IP Library Granted Patent US 12,503,526
Granted Patent B2
US 12,503,526 · App. 18/734,299 · Granted Dec 23, 2025

Nickel catalysts with single alkali ions for homopolymerization and copolymerization

Inventors: Loi H. Do (Manvel, TX); Thi V. Tran (Houston, TX)
Assignee: UNIVERSITY OF HOUSTON SYSTEM
C08F4/7098C08F2/06C08F10/02C08F210/02
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,503,526
App. No.
18/734,299
Granted
Dec 23, 2025
Kind
B2
Abstract

This invention relates to nickel catalysts with alkali ions for homopolymerization and copolymerization.

Claims (51)

1 . A catalyst having a structure selected from Formula (1) and Formula (2):

wherein in Formula (1) and Formula (2):

Ar is 2,6-dimethoxyphenyl;

L is an optionally substituted phenyl group;

X is selected from hydrogen, an electron donating group, and an electron withdrawing group,

Y and Z are each independently selected from hydrogen, an electron donating group, and an electron withdrawing group, provided that Y and Z are not both hydrogen; and

R 1 , R 2 , and R 3 are each independently selected from optionally substituted aryl, optionally substituted alkyl, and optionally substituted cycloalkyl.

2 . The catalyst of claim 1 , wherein the electron donating group is selected from the group consisting of: alkoxy, phenoxy, amino, alkylamino, dialkylamino, hydroxy, alkyl, and cycloalkyl; and the electron withdrawing group is selected from the group consisting of: —NO 2 , —CN, —C(O)-alkyl, —C(O)Oalkyl, —C(O)Nalkyl, —SO 3 H, —SO 2 alkyl, —PO 3 H, —PO 3 alkyl, —CF 3 , and -halo.

3 . The catalyst of claim 1 , wherein

Ar is 2,6-dimethoxyphenyl;

L is a phenyl group;

X is methyl;

Y and Z are each independently selected from hydrogen, an electron donating group, and an electron withdrawing group, provided that Y and Z are not both hydrogen; and

R 1 , R 2 , and R 3 are each methyl.

4 . A method for catalyzing copolymerization of a first optionally substituted olefin and at least one other optionally substituted olefin, comprising:

contacting a first optionally substituted olefin and at least one other optionally substituted olefin with at least one catalyst of claim 1 and at least one alkali salt, whereby the first optionally substituted olefin and the at least one other optionally substituted olefin undergoes copolymerization, and wherein the first optionally substituted olefin and the at least one other optionally substituted olefin are different from one another.

5 . The method of claim 4 , wherein the at least one alkali salt comprises an alkali cation and a weakly coordinating anion.

6 . The method of claim 5 , wherein the alkali cation is Li + , Na + , K + , or Cs + .

7 . The method of claim 5 , wherein the weakly coordinating anion is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(pentafluorophenyl)borate, tetraphenylborate, trifluoromethylsulfonate, hexafluorophosphate, hexafluoroantimonate, or tetrafluoroborate.

8 . The method of claim 4 , wherein the at least one alkali salt is lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, potassium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or cesium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or any combination thereof.

9 . The method of claim 4 , wherein the step of contacting the first optionally substituted olefin and the at least one other optionally substituted olefin with the at least one catalyst and the at least one alkali salt is performed in the presence of at least one solvent.

10 . The method of claim 2 , wherein the at least one solvent is a non-polar solvent, a polar solvent, or combination thereof.

11 . The method of claim 4 , further comprising contacting at least one activator with the at least one catalyst, the at least one alkali salt, the first optionally substituted olefin, and the at least one other optionally substituted olefin.

12 . The method of claim 11 , wherein the at least one activator is selected from the group consisting of Ni(COD) 2 , triarylborane, methylaluminoxane, and trialkylaluminum.

13 . The method of claim 4 , wherein the first optionally substituted olefin and the at least one other optionally substituted olefin are each independently an optionally substituted terminal olefin or an optionally substituted internal olefin.

14 . The method of claim 4 , wherein the first optionally substituted olefin is ethylene.

15 . The method of claim 14 , wherein the at least one other optionally substituted olefin is selected from the group consisting of propene, butene, 1-hexene, 1-heptene, 1-octene, styrene, acrylamide, acrylic acid, acrylic ester, vinyl halide, vinyl alcohol, allyl alcohol, allylbenzene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, and 4-octene.

16 . The method of claim 4 , wherein the at least one other optionally substituted olefin is selected from the group consisting of ethylene, propene, butene, 1-hexene, 1-heptene, 1-octene, styrene, acrylamide, acrylic acid, acrylic ester, vinyl halide, vinyl alcohol, allyl alcohol, allylbenzene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, and 4-octene.

17 . The method of claim 14 , wherein the at least one other optionally substituted olefin is a polar olefin.

18 . The method of claim 4 , wherein the at least one other optionally substituted olefin is a polar olefin.

19 . A method for catalyzing homopolymerization of an optionally substituted olefin, comprising:

contacting an optionally substituted olefin with at least one catalyst of claim 1 and at least one alkali salt, whereby the optionally substituted olefin undergoes homopolymerization.

20 . The method of claim 19 , wherein the at least one alkali salt comprises an alkali cation and a weakly coordinating anion.

21 . The method of claim 20 , wherein the alkali cation is Li + , Na + , K + , or Cs + .

22 . The method of claim 20 , wherein the weakly coordinating anion is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(pentafluorophenyl)borate, tetraphenylborate, trifluoromethylsulfonate, hexafluorophosphate, hexafluoroantimonate, or tetrafluoroborate.

23 . The method of claim 19 , wherein the at least one alkali salt is lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, potassium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or cesium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or any combination thereof.

24 . The method of claim 19 , wherein the step of contacting the optionally substituted olefin with the at least one catalyst and the at least one alkali salt is performed in the presence of at least one solvent.

25 . The method of claim 24 , wherein the at least one solvent is a non-polar solvent, a polar solvent, or combination thereof.

26 . The method of claim 19 , further comprising contacting at least one activator with the at least one catalyst, the at least one alkali salt, and the optionally substituted olefin.

27 . The method of claim 26 , wherein the at least one activator is selected from the group consisting of Ni(COD) 2 , triarylborane, methylaluminoxane, and trialkylaluminum.

28 . The method of claim 19 , wherein the optionally substituted olefin is an optionally substituted terminal olefin or an optionally substituted internal olefin.

29 . The method of claim 19 , wherein the optionally substituted olefin is selected from the group consisting of ethylene, propene, butene, 1-hexene, 1-heptene, 1-octene, styrene, acrylamide, acrylic acid, acrylic ester, vinyl halide, vinyl alcohol, allyl alcohol, allylbenzene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene 3-octene, and 4-octene.

30 . The method of claim 19 , wherein the optionally substituted olefin is a polar olefin.

31 . A method for catalyzing copolymerization of a first optionally substituted olefin and at least one other optionally substituted olefin, comprising:

contacting a first optionally substituted olefin and at least one other optionally substituted olefin with at least one catalyst of claim 3 and at least one alkali salt, whereby the first optionally substituted olefin and the at least one other optionally substituted olefin undergoes copolymerization, and wherein the first optionally substituted olefin and the at least one other optionally substituted olefin are different from one another.

32 . The method of claim 31 , further comprising contacting at least one activator with the at least one catalyst, the at least one alkali salt, the first optionally substituted olefin, and the at least one other optionally substituted olefin.

33 . The method of claim 31 , wherein the step of contacting the first optionally substituted olefin and the at least one other optionally substituted olefin with the at least one catalyst and the at least one alkali salt is performed in the presence of at least one solvent.

34 . A method for catalyzing homopolymerization of an optionally substituted olefin, comprising:

contacting an optionally substituted olefin with at least one catalyst of claim 3 and at least one alkali salt, whereby the optionally substituted olefin undergoes homopolymerization.

35 . The method of claim 34 , further comprising contacting at least one activator with the at least one catalyst, the at least one alkali salt, and the optionally substituted olefin.

36 . The method of claim 34 , wherein the step of contacting the optionally substituted olefin with the at least one catalyst and the at least one alkali salt is performed in the presence of at least one solvent.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 5, 2024
From: DO, LOI H.; TRAN, THI V.
To: UNIVERSITY OF HOUSTON SYSTEM
Reel/Frame 067631/0074 →
Continuity (4)
Continuation 17982767 · Nov 8, 2022
Provisional Application 63392560 · Jul 27, 2022
Provisional Application 63402749 · Aug 31, 2022
Related Publication 20240400726A1 · Dec 5, 2024
References Cited (135)
US 7153916B2 · Tanabiki et al. · 2006 [cited by applicant]
US 8618319B2 · Shimizu et al. · 2013 [cited by applicant]
US 11358134B2 · Do et al. · 2022 [cited by applicant]
US 11712686B2 · Do et al. · 2023 [cited by applicant]
US 12043688B2 · Do et al. · 2024 [cited by applicant]
US 12043689B2 · Do et al. · 2024 [cited by applicant]
US 12049532B2 · Do et al. · 2024 [cited by applicant]
US 20100121008A1 · Marks et al. · 2010 [cited by applicant]
US 20170137549A1 · Carrow et al. · 2017 [cited by applicant]
US 20210260567A1 · Do et al. · 2021 [cited by applicant]
US 20240101726A1 · Do et al. · 2024 [cited by applicant]
US 20240101727A1 · Do et al. · 2024 [cited by applicant]
US 20240117076A1 · Do et al. · 2024 [cited by applicant]
US 20240166775A1 · Do et al. · 2024 [cited by applicant]
CN 105061505A · 2015 [cited by applicant]
WO 2024025605A1 · 2024 [cited by applicant]
WO 2024025606A1 · 2024 [cited by applicant]
WO 2024025607A1 · 2024 [cited by applicant]
WO 2024025608A1 · 2024 [cited by applicant]
ISR and WO for PCT/US2022/079451, mailed Mar. 16, 2023, 11 pages. [cited by applicant]
ISR and WO for PCT/US2022/079469 mailed Feb. 2, 2023, 11 pages. [cited by applicant]
ISR and WO for PCT/US2022/079492, mailed Feb. 3, 2023, 10 pages. [cited by applicant]
ISR and WO for PCT/US2022/079504, mailed Mar. 16, 2023, 15 pages. [cited by applicant]
Tran et al., Nickel-Alkali Heterobimetallic Catalysts for Ethylene Polymerization, Aug. 2020, 15 pages. [cited by applicant]
Tran et al., Elucidating Secondary Metal Cation Effets on Nickel Olefin Polymerization catalysts, ACS Catalysts, Aug. 11, 2020, 10:18 pp. 10760-10772. [cited by applicant]
Liu et al., Stellated Ag—Pt bimetallic nanoparticles: An effective platform for catalytic activity tuning, Scientific Reports, 4:3969, Feb. 5, 2014 [retrieved on Jan. 3, 2023] Retrieved from the internet: <URL https://w… [cited by applicant]
Loi Do, Polymerization Catalysts On-Demand: Customizing Polyolefins by Cation Selection, Texas A&M University, Presentation, Nov. 10, 2021. [cited by applicant]
Tran et al., Customizing Polymers by Controlling Cation Switching Dynamics in Non-Living Polymerization, J. Am. Chem. Soc. 2022, 144, 37, 17129-17139. [cited by applicant]
Tran et al., Customizing Polymers by Controlling Cation Switching Dynamics in Non-Living Polymerization, J. Am. Chem. Soc. 2022, 144, 37, 17129-17139, Supporting Information. [cited by applicant]
Ogilvie et al., 31P-31P Spin-Spin Coupling in Complexes Containing Two Phosphorus Ligands. J. Am. Chem. Soc. 1970, 92, 1916-1923. [cited by applicant]
Xin et al., Nickel Catalyzed Copolymerization of Ethylene and Alkyl Scrylates. J. Am. Chem. Soc. 20117, 139, 3611-3614. [cited by applicant]
Xiong et al., Acrylate-Induced β-H Elimination in Coordination Insertion Copolymerization Catalyzied by Nickel. J. Am. Chem. Soc. 2023, 145, 26463-26471. [cited by applicant]
Zhang et al., Elaborate Tuning in Ligand Makes a Big Difference in Catalytic Performance: Bulky Nickel Catalysts for (Co)polymerization of Ethylene with Promising Vinyl Polar Monomers. ChemCatChem 2019, 11, 2329-2340. [cited by applicant]
Tahmouresilerd et al., Rigidifying cation-Tunable Nickel Catalysts Increases Activity and Polar Monomer Incorporation in Ethylene and Methyl Acrylate Copolymerization. Inorg. Chem. 2021, 60, 19035-19043. [cited by applicant]
Zheng et al., Noncovalent Ni-Phenyl Interactions Promoted α-Diimine Nicek-Catalyzed Copolymerization of Ethylene and Methyl Acrylate. Macromolecules 2024, 57, 5279-5288. [cited by applicant]
Berkefeld et al., Deactivation Pathways of Neutral Ni(II) Polymerization Catalysts. J. Am. hem. Soc. 2009, 131, 1565-1574. [cited by applicant]
Apilardmongkol et al., Exploring the Reaction Mechanism of Heterobimetallic Nickel-Alkali Catalyst for Ethylene Polymerization: Secondary-Metal-Ligand Cooperative Catalysis. ChemCatChem 2022, 14, e202200028. [cited by applicant]
Cai et al., Cooperative Heterobimetallic Catalysts in Coordination Insertion Polymerization. Comments Inorg. Chem. 2019, 39, 27-50. [cited by applicant]
McInnis et al., Multinuclear Group 4 Catalysis: Olefin Polymerization Pathways Modified by Strong Metal—Metal Cooperative Effects. Acc. Chem. Res. 2014, 47, 2545-2557. [cited by applicant]
Mu et al., Recent advances in nickel mediated coploymerization of olefin with polar monomers. Coord. Chem. Rev. 2021, 435, 213802. [cited by applicant]
Mu et al., Neutral Nickel Catalysts for Olefin Homo- and Copolymerization: Relationships between Catalyst Structures and Catalytic Properties. Chem. Rev. 2015, 115, 12091-12137. [cited by applicant]
Zou et al., A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites. Nat. Commun. 2022, 13, 1954. [cited by applicant]
Mitsushi et al., Ligand-controlled insertion regioselectivity accelerates copolymerisation of ethylene with methyl acrylate by cationic bisphosphine monoxide-palladium catalyst. Chem. Sci. 2016, 7, 737-744. [cited by applicant]
Matyjaszewski, Introduction to living polymerization. Living and/or controlled polymerization. J. Phys. Org. Chem. 1995, 8, 197-207. [cited by applicant]
Webster, Living Polymerization Methods. Science 1991, 251, 887-893. [cited by applicant]
Chien et al., Two-State Propagation Mechanism for Propylene Polymerization Catalyzed by rac-[anti-Ethylidene(1-n5-tetramethylcyclopentadienyl)(1-n5-indenyl)] dimethyltitanium. J. Am. Chem. Soc. 1991, 113, 8569-8570. [cited by applicant]
Llinas et al., Crystalline-Amorphous Block Polypropylene and Nonsymmetric ansa-Metallocene Catalyzed Polymerization. Macromolecules 1992, 25, 1242-1253. [cited by applicant]
Coates et al., Oscillating Stereocontrol: A Strategy for the Synthesis of Thermplastic Elastomeric Polypropylene. Science 1995, 267, 217-219. [cited by applicant]
Busico et al., “Oscillating” Metallicene Catalysts: How Do They Oscillate? Angew. Chem. Int. Ed. 2002, 41, 505-508. [cited by applicant]
Carrow et al., Transition-Metal-Catalyzed Functional Polyolefin Synthsis: Effecting Control Through Chelating Ancillary Ligand Desgin and Mechanistic Insights. Macromolecules 2014, 47, 2541-2555. [cited by applicant]
Huhtamaki et al., Surface-wetting characterization using contact-angle measurements. Nat. Protoc. 2018, 13, 1521-1538. [cited by applicant]
Hebbar et al., Chapter 12—Contact Angle Measurments. In Membrane Characterization; Hilal, N., Ismail, A.F., Matsura, T., Oatley-Radcliffe, D., Eds.; Elsevier: 2017, p. 219-255. [cited by applicant]
Wang et al., Lewis acid modulation in phosphorus phenol nickel catalyzed ethylene polymerization and copolymerization. Polm. Chem. 2023, 14, 4933-4939. [cited by applicant]
Na et al,. Catechol-Functionalized Polyolefins. Angew. Chem. Int. Ed. 2020, 59, 7953-7959. [cited by applicant]
Brewis et al., Adhesion to polyethylene and polypropylene. Polymer 1981, 22, 7-16. [cited by applicant]
Shiraki et al., Adhesion to Untreated Polyethylene and Polypropylene by Needle-like Polyolefin Crystals. Macromolecules 2023, 56, 2429-2436. [cited by applicant]
Rusanova et al., Adhesion Properties of Polyethylene and Ethylene-Vinyl Acetate Copolymer Blend with Acrylate Copolymers of Ethylene. Polym. Sci. Ser. D 2022, 15, 494-498. [cited by applicant]
Ballard et al., Catalytic oxidatve degradation of polyethylene crystals. Eur. Polym. J. 194, 10, 829-835. [cited by applicant]
Qin et al., Photo-oxidative degradation of polyethylene/montmorillonite nanocomposite. Polym. Degra. Stabil. 2003, 81, 497-500. [cited by applicant]
Hakkarainen et al., Environmental Degradation of Polyethylene. In Long Term properties of Polyolefins; Albertsson, A.-C., Ed.; Springer Berlin Heidelberg: Berlin, Heidelberg, 2004, p. 177-199. [cited by applicant]
Ahmad et al., Pyrolysis Study of Polypropylene and Polyethylene Into Premium Oil Products. Int. J. Green Energy 2015, 12, 663-671. [cited by applicant]
Miandad et al., Effect of plastic waste types on pyrolysis liquid oil. Int. Biodeter. 2017, 119, 239-252. [cited by applicant]
Kosloski-Oh et al., Cataytic methods for chemical recycling or upcycling of commercial polymers. mater. Horiz. 2021, 8, 1084-1129. [cited by applicant]
Arroyave et all., Catalytic Chemical Recycling of Post-Consumer Polyethylebe. J. Am. Chem. Soc. 2022, 144, 23280-23285. [cited by applicant]
Conk et al., Catlytic deconstruction of waste polyethylene with ethylene to form propylene. Science 2022, 377, 1561-1566. [cited by applicant]
Wang et al., Chemical Recycling of Polyethylene by Tandem Catalytic Conversion to Propylene. J. Am. Chem. Soc. 2022, 144, 18526-18531. [cited by applicant]
Yolsal et al., A versatile modification strategy to enhance polyethylene properties through solution-state peroxide modifications. Polm. Chem. 2024, 15, 1399-1412. [cited by applicant]
Bremner et al., Peroxide modification of linear low-density polyethylene: A comparison of dialkyl peroxides. J. App. Poly. Sci. 1993, 49, 785-798. [cited by applicant]
Huang et al., TGA-FTIR study on the effect of CaCO3 on the thermal degradation of EBA copolymer. J. Anal. Appl. Pyrol. 209, 84, 124-130. [cited by applicant]
Grynova et al., Revising the mechanism of polymer autooxidation. Org. Biomol. Chem. 2011, 9, 480-490. [cited by applicant]
Bracco et al., A review of experimental studies of the role of free-radicals in polyethylene oxidation. Polym. Degrad. Stabil. 2018, 155, 67-83. [cited by applicant]
Garrett et al., Reactivity off Polyolefins toward Cumyloxy Radical: Yields and Regioselectivity of Hydrogen Atom Transfer. Macromolecules 2014, 47, 544-551. [cited by applicant]
Speight, Chapter 3—Hydrocarbons from Petroleum. In Handbook of Industrial Hydrocarbon Processes; Speight, J. G., Ed.; Gulf Professional Publishing: Boston, 2011, p. 85-126. [cited by applicant]
Fortman et al., Approaches to Sustainable and Continually Recyclables Cross-Linked Polymers. ACS Sustain. Chem. Eng. 2018, 6, 11145-11159. [cited by applicant]
Hong et al., Chemically recyclable polymers: a circular economy approach to sustainability. Green Chem. 2017, 19, 3692-3706. [cited by applicant]
Lemmens et al., Upcycling polyethylene into closed-oop recyclable polymers through titanosilicate catalyzed C-H oxidation and in-chain heteroatom insertion. Nat. Commun. 2024, 15, 9188. [cited by applicant]
Millican et al., Plastic Pollution: A Material Problem? Macromolecules 2021, 54, 4455-4469. [cited by applicant]
Rhodes, Plastic Pollution and Potential Solutions. Sci. Prog. 2018, 101, 207-260. [cited by applicant]
Drent et al., Palladium Catalysed Copolymerisation of Ethene with Alkylacrylates: Polar Comonomer Built into the Linear Polymer Chain. Chem. Commun. 2002, 7, 744-745. [cited by applicant]
Do, Cations in Action: How Secondary Metal Cations Can Play Leading Roles in Olefin Polymerization, Gordon Research Conference in Organometallic Chemistry, Oral Presentation, Jul. 9, 2024. [cited by applicant]
Do et al., Cation Tunable Copolymerization of Ethylene and Alkyl Acrylate, Gordon Research Conference in Organometallic Chemistry, Poster Presentation, Jul. 7-12, 2024. [cited by applicant]
Tran et l., Development of highly productive nickel-sodium phenoxyphosphine ethylene polymerization catalysts and their reaction temperature profiles, Polymer Chemistry, 2019, 10, 3718-3721. [cited by applicant]
Chan et al., Density Functional Study of Neural Salicylaldimanto Nickel (II) Complexes as Olefin Polymerization Catalysts, Organometallics, 2000, 19, 2741-2750. [cited by applicant]
Gewert et al., Pathways for degradation of plastic polymers floating in the marine environment, Environ. Sci.: Processes Impacts, 2015, 17, 1513-1521. [cited by applicant]
Kruszynski et al., Tuning the Adhesive Strength of Functionalized Polyolefin-Based Hot Melt Adhesives: Unexpected Results Leading to New Opportunites, Macromolecules, 2025, 58, 2894-2904. [cited by applicant]
Liang et a., A imple and versatille nickel platform for the generation of branched high molecular weight polylefins, Nature Communications, 2020, 11, 372, 1-8. [cited by applicant]
Saki et al., Copolymerization of Ethylene and Methyl Acrylate by Pyridylimino Ni(II) Catalysts Affording Hyperbranced Poly(ethylene-co-methylacrylate)s with Tunable Structures of the Ester Groups, Macromolcules, 2020, 5… [cited by applicant]
Wang et al., Efficient Suppression of Chain Transfer and Branching via Cs-Type Shielding in a Neutral Nickel(II) Catalyst, Angew. Chem. Int. Ed. 2021, 60, 4018-4022. [cited by applicant]
Zheng et al., Advance on nickel- and palladium-catalyzed insertion copolymerization of ethylene and acrylate monomers, J. Polym. Sci., 2023, 61, 2987-3021. [cited by applicant]
Tan et al., Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers, Angew. Chem. Int. Ed. 2019, 58, 7192-7200. [cited by applicant]
Lu et al., Mild Catalytic Degradation of Crystalline Polyethylene Units in a Solid State Assissted by Carboxylic Acid Groups. J. Am. Chem. Soc. 2024, 146, 19599-19608. [cited by applicant]
Rhinehart et al., A Robust Ni(II) β-Diimine Catalyst for High Temperatue Ethylene Polymerization. J. Am. Chem. Soc. 2013, 135, 16316-16319. [cited by applicant]
Takeuchi et al., Ethylene Polymerization at High Temperatures Catalyzed by Double-Decker-Type Dinuclear Iron and Cobalt Complexes: Dimer Effect on Stability of the Catalyst and Polydispersity of the Product. Organometal… [cited by applicant]
Wang et al., Robust nd Reactive Neutral Nickel Catalysts for Ethylene Polymerization with a Challenging 1, 1-Disubstituted Difunctional Polar Monomer. ACS Catal. 2021, 11, 2902-2911. [cited by applicant]
Zhang et al., Robust Bulky [P, O] Neutral Nickel Cataalystss for Copolymerization of Ehtylene with Polar Vinyl Monomers. ACS Catal. 2018, 8, 5963-5976. [cited by applicant]
Nakano et al., Elucidating the Key Role of Phosphine—Sulfonate Ligands in Palladium-Catalyzed Ethylene Plymerization: Effect of Ligand Structure on the Molecular Weight and Linearity of Polyethylene. ACS Catal. 2016, 6,… [cited by applicant]
Xiong et al., Highly Active and Thermally Robust Nickel Enolate Catalysts for the Synthesis of Ethylene-Acrylate Copolymers. Angew. Chem., Int. Ed. 2022, 61, e202206637. [cited by applicant]
Tao et al., Copolymerization of Ethylene and Polar Monomers by Using Ni/IzQO Catalysts. Angewandte Chemie International Edition 2016, 55 (8), 2835-2839. [cited by applicant]
Hustad, Frontiers in Olefin Polymerization: Reinventing the World's Most Common Synthetic Polymers, Science 2009, 325 (5941), 704-707. [cited by applicant]
Zanchin et al., Polyolefin thermoplastic elastomers from polymerization catalysis: Advantages, pitfalls and future challenges. Prog. Polym. Sci. 2021, 113, 101342. [cited by applicant]
Feldman, Polyolefin, olefin copolymers and polyolefin polyblend nanocomposites. J. Macromol. Sci. A 2016, 53, 651-658. [cited by applicant]
Chung, Functional Polyolefins for Energy Applications. Macromolecules 2013, 46, 6671-6698. [cited by applicant]
Jasinska-Walc et al., Potential of Functionalized Polyolefins in a Sustainable Polymer Economy: Synthetic Strategies and Applications. Acc. Chem. Res. 2022, 55, 1985-1996. [cited by applicant]
Chen, Coordination Polymerization of Polar Vinyl Monomers by Single-Site Metal Catalysts. Chem. Rev. 2009, 109, 5157-5214. [cited by applicant]
Chen et al., Exploring Ethylene/Polar Vinyl Monmer Copolymerizations Using Ni and Pd β-Diimine Catalysts. Acc. Chem. Res. 2018, 51, 1831-1839. [cited by applicant]
Keyes et al., Olefins and Vinyl Polar Monomers: Bridging the Gap for Next Generation Materials. Angew. Chem. Int. Ed. 2019, 58, 12370-12391. [cited by applicant]
Chen et al., Early Transition Metal Catalysis for Olefin—Polar Monomer Copolymerization. Angew. Chem. Int. Ed. 2020, 59, 14726-14735. [cited by applicant]
Jiang et al., Polar Group-Promoted Copolymerization of Ethylene and Polar Olefins, Macromolecules 2023, 56, 1547-1553. [cited by applicant]
Wang et al., Direct Synthesis of Polar-Functionalized Polyolefin Elastomers. Angew. Chem. Int. Ed. 2025, e202423814. [cited by applicant]
Yang et al., Ultrahigh Molecular Weight Ethylene—Acrylate Copolymers Synthsized with Highly Activt Neutral Nickel Catalysts. Angew. Chem. Int. Ed. 2025, e202421904. [cited by applicant]
Xiong et al., Efficient Copolymerization of Acrylate and Ethylene with Neutral P, O-Che;ated Nickel Catalysts: Mechanistic Investigations of Monomer Insertion and Chelate Formation. J. Am. Chem/ Soc. 2021, 143, 6516-652… [cited by applicant]
Sui et al., Ethylene Polymerization and Copolymerization with Polar Monomers by Catonic Phospone Phosphonic Amide Palladium Complexes. ACS Catal. 2015, 5, 5932-5937. [cited by applicant]
Contrella et al., Copolymerization and Ethylebe and Methyl Acrylate by Cationic Palladium Catalysts That Contain Phosphine-Diethyl Phosphonate Ancillary Ligands. Organometallics 2014, 33, 3546-3555. [cited by applicant]
Sita, Ex Uno Plures (“Out of One, Many”): New Paradigms for Expanding the Range of Polyolefins through Reversible Group Transfers. Angew. Chem. Int. Ed. 2009, 48, 2464-2472. [cited by applicant]
Cai et al., Fine-Tuning Nickel Phenoxyimine Olefin Polymerization Catalysts: Performance Boosting by Alkali Cations. J. Am. Chem. Soc. 2015, 137, 15501-15510. [cited by applicant]
Cai et al., Thermally Robusty Heterobimetallic Palladium—Alkali Catalsysts for Ethylene and Alkyl Acrylate Copolymerization. Organometallics 2018, 37, 3874-3882. [cited by applicant]
Kaiser et al., Photochemical Regulation of a Redox-Active Olefin Polymerization Catalysts: Controlling Polyethylene Microstructure with Visible Light. Polym. Chem. 2018, 9, 1567-1570. [cited by applicant]
Yang et al., Redox Control in Olefin Polymerization Catalysis by Phosphine—Sulfonate Palladium and Nickel Complexes. Eur. J. Inorg. Chem. 2017, 2510-2514. [cited by applicant]
Anderson et al., Redox-Active Ligands: An Andvanced Tool To Modulate Polyethylene Microstructure. J. Am. Chem. Soc. 2016, 138, 774-777. [cited by applicant]
Anderson et al., Modulating Polyolefin Copolymer Composition via Redox-Active Olefin Polymerization Catalysts. ACS Macro Lett. 2016, 5, 1029-1033. [cited by applicant]
Kaiser et al.., Recent Developments in Redox-Active Olefin Polymerization Catalysts. Coord. Chem. Rev. 2018, 372, 141-152. [cited by applicant]
Cai et al., Enhancement of Chain Growth and Chain Transfers Rates in Ethylene Polymerizations by (Phosphine-sulfonate)PdMe Catalysts by Binding of B(C6F5)3 to the Sulfonate Group. ACS Catal. 2012, 2, 1187-1195. [cited by applicant]
Wilders et al., Allosteric Effects in Ethylene Polymerization Catalysis. Enhancement of Performancr of Phosphine-Phosphinate and Phosphine-Phosphonate Palladium Alkyl Catalysts by Remote Binding of B(C6F5)3. Organometal… [cited by applicant]
Tran et al., Tunable Modalities in Polyolefin Synthesis via Coordination Insertion Catalysis. Eur. Polym. J. 2021, 142, 110100. [cited by applicant]
Johnson et al., Copolymerization of Ethylene and Acrylates by Nickel Catalysts. In Beyond Meyallocenes; American Chemical Society: 2003; vol. 857, p. 131-142. [cited by applicant]
Xiong et al., Switchable Synthesis of Ethylene/Acrylate Copolymers by a Dinickel Catalyst: Evidence for Chain Growth on Both Nickel Centers and Concepts of Cation Exchange Polymerization. ACS Catal. 2024, 14, 5260-5268. [cited by applicant]
Xiong et al., Nickel-Based Heterometallic Catalysts for Ethylene-Acrylate Copolymerization: Interrogating Effects of Secondary Metal Additives. Organometallics 2023, 42, 2849-2855. [cited by applicant]
Chiu et al., Ethylene Polymerization Catalyzed by Bridging Ni/Zn Heterobimetallics. Dalton Trans. 2017, 46, 5513-5517. [cited by applicant]
Akita et al., Copolymerization of Ethylene and Methyl Acrylate by Palladium Catalysts Bearing IzQO Ligands Containing Methoxyethyl Ether Moieties and Salt Effects for Polymerization. Polym. J. 2021, 53, 1057-1060. [cited by applicant]
Baur et al., Polyethylene materials with in-chain ketones from non-alternating catalttic copolymerization. Science 2021, 374, 604-607. [cited by applicant]
Kochi et al., Sythesis of anionic methylpalladium complexes with phosphine-sulfonate ligands and their activities for olefin polymerization. Dalton Trans. 2006-, 25-27. [cited by applicant]
Chen et al., A Versatile Ligand Platform for Palladium- and Nickel-Catalyzed Ethylebe Copolymerization with Polar Monomers, Angew. Chem. Int. Ed., 2018, 57, 3094-3098. [cited by applicant]
Jian et al., A N-bridges strategy enables hemilabile phosphine-carbonyl palladium and nickel catalysts to mediate ethylene polymerization and copolymerization with polar vinyl monomers, Polym. Chem., 2020, 11, 6187-6193. [cited by applicant]
Xu et al., Enhancing Chain Initiation Efficiency in the Cationic Allyl-Nickel Catalyzed (Co)Polymerization of Ethylene and Methyl Acrylate, Inorg. Chem., 2020, 59, 4475-4482. [cited by applicant]
Chen et al., A Second-Coordination-Sphere Strategy to Modulate Nickel- and Palladium-Catalyzed Olefin Polymerization and Copolymerization, Angew. Chem. Int. Ed., 2017, 56, 11604-11609. [cited by applicant]
Cited By (1)
US 12,662,556