# US 9,751,998 B2 · Catalyst systems for olefin polymerization

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- Number: US 9,751,998 B2
- Document ID: US9751998B2
- Status: Granted
- Kind: B2
- Application number: 14/437,543
- Filed: 2013-12-10
- Published: 2015-10-15
- Granted: 2017-09-05
- Earliest claimed: 2012-12-27
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Jerzy Klosin; Ruth Figueroa; Pulikkottil J. Thomas; Mehmet Demirors; Sylvie Desjardins; Mridula Kapur; Philip P. Fontaine
- Web page: https://patentgrep.com/patent/US9751998B2

## CPC

- C08J 5/18: Manufacture of films or sheets
- B65D 51/26: with means for keeping contents in position, e.g. resilient means
- C07F 5/00: Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- C08F 4/64186: {Dianionic ligand}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08L 23/06: Polyethylene
- C08L 23/08: Copolymers of ethene (C08L23/16 takes precedence)
- C08L 23/0815: {with aliphatic 1-olefins containing one carbon-to-carbon double bond}
- C08F 4/60193: {OOOO}
- C08F 210/14: Monomers containing five or more carbon atoms
- C08F 2500/03: Narrow molecular weight distribution, i.e. Mw/Mn < 3
- C08J 2323/08: Copolymers of ethene (C08J2323/16 takes precedence)
- C08J 2423/08: Copolymers of ethene (C08J2423/16 takes precedence)
- C08L 23/02: not modified by chemical after-treatment
- C08L 2203/16: used for films
- C08L 2205/02: containing two or more polymers of the same C08L -group
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2205/03: containing three or more polymers in a blend
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- B65D: CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The instant invention provides procatalysts and catalyst systems for olefin polymerization, olefin based polymers polymerized therewith, and process for producing the same. In one embodiment, the instant invention provides a procatalyst comprising a metal-ligand complex of formula (I).

## Claims

### Claim 1

A catalyst system comprising the reaction product of a metal-ligand complex of formula (I):
wherein:
M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; and n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral; and each Z independently is O, S, N(C1-C40)hydrocarbyl, or P(C1-C40)hydrocarbyl; and L is (C3-C40)hydrocarbylene or (C3-C40)heterohydrocarbylene, wherein the (C3-C40)hydrocarbylene has a portion that comprises a 3-carbon atom to 10-carbon atom linker backbone linking the Z atoms in formula (I) (to which L is bonded) and the (C3-C40)heterohydrocarbylene has a portion that comprises a 3-atom to 10-atom linker backbone linking the Z atoms in formula (I), wherein each of the 3 to 10 atoms of the 3-atom to 10-atom linker backbone of the (C3-C40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN), wherein independently each RC is (C1-C30)hydrocarbyl, each RP is (C1-C30)hydrocarbyl; and each RN is (C1-C30)hydrocarbyl or absent; and
R1-24 are selected from the group consisting of a (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, halogen atom, hydrogen atom, and combination thereof; and, wherein at least R1, R16, or both comprise of formula (II),
wherein at least one of R22 or R19 is H, and when R22 is H, then R19 is a (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom; and when R19 is H, then R22 is a (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom; and
wherein at least one of R8 or R9 is H, and when R8 is H, then R9 is a (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom; and when R9 is H, then R8 is a (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom; and
optionally two or more R groups from R9-15, R9-13, R9-12, R2-8, R4-8, R5-8 can combine together into ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms;
each of the hydrocarbyl, heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more RS substituents;
each RS independently is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C1-C18)alkyl, F3C—, FCH2O—, F2HCO—, F3CO—, R3Si—, R3Ge—, RO—, RS—, RS(O)—, RS(O)2—, R2P—, R2N—, R2C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R2NC(O)—, or two of the RS are taken together to form an unsubstituted (C1-C18)alkylene, wherein each R independently is an unsubstituted (C1-C18)alkyl; and
one or more cocatalysts; wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more cocatalysts is from 1:10,000 to 100:1; and
wherein said catalyst system has a reactivity ratio r1 in the range of greater than 100.

### Claim 2 (depends on 1)

The procatalyst according to claim 1 wherein Z is O.

### Claim 3 (depends on 1)

A polymerization process comprising the steps of:
polymerizing one or more α-olefins in the presence of one or more catalyst systems of claim 1 under olefin polymerizing conditions; and thereby forming an olefin based polymer.

### Claim 4 (depends on 1)

An olefin based polymer comprising the polymerization reaction product of:
one or more α-olefins polymerized in the presence of one or more catalyst systems of claim 1 under olefin polymerizing conditions.

### Claim 5 (depends on 1)

The procatalyst of claim 1 wherein and R1 and R16 are the same.