Catalysts for Producing Polymers and Enhanced Properties

Patent metadata

Field	Value
Publication number	US-2018244816-A1
Application number	US-201815962891-A
Country	US
Kind code	A1
Filing date	Apr 25, 2018
Priority date	Dec 16, 2015
Publication date	Aug 30, 2018
Grant date	—

Abstract

Disclosed are novel hafnium-based metallocene catalyst compounds with the following characteristics: 1) 4,5-dialkyl substitutions on a fluorenyl ligand, and optionally additional substitutions, 2) a cyclopentadienyl ligand, optionally with substitutions, and 3) a bridging group from group 14 of the Periodic Table. Also disclosed are catalyst systems comprising such catalyst compounds and their uses thereof, and polymers produced using such catalyst systems.

First claim

1 . A syndiotactic propylene polymer having: 1) at least 50% allyl chain ends and/or 3-alkyl chain ends relative to the total number of unsaturated chain ends; 2) an Mw of 4000 g/mol or more; and 3) no detectable melting temperature by DSC, where the syndiotactic propylene homopolymer is prepared by a process comprising contacting propylene with a catalyst system, the catalyst system comprising an activator and at least one A catalyst compound represented by formula (I):

wherein each R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently hydrogen or a C 1 to C 10 alkyl, and wherein any of R 1 and R 2 , R 2 and R 3 , R 6 and R 7 , and R 7 and R 8 are optionally bonded together to form a ring structure;
each R 4 and R 5 is independently a C 1 to C 10 alkyl;
J is SiR 13 R 14 , GeR 13 R 14 or (CR 15 R 16 ) x , where x is 1 or 2; R 13 and R 14 are each independently selected from the group consisting of substituted or unsubstituted hydrocarbyl, halocarbyl, and silylcarbyl; R 15 and R 16 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl and silylcarbyl; and R 13 and R 14 , or R 15 and R 16 , when R 15 and R 16 are not hydrogen, are optionally bonded together to form a ring structure; and
each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

2 . The syndiotactic propylene polymer of claim 1 , wherein the compound is represented by formula (II):

wherein each R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , and R 12 is independently hydrogen or a C 1 to C 10 alkyl, and wherein any of R 1 and R 2 , R 2 and R 3 , R 6 and R 7 , and R 7 and R 8 are optionally bonded together to form a ring structure;
each R 4 and R 5 is independently a C 1 to C 10 alkyl;
each R 13 and R 14 is independently selected from the group consisting of substituted or unsubstituted hydrocarbyl, halocarbyl, and silylcarbyl; and
each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

3 . The syndiotactic propylene polymer of claim 1 , wherein the catalyst compound is represented by formula (III):

wherein each R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , and R 12 is independently hydrogen or a C 1 to C 10 alkyl, and wherein any of R 1 and R 2 , R 2 and R 3 , R 6 and R 7 , and R 7 and R 8 are optionally bonded together to form a ring structure;
each R 4 and R 5 is independently a C1 to C 10 alkyl;
x is 1 or 2;
each R 15 and R 16 is independently selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl and silylcarbyl; and R 15 and R 16 , when R 15 and R 16 are not hydrogen, are optionally bonded together to form a ring structure; and
each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

4 . The syndiotactic propylene polymer of claim 1 , wherein each R 4 and R 5 is independently selected from the group consisting of methyl, ethyl, propyl, butyl, and isomers thereof.

5 . The syndiotactic propylene polymer of claim 1 , wherein each R 4 and R 5 is independently selected from the group consisting of n-propyl, isopropyl, methyl, and ethyl.

6 . The syndiotactic propylene polymer of claim 1 , wherein each R 1 , R 2 , R 3 , R 6 , R 7 , and R 8 is independently hydrogen or a C 1 -C 5 alkyl.

7 . The syndiotactic propylene polymer of claim 1 , wherein J is Si or C and each R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9, and R 12 is independently hydrogen or a C 1 -C 5 alkyl.

8 . The syndiotactic propylene homopolymer of claim 1 , wherein each R 9 , R 10 and R 12 is independently hydrogen or a C 1 -C 5 alkyl.

9 . The syndiotactic propylene homopolymer of claim 1 , wherein each R 9 and R 12 is independently hydrogen or a C 1 -C 5 alkyl and R 10 and R 11 are hydrogen.

10 . The syndiotactic propylene polymer of claim 1 , wherein J is SiR 13 R 14 , and each R 13 and R 14 is independently selected from the group consisting of substituted or unsubstituted hydrocarbyl, halocarbyl, and silylcarbyl, and R 13 and R 14 are optionally bonded together to form a ring structure.

11 . The syndiotactic propylene polymer of claim 1 , wherein J is Si and R 13 and R 14 are joined together to form a 4, 5, or 6-membered ring structure.

12 . The syndiotactic propylene polymer of claim 1 , wherein J is Si or C and each R 13 and R 14 is independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, tolyl, benzyl, and isomers thereof.

13 . The syndiotactic propylene polymer of claim 1 , wherein J is selected from the group consisting of dimethylsilylene, diethylsilylene, methylethylsilylene, methylphenylsilylene, diphenylsilylene, and dipropylsilylene.

14 . The syndiotactic propylene polymer of claim 1 , wherein J is selected from the group consisting of cyclotrimethylenesilylene, cyclotetramethylenesilylene, and cyclopentamethylenesilylene.

15 . The syndiotactic propylene polymer of claim 1 , wherein J is (CR 15 R 16 ) x , where x is 1 or 2, each R 15 and R 16 is independently selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl, and silylcarbyl; and R 15 and R 16 , when R 15 and R 16 are not hydrogen, and are optionally bonded together to form a ring structure.

16 . The syndiotactic propylene polymer of claim 15 , wherein x is 1 and each R 15 and R 16 is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, tolyl, benzyl, and isomers thereof.

17 . The syndiotactic propylene polymer of claim 15 , wherein x is 1 and R 15 and R 16 are joined together to form a 4, 5, or 6-membered ring structure.

18 . The syndiotactic propylene polymer of claim 1 , wherein J is selected from the group consisting of dimethylmethylene, diethylmethylene, methylethylmethylene, methylphenylmethylene, diphenylmethylene, and dipropylmethylene.

19 . (canceled)

20 . The syndiotactic propylene polymer of claim 1 , wherein J is ethylene or methylene.

21 . The syndiotactic propylene polymer of claim 1 , wherein each X is independently methyl, benzyl, or halo, where halo includes fluoride, chloride, bromide, and iodide.

22 . The syndiotactic propylene polymer of claim 1 , wherein the catalyst compound is further contacted with an activator and an olefin.

23 . A syndiotactic propylene homopolymer having: 1) at least 50% allyl chain ends and/or 3-alkyl chain ends relative to the total number of unsaturated chain ends; 2) an Mw of 4000

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Canich Jo Ann M
• Stewart Ian C
• Borisov Ilya S
• Guzeev Bogdan A
• Uborsky Dmitry V
• Voskoboynikov Alexander Z

Classifications

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C07F17/00

  Metallocenes · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title