# US 2021/0332170 A1 · Modified ziegler-natta (pro) catalysts and system > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2021/0332170 A1 - Document ID: US20210332170A1 - Status: Published application - Kind: A1 - Application number: 17/371,728 - Filed: 2021-07-09 - Published: 2021-10-28 - Earliest claimed: 2016-09-29 - Assignees: Dow Global Technologies LLC - Applicants: Dow Global Technologies LLC - Inventors: Linfeng Chen; Mehmet Demirors - Web page: https://patentgrep.com/patent/US20210332170A1 ## CPC - C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers - C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond - C08F 2410/04: Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract A modified Ziegler-Natta procatalyst that is a product mixture of modifying an initial Ziegler-Natta procatalyst with a molecular (pro)catalyst, and optionally an activator, the modifying occurring before activating the modified Ziegler-Natta procatalyst with an activator and before contacting the modified Ziegler-Natta procatalyst with a polymerizable olefin. Also, a modified catalyst system prepared therefrom, methods of preparing the modified Ziegler-Natta procatalyst and the modified catalyst system, a method of polymerizing an olefin using the modified catalyst system, and a polyolefin product made thereby. ## Claims ### Claim at position 1 -15. (canceled) ### Claim 16 A modified Ziegler-Natta procatalyst that is prepared by mixing an initial Ziegler-Natta procatalyst and a molecular (pro)catalyst together in (C) a saturated or aromatic hydrocarbon liquid under modifying conditions comprising a modifying temperature less than 100° C. and a modifying time of at least 1 minute, and optionally an activator, to give the modified Ziegler-Natta procatalyst; wherein the modified Ziegler-Natta procatalyst is free of a trialkylaluminum; and wherein the activator is selected from the group consisting of: (i) a (A) hydrocarbylaluminoxane; (ii) an organoborate or an organoboron; and (iii) both (i) and (ii). ### Claim 17 (depends on 16) The modified Ziegler-Natta procatalyst of claim 16 wherein the activator is present and is selected from the group consisting of: (i) the (A) hydrocarbylaluminoxane or (iii) both (i) the (A) hydrocarbylaluminoxane and (ii) the organoborate or organoboron. ### Claim 18 (depends on 16) The modified Ziegler-Natta procatalyst of claim 16: (i) wherein the initial Ziegler-Natta procatalyst is (B) a magnesium halide-supported titanium procatalyst; wherein the (B) magnesium halide-supported titanium procatalyst has been prepared by contacting (D) a solid particulate consisting essentially of magnesium halide with (E) titanium tetrachloride in the (C) saturated or aromatic hydrocarbon liquid so as to give the (B) magnesium halide-supported titanium procatalyst; (ii) wherein the molecular (pro)catalyst consists essentially of a molecular ligand-metal complex (pro)catalyst; or (iii) both (i) and (ii). ### Claim 19 (depends on 16) The modified Ziegler-Natta procatalyst of claim 16 wherein the modifying conditions comprise: (i) a modifying temperature from 0° C. to 50° C.; (ii) a modifying time from 3 hours to 3 months; (iii) an inert gas atmosphere (e.g., molecular nitrogen, helium, argon, or a mixture of any two or more thereof); (iv) both (i) and (ii); (v) both (i) and (iii); (vi) both (ii) and (iii); or (vii) each of (i), (ii), and (iii). ### Claim 20 (depends on 16) The modified Ziegler-Natta procatalyst of claim 16 wherein: (i) the initial magnesium halide-supported titanium procatalyst is free of Al (molar ratio of Al/Mg=0); (ii) the initial magnesium halide-supported titanium procatalyst has a molar ratio of Al/Mg from >0 to <0.05; (iii) the magnesium halide of the initial magnesium halide-supported titanium procatalyst is magnesium chloride; (iv) the magnesium halide of the initial magnesium halide-supported titanium procatalyst is magnesium bromide; (v) both (i) and (iii); (vi) both (i) and (iv); (vii) both (ii) and (iii); (viii) both (ii) and (iv). ### Claim 21 (depends on 16) The modified Ziegler-Natta procatalyst of claim 16 wherein: (i) the (D) solid particulate consisting essentially of magnesium halide has a Brunauer, Emmett, Teller (BET) surface area of >200 square meters per gram (m2/g) as measured by Brunauer, Emmett, Teller (BET) Surface Area Method; or (ii) the (D) solid particulate consisting essentially of magnesium halide has been prepared by contacting a solution of (F) a dialkylmagnesium compound dissolved in the (C) saturated or aromatic hydrocarbon liquid with 1.95 to 2.05 mole equivalents of hydrogen halide to give a suspension of the (D) solid particulate consisting essentially of magnesium halide in the (C) saturated or aromatic hydrocarbon liquid; or (iii) both (i) and (ii). ### Claim 22 (depends on 16) The modified Ziegler-Natta procatalyst of claim 16 wherein the activator used with the modified Ziegler-Natta procatalyst comprises the (A) hydrocarbylaluminoxane. ### Claim 23 (depends on 16) The modified Ziegler-Natta procatalyst of claim 16 wherein the molecular ligand-metal (pro)catalyst comprises: (i) a cyclopentadienyl ligand-metal complex (pro)catalyst; (ii) a cyclopentadienyl-free ligand-metal complex (pro)catalyst; or (iii) both (i) and (ii). ### Claim 24 (depends on 16) A modified catalyst system comprising a product of a reaction of the modified Ziegler-Natta procatalyst of claim 16 with an activator. ### Claim 25 (depends on 24) The modified catalyst system of claim 24 further comprising (G) an organoborate or (H) an organoboron.