WO2025238198A1 - Method of preparing low residual monomer polymers - Google Patents

Abstract

Methods of producing polymers or polymer compositions are described herein. The method of preparing a polymer or a polymer composition includes mixing a catalyst deactivator and a polymer (e.g., caprolactone polymer or polycaprolactone) comprising monomers, and performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture, thereby forming the polymer or the polymer composition.

Description

METHOD OF PREPARING LOW RESIDUAL MONOMER POLYMERS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to, and the benefit of, U.S. Provisional Patent Application No. 63/649,140, filed 17 May 2024, which is incorporated by reference herein in its entirety for all purposes.

BACKGROUND OF THE INVENTION

[0002] Field of the Discovery. The present disclosure relates to methods for preparing polymers or polymer compositions and compositions using the same and methods of making the same.

[0003] Background Information. Residual monomers are present in polymers after their production due to the chemical equilibrium between the monomer and the polymer comprising the monomers. While devolatilization processes can be used to remove monomers, monomers will reform as the catalyst catalyzes the reaction towards monomer production. Furthermore, residual monomers can migrate, thereby limiting the use of the polymer in certain applications, such as the use in products that come into contact with food.

[0004] Thus, there remains a need in the art for methods to produce polymers or polymer compositions that have lower residual monomer content. The present disclose describes a novel method that surprisingly and unexpectedly provides polymers or polymer compositions with low residual monomer content. The present disclosure further provides compositions using the polymers or polymer compositions of the present disclosure, and methods of making the same.

SUMMARY

[0005] Presently described methods of preparing a polymer or polymer composition, as well as compositions comprising the same and methods of making the same.

[0006] Thus, in an aspect, the present disclosure provides a method of preparing a polymer or polymer composition, the method comprising, consisting essentially of, or consisting of: mixing a catalyst deactivator and a polymer (e.g., caprolactone polymer or poly caprolactone) comprising monomers; and performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture, thereby forming the polymer or polymer composition.

[0007] In any aspect or embodiment described herein, the catalyst deactivator is a metal deactivator.

[0008] In any aspect or embodiment described herein, the catalyst chelates or complexes with the active metal of the catalyst.

[0009] In any aspect or embodiment described herein, at least one of (i) the catalyst deactivator inhibits or prevents depolymerization of the polymer; (ii) the catalyst deactivator targets a catalyst that catalyzes the polymerization of the polymer; (iii) the catalyst deactivator targets a catalyst that catalyzes the depolymerization of the polymer; or (iv) a combination thereof.

[0010] In any aspect or embodiment described herein, the catalyst deactivator targets a ring-opening polymerization catalyst (e.g., a ring-opening polymerization catalyst that catalyzes the polymerization of the polymer).

[0011] In any aspect or embodiment described herein, the catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of a phosphate-based catalyst deactivator, a crown ether catalyst deactivator, a carboxylic acid catalyst deactivator, or a combination thereof.

[0012] In any aspect or embodiment described herein, at least one of (i) the phosphate- based catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of octadecyl phosphate (e.g., ADK STAB AX-71, CAS No. 39471-52-8; Adeka, Tokyo, Japan), ammonium phosphate dibasic, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (BOTDPU), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (e.g., IRGANOX® 1222, CAS No. 976-56-7; BASF, Ludwigshafen on the Rhine, Germany), triisodecyl phosphite (e.g., ADK STAB 3010, CAS No. 25448-25-3; Adeka, Tokyo, Japan), or a combination thereof; (ii) the crown ether catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of 18-crown 6, 12-crown 4, 15-crown 5, or a combination thereof; (iii) the catalyst deactivator includes or is ethanediamide, N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) (e.g., Tinuvin® 312); (iv) the carboxylic acid catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of: l,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (e.g., IRGANOX® MD 1024, CAS No. 32687-78-8; BASF, Ludwigshafen on the Rhine, Germany); tartaric acid; acrylic polymer (e.g., BIOSTRENGTH® 150; Arkema, Colombes, France); acrylic copolymer (e.g., BIOSTRENGTH® 700; Arkema, Colombes, France); 2-Propenoic acid, 2-methyl-, butyl ester, polymer with butyl 2-propenoate and methyl 2-methyl-2-propenoate, glycine, N-methyl-N-(l- oxododecyl)-, sodium salt, or a combination thereof (e.g., BIOSTRENGTH® 900; Arkema, Colombes, France); 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate (e.g., IRGANOX® 1035, CAS No. 41484-35-9; BASF, Ludwigshafen on the Rhine, Germany); 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (e.g., IRGANOX® 1520, CAS No. 110553-27-0; BASF, Ludwigshafen on the Rhine, Germany); or a combination thereof; or (v) a combination thereof.

[0013] In any aspect or embodiment described herein, the method further comprises adding the catalyst deactivator to the polymer, wherein the catalyst deactivator is a powder.

[0014] In any aspect or embodiment described herein, the method further comprises adding the catalyst deactivator to the polymer, wherein the catalyst deactivator is a liquid deactivator composition.

[0015] In any aspect or embodiment described herein, at least one of (i) the liquid deactivator composition comprises the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof (e.g., the liquid deactivator composition comprises about 0.1 wt% to about 45 wt% or about 5.0 wt% to about 15.0 wt% of the catalyst deactivator); (ii) the liquid deactivator composition is prepared by mixing the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof, at a temperature of about 70°C to about 110°C (e.g., about 75°C to about 105°C or about 80°C to about 100°C); (iii) the liquid deactivator composition is prepared by mixing the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof, in a mixer or a mixer heat exchanger; or (iv) a combination thereof.

[0016] In any aspect or embodiment described herein, the catalyst deactivator is present in an amount of about 100 parts per million (ppm) to about 2500 ppm of the polymer-catalyst deactivator mixture.

[0017] In any aspect or embodiment described herein, at least one of (i) mixing the catalyst deactivator and the polymer (e.g., caprolactone polymer or polycaprolactone) comprising monomers includes mixing the catalyst deactivator and the polymer in a mixer heat exchanger; (ii) performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer- catalyst deactivator mixture is performed in a devolatilization unit that includes or is at least one of an extruder (e.g., single screw extruder or a second screw extruder), a falling strand devolatilizer, a wiped-film evaporator, a large-volume kneader, a falling film evaporator, a tube evaporator, a flash evaporator, or a combination thereof; (iii) performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture is performed at a temperature equal to or less than about 300°C; or (iv) a combination thereof.

[0018] In any aspect or embodiment described herein, at least one of (i) the devolatilization unit is an extruder (e.g., single screw extruder or a second screw extruder); (ii) the polymer is a poly caprolactone (e.g., at least one of a poly caprolactone polyol, a thermoplastic poly caprolactone, a thermoplastic poly caprolactone polyol, or a combination thereof); (iii) the catalyst deactivator is present in an amount of about 500 parts per million (ppm) to about 1500 ppm (e.g., about 750 ppm to about 1250 ppm) of the polymer-catalyst deactivator mixture; (iv) performing devolatilization of the polymer-catalyst deactivator mixture is performed at a temperature of less than or equal to about 225°C (e.g., less than or equal to about 215°C, less than or equal to about 205°C, or less than or equal to about 200°C); or (v) a combination thereof.

[0019] In any aspect or embodiment described herein, at least one of (i) the monomer content in the polymer or polymer composition is less than about 5 wt% (e.g., less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1.5 wt%, less than about 1 wt%, less than about 0.5 wt%, or about 0.01 wt% to about 5.0 wt%); (ii) the polymer content in the polymer or polymer composition is greater than about 90 wt% or 95 wt% (e.g., about 90 wt% to about 100 wt%, about 90 wt% to about 99 wt%, or about 90 wt% to about 98 wt%); or (iii) a combination thereof.

[0020] In any aspect or embodiment described herein, the method further comprises, prior to mixing the catalyst deactivator and the polymer, polymerizing the monomers into the polymer with a catalyst (e.g., mixing and incubating the polymer or polymer composition with the catalyst).

[0021] In any aspect or embodiment described herein, the catalyst deactivator targets the catalyst.

[0022] The preceding general areas of utility are given by way of example only and are not intended to be limiting on the scope of the present disclosure and appended claims. Additional objects and advantages associated with the compositions, methods, and processes of the present disclosure will be appreciated by one of ordinary skill in the art in light of the instant claims, description, and examples. For example, the various aspects and embodiments of the present disclosure can be utilized in numerous combinations, all of which are expressly contemplated by the present disclosure. These additional advantages objects and embodiments are expressly included within the scope of the present disclosure. The publications and other materials used herein to illuminate the background of the invention, and in particular cases, to provide additional details respecting the practice, are incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate several embodiments of the present disclosure and, together with the description, serve to explain the principles of the disclosure. The drawings are only for the purpose of illustrating an embodiment of the disclosure and are not to be construed as limiting the disclosure. Further objects, features and advantages of the disclosure will become apparent from the following detailed description taken in conjunction with the accompanying figures showing illustrative embodiments of the disclosure.

[0024] Figure 1 shows that devolatilization effectively reduces the residual monomer (%) in the polycaprolactone composition and that the residual monomer (%) increased with the heat treatment.

[0025] Figure 2 shows melt flow index (MFI) of thermoplastic poly caprolactone (baseline) and thermoplastic poly caprolactone with catalyst deactivator ADK STAB AX-71, wherein the melt flow index was increased relative to the baseline and increased as the amount of catalyst deactivator ADK STAB AX-71 increased from 100 ppm to 750 ppm.

[0026] Figure 3 shows that the melt flow index (MFI) of the thermoplastic polycaprolactone did not increase with the treatment with catalyst deactivator IRGANOX® MD 1024, thereby demonstrating the stability of the thermoplastic poly caprolactone.

DETAILED DESCRIPTION

[0027] The present disclosure will now be described more fully hereinafter, but not all embodiments of the disclosure are shown. While the disclosure has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the disclosure. In addition, many modifications can be made to adapt a particular structure or material to the teachings of the disclosure without departing from the essential scope thereof.

[0028] Where a range of values is provided, it is understood that each intervening value between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges can independently be included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either/or both of those included limits are also included in the present disclosure.

[0029] The following terms are used to describe the present invention. In instances where a term is not specifically defined herein, that term is given an art-recognized meaning by those of ordinary skill applying that term in context to its use in describing the present invention.

[0030] The articles “a” and “an” as used herein and in the appended claims are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article unless the context clearly indicates otherwise. By way of example, “an element” means one element or more than one element.

[0031] The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements can optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0032] As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e., “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.”

[0033] As used herein in the specification and in the claims, “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from anyone or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a nonlimiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0034] In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to and do not exclude additional, unrecited element(s) or method step(s)). It is expressly contemplated that all embodiments, and claims reciting one of the open-ended transitional phrases can be written with any other transitional phrase, which may be more limiting, unless clearly precluded by the context or art. Only the transitional phrases “consisting of’ and “consisting essentially of’ shall be closed (e.g., excludes any additional, unrecited element or method step) or semi-closed transitional phrases (e.g., that is, only allows inclusion of additional, unrecited element(s) or method step(s) that do not materially affect the basic and novel characteristic(s) of that particular embodiment), respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

[0035] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from anyone or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements can optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a nonlimiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc. It should also be understood that, unless clearly indicated to the contrary, in any methods claimed herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited.

[0036] Surprisingly and unexpectedly, the inventors discovered a method of producing polymers and polymer compositions with low residual monomers. In any aspect or embodiment described herein, the polymer or polymer composition is made by a process comprising, consisting essentially of, or consisting of, mixing a catalyst deactivator and a polymer (e.g., caprolactone polymer or polycaprolactone) comprising monomers; and performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture, thereby forming the polymer or polymer composition.

[0037] METHOD OF MAKING POLYMERS OR POLYMER COMPOSITIONS

[0038] Thus, an aspect of the present disclosure relates to a method of preparing a polymer or polymer composition, the method comprising, consisting essentially of, or consisting of, mixing a catalyst deactivator and a polymer (e.g., caprolactone polymer or poly caprolactone) comprising monomers; and performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture, thereby forming the polymer or polymer composition.

[0039] In any aspect or embodiment described herein, the catalyst deactivator is a metal deactivator. In any aspect or embodiment described herein, the catalyst chelates or complexes with the active metal of the catalyst.

[0040] In any aspect or embodiment described herein, the catalyst deactivator inhibits or prevents depolymerization of the polymer. In any aspect or embodiment described herein, the catalyst deactivator targets a catalyst that catalyzes the polymerization of the polymer. In any aspect or embodiment described herein, the catalyst deactivator targets a catalyst that catalyzes the depolymerization of the polymer.

[0041] In any aspect or embodiment described herein, the catalyst deactivator targets a ring-opening polymerization catalyst. For example, in any aspect or embodiment described herein, the catalyst deactivator targets a ring-opening polymerization catalyst that catalyzes the polymerization of the polymer.

[0042] In any aspect or embodiment described herein, the catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of a phosphate-based catalyst deactivator, a crown ether catalyst deactivator, a carboxylic acid catalyst deactivator, or a combination thereof.

[0043] In any aspect or embodiment described herein, the phosphate-based catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of octadecyl phosphate (e.g., ADK STAB AX-71, CAS No. 39471-52-8; Adeka, Tokyo, Japan), ammonium phosphate dibasic, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (BOTDPU), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (e.g., IRGANOX® 1222, CAS No. 976-56-7; BASF, Ludwigshafen on the Rhine, Germany), triisodecyl phosphite (e.g., ADK STAB 3010, CAS No. 25448-25-3; Adeka, Tokyo, Japan), or a combination thereof.

[0044] In any aspect or embodiment described herein, the crown ether catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of 18-crown 6, 12-crown 4, 15-crown 5, or a combination thereof.

[0045] In any aspect or embodiment described herein, the catalyst deactivator includes or is ethanediamide, N-(2-ethoxyphenyl)-N’-(2-ethylphenyl) (e.g., Tinuvin® 312).

[0046] In any aspect or embodiment described herein, the carboxylic acid catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of: l,2-bis(3,5-di-tert-butyl- 4-hydroxyhydrocinnamoyl)hydrazine (e.g., IRGANOX® MD 1024, CAS No. 32687-78-8; BASF, Ludwigshafen on the Rhine, Germany); tartaric acid; acrylic polymer (e.g., BIOSTRENGTH® 150; Arkema, Colombes, France); acrylic copolymer (e.g., BIOSTRENGTH® 700; Arkema, Colombes, France); 2-Propenoic acid, 2-methyl-, butyl ester, polymer with butyl 2-propenoate and methyl 2-methyl-2-propenoate, glycine, N-methyl-N-(l -oxododecyl)-, sodium salt, or a combination thereof (e.g., BIOSTRENGTH® 900; Arkema, Colombes, France); 2-[2-[3-(3,5- ditert-butyl-4-hy droxypheny l)propanoy loxy] ethylsulfanyl] ethyl 3 -(3 , 5-ditert-butyl-4- hydroxyphenyl)propanoate (e.g., IRGANOX® 1035, CAS No. 41484-35-9; BASF, Ludwigshafen on the Rhine, Germany); 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (e.g., IRGANOX® 1520, CAS No. 110553-27-0; BASF, Ludwigshafen on the Rhine, Germany); or a combination thereof. [0047] In any aspect or embodiment described herein, the method further comprises adding the catalyst deactivator to the polymer or polymer composition. For example, in any aspect or embodiment described herein, the method further comprises adding the catalyst deactivator to the polymer or polymer composition, wherein the catalyst deactivator is a powder. By way of further example, in any aspect or embodiment described herein, the method further comprises adding the catalyst deactivator to the polymer or polymer composition, wherein the catalyst deactivator is a liquid deactivator composition.

[0048] In any aspect or embodiment described herein, the liquid deactivator composition comprises the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof. For example, in any aspect or embodiment described herein, the catalyst deactivator is present in the liquid deactivator composition in an amount of about 0.1 wt% to about 45.0 wt%, about 0.1 wt% to about 40.0 wt%, about 0.1 wt% to about 35.0 wt%, about 0.1 wt% to about 30.0 wt%, about 0.1 wt% to about 25.0 wt%, about 0.1 wt% to about 20.0 wt%, about 0.1 wt% to about 15.0 wt%, about 0.1 wt% to about 10.0 wt%, about 0.1 wt% to about 5.0 wt%, about 2.5 wt% to about 45.0 wt%, about 2.5 wt% to about 40.0 wt%, about 2.5 wt% to about 35.0 wt%, about 2.5 wt% to about 30.0 wt%, about 2.5 wt% to about 25.0 wt%, about 2.5 wt% to about 20.0 wt%, about 2.5 wt% to about 15.0 wt%, about 2.5 wt% to about 10.0 wt%, about 2.5 wt% to about 5.0 wt%, about 5.0 wt% to about 45.0 wt%, about 5.0 wt% to about 40.0 wt%, about 5.0 wt% to about 35.0 wt%, about 5.0 wt% to about 30.0 wt%, about 5.0 wt% to about 25.0 wt%, about 5.0 wt% to about 20.0 wt%, about 5.0 wt% to about 15.0 wt%, about 5.0 wt% to about 10.0 wt%, about 10.0 wt% to about 45.0 wt%, about 10.0 wt% to about 40.0 wt%, about 10.0 wt% to about 35.0 wt%, about 10.0 wt% to about 30.0 wt%, about 10.0 wt% to about 25.0 wt%, about 10.0 wt% to about 20.0 wt%, about 10.0 wt% to about 15.0 wt%, about 15.0 wt% to about 45.0 wt%, about 15.0 wt% to about 40.0 wt%, about 15.0 wt% to about 35.0 wt%, about 15.0 wt% to about 30.0 wt%, about 15.0 wt% to about 25.0 wt%, about 15.0 wt% to about 20.0 wt%, about 20.0 wt% to about 45.0 wt%, about 20.0 wt% to about 40.0 wt%, about 20.0 wt% to about 35.0 wt%, about 20.0 wt% to about 30.0 wt%, about 20.0 wt% to about 25.0 wt%, about 25.0 wt% to about 45.0 wt%, about 25.0 wt% to about 40.0 wt%, about 25.0 wt% to about 35.0 wt%, about 25.0 wt% to about 30.0 wt%, about 30.0 wt% to about 45.0 wt%, about 30.0 wt% to about 40.0 wt%, about 30.0 wt% to about 35.0 wt%, about 35.0 wt% to about 45.0 wt%, about 35.0 wt% to about 40.0 wt%, about 40.0 wt% to about 45.0 wt%.

[0049] In any aspect or embodiment described herein, the liquid deactivator composition is prepared by mixing the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof, at a temperature of about 70°C to about 110°C. For example, in any aspect or embodiment described herein, the liquid deactivator composition is prepared by mixing the catalyst deactivator and at least one the monomers, the polymer, or a combination thereof, at a temperature of about 70°C to about 110°C, about 70°C to about 100°C, about 70°C to about 90°C, about 70°C to about 80°C, about 80°C to about 110°C, about 80°C to about 100°C, about 80°C to about 90°C, about 90°C to about 110°C, about 90°C to about 100°C, or about 100°C to about

110°C.

[0050] In any aspect or embodiment described herein, the liquid deactivator composition is prepared by mixing the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof, in a mixer or a mixer heat exchanger.

[0051] In any aspect or embodiment described herein, the catalyst deactivator is present in an amount of about 100 parts per million (ppm) to about 2500 ppm of the polymer-catalyst deactivator mixture. For example, in any aspect or embodiment described herein, the catalyst deactivator is present in the polymer-catalyst deactivator mixture in an amount of about 100 ppm to about 2500 ppm, about 100 ppm to about 2250 ppm, about 100 ppm to about 2000 ppm, about 100 ppm to about 1750 ppm, about 100 ppm to about 1500 ppm, about 100 ppm to about 1250 ppm, about 100 ppm to about 1000 ppm, about 100 ppm to about 750 ppm, about 100 ppm to about 600 ppm, about 250 ppm to about 2500 ppm, about 250 ppm to about 2250 ppm, about 250 ppm to about 2000 ppm, about 250 ppm to about 1750 ppm, about 250 ppm to about 1500 ppm, about 250 ppm to about 1250 ppm, about 250 ppm to about 1000 ppm, about 250 ppm to about 750 ppm, about 500 ppm to about 2500 ppm, about 500 ppm to about 2250 ppm, about 500 ppm to about 2000 ppm, about 500 ppm to about 1750 ppm, about 500 ppm to about 1500 ppm, about 500 ppm to about 1250 ppm, about 500 ppm to about 1000 ppm, about 750 ppm to about 2500 ppm, about 750 ppm to about 2250 ppm, about 750 ppm to about 2000 ppm, about 750 ppm to about 1750 ppm, about 750 ppm to about 1500 ppm, about 750 ppm to about 1250 ppm, about 1000 ppm to about 2500 ppm, about 1000 ppm to about 2250 ppm, about 1000 ppm to about 2000 ppm, about 1000 ppm to about 1750 ppm, about 1000 ppm to about 1500 ppm, about 1250 ppm to about 2500 ppm, about 1250 ppm to about 2250 ppm, about 1250 ppm to about 2000 ppm, about 1250 ppm to about 1750 ppm, about 1500 ppm to about 2500 ppm, about 1500 ppm to about 2250 ppm, about 1500 ppm to about 2000 ppm, about 1750 ppm to about 2500 ppm, about 1750 ppm to about 2250 ppm, or about 2000 ppm to about 2500 ppm.

[0052] In any aspect or embodiment described herein, mixing the catalyst deactivator and the polymer (e.g., caprolactone polymer or polycaprolactone) comprising monomers includes mixing the catalyst deactivator and the polymer in a mixer heat exchanger.

[0053] In any aspect or embodiment described herein, performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture is performed in a devolatilization unit that includes or is at least one of an extruder (e.g., single screw extruder or a second screw extruder), a falling strand devolatilizer, a wiped-film evaporator, a large- volume kneader, a falling film evaporator, a tube evaporator, a flash evaporator, or a combination thereof.

[0054] In any aspect or embodiment described herein, performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture is performed at a temperature equal to or less than about 300°C. For example, in any aspect or embodiment described herein, performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer-catalyst deactivator mixture is performed at a temperature equal to or less than about 300°C, equal to or less than about 275°C, equal to or less than about 250°C, equal to or less than about 225°C, equal to or less than about 200°C, equal to or less than about 190°C, equal to or less than about 180°C, equal to or less than about 175°C, equal to or less than about 160°C, equal to or less than about 150°C, equal to or less than about 125°C, equal to or less than about 100°C, about 50°C to about 300°C, about 50°C to about 275°C, about 50°C to about 250°C, about 50°C to about 225°C, about 50°C to about 200°C, about 50°C to about 175°C, about 50°C to about 150°C, about 50°C to about 125°C, about 50°Cto about 300°C, about 50°C to about 275°C, about 50°C to about 250°C, about 50°C to about 225°C, about 50°C to about 200°C, about 50°C to about 175°C, about 50°C to about 150°C, about 50°C to about 125°C, about 50°C to about 100°C, about 75°C to about 300°C, about 75°C to about 275°C, about 75°C to about 250°C, about 75°C to about 225°C, about 75°C to about 200°C, about 75°C to about 175°C, about 75°C to about 150°C, about 75°C to about 125°C, about 100°C to about 300°C, about 100°C to about 275°C, about 100°C to about 250°C, about 100°C to about 225°C, about 100°C to about 200°C, about 100°C to about 175°C, about 100°C to about 150°C, about 125°C to about 300°C, about 125°C to about 275°C, about 125°C to about 250°C, about 125°C to about 225°C, about 125°C to about 200°C, about 125°C to about 175°C, about 150°C to about 300°C, about 150°C to about 275°C, about 150°C to about 250°C, about 150°C to about 225°C, about 150°C to about 200°C, about 175°C to about 300°C, about 175°C to about 275°C, about 175°C to about 250°C, about 175°C to about 225°C, about 200°C to about 300°C, about 200°C to about 275°C, about 200°C to about 250°C, about 225°C to about 300°C, about 225°C to about 275°C, or about 250°C to about 300°C. [0055] In any aspect or embodiment described herein, at least one of (i) the devolatilization unit is an extruder (e.g., single screw extruder or a second screw extruder); (ii) the polymer is a poly caprolactone (e.g., at least one of a poly caprolactone polyol, a thermoplastic poly caprolactone, a thermoplastic poly caprolactone polyol, or a combination thereof); (iii) the catalyst deactivator is present in an amount of about 500 parts per million (ppm) to about 1500 ppm (e.g., about 750 ppm to about 1250 ppm) of the polymer-catalyst deactivator mixture; (iv) performing devolatilization of the polymer-catalyst deactivator mixture is performed at a temperature of less than or equal to about 225°C (e.g., less than or equal to about 215°C, less than or equal to about 205°C, or less than or equal to about 200°C); or (v) a combination thereof.

[0056] In any aspect or embodiment described herein, the monomer content in the polymer or polymer composition is less than about 5 wt% (e.g., less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1.5 wt%, less than about 1 wt%, less than about 0.5 wt%, less than about 0.1 wt%, less than about 0.05 wt%, or about 0.01 wt% to about 5.0 wt%). For example, in any aspect or embodiment described herein, the monomer content in the polymer or polymer composition is less than about 5 wt% less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1.5 wt%, less than about 1 wt%, less than about 0.5 wt%, about 0.01 wt% to about 5.0 wt%, about 0.01 wt% to about 4.0 wt%, about 0.01 wt% to about 3.0 wt%, about 0.01 wt% to about 2.0 wt%, about 0.01 wt% to about 1.0 wt%, about 0.1 wt% to about 5.0 wt%, about 0.1 wt% to about 4.0 wt%, about 0.1 wt% to about 3.0 wt%, about 0.1 wt% to about 2.0 wt%, about 0.1 wt% to about 1.0 wt%, about 1.0 wt% to about 5.0 wt%, about 1.0 wt% to about 4.0 wt%, about 1.0 wt% to about 3.0 wt%, about 1.0 wt% to about 2.0 wt%, about 2.0 wt% to about 5.0 wt%, about 2.0 wt% to about 4.0 wt%, about 2.0 wt% to about 3.0 wt%, about 3.0 wt% to about 5.0 wt%, about 3.0 wt% to about 4.0 wt%, or about 4.0 wt% to about 5.0 wt%.

[0057] In any aspect or embodiment described herein, the polymer content in the polymer or polymer composition is greater than about 90 wt% or 95 wt% (e.g., about 90 wt% to about 100 wt%, about 90 wt% to about 99 wt%, or about 90 wt% to about 98 wt%). For example, in any aspect or embodiment described herein, the polymer content in the polymer or polymer composition is greater than or equal to about 90.0 wt%, greater than or equal to about 90.5 wt%, greater than or equal to about 91.0 wt%, greater than or equal to about 91.5 wt%, greater than or equal to about 92.0 wt%, greater than or equal to about 92.5 wt%, greater than or equal to about 93.0 wt%, greater than or equal to about 93.5 wt%, greater than or equal to about 94.0 wt%, greater than or equal to about 94.5 wt%, greater than or equal to about 95.0 wt%, greater than or equal to about 95.5 wt%, greater than or equal to about 96.0 wt%, greater than or equal to about

96.5 wt%, greater than or equal to about 97.0 wt%, greater than or equal to about 97.5 wt%, greater than or equal to about 98.0 wt%, greater than or equal to about 98.5 wt%, greater than or equal to about 99.0 wt%, greater than or equal to about 99.5 wt%, greater than or equal to about 99.9 wt%, greater than or equal to about 99.95 wt%, greater than about 99.95 wt%, about 90.0 wt% to about 100 wt%, about 90.0 wt% to about 99.95 wt%, about 90.0 wt% to about 99.9 wt%, about 90.0 wt% to about 99.5 wt%, about 90.0 wt% to about 99.0 wt%, about 90.0 wt% to about

98.5 wt%, about 90.0 wt% to about 98.0 wt%, about 90.0 wt% to about 97.5 wt%, about 90.0 wt% to about 97.0 wt%, about 92.5 wt% to about 100 wt%, about 92.5 wt% to about 99.95 wt%, about 92.5 wt% to about 99.9 wt%, about 92.5 wt% to about 99.5 wt%, about 92.5 wt% to about 99.0 wt%, about 92.5 wt% to about 98.5 wt%, about 92.5 wt% to about 98.0 wt%, about 92.5 wt% to about 97.5 wt%, about 92.5 wt% to about 97.0 wt%, about 95.0 wt% to about 100 wt%, about 95.0 wt% to about 99.95 wt%, about 95.0 wt% to about 99.9 wt%, about 95.0 wt% to about 99.5 wt%, about 95.0 wt% to about 99.0 wt%, about 95.0 wt% to about 98.5 wt%, about 95.0 wt% to about 98.0 wt%, about 95.0 wt% to about 97.5 wt%, about 97.5 wt% to about 100 wt%, about 97.5 wt% to about 99.95 wt%, about 97.5 wt% to about 99.9 wt%, about 97.5 wt% to about 99.5 wt%, about 97.5 wt% to about 99.0 wt%, about 97.5 wt% to about 98.5 wt%, about 98.5 wt% to about 100 wt%, about 98.5 wt% to about 99.95 wt%, about 98.5 wt% to about 99.9 wt%, about 98.5 wt% to about 99.5 wt%, about 99.0 wt% to about 100 wt%, about 99.0 wt% to about 99.95 wt%, about 99.0 wt% to about 99.9 wt%, about 99.0 wt% to about 99.5 wt%, about 99.5 wt% to about 100 wt%, about 99.5 wt% to about 99.95 wt%, about 99.5 wt% to about 99.9 wt%, about 99.8 wt% to about 100 wt%, about 99.8 wt% to about 99.95 wt%, about 99.85 wt% to about 100 wt%, about 99.85 wt% to about 99.95 wt%, about 99.9 wt% to about 100 wt%, or about 99.95 wt% to about 100 wt%.

[0058] In any aspect or embodiment described herein, the method further comprises, prior to mixing the catalyst deactivator and the polymer, polymerizing the monomers into the polymer with a catalyst. For example, in aspect or embodiment described herein, the method further comprises, prior to mixing the catalyst deactivator and the polymer, polymerizing the monomers into the polymer with a catalyst, thereby producing a polymer or a polymer composition, and mixing and/or incubating the polymer or the polymer composition with the catalyst.

[0059] In any aspect or embodiment described herein, the catalyst deactivator targets the catalyst utilized to polymerize the monomers into polymers.

[0060] In any aspect or embodiment described herein, at least one of the monomers are caprolactone (e.g., s-caprolactone), the polymer is poly caprolactone, or a combination thereof.

[0061] As used herein, the term “caprolactone” is intended to encompass unsubstituted caprolactone and substituted caprolactone. The term “s-caprolactone” is intended to encompass unsubstituted s-caprolactone and substituted s-caprolactone. Unsubstituted s-caprolactone is particularly preferred.

[0062] In any aspect or embodiment described herein, polymerization may include the polymerization of caprolactone, particularly s-caprolactone, with a mixture of different caprolactones, for example, substituted and unsubstituted caprolactones or a mixture of caprolactones having different substituents.

[0063] In any aspect or embodiment described herein, substituted s-caprolactone monomers that may be used in the production of the caprolactone polyols include C1-12 alkyl substituted s-caprolactone, C1-12 alkenyl substituted s-caprolactone, C1-12 alkynyl substituted s- caprolactone, CM 8 cycloalkyl substituted s-caprolactone, C1-12 alkoxy substituted s-caprolactone, Ci-i8 aryl substituted s-caprolactone, CMS alkaryl substituted s-caprolactone, CMS aralkyl substituted s-caprolactone, CMS aryloxy substituted s-caprolactone, and mixtures thereof.

[0064] In any aspect or embodiment described herein, substituted s-caprolactone monomers that may be used in the production of the auxiliary caprolactone polyols include mono- , di- or tri-substituted monomers. In any aspect or embodiment described herein, exemplary substituted s-caprolactone monomers include monomethyl s-caprolactone, monoethyl s- caprolactone, monopropyl s-caprolactone, monomethoxy s-caprolactone, monoethoxy s- caprolactone, monopropoxy s-caprolactone, monobenzyl s-caprolactone, monophenyl s- caprolactone, dimethyl s-caprolactone, diethyl s-caprolactone, dipropyl s-caprolactone, dimethoxy s-caprolactone, diethoxy s-caprolactone, dipropoxy s-caprolactone, dibenzyl s- caprolactone, diphenyl s-caprolactone, and mixtures thereof.

[0065] In any aspect or embodiment described herein, the polymer includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) of poly caprolactone, polyethylene (e.g., at least one of low density polyethylene, high density polyethylene, or a combination thereof), polypropylene, poly(vinyl chloride), poly(vinylidene chloride), polystyrene, polyacrylonitrile, polytetrafluoroethylene, poly(methyl methacrylate), poly(vinyl acetate), cis-polyisoprene, polychloroprene (at least one of cis, trans, or a combination thereof), rubber (e.g., at least one of synthetic rubber, natural rubber, or a combination thereof), or a combination thereof.

[0066] In any aspect or embodiment described herein, the monomers includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) of caprolactone, ethylene, propylene, vinyl chloride, vinylidene chloride, styrene, acrylonitrile, tetrafluoroethylene, methyl methacrylate, vinyl acetate, isoprene, chloroprene, lactic acid, Isoprene, 1,3-butadiene, or a combination thereof.

[0067] An additional aspect of the present disclosure relates to a polymer composition comprising at least one of a polymer content as described herein (e.g., greater than about 90 wt% or 95 wt%), a monomer content as described herein (e.g., less than about 0.5 wt%, less than about 0.1 wt%, or less than about 0.05 wt%), or a combination thereof.

[0068] ADDITIONAL METHODS AND COMPOSITIONS OF THE PRESENT

DISCLOSURE [0069] A further aspect of the present disclosure is a method of making a bioplastic, the method comprising: preparing the polymer or polymer composition (e.g., poly caprolactone or polycaprolactone composition) according to the method of the present disclosure, and blending and/or reacting the polymer or polymer composition with at least one (e.g., 1, 2, 3, 4, 5, 6, or more) bioplastic (e.g., one or more (e.g., 1, 2, 3, 4, 5, 6, or more). For example, in any aspect or embodiment described herein, the at least one bioplastic includes or is a polysaccharide-based bioplastic, a protein-based bioplastic, an aliphatic bio-polyester, a bio-derived polyethylene, a lipid-based bioplastic, or a mixture thereof). In any aspect or embodiment described herein, the bioplastic is a durable bioplastic (e.g., bio-polyethylene terephthalate (bio-PET), biopolyethylene, or a combination thereof, which are bio-based analogues of fossil-based polyethylene terephthalate and polyethylene) or a degradable bioplastics (e.g., polylactic acid, polybutylene succinate, polyhydroxyalkanoate, or a combination thereof).

[0070] Another aspect of the present disclosure is a method of preparing a polymer or blend, the method comprising: preparing the polymer or polymer composition (e.g., polycaprolactone or polycaprolactone composition) according to the method of the present disclosure, and blending and/or reacting the polymer or polymer composition with polylactic acid (PLA), poly(butylene adipate-co-terephthalate (PBAT), a polylactic acid (PLA) bioplastic, a poly hydroxy butyrate (PHB) bioplastic, a thermoplastic starch (TPS) bioplastic, a poly(l,4- butylene succinate) (PBS) bioplastic, a polyhydroxyalkanoates (PHA) bioplastic, or a mixture thereof.

[0071] EXAMPLES

[0072] The details of the examples are contemplated as further embodiments of the described methods and compositions. Therefore, the details as set forth herein are hereby incorporated into the detailed description as alternative embodiments. It was surprising and unexpected discovered that the methods of the present disclosure provides polymers or polymer compositions with low residual monomer content.

[0073] Example 1. Examination of Monomer Reversion

[0074] Monomer reversion occurs as the catalyst is still active at the end of the reaction, even after the devolitisation stage. This can be seen by taking devolitised material with a low residual monomer level, and reprocessing this in an extruder or polymer reactor and mixing the material at an elevated temperature (>150°C) for an extended period of time. It can be seen by measuring the material on a Gas Chromatography-Flame Ionization Detection (GC-FID) that the residual monomer level will increase over time as the polymer back-biting occurs.

[0075] Monomer reversion of CAPA® 2201 (2000 MW polycaprolactone polyol diol initiated with neopentyl glycol; Ingevity UK Ltd, Warrington, United Kingdom) was examined with a Gas Chromatography-Flame Ionization Detection (GC-FID) without treatment (baseline) or with treatment with one of diammonium hydrogenphosphate (DAP; Sigma-Aldrich, Saint Louis, Missouri), IRGANOX® MD 1024 (l,2-bis(3,5-di-tert-butyl-4- hydroxyhydrocinnamoyl)hydrazine, CAS No. 32687-78-8; BASF, Ludwigshafen on the Rhine, Germany), or ADK STAB AX-71 (CAS No. 39471-52-8; Adeka, Tokyo, Japan). The residual monomer (%) was examined prior to devolatilization, after devolatilization, as well as after a 5 minute, 7.5 minute, 10 minute, and 15 minute incubation after devolatilization, each at 250°C.

[0076] The data is shown in Figure 1. The data demonstrates that devolatilization effectively reduces the residual monomer (%) in the polycaprolactone composition and that the residual monomer (%) increased with the heat treatment.

[0077] Example 2. Examination of the Melt Flow Index (MFI) of Polycaprolactone Treated with an Exemplary Catalyst Deactivator

[0078] Melt flow index (MFI) of CAPA® 6500 D (50,000 MW linear thermoplastic poly caprolactone diol polymer, CAS No. 24980-41-4; Ingevity UK Ltd, Warrington, United Kingdom) was examined as a baseline, as well as with the treatment of the thermoplastic polycaprolactone composition with 100 ppm, 300 ppm, and 750 ppm of ADK STAB AX-71 (octadecyl phosphate, CAS No. 39471-52-8; Adeka, Tokyo, Japan). Melt flow index (MFI) was examined utilizing ASTM D1238-10 (2013) - Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer and/or ISO 1133-1:2022 - Plastics: Determination of the melt mass-flow rate (MFR) and melt volume-flow rate (MVR) of thermoplastics, wherein the melt flow index is the amount (grams) of the sample that flows through a capillary of a specific diameter and length in 10 minutes by a pressure applied. In particular, 2.16 kg weight was used with the barrel at 160°C.

[0079] The data is shown in Figure 2. The data demonstrates that melt flow index of thermoplastic poly caprolactone increased with the addition of ADK STAB AX-71, relative to baseline, with the melt flow index increasing as the amount of ADK STAB AX-71 increased from 100 ppm to 750 ppm. The data demonstrates that ADK STAB AX-71 is a highly efficient deactivator, but the high acid value of the deactivator composition results in some breakdown of the polymer chains of the thermoplastic polycaprolactone.

[0080] Melt flow index (MFI) of CAPA® 6500 D (50,000 MW linear thermoplastic poly caprolactone diol polymer, CAS No. 24980-41-4; Ingevity UK Ltd, Warrington, United Kingdom) was examined as a baseline, as well as with the treatment of the thermoplastic polycaprolactone composition with 750 ppm of IRGANOX® MD 1024 (l,2-bis(3,5-di-tert-butyl- 4-hydroxyhydrocinnamoyl)hydrazine, CAS No. 32687-78-8; BASF, Ludwigshafen on the Rhine, Germany).

[0081] The data is shown in Figure 3. The data demonstrates that a reduction in molecular weight was not observed when the thermoplastic poly caprolactone was treated with IRGANOX® MD 1024. Of note, the higher value for both the baseline and treated composition as the time period examined approached 365 days is believed to be due to the number of melting/solidification cycles.

[0082] Example 3. Examining Devolatilization Conditions and Catalyst Deactivator Loading Levels

[0083] Polycaprolactone (CAPA® 6500D, molecular weight of 50,000 g/mol (MW); Ingevity UK) and the deactivator (SONGNOX® 1024) were combined in a twin screw extruder at 160°C in amounts sufficient to achieve a Deactivator Masterbatch comprising 5 wt% of the deactivator in poly caprolactone. The torque was reduced from 71% to 67% and the melt pressure reduced from 14 bar to 13 bar when the deactivator was added to the poly caprolactone, thereby producing a Deactivator Masterbatch for subsequent use to examined devolatilization conditions and catalyst deactivator levels.

[0084] A multifactorial design of experiments was utilized to minimize caprolactone monomers and maintain the molecular weight of the caprolactone polymer in the polycaprolactone composition. A multifactorial design of experiments with four factors at different levels was utilized: (1) poly caprolactone mass flow rates of 6 kilograms/hour (k/g), 9 kg/h, and 12 kg/h; (2) screw speeds of 100 rotations per minute (rpm), 200 rpm, and 300 rpm; (3) profile temperatures of 160°C and 180°C; and (4) catalyst deactivator concentrations of 0 parts per million (ppm), 250 ppm, 750 ppm, and 1000 ppm. The initial design of experiments included 90 runs that were simplified to 36 runs as shown in Table 1 below. [0085] The Deactivator Masterbatch was created from the polycaprolactone (CAPA® 6500D, molecular weight of 50,000 g/mol (MW); Ingevity UK) as shown in Table 1 to achieve polycaprolactone-deactivator mixtures having deactivator at 0.0 wt% (0 parts per million (ppm)), 0.5 wt% 250 ppm), 1.5 wt% (750 ppm), and 2 wt% (1000 ppm), and the mixtures examined as shown in Table 2. The deactivator material was fed in via a side feeder set to 150 rotations per minute. The material was reprocessed with devolitisation for an extended period of time to assess monomer removal and reformation. The material properties were examined via gas chromatography flame ionization detection (GC-FID)) and gel permeation chromatography (GPC). The data from this examination is shown in Table 3, wherein the baseline standard (0) was CAPA® 6500D (polycaprolactone with a molecular weight of 50,000 g/mol (MW); Ingevity UK) without devolitisation.

Table 1. Polycaprolactone and deactivator mixtures examined

Table 2. Design of Experiment for Examination of Process of the Present Disclosure

*Polycaprolactone [Deactivator Masterbatch]

“Rotations Per Minutes

Table 3. Results for the Experiments Outlined in Table 2

[0086] Consistent devolatilization was achieved with all of the processing conditions examined with virtually all samples <0.1% residual monomer at about -0.9 Bar vacuum. Furthermore, observations on the vacuum ports confirmed that the vast majority of the devolatilization occurred in the first vacuum state with very little material by the third stage. The second port residues indicated that some of the oligomer materials have been removed from the melt. The levels of deactivator examined had no effect on the final residual monomer level that was achieved. Rather, the variables affecting devolatilization were screw speed, residence time, and temperature. Thus, devolatilization was more effective with longer residence time and higher surface renewal. While higher temperatures were shown to result in reduced residual monomer levels, it was not statistically significant.

[0087] Example 4. Examination of Monomer Revision from Reprocessing

[0088] Next the stability of the deactivated and non-deactivated poly caprolactone samples obtained during the devolitisation process was assessed during downstream processing. The processed devolitised samples, as shown in Table 3, were reprocessed under nitrogen in a single screw extruder - Collin 768, 25mm diameter, L/D =25.

[0089] The samples were reprocessed at 140°C with a screw speed of 20 rotations per minute (rpm). A purging time of at least 10 minutes between samples was in place, with 30 minutes of production (~1 kg/h) for each sample. No vacuum treatment was applied during reprocessing to avoid additional monomer removal during processing. Reprocessing data for the samples was recorded, and as shown in Table 4, a stable temperature during reprocessing was observed. Table 4. Reprocessing Data for Exemplary Samples of Table 3

[0090] After reprocessing, the samples were pelletised using a strand pelletiser - 4mm die diameter, water bath at 17-18°C, 6 meters/minute. At least 500 g of each sample was collected from the pelletiser. The pelletised samples was examined via gas chromatography flame ionization detection (GC-FID) to determine the final residual monomer content to determine if any monomer revision had taken place. The data is shown in Tables 5 and 6.

[0091] As shown in Tables 5 and 6, the majority of the undevolitised samples underwent reversion to reform residual monomer. None of the high loading level deactivated samples (1000 parts per million) underwent any reversion and were able to maintain the low monomer level after reprocessing. The samples were assessed at a relatively low temperature of 140°C to prevent any degradation of the samples which may have affected the results. It is believed that reprocessing at a higher temperature would result in the non-deactivated samples to have a greater level of reversion.

[0092] Thus, the data demonstrates that deactivating the catalyst prevents polymer back- biting. Table 5. Monomer Revision After Reprocessing Devolitised Samples Not Treated with Deactivator

Table 6. Monomer Revision After Reprocessing Devolitised Samples Treated with Deactivator [0093] Example 4. Examination of Shelf Life of Catalyst Deactivator in Caprolactone Monomers

[0094] Caprolactone monomer-catalyst deactivator mixtures were prepared at 3: 1, 5:1, 7:1, and 10: 1 ratios and examined for full solubility and shelf life. The samples were examined each day to determine if the sample was still a clear liquid or if the material was (a) discolored, (b) gelled, or (c) came out of solution. The results are shown in Table 7.

Table 7. Solubility and Shelf Life of Caprolactone Monomer-Catalyst Deactivator Mixtures at Varying Ratios

[0095] While several embodiments of the invention of the present disclosure have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the spirit of the invention. Rather, the present disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the present disclosure as defined by the following appended claims and their legal equivalents. Accordingly, it is intended that the description and appended claims cover all such variations as fall within the spirit and scope of the invention.

[0096] The contents of all references, patents, pending patent applications and published patents, cited throughout this application are hereby expressly incorporated by reference.

[0097] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims. It is understood that the detailed examples and embodiments described herein are given by way of example for illustrative purposes only, and are in no way considered to be limiting to the invention. Various modifications or changes in light thereof will be suggested to persons skilled in the art and are included within the spirit and purview of this application and are considered within the scope of the appended claims. For example, the relative quantities of the ingredients can be varied to optimize the desired effects, additional ingredients can be added, and/or similar ingredients can be substituted for one or more of the ingredients described. Additional advantageous features and functionalities associated with the systems, methods, and processes of the present invention will be apparent from the appended claims. Moreover, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

Claims

CLAIMS What Is Claimed Is:

1. A method of preparing a polymer composition, the method comprising, consisting essentially of, or consisting of: mixing a catalyst deactivator and a polymer (e.g., caprolactone polymer or poly caprolactone) comprising monomers; and performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer- catalyst deactivator mixture, thereby forming the polymer composition.

2. The method of claim 1 , wherein the catalyst deactivator is a metal deactivator.

3. The method of claim 1 or 2, wherein the catalyst chelates or complexes with the active metal of the catalyst.

4. The method of any one of claims 1-3, wherein at least one of: the catalyst deactivator inhibits or prevents depolymerization of the polymer; the catalyst deactivator targets a catalyst that catalyzes the polymerization of the polymer; the catalyst deactivator targets a catalyst that catalyzes the depolymerization of the polymer; or a combination thereof.

5. The method of any one of claims 1-4, wherein the catalyst deactivator targets a ring-opening polymerization catalyst (e.g., a ring-opening polymerization catalyst that catalyzes the polymerization of the polymer).

6. The method of any one of claims 1-5, wherein the catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of a phosphate-based catalyst deactivator, a crown ether catalyst deactivator, a carboxylic acid catalyst deactivator, or a combination thereof.

7. The method of claim 6, wherein at least one of: the phosphate-based catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of octadecyl phosphate (e.g., ADK STAB AX-71, CAS No. 39471-52-8; Adeka, Tokyo, Japan), ammonium phosphate dibasic, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9- diphosphaspiro[5.5]undecane (BOTDPU), diethyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate (e.g., IRGANOX® 1222, CAS No. 976-56-7; BASF, Ludwigshafen on the Rhine, Germany), triisodecyl phosphite (e.g., ADK STAB 3010, CAS No. 25448-25-3; Adeka, Tokyo, Japan), or a combination thereof; the crown ether catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of 18-crown 6, 12-crown 4, 15-crown 5, or a combination thereof; the catalyst deactivator includes or is ethanediamide, N-(2-ethoxyphenyl)-N'-(2- ethylphenyl) (e.g., Tinuvin® 312); the carboxylic acid catalyst deactivator includes or is one or more (e.g., 1, 2, 3, 4, 5, 6, or more) of: l,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (e.g., IRGANOX® MD 1024, CAS No. 32687-78-8; BASF, Ludwigshafen on the Rhine, Germany); tartaric acid; acrylic polymer (e.g., BIOSTRENGTH® 150; Arkema, Colombes, France); acrylic copolymer (e.g., BIOSTRENGTH® 700; Arkema, Colombes, France); 2-Propenoic acid, 2-methyl-, butyl ester, polymer with butyl 2-propenoate and methyl 2-methyl-2-propenoate, glycine, N-methyl- N-(l-oxododecyl)-, sodium salt, or a combination thereof (e.g., BIOSTRENGTH® 900; Arkema, Colombes, France); 2-[2-[3-(3,5-ditert-butyl-4- hydroxyphenyl)propanoyloxy] ethylsulfanyl] ethyl 3-(3,5-ditert-butyl-4- hydroxyphenyl)propanoate (e.g., IRGANOX® 1035, CAS No. 41484-35-9; BASF, Ludwigshafen on the Rhine, Germany); 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (e.g., IRGANOX® 1520, CAS No. 110553-27-0; BASF, Ludwigshafen on the Rhine, Germany); or a combination thereof; or a combination thereof.

8. The method of any one of claims 1-7, further comprising adding the catalyst deactivator to the polymer, wherein the catalyst deactivator is a powder.

9. The method of any one of claims 1-8, further comprising adding the catalyst deactivator to the polymer, wherein the catalyst deactivator is a liquid deactivator composition.

10. The method of claim 9, wherein at least one of: the liquid deactivator composition comprises the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof (e.g., the liquid deactivator composition comprises about 0.1 wt% to about 45 wt% or about 5.0 wt% to about 15.0 wt% of the catalyst deactivator); the liquid deactivator composition is prepared by mixing the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof, at a temperature of about 70°C to about 110°C (e.g., about 75°C to about 105°C or about 80°C to about 100°C); the liquid deactivator composition is prepared by mixing the catalyst deactivator and at least one of the monomers, the polymer, or a combination thereof, in a mixer or a mixer heat exchanger; or a combination thereof.

11. The method of any one of claims 1-10, wherein the catalyst deactivator is present in an amount of about 100 parts per million (ppm) to about 2500 ppm of the polymer-catalyst deactivator mixture.

12. The method of any one of claims 1-11, wherein at least one of : mixing the catalyst deactivator and the polymer (e.g., caprolactone polymer or poly caprolactone) comprising monomers includes mixing the catalyst deactivator and the polymer in a mixer heat exchanger; performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer- catalyst deactivator mixture is performed in a devolatilization unit that includes or is at least one of an extruder (e.g., single screw extruder or a second screw extruder), a falling strand devolatilizer, a wiped-film evaporator, a large-volume kneader, a falling film evaporator, a tube evaporator, a flash evaporator, or a combination thereof; performing devolatilization (e.g., polymer devolatilization or degassing) on the polymer- catalyst deactivator mixture is performed at a temperature equal to or less than about 300°C; or a combination thereof.

13. The method of any one of claims 1-12, wherein at least one of: the devolatilization unit is an extruder (e.g., single screw extruder or a second screw extruder); the polymer is a poly caprolactone (e.g., at least one of a poly caprolactone polyol, a thermoplastic poly caprolactone, a thermoplastic polycaprolactone polyol, or a combination thereof); the catalyst deactivator is present in an amount of about 500 parts per million (ppm) to about 1500 ppm (e.g., about 750 ppm to about 1250 ppm) of the polymer-catalyst deactivator mixture; performing devolatilization of the polymer-catalyst deactivator mixture is performed at a temperature of less than or equal to about 225°C (e.g., less than or equal to about 215°C, less than or equal to about 205°C, or less than or equal to about 200°C); or a combination thereof.

14. The method of any one of claims 1-13, wherein at least one of: the monomer content in the polymer composition is less than about 5 wt% (e.g., less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1.5 wt%, less than about 1 wt%, less than about 0.5 wt%, less than about 0.1 wt%, less than about 0.05 wt%, or about 0.01 wt% to about 5.0 wt%); the polymer content in the polymer composition is greater than about 90 wt% or 95 wt%

(e.g., about 90 wt% to about 100 wt%, about 90 wt% to about 99 wt%, or about 90 wt% to about 98 wt%); or a combination thereof.

15. The method of any one of claims 1-14, wherein the method further comprises, prior to mixing the catalyst deactivator and the polymer, polymerizing the monomers into the polymer with a catalyst (e.g., mixing and incubating the polymer or polymer composition with the catalyst).

16. The method of claim 15, wherein the catalyst deactivator targets the catalyst.