and R 5 independently are a C 1 to C 20 hydrocarbon group, a C 1 to C 20 aryl group or a C 1 to C 20 aralkyl group, and R 6 and R 7 are independently a linear, cyclic or branched C 2 to C 20 alkyl group or absent.

11. The catalyst system of claim 8 , wherein the one or more olefin polymerization catalyst compounds comprise a catalyst compound of Formula (IX) and n is 2 or 3.

12. A process to produce polymer comprising: i) contacting, in the gas phase or slurry phase, one or more olefin monomers, with the catalyst system of claim 1 , and ii) obtaining a polymer.

13. The process of claim 12 , wherein (2) the organosilica material comprises at least one monomer selected from the group consisting of:

(i) a monomer of Formula Z 3 OZ 4 Z 5 Z 6 Si (II), wherein Z 3 represents a hydrogen atom or a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; and Z 4 , Z 5 , and Z 6 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a nitrogen-containing C 1 -C 10 alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;

(ii) a monomer of Formula Z 7 Z 8 Z 9 Si—R 1 —SiZ 7 Z 8 Z 9 (III), wherein Z 7 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; Z 8 and Z 9 each independently represent a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkyl group, or an oxygen bonded to a silicon atom of another monomer; and R 1 is selected from the group consisting of a C 1 -C 8 alkylene group, a C 2 -C 8 alkenylene group, a C 2 -C 8 alkynylene group, a nitrogen-containing C 2 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkylene and an optionally substituted C 4 -C 20 heterocycloalkylene group;

(iii) a trivalent metal oxide monomer of Formula M 1 (OZ 10 ) 3 (IV), wherein M 1 represents a Group 13 metal and Z 10 represents a hydrogen atom, a C 1 -C 6 alkyl or a bond to a silicon atom of another monomer;

(iv) a trivalent metal oxide monomer of Formula (Z 11 O) 2 M 2 -O—Si(OZ 12 ) 3 (V), wherein M 2 represents a Group 13 metal and Z 11 and Z 12 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group, or a bond to a silicon atom of another monomer;

(v) a cyclic polyurea monomer of Formula:

 wherein each R 2 is a Z 13 OZ 14 Z 15 SiZ 16 group, wherein Z 13 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; Z 1A and Z 15 each independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; and Z 16 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and

(vi) combinations thereof.

14. The process of claim 12 , wherein (1) the catalyst support comprising an organosilica material has:

(i) an average pore diameter between about 2 nm and about 50 nm;

(ii) a pore volume about 0.1 cm 3 /g to about 10 cm 3 /g; and/or

(iii) a surface area of about 100 m 2 /g to about 2,500 m 2 /g.

15. The process of claim 12 , wherein (1) the catalyst support comprising the organosilica material:

has an X-Ray diffraction pectrum exhibiting substantially no peaks above 4 degrees 2θ; and/or

(ii) is made using substantially no added structure directing agent or porogen.

16. The process of claim 12 , wherein the one or more olefin polymerization catalyst compounds comprise at one least catalyst compound selected from the group consisting of:

(A) a compound represented by Formula (VII):

wherein:

M* is a Group 4 metal;

each E′ group is independently selected from carbon, silicon, or germanium;

each X′ is an anionic leaving group;

L* is a neutral Lewis base;

R′ 1 and R′ 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;

R′ 2 , R′ 3 , R′ 4 , R′ 5 , R′ 6 , R′ 7 , R′ 8 , R′ 9 , R′ 10 , R′ 11 , and R′ 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;

n′ is 1 or 2;

m′ is 0, 1, or 2; and

two X′ groups may be joined together to form a dianionic group;

two L* groups may be joined together to form a bidentate Lewis base;

an X′ group may be joined to an L* group to form a monoanionic bidentate group;

R′ 7 and R′ 8 may be joined to form a ring; and

R′ 10 and R′ 11 may be joined to form a ring;

(B) a compound represented by Formula (VIII):

wherein:

M is a Group 3-12 transition metal or a Group 13 or 14 main group metal;

each X is independently an anionic leaving group;

n is the formal oxidation state of M;

m is the formal charge of the ligand comprising Y, Z, and L;

Y is a Group 15 element;

Z is a Group 15 element;

R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom-containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, phosphorus, or a halogen, where R 1 and R 2 may also be interconnected to each other;

R 3 is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom-containing group;

R 4 and R 5 are independently an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system; and

R 6 and R 7 are independently absent, or hydrogen, halogen, heteroatom or a hydrocarbyl group; and

(C) a compound represented by Formula (IX);

wherein:

M comprises a transition metal from Group 7, 8 or 9 of the Periodic Table of Elements;

X is an atom or group covalently or ionically bonded to the transition metal M;

n is 1, 2, 3, 4, or 5; and

R 1 to R 7 are independently selected from the group consisting of hydrogen, halogens, hydrocarbyls, and substituted hydrocarbyls, provided that when any two or more of R 1 to R 7 are hydrocarbyl or substituted hydrocarbyl, two or more may be linked to form one or more cyclic substituents.

17. The process of claim 16 , wherein the one or more olefin polymerization catalyst compounds comprise a catalyst compound of Formula (VII), wherein M* is hafnium, each E′ group is carbon, each X′ is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, or alkylsulfonate, each L* is a an ether, amine, or thioether, each R′ 1 and R′ 13 is an aryl group, each R′ 7 and R′ 8 is joined to form a six-membered aromatic ring with the joined R′ 7 and R′ 8 group being —CH═CHCH═CH—, and R′ 10 and R′ 11 may be a five-membered ring with the joined R′ 10 R′ 11 group being —CH 2 CH 2 — or a six-membered ring with the joined R′ 10 R′ 11 group being —CH 2 CH 2 CH 2 —.

18. The process system of claim 16 , wherein the one or more olefin polymerization catalyst compounds comprise a catalyst compound of Formula (VIII), wherein M is zirconium or hafnium, n is +3, +4, or +5, m is 0, −1, −2 or −3, L is nitrogen; Y is nitrogen or phosphorus, Z is nitrogen or phosphorus, R 1 and R 2 are a C 2 to C 20 alkylene, arylene or aralkylene group, R 3 is absent, a linear, cyclic or branched alkyl C 1 to C 20 group, or hydrogen, R 4 and R 5 independently are a C 1 to C 20 hydrocarbon group, a C 1 to C 20 aryl group or a C 1 to C 20 aralkyl group, and R 6 and R 7 are independently a linear, cyclic or branched C 1 to C 20 alkyl group or absent.

19. The process of claim 16 , wherein the one or more olefin polymerization catalyst compounds comprise a catalyst compound of Formula (IX) and n is 2 or 3.

20. The process of claim 12 , wherein the polymer is an ethylene polymer or a propylene polymer.

21. The process of claim 12 , wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in a range of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.

22. The process of claim 12 , wherein the one or more olefin monomers comprise ethylene and one or more comonomer selected from propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene or a mixture thereof.

23. The process of claim 12 , wherein the 2) catalyst support comprising an organosilica material comprises a plurality of mesopores having an average pore diameter between about 2 nm and about 50 nm and the polymerization occurs within the mesopores.