Granted Patent B2

US 12,595,322 · App. 17/786,672 · Granted Apr 7, 2026

Inventors: Angela I. Padilla-Acevedo (Lake Jackson, TX); Andrew J. Young (Houston, TX); Roger L. Kuhlman (Lake Jackson, TX); Susan Brown (Pearland, TX); Matthew E. Belowich (Midland, MI); David R. Neithamer (Midland, MI); Jerzy Klosin (Midland, MI); David M. Pearson (Lake Jackson, TX); Leslie E. O'Leary (Sugar Land, TX); Joseph F. DeWilde (Midland, MI)

Assignee: Dow Global Technologies LLC

C08F110/02C08F2/34C08F4/65927C08F210/16

Abstract

Claims (30)

1 . A method for making a polymer, the method comprising:

contacting a supported gas-phase biphenylphenol polymerization catalyst with an olefin under polymerization conditions in a gas-phase polymerization reactor to make the polymer via a gas-phase polymerization process, wherein the supported gas-phase biphenylphenol polymerization catalyst is made from a gas-phase biphenylphenol polymerization precatalyst of Formula I:

wherein each of R 5 , R 7 , R 8 , and R 10 is independently is a (C 1 to C 20 ) alkyl, aryl, aralkyl, halogen, or a hydrogen;

wherein each of R 4 and R 11 independently is a halogen or a hydrogen;

wherein each of R 2 and R 13 independently is a (C 1 to C 20 ) alkyl, aryl or aralkyl or a hydrogen;

wherein each of R 15 and R 16 independently is a 2,7-disubstituted carbazol-9-yl or a 3,6-disubstituted carbazol-9-yl;

wherein L is a linear C 3 or C 4 alkylene that forms a 3-carbon bridge or 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded;

wherein each of R 1 , R 3 , R 12 , and R 14 independently is a (C 1 -C 5 ) alkyl, halogen, or a hydrogen;

wherein each of R 6 and R 9 is a hydrogen or (C 1 -C 8 ) alkyl;

wherein each X independently is a halogen, a hydrogen, a (C 1 -C 20 ) alkyl, a (C 7 -C 20 ) aralkyl, a (C 1 -C 6 ) alkyl-substituted (C 6 -C 12 ) aryl, or a (C 1 -C 6 ) alkyl-substituted benzyl,—CH 2 Si (RC) 3 , where RC is (C 1 -C 12 ) hydrocarbon;

wherein M is Zr or Hf; and

wherein the polymer formed at B-conditions (H 2 /C 2 =0.0017 and C 6 /C 2 =0.004 at 100° C. and 230 pounds per square inch (psi) ethylene) has a molecular weight (Mw) in a range of from about 150,000 Daltons to about 1,200,000 Daltons; or wherein the polymer formed at K-conditions (H 2 /C 2 =0.0068 and C 6 /C 2 =0.004 at 100° C. and 230 psi) has Mw of less than about 500,000 Daltons.

2 . The method of claim 1 , wherein each X is a methyl.

3 . The method of claim 1 , wherein each of R 1 , R 3 , R 12 , and R 14 is a hydrogen.

4 . The method of claim 1 , wherein the gas-phase biphenylphenol polymerization precatalyst of Formula I is selected from the group consisting of the structures of (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix)

5 . The method of claim 1 , wherein the gas-phase biphenylphenol polymerization precatalyst is selected from the group consisting of the structures of (iii) and (v)

6 . A gas-phase polymerization catalyst system to make a polymer via a gas-phase polymerization process, the gas-phase polymerization catalyst system comprising:

a metallocene olefin polymerization catalyst; and

the supported gas-phase biphenylphenol polymerization catalyst made from the gas-phase biphenylphenol polymerization precatalyst of Formula I:

wherein each of R 5 , R 7 , R 8 , and R 10 is independently is a (C 1 to C 20 ) alkyl, aryl, aralkyl, halogen, or a hydrogen;

wherein each of R 4 and R 11 independently is a halogen or a hydrogen;

wherein each of R 2 and R 13 independently is a (C 1 to C 20 ) alkyl, aryl or aralkyl or a hydrogen;

wherein L is a linear C 3 or C 4 alkylene that forms a 3 -carbon bridge or 4 -carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded;

wherein each of R 1 , R 3 , R 12 , and R 14 independently is a (C 1 -C 8 ) alkyl, halogen, or a hydrogen;

wherein each of R 6 and R 9 is a hydrogen or (C 1 -C 8 ) alkyl;

wherein each X independently is a halogen, a hydrogen, a (C 1 -C 20 ) alkyl, a (C 7 -C 20 ) aralkyl, a (C 1 -C 6 ) alkyl-substituted (C 6 -C 12 ) aryl, or a (C 1 -C 6 ) alkyl-substituted benzyl,—CH 2 Si (R C ) 3 , where RC is (C 1 -C 12 ) hydrocarbon;

wherein M is Zr or Hf; and

wherein each of R 15 and R 16 is a 3,6-di-t-butylcarbazol-9-yl.

7 . A gas-phase polymerization method to make a polymer, the method comprising:

polymerizing an olefin monomer in a gas-phase polymerization reactor in presence of the gas-phase polymerization catalyst system of claim 6 to make the polymer.

Assignments (1)

Continuity (2)

References Cited (26)