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WO2024155919A2 - Copolymères multiblocs recyclables - Google Patents

Copolymères multiblocs recyclables Download PDF

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Publication number
WO2024155919A2
WO2024155919A2 PCT/US2024/012214 US2024012214W WO2024155919A2 WO 2024155919 A2 WO2024155919 A2 WO 2024155919A2 US 2024012214 W US2024012214 W US 2024012214W WO 2024155919 A2 WO2024155919 A2 WO 2024155919A2
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formula
difunctionalized
compound
catalyst
copolymer
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WO2024155919A3 (fr
Inventor
Garret MIYAKE
Katherine HARRY
Yucheng Zhao
Emma RETTNER
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Colorado State University Research Foundation
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Colorado State University Research Foundation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • Embodiments of the present disclosure generally relate to multiblock copolymers and to uses thereof. Embodiments of the present disclosure also generally relate to processes for making multiblock copolymers, to processes for depolymerizing multiblock copolymers, and to processes for chemically recycling multiblock copolymers.
  • Valorization of plastics is an alternative approach to recapture resources but yields new chemicals rather than original monomer feedstocks.
  • PE polyethylene
  • hydrocarbons for new applications including liquid fuels or waxes.
  • conventional technologies are unable to achieve a closed-loop life cycle of plastics that are chemically depolymerizable back to the original monomers for purification and repolymerization. These technologies are not yet economically or technologically viable replacements for polyolefins because the complete depolymerization back to monomer maximizes the number of chemical bonds that must be broken and reformed during the recycling process, necessitating extreme reaction efficiency and increased energy inputs.
  • the step-growth condensation polymerization of diester-functionalized alkanes with diols results in PE-like materials possessing ester functionality that enables depolymerization back to the building blocks for repolymerization.
  • ester functionality does not drastically impact the unit-cell identity relative to PE but does lead to decreased lamellar thickness, destabilization of the crystal lattice, and lowering of the melting transition temperature (T m ).
  • condensation polymerization of dicarboxyl aliphatic oligomeric building blocks with small-molecule diols affords plastics with lower ester content for improved thermal and materials properties more comparable to PE
  • traditional step-growth polymerizations require precise stoichiometry matching of complimentary polymerizable groups (i.e., esters and alcohols) of the monomers to be coupled to achieve high molecular weight and technologically useful polymers. Even slight imbalances in stoichiometry result in drastically reduced polymer molecular weights and associated properties. Therefore, because of this constraint it is difficult to access polymers that possess disparate properties through a step-growth polymerization without completely changing the chemical identity of the building blocks.
  • Embodiments of the present disclosure generally relate to multiblock copolymers and to uses thereof. Embodiments of the present disclosure also generally relate to processes for making multiblock copolymers, to processes for depolymerizing multiblock copolymers, and to processes for chemically recycling multiblock copolymers.
  • embodiments described herein overcome the constraints of precise stoichiometric matching of chain end groups and allow for deviations in monomer feed ratios. Accordingly, and in contrast to conventional technologies, embodiments described herein can enable access to polymers that possess disparate properties through a step-growth polymerization without completely changing the chemical identity of the building blocks.
  • Embodiments described herein show various non-limiting advantages over conventional polyolefins such as chemical recyclability and diverse mechanical properties.
  • the inventors construct multiblock polymers from hard and soft oligomeric building blocks synthesized by, for example, ruthenium-mediated ring-opening metathesis polymerization of cyclooctenes.
  • the multiblock polymers can exhibit broad mechanical properties, spanning elastomers to plastomers to thermoplastics, while integrating, for example, a high melting transition temperature (T m ) and a low glass transition temperature (T g ), making them suitable for use across diverse applications.
  • T m high melting transition temperature
  • T g low glass transition temperature
  • multiblock polymers described herein may have a T m of about 128°C and/or a T g as low as -60°C, though other values are contemplated.
  • the different plastics can be combined and efficiently deconstructed back to the fundamental hard and soft building blocks for separation and repolymerization to realize a closed-loop recycling process.
  • a process for forming a copolymer includes forming a first reaction mixture comprising a first difunctionalized compound, and a second difunctionalized compound, wherein: the first difunctionalized compound comprises a compound having two first reactive chain end groups; the second difunctionalized compound comprising a compound having two second reactive chain end groups, the second difunctionalized compound being different from the first difunctionalized compound; and the two second reactive chain end groups of the second difunctionalized compound are identical to the two first reactive chain end groups of the first difunctionalized compound.
  • the process further includes introducing a catalyst, and an optional solvent with the first reaction mixture to form a second reaction mixture.
  • the process further includes reacting the second reaction mixture to induce step-growth polymerization of the first difunctionalized compound and the second difunctionalized compound to form a copolymer comprising a reaction product or an adduct of the first and second difunctionalized compounds.
  • a process for forming a copolymer includes forming a first reaction mixture comprising a first difunctionalized compound, and a second difunctionalized compound, wherein: the first difunctionalized compound comprises a linear aliphatic compound having two first reactive chain end groups; the second difunctionalized compound comprises a branched aliphatic compound having two second reactive chain end groups; and the two second reactive chain groups of the second difunctionalized compound are identical to the two first reactive chain end groups of the first difunctionalized compound.
  • the process further includes introducing a pincer catalyst, a base, and an optional solvent with the first reaction mixture to form a second reaction mixture.
  • the process further includes reacting the second reaction mixture to induce step-growth polymerization of the first difunctionalized compound and the second difunctionalized compound to form a copolymer comprising a reaction product or an adduct of the first and second difunctionalized compounds.
  • a process for decomposing a copolymer includes forming a first reaction mixture comprising a copolymer, a depolymerization pincer catalyst or a heterogeneous metal catalyst, an optional base, and an optional solvent.
  • the process further includes introducing hydrogen gas with the first reaction mixture to form a second reaction mixture.
  • the process further includes decomposing the copolymer to a reaction product mixture comprising a first difunctionalized compound and a second difunctionalized compound that is different from the first difunctionalized compound.
  • a process includes performing a step-growth polymerization on a reaction mixture to form a copolymer comprising a reaction product or an adduct of a first difunctionalized compound and a second difunctionalized compound.
  • the reaction mixture comprises the first difunctionalized compound comprising a linear aliphatic compound having two first reactive chain end groups; the second difunctionalized compound comprising a branched aliphatic compound having two second reactive chain end groups, the two second reactive chain groups of the second difunctionalized compound being identical to the two first reactive chain end groups of the first difunctionalized compound; a transition metal catalyst comprising a tridentate ligand and a Group 7 to Group 10 metal of the periodic table of the elements, the Group 7 to Group 10 metal selected from the group consisting of Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt; and a base.
  • FIGS. 1A and IB show a non-limiting overview of chemically recyclable polyolefin-like multiblock materials with tunable properties from polymerization of hard and soft oligomers according to at least one embodiment of the present disclosure.
  • FIG. 2A shows a 400 MHz proton nuclear magnetic resonance ( X H NMR) spectrum of cis-hexadec-6-ene-l,16-diol in deuterated chloroform (CDCh) collected at 298 K according to at least one embodiment of the present disclosure.
  • X H NMR proton nuclear magnetic resonance
  • FIG. 2B shows a 500 MHz 'H NMR spectrum of an example hard oligomeric block HO-HB-OH (hydrogenated HO-poly(cyclooctene)-OH) in deuterated toluene (toluene-d8) collected at 373 K according to at least one embodiment of the present disclosure.
  • FIG. 2C shows a 400 MHz 'H NMR spectrum of an example soft oligomeric block HO-SB-OH (hydrogenated HO-poly(3-hexylcyclooctene)-OH) in CDCh collected at 298 K according to at least one embodiment of the present disclosure.
  • FIG. 2D shows a 400 MHz 1 H NMR spectrum of an example polymer PE0 (0% hard blocks) in CDCh collected at 298 K according to at least one embodiment of the present disclosure.
  • FIG. 2E shows a 500 MHz 'H NMR spectrum of an example multiblock copolymer PE20 (20% hard blocks) in tetrachloroethane-d2 collected at 373 K according to at least one embodiment of the present disclosure.
  • FIG. 2F shows a 500 MHz 'H NMR spectrum of an example multiblock copolymer PE40 (40% hard blocks) in tetrachloroethane-d2 collected at 373 K according to at least one embodiment of the present disclosure.
  • FIG. 2G shows a 500 MHz 'H NMR spectrum of an example multiblock copolymer PE60 (60% hard blocks) in tetrachloroethane-d2 collected at 373 K according to at least one embodiment of the present disclosure.
  • FIG. 2H shows a 500 MHz 'H NMR spectrum of an example multiblock copolymer PE80 (80% hard blocks) in tetrachloroethane-d2 collected at 373 K according to at least one embodiment of the present disclosure.
  • FIG. 21 shows a 500 MHz 'H NMR spectrum of an example polymer PEI 00 (100% hard blocks) in tetrachloroethane-d2 collected at 373 K according to at least one embodiment of the present disclosure.
  • FIGS. 3A and 3B show high temperature-size exclusion chromatography (HT-SEC) traces of an example hard oligomeric block HO-HB-OH and an example soft oligomeric block HO-SB-OH, respectively, according to at least one embodiment of the present disclosure, (mobile phase: 1, 2, 4-tri chlorobenzene (TCB); temperature 160°C).
  • HT-SEC high temperature-size exclusion chromatography
  • FIGS. 3C and 3D show differential scanning calorimetry (DSC) traces of an example hard oligomeric block HO-HB-OH and an example soft oligomeric block HO-SB-OH, respectively, according to at least one embodiment of the present disclosure.
  • FIGS. 4A-4F show HT-SEC traces of example multiblock copolymers PEO, PE20, PE40, PE60, PE80, and PEI 00 in comparison to high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) according to at least one embodiment of the present disclosure.
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • FIG. 5A shows overlayed Fourier-transform infrared (FT-IR) spectra of an example PE 100 and HDPE according to at least one embodiment of the present disclosure.
  • FIG. 5B shows overlayed Fourier-transform infrared (FT-IR) spectra of an example multiblock copolymer PE80 and HDPE according to at least one embodiment of the present disclosure.
  • FIG. 6 shows stacked carbon ( 13 C) NMR spectra of HDPE, LLDPE, and an example multiblock copolymer PE80 according to at least one embodiment of the present disclosure.
  • FIG. 7 shows stacked 1 H NMR spectra and C6 branching (in mol%) of example multiblock copolymers PEO, PE20, PE40, PE60, PE80, and PE 100 according to at least one embodiment of the present disclosure.
  • FIG. 8 A shows stress-strain curves of example PE 100 made using catalyst Ru-1 at different catalyst loadings according to at least one embodiment of the present disclosure.
  • FIG. 8B shows stress-strain curves of example PE 100 made using catalyst Ru-2 at different catalyst loadings according to at least one embodiment of the present disclosure.
  • FIG. 8C shows Young’s modulus data of example PE 100 according to at least one embodiment of the present disclosure.
  • FIG. 9B shows photographs of example PE 100 made using catalyst Ru-2 according to at least one embodiment of the present disclosure.
  • FIGS. 10A-10H show thermogravimetric analysis data — decomposition temperature at 5% weight loss (Tas) — of example multiblock copolymers, HDPE, and LLDPE according to at least one embodiment of the present disclosure.
  • FIG. 11 shows normalized DSC traces and degree of crystallinity (X c ) values for example multiblock copolymers, HDPE, and LLDPE according to at least one embodiment of the present disclosure.
  • FIGS. 12A-12H shows DSC traces for example multiblock copolymers, HDPE, and LLDPE, including both heating and cooling scans (scan rate of about 10°C/min) according to at least one embodiment of the present disclosure. The data was collected from the second heating cycle.
  • FIG. 13 A shows dynamic mechanical relaxation behavior, specifically storage modulus (E’), for multiblock polymers and polyethylene controls (HDPE and LLDPE) according to at least one embodiment of the present disclosure.
  • FIG. 13B shows dynamic mechanical relaxation behavior, specifically loss modulus (E”), for multiblock polymers and polyethylene controls (HDPE and LLDPE) according to at least one embodiment of the present disclosure.
  • E loss modulus
  • FIG. 13C shows dynamic mechanical relaxation behavior, specifically tan( ⁇ 5), for multiblock polymers and polyethylene controls (HDPE and LLDPE) according to at least one embodiment of the present disclosure.
  • FIG. 14 shows melting temperature data for example multiblock copolymers, commercial olefin block copolymers (OBCs), HDPE, LLDPE, and statistical olefin copolymers as a function of density according to at least one embodiment of the present disclosure.
  • OBCs commercial olefin block copolymers
  • HDPE high density polyethylene
  • LLDPE low density polyethylene
  • statistical olefin copolymers as a function of density according to at least one embodiment of the present disclosure.
  • FIG. 15 shows overlaid X-ray scattering patterns for example multiblock polymers and polyethylene controls according to at least one embodiment of the present disclosure.
  • FIGS. 16A-16H show polarized light optical microscopy (PLOM) images, at 500* magnification, of example multiblock copolymers and polyethylene controls according to at least one embodiment of the present disclosure.
  • FIG. 17 shows the relationship of creep compliance with step time for example multiblock copolymers and polyethylene controls according to at least one embodiment of the present disclosure.
  • FIG. 18 shows stress-strain curves for example multiblock copolymers and polyethylene controls according to at least one embodiment of the present disclosure.
  • FIGS. 19A-19H show tensile stress-strain curves of example multiblock copolymers and polyethylene controls according to at least one embodiment of the present disclosure.
  • FIG. 20A-20F shows photographs of example multiblock copolymers after tensile testing according to at least one embodiment of the present disclosure.
  • FIG. 21 is a bar chart showing Young’s modulus (E) of example multiblock copolymers and polyethylene controls according to at least one embodiment of the present disclosure. Error bars represent standard deviations from the mean value of four to six samples.
  • FIG. 22A shows Young’s modulus data of example multiblock copolymers, commercial OBCs, random copolymers, HDPE, and LLDPE as a function of density according to at least one embodiment of the present disclosure.
  • FIG. 22B shows elongation at break data of example multiblock copolymers, commercial OBCs, random copolymers, HDPE, and LLDPE as a function of density according to at least one embodiment of the present disclosure.
  • FIG. 23 shows property comparison data of toughness and modulus (E) between example multiblock copolymers and polyethylene controls according to at least one embodiment of the present disclosure. Error bars represent standard deviations from the mean value of four to six samples.
  • FIG. 24 is a series of photographs showing the chemical recycling of mixed multiblock copolymers (PE0-PE100) according to at least one embodiment of the present disclosure.
  • FIG. 25 shows 500 MHz 'H NMR spectra of the mixed multiblock copolymers (PE0-PE100; tetrachloroethane-d2; 383 K) before recycling and after recycling (mixture of oligomers; toluene-d8; 383 K) according to at least one embodiment of the present disclosure.
  • FIG. 26A shows a 500 MHz 'H NMR spectrum (tetrachloroethane-d2; 383 K) of recycled and purified hard block oligomers (HO-HB-OH) according to at least one embodiment of the present disclosure.
  • FIG. 26B shows a 500 MHz 1 H NMR spectrum (tetrachloroethane-d2; 298 K) of recycled and purified soft block oligomers (HO-SB-OH) according to at least one embodiment of the present disclosure.
  • FIG. 27 shows overlaid HT-SEC traces of an example multiblock copolymer (virgin PE80), repolymerized 1 x (PE80 RP-1), repolymerized 2* (PE80 RP- 2), and repolymerized 3* (PE80 RP-3) according to at least one embodiment of the present disclosure.
  • FIG. 28A shows DSC traces of virgin PE80 and repolymerized samples — PE80 RP-1, PE80 RP-2, and PE80 RP-3 — according to at least one embodiment of the present disclosure.
  • FIG. 28B shows TGA traces of virgin PE80 and repolymerized samples — PE80 RP-1, PE80 RP-2, and PE80 RP-3 — according to at least one embodiment of the present disclosure.
  • FIG. 29A shows stress-strain curves of virgin PE80 and repolymerized samples — PE80 RP-1, PE80 RP-2, and PE80 RP-3 — according to at least one embodiment of the present disclosure.
  • FIG. 29B shows tensile strength and toughness data of virgin PE80 and repolymerized samples — PE80 RP-1, PE80 RP-2, and PE80 RP-3 — according to at least one embodiment of the present disclosure. Error bars represent standard deviations from the mean value of four to five samples.
  • FIG. 30A shows tensile testing data of recycled/repolymerized l x (PE80 RP-1) according to at least one embodiment of the present disclosure.
  • FIG. 30B shows tensile testing data of recycled/repolymerized 2x (PE80 RP-2) according to at least one embodiment of the present disclosure.
  • FIG. 30C shows tensile testing data of recycled/repolymerized 3x (PE80 RP-3) according to at least one embodiment of the present disclosure.
  • FIG. 30D shows modulus data comparing a virgin PE80 multiblock copolymer and recycled/repolymerized samples according to at least one embodiment of the present disclosure.
  • FIG. 31A shows a 500 MHz 'H NMR spectrum (tetrachloroethane-d2; 383 K) of recycled and purified hard block (HO-HB-OH) and soft block (HO-SB-OH) oligomers after depolymerization for about 72 hours according to at least one embodiment of the present disclosure.
  • FIG. 3 IB is a series of photographs showing the depolymerization of a mixture of polypropylene (PP) and example multiblock copolymer PE60 according to at least one embodiment of the present disclosure.
  • the photographs show the polyolefin waste stream in toluene (left panel), reaction after 72 hours (middle panel), and the separated and purified PP, hard block oligomer HO-HB-OH, and soft block oligomer HO-SB-OH (right panel).
  • FIG. 32A is a series of photographs of the depolymerization of a mixture of PP and example multiblock copolymer PE60 at about 175 °C for about 24 hours. The photographs show the PP/PE60 mixture (left panel), reaction after about 24 hours (center panel), and the separated and purified PP, hard block oligomer HO-HB-OH, and soft block oligomer HO-SB-OH (right panel).
  • FIG. 32B shows stacked 500 MHz 1 H NMR spectra (tetrachloroethane-d2) of separated and purified samples from the depolymerization of the PP/PE60 mixture according to at least one embodiment of the present disclosure.
  • the 1 H NMR spectra were collected at 298 K for HO-HB-OH, at 383 K for HO-SB-OH, and 403 K for PP.
  • Figures included herein illustrate various embodiments of the disclosure. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
  • Embodiments of the present disclosure generally relate to multiblock copolymers and to uses thereof. Embodiments of the present disclosure also generally relate to processes for making multiblock copolymers, to processes for depolymerizing multiblock copolymers, and to processes for chemically recycling multiblock copolymers.
  • the inventors have discovered a systems and processes that, e.g., address challenges in plastics recycling and mixed plastics recycling.
  • a system or process that includes forming multiblock materials (such as multiblock polyolefin-like polymers) with tunable properties that can be depolymerized back to their monomers or oligomers for purification and/or recycling.
  • the multiblock polymers can possess unique properties, such as a high T m and a low T g , with varying densities that can range from, e.g., 0.75 g/cm 3 to 1.20 g/cm 3 , though other densities are contemplated.
  • compositions can include component(s) of the composition, reaction product(s) of two or more components of the composition, a remainder balance of remaining starting component(s), or combinations thereof.
  • compositions of the present disclosure can be prepared by any suitable mixing process.
  • reaction mixture can include component(s) of the reaction mixture, reaction product(s) of two or more components of the reaction mixture, a remainder balance of remaining starting component(s), or combinations thereof. Reaction mixtures of the present disclosure can be prepared by any suitable mixing process.
  • reference to chemical compound without specifying a particular isomer expressly discloses all isomers (such as n-butanol, iso-butanol, sec-butanol, and tert-butanol).
  • reference to a chemical compound having 4 carbon atoms expressly discloses all isomers thereof.
  • a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomer, diastereomer, and enantiomer of the compound described individually or in any combination.
  • Polyolefins are types of polymers with the general formula (CH2CHR) n where R is an alkyl group and are derived from olefins or alkenes.
  • Traditional polyolefins include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), polypropylene, polyoctene, and polyalphaolefins (PAOs).
  • Embodiments described herein enable synthesis of, for example, polymers that are not polyolefins but have polyolefin properties and are therefore polyolefin-like.
  • polyolefin-like refers to an oligomer or polymer that may be characterized as having one or more polyolefin properties but includes functionality that is not strictly alkyl.
  • step-growth polymerization is the requirement of precise stoichiometric matching of complimentary polymerizable groups of the monomers to be coupled to achieve high molecular weight and technologically useful polymers. Even slight imbalances in stoichiometry result in drastically reduced polymer molecular weights and associated properties. Because of this constraint, it is difficult to access polymers that possess disparate properties through traditional step-growth polymerization without completely changing the chemical identity of the building blocks.
  • step-growth polymerization process that are free of precise stoichiometric matching of chain end groups and allow for deviations in monomer feed ratios.
  • a step-growth polymerization of monomers possessing identical chain end groups is described.
  • Such embodiments described herein overcome the challenges of traditional step growth polymerization, allows varying block ratios, and for modulation of the monomer feed composition to produce diverse high-molecular weight polymers with functionality designed for recyclability (FIG. 1A).
  • FIG. 1A shows a step-growth polymerization of monomers possessing identical chain end groups.
  • FIG. 1A shows a non-limiting overview 100 of chemically recyclable polyolefin-like multiblock materials 101 with tunable properties from polymerization 103 of telechelic oligomers 102 represented by a “hard” building block 102a (or hard oligomer) and a “soft” building block 102b (or soft oligomer).
  • the polymerization 103 is a step-growth polymerization with the oligomers having a common chain end-group to create diverse plastics such as thermoplastics 101a, plastomers 101b, and elastomers 101c.
  • the plastics e.g., polyolefin-like multiblock materials 101
  • telechelic oligomers 132 a functionalized linear aliphatic oligomer 132a (e.g., hard building block 102a) and a functionalized branched aliphatic oligomer 132b (e.g., soft building block 102b) — are polymerized by use of a catalyst 134, such as a transition metal Pincer type catalyst, to form a polyolefin-like multiblock polymer 131a as an example plastic 131.
  • a catalyst 134 such as a transition metal Pincer type catalyst
  • the hard and soft oligomers are functionalized with a hydroxyl group (-OH) on the chain ends (see chain ends 137 of the oligomers and polymer).
  • the polymer includes an ester linkage that chemically attaches the hard oligomer and the soft oligomers (see linker 139).
  • the polymerization 133 and depolymerization 135 can involve the removal and incorporation of hydrogen (H2), the simplest and smallest molecule possible for a condensation polymerization. It is noted that the chemical structures and functionality shown in FIG. IB are for illustrative purposes only and are not limiting.
  • R can be positioned on other carbons of the oligomer and the number of carbons in each oligomer can be different.
  • the hydroxyl groups on the chain ends 137 of the oligomers and polymers can be substituted for other functionality based on, e.g., the telechelic oligomers utilized for the polymerization, and the ester of linker 139 in the formed polymer can be different based on, e.g., the telechelic oligomers utilized for the polymerization.
  • the polyolefin-like multiblock polymer 131a is made from hard and soft aliphatic oligomeric building blocks and can have various desired properties that can be tuned based on, e.g., ratio of the two types of blocks.
  • the polyolefin-like multiblock polymer 131a can be depolymerized 135 back to hard and soft building blocks for separation and repolymerization to realize a closed-loop recycling process.
  • different multiblock polymers can be mixed and depolymerized back to their building blocks for purification and repolymerization, demonstrating the recycling of these different plastics.
  • the strategy shown in FIGS. 1A and IB represents closed-loop recycling of mixed plastics catalyzed by metal complexes.
  • the polymerization described herein can enable formation of multiblock polymers that can integrate multiple properties into a single macromolecule.
  • the polymerization can be used to form multiblock polymers with sequences of crystalline high-density PE and amorphous low-density polyolefin with both a high melting transition temperature (T m ) and a low glass transition temperature (T g ), which provide strength and elasticity across a wide range of operating temperatures and conditions.
  • T m high melting transition temperature
  • T g low glass transition temperature
  • the T m of ethylene and a-olefin statistical copolymers decreases with increasing a-olefin incorporation.
  • Embodiments of the present disclosure also generally relate to processes for forming a polymer or a copolymer.
  • the copolymer may be a multiblock copolymer.
  • the copolymer may be an adduct or reaction product of a first difunctionalized compound and a second difunctionalized compound.
  • the first difunctionalized compound can be a monomer, a pre-polymer, or an oligomer.
  • the second difunctionalized compound can be a monomer, a pre-polymer or an oligomer.
  • a process for forming a copolymer includes forming a composition (or a reaction mixture) that includes a first difunctionalized compound, a second difunctionalized compound, a catalyst (such as, e.g., a transition metal pincer complex, and/or a heterogeneous metal catalyst, where the transition metal pincer complex and/or the heterogeneous metal catalyst includes one or more metals), an optional base, and an optional solvent.
  • the process may further include converting (or reacting) the composition or reaction mixture under conditions effective to form a copolymer comprising a reaction product or an adduct of the first difunctionalized compound and the second difunctionalized compound. Converting the reaction mixture or composition includes inducing a step growth polymerization. Conversion, or polymerization, conditions are described below.
  • the first difunctionalized compound (e.g., a pre-polymer or oligomer) can be a “hard” building block 102a/132a while the second difunctionalized compound (e.g., a pre-polymer or oligomer) can be a “soft” building block 102b/132b.
  • a step-growth polymerization of the hard and soft building blocks can be used to form myriad polyolefin-like multiblock materials (e.g., plastics).
  • the terms “hard” and “soft” relate to the crystallinity and/or modulus of the monomer, prepolymer, or oligomer utilized for the polymerization. Generally, softer monomers, prepolymers, or oligomers have higher levels branching or a lower Tg and modulus while harder monomers, pre-polymers, or oligomers have less branching and are more linear and a higher modulus.
  • the first and second difunctionalized compound Prior to the polymerization, the first and second difunctionalized compound are formed.
  • Compounds for the polymerization include a first difunctionalized compound and a second difunctionalized compound, wherein the first and second difunctionalized compounds can be the same or different compounds.
  • the difunctionalized compounds can be monomers, oligomers, or polymers.
  • the term difunctionalized can be used interchangeably with the term “telechelic” unless specified to the contrary or the context clearly indicates otherwise.
  • the term “telechelic” refers to a monomer, oligomer, pre-polymer, or polymer having at least two reactive chain end groups that can be further polymerized by the reactive chain end groups.
  • the reactive chain end groups disclosed herein include, but are not limited to, hydroxy groups, thiol groups, amine groups, isocyanate groups, carboxylic acid groups, halogens, epoxy groups, aldehyde groups, alkene groups, or combinations thereof.
  • the two reactive ends of the telechelic monomer, oligomer, pre-polymer, or polymer can possess the same functionality or different functionality.
  • first difunctionalized pre-polymer “first difunctionalized oligomer”, “first telechelic pre-polymer”, “first telechelic oligomer”, and “first difunctionalized compound” are used interchangeably herein.
  • second difunctionalized pre-polymer “second difunctionalized oligomer”, “second telechelic pre-polymer”, “second telechelic oligomer”, and “second difunctionalized compound” are used interchangeably herein.
  • the first difunctionalized compound comprises two first reactive chain end groups.
  • the second difunctionalized compound comprises two second reactive chain end groups.
  • the two second reactive chain end groups of the second difunctionalized compound are identical to the two first reactive chain end groups of the first difunctionalized compound.
  • step-growth polymerization processes that are free of precise stoichiometric matching of chain end groups and allow for deviations in monomer feed ratios.
  • a step-growth polymerization of monomers, oligomers, or pre-polymers, possessing identical chain end groups is described.
  • Such embodiments described herein overcome the challenges of traditional step growth polymerization, allows varying block ratios, and for modulation of the monomer feed composition to produce diverse high- molecular weight polymers with functionality designed for recyclability.
  • the first difunctionalized compound can include a difunctionalized linear aliphatic compound and is a “hard” building block.
  • the first difunctionalized compound can be represented by Formula (I):
  • A can be a hydrocarbyl (CH2) P wherein p is any suitable number of carbon atoms such as from about 1 to about 400 carbon atoms, such as from about 2 to about 200 carbon atoms, such as from about 3 to about 200 carbon atoms, such as from about 5 to about 100 carbon atoms, such as from about 8 to about 60 carbon atoms, such as about 10 to about 40, such as from about 12 to about 30, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • m is an integer that can be from about 1 to about 1000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40 to about 60, or from about 10 to about 1000, such as from about 50 to about 250, such as from about 100 to about 200, or from about 1 to about 25, such as from about 2 to about 20, such as from about 4 to about 18, such as from about 6 to about 15, such as from about 8 to about 10, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • w represents methylene groups (-CH2-) and is an integer that can be from about 1 to about 20, such as from about 1 to about 15, such as from about 2 to about 10, such as from about 4 to about 8, such as from about 5 to about 7, such as about 7.
  • x represents methylene groups (-CH2-) and is an integer that can be from about 1 to about 20, such as from about 1 to about 15, such as from about 2 to about 10, such as from about 3 to about 8, such as from about 4 to about 6, such as about 5.
  • w and x can be the same or different.
  • Each of X 1 and X 2 of Formula (I) are functional groups that can be, independently, hydroxyl, thiol, amine, isocyanate, carboxylic acid, halogen, epoxy, aldehyde, or alkene, such as hydroxyl or thiol.
  • Each of X 1 and X 2 of Formula (I) can be the same or different.
  • These functional groups (X 1 and X 2 ) can be reactive chain end groups of the linear aliphatic chain.
  • the first difunctionalized compound is represented by Formula (IA): wherein: each of m, w, x, X 1 , and X 2 are discussed above.
  • Non-limiting examples of the first difunctionalized compound can include: wherein: m in Formula (IA-1) and Formula (IA-2) can be from about 1 to about 100, such as from about 1 to about 40, such as from about 5 to about 30, such as from about 8 to about 20, such as from about 10 to about 15, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the first difunctionalized compound can be formed by any suitable method as described below, such as a ring-opening polymerization of a cyclic alkene in the presence of a chain transfer agent or chain-growth polymerizations.
  • the methylene groups (-CH2-) represented by w and x in Formula (I) can come from any suitable chain transfer agent (CTA) used to form the difunctionalized compound. Suitable CTAs are described below.
  • the A group ((CH2) P )) of Formula (I) can come from any suitable cyclic alkene used to form the difunctionalized compound. Suitable cyclic alkenes are described below.
  • the second difunctionalized compound can include a difunctionalized branched aliphatic compound and is a “soft” building block.
  • the second difunctionalized compound can be represented by Formula (II):
  • B is a branched hydrocarbyl having any suitable number of carbon atoms such as from about 2 to about 400 carbon atoms, such as from about 2 to about 200 carbon atoms, such as from about 3 to about 200 carbon atoms, such as from about 5 to about 100 carbon atoms, such as from about 8 to about 60 carbon atoms, such as about 10 to about 40, such as from about 12 to about 30, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • n is an integer that can be from about 1 to about 1000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40 to about 60, or from about 10 to about 1000, such as from about 50 to about 250, such as from about 100 to about 200, or from about 1 to about 25, such as from about 2 to about 20, such as from about 4 to about 18, such as from about 6 to about 15, such as from about 8 to about 10, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • y represents methylene groups (-CH2-) and is an integer that can be from 1 to 20, such as from 1 to 15, such as from 2 to 10, such as from 4 to 8, such as from 5 to 7, such as about 7.
  • z represents methylene groups (-CH2-) and is an integer that can be from about 1 to about 20, such as from about 1 to about 15, such as from about 2 to about 10, such as from about 3 to about 8, such as from about 4 to about 6, such as about 5.
  • y and z can be the same or different.
  • Each of X 3 and X 4 of Formula (II) are functional groups that can be, independently, hydroxyl, thiol, amine, isocyanate, carboxylic acid, halogen, epoxy, aldehyde, or alkene, such as hydroxyl or thiol.
  • Each of X 3 and X 4 of Formula (II) can be the same or different.
  • These functional groups (X 3 and X 4 ) can be reactive chain end groups of the branched aliphatic chain.
  • the second difunctionalized compound can be formed by any suitable method as described below, such as a ring-opening polymerization of a cyclic alkene in the presence of a chain transfer agent or chain-growth polymerizations.
  • the methylene groups (-CH2-) represented by y and z in Formula (II) can come from any suitable chain transfer agent (CTA) used to form the difunctionalized compound. Suitable CTAs are described below.
  • CTA chain transfer agent
  • the B group of Formula (II) can come from any suitable cyclic alkene used to form the difunctionalized compound. Suitable cyclic alkenes are described below.
  • the second difunctionalized compound is represented by Formula (IIA): wherein: each of n, y, z, X 3 , and X 4 in Formula (IIA) are discussed above.
  • Each R group (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and/or R 8 ) of Formula (IIA) can be, independently, hydrogen, unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.
  • Each R group of Formula (IIA) can be, independently, linear or branched, saturated or unsaturated, cyclic or acyclic, aromatic or not aromatic.
  • R group (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and/or R 8 ) of Formula (IIA) is a functional group comprising at least one element from Group 13-17
  • an “unsubstituted hydrocarbyl” refers to a group that consists of hydrogen and carbon atoms only.
  • each group (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and/or R 8 ) of Formula (IIA) can be a substituted hydrocarbyl.
  • each group (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and/or R 8 ) of Formula (IIA) can be fully saturated, partially unsaturated, or fully unsaturated.
  • each R group of Formula (IIA) can have any suitable number of carbon atoms, such as from about 1 to about 40 carbon atoms, such as from about 1 to 20 carbon atoms, such as from about 1 to about 10 carbon atoms, such as from about 1 to about 6 carbon atoms, such as from about 1 to about 4 carbon atoms, though other values are contemplated.
  • each R group of Formula (IIA) can be linear or branched alkyl or aryl.
  • Illustrative, but non-limiting, examples of unsubstituted hydrocarbyl include an alkyl group having from about 1 to about 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl, or isomers thereof; a cycloaliphatic group having from about 3 to about 20 carbon atoms such as, for example, cyclopentyl or
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 of Formula (IIA) is, independently, hydrogen, an unsubstituted C1-C40 hydrocarbyl (such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6), or a substituted C1-C40 hydrocarbyl (such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6).
  • an unsubstituted C1-C40 hydrocarbyl such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6
  • a substituted C1-C40 hydrocarbyl such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6.
  • At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 of Formula (IIA) is an unsubstituted hydrocarbyl or a substituted hydrocarbyl.
  • one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 of Formula (IIA) is an unsubstituted hydrocarbyl or a substituted hydrocarbyl; and the seven remaining R groups of Formula (IIA) are hydrogen.
  • R 7 of Formula (IIA) is an unsubstituted C1-C10 hydrocarbyl; and each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 of Formula (IIA) is hydrogen.
  • Other suitable substitution patterns are contemplated.
  • Non-limiting examples of the second difunctionalized compound can include: wherein: R 7 of Formula (IIA-1) and Formula (IIA-2) can be any suitable R group described herein such as n-hexyl; and n in Formula (IIA-1) and Formula (IIA-2) can be from about 1 to about 100, such as from about 1 to about 40, such as from about 5 to about 30, such as from about 8 to about 20, such as from about 10 to about 15, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the first difunctionalized compound, the second difunctionalized compound, or both have functionality greater than two (e.g., the compounds are each, independently, trifunctionalized, tetrafunctionalized, etc).
  • the first and/or second difunctionalized compound can include a third reactive group that may be attached to any suitable site (a carbon atom) on the first and/or second difunctionalized compound.
  • the third reactive group may be the same or different than the first and second reactive chain end groups.
  • the third reactive group may be -OH while the two first second reactive chain end groups of the first difunctionalized compound are -OH, and the two second reactive chain groups of the second difunctionalized compound are -OH.
  • the third reactive group may be -SH while the two first second reactive chain end groups of the first difunctionalized compound are -OH, and the two second reactive chain groups of the second difunctionalized compound are -OH.
  • the third reactive end group can participate in a polymerization.
  • the first difunctionalized compound can be formed by any suitable method such as a ring-opening polymerization of a cyclic alkene in the presence of a chain transfer agent or a chain-growth polymerization and a suitable catalyst.
  • the methylene groups (-CH2-) represented by w and x in Formula (I) can come from any suitable chain transfer agent (CTA).
  • the methylene groups represented by p of Formula (I) can come from any suitable cyclic alkene.
  • the second difunctionalized compound can be formed by any suitable method such as a ring-opening polymerization (ROMP) of a cyclic alkene in the presence of a chain transfer agent and a suitable catalyst.
  • a ring-opening polymerization (ROMP) of a cyclic alkene in the presence of a chain transfer agent and a suitable catalyst.
  • the methylene groups (-CH2-) represented by y and z in Formula (II) can come from any suitable chain transfer agent (CTA).
  • CTA chain transfer agent
  • B of Formula (II) can come from any suitable cyclic alkene.
  • a reaction mixture that includes a chain transfer agent, cycloalkene, and an optional solvent, where a molar ratio of the chain transfer agent to the cycloalkene can be from about 1 : 1 to about 1 : 1,000, such as from about 1 :5 to about 1 : 100, such as from about 1 : 10 to about 1 :25, such as about 1 : 15 to about 1 :20, or from about 1 : 1 to about 1 :50, such as from about 1 :2 to about 1 :30, such as from about 1 :5 to about 1 :20, such as from about 1 :8 to about 1 : 12, such as about 1 : 10, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • (c) Converting the resulting reaction mixture, by ROMP, to form a first reaction product, where the conversion can be performed at a temperature that is from about 0°C to about 250°C, such as from about 20°C to 100°C, such as about 30°C to about 80°C, such as from about 40°C to about 60°C, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open- ended range or in combination to describe a close-ended range. Converting the resulting reaction mixture by ROMP can be performed for any suitable period such as from about 5 minutes to about 24 hours, such as form about 15 minutes to about 10 hours, such as from about 30 minutes to about 5 hours, though other values are contemplated.
  • any of the foregoing numbers can be used singly to describe an open- ended range or in combination to describe a close-ended range.
  • the converting the resulting reaction mixture by ROMP can be performed under a protective gas atmosphere, such as nitrogen or argon; and
  • step (d) Hydrogenating the first reaction product (formed from step (c)) to form a first or second difunctionalized compound, where the hydrogenation may be performed at a temperature that is from about 0°C to about 250°C, such as from about 50°C to about 150°C, such as from about 75°C to about 125°C, such as about 100°C, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the hydrogenation may be performed at a hydrogen pressure that is from about 1 bar to 100 bar, such as from about 10 bar to about 50 bar, such as from about 20 bar to about 40 bar, though other values are contemplated.
  • any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close- ended range.
  • the hydrogenation may be performed for a period that is from about 1 hour to about 72 hours, such as from about 5 hours to about 48 hours, such as from about 12 hours to about 36 hours, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • Optional solvents useful for step (a) can include any suitable solvent such as benzene, toluene, tetrahydrofuran, dichloromethane, di chloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, or combinations thereof.
  • suitable solvent such as benzene, toluene, tetrahydrofuran, dichloromethane, di chloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, or combinations thereof.
  • the catalyst added in step (b) can be added to the reaction mixture in solid form; or suspended or dissolved in a diluent such as benzene, toluene, tetrahydrofuran, dichloromethane, di chloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, heptane, or combinations thereof.
  • a diluent such as benzene, toluene, tetrahydrofuran, dichloromethane, di chloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, heptane, or combinations thereof.
  • the N-heterocyclic carbene (L 2 ) of the inorganic catalyst compound can be any suitable N-heterocyclic carbene such as those represented by Formula (IV): wherein: each of R a and R b are, independently, H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl and p-methoxyphenyl; and each of R la , R 2a , R 3a , R 4a , R 5a , R lb , R 2b , R 3b , R 4b , and R 5b are, independently, H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or methoxy.
  • Formula (IV) wherein: each of R a and R b are, independently, H, methyl, ethyl, n
  • the anionic ligand (Y 1 , Y 2 ) of the inorganic catalyst compound of Formula (III) is any suitable singly or multiply negatively charged ligand.
  • Each of Y 1 and Y 2 of Formula (III) can be selected from the group consisting of halide (fluoride, chloride, bromide and iodide, such as chloride), pseudohalide, tetraphenylborate, hexahalophosphate, methanesulphonate, trihalomethanesulphonate, arylsulphonate, alkoxide, aryloxide, carboxylate, sulphate, and phosphate.
  • Pseudohalides are ligands having similar chemical behaviour to the halides, such as cyanide (CN"), cyanate (OCN ), or thiocyanate (SCN ).
  • the uncharged 7t-binding ligand (L 1 ) of the inorganic catalyst compound of Formula (III) can be any suitable monocyclic or polycyclic arene which may also have substituents which may be identical or non-identical, where the substituents are selected from the group consisting of (Ci-C2o)-alkyl-, (Ce-Ci4)-aryl-, (Ci-C2o)-alkyloxy-, (Ce- Ci4)-aryloxy-, (Ci-C2o)-perfluoroalkyl-, (Ci-C2o)-alkylthio-, (C2-Cio)-alkenylthio-, (C2- Cio)-alkenyl-, (C2-Cio)-alkynyl-, (C2-Cio)-alkenyloxy-, (C2-Cio)-alkynyloxy-, and halogen.
  • substituents are selected from the group consisting of (
  • the substituents may in turn likewise be substituted, in which case these substituents are selected from the group consisting of halogen, (Ci-C 8 )-alkyl, (Ci-Cs)- alkyloxy, — NH2, —NO, — NO2, NH(Ci-C 8 )-alkyl, — N((Ci-C 8 )-alkyl) 2 , —OH, — CF3, — C n F2n+i (where n is 2, 3, 4 or 5), NH(Ci-C 8 )-acyl, — N((Ci-C 8 )-acyl)2, (Ci-C 8 )- acyl, (Ci-C 8 )-acyloxy, — SO2— (Ci-C 8 )-alkyl, — SO2— (C 6 -Ci 4 )-aryl, — SO— (Ci-C 8 )- alkyl, — SO— (C 6
  • uncharged 7t-binding ligands can include benzene, toluene, xylene, p-cymene, trimethylbenzene, tetramethylbenzene, hexamethylbenzene, tetrahydronaphthalene, or naphthalene.
  • the uncharged 7t-binding ligand is selected from the group consisting of benzene, p-cymene, and hexamethylbenzene.
  • the inorganic catalyst compound used as the ROMP catalyst can be any suitable catalyst useful for ROMP, including molybdenum, ruthenium, or organic catalysts, such as Grubbs 2nd generation catalyst ((l,3-Bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium)).
  • suitable catalysts for ROMP include those described in U.S. Patent No. 9,309,344, which is incorporated herein by reference in its entirety.
  • chain transfer agent refers to a compound or mixture of compounds, such as alkene compounds that may exchange, for example, a functional group on the chain transfer agent with the growing polymer chain on the catalyst, which generally results in termination of the polymer chain growth.
  • Suitable CTAs include acyclic alkenes, including acyclic internal alkenes.
  • chain transfer agents include those of Formula (V): wherein n of Formula (V) can be, independently, any suitable number such as from 1 to 40, such as from 1 to 20, such as from 1 to 10, such as 2 to 9, such as from 4 to 8, or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the double bond in Formula (V) can have cis or trans configuration. The number of carbon atoms on each side of the cis- or trans-double bond can be the same or different.
  • the CTA can be bio-based.
  • the CTA can be made from oxacycloheptadec- 10-en-2-one (ambrettolide), though other materials are contemplated.
  • An illustrative, but non-limiting example of a CTA can include cis-hexadec-6-ene-l,16-diol:
  • Suitable cycloalkenes can include those of Formula (VI): wherein: n of Formula (VI) can be, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, such as from about 1 to about 18, such as from about 4 to about 12, such as from about 6 to about 10, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the cycloalkene may be unsubstituted or substituted.
  • the difunctionalized compound is not branched (e.g., the “hard” block)
  • the cycloalkene of Formula (VI) is unsubstituted.
  • the difunctionalized compound is branched (e.g., the “soft” block)
  • one or more carbon atoms of the cycloalkene of Formula (VI) may be substituted such that the resulting B group of Formula (II) is branched.
  • one or more carbon atoms of the cycloalkene of Formula (VI) can be substituted with any suitable R group such as those described above, such as a substituted or unsubstituted C1-C40 hydrocarbyl (such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6).
  • a substituted or unsubstituted C1-C40 hydrocarbyl such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6
  • RJ-R 8 described above with respect to Formula (IIA) can be substituted or unsubstituted C1-C40 hydrocarbyl (such as Cl- C20, such as Cl -CIO, such as C1-C8, such as C1-C6).
  • Cycloalkenes useful to form the first and second difunctionalized compounds can include, cyclic alkenes of Formula (VI) having a ring size of 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, which may be unsubstituted or substituted, such as 5, 6, 7, 8, 9, or 10 carbon atoms such as unsubstituted or substituted cyclopentene, unsubstituted or substituted cyclohexene, unsubstituted or substituted cycloheptene, unsubstituted or substituted cyclooctene, unsubstituted or substituted cyclononene, unsubstituted or substituted cyclodecene.
  • Illustrative, but non-limiting, examples of cycloalkenes can include a cyclooctene of Formula (VI-1): wherein:
  • R d of Formula (VI-1) is positioned on any suitable carbon of the cyclooctene ring, and can be a substituted or unsubstituted Cl -C40 hydrocarbyl (such as C1-C20, such as Cl- C10, such as C1-C8, such as C1-C6), such as methyl, ethyl, n-propyl, isopropyl, n- butyl, iso-butyl, sec-butyl, and tert-butyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl, or isomers thereof; a cycloaliphatic group having from 3 to 20 carbon atoms such as, for example, cyclopentyl or cyclohexyl; an aromatic group having from 6 to 20 carbon atom
  • the numbering 1-8 in Formula (VI-1) represents carbon numbers.
  • R d is present on one or more of carbons 1, 2, 3, 4, 5, 6, 7, and/or 8, such as one or more of carbons 3, 4, 5, and/or 8.
  • Illustrative but non-limiting examples of cycloalkenes can include cyclooctene (VI-2) and 3-substituted-cyclooctene (VI-3):
  • R d group is positioned on carbon 3 and is positioned on any suitable carbon of the cyclooctene ring, and can be a substituted or unsubstituted C1-C40 hydrocarbyl (such as those Rd groups described above, such as hexyl).
  • the 3- substituted cyclooctene can be 3-hexylcyclooctene.
  • a molar ratio of the CTA to the cycloalkene can be any suitable molar ratio such as from about 1 : 1 to about 1 : 100, such as from about 1 :5 to about 1 :50, such as from about 1 : 10 to about 1 :20, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • a molar ratio of catalyst to cycloalkene can be from about 1 : 100,000 to about 1 : 10, such as from about 1 : 10,000 to about 1 : 100, such as from about 1 : 1,000 to about 1 :200, such as from about 1 :800 to about 1 :300, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the first reaction product formed in step (c) can include an alkene.
  • the alkene can be hydrogenated at step (d), optionally in the presence of a hydrogenation catalyst.
  • Suitable optional hydrogenation catalyst can include the residual ruthenium from the catalyst added in step (b).
  • Other suitable and optional hydrogenation catalysts can include those active metals such as ruthenium (Ru), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), or nickel (Ni), or combinations thereof.
  • the active metal may be present in the hydrogenation catalyst either (a) as they are or in the form of oxides or (b) as metal complexes. In case (a), the metal or metal oxide can either be applied to a support or be used as particles.
  • the support material can be any suitable support such as aluminum oxide, silicon dioxide, iron oxide, magnesium oxide, zirconium dioxide, carbon or similar supports in the art in the field of hydrogenation.
  • the content of metal or metal oxide on the support can be from 1% by weight to 25% by weight, based on the total weight of the catalyst, such as from 1% to 5% by weight of metal or metal oxide on the support.
  • hydrogenation catalysts are Pt/C, Pd/C, Ru/C, Pd/CaCOs, Pd/AhCh, Ru/AhCh.
  • the metals can also be used in the form of metal complexes as hydrogenation catalysts. Examples thereof are metal complexes of the metals Rh, Ir or Ru, such as e.g.
  • Optional solvents useful for hydrogenation can include any suitable solvent such as benzene, toluene, tetrahydrofuran, di chloromethane, dichloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, or combinations thereof.
  • suitable solvent such as benzene, toluene, tetrahydrofuran, di chloromethane, dichloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, or combinations thereof.
  • the first difunctionalized (or telechelic) compound (“hard” building block) and the second difunctionalized (or telechelic) compound are formed.
  • the first difunctionalized compound (“hard” building block) can have one or more of the following properties:
  • a weight-average molecular weight (M w ) of the first difunctionalized compound can be from about 0.35 kilodalton (kDa) to about 20.0 kDa, such as from about 0.5 kDa to about 7.0 kDa, such as from about 1.0 kDa to about 5.0 kDa, such as from about 1.5 kDa to about 4.5 kDa, such as from about 2.0 kDa to about 4.0 kDa, such as from about 2.4 kDa to about 3.6 kDa, such as from about 2.8 kDa to about 3.3 kDa, such as from about 3.0 kDa to about 3.2 kDa, or about 3.3 kDa, though other values are contemplated.
  • the M w of the first difunctionalized compound determined by High Temperature Size Exclusion Chromatography (HT-SEC) as described in the Examples Section.
  • a number-average molecular weight (M n ) of the first difunctionalized compound can be from about 1.0 kDa to about 20.0 kDa, such as from about 1.25 kDa to about 10 kDa, such as from about 1.5 kDa to about 2.5 kDa, such as from about 1.6 kDa to about 2.4 kDa, such as from about 1.8 kDa to about 2.2 kDa, such as about 1.9 kDa, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the M n of the first difunctionalized compound is determined by HT-SEC as described in the Examples Section.
  • the dispersity of the first difunctionalized compound is calculated from M w and M n as determined by HT-SEC as described in the Examples Section.
  • the second difunctionalized compound (“soft” building block) can have one or more of the following properties:
  • a weight-average molecular weight (M w ) of the first difunctionalized compound can be from about 0.35 to about 20.0 kDa, such as from about 0.5 kDa to about 7.0 kDa, such as from about 1.0 kDa to about 5.0 kDa, such as from about 1.5 kDa to about 4.5 kDa, such as from about 2.0 kDa to about 4.0 kDa, such as from about 2.4 kDa to about 3.6 kDa, such as from about 2.8 kDa to about 3.3 kDa, such as from about 3.0 kDa to about 3.2 kDa, or about 3.0 kDa, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the M w of the second difunctionalized compound is determined by HT-SEC as described in the Examples Section.
  • a number-average molecular weight (M n ) of the second difunctionalized compound can be from about 1.0 kDa to about 20.0 kDa, such as from about 1.25 kDa to about 10 kDa, such as from about 1.5 kDa to about 2.5 kDa, such as from about 1.6 kDa to about 2.4 kDa, such as from about 1.8 kDa to about 2.2 kDa, such as about 1.8 kDa or about 1.9 kDa, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the dispersity (D) of the second difunctionalized compound is calculated from M w and M n as determined by HT-SEC as described in the Examples Section.
  • the first and second difunctionalized compounds can be submitted to polymerization to form a polymer or a copolymer.
  • the copolymer may be a multiblock copolymer.
  • the copolymer may be an adduct or reaction product of a first difunctionalized compound and a second difunctionalized compound.
  • the polymer can be an adduct or reaction product of a first difunctionalized compound reacting with another first difunctionalized compound, or the polymer can be an adduct or reaction product of a second difunctionalized compound reacting with another second difunctionalized compound.
  • Polymers and copolymers formed according to embodiments described herein can be plastics, thermoplastics, plastomers, or elastomers.
  • the copolymer can be a polyolefin-like material as described herein.
  • a process for forming a copolymer includes forming a composition (or a reaction mixture) that includes a first difunctionalized compound, a second difunctionalized compound, a catalyst (such as, e.g., a heterogeneous metal catalyst, a pincer catalyst, and/or complex thereof), an optional base, and an optional solvent.
  • the catalyst may be a metal complex (such as a heterogeneous metal complex, a pincer complex, or both) combined with the optional base.
  • the process may further include converting (or reacting) the composition or reaction mixture under conditions effective to form a copolymer comprising a reaction product or an adduct of the first difunctionalized compound and the second difunctionalized compound. Converting the reaction mixture or composition includes inducing a step growth polymerization. Conversion, or step growth polymerization, conditions are described below.
  • a process for forming a polymer (and/or copolymer) includes one or more of the following operations:
  • reaction mixture or composition
  • first difunctionalized compound a reaction mixture that includes a first difunctionalized compound, a second difunctionalized compound, and an optional solvent, where the first and second difunctionalized compounds are the same or different;
  • any suitable molar ratio of the first difunctionalized compound to the second difunctionalized compound can be utilized for the reaction mixture (or composition) in operation (a), such as from about 1 :99 to about 99: 1, such as from about 5:95 to about 95:5, such as from about 10:90 to about 90: 10, such as from about 15:85 to about 85: 15, such as from about 20:80 to about 80:20, such as from about 30:70 to about 70:30, such as from about 35:65 to about 65:35, such as from about 40:60 to about 60:40, such as from about 45:55 to about 55:45, such as about 50:50, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close- ended range.
  • an additional functionalized compound e.g., a third difunctionalized compound
  • the additional functionalized compound having identical reactive chain end groups as the first and second difunctionalized compounds.
  • the third difunctionalized compound is different from the first and second difunctionalized compounds.
  • the catalyst utilized can be any suitable catalyst.
  • the catalyst (or complex) can include a pincer catalyst (or pincer complex) having a structure represented by the general Formula (VII).
  • M 2 can be any suitable transition metal such as a Group 7 to Group 10 metal of the periodic table of the elements, such as manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), or combinations thereof, such as Ru, Rh, Ir, Mn, Co, Fe, or combinations thereof, such as Ru, Ir, Mn, Co, or Fe, such as Ru, Mn, or Fe, such as Ru, Mn, or Fe, such as Ru, Mn, or Fe, such as Ru
  • Each of Z, Y 3 , and Y 4 of Formula (VII) can be, independently, carbon monoxide (CO), triphenylphosphine, pyridine, tetrahydrofuran, dimethylsulfoxide, hydrogen, hydrogen anion hydroxide, halogen (e.g., chlorine, bromine, iodine, or ion thereof), BEU or anion thereof (BEU ), BEUCN or anion thereof (BEUCN ), BH(Et)3 or anion thereof (BH(Et)3 ), BH(sec-Bu)3 or anion thereof (BH(sec-Bu)3 ), Al Ph or anion thereof (A1FU ), or combinations thereof.
  • CO carbon monoxide
  • triphenylphosphine pyridine
  • tetrahydrofuran dimethylsulfoxide
  • hydrogen hydrogen anion hydroxide
  • halogen e.g., chlorine, bromine, iodine, or ion thereof
  • L 3 in Formula (VII) is a tridentate pincer ligand represented by Formula (VIII): wherein: each of mi and m2 of Formula (VIII) is, independently, an integer from 1 to 3, such as 1, 2, or 3; each of D 1 and D 2 of Formula (VIII) are electron donor atoms coordinated to a metal atom (M), and each of D 1 and D 2 is, independently, carbon (C), phosphorous (P), nitrogen (N), or sulfur (S), such as P, N, or S; R 20 of Formula (VIII) is hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or un substituted Ce-C24aryl, substituted or unsubstituted C7-C25 arylalkyl, substituted or unsubstituted C4-C20 heteroaryl; each of R 21 , R 22 , R 31 , and R 32 of Formula (VIII)
  • an “unsubstituted” group refers to a group that consists of hydrogen and carbon atoms only.
  • a “substituted” group refers to one or more hydrogen atoms of a group is substituted by a substituent comprising: a hydrogen, C1-C4 alkyl, C1-C4 halogenated alkyl, C2-C6 alkenyl, C2-C6 alkynyl, Ci-Ce alkoxy, amido, or combinations thereof.
  • the catalyst of Formula (VIII) can have one or more of the following characteristics:
  • R 20 is H, C1-C4 alkyl (e.g., methyl, ethyl, or n-butyl, or an isomer thereof), or phenyl;
  • each of R 21 , R 22 , R 31 , and R 32 is, independently, phenyl, ethyl, isopropyl, t-butyl, cyclohexyl or adamantane;
  • each of R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 is, independently, hydrogen, phenyl, or pyridyl; and/or
  • M 2 is Ru or Ir, such as Ru.
  • the catalyst can include a complex (e.g., a pincer complex) having the structure of one or more of the following Formulas:
  • Et is ethyl
  • iPr is isopropyl
  • tBu is tert-butyl. More than one pincer catalyst can be utilized for the polymerization.
  • the optional base can be an alkali metal salt of an alcohol, an alkali metal hydroxide, an alkali metal carbonate, or combinations thereof.
  • Suitable alcohols for use in the alcohol of the alkali metal salt of an alcohol include those of Formula R-OH (IX), where R of Formula (IX) is a linear or branched, substituted or unsubstituted, cyclic or acyclic, saturated or unsaturated, aromatic or nonaromatic hydrocarbyl.
  • R of Formula (IX) can be any suitable number of carbon atoms such as from 1 to 40 carbon atoms, such as from 1 to 20 carbon atoms, such as from 1 to 10 carbon atoms, such as from 1 to 6 carbon atoms, such as from 1 to 4 carbon atoms, though other values are contemplated.
  • R of Formula (IX) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl, or isomers thereof; a cycloaliphatic group having from 3 to 20 carbon atoms such as, for example, cyclopentyl or cyclohexyl; an aromatic group having from 6 to 20 carbon atoms such as, for example, phenyl or naphthyl.
  • the alcohol of the alkali metal salt of an alcohol includes methanol, ethanol, isopropanol, tert-butanol, phenol, or combinations thereof.
  • the cation of the alkali metal salt can include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), or cesium (Cs).
  • Illustrative, but non-limiting examples of alkali metal salts of an alcohol can include sodium ethoxide (NaOEt), potassium tert-butoxide (KOtBu or t-BuOK), or combinations thereof.
  • alkali metal hydroxides useful as the optional base can include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), or combinations thereof.
  • LiOH lithium hydroxide
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • RbOH rubidium hydroxide
  • CsOH cesium hydroxide
  • alkali metal carbonates useful as the optional base can include sodium carbonate (Na2COs), sodium hydrogen carbonate (NaHCOs), sodium bicarbonate (NaHCCh), potassium carbonate (K2CO3), potassium bicarbonate (KHCO3), beryllium hydroxide (Be(OH)2), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), strontium hydroxide (Sr(OH)2), barium hydroxide (Ba(OH)2), or combinations thereof.
  • Na2COs sodium carbonate
  • NaHCOs sodium hydrogen carbonate
  • NaHCCh sodium bicarbonate
  • K2CO3 potassium carbonate
  • KHCO3 potassium bicarbonate
  • Be(OH)2 beryllium hydroxide
  • Be(OH)2 magnesium hydroxide
  • Ca(OH)2 calcium hydroxide
  • strontium hydroxide Sr(OH)2
  • barium hydroxide barium hydroxide
  • the optional base can include NaOEt, KOtBu, LiOH, NaOH, KOH, RbOH, CsOH, Na 2 CO 3 , NaHCO 3 , NaHCO 3 , K2CO3, KHCO3, or combinations thereof, such as NaOEt, KOtBu, LiOH, NaOH, KOH, RbOH, CsOH, such as NaOEt, KOtBu, LiOH, NaOH, KOH, or combinations thereof, such as KOtBu.
  • the optional solvent can include any suitable solvent such as xylene, di chlorobenzene, anisole, tetrahydrofuran, toluene, benzene, di chloromethane, dichloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, or combinations thereof, such as di chlorobenzene, xylene, anisole, tetrahydrofuran, toluene, or combinations thereof.
  • any suitable solvent such as xylene, di chlorobenzene, anisole, tetrahydrofuran, toluene, benzene, di chloromethane, dichloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, or combinations thereof, such as di chlorobenzene,
  • the solvents can be mixed at any suitable ratio such as from 10:90 to about 90: 10, such as from about 20:80 to about 80:20, such as from about 30:70 to about 70:30, such as from about 40:60 to about 60:40, such as about 50:50, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open- ended range or in combination to describe a close-ended range.
  • a molar ratio of the pincer catalyst (moles) to the total amount (in moles) of the first and/or second difunctionalized compounds can be any suitable molar ratio, such as from about 1 :2,000 to about 1 :100, such as from about 1 : 1000, to about 1 : 150, such as from about 1 :800 to about 1 :200, such as from about 1 :600 to about 1 :400, such as about 1 :500, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • a molar ratio of the heterogeneous metal catalyst and/or pincer catalyst to the optional base can be any suitable molar ratio, such as from about 1 : 100 to about 1 : 1, such as from about 1 :40 to about 1 : 1, such as from about 1 :32 to about 1 :4, such as from about 1 : 16 to about 1 :8, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the converting or the reacting of the resultant reaction mixture (or the resultant composition) formed after operation (b) can occur by a step-growth polymerization to form the polymer and/or copolymer.
  • Operation (c) of the process to form the polymer and/or copolymer can be performed under conditions effective to polymerize one or more components of the resultant reaction mixture (or the resultant composition) formed from operation (b).
  • Such conditions for operation (c) of the process to form the polymer and/or copolymer can include any suitable reaction temperature, such as from about 25°C to about 250°C, such as from about 50°C to about 250°C, such as from about 75°C to about 225°C, such as from about 100°C to about 200°C, such as from about 125°C to about 175°C, such as from about 135°C to about 165°C, or about 130°C, or about 150°C, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close- ended range.
  • Conditions for operation (c) can include a reaction time that is from about 0.1 hours to about 200 hours, such as from about 2 hours to about 160 hours, such as from about 10 hours to about 120 hours, such as from about 24 hours to about 96 hours, such as from about 36 hours to about 72 hours, such as about 48 hours, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the reacting or converting of operation (c) of the process to form the polymer and/or copolymer can be performed in any suitable vessel or reactor.
  • the vessel pressure can be from about 70 kPa (absolute) to about 130 kPa (absolute), such as from about 80 kPa (absolute) to about 120 kPa (absolute), such as from about 90 kPa (absolute) to about 110 kPa (absolute), such as about 100 kPa (absolute), though other pressures are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the components of the reaction mixture at operation (c) of the process to form the polymer and/or copolymer can be mixed, stirred, or agitated by using suitable devices such as a mechanical stirrer, such as an overhead stirrer, a magnetic stirrer (for example, placing a magnetic stir bar in the vessel above a magnetic stirrer), or other suitable devices.
  • a mechanical stirrer such as an overhead stirrer, a magnetic stirrer (for example, placing a magnetic stir bar in the vessel above a magnetic stirrer), or other suitable devices.
  • a stirrer having a blade or propeller can be rotated by receiving rotational power from a stirring motor to stir the one or more materials at suitable rotation speeds.
  • the stirrer having a blade or propeller can be rotated by receiving rotational power from a stirring motor to stir the one or more materials at suitable rotation speeds, such as from about 50 revolutions per minute (rpm) to about 1,500 rpm, such as from about 75 rpm to about 1,000 rpm, such as from about 100 rpm to about 900 rpm, such as from about 200 rpm to about 800 rpm, such as from about 300 rpm to about 700 rpm, such as from about 400 rpm to about 600 rpm, such as from about 450 rpm to about 550 rpm, such as about 500 rpm.
  • suitable rotation speeds such as from about 50 revolutions per minute (rpm) to about 1,500 rpm, such as from about 75 rpm to about 1,000 rpm, such as from about 100 rpm to about 900 rpm, such as from about 200 rpm to about 800 rpm, such as from about 300 rpm to about 700 rpm, such as from about 400 rpm
  • Components of the reaction mixture at operation (c) can be mixed, stirred, or agitated in the presence of a non-reactive gas, such as nitrogen (N2), argon (Ar), or combinations thereof.
  • a non-reactive gas such as nitrogen (N2), argon (Ar), or combinations thereof.
  • a non-reactive gas can be introduced with one or components in the reaction mixture to degas various components or otherwise remove unwanted gases such as oxygen from the mixture.
  • Operation (c) of the process to form the polymer and/or copolymer results in formation of a polymer or copolymer.
  • the percent (%) yield of the polymerization can be about 50% or more such as about 60% or more, such as about 70% or more, such as about 80% or more, such as about 85% or more, such as about 90% or more, such as about 95% or more, such as about 99% or more, such as about 100%, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • Polymers formed by processes described herein include those that are free of hard blocks (e.g., operation (a) is free of first difunctionalized compound) and those that are free of soft blocks (e.g., operation (a) is free of second difunctionalized compound).
  • Copolymers formed by processes described herein include those that include both hard blocks and soft blocks.
  • Various polymers and copolymers formed according to embodiments of the present disclosure are described below.
  • the polymers and copolymers, such as multiblock copolymers, formed by processes described herein can be plastics, thermoplastics, plastomers, or elastomers.
  • the polymer and/or copolymer can be a polyolefin-like material as described herein.
  • Polymers and copolymers described herein can comprise a reaction product or an adduct of the first difunctionalized compound of Formula (I) and/or the second difunctionalized compound of Formula (II).
  • the reaction product formed from the polymerization can include a polymer.
  • Non-limiting examples of such polymers are shown by example polymer PE0 and example polymer PEI 00.
  • the reaction product formed from the polymerization can include a copolymer.
  • An example copolymer formed by embodiments of the present disclosure comprises Formula (X): wherein:
  • xi of Formula (X) is an integer that can be from about 1 to about 30, such as from about 1 to about 20, such as from about 2 to 15, such as from about 3 to about 10, such as from about 4 to about 8, though other values are contemplated, and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range;
  • X2 of Formula (X) is an integer that can be from about 1 to about 30, such as from about 1 to about 20, such as from about 2 to 15, such as from about 3 to about 10, such as from about 4 to about 8, though other values are contemplated, and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range;
  • X3 of Formula (X) is an integer that can be from about 1 to about 30, such as from about 1 to about 20, such as from about 2 to 15, such as from about 3 to about 10, such as from about 4 to about 8, though other values are contemplated, and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range;
  • X4 of Formula (X) is an integer that can be from about 1 to about 30, such as from about 1 to about 20, such as from about 2 to 15, such as from about 3 to about 10, such as from about 4 to about 8, though other values are contemplated, and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range; and c of Formula (X) is an integer that can be from about 1 to about 10,000, such as from about 1 to about 1,000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40 to about 60, or from about 10 to about 1,000, such as from about 50 to about 250, such as from about 100 to about 200, or from about 1 to about 25, such as from about 2 to about 20, such as from about 4 to about 18, such as from about 6 to about 15, such as from about 8 to about 10, though other values are contemplated, and any of the foregoing numbers can be used singly to describe an open- ended range or in combination to describe a close-ended range.
  • n/m*100 of Formula (X) is from about 0% to about 100%, such as from about 5% to about 95%, such as from about 10% to about 90%, such as from about 15% to about 85%, such as from about 20% to about 80%, such as from about 25% to about 75%, such as from about 30% to about 70%, such as from about 35% to about 65%, such as from about 40% to about 60%, such as from about 45% to about 55%, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • copolymers of the present disclosure can include an ester linkage that chemically couples a linear aliphatic group (“hard” building block) with a branched aliphatic group (“soft” building block).
  • copolymers of the present disclosure can include any suitable amount of hard block (linear aliphatic group, A) and any suitable amount of soft block (branched aliphatic group, B).
  • a molar ratio of the hard block (linear aliphatic group, A) to the soft block (branched aliphatic group, B) can be from about 1 :99 to about 99: 1, such as from about 5:95 to about 95:5, such as from about 10:90 to about 90: 10, such as from about 15:85 to about 85: 15, such as from about 20:80 to about 80:20, such as from about 30:70 to about 70:30, such as from about 35:65 to about 65:35, such as from about 40:60 to about 60:40, such as from about 45:55 to about 55:45, such as about 50:50, though other values are contemplated.
  • the molar ratio of the hard block to the soft block is determined according to J H NMR and calculated according to Equation 2 and as described in the Examples Section.
  • R* of Formula (X-l) is an unsubstituted C1-C40 hydrocarbyl (such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6), or a substituted C1-C40 hydrocarbyl (such as C1-C20, such as Cl -CIO, such as C1-C8, such as C1-C6).
  • R* of Formula (X-l) can include those groups described above for R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 of Formula (IIA).
  • An example of a polymer formed according to embodiments described herein includes the polymer represented by Formula (XI-1): wherein, in Formula (XI-1): each x is, independently, an integer that can be from 2 to 10, such as from 3 to 8, such as from 4 to 6, such as 6 or 4; y is an integer that can be from 2 to 10, such as from 4 to 8, such as from 5 to 7, such as 7 or 5; m is an integer that can be from about 1 to about 1000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40 to about 60, or from about 10 to about 1000, such as from about 50 to about 250, such as from about 100 to about 200, or from about 1 to about 25, such as from about 2 to about 20, such as from about 4
  • FIG. 2D shows a J H NMR spectrum of an example polymer (example PE0) with 0% hard blocks (first difunctionalized compound) and 100% soft blocks (and second difunctionalized compound).
  • x is about 6 or about 4
  • y is about 7 or about 5
  • m + n is about 20.
  • An example of a copolymer formed according to embodiments described herein includes the copolymer represented by Formula (XI-2):
  • R* can be H or n-hexyl; each x is, independently, an integer that can be from 2 to 10, such as from 3 to 8, such as from 4 to 6 such as 6 or 4; each y is, independently, an integer that can be from 2 to 10, such as from 4 to 8, such as from 5 to 7, such as 7 or 5; m is an integer that can be from about 1 to about 1000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40 to about 60, or from about 10 to about 1000, such as from about 50 to about 250, such as from about 100 to about 200, or from about 1 to about 25, such as from about 2 to about 20, such as from about 4 to about 18, such as from about 6 to about 15, such as from about 8 to about 10; n is an integer that can be from about 1 to about 1000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40 to about 60, or from about 10 to about 1000, such as from about 50 to about 250, such as from about 100
  • Z2 is an integer that can be from about 9 to about 19, such as from about 11 to about 17, such as from about 13 to about 15, such as about 14;
  • Z3 is an integer that can be equal to zi or Z2.
  • n/m*100 of Formula (XI-2) is from about 0% to about 100%, such as from about 5% to about 95%, such as from about 10% to about 90%, such as from about 15% to about 85%, such as from about 20% to about 80%, such as from about 25% to about 75%, such as from about 30% to about 70%, such as from about 35% to about 65%, such as from about 40% to about 60%, such as from about 45% to about 55%, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • Examples of copolymers represented by Formula (XI-2) include: example polymer PE20, with a representative J H NMR spectra shown in FIG. 2E; example copolymer PE40 with a representative J H NMR spectra shown in FIG. 2F; example copolymer PE60 with a representative J H NMR spectra shown in FIG. 2G; example copolymer PE80 with a representative J H NMR spectra shown in FIG. 2H.
  • FIG. 2E shows a J H NMR spectrum of an example polymer (example PE0) with 0% hard blocks (first difunctionalized compound) and 100% soft blocks (and second difunctionalized compound).
  • FIG. 2E shows a J H NMR spectrum of an example polymer (example PE0) with 0% hard blocks (first difunctionalized compound) and 100% soft blocks (and second difunctionalized compound).
  • FIG. 2E shows a J H NMR spectrum of an example polymer (example PE0) with 0% hard blocks (first difunctionalized compound) and
  • FIG. 2F shows a J H NMR spectrum an example copolymer PE40 (40% hard blocks (first difunctionalized compound) and 60% soft blocks (second difunctionalized compound)).
  • FIG. 2G shows a J H NMR spectrum an example copolymer PE60 (60% hard blocks (first difunctionalized compound) and 40% soft blocks (second difunctionalized compound).
  • FIG. 2H shows a 'H NMR spectrum an example copolymer PE80 (80% hard blocks (first difunctionalized compound) and 20% soft blocks (second difunctionalized compound).
  • a polymer formed according to embodiments described herein includes the polymer represented by Formula (XI-3): wherein, in Formula (XI-3): each x is, independently, an integer that can be from 2 to 10, such as from 3 to 8, such as from 4 to 6, such as 6 or 4; y is an integer that can be from 2 to 10, such as from 4 to 8, such as from 5 to 7, such as 7 or 5; m is an integer that can be from about 1 to about 1000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40 to about 60, or from about 10 to about 1000, such as from about 50 to about 250, such as from about 100 to about 200, or from about 1 to about 25, such as from about 2 to about 20, such as from about 4 to about 18, such as from about 6 to about 15, such as from about 8 to about 10; and and n is an integer that can be from about 1 to about 1000, such as from about 10 to about 100, such as from about 20 to about 80, such as from about 40
  • FIG. 21 shows a J H NMR spectrum of an example polymer (example PE0) with 100% hard blocks (first difunctionalized compound) and 0% soft blocks (and second difunctionalized compound).
  • x is about 6 or about 4
  • y is about 7 or about 5
  • m + n is about 11.
  • polymers and copolymers formed according to embodiments described herein can have various properties.
  • polymers and copolymers of the present disclosure can have one or more of the following non-limiting properties: [0193] (a) A M w that can be from about 10.0 kDa to about 1,000.0 kDa, such as from about 15.0 kDa to about 200 kDa, 20.0 kDa to about 130.0 kDa, such as from about 30.0 kDa to about 120.0 kDa, such as from about 40.0 kDa to about 110.0 kDa, such as from about 50.0 kDa to about 100.0 kDa, such as from about 60.0 kDa to about 90.0 kDa, such as from about 65.0 kDa to about 85.0 kDa, such as from about 70.0 kDa to about 85.0 kDa, such as from about 71.0 kDa to about 81.0 kDa, or from about 5
  • the M w of the copolymer is calculated from M w and M n as determined by HT-SEC as described in the Examples Section.
  • a dispersity (D) that can be from about 1.7 to about 3.0, such as from about 1.9 to about 2.8 or from about 2.0 to about 3.0, such as from about 2.0 to about 2.7, such as from about 2.1 to about 2.6, such as from about 2.2 to about 2.5, such as from about 2.3 to about 2.4, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the dispersity (D) of the second difunctionalized compound is calculated from M w and M n as determined by HT-SEC as described in the Examples Section.
  • a branching number value (per 1000 carbons) that can be from about 1 to about 99, such as from about 5 to about 95, such as from about 10 to about 90, such as from about 15 to about 85, such as from about 20 to about 80, such as from about 25 to about 75, such as from about 30 to about 70, such as from about 35 to about 65, such as from about 40 to about 60, such as from about 45 to about 55, such as about 50, or from about 20 to about 70, such as from about 25 to about 65, such as from about 30 to about 60, such as from about 35 to about 55, such as from about 40 to about 50, though other values are contemplated.
  • the branching number values is the number of branches per 1,000 carbons.
  • the branching number value is calculated based on Equation IB and described in the Examples Section.
  • a CO2 content (per 1000 carbons) that can be from about 0.5 to about
  • the CO2 content is the number of ester bonds per 1,000 carbons.
  • the CO2 content is calculated according to Equation 3 and described in the Examples Section.
  • T c A crystallization temperature (T c ) that can be from about -50°C to about
  • Crystallization temperature (T c ) is determined as described in the Examples Section.
  • J/g to about 200 J/g, such as from about 20 J/g to about 190 J/g, such as from about 30 J/g to about 150 J/g, such as from about 40 J/g to about 120 J/g, such as from about 50 J/g to about 100 J/g, such as from about 60 J/g to about 90 J/g, such as from about 70 J/g to about 80 J/g, though other values are contemplated.
  • Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • Enthalpy of fusion AHf is determined as described in the Examples Section.
  • a degree of crystallinity (X c ) that can be from 0% to about 70%, such as from greater than 0% to about 65%, such as from about 5% to about 50%, such as from about 10% to about 45%, such as from about 15% to about 30%, such as from about 20% to about 25%, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Degree of crystallinity (X c ) is determined as described in the Examples Section.
  • a glass transition temperature (T g ) that can be from about -70.0°C to about -40.0°C, such as from about -65.0°C to about -45.0°C, such as from about - 60.0°C to about -50.0°C, such as from about -60°C to about -55.0°C, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Glass transition temperature (T g ) is determined as described in the Examples Section.
  • a melting transition temperature (T m ) that can be from about 95°C to about 135°C to about, such as from about 100°C to about 130°C, such as from about 105°C to about 125°C to about, such as from about 110°C to about 120°C, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Melting transition temperature (T m ) is determined as described in the Examples Section.
  • a decomposition temperature at 5% weight loss that can be from about 390°C to about 435°C, such as from about 400°C to about 425°C, such as from about 405°C to about 420°C, such as from about 405°C to about 415°C, or from about 410°C to about 420°C, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Decomposition temperature at 5% weight loss (Tas) is determined as described in the Examples Section.
  • a Young’s modulus (E) that can be from about 0.1 megapascals (MPa) to about 1,000 MPa, such as from about 0.5 MPa to about 20 MPa, such as from about 1.0 MPa to about 15 MPa, such as from about 2.0 MPa to about 10 MPa, such as from about 4.0 MPa to about 8.0 MPa, or from about 75 MPa to about 850 MPa, such as from about 80 MPa to about 800 MPa, such as from about 100 MPa to about 600 MPa, such as from about 200 MPa to about 400 MPa, such as from about 250 MPa to about 350 MPa, though other values are contemplated.
  • MPa megapascals
  • Young’s modulus (E) is determined as described in the Examples Section. [0205] (1) A tensile strength (OUTS) that can be from greater than 0 MPa to about 30
  • MPa such as from about 2.0 MPa to about 26 MPa, such as from about 3 MPa to about 25 MPa, such as from about 5 MPa to about 15 MPa, such as from about 8 MPa to about 13 MPa, such as from about 10 MPa to about 12.5 MPa, or from about 15 MPa to about 30 MPa, such as from about 20 MPa to about 27 MPa, such as from about 22 MPa to about 26 MPa, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Tensile strength (OUTS) is determined as described in the Examples Section.
  • 1,100% such as from about 650% to about 1,000%, such as from about 700% to about 900%, such as from about 750% to about 850%, or from about 900% to about 1,100%, or from about 700% to about 850%, such as from about 700% to about 750%, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Elongation at break (sb) is determined as described in the Examples Section.
  • a tensile toughness (UT) that can be from greater than 0 megajoule per cubic meter (MJ/m 3 ) to about 200 MJ/m 3 , such as from about 20 MJ/m 3 to about 180 MJ/m 3 , such as from about 40 MJ/m 3 to about 130 MJ/m 3 , such as from about 60 MJ/m 3 to about 120 MJ/m 3 , such as from about 70 MJ/m 3 to about 100 MJ/m 3 , such as from about 80 MJ/m 3 to about 90 MJ/m 3 , though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Tensile toughness (UT) is determined as described in the Examples Section.
  • Embodiments described herein also relate to processes for decomposing polymers.
  • the terms “decomposing” and “depolymerizing” may, in various nonlimiting embodiments, be used interchangeably herein.
  • the polymer decomposed may be any suitable polymer such as polymers described herein or any suitable copolymer such as copolymers described herein, such as plastics, thermoplastics, plastomers, or elastomers.
  • a process for decomposing (or depolymerizing) a polymer or copolymer comprises decomposing the polymer or the copolymer in the presence of a depolymerization catalyst (such as a pincer catalyst), an optional base, a reducing agent (such as hydrogen gas), and an optional solvent to form a reaction product mixture comprising a first difunctionalized compound and/or a second difunctionalized compound.
  • a depolymerization catalyst such as a pincer catalyst
  • a reducing agent such as hydrogen gas
  • a process for decomposing a polymer (and/or copolymer) comprises one or more of the following operations:
  • the depolymerization catalyst can include any suitable depolymerization catalyst such as a pincer catalyst, a heterogeneous metal catalyst, or combinations thereof. Suitable pincer catalysts and heterogeneous metal catalysts useful for the depolymerization can include one or more of those described herein.
  • the optional base can include one or more of those bases described herein, such as those alkali metal salts of an alcohol, an alkali metal hydroxides, an alkali metal carbonates, or combinations thereof described herein.
  • the optional solvent can include any suitable solvent such as xylene, di chlorobenzene, anisole, tetrahydrofuran, toluene, benzene, dichloromethane, di chloroethane, trichloromethane, o-xylene, m-xylene, p-xylene, xylene isomer mixture, hexane, or combinations thereof, such as xylene, di chlorobenzene, anisole, tetrahydrofuran, toluene, or combinations thereof.
  • the solvents can be mixed at any suitable ratio such as from 10:90 to about 90:10, such as from about 20:80 to about 80:20, such as from about 30:70 to about 70:30, such as from about 40:60 to about 60:40, such as about 50:50, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close- ended range.
  • the depolymerization catalyst can be combined with the optional base and/or the optional solvent.
  • the resulting catalyst solution/suspension can then be introduced with the polymer (and/or copolymer) to form the first reaction mixture.
  • a solid form of the depolymerization catalyst can be added to the polymer (and/or copolymer).
  • the first reaction mixture of operation (a) can include any suitable molar ratio of the depolymerization catalyst (moles) to the total amount (in moles) of the polymer and/or the copolymer, such as from about 1 : 10,000 to about 1 : 1, such as from about 1 :5,000 to about 1 : 1, such as from about 1 :2,000 to about 1 : 100, such as from about 1 : 1000, to about 1 : 150, such as from about 1 :800 to about 1 :200, such as from about 1 :600 to about 1 :400, such as about 1 :500, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • mixtures of polymers and copolymers described herein can be depolymerized together.
  • mixtures of polymers made from hard blocks alone, soft blocks alone, hard and soft blocks, or combinations thereof can be subjected to depolymerization. That is, and in some embodiments, mixed-plastic waste can be depolymerized.
  • the first reaction mixture of operation (a) can include any suitable molar ratio of depolymerization catalyst to the optional base, such as from about 1 :200 to about 1 : 1, such as from about 1 : 100 to about 1 : 1, such as from about 1 :40 to about 1 : 1, such as from about 1 :32 to about 1 :4, such as from about 1 : 16 to about 1 :8, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • the components of the reaction mixture of operation (a) can be mixed, stirred, or agitated, at room temperature or a different temperature, by using suitable devices such as a mechanical stirrer, such as an overhead stirrer, a magnetic stirrer (for example, placing a magnetic stir bar in the vessel above a magnetic stirrer), or other suitable devices.
  • Components of the reaction mixture at operation (c) can be mixed, stirred, or agitated in the presence of a non-reactive gas, such as nitrogen (N2), argon (Ar), or combinations thereof.
  • a non-reactive gas can be introduced with one or components in the reaction mixture to degas various components or otherwise remove unwanted gases such as oxygen from the mixture.
  • a reducing agent is introduced with the first reaction mixture to form a second reaction mixture.
  • the reducing agent may be any reducing agent known in the art and typically includes hydrogen gas (H2), metal hydrides catalyzed by transition metals, and combinations thereof, such as H2.
  • H2 alone can be utilized, or H2 modified with a second gas such as N2 or Ar.
  • the reducing agent may react with any suitable component present in the reaction mixture.
  • the reducing agent can react with functional groups (e.g., esters) present in the polymers (and/or copolymers) and/or can react in concert with the depolymerization catalyst to at least partially reduce functional groups present polymers (and/or copolymers).
  • Operation (b) can be performed in any suitable vessel or reactor such as a pressure reactor.
  • the reducing agent may be added to the vessel that includes the first reaction mixture in any amount and at any pressure.
  • the reducing agent is introduced in an amount that is from about 0.1 to about 20 moles per one mole of polymer repeat unit (and/or copolymer), such as from about 0.25 to about 10 moles per one mole of the polymer (and/or copolymer), such as from about 0.5 to about 5 moles per one mole of the polymer (and/or copolymer), such as from about 0.6 to about 2 moles per one mole of the polymer (and/or copolymer), such as from about 0.7 to about 1 mole per one mole of the polymer (and/or copolymer), though other amounts are contemplated.
  • the reducing agent is introduced to the first reaction mixture at a pressure that is from about 1 bar (about 0.1 MPa) to about 100 bar (about 10 MPa), such as from about 1 bar (about 0.1 MPa) to about 80 bar (about 8 MPa), such as from about 10 bar (about 1.0 MPa) bar to about 50 bar (about 5.0 MPa), such as from about 20 bar (about 2.0 MPa) to about 40 bar (about 2.0 MPa), though other values are contemplated.
  • the components of the reaction mixture of operation (b) can be mixed, stirred, or agitated, at room temperature or a different temperature, by using suitable devices.
  • operation (b) can include sealing the vessel containing the first reaction mixture and cycling the vessel from about 1 to 5 times with about 1.0 MPa to about 3.0 MPa of H2, and then charging the vessel with about 3.0 MPa to about 5.0 MPa of H2.
  • the polymer (and/or copolymer) is decomposed or converted into a first difunctionalized compound and/or a second difunctionalized compound.
  • This decomposing and converting can include heating the vessel containing the hydrogen gas, polymer (and/or copolymer), depolymerization catalyst, optional base, and optional solvent.
  • Temperatures for heating can include any suitable temperature, such as from about 25°C to about 250°C, such as from about 50°C to about 250°C, such as from about 75°C to about 225°C, such as from about 100°C to about 200°C, such as from about 125°C to about 175°C, such as from about 135°C to about 165°C, or about 130°C, or about 150°C, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
  • Conditions for operation (c) can include a reaction time that is from about 0.1 hours to about 200 hours, such as from about 2 hours to about 160 hours, such as from about 10 hours to about 120 hours, such as from about 24 hours to about 96 hours, such as from about 36 hours to about 72 hours, such as about 48 hours, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close- ended range.
  • the components of the reaction mixture of operation (c) can be mixed, stirred, or agitated, by using suitable devices.
  • the decomposition or depolymerization reaction produces a reaction product mixture that includes the first difunctionalized compound and/or the second difunctionalized compound.
  • the percent (%) conversion of the decomposition or depolymerization can be about 50% or more such as about 60% or more, such as about 70% or more, such as about 80% or more, such as about 85% or more, such as about 90% or more, such as about 95% or more, such as about 99% or more, such as about 100%, though other values are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close- ended range. Percent (%) conversion is determined by J H NMR in the appropriate deuterated solvent by analyzing the integration of ester bonds before and after depolymerization as described in the Examples Section.
  • depolymerization of polymers and copolymers of the present disclosure can be performed in the presence of one or more polyolefins.
  • Any suitable polyolefin can be present such as polyethylene, polypropylene, polystyrene, or combinations thereof, among others.
  • Polyethylenes can include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, combinations thereof, among others.
  • the reaction mixture including the polymer (and/or copolymer) can further include one or more polyolefins.
  • the polymers (and/or copolymers) with the polyolefins can then be subjected to decomposition (or depolymerization) conditions described herein. % conversion for this decomposition in the presence of one or more polyolefins can be the same or similar to that described above.
  • Embodiments of the present disclosure also relate to processes for recycling polymers.
  • the terms “recycling” and “re-polymerizing” may, in various non-limiting embodiments, be used interchangeably herein.
  • the polymer decomposed may be any suitable polymer such as polymers described herein or any suitable copolymer such as copolymers described herein, such as plastics, thermoplastics, plastomers, or elastomers.
  • a process for recycling a polymer (and/or copolymer) comprises one or more of the following operations:
  • the decomposition or depolymerization process of operation (a) of the recycling process can be performed according to any suitable embodiment described herein.
  • the conversion process of operation (b) of the recycling process can be performed according to any suitable embodiment described herein such as those embodiments described herein with respect to polymerization processes.
  • any suitable technique can be utilized such as crystallization, recrystallization, precipitation, chromatography, distillation, under various temperatures, pressures, and use of solvents or co-solvents, among other suitable methods.
  • the conversion process of operation (c) of the recycling process polymerizes the first difunctionalized compound and/or the second difunctionalized compound to a selected polymer or copolymer (a recycled polymer and/or recycled copolymer).
  • the recycled polymer has properties that are within ⁇ 30%, such as within ⁇ 20%, such as within ⁇ 15%, such as within ⁇ 10%, such as within ⁇ 5% of the virgin polymer or virgin copolymer submitted to the recycling process.
  • the virgin polymer or virgin copolymer submitted to the recycling process is the polymer or copolymer subjected to the decomposition or depolymerization process of operation (a).
  • Non-limiting examples of copolymers described herein and comparative example copolymers were made using various materials set out in the Materials and are described further below. Selected properties of the compositions were measured using Test Methods.
  • Oxacycloheptadec- 10-en-2-one was purchased from Perfumer Supply House.
  • Lithium aluminum hydride (LAH), cis-cyclooctene (COE), N-bromosuccinimide (NBS), azobisisobutyronitrile (AIBN), magnesium turnings, cuprous iodide (Cui), potassium t-butoxide were purchased from Sigma Aldrich.
  • 1- bromohexane was purchased from Oakwood Chemicals.
  • H2lMes)(PPh3)(Cl)2RuCHPh (Grubbs II) was purchased from Umicore.
  • Anhydrous anisole, anhydrous diethyl ether, tetrahydrofuran (THF), toluene, isopropanol, cyclohexane, and other solvents were purchased from Sigma Aldrich or Fisher. Tetrahydrofuran and toluene were obtained and purified using an mBraun MB- SPS-800 solvent purification system and kept under a nitrogen atmosphere. Ciscyclooctene was dried by stirring over calcium hydride, distilled under vacuum, and then transferred to amber vials in a nitrogen filled glovebox.
  • NMR nuclear magnetic resonance
  • spectra were obtained using a Bruker 400 MHz NMR Spectrometer at 298 K and a Varian 500 MHz NMR Spectrometer at 383 K.
  • Mn Number-average molecular weight
  • M w weight-average molecular weight
  • D dispersity
  • Size exclusion chromatography molecular weight determination High Temperature Size Exclusion Chromatography (HT-SEC) analysis of the polymer samples were performed using a Tosoh EcoSec HLC-8321 High Temperature SEC System with autosampler and a differential refractive index (DRI) detector.
  • the mobile phase used was 1,2,4-trichlorobenzene (TCB) (Fischer Scientific-HPLC Grade) which was used as-received with no inhibitor added.
  • TSKgel guard column HHR (30) HT2 7.5 mm internal diameter (I D.) x 7.5 cm., PN 22891)
  • TSKgel GMHHR (20) HT2 (7.8 mm I.D. x 30 cm columns, PN 22888)
  • two sequential TSKgel G2000 columns HHR (20) HT2 7.8 mm I.D. x 30 cm columns, PN 22890
  • a reference column specifically a TSKgel GMH HR-H (S) HT2 (7.8 mm I.D. x 30cm column, PN 22889) was used.
  • the solvent stock was set to 40°C while the pump oven was set to 50°C.
  • the columns, RI detector, injector valve, and autosampler were all set to 160°C.
  • Samples were prepared in Tosoh 10 mL high temperature sample vials with PTFE caps. 6-20 mg of sample were placed in a Tosoh high temperature 26 pm stainless steel mesh filter and TCB solvent was added to reach an end concentration of about 1.7 mg/mL and heated on the autosampler for two hours with occasional agitation. Samples were injected into a 300 pL sample loop and ran at an operating flow rate of 1.0 mL/min for the sample columns. Meanwhile, the reference column was set to an operating flow rate of 0.5 mL/min. Run times for all standards and samples was 60 minutes. Eco-Sec 8321 software (Tosoh) was used for data processing.
  • DSC Differential scanning calorimetry
  • T m melting transition temperature
  • T g glass transition temperature
  • AHf enthalpy of fusion
  • M w 60.7 kDa
  • TGA Thermogravimetric Analysis
  • WAXS Wide-Angle X-Ray Scattering
  • DMTA Dynamic Mechanical Thermal Analysis
  • a daily performance check was also run which ensured that the instrument was operating properly and obtained a CeO + :Ce + less than 0.025 and a Ce ++ :Ce of less than 0.030.
  • a calibration curve was prepared in Milli Q water by serial dilution of commercially available single-element inductively coupled plasma mass spectrometry (ICP-MS) stock solutions. Internal standard solution consisting of a final concentration of 10 pg/L of iridium (Ir), 10 pg/L rhodium (Rh) and 2500 pg/L lithium-6 ( 6 Li) were infused to each sample during analysis.
  • Ir iridium
  • Rh pg/L rhodium
  • 6 Li 2500 pg/L lithium-6
  • Ru analysis was subjected to internal standard corrections and subsequently drift corrected. Corrections were chosen based on minimizing the coefficient of variance (CV) for the QC samples. Limits of detection (LOD) and limits of quantification (LOQ) were calculated as 3 times or 10 times the standard deviation of the blank divided by the slope of the calibration curve respectively. Final concentrations are given in pg/g. Measured calculations below the LOD were assigned as ⁇ LOD.
  • LOD Limits of detection
  • LOQ limits of quantification
  • FIGS. 2 A, 2B, and 2C show J H NMR spectra of the chain transfer agent, the hard block oligomer, and the soft block oligomer, respectively.
  • the crystallizable hard block was designed to, e.g., imbue high T m and modulus into the polymer
  • the hexyl-functionalized soft block was designed to introduce controlled short-chain C6 branching to create noncrystallizable, elastomeric soft domains. Branching can have substantial influences on polyolefin thermal and mechanical properties by reducing the allowable degree of crystallinity and increasing free volume.
  • FIGS. 2D-2I show J H NMR spectra of the example polymers formed by the polymerizations — PE0, PE20, PE40, PE60, PE80, and PEI 00, where 0, 20, 40, 60, 80, and 100 refers to the % hard blocks in the polymers.
  • the step-growth polymerization of the oligomers was performed by using a ruthenium- catalyzed dehydrogenation polymerization. As further described below with respect to FIGS. 4A-4F, FIGS. 5A-5B, and FIG.
  • the polymers were determined to be high molecular weight polymers (M w that is from about 62.7 kDa to about 90.4 kDa), with high dispersity (D greater than about 2.2).
  • M w that is from about 62.7 kDa to about 90.4 kDa
  • D greater than about 2.2
  • the branching content of the polymers was determined by proton nuclear magnetic resonance spectroscopy ( J H NMR) and was determined to be consistent with the block feed ratios as shown by the stacked 'HNMR of FIG. 7.
  • Tables 1 A and IB show selected properties of various example copolymers PEO, PE20, PE40, PE60, PE80, and PEI 00 of the present disclosure as well as conventional HDPE and conventional LLDPE.
  • x represents the feed ratio of hard block in copolymers.
  • M w refers to weight average molecular weight
  • D refers to dispersity
  • X c degree of crystallinity
  • T g glass transition temperature
  • T m melting transition temperature
  • Tas decomposition temperature at 5% weight loss
  • E Young’s modulus
  • OUTS tensile strength
  • 8b elongation at break
  • UT tensile toughness
  • ro zero-shear viscosity.
  • Average values for E, GUTS, Sb, and UT are provided with standard deviations from the mean value of four to six samples.
  • Tables 1A and IB indicate that embodiments described herein can be utilized to form multiblock copolymers having a variety of properties.
  • the data also demonstrates that various properties of the multiblock copolymers can be changed by controlling the hard-block incorporation.
  • the resulting polymers were determined to be thermally stable, with high decomposition temperatures at 5% weight loss, with Tas values ranging from about 406°C (PE20) to about 421 °C (PE60). These results are consistent with commercially available high-density PE (HDPE; Tas of about 430°C) or linear low-density PE (LLDPE; Tas of about 434°C) samples.
  • HDPE high-density PE
  • LLDPE linear low-density PE
  • crystallinity (X c ) of the polymers increased from 0% (PEO) to about 68% (PE 100) with increasing hard content.
  • Polymers with a hard content that was less than about 80% exhibited low glass temperatures, with a T g value ranging from about -46.5°C (PE60) to about -60.0°C (PE20).
  • T g value ranging from about -46.5°C (PE60) to about -60.0°C (PE20).
  • T m A high melting transition temperature (T m ranging from about 106° to about 124°C) was observed for all multiblock polymers containing hard blocks, a result that is similar to olefin-block copolymers (OBCs).
  • OBCs olefin-block copolymers
  • ro was determined to increase with increasing hard content from PEO (ro of about 3.45> ⁇ 10 5 Pa s) to PE100 (ro of about 447* 10 5 Pa s), indicating that the introduction of short-chain branching reduced entanglement. (See also FIG. 17 and Table 9).
  • these multiblock polymers exhibit increased qo, which can suggest different interactions that may prove advantageous for use at temperatures approaching the T m with reduced concern for material deformation (Table 9). While not wishing to be bound by any particular theory, this result may be due to structural effects imparted by functional group interactions from the addition of esters or from the block-polymer organization and effects due to the disparity in block sequences across varying compositions.
  • PEO a hard content of 0%
  • PE100 a hard content of about 100%
  • sb average strain at break
  • these copolymers also exhibited tunable tensile toughness (UT) ranging from about 0.19 MJ/m 3 (PEO) to about 150 MJ/m 3 (PE100).
  • Example multiblock copolymers PE60, PE80, and PE100 all exhibited thermoplastic behavior with yield points and strain hardening, whereas a yield point was not observed for elastomeric polymers containing lower PE content.
  • the overall thermal and materials properties of these multiblock copolymers are similar to commercial OBCs. They also exhibit greater strain at break relative to commercially available HDPE and LLDPE samples tested in this work, and the toughness of PE80 and PEI 00 are comparable to or exceed that of very tough engineering plastics (greater than about 100 MJ/m 3 ). (See Tables 8A and 8B).
  • the hard and soft oligomeric building blocks were separated and purified in an isolated yield of about 92% with no observable signs of oligomer decomposition by 1 H NMR.
  • the hard and soft blocks were separated through industrially viable selective-solvent isolation by precipitation of the hard block and purified to remove catalyst residues to low parts- per-million levels such that ruthenium levels did not increase during subsequent polymerizations.
  • These recovered oligomers were successfully repolymerized to PE80, which was subsequently depolymerized and repolymerized back into PE80 for two additional cycles with all steps proceeding in high yields. (See Table 11 and Table 12). As shown in FIG. 27 and FIGS.
  • Examples described herein demonstrate that multiblock copolymers can be separated from technologically important isotactic polypropylene (PP) as shown in FIGS. 31A-31B and FIGS. 32A-32B.
  • PP polypropylene
  • Cis-hexadec-6-ene-l,16-diol (CTA, 1-1) was prepared according to the following non-limiting procedure. To a 500 mL round bottom flask with a stir bar was charged with lithium aluminum hydride (LAH, 22.8 g, 0.601 mol) and THF (250 mL) in an ice bath. Ambrettolide (53.2 g, 0.211 mol) in 100 mL THF was dropwise added to the solution with vigorous stirring. The reaction was stirred at room temperature for 12 h.
  • LAH lithium aluminum hydride
  • THF 250 mL
  • Ambrettolide 53.2 g, 0.211 mol
  • Scheme 1 shows an example reaction diagram for a non-limiting synthetic route for hard block and soft block oligomers.
  • R H (hard block) (S1-4a)
  • Hard block oligomer (HO-HB-OH, l-4a) and soft block oligomer (HO-SB-OH, l-4b) were prepared according to the following general non-limiting procedure.
  • a stock solution of catalyst was prepared by dissolving Grubbs II (76.5 mg, 0.09 mmol) and cis-hexadec-6-ene-l,16-diol (CTA, 1- 1, 119 mg, 0.464 mmol) in 1.20 mL THF and stirred for 10 min.
  • the diene oligomers (HO-HB-OH (l-3a) and HO-SB-OH (l-3b)) were dissolved in THF (100 mL) and transferred to a pressure reactor.
  • the reactor was sealed and cycled 4 times with 20 bar (2.0 MPa) H2, and then charged with 40 bar (4.0 MPa) H2.
  • the reactor was heated to 100°C, and stirred at 100 rpm for 12 h.
  • the reactor was cooled to room temperature, recharged with H2 to 40 bar (4.0 MPa), and heated to 100°C and reacted for 24 h. After cooling to room temperature, the reactor was depressurized, and the chamber flushed with nitrogen.
  • HO-HB-OH (l-4a, FIG. 2B): cis-cyclooctene (16.53 g, 0.150 mol) was used as the monomer. After polymerization and hydrogenation, the mixture was washed with THF and dried under vacuum at 100°C for 24 h to afford 13.52 g white solid as the hard block oligomer HO-HB-OH (hydrogenated HO-poly(cyclooctene)-OH, l-4a). A 500 MHz 'H NMR (toluene-d8, 383 K) of HO-HB-OH is shown in FIG. 2B.
  • HO-SB-OH (l-4b, FIG. 2C): 3 -hexylcyclooctene (29.15 g, 0.150 mol) and used as the monomer. After polymerization and hydrogenation, the mixture was precipitated from methanol, dried under vacuum at 100°C for 24 h to afford 21.53 g colorless oil as the soft block HO-SB-OH (hydrogenated HO-poly(3- hexylcyclooctene)-OH, l-4b). A 400 MHz 'H NMR (CDCh, 298 K) of HO-SB-OH is shown in FIG. 2C.
  • the MII,NMR of the hydrogenated oligomer HO-SB-OH (l-4b), calculated by 'H NMR (in CDCh, 298 K) of FIG. 2C is 2.3 kDa.
  • Example 2.D General Procedure for Polymerization/Copolymerization to Form Example Polymers and Example Multiblock Copolymers
  • Method A 1.00 g polymer and 100 mL xylene were combined in a 500 mL flask. After the polymer was completely dissolved at 140°C, the solution was precipitated in 200 mL THF with vigorous stirring. The precipitation was repeated three times and the solid was dried under vacuum for 24 h to give the polyolefin.
  • Method B 1.00 g polymer and 100 mL xylene were combined in a 500 mL flask. After the polymer was completely dissolved at 140°C, the solution was cooled to room temperature. The solid was filtered and washed with THF. The recrystallization was repeated three times and the solid was dried under vacuum for 24 h to give the polyolefin.
  • Method C 1.00 g polymer was dissolved in 100 mL xylene at 135°C. Then, the temperature was set to 90°C. When the temperature stabilized, 2.00 mmol 2- aminoethanethiol (coordinating ligand) was added. After 30 minutes, the solution was precipitated into isopropanol to afford white solid. The solid was washed with isopropanol 3 times and dried under vacuum for 24 h.
  • Method D The soft block was purified by flash chromatography (eluting with THF) on silica gel. The purified samples were analyzed by ICP-MS to determine the residual Ru in the copolymers.
  • the degree of branching and branching number in copolymers can be calculated based on FIGS. 2D-2I.
  • C6 branching and branching numbers for example multiblock copolymers PE0-PE100 and commercial polyethylene references (HDPE and LLDPE) are shown in Table 2.
  • C6 branching was calculated according to Equation 1 A, and the branching number was calculated according to Equation IB.
  • the HDPE sample contains 0.027% methyl branches, 0.049% ethyl branches, 0.058% butyl branches, and 0.063% long branches based on the 13 C NMR spectroscopy of HDPE in tetrachloroethane-d2 (at 403 K).
  • the LLDPE sample contains 1.70% methyl branches, 0.75% ethyl branches, and 0.53% long branches calculated based on the 13 C NMR spectroscopy of LLDPE in tetrachloroethane-d2 (at 403 K).
  • the hard block (mol%) in copolymers can be calculated by: n (hard)
  • Hard (%) — - — X 100% n (hard) + n (soft)
  • the ratio of -CH2- to the -CH2OH (FIG. 2B) for the hard block can be calculated based on the ratio of integration of Hb (208.09) and H a (4.00) as 52.02.
  • the ratio of -CH2- to -CH3 (FIG. 2C) in soft block can be calculated based on the ratio of integration of Hb (291.03) and H c (32.29), which is 9.01.
  • Equation 2 is utilized to calculate hard block (in mol%) in multiblock copolymers:
  • Hard (%) is the molar ratio of hard block in copolymers.
  • the hard block (mol%) and branching number in copolymers can be calculated based on FIGS. 2D-2H.
  • the hard block (in mol%) calculated by Equation 2 can be referred to as HardNMR.
  • the ester bond (-CO2-) per 1000 carbons (C) in copolymers is calculated according to Equation 3 :
  • Example 2.1 Characterizations of Example Copolymers, HDPE, and LLDPE
  • FIGS. 4A-4F show HT-SEC traces (TCB as solvent at 160 °C) of synthesized copolymers PE0-PE100 in comparison with conventional HDPE and LLDPE.
  • FIGS. 5A and 5B show overlayed FT-IR spectra for (A) example PE100 and conventional HDPE, (B) example copolymer PE80 and conventional LLDPE.
  • FIG. 6 shows 13 C NMR spectra (403 K, 125 MHz, tetrachloroethane-d2) of conventional HDPE, conventional LLDPE, and example copolymer PE80.
  • Table 3 presents a summary of selected properties of example copolymers described herein. The CO2 per 1000 C data for PE0-PE100 were calculated based on FIGS.
  • Table 3 also shows crystallinity data for copolymers and commercial polyethylene references.
  • Hardtheo mol%) refers to the theoretical molar ratio of hard blocks in multiblock copolymers.
  • Hardwik (mol%) refers to the molar ratio of hard blocks in according to copolymers determined by 'H NMR and calculated according to Equation 2.
  • CO2 content was calculated according to Equation 3.
  • Mn,sEc (kDa) refers to number-average molecular weight determined by HT-SEC, MW.SEC (kDa) refers to weight-average molecular weight determined by HT-SEC, and D refers to molecular weight distribution.
  • T c refers to crystallization temperature
  • AHf refers to enthalpy of fusion.
  • Table 4 shows the residual content of ruthenium in copolymers and oligomers.
  • polyolefin copolymers and oligomers were weighed into Teflon weighing cups and these were placed into 75 mL Teflon microwave vessels along with a blank sample. Digestion was performed by adding 9.5 mL of redistilled concentrated nitric acid (67-70% HNO3). Each vessel was left to react for 15 minutes after which 0.5 mL of concentrated hydrochloric acid (HC1) was added to each vessel. Each vessel was left to react for 15 minutes prior to sealing to allow any pre-reactions to occur safely before being capped.
  • HC1 concentrated hydrochloric acid
  • Table 4 The data in Table 4 indicates that the catalyst can be removed. It was noted that depolymerization could be successfully performed with this residual catalyst. (See also Table 10, entry 2-22).
  • Table 5 shows a Titan MPS digestion program for digestion of polymer samples. The parameters in Table 5 used for the conditions that give the data in Table 4.
  • Catalyst Ru-1 is carbonylchlorohydrido[6-(di-t-butylphosphinomethyl)-2-(N,N- diethylaminomethyl)pyridine]-ruthenium(II) and has the structure:
  • Catalyst Ru-2 is carbonylchlorohydrido ⁇ bis[2-
  • Table 6 shows example polymerization results using different Pincer catalysts Ru-1 and Ru-2.
  • Temp refers to the reaction temperature
  • time refers to the reaction time
  • [-OH]:[cat] refers to molar ratio of -OH of the block to the catalyst
  • M n ,sEc (kDa) refers to numberaverage molecular weight determined by HT-SEC
  • MW.SEC (kDa) refers to weightaverage molecular weight determined by HT-SEC
  • D refers to molecular weight distribution
  • T m refers to melting transition temperature as measured by DSC
  • AHf refers to enthalpy of fusion
  • X c refers to crystallinity as measured by DSC.
  • FIG. 8 A shows representative stress-strain curves of PEI 00 using catalyst Ru-1 with different loadings. The sample in entry 2-3 was not measured due to the low molecular weight. Representative stress-strain curves of example PEI 00 using catalyst Ru-2 with different loadings is shown in FIG. 8B. Young’s modulus data of various example PElOOs are shown in FIG. 8C.
  • FIGS. 9A-9B shows photographs of example PEI 00 in Table 6.
  • Catalyst Ru-1 was used to make those samples shown in FIG. 9 A (entry 2-1, entry 2-2, and entry 2-4). The sample in entry 2-3 was not processed due to its low molecular weight.
  • Catalyst Ru-2 was used to make those samples shown in FIG. 9B (entry 2-5, entry 2-6, and entry 2-7). Under the conditions tested, catalyst Ru-2 produced pale-yellow materials while Ru-1 produced darker materials.
  • the data in Table 6 and FIGS. 8A-8C and the images of FIGS. 9A-9B indicated that lowering the catalyst concentration or using different ruthenium complexes can produce less colored materials. This indicates that embodiments described herein can be utilized when plastics of higher transparency or lower colored materials are desired such as in biomedical and food packaging applications.
  • FIGS. 10A-10H shows that example copolymers PE0-PE100 have comparable Tas values with conventional HDPE and conventional LLDPE.
  • Example 2.M Differential Scanning Calorimetry Analysis for Example Copolymers, HDPE, and LLDPE
  • FIGS. 13A-13C provide non-limiting data of the dynamic mechanical relaxation behavior for multiblock polymers and polyethylene controls, showing storage modulus E’ (FIG. 13 A), loss modulus E” (FIG. 13B), and tan( ⁇ 5) (FIG. 13C).
  • T g was determined as the peak of the loss modulus E” .
  • T g was not detected for samples PE80, PEI 00, and HDPE which is consistent with high degrees of crystallinity and low amorphous content, limiting detection of the glass transition.
  • Non-limiting results are presented in Table 7.
  • Table 7 show that copolymers described herein have properties that can be polyolefin-like and/or superior to conventional polyolefins.
  • Table 7 Locations of characteristic peaks from DMTA and comparison to T g from
  • Example 2.0 Selected Properties of Olefin Copolymers, PE0-PE100, and Commercial Polyolefins
  • Tables 8 A and 8B shows selected properties of example olefin copolymers PE0-PE100 made by step-growth polymerization described herein. Commercial polyolefins are shown as comparative examples. Ethyl ene-octene block copolymers are formed by the chain shuttling method. Glass transition temperature (T g ) was determined by DMTA and crystallinity (X c ) was determined by DSC. Densities for PE0-PE100 prepared by melt compression at 150°C and quenching at 30°C/min to room temperature.
  • Tables 8A and 8B includes the following:
  • b Data is from H. P. Wang et al., Characterization of Some New Olefinic Block Copolymers, Macromolecules 40, 2852-2862 (2007).
  • d Data is from D. J. Arriola et al., Catalytic production of olefin block copolymers via chain shuttling polymerization, Science 312, 714-719 (2006).
  • f Data is from ENGAGETM Polyolefin Elastomer: Product Selection Guide, form no. 777-088-0 IE-0819, The Dow Chemical Company.
  • g Data is from PETILEN YY S0464 High Density Polyethylene (HDPE), Petkim Petrochemical Holding Inc.
  • h Data is from M. P. F. Pepels et al., From polyethylene to polyester: Influence of ester groups on the physical properties, Macromolecules 46, 7668-7677 (2013).
  • 1 Data is from Y. Na et al., Direct synthesis of polar-functionalized linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE), Macromolecules 51, 4040-4048 (2016).
  • j Data is from DOW ELITETM 5940G Technical Data Sheet, form no. 400- 00130293 en, The Dow Chemical Company (2009).
  • Example 2.P Wide-angle X-ray Scattering of Example Copolymers, HDPE, and LLDPE
  • FIG. 15 shows overlaid X-ray scattering patterns for multiblock polymers PE0-PE100, conventional LLDPE, and conventional HDPE.
  • the X-ray scattering patterns illustrate the contributions from the orthorhombic unit cell of polyethylene as well as amorphous polyethylene. As shown in FIG. 15, the relative intensities of the crystalline components increase while the amorphous component decreases with increasing hard content.
  • FIG. 16A-16H shows PLOM images at 500* magnification of example multiblock polymers and polyethylene controls. As shown, crystallites were evident in all samples possessing hard blocks and can be observed to increase in size as a function of hard block content. Overall, multiblock crystallites are reduced in size compared to control polyethylene samples with no ester content (e.g., PEI 00 to HDPE, PE80 to LLDPE).
  • Creep testing was performed on example copolymers, conventional HDPE, and conventional LLDPE. Creep tests can be utilized to determine the amount of deformation a material experiences over time while under a continuous tensile or compressive load at a constant temperature.
  • creep compliance is a metric of the rate at which strain increases for a constant applied stress. The relationship of creep compliance of melted copolymers and step time were measured by rheology at 150°C to determine the zero-shear viscosity of copolymers from the creep compliance /(t') according to Equation 5: wherein: T o is zero-shear viscosity; t' is time; and J is creep compliance.
  • FIG. 17 shows the relationship of creep compliance with step time for example copolymers PE0-PE100, conventional HDPE, and conventional LLDPE.
  • Per Equation 5 zero-shear viscosity was extrapolated from curves shown in FIG. 17 to the limit of zero-shear.
  • linear PE a direct correlation between zero-shear viscosity and the molecular weight is expected.
  • Table 9 shows molecular weight data and zero shear-rate viscosities of example copolymers, and comparative examples including HDPE and LLDPE. Unless otherwise indicated, zero-shear viscosity (T o , Pa s) was determined by creep testing at 150°C, and branches per 1000C were determined by 'H and 13 C NMR. mHDPE refers to metallocene-HDPE and mLLDPE refers to metallocene-LLDPE. For samples OBC- R01, OBC-R03, OBC-R09, and OBC-R17, the zero-shear viscosity (T] 0 , Pa s) was tested at 135°C.
  • Table 9 includes the following:
  • Example 2 Uniaxial Tensile Testing of Example Copolymers, HDPE, and LLDPE
  • FIGS. 19A-19H show tensile stress-strain curves for samples PE0-PE100, conventional LLDPE, and conventional HDPE. Material toughness of these samples were calculated by manual integration of the area under the tensile curve. The Young’ s modulus (E), tensile strength (OUTS), elongation at break (8b) and toughness (UT) were determined based on the stress-strain curves as presented in Tables 1 A and IB (above).
  • FIGS. 20A-20F shows images of PE samples after tensile testing.
  • Example 2.T Mechanical Properties of Example Copolymers, Olefin Block Copolymers, and Random Copolymers
  • FIGS. 22 A and 22B show selected mechanical properties of example copolymers (PE0-PE100), conventional olefin block copolymers (OBCs), and conventional random copolymers. Specifically, FIGS. 22A and 22B shows Young’s modulus (E) of copolymers as a function of density and elongation at break of copolymers as a function of density, respectively. Data of copolymers and OBC is from Tables 8A and 8B. Data for random copolymer is from EO87 and Dow’s commercial random copolymers (Tables 8A and 8B). Example 2.U. Example Depolymerization Conditions
  • Table 10 shows non-limiting depolymerization conditions tested for the depolymerization of PEO. Unless otherwise indicated, the conditions for the data in Table 10 included use of 0.02 mmol PEO and catalyst Ru-1 (2.22 mM in solvent). For entry 2-23, catalyst Ru-2 was used. For entry 2-24, PE 100 was used after removing the catalyst (89 ppm Ru in polymer). Conversions were determined by J H NMR in tetrachloroethane-d2 (383 K) by analyzing the integration of ester bonds before and after reactions. In Table 10, “[ester]: [cat] :[t-BuOK]” refers to the molar ratio of the ester of the polymer to the catalyst to the t-BuOK base. For entry 2-22, residual catalyst from the polymerization catalyzed the depolymerization after about 24 hours.
  • FIG. 24 is a series of photographs showing the mixture of PE0-PE100 samples (left panel), the depolymerization products (HO-SB-OH and HO-HB-OH) in different vials (center panel) and repolymerized/recycled products as an example multiblock copolymer PE80 (right panel). It is noted that the soft block oligomer HO-SB-OH is liquid and the hard block oligomer HO-HB-OH is solid.
  • FIG. 25 shows 'H NMR spectra (383 K, 500 MHz, tetrachloroethane-d2) of mixed copolymers and recycled oligomers (mixture in toluene).
  • FIG. 26A and FIG. 26B show 1 H NMR spectra (500 MHz, tetrachloroethane-d2) of recycled and purified oligomers. Specifically, FIG. 26A shows the recycled and purified hard blocks (383 K), and FIG. 26B shows the recycled and purified soft blocks (298 K).
  • this example demonstrates that copolymers described herein can be depolymerized according to embodiments described herein.
  • PE80 was recycled (repolymerized) from de-polymerized copolymers.
  • the hard block oligomer HO-HB-OH (2.52 g) and the soft block oligomer HO-SB-OH (1.10 g) from the depolymerization of mixed copolymers were dried in a 50 mL Schlenk tube at 130°C under vacuum for 2 h. Under N2 flow, a 20.0 mL anisole solution of catalyst Ru-1 (1.00 mg/mL, 1.00 mol% to the -OH bond) was added to the storage tube via syringe, and the temperature was raised to 150°C with stirring.
  • the mixture was stirred for 48 h. Then, the mixture was diluted with 25.0 mL xylene at 140°C, precipitated in isopropanol (150 mL) to give re-polymerized PE80-RP1.
  • the isolated PE80-RP1 was dried under vacuum at 130°C for 24 h.
  • FIG. 27 shows overlaid HT-SEC traces of the virgin PE80, recycled/repolymerized 1 * (PE80 RP-1), recycled/repolymerized 2* (PE80 RP-2), and recycled/repolymerized 3* (PE80 RP-3). After complete depolymerization and repolymerization (recycling), the attainable molecular weight of chemically recycled copolymers was similar compared to the virgin PE80 polymer.
  • FIG. 28A shows DSC traces of virgin PE80, repolymerized 1 * (PE80 RP- 1), repolymerized 2* (PE80 RP-2), and repolymerized 3* (PE80 RP-3).
  • FIG. 28B shows TGA traces of virgin PE80, re-polymerized 1 x (PE80 RP-1), re-polymerized 2* (PE80 RP-2), and re-polymerized 3* (PE80 RP-3).
  • FIG. 30A-30D shows tensile testing of (A) recycled PE80 RP-1, (B) recycled PE80 RP-2, (C) recycled PE80 RP-3, and (D) comparison of moduli for virgin and recycled PE80 samples.
  • PE80-RP1 was depolymerized back to the oligomers using the general procedure described above. Hard blocks were purified by recrystallization and soft blocks were purified by flash chromatography (THF as eluting solvent). The obtained oligomers were used to make new PE80.
  • an example copolymer (PE60) was depolymerized in the presence of polypropylene.
  • This example illustrates, e.g., a potential polyolefin waste stream and that embodiments of the present disclosure can be utilized with waste streams.
  • FIG. 3 IB is a series of photographs showing the depolymerization of a mixture of polypropylene (PP) and example multiblock copolymer PE60 according to at least one embodiment of the present disclosure.
  • the photographs show the polyolefin waste stream in toluene (left panel), reaction after 72 hours (middle panel), and the separated and purified PP, hard block oligomer HO-HB-OH, and soft block oligomer HO-SB-OH (right panel).
  • Example 2.Y Example Depolymerization of PE60 in the Presence of Polypropylene at 175°C
  • an example copolymer (PE60) was depolymerized in the presence of polypropylene at a temperature of 175°C.
  • This example illustrates, e.g., a potential polyolefin waste stream and that embodiments of the present disclosure can be utilized with waste streams.
  • FIG. 32A shows photographs of the depolymerization of PP/PE60 at 175°C for 24 h, separated and purified oligomers (HO-HB-OH and HO-SB-OH) and PP.
  • 32B shows a 'H NMR spectra (500 MHz, tetrachloroethane-d2) of purified HO-SB-OH (298 K), purified HO-HB-OH (383 K), and purified PP (403 K).
  • Depolymerization was performed according to the following non-limiting procedure. In a N2 filled glovebox, PE60 (0.642 g) and a polypropylene (PP) microcentrifuge tube (0.997 g) were combined in a 25 mL vial with a stir bar. Potassium tert-butoxide (24.2 mg) and a 11.30 mL toluene solution of catalyst Ru-1 (1.00 mg/mL) were added to the vial. The vial was taken out of the glovebox and transferred to the pressure reactor. The pressure reactor was sealed and cycled 4 times with 20 bar (2.0 MPa) H2, and then charged with 40 bar (4.0 MPa) H2.
  • Separation was performed according to the following nonlimiting procedure: The mixture was heated to 90°C for 1 h to dissolve the oligomers. After separating undissolved solid from the mixture, the solution was cooled to room temperature. Excess hexanes was added and the mixture was stirred for 30 minutes, then centrifuged to separate the solid and the solution. The solid was recrystallized in a 10.0 mL toluene solution of 2-aminoethanethiol (0.02 M' 1 ), washed with isopropanol (3x5.0 mL), and dried under vacuum at 80°C for 24 h to give 0.285 g hard blocks (HO-HB-OH, 87.2% isolated yield).
  • Embodiments of the present disclosure generally relate to multiblock copolymers and to uses thereof. Embodiments of the present disclosure also generally relate to processes for making multiblock copolymers, to processes for depolymerizing multiblock copolymers, and to processes for chemically recycling multiblock copolymers.
  • the ability to synthesize multiblock polymers remains a challenge most commonly met through tedious sequential monomer additions.
  • synthesizing multiblock polymers from hard and soft aliphatic oligomers possessing identical chain end groups as described herein can create a platform to produce highly tunable polyolefin-like materials and their closed-loop chemical recycling process, including in the presence of other commercially important plastics.
  • a process for forming a copolymer comprising: forming a first reaction mixture comprising a first difunctionalized compound, and a second difunctionalized compound, wherein: the first difunctionalized compound comprises a compound having two first reactive chain end groups; the second difunctionalized compound comprises a compound having two second reactive chain end groups, the second difunctionalized compound being different from the first difunctionalized compound; and the two second reactive chain end groups of the second difunctionalized compound are identical to the two first reactive chain end groups of the first difunctionalized compound; introducing a catalyst, and an optional solvent with the first reaction mixture to form a second reaction mixture; and reacting the second reaction mixture to induce step-growth polymerization of the first difunctionalized compound and the second difunctionalized compound to form a copolymer comprising a reaction product or an adduct of the first and second difunctionalized compounds.
  • a process for forming a copolymer comprising: forming a first reaction mixture comprising a first difunctionalized compound, and a second difunctionalized compound, wherein: the first difunctionalized compound comprises a linear aliphatic compound having two first reactive chain end groups; the second difunctionalized compound comprises a branched aliphatic compound having two second reactive chain end groups; and the two second reactive chain groups of the second difunctionalized compound are identical to the two first reactive chain end groups of the first difunctionalized compound; introducing a pincer catalyst, a base, and an optional solvent with the first reaction mixture to form a second reaction mixture; and reacting the second reaction mixture to induce step-growth polymerization of the first difunctionalized compound and the second difunctionalized compound to form a copolymer comprising a reaction product or an adduct of the first and second difunctionalized compounds.
  • Clause 3 The process of Clause 1 or Clause 2, wherein: a molar ratio of the pincer catalyst to the first and second difunctionalized compounds is from about 1 : 10 to about 1 : 10,000; a molar ratio of the pincer catalyst to the base is from about 1 : 100 to about 1 : 1; the reacting the second reaction mixture is performed at a temperature that is from about 25°C to about 250°C; when the optional solvent is present, the optional solvent comprises xylene, di chlorobenzene anisole, tetrahydrofuran, toluene, or combinations thereof; or combinations thereof.
  • Clause 4 The process of any one of Clauses 1-3, wherein the first difunctionalized compound is represented by Formula (I): wherein: A of Formula (I) comprises or is a linear C2-C200 hydrocarbyl; m of Formula (I) is an integer from about 1 to about 1000; w of Formula (I) is an integer from about 1 to about 20; x of Formula (I) is an integer from about 1 to about 20; and each of X 1 and X 2 of Formula (I) is, independently, hydroxyl, thiol, amine, isocyanate, carboxylic acid, halogen, epoxy, aldehyde, or alkene.
  • a of Formula (I) comprises or is a linear C2-C200 hydrocarbyl
  • m of Formula (I) is an integer from about 1 to about 1000
  • w of Formula (I) is an integer from about 1 to about 20
  • x of Formula (I) is an integer from about 1 to about 20
  • each of X 1 and X 2 of Formula (I) is, independently, hydroxyl or thiol; w of Formula (I) is about 7; x of Formula (I) is about 5; or combinations thereof.
  • Clause 7 The process of any one of Clauses 1-6, wherein the second difunctionalized compound is represented by Formula (IIA): wherein: at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 of Formula (IIA) is an unsubstituted C1-C20 hydrocarbyl or a substituted C1-C20 hydrocarbyl; n of Formula (IIA) is an integer from about 1 to about 1000; y of Formula (IIA) is, independently, an integer from about 1 to about 20; z of Formula (IIA) is, independently, an integer from about 1 to 20; and each of X 3 and X 4 of Formula (IIA) is, independently, hydroxyl, thiol, amine, isocyanate, carboxylic acid, halogen, epoxy, aldehyde, or alkene.
  • Formula (IIA) wherein: at least one of R 1 , R 2
  • Clause 8 The process of Clause 7, wherein: one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 of Formula (IIA) is an unsubstituted C1-C20 hydrocarbyl or a substituted Cl- C20 hydrocarbyl; and the seven remaining R groups of Formula (IIA) are hydrogen.
  • Clause 9 The process of Clause 7 or Clause 8, wherein: R 7 of Formula (IIA) is an unsubstituted Cl -CIO hydrocarbyl; and each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 8 of Formula (IIA) is hydrogen.
  • Clause 10 The process of any one of Clauses 7-9, wherein: each of X 3 and X 4 of Formula (IIA) is, independently, hydroxyl or thiol; y of Formula (IIA) is about 7; and z of Formula (IIA) is about 5.
  • Clause 11 The process of any one of Clauses 1-10, wherein the catalyst comprises a metal complex combined with a base and the base comprises an alkali metal salt of an alcohol, an alkali metal hydroxide, an alkali metal carbonate, or combinations thereof.
  • Clause 12 The process of Clause 11, wherein: when the base comprises the alkali metal salt of the alcohol, the alkali metal salt of the alcohol comprises an alkali metal salt of methanol, alkali metal salt of ethanol, alkali metal salt of isopropanol, alkali metal salt of tert-butanol, alkali metal salt of phenol, or combinations thereof; when the base comprises the alkali metal hydroxide, the alkali metal hydroxide comprises LiOH, NaOH, KOH, or combinations thereof; or combinations thereof.
  • Clause 13 The process of any one of Clauses 1-11, wherein the catalyst comprises a pincer catalyst having a structure represented by Formula (VII): M 2 (L 3 )ZY 3 Y 4 (VII), wherein:
  • M of Formula (VII) is a Group 7 to Group 10 metal of the periodic table of the elements; each of Z, Y 3 , and Y 4 of Formula (VII) is, independently, carbon monoxide (CO), triphenylphosphine, pyridine, tetrahydrofuran, dimethylsulfoxide, hydrogen, hydrogen anion hydroxide, chlorine or anion thereof, bromine or anion thereof, iodine or anion thereof, BH4 or anion thereof (BH4 ), BH3CN or anion thereof (BH3CN ), BH(Et)3 or anion thereof (BH(Et)3 ), BH(sec-Bu)3 or anion thereof (BH(sec-Bu)3 ), AIH4 or anion thereof (AIH4 ), or combinations thereof; and L 3 in Formula (VII) is a tridentate ligand represented by Formula (VIII): wherein: each of mi and m2 of Formula (VIII) is, independently, an integer from 1 to 3 ;
  • R 20 of Formula (VIII) is hydrogen, substituted or unsubstituted Ci- C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C7-C25 arylalkyl, substituted or unsubstituted C4-C20 heteroaryl; each of R 21 , R 22 , R 31 , and R 32 of Formula (VIII) is, independently, hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C4-C24aryl or heteroaryl, or R 21 and R 22 , or R 31 and R 32 can connect to form a C3-C10 cycloalkyl, C4-C24 aryl, or C4-C24 heteroalkyl; and each of R 23 ,
  • Clause 15 The process of any one of Clauses 1-14, wherein the catalyst comprises a heterogeneous metal catalyst comprising one or more metals.
  • Clause 16 The process of any one of Clauses 1-15, wherein a molar ratio of the first difunctionalized compound to the second difunctionalized compound is from about 1 :99 to about 99: 1.
  • Clause 17 The process of any one of Clauses 1-16, wherein the first difunctionalized compound, the second difunctionalized compound, or both have functionality greater than two.
  • Clause 18 The process of any one of Clauses 1-17, further comprising introducing a third difunctionalized compound with the first reaction mixture or to the second reaction mixture and prior to reacting the second reaction mixture, wherein: the third difunctionalized compound comprises a compound having two third reactive chain end groups; the two third reactive chain end groups of the third difunctionalized compound are identical to the two first reactive chain end groups of the first difunctionalized compound and to the two second reactive chain end groups of the second difunctionalized compound; and the third difunctionalized compound is different from the first and second difunctionalized compounds.
  • a process for decomposing a copolymer comprising: forming a first reaction mixture comprising a copolymer, a depolymerization pincer catalyst or a heterogeneous metal catalyst, an optional base, and an optional solvent; introducing hydrogen gas with the first reaction mixture to form a second reaction mixture; and decomposing the copolymer to a reaction product mixture comprising a first difunctionalized compound and a second difunctionalized compound that is different from the first difunctionalized compound.
  • a molar ratio of the depolymerization pincer catalyst or the heterogeneous metal catalyst to the copolymer comprises from about 1 : 10,000 to about 1 : 1; a molar ratio of the depolymerization pincer catalyst to the optional base is from about 1 :200 to about 1 :1; when the optional solvent is present, the optional solvent comprises xylene, dichlorbenzene, anisole, tetrahydrofuran, toluene, or combinations thereof; the hydrogen gas is introduced with the first reaction mixture at a pressure that is from about 0.5 MPa to about 8.0 MPa; the decomposing the copolymer to the reaction product mixture is performed at a temperature that is from about 25°C to about 250°C; the decomposing the copolymer to the reaction product mixture is performed for a period that is from about 1 hour to about 96 hours; or combinations thereof.
  • Clause 21 The process of Clause 19 or Clause 20, wherein the first reaction mixture further comprises a polyolefin that is different from the copolymer.
  • Clause 22 The process of Clause 21, wherein the polyolefin comprises polyethylene, polypropylene, polystyrene, or combinations thereof.
  • a process comprising: performing a step-growth polymerization on a reaction mixture to form a copolymer comprising a reaction product or an adduct of a first difunctionalized compound and a second difunctionalized compound, the reaction mixture comprising: the first difunctionalized compound comprising a linear aliphatic compound having two first reactive chain end groups; the second difunctionalized compound comprising a branched aliphatic compound having two second reactive chain end groups, the two second reactive chain groups of the second difunctionalized compound being identical to the two first reactive chain end groups of the first difunctionalized compound; a transition metal catalyst comprising a tridentate ligand and a Group 7 to Group 10 metal of the periodic table of the elements, the Group 7 to Group 10 metal selected from the group consisting of Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt; and a base.
  • Clause 24 The process of Clause 23, wherein the copolymer has one or more of the following properties: a M w that is from about 10.0 kDa to about 1000.0 kDa as determined by HT-SEC; a dispersity according to HT-SEC that is from about 2.0 to about 3.0 as determined by HT-SEC; a branching number per 1,000 carbons that is from about 20 to about 70; and a CO2 content per 1,000 carbons that is from about 1.0 to about 20.0.
  • a M w that is from about 10.0 kDa to about 1000.0 kDa as determined by HT-SEC
  • a dispersity according to HT-SEC that is from about 2.0 to about 3.0 as determined by HT-SEC
  • a branching number per 1,000 carbons that is from about 20 to about 70
  • a CO2 content per 1,000 carbons that is from about 1.0 to about 20.0.
  • Clause 25 The process of Clause 23 or Clause 24, wherein the first difunctionalized compound, the second difunctionalized compound, or both have functionality greater than two.
  • Clause 26 The process of any one of Clauses 23-26, wherein the reaction mixture further comprises an additional functionalized compound, the additional functionalized compound having two third reactive chain end groups as the first and second difunctionalized compounds, the additional functionalized compound being different from both the first and the second difunctionalized compounds.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “Is” preceding the recitation of the composition, element, or elements and vice versa, such as the terms “comprising,” “consisting essentially of,” “consisting of’ also include the product of the combinations of elements listed after the term.
  • the recitation of the numerical range 1 to 5 includes the subranges 1 to 4, 1.5 to 4.5, 1 to 2, among other subranges.
  • the recitation of the numerical ranges 1 to 5, such as 2 to 4 includes the subranges 1 to 4 and 2 to 5, among other subranges.
  • within a range includes every point or individual value between its end points even though not explicitly recited.
  • the recitation of the numerical range 1 to 5 includes the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, among other numbers.
  • every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
  • the indefinite article “a” or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise.
  • embodiments comprising “a base” includes embodiments comprising one, two, or more bases, unless specified to the contrary or the context clearly indicates only one base is included.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyethers (AREA)

Abstract

Des modes de réalisation de la présente invention concernent de manière générale des copolymères multiblocs et leurs utilisations. Des modes de réalisation de la présente invention concernent également de manière générale des procédés de fabrication de copolymères multiblocs, des procédés de dépolymérisation de copolymères multiblocs, et des procédés de recyclage chimique de copolymères multiblocs. Dans un mode de réalisation, un procédé permettant de constituer un copolymère est prévu. Le procédé consiste à constituer un premier mélange réactionnel comprenant un premier composé difonctionnalisé présentant deux premiers groupes réactifs de terminaison de chaîne, et un deuxième composé difonctionnalisé présentant deux deuxièmes groupes réactifs de terminaison de chaîne. Le procédé comprend en outre l'introduction d'un catalyseur et d'un solvant facultatif dans le premier mélange réactionnel pour constituer un deuxième mélange réactionnel ; et la réaction du deuxième mélange réactionnel pour induire une polymérisation par étapes du premier composé difonctionnalisé et du deuxième composé difonctionnalisé pour constituer un copolymère comprenant un produit de réaction ou un adduit du premier et du deuxième composés difonctionnalisés.
PCT/US2024/012214 2023-01-19 2024-01-19 Copolymères multiblocs recyclables Ceased WO2024155919A2 (fr)

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US63/449,634 2023-03-03

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EP1273626B1 (fr) * 2001-07-06 2006-05-17 Toyo Boseki Kabushiki Kaisha Composition de résine aqueuse, matériau aqueux de revétement contenant cette composition, revétement de ce matériau et tôle de metal enduite de cette composition
WO2007119305A1 (fr) * 2006-03-15 2007-10-25 Kansai Paint Co., Ltd. Composition de revêtement et procédé de formation d'un film de revêtement
CA2707101A1 (fr) * 2007-11-29 2009-06-04 University Of Saskatchewan Procede de fabrication de catalyseurs a base de polyol
CA2928181A1 (fr) * 2013-10-22 2015-04-30 Elevance Renewable Sciences, Inc. Polyols de polyester et leurs procedes de production et d'utilisation
CN109415304B (zh) * 2016-06-27 2022-07-22 株式会社可乐丽 铁络合物的制造方法和使用了铁络合物的酯化合物的制造方法
CN109971552B (zh) * 2019-03-28 2022-12-02 浙江嘉澳环保科技股份有限公司 一种由废弃油脂制备环氧增塑剂以及氯代增塑剂的方法

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