INVENTORS: Yaxian Wang, Ke Ran Chen, Wenxi Gao, Saifudin M. Abubakar

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to US Provisional Application No. 63/375,077 filed September 9, 2022, the disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

[0002] This disclosure relates generally to a polyolefin vitrimer with reversible borate moiety, to a process for preparing the polyolefin vitrimer and to a polymer composition comprising polyolefin vitrimer with reversible borate moiety.

BACKGROUND OF THE INVENTION

[0003] Vitrimers are a new class of polymeric materials displaying dynamically cross- linked networks. The topology of such networks is not fixed, as the bonds connecting the different polymer chains undergo associative exchange reactions that allows them to exchange in the network. These exchange reactions are activated at temperatures above the topological freezing transition temperature (Tv). Below Tv, vitrimers behave as solid elastic networks (i.e., as thermosets or vulcanized elastomers), and above Tv, they behave as viscoelastic liquids (F., as melts). Therefore, vitrimers represent a very attractive class of polymers that breaks the paradigm of non-recyclability of thermosets and vulcanized rubbers.

[0004] Polyolefin are widely used in various applications. In order to get enhanced properties to better fit into certain applications, crosslinking is normally applied. However, the cross-linked material is then hard to reprocess and recycle. Usually, waste material is buried and incinerated, which causes serious waste of resources and environmental pollution. Therefore, the development of crosslinked polyolefin that can be recycled and reprocessed has become a very important issue.

SUMMARY OF THE INVENTION

[0005] In a first general aspect, this disclosure provides a polyolefin vitrimer, which is formed from an epoxy-functionalized polyolefin and at least one compound (1) and/or at least one compound (2), wherein compound (1) contains at least one reversible borate moiety or derivative thereof and at least two epoxy reactive groups (g1); and there is a reversible borate moiety or derivative thereof between any two epoxy reactive groups (g1) in compound (1) and the epoxy reactive group (g1) does not contain B atom; wherein compound (2) contains at least two epoxy reactive groups, wherein said at least two epoxy reactive groups comprise at least one epoxy reactive group (g2) capable of forming the reversible borate moiety or derivative thereof with the epoxy group; wherein the derivative of borate moiety represents a moiety with the oxygen in the borate moiety being replaced with other element of the sixth main group, for example sulfur.

[0006] In a second general aspect, this disclosure provides a process for preparing the polyolefin vitrimers of this disclosure, which comprises reacting the epoxy-functionalized polyolefin with at least one compound (1) and/or at least one compound (2).

[0007] In a third general aspect, this disclosure provides a composition comprising the polyolefin vitrimers of this disclosure and at least one additive.

[0008] In a fourth general aspect, this disclosure provides an article comprising the polyolefin vitrimers of this disclosure or the composition of this disclosure.

[0009] Certain aspects of the first, second, third and fourth general aspects may include one or more of the following features.

[0010] In some aspects, the reversible borate moiety or derivative thereof has a structure of Formula (I): (I), wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur, more preferably oxygen.

[0011] In some aspects, the -Q-B-Q- moiety in Formula (I) forms a boron-containing ring having 5 to 8 ring members together with 2 to 5 carbon atoms, preferably forms a boron- containing ring containing 5 or 6 ring members together with 2 or 3 carbon atoms, optionally the boron-containing ring is fused with a further ring to form a fused ring system.

[0012] In some aspects, the boron-containing ring has the following structure: the fused ring system containing the boron-containing ring has the following structure: wherein A is a ring having 5 to 10 ring members, and wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur, more preferably oxygen.

[0013] In some aspects, compound (1) contains 1 to 3 (1 , 2 or 3) reversible borate moieties or derivative thereof and 2 to 4 epoxy reactive groups (g1); or compound (1) contains 1 or 2 reversible borate moieties or derivative thereof and 2 or 3 epoxy reactive groups (g1).

[0014] In some aspects, compound (1) is selected from at least one compound having following structure:

(A)

(B)

(C)

(D)

(E) (F)

(G) (H) wherein each R ₁ is independently a direct bond or a divalent organic group having 1 to 20 carbon atoms; each R ₂ is independently a direct bond or an organic group having 1 to 20 carbon atoms; OP is an epoxy reactive group (g1); each A is independently a ring having 5 to 10 ring members; each Q is independently an element of the sixth main group, or oxygen or sulfur; and n is 2, 3 or 4.

[0015] In some aspects, the variables in the compounds of Formulae (A) to (H) have the following definitions: each R ₁ is independently a direct bond or a divalent hydrocarbyl having 1 to 12 carbon atoms, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; each R ₂ is independently a direct bond or a linear or branched hydrocarbyl having 1 to 12 carbon atoms; or C ₄ -C ₈ -cycloalkyl, C ₅ -C ₁₀ -cycloalkenyl, C ₆ -C ₁₀ aryl, C ₁ -C ₁₂ alkyl- C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ - C ₁₀ aryl, C ₄ -C ₁₀ heterocycloalkyl, C ₄ -C ₁₀ heterocycloalkenyl, C ₄ -C ₁₀ hetaryl or C ₄ -C ₁₀ hetaryl- C ₄ -C ₁₀ hetaryl, wherein the hydrocarbyl and the C ₁ -C ₁₂ alkylene (in C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl) can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the hydrocarbyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO and wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contains 1 to 3 heteroatoms selected from N, O, and S; and wherein the valence of R ₂ corresponds to the value of n; OP is an epoxy reactive group (g1); each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2 or 3. [0016] In some aspects, each R ₁ is independently a direct bond or C ₁ -C ₁₂ alkylene, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO; and each R ₂ is independently a direct bond, divalent or trivalent C ₁ -C ₁₂ alkyl, divalent or trivalent C ₄ -C ₈ -cycloalkyl, divalent or trivalent C ₅ -C ₁₀ -cycloalkenyl, divalent or trivalent C ₆ -C ₁₀ aryl, divalent or trivalent C ₁ -C ₁₂ alkyl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkyl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkenyl, divalent or trivalent C ₄ -C ₁₀ hetaryl, divalent or trivalent C ₄ -C ₁₀ hetaryl- C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 heteroatoms selected from N, O, and S, wherein the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene (in C ₆ -C ₁₀ aryl- C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl) can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0017] In some aspects, the epoxy reactive group (g1) is selected from hydroxy, carboxyl, amino, sulfhydryl or acid anhydride.

[0018] In some aspects, compound (2) contains 2, 3 or 4 epoxy reactive groups, wherein said 2, 3 or 4 epoxy reactive groups comprise at least one epoxy reactive group (g2) capable of forming the reversible borate moiety or derivative thereof with the epoxy group.

[0019] In some aspects, the epoxy reactive group (g2) capable of forming the reversible borate moiety or derivative thereof with the epoxy group in compound (2) is a -B(QH) ₂ group, wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur.

[0020] In some aspects, compound (2) has the following structure (OP) _w -R ₃ -[B-(QH) ₂ ] _m (II) each Q is independently an element of the sixth main group, preferably oxygen or sulfur; eachR ₃ is independently a direct bond or an organic group having 1 to 30 carbon atoms, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the organic group can optionally be replaced with -(CO)-O- and/or CO; OP is an epoxy reactive group (g1); w is an integer of 0, 1, 2 or 3; and m is an integer of 1, 2, 3 or 4 and if w is 0, m is an integer of 2, 3 or 4.

[0021] In Formula (II), the valence of group R ₃ corresponds to the sum of w and m. In an embodiment, each R ₃ is independently a direct bond or an organic group having 1 to 20 carbon atoms, which can optionally be interrupted by one or more nonadj acent oxygen atoms, and/or one or more non adjacent carbon atoms in the organic group can optionally be replaced with -(CO)-O- and/or CO.

[0022] In some aspects, the variables in the compound of Formula (II) have the following definitions: each Q is independently oxygen or sulfur, preferably oxygen; each R ₃ is independently a direct bond, divalent or trivalent C ₁ -C ₁₂ alkyl, divalent or trivalent C ₄ -C ₈ - cycloalkyl, divalent or trivalent C ₅ -C ₁₀ -cycloalkenyl, divalent or trivalent C ₆ -C ₁₀ aryl, divalent or trivalent C ₁ -C ₁₂ alkyl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkyl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkenyl, divalent or trivalent C ₄ -C ₁₀ hetaryl, divalent or trivalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 heteroatoms selected from N, O, and S, wherein the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene (in C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl) can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO; OP is an epoxy reactive group (g1); w is an integer of 0, 1 or 2; and m is an integer of 1 , 2 or 3 and if w is 0, m is an integer of 2 or 3.

[0023] In some aspects, the compound (2) is selected from benzen- 1 ,4-diboronic acid, 2,5- thiophenediboranic acid, 4,4-biphenyldiboronic acid, carboxyphenylboronic acid, aminobenzeneboronic acid, hydroxyphenylboronic acid, (Hydroxymethyl)phenylboronic acid, polyboric acid, tetrahydroxydiboron, and ((((oxybis(ethane-2,1- diyl))bis(oxy))bis(methylene))bis(4, 1 -phenylene))diboronic acid.

[0024] In some aspects, the amount of the moiety derived from at least one compound (1) and/or at least one compound (2) is in the range from about 0.1 wt% to about 30 wt%, from about 0.12 wt% to about 15 wt%, from about 0.15 wt% to about 8 wt%, or from about 0.15 wt% to about 5 wt%, based on the weight of the polyolefin vitrimer.

[0025] In some aspects, the tensile strength of the polyolefin vitrimer is at least about 110%, or at least about 120% of the tensile strength of the neat polyolefin.

[0026] In some aspects, the creep resistance at 80°C of the polyolefin vitrimer is at least about 5%, or at least about 8% better than the creep resistance of the neat polyolefin. [0027] In some aspects, the hysteresis of the polyolefin vitrimer is at least about 5%, or at least about 8% better than the hysteresis of the neat polyolefin.

[0028] In some aspects, the polyolefin vitrimer has thermoplastic property, preferably is able to be processed by pressing, injection molding, extrusion molding, blow molding, calendaring, foaming, solvent plasticizing, mold pressing, casting, or reaction molding.

[0029] In some aspects, the tensile strength of the polyolefin vitrimer after being reprocessed once is at least about 65%, or at least about 75%, preferably at least about 78% of the tensile strength of the polyolefin vitrimer before reprocessing.

[0030] In some aspects, the epoxy-functionalized polyolefin comprises a repeat unit carrying an epoxy group, preferably the amount of the repeat unit carrying an epoxy group is in the range from about 0.5 mol% to about 30 mol%, from about 0.8 mol% to about 20 mol%, from 0.8 mol% to 8 mol%, based on the total amount of the repeat units in the epoxy- functionalized polyolefin.

[0031] The polyolefin vitrimer of this disclosure has enhanced properties including high tensile strength, high use temperature, excellent creep resistant and excellent elasticity etc. Moreover, unlike traditional crosslinked material, the polyolefin vitrimer of this disclosure could not only be remold and reprocess, but also the recycled material has comparable mechanical properties with the virgin materials.

[0032] These and other features and attributes of the disclosed polyolefin vitrimer of the present disclosure and their advantageous applications and/or uses will be apparent from the detailed description which follows.

DESCRIPTION OF THE DRAWING

[0033] Figure 1 shows DMA of comparison on PE-GMA-B linker(2.5%) and PE-GMA.

[0034] Figure 2 shows Creep recovery test of PE-GMA and PE-GMA-B linker (2.5%) under different temperature.

[0035] Figure 3 shows Recycle and reprocess demo for PE-GMA-B linker(2.5%).

[0036] Figure 4 shows Hysteresis comparison for PE-GMA and PE-GMA-B linker (2.5%).

DETAILED DESCRIPTION OF THE INVENTION

[0037] Various specific embodiments, versions, and examples are described herein; including exemplary embodiments and definitions that are adopted for purposes of understanding the claimed invention. While the following detailed description gives specific preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only and that the invention can be practiced in other ways. For purposes of determining infringement, the scope of the invention will refer to any one or more of the appended claims, including their equivalents, and elements or limitations that are equivalent to those that are recited. Any reference to the “invention” may refer to one or more, but not necessarily all, of the inventions defined by the claims.

[0038] All numerical values within the detailed description and the claims herein are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by those skilled in the art.

[0039] In a first general aspect, this disclosure provides a polyolefin vitrimer, which is formed from an epoxy-functionalized polyolefin and at least one compound (1) and/or at least one compound (2), wherein compound (1) contains at least one reversible borate moiety or derivative thereof and at least two epoxy reactive groups (g1); and there is a reversible borate moiety or derivative thereof between any two epoxy reactive groups (g1) in compound (1) and the epoxy reactive group (g1) does not contain B atom; wherein compound (2) contains at least two epoxy reactive groups, wherein said at least two epoxy reactive groups comprise at least one epoxy reactive group (g2) capable of forming the reversible borate moiety or derivative thereof with the epoxy group; wherein the derivative of borate moiety represents a moiety with the oxygen in the borate moiety being replaced with other element of the sixth main group, for example sulfur.

[0040] In the present disclosure, the element of the sixth main group is preferably O or S, more preferably O. The “other element of the sixth main group” can be S.

[0041] According to this disclosure, the phrase “the oxygen in the borate moiety being replaced with other element of the sixth main group” means the oxygen in the borate moiety is replaced with an element of the sixth main group, which is different from oxygen, for example the oxygen in the borate moiety can be replaced with S.

[0042] In an embodiment, the derivative of borate moiety represents a moiety with the oxygen in the borate moiety being replaced with S.

[0043] According to this disclosure, there is no substituent on Q.

[0044] In an embodiment, the reversible borate moiety or derivative thereof has a structure of Formula (I):

(I), wherein each Q is independently an element of the sixth main group, preferably O or S, more preferably O.

[0045] In an embodiment, the -Q-B-Q- moiety in Formula (I) forms a boron-containing ring having 5 to 8 ring members together with 2 to 5 carbon atoms, preferably forms a boron- containing ring containing 5 or 6 ring members together with 2 or 3 carbon atoms, optionally the boron-containing ring is fused with a further ring to form a fused ring system.

[0046] In an embodiment, the boron-containing ring has the following structure: the fused ring system containing the boron-containing ring has the following structure: wherein A is a ring having 5 to 10 ring members and wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur.

[0047] According to this disclosure, the ring (A) fused with the boron-containing ring is a ring having 5 to 10 ring members, such as 5 to 8, or 5, 6, or 7 ring members. The ring (A) can be saturated, or partially unsaturated or aromatic carbo-or heterocyclic ring, which contains 1 to 4 (1, 2, 3, 4) heteroatoms selected from N, O, and S, and wherein the aforementioned carbo- or heterocyclic rings system can be unsubstituted or substituted, wherein the substituents on the ring can join to form additional rings.

[0048] Examples of the heterocyclic rings as ring (A) include one of following:

[0049] Examples of aromatic ring as ring (A) comprise phenyl ring or naphthalene ring. [0050] In an embodiment, the fused ring system containing the boron-containing ring has the following structure: wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur.

[0051] In an embodiment, compound (1) contains 1 to 3 (for example 1, 2 or 3) reversible borate moieties or derivative thereof and 2 to 4 (for example 2, 3 or 4) epoxy reactive groups (g1). In an embodiment, compound (1) contains 1 to 3 (for example 1, 2 or 3) reversible borate moieties or derivative thereof and 2 epoxy reactive groups (g1). In an embodiment, compound (1) contains 1 to 3 (for example 1, 2 or 3) reversible borate moieties or derivative thereof and 3 epoxy reactive groups (g1). In an embodiment, compound (1) contains 1 or 2 reversible borate moieties or derivative thereof and 2 or 3 epoxy reactive groups (g1). In an embodiment, compound (1) contains 1 or 2 reversible borate moieties or derivative thereof and 2 epoxy reactive groups (g1). In an embodiment, compound (1) contains 2 reversible borate moieties or derivative thereof and 2 epoxy reactive groups (g1). In an embodiment, compound (1) contains 2 reversible borate moieties and 2 epoxy reactive groups (g1).

[0052] In an embodiment, compound (1) is selected from at least one compound having following structure:

(A)

(B) (C) (D)

(E)

(F)

(G)

(H) wherein each R ₁ is independently a direct bond or a divalent organic group having 1 to 20 carbon atoms; each R ₂ is independently a direct bond or an organic group having 1 to 20 carbon atoms; OP is an epoxy reactive group (g1); each A is independently a ring having 5 to 10 ring members; each Q is independently an element of the sixth main group, or oxygen or sulfur; and n is 2, 3 or 4.

[0053] In an embodiment, each R ₁ is independently a direct bond or a divalent hydrocarbyl having 1 to 12 carbon atoms (for example 1 to 6 carbon atoms, or 1 to 4 carbon atoms), which can optionally be interrupted by one or more nonadjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)- O- and/or CO. [0054] In an embodiment, each R ₂ is independently a direct bond or a hydrocarbyl having 1 to 20 carbon atoms (for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, or 1 to 20, 1 to 16, Ito 10, 1 to 12, 1 to 6, 2 to 20, 2 to 16, 2 to 12, 2 to 10, 2 to 6, 3 to 20, 3 to 16, 3 to 10, 3 to 12, 3 to 6, 4 to 20, 4 to 16, 4 to 10, 4 to 12, 4 to 6, 5 to 20, 5 to 16, 5 to 10, 5 to 12, 5 to 6, 6 to 20, 6 to 16, 6 to 10 carbon atoms), which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; and a 5-20-membered (for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, 5-18, 5-16, 5-12, 5-10- membered) heterocyclic ring which contains 1 to 3 (for example 1, 2, 3) heteroatoms selected fromN, O, and S.

[0055] A person skilled in the art could understand that, the valence of R ₂ corresponds to the value of n, for example if n is 2, valence of R ₂ is 2; if n is 3, valence of R ₂ is 3; if n is 4, valence of R ₂ is 4.

[0056] The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group” are used interchangeably throughout this document unless otherwise specified. For purposes of this disclosure, a hydrocarbyl radical is defined to be C ₁ to C20 radicals (for example, C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₁₀ , C ₁₂ , C ₁₆ , C ₁₈ , or C ₂₀ ) or C ₁ to C ₁₂ radicals, C ₁ to C ₆ radicals, C ₂ to C ₁₂ radicals, C ₃ to C ₁₂ radicals, or C ₄ to C ₁₂ radicals, or C ₅ to C ₂₀ radicals, C ₆ to C ₂₀ radicals, or C ₇ to C ₂₀ radicals or C ₅ to C ₁₀ radicals, or C ₅ to C ₁₀ radicals or C ₆ to C ₁₀ radicals that may be linear, branched, or cyclic where appropriate (aromatic or non-aromatic, such as saturated or unsaturated); and can further include hydrocarbyl radicals substituted with other hydrocarbyl radicals and/or one or more functional groups.

[0057] In an embodiment, each R ₁ is independently a direct bond or C ₁ -C ₁₂ alkylene, which can optionally be interrupted by one or more nonadjacent oxygen atoms, and/or one or more nonadjacent carbon atoms in the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO. In an embodiment, each R ₁ is independently a direct bond or C ₁ -C ₆ alkylene, which can optionally be interrupted by one or more nonadjacent oxygen atoms, and/or one or more nonadjacent carbon atoms in the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)- O- and/or CO. In an embodiment, R ₁ is methylene or ethylene.

[0058] In an embodiment, each R ₂ is independently a direct bond, a liner or branched C ₁ -C ₂₀ hydrocarbyl, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; a saturated, or partially unsaturated or aromatic carbo-or heterocyclic ring having 3 to 20 carbon atoms, which contains 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S. The number of carbon atoms of the liner or branched hydrocarbyl and the number of carbon atoms of ring are as mentioned above for the organic groups.

[0059] In an embodiment, each R ₂ is independently a direct bond or a liner or branched hydrocarbyl having 1 to 12 carbon atoms (for example 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or 2 to 12, or 4 to 12, or 2 to 6, or 4 to 6, or 6 to 10 carbon atoms); C ₄ -C ₈ -cycloalkyl, C ₅ -C ₁₀ -cycloalkenyl, C ₆ -C ₁₀ aryl, C ₁ -C ₁₂ alkyl -C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, C ₄ -C ₁₀ heterocycloalkyl, C ₄ -C ₁₀ heterocycloalkenyl, C ₄ -C ₁₀ hetaryl, C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the hydrocarbyl and the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the hydrocarbyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO and wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S; and wherein the valence of R ₂ corresponds to the value of n.

[0060] In an embodiment, each R ₂ is independently a direct bond, divalent or trivalent C ₁ -C ₁₂ alkyl, divalent or trivalent C ₄ -C ₈ -cycloalkyl, divalent or trivalent C ₅ -C ₁₀ -cycloalkenyl, divalent or trivalent C ₆ -C ₁₀ aryl, divalent or trivalent C ₁ -C ₁₂ alkyl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkyl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkenyl, divalent or trivalent C ₄ -C ₁₀ hetaryl, divalent or trivalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0061] Taking divalent or trivalent C ₁ -C ₁₂ alkyl-C ₆ -C ₁₀ aryl as an example, it means the total valence of C ₁ -C ₁₂ alkyl-C ₆ -C ₁₀ aryl is divalence or trivalence.

[0062] In an embodiment, each R ₂ is independently a direct bond, divalent or trivalent C ₁ -C ₆ alkyl, or divalent or trivalent C ₄ -C ₈ -cycloalkyl, divalent or trivalent C ₅ -C ₁₀ -cycloalkenyl, divalent or trivalent C ₆ -C ₁₀ aryl, divalent or trivalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkyl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkenyl, divalent or trivalent C ₄ -C ₁₀ hetaryl, divalent or trivalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the divalent or trivalent C ₁ -C ₆ alkyl and the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent or trivalent C ₁ -C ₆ alkyl and the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0063] In an embodiment, each R ₂ is independently a direct bond, divalent or trivalent C4-C ₁₂ alkyl, or divalent or trivalent C ₄ -C ₈ -cycloalkyl, divalent or trivalent C ₅ -C ₁₀ -cycloalkenyl, divalent or trivalent C ₆ -C ₁₀ aryl, divalent or trivalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkyl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkenyl, divalent or trivalent C ₄ -C ₁₀ hetaryl, divalent or trivalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the divalent or trivalent C ₄ -C ₁₂ alkyl and the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent or trivalent C ₄ -C ₁₂ alkyl and the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0064] In an embodiment, each R ₂ is independently a direct bond, C ₁ -C ₁₂ alkylene (i.e., divalent C ₁ -C ₁₂ alkyl), or divalentC ₄ -C ₈ -cycloalkyl, divalent C ₅ -C ₁₀ -cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl, divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0065] In an embodiment, each R ₂ is independently a direct bond, C ₄ -C ₁₂ alkylene (i.e., divalent C ₄ -C ₁₂ alkyl), or divalent C ₄ -C ₈ -cycloalkyl, divalent C ₅ -C ₁₀ -cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl, divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₄ -C ₁₂ alkylene and the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₄ -C ₁₂ alkylene and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0066] In an embodiment, each R ₂ is independently a direct bond, C ₁ -C ₆ alkylene (i.e., divalent C ₁ -C ₆ alkyl), or divalent C ₄ -C ₈ -cycloalkyl, divalent C ₅ -C ₁₀ -cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0067] In an embodiment, each R ₂ is independently a divalent C ₄ -C ₈ -cycloalkyl, divalent C ₅ -C ₁₀ -cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected fromN, O, and S, wherein the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO; preferably divalent C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the hetaryl contains 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S.

[0068] In an embodiment, each R ₂ is independently a phenylene, phenylene-phenylene, or divalent thiophene radical.

[0069] A is as defined above. In an embodiment, each A is independently a ring having 5 or 6 ring members.

[0070] In an embodiment, n is 2 or 3, for example 2, for example 3.

[0071] In an embodiment, Q is S or O, preferably O.

[0072] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F),

(G) and (H) have the following definition: each R ₁ is independently a direct bond or a divalent hydrocarbyl having 1 to 12 carbon atoms, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; each R ₂ is independently a direct bond or a linear or branched hydrocarbyl having 1 to 12 carbon atoms; C ₄ -C ₈ -cycloalkyl, C ₅ -C ₁₀ -cycloalkenyl, C ₆ -C ₁₀ aryl, C ₁ -C ₁₂ alkyl -C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene- C ₆ -C ₁₀ aryl, C ₄ -C ₁₀ heterocycloalkyl, heterocycloalkenyl, C ₄ -C ₁₀ hetaryl or C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the hydrocarbyl and the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the hydrocarbyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO; and wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S; and wherein the valence of R ₂ corresponds to the value of n; OP is an epoxy reactive group (g1); each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2 or 3.

[0073] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F), (G) and (H) have the following definition: each R ₁ is independently a direct bond or C ₁ -C ₁₂ alkylene, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO; each R ₂ is independently a direct bond, divalent or trivalent C ₁ -C ₁₂ alkyl, divalent or trivalent C ₄ -C ₈ -cycloalkyl, divalent or trivalent C ₅ -C ₁₀ -cycloalkenyl, divalent or trivalent C ₆ -C ₁₀ aryl, divalent or trivalent C ₁ -C ₁₂ alkyl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkyl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkenyl, divalent or trivalent C ₄ -C ₁₀ hetaryl, or divalent or trivalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO; OP is an epoxy reactive group (g1); each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2 or 3.

[0074] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F), (G) and (H) have the following definition: each R ₁ is independently a direct bond or C ₁ -C ₆ alkylene, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO; each R ₂ is independently a direct bond, C ₁ -C ₆ alkylene, divalent C ₄ -C ₈ -cycloalkyl, divalent C ₅ -C ₁₀ -cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ - C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO; OP is an epoxy reactive group (g1); each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2.

[0075] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F), (G) and (H) have the following definition: each R ₁ is independently a direct bond or C ₁ -C ₆ alkylene, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO; each R ₂ is independently a C ₄ -C ₁₂ alkylene, divalent C ₄ -C ₈ - cycloalkyl, divalent C ₅ -C ₁₀ -cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkyl ene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₄ -C ₁₂ alkylene and the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₄ -C ₁₂ alkylene and the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO; OP is an epoxy reactive group (g1); each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2.

[0076] In this disclosure, the epoxy reactive group (g1) in compound (1) does not contain B atom. In an embodiment, the epoxy reactive group (OP) (g1) is selected from hydroxy, carboxyl, amino, sulfhydryl or acid anhydride, for example hydroxy or sulfhydryl, preferably sulfhydryl (SH).

[0077] Taking compound of Formula (B) as an example, this compound can be prepared by reacting a compound of Formula (B1) (B1), wherein R ₂ , Q and n are as defined above, with a compound of Formula (B2) or a compound of Formula (B2’)

(B2) (B2’) wherein R ₁ is as defined above, and OP is an epoxy reactive group (g1); to obtain a compound of Formula (B).

[0078] Examples of compound (B1) can include 1 ,4-phenylenediboronic acid, 2,5-thiophenediboranic acid , 4,4-biphenyldiboronic acid, polyboric acid, and tetrahydroxydiboron.

[0079] Examples of compound (B2) can include 3 -mercaptopropane- 1,2-diol.

[0080] The reaction can be carried out at room temperature. The reaction time can be in the range from 8 to 30 hours, or from 12 to 26 hours.

[0081] Specific examples of compound (1) can include, but not limited to, 1,4- phenylenebis(1,3,2-dioxaborolane-2,4-diyl)dimethanethiol, thiophene-2, 5-diylbis(1, 3,2- dioxaborolane-2,4-diyl)dimethanethiol , and [1,1 ’-biphenyl-4,4’-diylbis(1,3,2-dioxaborolane- 2,4-diyl)] dimethanethiol.

[0082] In this disclosure, compound (2) contains at least two epoxy reactive groups, wherein said at least two epoxy reactive groups comprise at least one epoxy reactive group (g2) capable of forming the reversible borate moiety or derivative thereof with the epoxy group. In compound (2), in addition to the epoxy reactive group (g2), the remaining epoxy reactive group (if present) can be epoxy reactive group (g1). In an embodiment, one, two or more or all of epoxy reactive groups in compound (2) can be the epoxy reactive group (g2), the remaining epoxy reactive group (if present) can be epoxy reactive group (g1).

[0083] In an embodiment, compound (2) contains 2, 3 or 4 epoxy reactive groups, wherein said 2, 3 or 4 epoxy reactive groups comprise at least one (for example 1, 2, 3 or 4) epoxy reactive group (g2) capable of forming the reversible borate moiety or derivative thereof with the epoxy group, and the remaining epoxy reactive group (if present) can be epoxy reactive group (g1).

[0084] In an embodiment, the epoxy reactive group (g2) capable of forming the reversible borate moiety or derivative thereof with the epoxy group in compound (2) is a -B(QH) ₂ group, wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur.

[0085] In an embodiment, compound (2) has the following structure (OP) _w -R ₃ -[B-(QH) ₂ ] _m (II) each Q is independently an element of the sixth main group, preferably oxygen or sulfur; eachR ₃ is independently a direct bond or an organic group having 1 to 30 carbon atoms, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the organic group can optionally be replaced with -(CO)-O- and/or CO; OP is an epoxy reactive group (g1); w is an integer of 0, 1, 2 or 3; and m is an integer of 1, 2, 3 or 4 and if w is 0, m is an integer of 2, 3 or 4.

[0086] In this disclosure, R ₃ has the definition given for R ₂ . In an embodiment, each R ₃ is independently a direct bond or an organic group having 1 to 20 carbon atoms, which can optionally be interrupted by one or more nonadj acent oxygen atoms, and/or one or more non adjacent carbon atoms in the organic group can optionally be replaced with -(CO)-O- and/or CO.

[0087] In an embodiment, the variables in the compound of Formula (II) have the following definitions: each Q is independently oxygen or sulfur, preferably oxygen; each R ₃ is independently a direct bond, divalent or trivalent C ₁ -C ₁₂ alkyl, divalent or trivalent C ₄ -C ₈ - cycloalkyl, divalent or trivalent C ₅ -C ₁₀ -cycloalkenyl, divalent or trivalent C ₆ -C ₁₀ aryl, divalent or trivalent C ₁ -C ₁₂ alkyl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent or trivalent C ₆ -C ₁₀ aryl-C ₁ -C ₁₂ alkylene-C ₆ -C ₁₀ aryl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkyl, divalent or trivalent C ₄ -C ₁₀ heterocycloalkenyl, divalent or trivalent C ₄ -C ₁₀ hetaryl, divalent or trivalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 heteroatoms selected from N, O, and S, wherein the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the divalent or trivalent C ₁ -C ₁₂ alkyl and the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO; and m is an integer of 2 or 3. [0088] definitions: each Q is independently oxygen or sulfur, preferably oxygen; each R ₃ is independently a direct bond, C ₁ -C ₆ alkylene, divalent C ₄ -C ₈ -cycloalkyl, divalent C ₅ -C ₁₀ - cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ - C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO; and OP is an epoxy reactive group (gl); w is an integer of 0 or 1 ; and m is an integer of 1 or 2 and if w is 0, m is an integer of 2.

[0089] In an embodiment, the variables in the compound of Formula (II) have the following definitions: each Q is independently oxygen or sulfur, preferably oxygen; each R ₃ is independently a direct bond, C ₄ -C ₁₂ alkylene, divalent C ₄ -C ₈ -cycloalkyl, divalent C5-C10- cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ - C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent C ₄ -C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₄ -C ₁₂ alkylene and the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₄ -C ₁₂ alkylene and the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO; and w is 0; and m is an integer of 2.

[0090] In an embodiment, each R ₃ is independently a C ₄ -C ₁₂ alkylene, divalent C ₄ -C ₈ - cycloalkyl, divalent C ₅ -C ₁₀ -cycloalkenyl, divalent C ₆ -C ₁₀ aryl, divalent C ₁ -C ₆ alkyl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₆ -C ₁₀ aryl, divalent C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkylene-C ₆ -C ₁₀ aryl, divalent C4- C ₁₀ heterocycloalkyl, divalent C ₄ -C ₁₀ heterocycloalkenyl, divalent C ₄ -C ₁₀ hetaryl or divalent C ₄ -C ₁₀ hetaryl-C ₄ -C ₁₀ hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C ₄ -C ₁₂ alkylene and the C ₁ -C ₆ alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C ₄ -C ₁₂ alkylene and the C ₁ -C ₆ alkylene can optionally be replaced with -(CO)-O- and/or CO. In an embodiment, each R ₃ is independently phenylene, phenylene-phenylene or divalent thiophene radical. [0091] In an embodiment, the compound (2) is selected from benzen-1,4-diboronic acid, 2,5-thiophenediboranic acid, 4,4-biphenyldiboronic acid, carboxyphenylboronic acid, aminobenzeneboronic acid, hydroxyphenylboronic acid, (Hydroxymethyl)phenylboronic acid, polyboric acid, tetrahydroxydiboron, and ((((oxybis(ethane-2,1- diyl))bis(oxy))bis(methylene))bis(4,1-phenylene))diboronic acid, preferably benzen-1,4- diboronic acid, 2,5-thiophenediboranic acid, 4,4-biphenyldiboronic acid, polyboric acid, and tetrahydroxydiboron.

[0092] In the polyolefin vitrimer of this disclosure, the amount of the moiety derived from at least one compound (1) and/or at least one compound (2) can be in the range from about 0.1 wt% to about 30 wt% (for example about 0.12 wt%, about 0.15 wt%, about 0.18 wt%, about 0.2 wt%, about 0.22 wt%, about 0.25 wt%, about 0.28 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.8 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 3 wt%, about

4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, or about 8 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, or about 30 wt%), or from about 0.12 wt% to about 25 wt%, or from about 0.12 wt% to about 20 wt%, or from about 0.12 wt% to about 15 wt%, or from about 0.12 wt% to about 10 wt%, or from about 0.12 wt% to about 8 wt%, or from about 0.12 wt% to about 6 wt%, or from about 0.15 wt% to about 8 wt%, or from about 0.15 wt% to about

5 wt%, based on the weight of the polyolefin vitrimer.

[0093] In this disclosure, the polyolefin vitrimer is formed from an epoxy-functionalized polyolefin and at least one compound (1) and/or at least one compound (2). As used herein, the term " epoxy-functionalized polyolefin " refers to a polyolefin carrying epoxy groups.

[0094] Polyolefin refers to a polymer made up of at least 50 wt% olefin-derived units, examples of which include ethylene and C _3-16 olefins, (for example C _3-12 olefins, C _3-8 olefins or C _3-6 olefins), preferably alpha-olefins, and combinations thereof. Examples of the olefin include ethylene, propylene, 1 -butene, isobutylene, 2-butene, cyclobutene, 1 -pentene,

1 -hexene, 4-methyl-1-pentene, 1 -octene, 3 -methyl-1-butene, 4-methyl-1-butene, cyclopentene, 1 -hexene, cyclohexene, 1 -octene, 1 -decene, 1 -dodecene, etc. These may be used singly or in combinations of two or more kinds thereof.

[0095] In an embodiment, the polyolefins are polyolefin elastomers. In an embodiment, the polyolefins are those that comprise at least 50 wt% of ethylene, or propylene, or butene- derived units.

[0096] The polyolefin may be a random copolymer (the comonomer-derived units are randomly distributed along the polymer backbone), a block copolymer (the comonomer- derived units occur along long sequences), or any variation thereof. The presence of randomness or triad tacticity in a copolymer can be determined by ¹³ C NMR as is known in the art and described in, for example, 18 J. Poly. Set.: Poly. Lett. Ed. pp. 389-394 (1980).

[0097] In an embodiment, the polyolefin is selected from polyethylene (PE) homopolymers, polyethylene random or block copolymers, polypropylene (PP) homopolymers, polypropylene random or block copolymers, ethylene/propylene copolymers, a mixture of polypropylene and polyethylene or a mixture of different types of polyethylene. In an embodiment, the polyolefin is polypropylene. Polyethylene can be linear low density (LLDPE), low density (LDPE), medium density (MDPE) or high density (HDPE). Mixtures mentioned above are for example PP/HDPE, PP/LDPE and LDPE/HDPE. Mixtures mentioned above are for example ternary mixtures such as PP/HDPE/LLDPE.

[0098] In an embodiment, the polyolefin is selected from the propylene-based polyolefin and the ethylene-based polyolefin.

[0099] In a preferred embodiment, the polyolefin of this disclosure is a propylene-based polyolefin comprising at least about 60 wt% propylene-derived units, based on total weight of the propylene-based polyolefin.

[0100] In an embodiment, the propylene-based polyolefin may be a polypropylene homopolymer, polypropylene copolymer, such as a polypropylene random copolymer, alternating or segmented copolymer or block copolymer containing one or more comonomers selected from the group consisting of ethylene, C ₄ -C ₃₀ α-olefins, vinylcyclohexane, vinylcyclohexene, C ₄ -C ₂₀ alkandienes, C ₅ -C ₁₂ cycloalkandienes and norbomene derivatives.

[0101] Polypropylene copolymer also covers long chain branched polypropylene copolymer.

[0102] Examples of suitable C ₄ -C ₃₀ α-olefins are 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, 1 -nonene, 1 -decene, 1 -undecene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1- octadecene, 1-eicosene, 4-methyl-1-pentene, 1-eicosene, 1-docosene, 1 -tetracosene, 1- hexacosene, 1 -octacosene and 1-triacontene.

[0103] Examples of suitable C ₄ -C ₂₀ alkandienes are hexadiene and octadiene.

[0104] Examples of suitable C ₅ -C ₁₂ cycloalkandienes are cyclopentadiene, cyclohexadiene and cyclooctadiene.

[0105] Examples of suitable norbomene derivatives are 5-ethylidene-2-norbomene (ENB), dicyclopentadiene (DCP) and methylene-domethylene-hexahydronaphthaline (MEN). [0106] A propylene/ethylene copolymer contains for example 50% to 99.9%, preferably 80% to 99.9%, in particular 90% to 99.9%, by weight of propylene.

[0107] A propylene copolymer wherein the comonomer is a C ₉ -C ₂₀ olefin such as e.g. 1 -nonene, 1 -decene, 1 -undecene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene or 1-eicosene; C ₉ -C ₂₀ alkandiene, C ₉ -C ₁₂ cycloalkandiene or a norbomene derivative such as e.g. 5-ethylidene-2-norbomene (ENB) or methylene-domethylene-hexahydronaphthaline (MEN) contains preferably at least 90 mol%, in particular 90 mol% to 99.9 mol% or 90 mol% to 99 mol%, of propylene.

[0108] A propylene copolymer wherein the comonomer is a C ₄ -C ₈ α-olefin such as e.g. 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene or 4-methyl-1-pentene; vinylcyclohexane, vinylcyclohexene, C ₄ -C ₈ alkandiene or C ₅ -C ₈ cycloalkandiene contains preferably at least 80 mol%, in particular 80 mol% to 99.9 mol% or 80 mol% to 99 mol%, of propylene.

[0109] Further examples of polypropylene are propylene/isobutylene copolymer, propylene/butadiene copolymer, propylene/cycloolefin copolymer, terpolymers of propylene with ethylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbomene; propylene/1 -olefin copolymers where the 1 -olefin is generated in situ; and propylene/carbon monoxide copolymers.

[0110] In an embodiment, Exemplary polyolefin useful in this invention may include ethylene-based polyolefin. Useful ethylene-based polyolefin may have one or more of the following properties: (1) an ethylene content of about 60 wt% to about 100 wt%, or about 65 wt% to about 90 wt%, or about 65 wt% to about 85 wt%, or about 65 wt% to about 80 wt%, or about 65 wt% to about 75 wt%; (2) an ethylene content of about 80 mol% to about 96 mol%, or about 82 mol% to about 92 mol%, or about 82 mol% to about 88 mol%, or about 84 mol% to about 86 mol%; (3) a propylene content of about 10 wt% to about 20 wt%; (4) a 1 -butene content of about 15 wt% or more, preferably about 20 wt% or more, preferably about 25 wt% or more; (5) a 1 -hexene content of about 20 wt% or more, preferably about 25 wt% or more, preferably about 30 wt% or more; (6) a 1 -octene content of about 25 wt% or more, preferably about 30 wt% or more, preferably about 35 wt% or more; (7) a density of about 0.9 g/cm ³ or less, preferably 0.89 g/cm ³ or less, preferably 0.88 g/cm ³ or less, preferably 0.87 g/cm ³ or less, preferably 0.86 g/cm ³ or less, preferably 0.83 g/cm ³ or more, preferably 0.84 g/cm ³ or more, preferably 0.85 g/cm ³ or more, preferably 0.855 g/cm ³ or more, preferably about 0.83 g/cm ³ to about 0.9 g/cm ³ , preferably from about 0.85 g/cm ³ to about 0.89 g/cm ³ , preferably from about 0.85 g/cm ³ to about 0.88 g/cm ³ , or preferably from about 0.85 g/cm ³ to about 0.87 g/cm ³ ; (8) a heat of fusion (H _f ) of about 90 J/g or less, preferably about 70 J/g or less, preferably about 50 J/g or less, preferably about 30 J/g or less, preferably about 10 J/g to 70 J/g, preferably about 10 J/g to about 50 J/g, preferably about 10 J/g to about 30 J/g; (9) a crystallinity of about 40% or less, preferably about 30% or less, preferably about 20% or less, and at least about 5%, preferably about 5% to about 30%, preferably about 5% to about 20%; (10) a melting point (T _m , peak first melt) of about 100°C or less, preferably about 90°C or less, preferably about 80°C or less, preferably about 70°C or less, preferably about 60°C or less, preferably about 50°C or less; (1 1) a crystallization temperature (T _c , peak) of about 90°C or less, preferably about 80°C or less, preferably about 70°C or less, preferably about 60°C or less, preferably about 50°C or less, preferably about 40°C or less; (12) a glass transition temperature (T _g ) of about -20°C or less, preferably about -30°C or less, preferably about -40°C or less; (13) a M _w of about 30,000 g/mol to about 2,000,000 g/mol, preferably about 50,000 g/mol to about 1,000,000 g/mol, preferably about 90,000 g/mol to about 500,000 g/mol; (14) a M _w /M _n of about 1 to about 40, preferably about 1.4 to about 20, preferably about 1.6 to about 10, preferably about 1.8 to about 3.5, preferably about 1.8 to about 2.5; (15) a branching index (g') of about 0.9 or greater, preferably about 0.95 or greater, preferably about 0.99 or greater; and (16) a melt index (MI) of about 0.1 g/10min to about 100 g/10min, preferably about 0.3 g/10min to about 60 g/10min, preferably about 0.5 g/10min to about 40 g/10min, preferably about 0.7 g/10min to about 20 g/10min.

[0111] In certain preferred embodiments, the ethylene-based polyolefin comprises at least 30 wt% of one or more C ₄ -C ₂₀ olefin comonomers, for example, 1 -butene, 1 -hexene, and/or

1- octene. In some embodiments, the ethylene-based polyolefin can be a random copolymer, a statistical copolymer, a block copolymer, or blends thereof. The invention is not limited by any particular polymerization method for preparing the ethylene-based polyolefin. In certain preferred embodiments, the ethylene-based polyolefin is produced using a metallocene catalyst system.

[0112] For the epoxy-functionalized polyolefin, the epoxy group can be incorporated via an ethylenically unsaturated, epoxy functional monomer (3) into the polyolefin to form the “epoxy-functionalized polyolefin”. The ethylenically unsaturated, epoxy functional monomer (3) comprises both ethylenically unsaturated bond (for example carbon-carbon double bond) and epoxy group. In an embodiment, the ethylenically unsaturated, epoxy functional monomer (3) can comprise one ethylenically unsaturated double bond and one epoxy group. [0113] The ethylenically unsaturated, epoxy functional monomer (3) can be epoxy (meth)acrylate and/or epoxy allyl ether.

[0114] For example, the epoxy (meth)acrylate can include a compound of Formula (III) epoxy group (III) where R’ is H or CH ₃ and R is a divalent organic group having 1 to 20 carbon atoms, preferably hydrocarbyl having 1 to 20 carbon atoms, which can optionally be interrupted by one or more nonadj acent oxygen atoms, and/or one or more nonadj acent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO. In an embodiment, R is selected from C ₁ -C ₁₂ alkylene, or divalent C ₆ -C ₁₀ aromatic group, wherein the C ₁ -C ₁₂ alkylene can optionally be interrupted by one or more nonadj acent oxygen atoms, and/or one or more nonadjacent carbon atoms in the C ₁ -C ₁₂ alkylene can optionally be replaced with -(CO)-O- and/or CO. In an embodiment, R is selected from C ₁ -C ₆ alkylene (for example methylene or ethylene) and divalent C ₆ -C ₁₀ aromatic group (for example phenylene).

[0115] The epoxy group in the epoxy-functionalized polyolefin can be selected from ethylene oxide group and oxetane group, preferably ethylene oxide group.

[0116] In an embodiment, the ethylenically unsaturated, epoxy functional monomer (3) is selected from glycidyl (meth)acrylate and allyl glycidyl ether.

[0117] The epoxy-functionalized polyolefin can be prepared from the ethylenically unsaturated, epoxy functional monomer (3) and the monomers for preparing the polyolefin via the free radical initiated polymerization. The specific monomers for the preparing the polyolefin are as mentioned above.

[0118] In the epoxy-functionalized polyolefin, the molar amount of the epoxy group is in the range from about 0.5 mol% to about 30 mol% (such as about 0.5% mol%, about 0.8 mol%, about 1 mol%, about 1.2 mol%, about 1.5 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol% or about 8 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 30 mol%), or from about 0.8 mol% to about 20 mol%, or from about 0.8 mol% to about 10 mol%, or from about 0.8 mol% to about 8 mol%, or from about 0.8 mol% to about 5 mol%, or from about 1 mol% to about 3 mol%, based on the total molar amount of repeat unit of the epoxy-functionalized polyolefin. [0119] In an embodiment, the epoxy-functionalized polyolefin comprises a repeat unit carrying an epoxy group, preferably the molar amount of the repeat unit carrying the epoxy group is in the range from about 0.5 mol% to about 30 mol% (such as about 0.5 mol%, about 0.8 mol%, about 1 mol%, about 1.2 mol%, about 1.5 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol% or about 8 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 30 mol%), or from about 0.8 mol% to about 20 mol%, or from about 0.8 mol% to about 10 mol%, or from about 0.8 mol% to about 8 mol%, or from about 0.8 mol% to about 5 mol%, or from about 1 mol% to about 3 mol%, based on the total molar amount of the repeat units in the epoxy-functionalized polyolefin.

[0120] In the epoxy-functionalized polyolefin, the molar amount of the repeat unit derived from monomer (3) is in the range from about 0.5 mol% to about 30 mol% (such as about 0.5 mol%, about 0.8 mol%, about 1 mol%, about 1.2 mol%, about 1.5 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol% or about 8 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 30 mol%), or from about 0.8 mol% to about 20 mol%, or from about 0.8 mol% to about 10 mol%, or from about 0.8 mol% to about 8 mol%, or from about 0.8 mol% to about 5 mol%, or from about 1 mol% to about 3 mol%, based on the total molar amount of repeat unit of the epoxy-functionalized polyolefin.

[0121] The epoxy-functionalized polyolefin may have a weight average molecular weight (M _w ) of about 5,000 to about 5,000,000 g/mole, or about 10,000 to about 1,000,000 g/mole, or about 50,000 to about 400,000 g/mole.

[0122] The epoxy-functionalized propylene-based polyolefin may have a T _m of about 110°C or less, or about 105°C or less.

The polyolefin vitrimer

[0123] The polyolefin vitrimer of this disclosure has enhanced properties including high tensile strength, high use temperature, excellent creep resistant and excellent elasticity etc.

[0124] In an embodiment, the tensile strength of the polyolefin vitrimer of this disclosure is at least about 110%, or at least about 120% of the tensile strength of the neat polyolefin. In an embodiment, the tensile strength of the polyolefin vitrimer of this disclosure is about 110% to about 180%, or about 120% to about 160%, or about 120% to about 150% of the tensile strength of the neat polyolefin.

[0125] As used herein, neat polyolefin means the epoxy-functionalized polyolefin, i.e., it has not reacted with the at least one compound (1) and/or at least one compound (2). [0126] In an embodiment, the creep resistance at 80°C of the polyolefin vitrimer is at least about 5%, or at least about 8% better than the creep resistance of the neat polyolefin. In an embodiment, the creep resistance at 80°C of the polyolefin vitrimer is about 5% to about 15%, or about 8% to 12% better than the creep resistance of the neat polyolefin. The creep resistance can be determined by testing the strain (%) of the sample (15mmx4mmx2mm) by applying a constant axial force of 10N for a certain time (for example 1200s) for example on TA Instruments RSA-G2 SOLIDS ANALYZER.

[0127] In an embodiment, the hysteresis of the polyolefin vitrimer is at least about 5%, or at least about 8% better than the hysteresis of the neat polyolefin. The hysteresis curve of samples (ISO 37:2017 type 3 specimen) can be characterized for example by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm/min , wherein 10 cycles are carried out between a maximum tensile strain of 100.00% and a minimum force of 0.10N.

[0128] Unlike traditional crosslinked material, the polyolefin vitrimer of this disclosure could not only be remold and reprocess, but also the recycled material has comparable mechanical properties with virgin materials.

[0129] In an embodiment, the tensile strength of the polyolefin vitrimer after being reprocessed once is at least about 65% (for example about 68%, about 70%, about 75%, about 78%, or about 80%, or about 82%, or about 85%, or about 88%, or about 90%, or about 92%), or at least about 75%, preferably at least about 78% of the tensile strength of the polyolefin vitrimer before reprocessing. In an embodiment, the tensile strength of the polyolefin vitrimer after being reprocessed once is in the range from about 65% to about 95%, or from about 70% to about 92%, or from about 75% to about 90% of the tensile strength of the polyolefin vitrimer before reprocessing.

[0130] In an embodiment, the polyolefin vitrimer of this disclosure has a crystallinity of 32% to 38% (for example 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5% or 38%), or 33% to 37.5%, or 34% to 36.5%.

[0131] The polyolefin vitrimer of this disclosure has thermoplastic property, preferably is able to be processed by pressing, injection molding, extrusion molding, blow molding, calendering, foaming, solvent plasticizing, mold pressing, casting, reaction molding, for example by granulation and further hot press or extrusion. By "thermoplastic polymer(s)" is meant a polymer that can be melted by heat and then cooled without appreciable change in solid-state properties before and after heating. [0132] In an embodiment, the polyolefin vitrimer is reprocessed by physical recycle. For example, the polyolefin vitrimer can be pulverized and hot pressed for example at 150°C, 0.5 MPa for 5 minutes.

Process for preparing polyolefin vitrimer

[0133] A further aspect of this disclosure is directed to a process for preparing the polyolefin vitrimers of this disclosure, which comprises reacting the epoxy-functionalized polyolefin with at least one compound (1) and/or at least one compound (2).

[0134] In an embodiment, the amount of at least one compound (1 ) and/or at least one compound (2) is in the range from about 0.1 wt% to about 30 wt% (for example about 0.12 wt%, about 0.15 wt%, about 0.18 wt%, about 0.2 wt%, about 0.22 wt%, about 0.25 wt%, about 0.28 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.8 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, or about 8 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, or about 30 wt%), or from about 0.12 wt% to about 25 wt%, or from about 0.12 wt% to about 20 wt%, or from about 0.12 wt% to about 15 wt%, or from about 0.12 wt% to about 10 wt%, or from about 0.12 wt% to about 8 wt%, or from about 0.12 wt% to about 6 wt%, or from about 0.15 wt% to about 8 wt%, or from about 0.15 wt% to about 5 wt%, based on the weight of the polyolefin vitrimer.

[0135] With respect to the reaction of the epoxy-functionalized polyolefin with compound (1), the reaction can be carried out in the presence of a base. The base can include for example inorganic base and organic base. The organic base can include for example nitrogen-containing bases, such as cyclic nitrogen-containing bases, such as monocyclic nitrogen-containing bases or Bicylic nitrogen-containing bases.

[0136] The monocyclic nitrogen-containing bases, preferably pyridines or imidazoles.

[0137] Bicylic nitrogen-containing bases are selected from the groups comprising indoles, quinolines, isoquinolines, purines, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene, 1, 4-diazabicyclo[2.2.2]octane and 4-(N- pyrrolidinyl)pyridine.

[0138] In an embodiment, the organic base is selected from N-methylimidazole, 2-methylimidazole, 4-methylimidazole, pyridine, 3-methylpyridine, 2-methylpyridine, 4-methylpyridine, 4-dimethylaminopyridine, 4-(N-pyrrolidinyl)pyridine, 5-ethyl-2- methylpyridine and nicotine. [0139] With respect to the reaction of the epoxy-functionalized polyolefin with compound (2), the reaction can be carried out in the presence of water trapping agent, such as magnesium sulphate or molecular sieve for example, or by using a Dean-Stark apparatus which allows water formed during condensation to be removed by distillation. Preferably, the reaction is carried out at an elevated temperature, for example at from 105°C to 160°C, or at from 110°C to 150°C. The reaction is preferably carried out at inert atmosphere, for example at nitrogen atmosphere. The reaction time can be in the range from 3 hours to 30 hours, or 5 hours to 25 hours. The reaction can be carried out in the presence of sulfonic acid, for example toluenesulfonic acid.

[0140] Taking benzen-l,4-diboronic acid as an example of compound (2) and PE- GMA as an example of epoxy-functionalized polyolefin, the reaction between the epoxy- functionalized polyolefin and compound (2) can be carried out as follows:

Composition

[0141] A further aspect of this disclosure is directed to a composition comprising the polyolefin vitrimer of this disclosure and at least one additive. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates and hydrogenated rosins; UV stabilizers; heat stabilizers; antiblocking agents; release agents; anti static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; modifier; Blending and Processing of polyolefin vitrimer and composition

[0142] The polyolefin vitrimer and composition described herein may be processed or formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twinscrew extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process. Additionally, additives may be included in the polymer, blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired. Examples of additives are as described above.

[0143] The polyolefin vitrimer can be in any physical form. In an embodiment, reactor granules, defined as the granules of polymer that are isolated from the polymerization reactor prior to any processing procedures, are used. In another embodiment, the polymer is in the form of pellets that are formed from melt extrusion. The polymers can be in above mentioned physical form when used to blend with the additive.

[0144] The components can be blended by any suitable means, and are typically blended to yield an intimately mixed composition. For example, they may be blended in a static mixer, batch mixer, extruder, or a combination thereof, that is sufficient to achieve an adequate dispersion of additive in the polymer.

[0145] The mixing step may involve first dry blending using, for example, a tumble blender, where the polymer and additive are brought into contact first, without intimate mixing, which may then be followed by melt blending in an extruder. Another method of blending the components is to melt blend the polyolefin vitrimer pellets with the additive directly in an extruder or batch mixer. It may also involve a "master batch" approach, where the final additive concentration is achieved by combining neat polymer with an appropriate amount of additive that had been previously prepared at a higher additive concentration. The mixing step may take place as part of a processing method used to fabricate articles, such as in the extruder on an injection molding machine or blown-film line or fiber line.

[0146] In a preferred aspect of this disclosure, the polyolefin vitrimer and additive are "melt blended" in an apparatus such as an extruder (single or twin screw) or batch mixer. The polymer may also be "dry blended" with the additive using a tumbler, double-cone blender, ribbon blender, or other suitable blender. In yet another embodiment, the polymer and additive are blended by a combination of approaches, for example a tumbler followed by an extruder. A preferred method of blending is to include the final stage of blending as part of an article fabrication step, such as in the extruder used to melt and convey the composition for a molding step like injection molding or blow molding. This could include direct injection of the additive into the extruder, either before or after the polymer is fully melted. Extrusion technology for polymer can reference, for example, PLASTICS EXTRUSION TECHNOLOGY 26-37 (Friedhelm Hensen, ed. Hanser Publishers 1988).

[0147] In another aspect of this disclosure, the composition may be blended in solution by any suitable means, by using a solvent that dissolves components to a significant extent. The blending may occur at any temperature or pressure where the additive and the polyolefin vitrimer remain in solution. As with the solution process the additive is added directly to the finishing train, rather than added to the dry polymer in another blending step altogether.

[0148] Thus, in the cases of fabrication of articles using methods that involve an extruder, such as injection molding or blow molding, any means of combining the polyolefin vitrimer and additive to achieve the desired composition serve equally well as fully formulated pre- blended pellets, since the forming process includes a re-melting and mixing of the raw material; example combinations include simple blends of neat polymer pellets and additive, of neat polymer granules and additive, of neat polymer pellets and pre-blended pellets, and neat polymer granules and pre-blended pellets. Here, "pre-blended pellets" means pellets of a composition comprising polyolefin vitrimer and additive at some concentration. In the process of compression molding, however, little mixing of the melt components occurs, and pre-blended pellets would be preferred over simple blends of the constituent pellets (or granules) and additive. Those skilled in the art will be able to determine the appropriate procedure for blending of the polymers to balance the need for intimate mixing of the component ingredients with the desire for process economy.

Article

[0149] A further aspect of the present invention is directed to an article comprising the polyolefin vitrimers or the composition of this disclosure.

[0150] The article can be an extruded article, molded article, hose, sheet, film, jacket or foam. For example, the article includes, but are not limited to, an extruded article, such as an auto weather-seal, a non-auto weather-seal, a building profile, etc.; a molded article, such as a seal, a gasket, etc.; a hose, such as air hose, heat hose, garden hose, industry hose, etc.; a sheet, such as a roof sheet; a film; a jacket, such as a cable jacket, or a foam. Examples [0151] Materials: Lotader AX8840 (PE-GMA) : poly(ethylene-co-glycidyl methacrylate), Tm=106°C, Mw=l 05000 g/mol, the content of glycidyl methacrylate = 1.68 mol% (8 wt%), melt index =5 g/10min at 190°C/2.16 kg according to ISO 1133/ASTM D 1238. GMA: glycidyl methacrylate.

Example 1- Synthesis of HS-Boronic ester-SH crosslinkers

[0152] The HS-Boronic ester-SH crosslinkers were synthesized according to scheme 1 :

[0153] Synthesis of 1 ,4-phenylenebis(1,3,2-dioxaborolane-2,4-diyl)dimethanethiol (crosslinker 1): 6 g 1,4-phenylenediboronic acid (36.2 mmol), and 7.83 g (6.3 ml) 1- thioglycerol (72.4 mmol) were weighted. Two components were dissolved in tetrahydrofuran (160 ml) and water (0.1 ml), with adding magnesium sulfate (10 g) in round bottom flask. After stirring at room temperature for 24 hours, the mixture was filtered and concentrated. Thereafter, the resulted white solid was purified by repeatedly filtering and washing with abundant heptane, concentrating and vacuum to remove residual of solvent to obtain the title compound as white solid (10.5 g). Experimental phenomenon: The resulted compound could be dissolved in THE, and the mixture was clear color after stirring. Chemical Shift δ assignment: 7.85 (s, 4H); 4.75 (m, 2H); 4.50 (dd, J = 9Hz, 8Hz, 2H); 4.18 (dd, J = 9Hz, 7Hz, 2H); 2.82 (dd, J = 9Hz, 6Hz, 4H); 1.51 (t, J = 9Hz, 2H).

[0154] Synthesis ooff (thiophene-2, 5-diylbis(1,3,2-dioxaborolane-2, 4- diyl)dimethanethiol (crosslinker 2): 6.2 g 2,5-Thiophenediboronic acid (36.2 mmol), and 7.83 g (6.3 ml) 1 -thioglycerol (72.4 mmol) were weighted. Two components were dissolved in tetrahydrofuran (160 ml) and water (0.1 ml), with adding magnesium sulfate (10 g) in round bottom flask. After stirring at room temperature for 24 hours, the mixture was filtered and concentrated. Thereafter, the resulted yellow oil was purified by repeatedly washing with abundant heptane, and vacuum drying to remove residual of solvent to obtain the title compound as yellow oil. Experimental phenomenon: the resulted compound could be dissolved in THF, and the mixture was clear light yellow color after stirring.

[0155] Synthesis of [1,1’-biphenyl-4,4’-diylbis(1,3,2-dioxaborolane-2,4- diyl)]dimethanethiol (crosslinker 3): 8.75 g 4,4-bisphenyldiboronic acid (36.2 mmol), and 7.83 g (6.3 ml) 1 -thioglycerol (72.4 mmol) were weighted. Two components were dissolved in tetrahydrofuran (160 ml) and water (0.1 ml), with adding magnesium sulfate (10 g) in round bottom flask. After stirring at room temperature for 24 hours, the mixture was filtered and concentrated. Thereafter, the resulted white solid was purified by repeatedly washing with abundant heptane, and vacuum drying to remove residual of solvent to obtain the title compound as white solid. Experimental phenomenon: The resulted compound was hardly dissolved in THF, and the mixture was turbid white liquid after stirring.

Example 2- Polyolefin vitrimers prepared by 1,4-phenylenediboronic acid

[0156] Poly(Ethylene-co-glycidyl methacrylate) (PE-GMA), 1,4-Phenylenediboronic acid and 1000 ppm phenolic antioxidant (AO 1010) were dry blended in amount as shown in table 1 below and then blended in TSE11 at 140°C. Detailed formulation was fisted in the below

Table 1.

Table 1

FTIR

[0157] PE-GMA-B linker (50%) sample was prepared by mixing 10 g PE-GMA with 0.46 g 1,4-Phenylenediboronic acid directly, and hot pressed at 100°C to a thin film under pressure of 1 MPa for 5 seconds. The FTIR was conducted via Thermo Scientific™ Nicolet™ Continupm ™ Infrared Microscope, the spectrum was collected under transmission mode with hot stage under 160°C after a certain period (1.25 min, 5 min, 10 min, 15 min, 30 min, 40 min, 50 min). Then the spectrum was normalized by peak at 720 cm ^-1 (assigned to long CH ₂ chain), which kept constant regardless of the reaction. As the reaction proceeds, the peak at 657 cm ^-1 and 1313 cm ^-1 (assigned to the B-O bond) increased, the peak at 848 cm ^-1 , 912 cm ^-1 (assigned to epoxide) decreased, the peak at 1007 cm ^-1 (assigns to the B- OH) also decreased. The results provided the semi-quantitative proof of the crosslinking reaction.

DMA test

[0158] Dynamical mechanical analysis (DMA) was used to analysis the rheology behavior of the polymer to indicate the processability. Storage modulus (G’), loss modulus (G’ ’) and complex viscosity were measured using an ARES-G2 rheometer (TA Instruments) with 8 mm parallel plates geometry, performed in temperature ramp of 225°C to 25°C with cooling rate 10°C/min, strain amplitude controlled in linear region, and frequency at 1 Hz.

[0159] The curves of storage/loss modulus (G7G’ ’) vs T and complex viscosity vs T were shown in Figure 1. From DMA curve, it could be seen for the PE-GMA, after the PE crystals melt, the modulus and viscosity of the material dropped a lot and it quickly went into visco- elastic region, the cross-over temperature was around 118°C. Thus, at a temperature above 118°C, the material would flow and lose its shape. However, for PE-GMA-B linker (2.5%) sample, even under such low crosslinking density, after the crystals melt, the material went into the rubbery stage, the viscosity dropped much slowly and value of storage modulus was continually above the value of loss modulus, meaning the material didn’t have macro-flow and could maintain its shape even at higher temperature.

Creep-recovery test

[0160] Creep-recovery test on PE-GMA and PE-GMA-B linker (2.5%) samples (20mm× 5mm×lmm) were conducted at 60°C and 80°C on TA Instruments RSA-G2 SOLIDS ANALYZER by applying a constant axial force of 1 ON. And the force is removed after 1200s to record the strain recovery. As shown in Figure 2, the network still showed a better elasticity compare to un-crosslinked PE-GMA, especially at higher temperature. Strain of PE-GMA and PE-GMA-B linker (2.5%) under different temperature at 1200s and 3500s in creep recovery test was shown in table 2. Table 2: Strain of PE-GMA and PE-GMA-B linker (2.5%) under different temperature at 1200s and 3500s in creep recovery test

In creep-recovery test, when a constant force of ION was applied to PE-GMA-B linker (2.5%) and PE-GMA for 1200s at 60°C or 80°C, PE-GMA-B linker (2.5%) exhibited an initial elastic response then a low plastic deformation while PE-GMA crept rapidly and give a much higher strain especially at high T (59.9 vs 91.1 at 80°C), which reveals PE-GMA-B linker (2.5%) samples perform a better creep resistance (12% less strain at 60°C and 34% less at 80°C) than PE-GMA. In the recovery stage, PE-GMA-B linker (2.5%) samples recovered the deformation much better than PE-GMA samples.

Reprocess

[0161] The PE-GMA-B linker (2.5%) sample was compression molded into a thick film at 180°C, 0.5 MPa for 10 minutes, the thick film was then cut into small pieces and remolded under same conditions. The material was able to remold into the thick film sample again as shown in figure 3.

[0162] In order to have more quantitative analysis, mechanical property test was conducted on the raw resin (PE-GMA), fresh cured sample (PE-GMA-B linker (2.5%)) and remold sample (Recycled sample). The material was molded by hot press at 180°C, 0.5 MPa for 10 minutes to obtain the testing bar (ISO 37:2017 type 3 specimen). The stress-strain curve of samples was characterized by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 5 mm/min. Detailed properties were shown in blow Table 3. For the recycled sample, the tensile strength retain rate was about 85%.

Table 3. Mechanical property comparison Hysteresis test

[0163] The hysteresis curve of samples (ISO 37:2017 type 3 specimen) was characterized by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm/min . 10 cycles were carried out between a maximum tensile strain of 100.00% and a minimum force of 0.1 ON. Figure 4 showed the hysteresis comparison for PE-GMA and PE-GMA-B linker (2.5%), wherein PE-GMA-B linker (2.5%) showed 10% better elasticity comparing with the PE-GMA. Residual Strain of PE-GMA and PE-GMA-B linker (2.5%) in hysteresis comparison was shown in Table 4.

Table 4. Residual Strain of PE-GMA and PE-GMA-B linker (2.5%) in hysteresis comparison

[0164] The resilience of the material was characterized by hysteresis test. The residual the strain of PE-GMA-B linker (2.5%) decrease by 8.64%-12.05% compared with PE-GMA’s during 10 cycles.

Example 3- Polyolefin vitrimers prepared by crosslinker 1

[0165] PE-GMA, crosslinker 1 and the catalyst (4-Dimethylaminopyridine, DMAP) were directly mixed in Brabender mixer 350E at 180°C for 15-30 minutes, until the torque reached to the constant value. Formulation details and related mechanical properties were shown in the below Table 5. The polyolefin vitrimer was synthesized according to the following scheme 2.

Table 5. Formulation and tensile properties

[0166] The mechanical property of the control sample without SHB linker nor catalyst are even worse compared under neat PE-GMA after Brabender mixing, which might due to the thermal degradation during the process.

[0167] In contrast, the tensile strength of crosslinked sample increased with the increase of the SHB linker amount, attributing to the success formation of the robust crosslink network.

OTHER EMBODIMENTS

[0168] It is to be understood that while the present application has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the present application, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.