Polymerizable composition, method for manufacturing a reversibly crosslinked polymer, and reversibly crosslinked polymer

Description

30 POLYMERIZABLE COMPOSITION, METHOD FOR MANUFACTURING A REVERSIBLY CROSSLINKED POLYMER, AND REVERSIBLY CROSSLINKED POLYMER FIELD OF THE INVENTION

[001] This invention generally relates to the field of preparing reversibly crosslinked polymers for reprocessing / recycling of polymers. FUNDAMENTALS OF THE INVENTION

[002] Conventional polymer networks, also known as thermosets, consist of permanent covalent cross-links that make reprocessing and recycling of these polymers impractical. Examples of conventional polymer networks produced in high-pressure polymerizations are low-density polyethylene (LDPE) and ethylene / VA copolymer (EVA).

[003] Efforts have been made to incorporate inherently reversible crosslinks into a polymer network, allowing polymer networks to be reprocessed and recycled. However, complete recovery of crosslinks after multiple reprocessing steps remains a challenge for current technology.

[004] Therefore, there remains a continuing need in the art to develop a new crosslinking chemistry to obtain a reversibly crosslinked polymer that is fully reprocessable and recyclable while maintaining the properties of the original polymer. SUMMARY OF THE INVENTION

[005] In one aspect, a polymerizable composition is provided in this document, comprising a crosslinker comprising an Sn- moiety and having at least two polymerizable groups, wherein n is an integer from 2 to 8; one or more monomers, each monomer having at least one C=C double bond capable of undergoing a polymerization reaction; and a Petition 870250108046, dated 11 / 26 / 2025, page 6 / 68 / 30 polymerization initiator.

[006] In another aspect, a method is provided in this document for manufacturing a reversibly crosslinked polymer, comprising: reacting a crosslinker comprising an -Sn- moiety and having at least two polymerizable groups, wherein n is an integer from 2 to 8, and one or more monomers, each monomer having at least one C=C double bond capable of undergoing a polymerization reaction, in the presence of the polymerization initiator, to produce a reversibly crosslinked polymer which, when reprocessed at temperatures greater than 50°C, dissociates the crosslinking of the reversibly crosslinked polymer.

[007] Another aspect of the invention relates to a reversibly crosslinkable polymer, comprising the reaction product of the polymerizable composition as described in the above aspect of the invention, wherein the reversibly crosslinkable polymer contains an -SS- moiety.

[008] Another aspect of the invention relates to the reversibly crosslinkable polymer obtained according to the method described in the above aspect of the invention.

[009] Aspects, advantages and additional features of the invention are presented in this descriptive report and, in part, will become apparent to those skilled in the art by examining the following, or may be learned by practicing the invention. The inventions described in this application are not limited to any particular set or combination of aspects, advantages and features. It is contemplated that various combinations of the aspects, advantages and features set forth constitute the inventions described in this application. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1A is a schematic illustrating a reaction scheme for high-pressure polymerization with a dynamic disulfide crosslinker (A).

[0011] Figure 1B illustrates examples of disulfide crosslinkers. Petition 870250108046, dated 11 / 26 / 2025, p. 7 / 68 / 30 dynamic according to the present invention.

[0012] Figure 2A shows DSC results of an exemplary reversibly crosslinked DSDMA / ethylene copolymer, in which the DSC chromatographs increase as the crosslinker concentration increases.

[0013] Figure 2B shows DSC results of an exemplary reversibly crosslinked DSDMA / ethylene copolymer, in which the Tc and Tm trends increase as the crosslinker concentration increases.

[0014] Figure 3A shows the storage modulus and tan delta results of an exemplary DSDMA / ethylene reversibly crosslinked copolymer.

[0015] Figure 3B shows the swelling studies for such an exemplary copolymer (reversibly crosslinked DSDMA / ethylene copolymer).

[0016] Figure 4 shows the normalized results of the stress relaxation of an exemplary reversibly crosslinked DSDMA / ethylene copolymer.

[0017] Figure 5 describes the reprocessability study of one of the exemplary samples (A5). DETAILED DESCRIPTION OF THE INVENTION

[0018] The description provides a polymerizable composition and a method for manufacturing a reversibly crosslinked polymer, employing a dynamic crosslinker containing polymerizable groups, allowing its incorporation into a polymer network through polymerization and a reversible link that dissociates at elevated temperature and reassociates when cooled. This dynamic crosslinking produces polymer networks that are reversible and can be reprocessed and recycled. Polymerizable composition Petition 870250108046, dated 11 / 26 / 2025, page 8 / 68 / 30

[0019] One aspect of the invention relates to a polymerizable composition comprising a crosslinker comprising an Sn- moiety and having at least two polymerizable groups, wherein n is an integer from 2 to 8; one or more monomers, each monomer having at least one C=C double bond capable of undergoing a polymerization reaction; and a polymerization initiator.

[0020] The crosslinker is a dynamic crosslinker, meaning that the polymer chains of the polymers, formed by the polymerization of the crosslinkers and monomers, are covalently linked by means of a reversible bond provided by the crosslinker that dissociates at high temperature and reassociates after cooling. The crosslinker also contains a polymerizable group that allows its incorporation into a polymer network by means of polymerization.

[0021] The crosslinker comprises an -Sn- fraction (n is an integer from 2 to 8, for example, 2 or 3) and has at least two polymerizable groups. The dynamic nature comes from the disulfide or polysulfide bond which dissociates to form a stable thi-yl radical when heated and reassociates again to reform the disulfide or polysulfide bond when cooled to room temperature. The polymerizable group may comprise an unsaturated bond capable of polymerization reaction to allow incorporation of the crosslinker into a polymer network during the polymerization reaction. For example, the polymerizable group may comprise a C=C double bond. The two polymerizable groups may be the same or different.

[0022] The unsaturated bond (e.g., C=C double bond) capable of undergoing a polymerization reaction is in a functional group including, but not limited to, an alkene, an alkyne, a nitrile, a vinyl group, an acyl group, an acrylate, a (meth)acrylate, a styrene, and a vinylpyridine.

[0023] In some embodiments, the crosshair can be represented Petition 870250108046, dated 11 / 26 / 2025, p. 9 / 68 / 30 by Formula (I), (II), (III), (IV) or (V): R1R2R3C-Sn-CR4R5R6(I) R7-CH(X)-Sn-CH(Y)-R8(II) R7-Bi-Ai-Sn-A2-B2-R8(III) R15-O-Sn-O-R16(IV) (R17)(R18)-P-Sn-P-(R19)(R20) (V).

[0024] The integer n is from 2 to 8, such as 2 or 5, 2 to 4, or 2 to 3. Normally, n is 2 or 3. In one form, n is 2. In another form, n is 3.

[0025] Each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 is independently a hydrogen atom, a halogen atom, a linear or branched C1-20 alkyl, a C2-20 alkenyl, a C2-20 alkynyl, a nitrile, a hydroxyl, an ester having from 1 to 20 carbon atoms, an ether having from 1 to 20 carbon atoms, a thioether having from 1 to 20 carbon atoms, a ketone having from 1 to 20 carbon atoms, an imine, an amide, a primary amine, a secondary amine, a tertiary amine, a trifluoromethyl, a phenyl, a benzyl, a Phenol, a pentafluorophenyl, a nitroxyl, or a silcone having from 1 to 20 carbon atoms. Each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20 may be optionally replaced by one or more alkyl, alkenyl, hydroxyl, or halide groups. Optional substituents replace the hydrogen atom(s) of these R variables.Exemplary substituents are C1-C6 alkyl groups (linear or branched), C2-C6 alkenyl groups, hydroxyl groups, or halide groups.

[0026] X represents CHR9R10, OH, SH or NHR11. Y represents CHR12R13, OH, SH or NHR14.

[0027] Each of A1 and A2 is independently absent, a C1-C20 alkylene, a C2-C20 cycloalkylene, a C2-C20 divalent alkene form, a C2-C20 divalent alkyne form, an arylene, or combinations thereof. Petition 870250108046, dated 11 / 26 / 2025, p. 10 / 68 / 30 same; each optionally replaced by one or more alkyl, alkenyl, hydroxyl or halogen atoms.

[0028] Each of Bi and B2 is independently absent or is a divalent form of an imine, amine, carbonyl, amide, ether, or ester, or combinations thereof.

[0029] The term “divalent form” refers to a divalent radical that is formed when a hydrogen atom is removed from a functional group, for example, an alkyl, alkenyl, cycloalkyl, or alkynyl radical, etc., or when terminal hydrogen atoms are removed from a hydrocarbon, for example, an alkane, alkene, cycloalkane, or alkyne, etc. For example, in the case of the divalent form of alkene (alkenylene), the term refers to a divalent radical that has hydrogen atoms removed from each of the two terminal carbon atoms of the alkene chain. A divalent form of a fraction is defined to represent the fraction present in the middle of a structural formula, with each end of the fraction bonding to another fraction, bond, or hydrogen atom.

[0030] In some embodiments, the crosslinker is represented by Formula (I). In Formula (I), at least one of R1, R2, and R3 comprises a C=C double bond and at least one of R4, R5, and R6 comprises a C=C double bond. R1, R2, R3, R4, R5, and R6 may be the same or different. (R1R2R3) and (R4R5R6) may be the same or different. In some embodiments, each of R1 and R4 is H; each of R2 and R5 may be H or alkyl, and each of R3 and R6 comprises a C=C double bond. In some embodiments, each of R3 and R6 independently comprises an alkene, an alkyne, a nitrile, an acyl, an acrylate, a (meth)acrylate, a styrene, or a vinylpyridine.

[0031] In some embodiments, the crosshair is represented by Formula (II). In Formula (II), each of R7 and R8 comprises a C=C double bond. X and Y may be the same or different. R7 and R8 may be Petition 870250108046, dated 11 / 26 / 2025, p. 11 / 68 / 30 equal or different. R7-CH(X)- and -CH(Y)-R8 may be equal or different. In some embodiments, each of X and Y independently represents CHR9R10, OH, SH, or NHR11, wherein each of R9, R10, and R11 is independently H or alkyl. In some embodiments, each of X and Y independently represents CHR9R10 or NHR11, wherein each of R9, R10, and R11 is independently H or methyl. In some embodiments, each of R7 and R8 independently comprises an alkene, an alkyne, a nitrile, an acyl, an acrylate, a (meth)acrylate, a styrene, or a vinylpyridine.

[0032] In some embodiments, the crosslinker is represented by Formula (III). In Formula (III), each of R7 and R8 comprises a C=C double bond. A1 and A2 may be the same or different. B1 and B2 may be the same or different. R7 and R8 may be the same or different. R7-B1-A1- and A2-B2-R8 may be the same or different. In some embodiments, each of A1 and A2 is independently absent, a C1-C5 alkylene, a C2-C6 cycloalkylene, or a phenylene; each optionally substituted by one or more alkyl, hydroxyl, or halogen atoms. In some embodiments, each of B1 and B2 is independently absent or is a divalent form of an amine, amide, or ester. In some embodiments, each of R7 and R8 is independently a C2-C6 alkenyl, optionally substituted by one or more C1-C3 alkyl groups. In some embodiments, each of R7 and R8 is independently an unsubstituted C2C6 alkenyl group.In some embodiments, each of R7 and R8 is independently composed of a C2-C6 alkynyl group optionally substituted by one or more C1-C3 alkyl groups or nitriles.

[0033] In some embodiments, the crosslinker is represented by (III), where n is 2 or 3; each of R7 and R8 is independently a C2-C20 alkenyl, optionally substituted by one or more alkyl or alkenyl groups; each of A1 and A2 is independently absent, one Petition 870250108046, dated 11 / 26 / 2025, p. 12 / 68 8 / 30 C1-C20 alkylene or a divalent form of phenyl; each optionally substituted with one or more alkyl, alkenyl, hydroxyl or halogen atoms; each of Bi and B2 is independently absent or is a divalent form of amine, amide, ether or ester.

[0034] In some forms, the crosshair has the structure of the formula: The integer n is 2 or 3. In one embodiment, n is 2. In one embodiment, n is 3. The integer t is from 1 to 5, for example, from 1 to 4 or from 1 to 3. In one embodiment, t is 1. In one embodiment, t is 2. In one embodiment, t is 3. Each of R7 and R8 is independently a C2-C6 alkenyl, optionally substituted by one or more C1-C3 alkyl groups. In some embodiments, each of R7 and R8 is independently an unsubstituted C2-C6 alkenyl. In some embodiments, each of R7 and R8 is independently a C2C4 alkenyl, substituted by one or more methyl groups. Each of Bi and B2 is independently absent, -O-, -OC(O)-, -C(O)O-, -C(O)-, -N(H)-, N(H)C(O)- or -C(O)N(H)-. In some embodiments, each of Bi and B2 is independently absent, -OC(O)-, -C(O)O-, -N(H)C(O)- or C(O)N(H)-.

[0035] In some forms, the crosshair has the structure of the formula: R7R8 B'-P JJ T 4-b'í. The integer n is 2 or 3. In one embodiment, n is 2. In another embodiment, n is 3. Each of R7 and R8 is independently a C2-C6 alkenyl, optionally substituted by one or more C1-C3 alkyl groups. In some embodiments, each of R7 and R8 is independently an unsubstituted C2-C6 alkenyl. In some embodiments, each of R7 and R8 is independently a C2C4 alkenyl, substituted by one or more methyl groups. Each of Bi and B2 is... Petition 870250108046, dated 11 / 26 / 2025, p. 13 / 68 9 / 30 regardless absent, -O-, -OC(O)-, -C(O)O-, -C(O)-, -N(H)-, -N(H)C(O)- or C(O)N(H)-. In some forms, each of Bi and B2 is independently -OC(O)-, -C(O)O-, -N(H)C(O)- or -C(O)N(H)-.

[0036] Examples of crosslinking agents are: diallyl disulfide, diallyl trisulfide (Xx-S's's'^ / ^), bis(2-methacryloyl)oxyethyl disulfide S^.O^CH2 CH3)? 2,2'-Disulphanodi-Diallyl Dibenzoate Ch3 H2C^f THE 2,2′-disulphanodi-diallyl diacetate 4,4′-disulphanodi-diallyl diyldibutyrate 3,3' -disulfanodi-diallyl dipropionate ), disulfanodi-ylbis(3,l) diacrylate, disulfanodi-ylbis(ethane-2,phenylene) diacrylate ( Petition 870250108046, dated 11 / 26 / 2025, p. 14 / 68 10 / 30 Ν,Ν' -(of sulphanode-ilbis(2,1 -phenylene))diacrylamide N,N' -(disulfanodi-ilbis(4,1 -phenylene))diacrylamide Bis(acryloyl)cystamine

[0037] In some embodiments, the crosslinker comprises diallyl disulfide. In one embodiment, the crosslinker consists of diallyl disulfide.

[0038] The one or more monomers in the polymerizable composition for making a reversibly crosslinked polymer may comprise an olefin monomer, a vinyl monomer, or a vinyl ester monomer.

[0039] A suitable olefin monomer may include a linear or branched olefin (e.g., an α-olefin) having 2 to 12 carbon atoms, 2 to 10 carbon atoms, or 2 to 8 carbon atoms. Exemplary linear or branched olefins include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, 3,5,5-trimethyl-1-hexene, 4,6-dimethyl-1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. These olefins may contain one or more heteroatoms, such as oxygen, nitrogen, or silicon.

[0040] Suitable vinyl monomers may include a substituted vinyl, for example, RaRbC=CRcRd, wherein Ra and Rb may each independently be hydrogen, halogen, alkyl, aryl (e.g., phenyl), arylalkyl (e.g., benzyl), heteroaryl (e.g., Petition 870250108046, dated 11 / 26 / 2025, page 15 / 68 11 / 30 pyridinyl), alkenyl, arylalkenyl, hydroxylcarbonyl, alkoxycarbonyl, alkylaminecarbonyl, alkylcarbonyloxy, arylcarbonyloxy, or nitrile. Exemplary vinyl monomers include, but are not limited to, styrene, vinylpyridine, acrylate, methacrylate, acrylonitrile, vinyl ester, vinyl chloride, isoprene.

[0041] Suitable vinyl ester monomers include aliphatic vinyl esters having 3 to 20 carbon atoms (e.g., 4 to 10 carbon atoms or 4 to 7 carbon atoms). Exemplary vinyl esters are vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl verstatate. Aromatic vinyl esters, such as vinyl benzoate, can also be used as vinyl ester monomers. Common vinyl ester monomers are vinyl acetate, vinyl propionate, vinyl laurate, or vinyl versatate (e.g., versatic acid vinyl ester, vinyl neonanoate, or vinyl neodecanoate). Vinyl acetate is typically used based on its commercial availability and efficiency in handling impurities during production.Vinyl esters of neononanoic acid (vinyl neononanoate) and neodecanoic acid (vinyl neodecanoate) are commercial products obtained from the reaction of acetylene with neononanoic acids and neodecanoic acids, respectively, which are commercially available as Versatile Acid 9 and Versatile Acid 10.

[0042] The monomer can be used alone, or two or more different monomers can be used in combination, when used in the polymerizable composition to manufacture a reversibly crosslinked polymer.

[0043] In some embodiments, one or more monomers in the polymerizable composition are used to manufacture a reversibly polymer. Petition 870250108046, dated 11 / 26 / 2025, page 16 / 68 / 30 crosslinked comprise at least one member selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and vinyl acetate.

[0044] In one embodiment, the monomer in the polymerizable composition for making a reversibly crosslinked polymer is ethylene.

[0045] In one embodiment, ethylene and vinyl acetate are used as monomers in the polymerizable composition to manufacture a reversibly crosslinked polymer.

[0046] The polymerization initiator may comprise a peroxide (e.g., a bifunctional peroxide, a peracetate compound, etc.), an azo compound, a nitroxide, other free radical initiators -CC- and a mixture thereof.

[0047] Suitable peroxide compounds used as the polymerization initiator include, but are not limited to, a cyclic ketone peroxide, a bifunctional peroxide, a dialkyl peroxide, a monoperoxycarbonate, a poly(t-butyl)peroxycarbonate polyether, a diperoxyacetal, a perester (e.g., a peracetate), and mixtures thereof. In some embodiments, the peroxide compound is a cyclic ketone peroxide, a bifunctional peroxide, a dialkyl peroxide, or a mixture thereof.

[0048] Exemplary peroxide compounds used as polymerization initiators are benzoyl peroxide; dicumyl peroxide; di-tert-butyl peroxide; tert-butyl cumyl peroxide; t-butyl-peroxy-2-ethylhexanoate; tert-butyl peroxypivalate; tertiary butyl peroxyneodecanoate; t-butyl-peroxybenzoate; t-butyl-peroxy-2-ethyl hexanoate; tert-butyl peroxide 3,5,5-trimethylhexanoate; tert-butyl peroxybenzoate; 2-ethylhexyl carbonate tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane; 1,1-di(tert-butylperoxide)-3,3,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyne-3; 3,3,5,7,7-pentamethyl-1,2,4-TitiCtion 870250108046, dated 11 / 26 / 2025, page 17 / 68 / 30 trioxepane; butyl 4,4-di(tert-butylperoxide) valerate; di(2,4-dichlorobenzoyl)peroxide; di(4-methylbenzoyl)peroxide; di(tert-butylperoxy-isopropyl)benzene peroxide; 2,5-di(cumylperoxy)-2,5-dimethylhexane; 2,5-di(cumylperoxy)-2,5-dimethylhexyne; 3,4-methyl-4-(t-butylperoxy)-2-pentanol;4-methyl-4-(t-amylperoxy)-2-pentane; 4-methyl-4-(cumylperoxy)-2-pentanol; 4-methyl-4-(t-butylperoxy)-2-pentanone; 4-methyl-4-(t-amylperoxy)-2-pentanone; 4-methyl-4-(cumylperoxy)-2-pentanone; 2,5-dimethyl-2,5-di-t-butylperoxy)hexane; 2,5-dimethyl-2,5-di(t-amylperoxy)hexane; 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3, 2,5-dimethyl-2t-butylperoxy-5-hydroperoxy-hexane; 2,5-dimethyl-2-cumylperoxy-5-hydroperoxyhexane; 2,5-dimethyl-2-t-amylperoxy-5-hydroperoxyhexane; m / p-alpha, alpha-di[(t-butylperoxy)isopropyl]benzene; 1,3,5-tris(t-butylperoxyisopropyl)benzene; 1,3,5-tris(t-amylperoxyisopropyl)benzene; l,3,5-tris(cumylperoxyisopropyl)benzene; di[l,3-dimethyl-3-(t-butylperoxy)butyl]carbonate; di[1,3-dimethyl-3-(t-amylperoxy)butyl]carbonate; di[l,3-dimethyl-3(cumylperoxy)butyl]carbonate; di-t-amyl peroxide; t-amyl cumyl peroxide; t-butyl-isopropenylcumyl peroxide; 2,4,6-tri(butylperoxy)-s-triazine; l,3,5-tri[l-(t-butylperoxy)-l-methylethyl]benzene;l,3,5-tri-[(t-butylperoxy)isopropylbenzene; 1,3-dimethyl-3-(t-butylperoxy)butanol; 1,3-dimethyl-3-(tamylperoxy)butanol; di(2-phenoxyethyl)peroxydicarbonate; di(4-t-butylcyclohexyl)peroxydicarbonate; dimyristyl peroxydicarbonate; dibenzyl peroxy decarbonate; di(isoboyl)peroxydicarbonate; 3-cumylperoxy-1,3-dimethylbutyl methacrylate; 3-t-butylperoxy-l,3-dimethylbutyl methacrylate; 3-t-amylperoxy-l,3-dimethylbutyl methacrylate; tri(l,3-dimethyl-3-t-butylperoxy butyloxy)vinyl silane; 1,3-dimethyl-3-(t-butylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl)-1-methylethyl]carbamate; 1,3-dimethyl-3-(t-amylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate; 1,3-dimethyl-3-(cumylperoxy))butyl N-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate; 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(t-butylperoxy)cyclohexane; Petition 870250108046, dated 11 / 26 / 2025, page 18 / 68 / 30 n-butyl 4,4-di(t-amylperoxy)valerate; ethyl 3,3-di(t-butylperoxy)butyrate; 2,2-di(tamylperoxy)propane; 3,6,6,9,9-pentamethyl-3-ethoxycarbonylmethyl-1,2,4,5-tetraoxacyclononane; n-butyl 1-4,4-bis(t-butylperoxy)valerate; ethyl-3,3-di(tamylperoxy)butyrate; benzoyl peroxide; OO-t-butyl-O-hydrogen monoperoxysuccinate; OO-t-amyl-O-hydrogen monoperoxysuccinate; 3,6,9, triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or cyclic methyl ethyl ketone peroxide trimer); cyclic methyl ethyl ketone peroxide dimer; 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane; 2,5-dimethyl-2,5di(benzoylperoxy)hexane; t-butyl perbenzoate, t-butylperoxy acetate; t-butylperoxy-2-ethyl hexanoate; t-amyl perbenzoate; t-amyl peroxy acetate; t-butyl peroxy isobutyrate; 3-hydroxy-1,1-dimethyl-t-butyl peroxy-2ethyl hexanoate; OO-t-amyl-O-hydrogen-monoperoxy succinate; OO-t-butyl-Ohydrogen-monoperoxy succinate; di-t-butyl diperoxyphthalate;t-butylperoxy (3,3,5-trimethylhexanoate); 1,4-bis(t-butylperoxycarbo)cyclohexane; tbutylperoxy-3,5,5-trimethylhexanoate; t-butyl-peroxy-(cis-3carboxy)propionate; allyl 3-methyl-3-t-butylperoxy butyrate; OO-t-butyl-Oisopropylmonoperoxy carbonate; OO-t-butyl-O-(2-ethyl hexyl) monoperoxy carbonate; 1,1,1-tris[2-(t-butylperoxycarbonyloxy)ethoxymethyl]propane; 1,1,ltris[2-(t-amylperoxy-carbonyloxy)ethoxymethyl]propane; 1,1,-tris[2-(cumylperoxycabonyloxy)ethoxymethyl]propane; OO-t-amyl-O-isopropylmonoperoxy carbonate; di(4-methylbenzoyl)peroxide; di(3-methylbenzoyl)peroxide; di(2-methylbenzoyl)peroxide; didecanoyl peroxide; dilauroyl peroxide; 2,4-dibromobenzoyl peroxide; succinic acid peroxide; dibenzoyl peroxide; di(2,4-dichlorobenzoyl)peroxide; and combinations thereof.

[0049] Suitable azo compounds used as polymerization initiators include, but are not limited to, azobisisobutyronitrile (AIBN); 2,2'-azobis(amidinopropyl) dihydrochloride; and azoperoxide initiators containing mixtures of a peroxide with one or more azodinitrile compounds, including, for example, 2,2'-azobis(2-methylpentanenitrile); Petition 870250108046, dated 11 / 26 / 2025, page 19 / 68 / 30 2,2'-azobis (2-methyl-butanenitrile); 2,2'-azobis (2-ethyl-pentanonitrile); 2-[(1cyano-1-methylpropyl)azo]-2-methyl-pentanonitrile; 2-[(1-cyano-1-ethylpropyl)azo]2-methyl-butanenitrile; and 2-[(1-cyano-1-methylpropyl)azo]-2-ethyl-pentanonitrile.

[0050] Suitable nitroxide compounds used as the polymerization initiator include, but are not limited to, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy, 3-carboxy-2,2,5,5-tetramethyl-pyrrolidinyloxy, 2,2,6,6-tetramethyl-1-piperidinyloxy, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy, 4-methoxy-2,2,6,6-tetramethyl-1-piperidinyloxy, 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, bis-(1-oxy-1-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 2,2,.6,6-tetramethyl-4-hydroxypiperidin-1-oxyl) monophosphonate, N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide, N-tert-butyl-1-di(2,2,2-trifluoroethyl)phosphono-2,2-dimethylpropyl nitroxide, N-tert-butyl-(1-diethylphosphono)-2-methylpropyl nitroxide, N-(1-methylethyl)-1-cyclohexyl-1-(diethylphosphono) nitroxide, N-(1-phenylbenzyl-1)-(1-diethylphosphono)-1-methylethylnitroxide, N-phenyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, N-phenyl-1-diethylphosphono-1-methylethyl nitroxide, N-(1-phenyl 2-methyl propyl)-1-diethylphosphono-1-methyl ethyl nitroxide, N-tert-butyl-1-phenyl-2-methyl propyl nitroxide, N-tert-butyl-1-(2-naphthyl)-2-methyl propyl nitroxide and combinations thereof.

[0051] Thus, one embodiment of this application relates to a polymerizable composition having a polymerization initiator comprising at least one member selected from the group consisting of azobisisobutyronitrile (AIBN); 2,2'-azobis(amidinopropyl) dihydrochloride; and azo-peroxide initiators containing mixtures of a peroxide with one or more azodinitrile compounds selected from the group consisting of 2,2'-azobis(2-methyl-pentanenitrile); 2,2'-azobis(2-methyl-butanenitrile); 2,2'-azobis(2-ethyl-pentanenitrile); 2-[(1-cyano-1-methylpropyl)azo]-2-methyl-pentanenitrile; 2-[(1-cyano-1-ethylpropyl)azo]-2-methylbutanenitrile; and 2-[(1-cyano-1-methylpropyl)azo]-2-ethyl-pentanonitrile. Other Petition 870250108046, dated 11 / 26 / 2025, page 20 / 68 / 30. This embodiment of the invention relates to a polymerizable composition having a polymerization initiator comprising (a) at least one member selected from the group consisting of a peroxide, an azo compound, a peracetate compound, a nitroxide, azobisisobutyronitrile (AIBN); 2,2'-azobis(amidinopropyl) dihydrochloride; or (b) an azoperoxide initiator comprising a mixture of a peroxide with one or more azodinitrile compounds selected from the group consisting of 2,2'-azobis(2-methyl-pentanenitrile); 2,2'-azobis(2-methyl-butanenitrile); 2,2'-azobis(2-ethyl-pentanenitrile); 2-[(1-cyano-1-methylpropyl)azo]-2-methylpentanonitrile; 2-[(1-cyano-1-ethylpropyl)azo]-2-methyl-butanenitrile; and 2-[(1cyano-1-methylpropyl)azo]-2-ethyl-pentanonitrile.

[0052] In some embodiments, the polymerization initiator comprises at least one member selected from the group consisting of 2,3-dimethyl-2,3-diphenylbutane; 3,4-dimethyl-3,4-diphenylhexane; 3,4-diethyl-3,4-diphenylhexane; 3,4-dibenzyl-3,4-ditolylhexane; 2,7-dimethyl-4,5-diethyl-4,5-diphenyloctane; and 3,4-dibenzyl-3,4-diphenylhexane. Polymerization and crosslinking reaction

[0053] Another aspect of the invention relates to a method for manufacturing a reversibly crosslinked polymer, comprising: reacting a crosslinker comprising a -Sn moiety— and having at least two polymerizable groups, wherein n is an integer from 2 to 8, and one or more monomers, each monomer having at least one C=C double bond capable of undergoing a polymerization reaction, in the presence of the polymerization initiator, to produce a reversibly crosslinked polymer which, when reprocessed at temperatures greater than 50°C, dissociates the crosslinking bonds of the reversibly crosslinked polymer.

[0054] All the above descriptions and all embodiments relating to the polymerizable composition for making the reversibly crosslinked polymer, including the crosslinkers, one or more monomers and initiators. Petition 870250108046, dated 11 / 26 / 2025, p. 21 / 68 / 30, regarding polymerization, discussed above in the aspect of the invention related to the polymerizable composition, are applicable to this aspect of the invention.

[0055] During the reaction step, one or more monomers form a polymer network through at least one C=C double bond that allows the monomers to undergo a polymerization reaction. The dynamic crosslinker has at least two polymerizable groups (e.g., a C=C double bond) that allow the incorporation of the crosslinker into the polymer network during the polymerization reaction. Due to the polymerizable groups contained in the dynamic crosslinker, the dynamic crosslinker can serve as another monomer during polymerization, forming a copolymer or terpolymer with the monomer or monomers. For example, the polymerization of an ethylene monomer using a diallyl disulfide as the crosslinker can generate an ethylene / diallyl disulfide copolymer; The polymerization of ethylene monomer and vinyl acetate monomer using a diallyl disulfide as the crosslinker can generate an ethylene / vinyl acetate / diallyl disulfide terpolymer.The dynamic crosslinker also serves to link polymer chains formed by one or more monomers, forming an extensive crosslinking network.

[0056] The polymerization reaction can be carried out by several polymerization mechanisms known to one skilled in the art. For example, free radical polymerization is a common polymerization mechanism and is suitable for the reaction described in this document. Free radical polymerization is a type of chain-growth (chain addition) polymerization that begins with the initiation of free radicals that add monomer units, thus increasing the polymer chain. Any type of initiation to generate free radicals (free radical initiation) may be suitable in this document for the polymerization reactions. For example, free radicals may be initiated by thermal initiation, Petition 870250108046, dated 11 / 26 / 2025, page 22 / 68 / 30 initiation by radiation (such as photoinitiation), initiation by irradiation (such as ionizing radiation, for example, gamma rays and X-rays) or combinations thereof.

[0057] The reaction is normally carried out under a pressure above atmospheric pressure. For example, the pressure for the polymerization and / or crosslinking reaction is at least 0.5 MPa (5 bar) and typically ranges from 0.5 MPa (5 bar) to 500 MPa (5,000 bar), from 0.5 MPa (5 bar) to 50 MPa (500 bar), from 0.5 MPa (5 bar) to 20 MPa (200 bar), from 100 MPa (1,000 bar) to 500 MPa (5,000 bar), from 150 MPa (1,500 bar) to 500 MPa (5,000 bar), from 100 MPa (1,000 bar) to 300 MPa (3,000 bar), from 150 MPa (1,500 bar) to 300 MPa (3,000 bar), from 100 MPa (1,000 bar) to 200 MPa (2,000 bar) or from 100 MPa (1,000 bar) to 300 MPa (3,000 bar).

[0058] The reaction is normally carried out at an elevated temperature and over a wide temperature range. The reaction temperature for the polymerization and / or crosslinking reaction is normally at least 30°C, and may vary from 30°C to 350°C, for example, from 150°C to 350°C, from 150°C to 280°C, from 150°C to 230°C, from 150°C to 180°C, from 30°C to 280°C, from 30°C to 230°C, from 30°C to 180°C or from 30°C to 130°C. Suitable reaction temperatures should take into account the polymerization initiator and dynamic crosslinker used. For example, suitable reaction temperatures should be at least higher than the decomposition temperature of the polymerization initiator. The appropriate reaction temperatures should also not exceed the dissociation temperature of the crosslinker, so that the crosslinking bonds (i.e., disulfide or polysulfide bonds) in the crosslinker do not dissociate during the reaction.

[0059] The reaction conditions may also involve the use of an inert gas (e.g., N2 gas).

[0060] The reaction can be carried out in the presence or absence of a solvent. The solvent can be used to dissolve the monomer or the Petition 870250108046, dated 11 / 26 / 2025, p. 23 / 68 / 30 dynamic crosslinker. Suitable solvents include, but are not limited to, deep eutectic solvents; eutectic mixtures; ionic liquids; dimethyl carbonate (green solvent); ethers, such as petroleum ether, tetrahydrofuran or 1,4-dioxane; hydrocarbon solvents, such as cyclohexane, heptane or toluene; esters, such as ethyl acetate; ketones (such as acetone, butanone or cyclohexanone); chlorinated solvents, such as dichloromethane; alcohols, such as methanol, ethanol, butan-2-ol, butan-1-ol, isopropanol, ethylene glycol or glycerol; and combinations thereof. In some embodiments, the solvent is water, DMSO, dimethylformamide, butyrolactone, or 1,4-dioxane. In some embodiments, the solvent is an anhydrous liquid. In one embodiment, the solvent is dimethyl carbonate.

[0061] The polymerization and / or crosslinking reaction can be carried out in a batch process as a bulk reaction or in a continuous process as a continuous reaction, under the reaction temperature and pressure discussed above.

[0062] To initiate the polymerization and / or crosslinking reaction, the amount of polymerization initiator present in the polymerizable composition typically varies from 1*10-7% by weight to 5.0% by weight, for example, from 0.001% by weight to 5.0% by weight, from 0.05% by weight to 5.0% by weight, from 0.01% by weight to 5.0% by weight, from 0.05% by weight to 5.0% by weight, from 0.01% by weight to 4.0% by weight, from 0.05% by weight to 4.0% by weight, from 0.01% by weight to 3.0% by weight, from 0.05% by weight to 3.0% by weight, from 0.01% by weight to 2.0% by weight, from 0.05% by weight to 2.0% by weight, from 0.01% by weight to 1.0% by weight, 0.05% by weight to 1.0% by weight, 0.1% by weight to 1.0% by weight, or 0.1% by weight to 0.5% by weight, relative to 100% by weight of the total quantity of the polymerizable composition (comprising the crosslinker, monomers and polymerization initiator).

[0063] The monomers suitable for the polymerization and / or crosslinking reaction are those described above. In some embodiments, one or Petition 870250108046, dated 11 / 26 / 2025, page 24 / 68 / 30 more monomers for the polymerization and / or crosslinking reaction comprise at least one member selected from the group consisting of ethylene, propylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene, 1-octene and vinyl acetate.

[0064] In one embodiment, the monomer for the polymerization and / or crosslinking reaction is ethylene. The ethylene polymer by polymerization can form high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), or medium-density polyethylene (MDPE).

[0065] In one embodiment, ethylene and vinyl acetate are used as monomers for the polymerization and / or crosslinking reaction. The ethylene-vinyl acetate copolymer formed by polymerization can produce ethylene-vinyl acetate copolymer (EVA), also known as poly(ethylene-vinyl acetate) (PEVA), the type of which depends on the different vinyl acetate (VA) content: for example, low VA EVA (approximately up to 4%), which has properties similar to LDPE but has greater gloss, softness and flexibility; medium VA EVA (approximately 4 to 30%), having properties of a thermoplastic elastomer material; and high VA EVA (greater than 33%), having properties similar to rubber.

[0066] The dynamic crosslinkers suitable for the polymerization and / or crosslinking reaction are those described above. In some embodiments, the crosslinker comprises at least one member selected from the group consisting of diallyl disulfide, diallyl trisulfide, bis(2-methacryloyl)oxyethyl disulfide (DSDMA), ((((disulfanedi-ylbis(4,1-phenylene))bis(azanodi-yl))bis(carbonyl))bis(azanodi-yl))bis(ethane-2,1-di-yl) bis(2-methylacrylate) (4MUPD), diallyl 2,2'-disulfanedi-yldibenzoate, diallyl 2,2'-disulfanedi-yldiacetate, diallyl 4,4'-disulfanedi-yldibutyrate, diallyl 3,3'-disulfanedi-yldipropionate, disulfanediylbis(3,1-phenylene) diacrylate, diacrylate disulfanedi-ylbis(ethane-2,1-di-yl), N,N' Petition 870250108046, of 11 / 26 / 2025, page 25 / 68 / 30 (disulfanedi-ylbis(2,1-phenylene))diacrilamide, N,N'-(disulfanedi-ylbis(4,1-phenylene))diacrilamide and N,N'-bis(acryloyl)cystamine. In one embodiment, the crosslinker comprises diallyl disulfide.

[0067] The dynamic crosslinker may be present in the polymerizable composition in various amounts, for example, in an amount ranging from 0.01% by weight to 50% by weight, from 0.05% by weight to 50% by weight, from 0.1% by weight to 50% by weight, from 0.5% by weight to 50% by weight, from 1% by weight to 50% by weight, from 5% by weight to 50% by weight, from 0.1% by weight to 40% by weight, from 0.5% by weight to 40% by weight, from 1% by weight to 40% by weight, from 5% by weight to 40% by weight, from 0.1% by weight to 30% by weight, from 0.5% by weight to 30% by weight, from 0.1% by weight to 20% by weight, from 0.5% by weight to 20% by weight, from 1% by weight to 20% by weight, from 5% by weight to 20% by weight, from 0.1% by weight to 10% by weight, from 0.5% by weight to 10% by weight, from 1% by weight to 10% by weight or from 5% by weight to 10% by weight, in relation to 100% by weight of the total quantity of the polymerizable composition (comprising the crosslinker, monomers and polymerization initiator).In terms of mol%, the dynamic crosslinker may be present in the polymerizable composition in an amount of at least 0.01 mol%, at least 0.05 mol%, at least 0.1 mol%, at least 0.5 mol%, at least 1 mol%, at least 2 mol%, at least 3 mol%, at least 4 mol%, at least 5 mol%, or in a range from 0.01 mol% to 35 mol% (e.g., from 0.05 mol% to 35 mol%, from 0.1 mol% to 35 mol%, from 0.5 mol% to 35 mol%, from 1 mol% to 35 mol%, from 5 mol% to 35 mol%, from 1 mol% to 30 mol%, from 5% by mol to 30% by mol, 1% by mol to 25% by mol, 5% by mol to 25% by mol, 1% by mol to 20% by mol, 5% by mol to 20% by mol, 1% by mol to 15% by mol, 5% by mol to 15% by mol, 1% by mol to 10% by mol or 5% by mol to 10% by mol), in relation to 100% by mol of the total amount of the polymerizable composition (comprising the. Petition 870250108046, dated 11 / 26 / 2025, p. 26 / 68 / 30 crosslinker, monomers and polymerization initiator). Reversibly crosslinkable polymer and its reprocessing

[0068] The method discussed above results in a reversibly crosslinkable polymer. Thus, another aspect of the invention relates to the reversibly crosslinkable polymer obtained according to the method as described in the above aspect of the invention.

[0069] All the above descriptions and all embodiments relating to the polymerizable composition for manufacturing the reversibly crosslinked polymer, including the crosslinkers, one or more monomers and polymerization initiators, discussed above in the aspect of the invention relating to the polymerizable composition are applicable to this aspect of the invention.

[0070] All the above descriptions and all embodiments relating to the method for manufacturing a reversibly crosslinked polymer, including various suitable reagents, reaction mechanisms and reaction conditions discussed above in the aspect of the invention relating to the method for manufacturing a reversibly crosslinked polymer, are applicable to this aspect of the invention.

[0071] As discussed above, the method generates a reversibly crosslinkable polymer, comprising the reaction product of the polymerizable composition, as discussed above. In the resulting reversibly crosslinkable polymer, the dynamic crosslinker can be incorporated into the reversibly crosslinkable polymer in an amount of about 0.01% by weight to about 50% by weight, for example, in an amount ranging from 0.05% by weight to 50% by weight, from 0.1% by weight to 50% by weight, from 0.5% by weight to 50% by weight, from 1% by weight to 50% by weight, from 5% by weight to 50% by weight, from 0.1% by weight to 40% by weight, from 0.5% by weight to 40% by weight, from 1% by weight to 40% by weight, from 5% by weight to 40% by weight, from 0.1% by weight to 30% by weight, from 0.5% by weight to 30% by weight, from 0.1% by weight to 20% by weight. weight, from 0.5% by weight to 20% by weight Petition 870250108046, dated 11 / 26 / 2025, page 27 / 68 / 30 weight, from 1% by weight to 20% by weight, from 5% by weight to 20% by weight, from 0.1% by weight to 10% by weight, from 0.5% by weight to 10% by weight, from 1% by weight to 10% by weight, or from 5% by weight to 10% by weight, in relation to 100% by weight of the total quantity of the reversibly crosslinkable polymer.

[0072] The resulting polymer network in the reversibly crosslinkable polymer contains an SS-link that is dynamic and can undergo dissociation and reassociation under different conditions (e.g., by changing the temperature), allowing the polymer to be reprocessed and recycled when subjected to a stimulus.

[0073] The resulting reversibly crosslinkable polymer can be reprocessed by heating from a temperature at which the dissociation of reversible crosslinking bonds (e.g., -SS- bonds) is inactive or substantially inactive (e.g., at room temperature) to an elevated temperature at which the dissociation of reversible crosslinking bonds (e.g., -SS- bonds) is activated or significantly increased (e.g., at temperatures greater than 50°C, greater than 60°C, greater than 70°C, greater than 80°C, greater than 90°C, greater than 100°C, greater than 110°C, greater than 120°C, greater than 130°C, greater than 140°C, or greater than 150°C, depending on the individual crosslinker used).Thus, suitable reprocessing / recycling temperatures may be at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 120°C, at least 130°C, at least 140°C, or at least 150°C, depending on the individual crosslinker used. In some embodiments, the reprocessing / recycling temperatures are in a range of 120°C to 160°C. The polymers may be reshaped (e.g., remolded) at the reprocessing / recycling temperatures. The reprocessed / recycled polymers may then be cooled, for example, back to room temperature. During cooling, the reversible linkage (e.g.,...) Petition 870250108046, dated 11 / 26 / 2025, page 28 / 68 / 30 example, -SS linkage) reassociates, thus reforming the polymer network. A single reprocessing / recycling cycle can be a single round of heating, reshaping, and cooling. The heating used to reprocess / recycle reversibly crosslinkable polymers can be relatively short (e.g., 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, 30 minutes or less) and still provide the reprocessed polymer network with full recovery of crosslinking density (compared to the initial polymer network before any reprocessing / recycling).

[0074] The reversibly crosslinkable polymer after a reprocessing / recycling cycle retains the polymer properties (compared to those of the original polymer before any reprocessing / recycling). Thus, the polymerizable composition and method described in this document allow the preparation of a fully reprocessable / recyclable polymer (compared to conventional polymers prepared without the use of the dynamic crosslinkers described in this document). EXAMPLES

[0075] The following examples are for illustrative purposes only and should not in any way limit the scope of the present invention. Example 1 - Synthesis of an exemplary reversibly cross-linked polymer

[0076] In this example, an exemplary reversibly crosslinked polymer was synthesized using ethylene as a monomer and different dynamic disulfides as dynamic crosslinkers. Dynamic crosslinkers A to D, as shown in Figure 1, were used to produce the examples.

[0077] The polymers were produced in a reactor by means of free radical polymerization. Due to the nature of the polymers produced Petition 870250108046, dated 11 / 26 / 2025, page 29 / 68 / 30, to determine the presence of crosslinking agents, differential scanning calorimetry (DSC) was performed on the resulting polymer samples to determine the incorporation of comonomer (dynamic crosslinker) into the polymer network. It is known that, in ethylene-based polymers, increasing the comonomer (and / or dynamic crosslinker) content results in a decrease in the crystallization temperature (Tc) and melting temperature (Tm).

[0078] DSC was performed under nitrogen on a TA Q2000 instrument. A sample was heated to 300°C at 10°C / min, held at that temperature for 1 minute, cooled to -20°C at 10°C / min and held at that temperature for 1 minute. Then, the sample was heated to 300°C at 10°C / min. Table 1 shows the crystallization temperature (Tc), melting temperature (Tm, second melting cycle) and endothermic Δη (J / g, second melting cycle).

[0079] For the swelling studies, ~0.1 g of polymer sample was placed in 10 mL of toluene or 10 mL of xylene and heated to ~100°C for 2 hours. Table 2 shows the observations recorded in the swelling studies of the polymer samples.______________________ Table 1. DSC Results Samples Monomer Concentration Peak Tc (°C) Peak Tm (°C) Endothermic AH (J / g) A1 0.265 g 102.9 114.6 106.7 A2 0.509 g 103.7 115.1 106.4 A3 1.002 g 102.2 114.9 105.7 A4 2.007 g 94.6 108.7 31.8 A5 0.499 g - - - B1 0.5 ml 97.5 104.3 69.0 B2 1.0 ml 87.0 96.24 23.2 C1 0.258 g 98.8 110.5 14.6 C2 0.997 g 94.9 109.08 16.5 C3 2.075 g 88.7 101.89 63.5 D1 0.258 g 96.4 107.2 120.37 D2 0.504 g 94.8 104.2 124.9 D3 1.005 g 94.9 106.35 72.2 D4 0.260 g 99.3 110.0 47.5 Petition 870250108046, dated 11 / 26 / 2025, page 30 / 68 / 30 D5 0.517 g 98.2 107.3 37.9 D5 0.517 g 98.2 107.3 37.9 Table 2. Swelling Study Samples Monomer Concentration Xylenes (~100°C) Toluene (~100°C) A1 0.265 g yes yes A2 0.509 g partially partially A3 1.002 g no yes A4 2.007 g no no A5 0.499 g - - B1 0.504 g yes yes B2 1.016 g yes yes C1 0.258 g partially partially C2 0.997 g no no C3 2.075 g - - D1 0.258 g - - D2 0.504 g - - D3 1.005 g - - D4 0.260 g - - D5 0.517 g - - Example 1a - Synthesis of an exemplary reversibly crosslinked polymer (crosslinker A)

[0080] In this example, ethylene-based polymers incorporating dynamic crosslinker A, bis(2-methacryloyl)oxyethyl disulfide (DSDMA), were produced at various dynamic crosslinker concentrations via free-radical polymerization. Ethylene (99.95%, Air Liquide, 8.27 MPa (1200 psi)), bis(2-methacryloyl)oxyethyl disulfide (Sigma Aldrich), 2,2'-azobisisobutyronitrile (AIBN, 98%, Sigma Aldrich), and dimethyl carbonate (DMC, anhydrous 99%, Sigma Aldrich) were used as received. In a Parr reactor, 100 mL of DMC, 0.1 g of AIBN, and DSDMA (0.25, 0.5, 1.0, or 2.0 g) were added.

[0081] The reactor was sealed and purged three times with nitrogen under agitation. After the final nitrogen purge, the system was filled with 50 L of ethylene and heated to 90°C for 4 hours. The reactors reached a final pressure ranging from 9 to 10.5 MPa (90 to 105 bar). The reaction mixture was Petition 870250108046, dated 11 / 26 / 2025, page 31 / 68 / 30 collected and washed with additional DMC. The polymer was dried overnight in a vacuum oven (samples A1 to A5, Tables 1 to 2).

[0082] Figure 2A depicts DSC chromatographs of crosslinker A ethylene polymers with varying concentrations of crosslinker A (concentrations A1 to A5, as shown in Tables 1 and 2). The expected trend is observed: as the comonomer concentration increases, both Tm and Tc decrease, as illustrated in Figure 2B. Figure 3A depicts the storage modulus and tan delta of the 1 g DSMDA-ethylene copolymer (sample A3). Dynamic mechanical analysis (DMA) measurements were performed on a TA 800 DMA instrument in tensile mode. Thin film samples were prepared using a carver press at 175°C and 10 tons for 1 hour. The sample is cooled to 100°C and a temperature scan is performed at 80°C at 3°C / min to determine the viscoelastic response. A preload force of 0.01 N with a frequency of 1 Hz was applied, and a defined amplitude is predetermined by means of strain sweep.

[0083] For swelling studies, ~0.1 g of polymer was placed in 10 mL of toluene or 10 mL of xylenes. Both samples were heated to ~100°C for 2 hours. The samples did not dissolve after 2 hours, indicating a cross-linked polymer network, as shown in Figure 3B. DSDMA contains a dynamic disulfide bond, therefore a polymer containing DSDMA will be a dynamic polymer. To examine the dynamic nature of the polymer, stress relaxation tests (G(t) / G(0)) were performed. The stress relaxation experiments were performed on an ARES G2 Rheometer, using a parallel plate geometry with a diameter of 25.0 mm and a gap of 1.0 mm. The samples were prepared in a Carver press at 175°C for 1 hour and 10 tons of pressure. Each sample undergoes a strain scan from 0.1 to 100% to determine a strain that falls within the viscoelastic region. Petition 870250108046, dated 11 / 26 / 2025, page 32 / 68 / 30 linear of the material and each sample is conditioned to the test temperature for 30 minutes before testing. The tests were performed with a constant deformation of 1% for 10,000 s at the selected temperature.

[0084] Figure 4 shows the normalized stress relaxation of sample A3 at 160, 170, 180, and 190°C. The sample performed at 160°C did not exhibit stress relaxation, but the samples performed at 170, 180, and 190°C exhibited rapid stress relaxation on longer timescales.

[0085] In addition to stress relaxation, indicating the dynamic nature of these polymers, reprocessability studies were performed. Figure 5 describes the reprocessability study of sample A5. A polymer sample obtained from the reactor was molded in a Carver press at 160°C for 1 hour with 8 to 10 tons of pressure and then placed in a cold press (room temperature) for 5 minutes with 8 to 10 tons of pressure. The molded sample was homogeneous, with no visible weld lines (press 1x). The sample molded in press 1x was then cut into 3 to 5 mm pieces and pressed under the same conditions (160°C for 1 hour with 8 to 10 tons of pressure). The molded sample (press 2x) was homogeneous. The same process was performed to obtain a sample molded in press 3x, also homogeneous. Reprocessability indicates the dynamic nature of the polymer network. Example 1b - Synthesis of an exemplary reversibly crosslinked polymer (crosslinker B)

[0086] In this example, ethylene-based polymers incorporating the dynamic crosslinker B, diallyl disulfide (DADS), were produced at various dynamic crosslinker concentrations via free-radical polymerization. Ethylene (99.95%, Air Liquide, 8.27 MPa (1200 psi)), diallyl disulfide (>80% FG, Sigma Aldrich), 2,2'-azobisisobutyronitrile (AIBN, 98%, Sigma Aldrich), and dimethyl carbonate (DMC, anhydrous 99%, Sigma Aldrich) were used as received. In a Parr reactor, they were Petition 870250108046, dated 11 / 26 / 2025, page 33 / 68 / 30 added 100 mL of DMC, 0.1 g of AIBN and DADS (0.5 or 1 mL). The reactor was sealed and purged three times with nitrogen under agitation. After the final nitrogen purge, the system was filled with 50 L of ethylene and heated to 90°C for 4 hours. The reactors reached a final pressure ranging from 10 to 10.5 MPa (100 to 105 bar). The reaction mixture was collected and washed with additional DMC. The polymer was dried overnight in a vacuum oven (samples B1 and B2; Tables 1 to 2). Example 1c - Synthesis of an exemplary reversibly crosslinked polymer (crosslinker C)

[0087] In this example, ethylene-based polymers incorporating the dynamic crosslinker C,N,N'-Bis(acryloyl)cystamine (BAC) were produced at various concentrations of dynamic crosslinker via free radical polymerization. Ethylene (99.95%, Air Liquide, 8.27 MPa (1200 psi)), N,N'-Bis(acryloyl)cystamine (Sigma Aldrich), 2,2'-azobisisobutyronitrile (AIBN, 98%, Sigma Aldrich), and acetone (99.5% reagent ACS, Sigma Aldrich) were used as received. In a Parr reactor, 100 mL of acetone, 0.1 g of AIBN, and BAC (0.25, 1, or 2 g) were added. The reactor was sealed and purged three times with nitrogen under stirring. After the final nitrogen purge, the system was filled with 50 L of ethylene and heated to 90°C for 4 hours. The reactors reached a final pressure ranging from 9 to 10.5 MPa (90 to 105 bar). The reaction mixture was collected and washed with additional acetone. The polymer was dried overnight in a vacuum oven (samples C1 to C3; Tables 1 to 2). Example 1d - Synthesis of an exemplary reversibly crosslinked polymer (crosslinker D)

[0088] In this example, ethylene-based polymers incorporating a dynamic crosslinker D, ((((disulfanedi-ylbis(4,1-phenylene))bis(azanodiyl))bis(carbonyl))bis(azanodiyl))bis(ethane-2,1-diyl)bis(2-methylacrylate) (4MUPD), were produced at various crosslinker concentrations. Petition 870250108046, dated 11 / 26 / 2025, page 34 / 68 / 30 dynamic by means of free radical polymerization. Ethylene (99.95%, Air Liquide, 8.27 MPa (1200 psi)), 2,2'-azobisisobutyronitrile (AIBN, 98%, Sigma Aldrich), acetone (99.5% ACS reagent, Sigma Aldrich) and tetrahydrofuran (THF, anhydrous 99%, Sigma Aldrich) were used as received. 4MUPD was synthesized using a predetermined method.2 In a Parr reactor, 100 mL of THF or acetone, 0.1 g of AIBN and 4MUPD (0.25, 0.5 or 1 g) were added. The reactor was sealed and purged three times with nitrogen under stirring. After the final nitrogen purge, the system was filled with 50 L of ethylene and heated to 90°C for 4 hours. The reactors reached a final pressure ranging from 9 to 9.5 MPa (90 to 95 bar). The reaction mixture was collected and washed with additional THF or acetone. The polymer was dried overnight in a vacuum oven.Polymers D1 to D3 were polymerized in acetone, and polymers D4 and D5 were polymerized in THF (Tables 1 and 2). Petition 870250108046, dated 11 / 26 / 2025, page 35 / 68

Claims

1 / 7 CLAIMS 1. Polymerizable composition, characterized in that it comprises: a crosslinker comprising an -Sn- moiety and having at least two polymerizable groups, wherein n is an integer from 1 to 8, one or more monomers, each monomer having at least one C=C double bond capable of undergoing a polymerization reaction, and a polymerization initiator.

2. Polymerizable composition according to claim 1, characterized in that the crosslinker is represented by Formula (I), (II), (III), (IV) or (V): R1R2R3C-Sn-CR4R5R6 (I) R7-CH(X)-Sn-CH(Y)-R8 (II) R7-B1-A1-Sn-A2-B2-R8 (III) R15-O-Sn-O-R16 (IV) (R17)(R18)-P-Sn-P-(R19)(R20) (V) where: n is an integer from 2 to 8, X represents CHR9R10, OH, SH or NHR11; Y represents CHR12R13, OH, SH or NHR14;Each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 is independently selected from the group consisting of a hydrogen atom, a halogen atom, a linear or branched C1-20 alkyl, a C2-20 alkenyl, a C220 alkynyl, a nitrile, a hydroxyl, an ester having from 1 to 20 carbon atoms, an ether having from 1 to 20 carbon atoms, a thioether having from 1 to 20 carbon atoms, a ketone having from 1 to 20 carbon atoms, an imine, an amide, a primary amine, a secondary amine, a tertiary amine, a trifluoromethyl, a phenyl, a benzyl, a phenol, a pentafluorophenyl, Petition 870250104449, dated 11 / 14 / 2025, p. 36 / 46 2 / 7 a nitroxyl and a silcone having from 1 to 20 carbon atoms; each optionally substituted by one or more alkyl, alkenyl, hydroxyl or halogen atoms;each of A1 and A2 is independently absent, a C1-C20 alkylene, a C2-C20 cycloalkylene, a divalent form of a C2-C20 alkene, a divalent form of a C2-C20 alkyne, an arylene or combinations thereof, each optionally substituted by one or more alkyl, alkenyl, hydroxyl or halogen atoms; each of B1 and B2 is independently absent or is a divalent form of an imine, amine, amide, ether or ester, or combinations thereof; provided that the following: in Formula (I), at least one of R1, R2 and R3 comprises a C=C double bond and at least one of R4, R5 and R6 comprises a C=C double bond, and in Formulas (II) and (III), each of R7 and R8 comprises a C=C double bond.

3. Polymerizable composition according to claim 2, characterized in that n is 2 or 3.

4. Polymerizable composition according to claim 1 or 2, characterized in that the C=C double bond capable of undergoing a polymerization reaction is in a functional group comprising at least one member selected from the group consisting of an alkene, an alkyne, a nitrile, a vinyl group, an acyl group, an acrylate, a (meth)acrylate, a styrene and a vinylpyridine.

5. Polymerizable composition according to claim 2, characterized in that the crosslinker is represented by Formula (III), and where: n is 2 or 3; Petition 870250104449, dated 11 / 14 / 2025, p. 37 / 46 3 / 7 each of R7 and R8 is a C2-20 alkenyl, optionally substituted by one or more alkyl or alkenyl groups; each of A1 and A2 is independently absent, a C1-C20 alkylene or a divalent form of phenyl; each optionally substituted by one or more alkyl, alkenyl, hydroxyl or halogen atoms; and each of B1 and B2 is independently absent or is a divalent form of amine, amide, ether or ester.

6. Polymerizable composition according to claim 1 or 2, characterized in that the crosslinker comprises at least one member selected from the group consisting of diallyl disulfide, diallyl trisulfide, bis(2-methacryloyl)oxyethyl disulfide, diallyl 2,2'-disulfanediyldibenzoate, diallyl 2,2'-disulfanediyldiacetate, diallyl 4,4'-disulfanediyldibutyrate, diallyl 3,3'-disulfanediyldipropionate, disulfanediylbis(3,1-phenylene) diacrylate, disulfanediylbis(ethane-2,1-diyl) diacrylate, N,N'-(disulfanediylbis(2,1-phenylene))diacrilamide, N,N'-(disulfanediylbis(4,1-phenylene))diacrylamide and N,N'-Bis(acryloyl)cystamine.

7. Polymerizable composition according to claim 6, characterized in that the crosslinker comprises at least one of diallyl disulfide, bis(2-methacryloyl)oxyethyl disulfide (DSDMA) and ((((disulfanedi-ylbis(4,1-phenylene))bis(azanodi-yl))bis(carbonyl))bis(azanodiyl))bis(ethane-2,1-di-yl) bis(2-methylacrylate) (4MUPD).

8. Polymerizable composition according to claim 7, characterized in that the crosslinker consists of at least one of diallyl disulfide, bis(2-methacryloyl)oxyethyl disulfide (DSDMA) and ((((disulfanedi-ylbis(4,1-phenylene))bis(azanodi-yl))bis(carbonyl))bis(azanodiyl))bis(ethane-2,1-di-yl) bis(2-methylacrylate) (4MUPD).

9. Polymerizable composition according to claim 1 or 2, characterized in that one or more monomers comprise an olefin monomer or a vinyl monomer.

10. Polymerizable composition according to claim 9, characterized in that one or more monomers comprise at least one member selected from the group consisting of ethylene, propylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene, 1-octene and vinyl acetate.

11. Polymerizable composition according to claim 10, characterized in that one or more monomers are ethylene, or ethylene and vinyl acetate.

12. Polymerizable composition according to claim 1, characterized in that the polymerization initiator comprises at least one member selected from the group consisting of a peroxide, an azo compound, a peracetate compound and a nitroxide.

13. Polymerizable composition according to claim 1, characterized in that the polymerization initiator comprises at least one member selected from the group consisting of azobisisobutyronitrile (AIBN); 2,2'-azobis(amidinopropyl) dihydrochloride; and azo-peroxide initiators containing mixtures of a peroxide with one or more azodinitrile compounds selected from the group consisting of 2,2'-azobis(2-methyl-pentanenitrile); 2,2'-azobis(2-methyl-butanenitrile); 2,2'-azobis(2-ethyl-pentanenitrile); 2-[(1-cyano-1-methylpropyl)azo]-2-methyl-pentanenitrile; 2-[(1-cyano-1-ethylpropyl)azo]-2-methyl-butanenitrile; and 2-[(1cyano-1-methylpropyl)azo]-2-ethyl-pentanonitrile.

14. Polymerizable composition according to claim 1, characterized in that the polymerization initiator comprises at least one member selected from the group consisting of 2,3-dimethyl-2,3-diphenylbutane; 3,4-dimethyl-3,4-diphenylhexane; 3,4-diethyl-3,4-diphenylhexane; 3,4-dibenzyl-3,4-ditolylhexane; 2,7-dimethyl-4,5-diethyl-4,5-diphenyloctane; and 3,4-dibenzyl-3,4-diphenylhexane.

15. Method for manufacturing a reversibly crosslinked polymer, characterized in that it comprises: reacting a crosslinker comprising a -Sn moiety and having at least two polymerizable groups, wherein n is an integer from 1 to 8, and one or more monomers, each monomer having at least one C=C double bond capable of undergoing a polymerization reaction, in the presence of the polymerization initiator, to produce a reversibly crosslinked polymer which, when reprocessed at temperatures greater than 50°C, dissociates the crosslinking bonds of the reversibly crosslinked polymer.

16. Method according to claim 15, characterized in that said reaction step is carried out by free radical initiation, thermal initiation, radiation initiation or irradiation, or combinations thereof.

17. Method according to claim 15, characterized in that said reaction step is carried out under a pressure of at least 500 kPa (5 bar).

18. Method according to claim 17, characterized in that said reaction step is carried out under a pressure of 500 kPa (5 bar) to 500,000 kPa (5,000 bar).

19. Method according to claim 18, characterized in that said reaction step is carried out under a pressure of 100,000 kPa (1,000 bar) to 300,000 kPa (3,000 bar).

20. Method according to claim 15, characterized in that said polymerization initiator is present in an amount of 1*10-7 to 5% by weight, relative to 100% by weight of the total amount of crosslinker, monomers and polymerization initiator.

21. Method according to claim 15, characterized in that said reaction step is carried out as a bulk reaction or a continuous reaction, under a pressure of at least 2,000 kPa (20 bar).

22. Method according to claim 15, characterized in that said reaction step is carried out at a temperature of at least 30°C.

23. Method according to claim 19, characterized in that said reaction step is carried out at a temperature of 30°C to 350°C.

24. Method according to claim 23, characterized in that said reaction step is carried out at a temperature of 150°C to 350°C.

25. Method according to claim 15, characterized in that the crosslinker comprises at least one member selected from the group consisting of diallyl disulfide, diallyl trisulfide, bis(2-methacryloyl)oxyethyl disulfide, diallyl 2,2'-disulfanediyldibenzoate, diallyl 2,2'-disulfanediyldiacetate, diallyl 4,4'-disulfanediyldibutyrate, diallyl 3,3'-disulfanediyldipropionate, disulfanediylbis(3,1-phenylene) diacrylate, disulfanediylbis(ethane-2,1-di-yl) diacrylate, N,N'-(disulfanediylbis(2,1-phenylene))diaacrylamide, N,N'-(disulfanediylbis(4,1-phenylene))diaacrylamide and N,N'- Bis(acryloyl)cystamine.

26. Method according to claim 25, characterized in that the crosslinker comprises diallyl disulfide.

27. Method according to claim 15, characterized in that the crosslinking links are sulfur-sulfur bonds that dissociate at temperatures above 50°C.

28. Method according to claim 15, characterized in that one or more monomers comprise at least one member selected from the group consisting of ethylene, propylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene, 1-octene and vinyl acetate. Petition 870250104449, dated 11 / 14 / 2025, pp. 41 / 46 7 / 7 29. Method according to claim 28, characterized in that one or more monomers are ethylene, or ethylene and vinyl acetate.

30. Reversibly crosslinkable polymer, characterized in that it comprises the reaction product of the polymerizable composition as defined in claim 1, wherein the reversibly crosslinkable polymer contains an -SS- moiety.

31. Reversibly crosslinkable polymer, characterized in that it is obtained according to the method defined in claim 15.

32. Reversibly crosslinkable polymer according to claim 31, characterized in that the crosslinker is incorporated into the reversibly crosslinkable polymer in an amount of about 0.01% by weight to about 50% by weight, relative to 100% by weight of the total amount of the reversibly crosslinkable polymer. Petition 870250104449, dated 11 / 14 / 2025, pp. 42 / 46

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