WO2024044481A1

WO2024044481A1 - Polyolefin elastomer vitrimer prepared with multi-functional boron-ester crosslinkers

Info

Publication number: WO2024044481A1
Application number: PCT/US2023/072183
Authority: WO
Inventors: Carlos R. LOPEZ-BARRON; Jiemin Lu; Jason A. MANN; Yaxian WANG; Ke R. CHEN; Wenxi GAO; Saifudin M. ABUBAKAR
Original assignee: Exxonmobil Chemical Patents Inc.
Priority date: 2022-08-23
Filing date: 2023-08-15
Publication date: 2024-02-29

Abstract

This disclosure relates generally to polyolefin elastomer vitrimer prepared with multi-functional boron-ester crosslinkers, to a process for preparing the polyolefin elastomer vitrimer and to a process for preparing the multi-functional boron-ester crosslinkers.

Description

Polyolefin Elastomer Vitrimer Prepared with Multi-Functional Boron-Ester Crosslinkers

INVENTORS: Carlos R. Lopez-Barron, Jiemin Lu, Jason A. Mann, Yaxian Wang, Ke R. Chen,

Wenxi Gao, Saifudin Abubakar

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to US Provisional Application No. 63/373,265 filed August 23, 2022, the disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

[0002] This disclosure relates generally to a polyolefin elastomer vitrimer prepared with multifunctional boron-ester crosslinkers, to a process for preparing the polyolefin elastomer vitrimer and to a process for preparing the multi-functional boron-ester crosslinkers.

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 “dissociate” from a given location and “re-associate” in a different location 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 (i.e., as melts). Therefore, vitnmers represent a very attractive class of polymers that breaks the paradigm of non-recy cl ability of thermosets and vulcanized rubbers.

[0004] Therefore, the development of the polyolefin elastomer vitrimer 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 elastomer vitrimer, which is formed from the polyolefin elastomer and at least one compound (1) containing at least one reversible borate moiety or derivative thereof and at least two free-radically polymerizable groups, wherein there is a reversible borate moiety or derivative thereof between any two free-radically polymerizable groups in compound (1), and wherein the denvative 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 elastomer vitrimers of this disclosure, which comprises reacting the polyolefin elastomer with at least one compound (1) in the presence of a free-radical polymerization initiator. [0007] In a third general aspect, this disclosure provides a process for preparing compound (1).

[0008] In a fourth general aspect, this disclosure provides a composition comprising the polyolefin elastomer vitrimers of this disclosure and at least one additive.

[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):

wherein each Q is independently an element of the sixth main group, or oxygen or sulfur.

[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, or oxygen or sulfur.

[0013] In some aspects, wherein compound (1) contains 1 to 3 reversible borate moieties or derivative thereof and 2 to 4 free-radically polymerizable groups.

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

wherein each Ri 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;

FP is a free-radically polymerizable group; each A is independently a ring having 5 to 10 ring members; each Q is independently an element of the sixth main group; and n is 2, 3 or 4.

[0015] In some aspects, each Ri 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 R2 is independently a direct bond or a linear or branched 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 hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; C4-Cs-cycloalkyl, Cs-Cio-cycloalkenyl, Ce-Cio aryl, Ce-Cio aryl-Ce-Cio aryl, C4-C10 heterocycloalkyl, C4-C10 heterocycloalkenyl, C4-C10 hetaryl or C4-C10 hetaryl-C4-Cio hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 heteroatoms selected from N, O, and S; and wherein the valence of R2 corresponds to the value of n; FP is a free- radically polymerizable group; 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 Ri is C2-C12 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 C2-C12 alkylene can optionally be replaced with -(CO)-O- and/or CO; and each R2 is independently a direct bond, divalent or trivalent C1-C12 alkyl, divalent or trivalent C4-Cs-cycloalkyl, divalent or trivalent Cs-Cio-cycloalkenyl, divalent or trivalent Ce-Cio aryl, divalent or trivalent Ce-Cio aryl-Ce-Cio aryl, divalent or trivalent C4-C10 heterocycloalkyl, divalent or trivalent C4-C10 heterocycloalkenyl, divalent or trivalent C4-C10 hetaryl, divalent or trivalent C4-C10 hetaryl-C4-Cw hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 heteroatoms selected from N, O, and S, wherein the divalent or trivalent C1-C12 alkyl 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 Ci- C12 alkyl can optionally be replaced with -(CO)-O- and/or CO.

[0017] In some aspects, each Ri is independently a R11-O-R12, wherein Rn is 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; and R12 is 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.

[0018] In some aspects, R12 is -C(O)-RB, wherein R13 is a direct bond or a divalent hydrocarbyl having 1 to 11 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.

[0019] In some aspects, the free-radically polymerizable group is selected from allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamido, methacrylamido or acety lenyl.

[0020] In some aspects, the elastic modulus of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of 10'²⁹ rad/s is at least 1.5, or at least 2 orders of magnitude larger than that of the neat polyolefin elastomer.

[0021] In some aspects, the viscosity of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of IO"²⁹ rad/s is at least 1, or at least 1.5 orders of magnitude larger than that of the neat polyolefin elastomer.

[0022] In some aspects, the polyolefin elastomer vitrimer shows improved shear-thinning behavior comparing with the neat polyolefin elastomer.

[0023] In some aspects, the polyolefin elastomer vitrimer displays extensional strain hardening.

[0024] The polyolefin elastomer vitrimer of this disclosure shows improved melt strength, improved shear-thinning behavior, extensional strain hardening, has thermoplastic property and can be recycled and reprocessed and still possesses good mechanical properties after being reprocessed multiple times.

[0025] These and other features and attributes of the disclosed polyolefin elastomer 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

[0026] Figure 1 shows the results of cure kinetics test for neat Vistamaxx (VMX 6100) and vitrimers. [0027] Figure 2 shows DSC thermograms of VMX 6100 and the vitrimer VMX-V5.

[0028] Figure 3 shows Dynamic thennal -mechanical analysis (DMTA) result of the neat polymer

(VMX 6100) and the vitrimer VMX-V5.

[0029] Figure 4 shows the DFS result of the sample after remolding.

[0030] Figure 5 shows the comparison of the extensional viscosity of the neat polymer (VMX 6100) and the vitrimer VMX-V5.

DETAILED DESCRIPTION OF THE INVENTION

[0031] 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.

[0032] 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.

[0033] In a first general aspect, this disclosure provides a polyolefin elastomer vitrimer, which is formed from the polyolefin elastomer and at least one compound (1) containing at least one reversible borate moiety or derivative thereof and at least two free-radically polymerizable groups, wherein there is a reversible borate moiety or derivative thereof between any two free- radically polymerizable groups in compound (1), and 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.

[0034] 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.

[0035] 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.

[0036] In an embodiment, the derivative of borate moiety represents a moiety with the oxygen in the borate moiety being replaced with S.

[0037] According to this disclosure, there is no substituent on Q. [0038] In one embodiment, the reversible borate moietv or derivative thereof has a structure of

Formula (I):

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

[0039] In one 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.

[0040] In one embodiment, the boron-containing nng 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.

[0041] 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.

[0042] Examples of the heterocyclic rings as ring (A) include one of following:

[0043] Examples of aromatic ring as ring (A) comprise phenyl ring or naphthalene ring.

[0044] In one 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.

[0045] In one 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) free-radically polymerizable groups. In one embodiment, compound (1) contains 1 to 3 (for example 1, 2 or 3) reversible borate moieties or derivative thereof and 2 free-radically polymerizable groups. In one embodiment, compound (1) contains 1 to 3 (for example 1, 2 or 3) reversible borate moieties or derivative thereof and 3 free- radically polymerizable groups. In one embodiment, compound (1) contains 1 or 2 reversible borate moieties or derivative thereof and 2 free-radically polymerizable groups. In one embodiment, compound (1) contains 2 reversible borate moieties or derivative thereof and 2 free-radically polymerizable groups. In one embodiment, compound (1) contains 2 reversible borate moieties and 2 free-radically polymerizable groups.

[0046] In one embodiment, compound (1) is selected from at least one compound having following structure:

wherein each Ri is independently a direct bond or a divalent organic group having 1 to 20 carbon atoms; each R2 is independently a direct bond or an organic group having 1 to 20 carbon atoms; FP is a free-radically polymerizable group; 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.

[0047] In an embodiment, each Ri is independently a divalent Ci to C20 hydrocarbyl, which can optionally be interrupted by one or more nonadj acent 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.

[0048] In an embodiment, each R2 is independently a Ci to C20 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 divalent 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 from N, O, and S.

[0049] A person skilled in the art could understand that, the valence of R2 corresponds to the value of n, for example if n is 2, valence of R2 is 2; if n is 3, valence of R2 is 3 and if n is 4, valence of R2 is 4.

[0050] 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 Ci to C20 radicals (for example, Ci, C2, C3, C4, Cs, Cg, Cs, C10, C12, Ci6, Cis, or C20), or Ci to C12 radicals, Ci to Cg radicals, C2 to C12 radicals, C3 to C12 radicals, C4 to C12 radicals, or Cs to C20 radicals, Cg to C20 radicals, or C7 to C20 radicals or Cs to C10 radicals or Cg to C10 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.

[0051] In an embodiment, each Ri is independently a direct bond or a divalent hydrocarbyl having 2 to 12 carbon atoms, which can optionally be interrupted by one or more nonadj acent oxygen atoms, and/or one or more nonadjacent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO. In an embodiment, each Ri is C2-C12 alkylene, which can optionally be interrupted by one or more nonadjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C2-C12 alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0052] In an embodiment, each Ri is independently a R11-O-R12, wherein Rn is 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; and R12 is 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.

[0053] In an embodiment, R12 is -C(O)-RB, wherein RB is a direct bond or a divalent hydrocarbyl having 1 to 11 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 R2 is independently a direct bond, a liner or branched

C1-C20 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.

[0055] In an embodiment, each R2 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), 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; C4-Cg-cycloalkyl, C5-C10- cycloalkenyl, Ce-Cio aryl, Ce-Cio aryl-Ce-Cio aryl, C4-C10 heterocycloalkyl, C4-C10 heterocycloalkenyl, C4-C10 hetaryl, C4-C10 hetaryl-C4-Cio hetaryl, 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 R2 corresponds to the value of n.

[0056] In an embodiment, each R2 is independently a direct bond, divalent or trivalent

C1-C12 alkyl, , divalent or trivalent Cr-Cs-cycloalkyl, divalent or trivalent Cs-Cio-cycloalkenyl, divalent or trivalent Ce-Cio aryl, divalent or trivalent Ce-Cio aryl-Ce-Cio aryl, divalent or trivalent C4- C10 heterocycloalkyl, divalent or trivalent C4-C10 heterocycloalkenyl, divalent or trivalent C4-C10 hetaryl, divalent or trivalent C4-C10 hetaryl-C4-Cio 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 C1-C12 alkyl 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 Ci- C12 alkyl can optionally be replaced with -(CO)-O- and/or CO.

[0057] In an embodiment, each R2 is independently a direct bond, divalent or trivalent

Ci-Ce alkyl, or divalent or trivalent Cr-Cs-cycloalkyl, divalent or trivalent Cs-Cio-cycloalkenyl, divalent or trivalent Ce-Cio aryl, divalent or trivalent Ce-Cio aryl-Ce-Cio aryl, divalent or trivalent C4- Cio heterocycloalkyl, divalent or trivalent C4-C10 heterocycloalkenyl, divalent or trivalent C4-C10 hetaryl, divalent or trivalent C4-C10 hetaryl-C4-Cio 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 Cr-Ce alkyl 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 Ci-Ce alkyl can optionally be replaced with -(CO)-O- and/or CO.

[0058] In an embodiment, each R2 is independently a direct bond, divalent or trivalent

C4-C12 alkyl, or divalent or trivalent C4-Cs-cycloalkyl, divalent or trivalent Cs-Cio-cycloalkenyl, divalent or trivalent Cg-Cio aryl, divalent or trivalent Cg-Cio aryl-Cg-Cio aryl, divalent or trivalent C4- C10 heterocycloalkyl, divalent or trivalent C4-C10 heterocycloalkenyl, divalent or trivalent C4-C10 hetaryl, divalent or trivalent C4-C10 hetaryl-C4-Cio 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 C4-C12 alkyl 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 C4- C12 alkyl can optionally be replaced with -(CO)-O- and/or CO.

[0059] In an embodiment, each R2 is independently a direct bond, C1-C12 alkylene (i.e., divalent C1-C12 alkyl), or divalentC -Cs-cycloalkyl, divalent Cs-Cio-cycloalkenyl, divalent

-Cio aryl, divalent Cg-Cio aryl-Cg-Cio aryl, divalent C4-C10 heterocycloalkyl, divalent C4-C10 heterocycloalkenyl, divalent C4-C10 hetaryl, divalent C4-C10 hetaryl-Cr-C 10 hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetary l contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C1-C12 alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C1-C12 alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0060] In an embodiment, each R2 is independently a direct bond, C4-C12 alkylene (i.e., divalent C4-C12 alkyl), or divalent C4-Cs-cycloalkyl, divalent Cs-Cio-cycloalkenyl, divalent

Cs-Cio aryl, divalent Cg-Cio aryl-Cg-Cio aryl, divalent C4-C10 heterocycloalkyl, divalent C4-C10 heterocycloalkenyl, divalent C4-C10 hetaryl, divalent C4-C10 hetaryl-C4-Cio hetaryl. wherein the heterocycloalkyl, heterocycloalkenyl and hetary l contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C4-C12 alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C4-C12 alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0061] In an embodiment, each R2 is independently a direct bond, Ci-Ce alkylene (i.e., divalent Ci-Cg alkyl), or divalent Cr-Cs-cycloalkyl, divalent Cs-Cio-cycloalkenyl, divalent

Cs-Cio aryl, divalent Cg-Cio aryl-Cg-Cio aryl, divalent C4-C10 heterocycloalkyl, divalent C4-C10 heterocycloalkenyl, divalent C4-C10 hetaryl or divalent C4-C10 hetaryl-C4-Cio hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetary l contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the Ci-Ce alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the Ci-Cg alkylene can optionally be replaced with -(CO)-O- and/or CO.

[0062] In an embodiment, each R2 is independently a divalent C4-Cs-cycloalkyl, divalent C5-C10- cycloalkenyl, divalent Cg-Cio aryl, divalent Cg-Cw aryl-Cg-Cio aryl, divalent C4-C10 heterocycloalkyl, divalent C4-C 10 heterocycloalkenyl, divalent C4-C 10 hetaryl or divalent

C4-C10 hetaryl-C4-Cio hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, preferably divalent Cr,-C 10 aryl, divalent Cg-Cio aryl-Cg-Cio aiyl, divalent C4-C10 hetaiyl or divalent C4-C10 hetaryl-C4-Cio hetaryl, wherein the hetaryl contains 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S.

[0063] In an embodiment, each R2 is independently a phenylene, phenylene-phenylene, or divalent thiophene radical.

[0064] A is as defined above. In an embodiment, each A is independently a ring having 5 or 6 ring members.

[0065] In an embodiment, n is 2 or 3, for example 2, for example 3.

[0066] In an embodiment, Q is S or O, preferably O.

[0067] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F), (G) and (H) have the following meanings: each Ri 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 R2 is independently a direct bond or a linear or branched 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 hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; C4-Cs-cycloalkyl, Cs-Cio-cycloalkenyl, Cg-Cio aryl, Cg-Cio aryl-Cg-Cio aryl, C4-C10 heterocycloalkyl, C4-C10 heterocycloalkenyl, C4-C10 hetaryl or C4-C10 hetaryl-C4-Cio hetaryl, 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 R2 corresponds to the value of n; FP is a free-radically polymerizable group; each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2 or 3.

[0068] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F), (G) and (H) have the following meanings: each Ri is C2-C12 alky lene, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C2-C12 alkylene can optionally be replaced with -(CO)-O- and/or CO; each R2 is independently a direct bond, divalent or trivalent C1-C12 alkyl, divalent or trivalent C4-Cs-cycloalkyl, divalent or trivalent C5-C10- cycloalkenyl, divalent or trivalent Cs-Cio aryl, divalent or trivalent Cs-Cw ar l-Ce-Cio aryl, divalent or trivalent C4-C10 heterocycloalkyl, divalent or trivalent C4-C10 heterocycloalkenyl, divalent or trivalent C4-C10 hetaryl, or divalent or trivalent C4-C10 hetaryl-C4-Cio hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected fromN, O, and S, wherein the divalent or trivalent C1-C12 alkyl 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 C1-C12 alkyl can optionally be replaced with -(CO)-O- and/or CO; FP is a free- radically polymerizable group; each A is independently a ring having 5 or 6 ring members; each Q is oxygen, and n is 2 or 3.

[0069] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F), (G) and (H) have the following meanings: each Ri is C2-C12 alky lene, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C2-C12 alkydene can optionally be replaced with -(CO)-O- and/or CO; each R2 is independently a direct bond, Ci-Ce alkylene, divalent C4-Cs-cycloalkyl, divalent Cs-Cio-cycloalkenyl, divalent Ce-Cw aryl, divalent Ce-Cio aryl-Cs-Cio aryl, divalent C4-C10 heterocycloalkyl, divalent C4-C10 heterocycloalkenyl, divalent C4-C 10 hetaryl or divalent

C4-C10 hetaryl-C4-Cio 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 Ci-Ce alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the Ci-Ce alkylene can optionally be replaced with

-(CO)-O- and/or CO; each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2.

[0070] In an embodiment, the variables in the above formulae (A), (B), (C), (D), (E), (F), (G) and (H) have the following meanings: each Ri is C2-C12 alky lene, which can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C2-C12 alkyd ene can optionally be replaced with -(CO)-O- and/or CO; each R2 is independently a C4-C12 alkyd ene, divalent C4-C8-cycloalkyl, divalent Cs-Cw-cycloalkenyl, divalent Ce-Cio aryl, divalent Ce- Cw aryl-Ce-Cio aryl, divalent C4-C10 heterocycloalkyl, divalent C4-C10 heterocycloalkenyl, divalent C4-C10 hetaryl or divalent C4-C10 hetaryl-C4-Cio hetaryl, wherein the heterocycloalkyd, heterocycloalkenyl and hetaryl contain 1 to 3 (for example 1, 2, 3) heteroatoms selected from N, O, and S, wherein the C4-C12 alkylene can optionally be interrupted by one or more non adjacent oxygen atoms, and/or one or more non adjacent carbon atoms in the C4-C12 alkylene can optionally be replaced with -(CO)-O- and/or CO; each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2.

[0071] In this disclosure, the free-radically polymerizable group (FP) is selected from allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, acrylamido, methacrylamido or acetylenyl, for example acrylate or methacrylate.

[0072] In the polyolefin elastomer vitrimer of this disclosure, the amount of the moiety derived from compound (1) can be in the range from about 0. 1 to about 8 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%), or from about 0.12 wt% to about 6 wt%, or from about 0.15 to about 5 wt%, based on the weight of the polyolefin elastomer.

[0073] According to the present disclosure, compound (1 ) containing the reversible borate moiety or derivative thereof and multi free-radically polymerizable groups as the crosslinker can be directly grafted onto the polyolefin elastomer chains to form vitrimers in one step.

Polyolefin elastomer

[0074] As used herein, the term "polyolefin elastomer" refers to a polymeric elastomer made up of at least 50 wt% olefin-derived units, examples of which include ethylene and C3-16 olefins, (for example C3-12 olefins, C3-8 olefins or C3-6 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-methy 1-1 -pentene, 1 -octene, 3 -methyl- 1 -butene, 4-methyl-l -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. In certain preferred embodiments, the polyolefin elastomers are those that comprise at least 50 wt% of ethylene, or propylene, or butene- derived units.

[0075] The polyolefin elastomer 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 ¹³C NMR as is known in the art and described in, for example, 18 J. Poly. Sci.: Poly. Lett. Ed. pp. 389-394 (1980).

[0076] In certain embodiments, the polyolefin elastomer may have a Shore A hardness of from a lower limit of about 10, about 20, about 30, about 40, about 50, or about 60 to an upper limit of about 70, about 75, about 80, about 85, about 90, or about 95, as determined by ASTM D2240. [0077] In one or more preferred embodiments, the polyolefin elastomer may have a melt flow rate (MFR), as determined by ASTM D1238, 2.16 kg at 230°C, of greater than about 0.1 g/lOmin, about 0.5 g/lOmin, about 1 g/lOmin, about 2 g/lOmin, about 5 g/lOmin, or about 10 g/lOmin, and preferably up to about 20 g/lOmin, about 40 g/lOmin, about 80 g/lOmin, about 100 g/lOmin, or about 200 g/lOmin.

[0078] In certain embodiments, the polyolefin elastomer of this disclosure has an elongation at break, as determined by ASTM D412, of at least about 100%, at least about 200%, at least about 300%, and may be up to about 800%, about 1000% or about 2000%, and preferably in the range of from about 100% to about 2000%.

[0079] In certain embodiments, the polyolefin elastomer of this disclosure has a density, as determined by ASTM D1505, of from about 0.83 g/cm³ to about 0.9 g/cm³, preferably from about 0.85 g/cm³ to about 0.89 g/cm³, from about 0.86 g/cm³ to about 0.88 g/cm³, or from about 0.86 g/cm³ to about 0.87 g/cm’.

[0080] In certain embodiments, the polyolefin elastomer of this disclosure has a flexural modulus at 1% Secant (73°F) (23°C), as determined by ASTM D790, of from about 8 MPa to about 100 MPa. [0081] In an embodiment, the polyolefin elastomer is selected from the propylene-based elastomer and the ethylene-based elastomers.

[0082] In a preferred embodiment, the polyolefin elastomer of this disclosure is a propylene- based elastomer comprising at least about 60 wt% propylene-derived units and about 5 wt% to about 25 wt% ethylene-derived units, based on total weight of the propylene-based elastomer, wherein the propylene-based elastomer has a heat of fusion of less than about 80 J/g. The propylene-based elastomer is a copolymer of propylene-derived units and units derived from at least one of ethylene or a C4-C10 olefin (for example C4-C8 olefin or C4-C5 olefin), preferably alpha-olefin. Examples of the olefin include 1-butene, isobutylene,

2-butene, cyclobutene, 1-pentene, 1-hexene, 4-methyl-l -pentene, 1-octene, 3-methyl- 1-butene, 4- methy 1-1 -butene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, etc. The propylene- based elastomer has limited crystallinity due to adj acent isotactic propylene units and a melting point as described herein. The crystallinity and the melting point of the propylene-based elastomer are reduced compared to highly isotactic polypropylene by the introduction of errors in the insertion of propylene. The propylene-based elastomer is generally devoid of any substantial intermolecular heterogeneity in tacticity and comonomer composition, and also generally devoid of any substantial heterogeneity in intramolecular composition distribution.

[0083] Tire units, or comonomers, derived from at least one of ethylene or a C4-C10 olefin may be present in the propylene-based elastomer in an amount of about 1 wt% to about 35 wt%, or about 5 wt% to about 35 wt%, preferably about 7 wt% to about 32 wt%, more preferably about 8 wt% to about 25 wt%, even more preferably about 8 wt% to about 20 wt%, and most preferably about 8 wt% to about 18 wt% of the propylene-based elastomer. The propylene-based elastomer may have a heat of fusion of less than about 80 J/g. The propylene-based elastomer may have a melting point of about 105°C or less. The propylene-based elastomer may have a crystallinity of about 2% to about 65% of isotactic polypropylene. The propylene-based elastomer may have a MFR of about 1.5 to about 20 g/lOmin, or of about 2 to about 20 g/lOmin, or of about 2 to about 15 g/lOmin, or of about 2 to about 10 g/lOmin, or of about 2 to about 8 g/lOmin.

[0084] The propylene-based elastomer may comprise more than one comonomer. Embodiments of a propylene-based elastomer having more than one comonomer include propylene- ethylene-octene, propylene-ethylene-hexene, and propylene-ethylene- butene polymers. In some embodiments where more than one comonomer derived from at least one of ethylene or a C4-10 alphaolefin is present, the amount of one comonomer may be less than about 5 wt% of the propylene-based elastomer, but the combined amount of comonomers of the propylene-based elastomer is about 5 wt% or greater.

[0085] In an embodiment, the comonomer is ethylene, 1 -hexene, or 1 -octene. In one embodiment, the propylene-based elastomer comprises ethylene-derived units. The propylene- based elastomer may comprise about 5 wt% to about 25 wt%, preferably about 8 wt% to about 20 wt%, or about 10 wt% to about 18 wt% ethylene-derived units of the propylene-based elastomer. In some embodiments, the propylene-based elastomer consists essentially of units derived from propylene and ethylene, i.e., the propylene-based elastomer does not contain any other comonomer in an amount typically present as impurities in the ethylene and/or propylene feed streams used during polymerization or an amount that would materially affect the heat of fusion, melting point, crystallinity, or MFR of the propylene-based elastomer, or any other comonomer intentionally added to the polymerization process.

[0086] The propylene-based elastomer may have a triad tacticity of three propylene units, as measured by ¹³C NMR, of at least about 75%, at least about 80%, at least about 82%, at least about 85%, or at least about 90%. Preferably, the propylene-based elastomer has a triad tacticity of about 50% to about 99%, about 60% to about 99%, more preferably about 75% to about 99%, or about 80% to about 99%. In some embodiments, the propylene-based elastomer may have a triad tacticity of about 60% to 97%.

[0087] The propylene-based elastomer has a heat of fusion (“Hf ’), as determined by DSC, of about 80 J/g or less, preferably about 70 J/g or less, about 50 J/g or less, or about 35 J/g or less. The propylene-based elastomer may have a lower limit Hf of about 0.5 J/g, about 1 J/g, or about 5 J/g. For example, the Hf value may be anywhere from 1.0, 1.5, 3.0, 4.0, 6.0, or 7.0 J/g, to 30, 35, 40, 50, 60, 70, 75, or 80 J/g.

[0088] The propylene-based elastomer may have a percent cr stallinity, as determined according to the DSC procedure described herein, of about 2% to about 65%, preferably about 0.5% to about 40%), preferably about 1% to about 30%, and more preferably about 5% to about 35%), of isotactic polypropylene. The thermal energy for the highest order of propylene (i.e., 100% crystallinity) is estimated at 189 J/g. In some embodiments, the copolymer has crystallinity less than 40%, in the range of about 0.25% to about 25%, or about 0.5% to about 22% of isotactic polypropylene. Embodiments of the propylene-based elastomer may have a tacticity index m/r from a lower limit of about 4 or about 6 to an upper limit of about 8 or about 10 or about 12. In some embodiments, the propylene-based elastomer has an isotacticity index greater than 0%, or within the range having an upper limit of about 50% or about 25%, and a lower limit of about 3% or about 10%.

[0089] In some embodiments, the crystallinity of the propylene-based elastomer is reduced by copolymerization of propylene with limited amounts of one or more comonomers selected from: ethylene, C4-C20 alpha-olefins, and polyenes. In these copolymers, the amount of propylene-derived units present in the propylene-based elastomer ranges from an upper limit of about 95 wt%, about 94 wt%, about 92 wt%, about 90 wt%, or about 85 wt%, to a lower limit of about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 84 wt%, or about 85 wt% of the propylene-based elastomer.

[0090] The polyolefin elastomer of this disclosure may comprise optional polyene (for example diene). The optional polyene may be any hydrocarbon structure having at least two unsaturated bonds wherein at least one of the unsaturated bonds is readily incorporated into a polymer. For example, the optional polyene may be selected from straight chain acyclic olefins, such as 1 ,4- hexadiene and 1 ,6-octadiene; branched chain acyclic olefins, such as

5- methyl- 1 ,4-hexadiene, 3,7-dimethyl-l ,6-octadiene, and 3,7-dimethyl-l ,7-octadiene; single ring alicyclic olefins, such as 1 ,4-cyclohexadiene, 1 ,5-cyclooctadiene, and

1 ,7- cyclododecadiene; multi-ring alicyclic fused and bridged ring olefins, such as tetrahydroindene, norbomadiene, methyl-tetrahydroindene, dicyclopentadiene, bicyclo- (2.2.1)-hepta-2,5-diene, norbomadiene, alkenyl norbomenes, alkylidene norbomenes, e.g., ethylidiene norbomene ("ENB"), cycloalkenyl norbomenes, and cycloalkyliene norbomenes (such as 5-methylene-2-norbomene, 5- ethylidene-2 -norbomene, 5-propenyl-2 -norbomene, 5- isopropylidene-2-norbomene, 5-(4- cyclopentenyl)-2-norbomene, 5-cyclohexylidene-2- norbomene, 5-vinyl-2-norbomene); and cycloalkenyl-substituted alkenes, such as vinyl cyclohexene, allyl cyclohexene, vinyl cyclooctene, 4- vinyl cyclohexene, allyl cyclodecene, vinyl cyclododecene, and tetracyclo (A-l l,12)-5,8-dodecene. The amount of optional polyene-derived units present in the polyolefin elastomer (preferably propylene-based elastomer) ranges from an upper limit of about 15%, about 10%, about 7%, about 5%, about 4.5%, about 3%, about 2.5%, or about 1.5%, to a lower limit of about 0%, about 0.1 %, about 0.2%, about 0.3%, about 0.5%, or about 1%, based on the total weight of the propylene-based elastomer. In a preferred embodiment, the polyolefin elastomer (preferably propylene-based elastomer) does not contain any diene-derived units.

[0091] The propylene-based elastomer may have a single peak melting transition as determined by DSC. In one embodiment, the copolymer has a primary peak transition of about 90°C or less, with a broad end-of-melt transition of about 110°C or greater. The peak "melting point" ("T_m") is defined as the temperature of the greatest heat absorption within the range of melting of the sample. However, the copolymer may show secondary melting peaks adjacent to the principal peak, and/or at the end-of-melt transition. For the purposes of this disclosure, such secondary melting peaks are considered together as a single melting point, with the highest of these peaks being considered the T_m of the propylene-based elastomer. The propylene-based elastomer may have a T_m of about 110°C or less, about 105°C or less, about 100°C or less, about 90°C or less, about 80°C or less, or about 70°C or less. In one embodiment, the propylene-based elastomer has a T_m of about 25°C to about 105°C, preferably about 60°C to about 105°C, about 70°C to about 105°C, or about 90°C to about 105°C.

[0092] The propylene-based elastomer may have a density of about 0.850 g/cm³ to about 0.900 g/cm³, preferably about 0.860 g/cm³ to about 0.880 g/cm', at room temperature as measured per ASTM DI 505.

[0093] The propylene-based elastomer may have a MFR, as measured per ASTM D1238, 2.16 kg at 230°C, of at least about 2 g/10 min. In one embodiment, the propylene-based elastomer has a MFR about 2 to about 20 g/10 min, about 2 to about 10 g/10 min, or about 2 to about 5 g/10 min.

[0094] The propylene-based elastomer may have an Elongation at Break of less than about 2,000%, less than about 1,000%, or less than about 800%, as measured per ASTM D412.

[0095] The propylene-based elastomer may have a weight average molecular weight (M_w) of about 5,000 to about 5,000,000 g/mole, preferably about 10,000 to about 1 ,000,000 g/mole, and more preferably about 50,000 to about 400,000 g/mole; a number average molecular weight (M_n) of about 2,500 to about 250,000 g/mole, preferably about 10,000 to about 250,000 g/mole, and more preferably about 25,000 to about 250,000 g/mole; and/or a z- average molecular weight (M_z) of about 10,000 to about 7,000,000 g/mole, preferably about 80,000 to about 700,000 g/mole, and more preferably about 100,000 to about 500,000 g/mole. The propylene-based elastomer may have a molecular weight distribution ("MWD") of about 1.5 to about 20, or about 1.5 to about 15, preferably about 1.5 to about 5, and more preferably about 1.8 to about 3, and most preferably about 1.8 to about 2.5.

[0096] Preferred propylene-based elastomers are available commercially under the trade names VISTAMAXX™ (ExxonMobil Chemical Company, Houston, TX, USA), VERSIFY™ (The Dow Chemical Company, Midland, Michigan, USA), certain grades of TAFMER™ XM or NOTIO™ (Mitsui Company, Japan), and certain grades of SOFTEL™ (Basell Polyolefins of the Netherlands). The particular grade(s) of commercially available propylene-based elastomer suitable for use in this disclosure can be readily determined using methods commonly known in the art.

[0097] In certain embodiments, the propylene-based elastomer is an elastomer including propylene- crystallinity, a melting point by DSC equal to or less than 105°C, and a heat of fusion of from about 5 J/g to about 30 J/g. The propylene-derived units are present in an amount of about 80 wt% to about 90 wt%, based on the total weight of the propylene-based elastomer. The ethylenederived units are present in an amount of about 9 wt% to about 20 wt%, for example, about 9 wt%, about 9.5 wt%, about 10 wt%, about 10.5 wt%, about 11 wt%, about 11.5 wt%, about 12 wt%, about 12.5 wt%, about 13 wt%, about 13.5 wt%, about 14 wt%, about 14.5 wt%, about 15 wt%, about 15.5 wt%, about 16 wt%, about 16.5 wt%, about 17 wt%, about 17.5 wt%, about 18 wt%, about 19 wt%, about 20 wt%, or from about 10 wt% to about 18 wt% based on the total weight of the propylene- based elastomer.

[0098] The propylene-based elastomer may comprise copolymers prepared according to the procedures described in W02002/036651, U.S. Patent No. 6,992,158, and/or WO 2000/001745, the contents of which are incorporated herein by reference. Preferred methods for producing the propylene-based elastomer may be found in U.S. Patent Nos. 7,232,871 and 6,881,800, the contents of which are incorporated herein by reference. The invention is not limited by any particular polymerization method for preparing the propylene-based elastomer, and the polymerization processes are not limited by any particular type of reaction vessel.

[0099] Exemplary polyolefin elastomers useful in this invention may include ethylene-based elastomers. Useful ethylene-based elastomers may have one or more of the following properties: (1) an ethylene content of about 60 wt% to about 90 vit%, preferably about 65 wt% to about 85 wt%, preferably about 65 wt% to about 80 wt%, preferably about 65 wt% to about 75 wt%; (2) an ethylene content of about 80 mol% to about 96 mol%, preferably about 82 mol% to about 92 mol%, preferably about 82 mol% to about 88 mol%, preferably 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/cm³ or less, preferably 0.89 g/cm³ or less, preferably 0.88 g/cm³ or less, preferably 0.87 g/cm³ or less, preferably 0.86 g/cm³ or less, preferably 0.83 g/cm³ or more, preferably 0.84 g/cm³ or more, preferably 0.85 g/cm³ or more, preferably 0.855 g/cm³ or more, preferably about 0.83 g/cm³ to about 0.9 g/cm³, preferably from about 0.85 g/cm³ to about 0.89 g/cm³, preferably from about 0.85 g/cm³ to about 0.88 g/cm³, or preferably from about 0.85 g/cm³ to about 0.87 g/cm³; (8) a heat of fusion (Hf) 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; (11) 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/lOmin to about 100 g/lOmin, preferably about 0.3 g/lOmin to about 60 g/lOmin, preferably about 0.5 g/lOminto about 40 g/lOmin, preferably about 0.7 g/lOmin to about 20 g/lOmin. [0100] In certain preferred embodiments, the ethylene-based elastomer comprises at least 30 wt% of one or more C4-C20 olefin comonomers, for example, 1 -butene, 1 -hexene, and/or 1- octene. In some embodiments, the ethylene-based elastomer 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 elastomer. In certain preferred embodiments, the ethylenebased elastomer is produced using a metallocene catalyst system.

[0101] Ethylene-based elastomer useful in this disclosure include those commercially available under the trade names EXACT™ (ExxonMobil Chemical Company, Houston, TX, USA), ENGAGE and INFUSE^1M (The Dow Chemical Company, Midland, Michigan, USA), and certain grades of TAFMER™ (Mitsui Company, Japan). [0102] The polyolefin elastomer for forming the polyolefin elastomer vitrimer of the present disclosure can include one or more different polyolefin elastomers (especially one or more different propylene-based elastomers), i.e., polyolefin elastomers (especially one or more different propylene- based elastomers) each having one or more different properties such as, for example, different comonomer or comonomer content. Such combinations of various polyolefin elastomers are all within the scope of the invention.

The polyolefin elastomer vitrimer

[0103] The polyolefin elastomer vitrimer of this disclosure has improved melt strength. In an embodiment, the elastic modulus of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of 10‘²⁹ rad/s is at least 1.5, or at least 1.8, or at least 2, or at least 2.5, or event at least 3 orders of magnitude larger than that of the neat polyolefin elastomer. In an embodiment, the elastic modulus of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of 10'^{2 9} rad/s is from 1.5 to 5, or from 1.8 to 4.5, or from 2 to 4, or from 2.5 to 3.5 orders of magnitude larger than that of the neat polyolefin elastomer.

[0104] The polyolefin elastomer vitrimer of this disclosure has improved melt strength, as indicated by the increase in zero-shear viscosity. In an embodiment, the viscosity of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of 10'^{2 9} rad/s is at least 1, or at least 1.2, or at least 1.5, or at least 1.8, or at least 2 orders of magnitude larger than that of the neat polyolefin elastomer. In an embodiment, the viscosity of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of 10‘²⁹ rad/s is from 1 to 4.5, or from 1.5 to 4, or from 2 to 3.5 orders of magnitude larger than that of the neat polyolefin elastomer.

[0105] The polyolefin elastomer vitrimer of this disclosure also shows improved shear-thinning behavior comparing with the neat polyolefin elastomer. The polyolefin elastomer vitrimer shows high zero-shear viscosity, and low high-shear viscosity.

[0106] The polyolefin elastomer vitrimer of this disclosure displays the development of extensional strain hardening.

[0107] The polyolefin elastomer vitrimer of this disclosure can also be easily reprocessed via various technical means, such as physical recycle such as hot press, injection molding or chemical recycle.

[0108] In an embodiment, the polyolefin elastomer vitrimer is reprocessed by chemical recycle. In this regard, the polyolefin elastomer vitrimer can be subjected to dissolving in a solvent and then molded by hot press or injection molding after removing the solvent. [0109] In an embodiment, the polyolefin elastomer vitrimer is reprocessed by physical recycle. For example, the polyolefin elastomer vitrimer can be pulverized and hot pressed for example at 150°C, 0.5 MPa for 5 minutes.

[0110] In an embodiment, the elastic modulus of the polyolefin elastomer vitrimer after being reprocessed one time tested at 120°C and at a frequency of 10'² rad/s is at least about 50%, or at least about 55%, or at least about 65%, preferably at least about 70%, more preferably at least about 72% or 73% or 74% of the elastic modulus of the polyolefin elastomer vitrimer before reprocessing. For example, the elastic modulus of the polyolefin elastomer vitrimer after being reprocessed one time tested at 120°C and at a frequency of 10'² rad/s can be in the range from about 50% to about 90%, or from about 55% to about 85%, from about 55% to about 80%, from about 55% to about 75%, or from about 60% to about 85%, from about 60% to about 80%, from about 60% to about 75%, or from about 65% to about 85%, from about 65% to about 80%, from about 70% to about 85%, from about 70% to about 80%, from about 72% to about 85%, from about 72% to about 80% of the elastic modulus of the polyolefin elastomer vitrimer before reprocessing.

[0111] The polyolefin elastomer 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, or 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.

Process for preparing polyolefin elastomer vitrimer

[0112] A further aspect of this disclosure is directed to a process for preparing the polyolefin elastomer vitrimer of this disclosure, which comprises reacting the polyolefin elastomer with at least one compound (1) as described above in the presence of a free-radical polymerization initiator.

[0113] In an embodiment, the amount of the at least one compound (1) is in the range from about 0.1 wt% to about 8 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%), or from about 0.12 wt% to about 6 wt%, or from about 0. 15 wt% to about 5 wt%, based on the weight of the polyolefin elastomer. [0114] Suitable free-radical polymerization initiator can include for example peroxide initiator. Suitable peroxides are, for example, acetylcyclohexanesulfonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl pemeodecanoate, t-butyl pemeodecanoate, t-butyl perpivalate, t-amyl perpivalate, bis(2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2 -methylbenzoyl) peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per-2-ethylhexanoate, bis(4-chlorobenzoyl) peroxide, t-butyl perisobutyrate, t-butyl permaleate, l,l-bis(t-butylperoxy)-3,5,5- trimethylcyclohexane, l,l-bis(t-butylperoxy)cyclohexane, t-butylperoxy isopropyl carbonate, t- butyl perisononanoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t- butylperoxy)butane, 2,2-bis-10-(t-butylperoxy)propane, dicumyl peroxide, 2,5-dimethyl-2,5- bis(t-butylperoxy)hexane, 3-(t-butylperoxy)-3-phenylphthalide, di(t-amyl) peroxide, a,a'-bis(t- butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)-3,5-dimethyl-l ,2-dioxolane, di(t-butyl) peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne, 3,3,6,6,9,9-hexamethyl-l,2,4,5- tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene, mono-a-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

[0115] The reaction for preparing the vitrimer can be carried out at from 110°C to 250°C, or from 120°C to 200°C.

Process for preparing compound of formula (B)

[0116] A further aspect of this disclosure is directed to a process for preparing compound of Formula (B),

wherein R2 is as defined above, Q is oxygen, each Ri is independently R11-O-R12, wherein Rn is 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; R12 is 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; FP is a free-radically polymerizable group; and n is 2, 3 or 4, wherein the process comprises (1) reacting a compound of Formula (Bl)

(Bl), wherein R2, Q and n are as defined above, with a compound of Formula (B2) or a compound of Formula (B2’)

(B2)

(B2’) wherein Rn is as defined above, to obtain a compound of Formula (B3)

wherein R2, R11, Q and n are as defined above, and (ii) reacting the compound of Formula (B3) with a compound of Formula (B4)

X— R12-FP (B4) wherein X is halogen; and R12 and FP are as defined above; to obtain the compound of Formula (B). [0117] A further aspect of this disclosure is directed to a process for preparing compound of Formula (D),

wherein R2 is as defined above; Q is oxygen; each A is independently a ring having 5 to 10 ring members, or each A is independently a ring having 5 or 6 ring members; each Ri is independently R11-O-R12; wherein Rn is 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; R12 is 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; FP is a free-radically polymerizable group; and n is 2, 3 or 4; wherein the process comprises (i) reacting a compound of Formula (Bl)

(Bl), wherein R2, Q and n are as defined above, with a compound of Formula (D2) or a compound of

Formula (D2’)

(D2)

(D2’) wherein A and Rn are as defined above, to obtain a compound of Formula (D3)

wherein R2, R11, A, Q and n are as defined above, and (ii) reacting the compound of Formula (D3) with a compound of Formula (B4)

X R-12- FP (34) wherein x is halogen; and R12 and FP are as defined above; to obtain the compound of Formula (D). [0118] A further aspect of this disclosure is directed to a process for preparing compound of Formula (F)

wherein R2 is as defined above; Q is oxygen; each Ri is independently R11-O-R12; wherein Rn is 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; R12 is 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; n is 2, 3 or 4; and FP is a free-radically polymerizable group; wherein the process comprises (i) reacting a compound of Formula (Bl)

wherein R2, Q and n are as defined above, with a compound of Formula (F2) or a compound of Formula (F2’)

wherein Rn is as defined above, to obtain a compound of Formula (F3)

wherein R2, Rn, Q and n are as defined above, and (ii) reacting the compound of Formula (F3) with a compound of Formula (B4)

X - R12-FP (B4) wherein x is halogen: and R12 and FP are as defined above; to obtain the compound of Formula (F). [0119] A further aspect of this disclosure is directed to a process for preparing compound of Formula (H)

-(CO)-O- and/or CO; R12 is 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; n is 2, 3 or 4; and FP is a free-radically polymerizable group; wherein the process comprises (i) reacting a compound of Formula (Bl)

wherein R2, Q and n are as defined above, with a compound of Formula (H2) or a compound of Formula (H2’)

(H2 ) wherein A and Rn are as defined above, to obtain a compound of Formula (H3)

wherein R2, R11, Q, A and n are as defined above, and (ii) reacting the compound of Formula (H3) with a compound of Formula (B4)

X Ri2^— FP (B4) wherein x is halogen; and R12 and FP are as defined above; to obtain the compound of Formula (H). [0120] In an embodiment, R12 is -C(O)-RB, wherein RB is a direct bond or a divalent hydrocarbyl having 1 to 11 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.

[0121] The reaction in step (i) 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 to 30 hours, or 5 to 25 hours. The reaction can be carried out in the presence of sulfonic acid, for example toluenesulfonic acid.

[0122] In an embodiment, the compound of Formula (Bl) is selected from 1,4- phenylenediboronic acid, 2,5-thiophenediboranic acid, 4,4-biphenyldiboronic acid, polyboric acid, and tetrahydroxy diboron.

[0123] In the compound of Formula (B4), X is halogen, preferably Ci.

[0124] In step (ii), the reaction is preferably carried out in the presence of an organic base. Suitable organic base comprises amine, especially tertiary amine. The tertiary amine can contain three identical or different, unbranched or branched hydrocarbyl radicals (especially alkyl radicals) having 1 to 20 carbon atoms (or 1 to 12, or 1 to 6, or 2 to 12, or 2 to 6 carbon atoms) in each case, where individual carbon atoms can also be, independently of another, replaced by a hetero atom selected from the group consisting of N or O and/or two or three radicals can also be joined to one another to form a chain comprising at least four atoms.

[0125] In an embodiment, the tertiary amine is selected from the group consisting of trimethyl amine, triethyl amine, tripropyl amine, triisopropyl amine, ethyl diisopropyl amine, tri-n-butyl amine, tripentyl amine, trihexyl amine, tricyclohexyl amine, triisoamyl amine, trioctyl amine, tris(2- ethylhexyl) amine, tristearyl amine, trioleyl amine, tridecyl amine, dimethyl stearyl amine, N,N- dimethyl benzyl amine, N,N-dibutyl benzyl amine, N,N-dimethyl aniline, N,N-dihexyl aniline, N,N- diethyl aniline, N,N-dimethyltoluidine, pyridine, quinoline, picoline, 2,4-lutidine, 2,6-lutidine, trimethylpyridine, 2-methyl-5-ethylpyridine (collidine), N-methylpiperidine, N,N'-dimethylpiperazine, N-methyl morpholine, N-methyl pyrrolidine, sparteine, tris(2-hydroxyethyl) amine, tris(2 -hydroxypropyl) amine, methyl di(2-hydroxyethyl) amine, (N,N-Dimethylaminopropyl)-acetamide, octyldiethyl amine, N-octyl-N- hydroxyethylmethylamine, N,N-didecylmethyl amine, N-dodecyl-N-tetradecylhydroxyethylamine, N,N-ditetradecylmethylamine, N-tetradecyldimethylamine, N-hexadecyl-N-ethylmethylamine, N-octadecyl-N-eicosylmethylamine, N-docosyldimethylamine, N-tetracosyldimethylamine, triethylenediamine, tetramethyl guanidine, DABCO, N,N,N’,N”,N”-Pentamethyldiethylenetriamine, N, N,N\N’ -Tetraethyl- 1,3- propanediamine, N, N,N’,N’ -Tetramethyl -1 ,4-butanediamine, N,N,N’,N’-Tetramethyl-2-butene-l ,4- diamine, N,N,N’,N’-Tetramethyl-l,6-hexanediamine, 1,4, 8,11 -Tetramethyl- 1,4, 8,11- tetraazacyclotetradecane, l,3,5-Trimethylhexahydro-l,3,5-triazine, DBU, DBN and mixtures thereof. [0126] In step (ii), the organic base can be added (preferably dropwise) to the solution of compound of Formula (B3), (D3), (F3) or (H3), followed by the addition (preferably dropwise) of compound of Formula (B4). Usually, the addition is carried out at a lower temperature, for example no more than 5°C or no more than 2°C. After the completion of the addition, the reaction can be carried out at 15°C to 35°C. The reaction time can be in the range from 5 to 30 hours, or 8 to 20 hours. The reaction is preferably carried out at inert atmosphere, for example at nitrogen atmosphere. [0127] According to the present disclosure, compound of Formula (B) can be obtained via a process consisting of only two steps. Therefore, the process for preparing compound of Formula (B) of the present disclosure is very simple and cheap.

Composition

[0128] A further aspect of this disclosure is directed to a composition comprising the polyolefin elastomer 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; and the like. Blending and Processing of polyolefin elastomer vitrimer and composition

[0129] The polyolefin elastomer 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.

[0130] The polyolefin elastomer vitrimer can be in any physical form. In one 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 extmsion. The polymers can be in above mentioned physical form when used to blend with the additive.

[0131] The components can be blended by any suitable means, and are typically blended to yield an intimately mixed composition which may be a homogeneous, single phase mixture. 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.

[0132] 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 elastomer 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.

[0133] In a preferred aspect of this disclosure, the polyolefin elastomer 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). [0134] 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 elastomer 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.

[0135] 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 elastomer 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 preblended pellets. Here, "pre-blended pellets" means pellets of a composition comprising polyolefin elastomer 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

[0136] A further aspect of the present invention is directed to an article comprising the polyolefin elastomer vitrimers or the composition of this disclosure.

[0137] Tire 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 weatherseal, 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

Materials

[0138] Vistamaxx 6100 (VMX 6100): a random copolymer of propylene (C3) and ethylene (C2), with 16 mol% C2. It has no diene. It has an MFR of 3 (2.16 kg at 230°C, ASTM D1238). DBDA: boronic crosslinker, product 1 in Scheme 1 DCP: dicumyl peroxide.

Example 1- Synthesis of boronic ester diacrylate crosslinker [0139] The boronic ester diacrylate crosslinker (1) was synthesized according to scheme 1 :

Scheme 1. Synthesis of product (1) from commercially available (3) by a two-step sequence Synthesis of 4,4'-(l,4-phenylenebis(l,3,2-dioxaborolane-2,4-diyl))bis(butan-l-ol) (2).

[0140] Under nitrogen atmosphere, to a 250 mL single-neck round bottom flask equipped with a magnetic stir bar was added benzene- 1,4-diboronic acid (3) (1.5 g, 9.05 mmol), 1,2,6-hexanetriol (4) (2.43 g, 18.1 mmol), toluene (150 mL) and p-toluenesul Ionic acid (20 mg). The reaction mixture was refluxed with a Dean-Stark trap for 18 hours. The solvent was removed by rotary evaporation. To the same flask was added cold toluene (100 mL) and the mixture was stirred at room temperature for 30 minutes before it was filtered to remove any solids and condensed brown oil. The solvent in the filtrate was removed by rotary evaporation and dried under 60°C vacuum for 3 hours to afford product (2) as a yellow oil (1.64 g, 50% yield). ¹ H NMR (500 MHz, THF-cfe) 8 7.75 (s, 4H), 4.55 (m, 2H), 4.39 (t, 2H), 3.91 (t, 2H), 3.51 (t, 4H), 1.80-1.40 (m, 12H). These H NMR data excluded the ones in -OH grops, which were labile.

Preparation of triethylamine-in-dichloromethane solution (5)

[0141] Under nitrogen atmosphere, to a 40 mL oven-dried scintillation vial was added distilled tri ethylamine (3 mL) and anhydrous di chloromethane (15 mL).

Preparation of acryloyl chloride-in-dichloromethane solution (6)

[0142] Under nitrogen atmosphere, to a 25 mL oven-dried scintillation vial was added acryloyl chloride (1.7 mL) and anhydrous dichloromethane (6 mL). Synthesis of (l,4-phenylenebis(l,3,2-dioxaborolane-2,4-diyl))bis(butane-4,l-diyl) diacrylate (1) [0143] Under nitrogen atmosphere, to the 250 mL single-neck round bottom flask containing product (2) (1.64 g, mmol) was added a magnetic stir bar and anhydrous toluene (150 mL). The mixture was cooled in ice-water bath for 30 minutes and solution (5) was added dropwise via an addition funnel followed by dropwise addition of solution (6). The reaction mixture was allowed to warm to room temperature overnight. The reaction mixture was filtered and the filtrate was reduced by rotary evaporation. The residue was dissolved in 20 mL of dichloromethane and extracted twice with 20 mL of water. The organic layer was separated and dned over Mg^SOi. After filtration, the solvent in the filtrate was removed by rotary evaporation and dried under 60°C vacuum oven for 3 hours to afford product (1) as a yellow oil (1.62 g, 76 % yield). ^JH NMR (500 MHz, THF- s) 5 7.74 (s, 4H), 6.34 (d, 2H), 6.12 (t, 2H), 5.79 (d, 2H), 4.56 (m, 2H), 4.40 (t, 2H), 4.15 (t, 4H), 3.92 (t, 2H), 1.80-1.20 (m, 12H).

Example 2- Synthesis of Vistamaxx vitrimers

Solution blending

[0144] Six samples of 5 g of Vistamaxx 6100 (VMX) were dissolved in hexanes at room temperature with magnetic stirring. Solutions of dicumyl peroxide (DCP) in hexane (1 g/100 ml) and of the boronic crosslinker (DBDA, product 1 in Scheme 1) in THF (0.5 g/100 ml) were added to the VMX solutions according to the quantities listed in Table 1. The solutions were poured into Teflon dishes, and the solvent was evaporated under the hood for 24 hours. Traces of solvent were removed in the vacuum oven at 60°C for 3 hours.

Crosslinking

[0145] To measure the kinetics of crosslinking of the VMX vitrimers, dynamic time sweeps were performed in the rheometer (ARES-G2) using a frequency of 1 Hz and a strain amplitude of 1%. Cylindrical specimens of diameter = 8 mm and height = ~4 mm were loaded in the rheometer oven previously thermalized at 80°C. The temperature in the oven was rapidly ramped up to 140°C and maintained for 1 hour, while the dynamic moduli were recorded. Figure 1 showed the result of this test. Neat Vistamaxx 6100 was included as control. For this sample (Vistamaxx 6100), both the complex modulus (|G*|) and the tan 5 (=G"/G') remained unchanged during the tests, indicating that neither degradation, nor crosslinking occurred on the neat polymer at 140°C. The sample containing only the peroxide (VMX-DCP) showed a linear decrease in modulus with time, which was due to the well know beta-scission of the polypropylene units in Vistamaxx induced by the peroxide free radicals. For the samples containing the crosslinker DBDA, an initial increase in modulus indicated crosslinking reaction taking place during the first 20 minutes of reaction. After 20 minutes the modulus started to drop, presumably due to peroxide-induced thermal cracking. During the crosslinking stage of the reaction, the value of tan 8 dropped to values close or lower than 1, indicating that the sample became elastic in nature, which was additional evidence of network formation. Note that, as expected, the level of increase in modulus was proportional to the amount of DBDA added to the polymer.

Example 3- Characterization of Vitrimers

Thermal behavior

[0146] DSC scans of the neat Vistamaxx 6100 sample and the vitrimer VMX-V5 were shown in Figure 2. Temperature ramps were performed at a heating and cooling rates of 10°C/min. The melting and glass transition temperatures (Tm and Tg) were slightly higher in the vitrimer compared to the neat polymer.

Rheological response

[0147] Dynamic thermal-mechanical analysis (DMTA) data of the neat polymer and the vitrimer VMX-V5 were shown in Figure 3. Temperature ramps were performed at a heating rate of 2°C/min. Above the melting temperature (marked by the shar drop in moduli), the neat polymer showed the typical steady decrease in moduli and the crossover temperature above which G’ became less than G” (and tan 8 >1), which indicated that the polymer lost elasticity and became more “liquid-like”. This crossover was not observed in the vitrimer samples, which indicates that the sample remains highly elastic at temperature up to 150°C.

[0148] Additional evidence of network formation was provided in Figure 4, which showed the dynamic frequency sweeps (DFS), measured at 120°C, ofthe neat VMX 6100 and the vitrimer sample VMX-V5. The neat polymer showed the typical low-frequency slope of 1 and 2 in G’ and G ". respectively, and the viscosity plateau corresponding to the zero-shear viscosity, which corresponded to the relaxation process of an entangled polymer melt. The low-frequency elastic modulus in the vitrimer sample was about three orders of magnitude larger than that in the neat polymer. This and the pseudo plateau in G’ at low frequencies indicated solid-like behavior in this sample. However, die vitrimer samples could be reprocessed at temperatures above the melting temperature. Figure 4 also showed the DFS data of the sample after remolding. This sample showed slightly lower low- frequency elastic modulus (~ 500 Pa) compared to the sample after the first molding (~ 1200 Pa), measured at a frequency of 0.001 rad/s.

[0149] The viscosity plots in Figure 4 showed that the low-shear viscosity data of the vitrimer sample VMX-V5 (> 6 E6 Pa-s) was at least two orders of magnitude larger than the neat polymer (4 E4 Pa-s). This indicated a very' high melt strength value in the vitrimer sample. This also suggested that these samples might display extensional strain hardening (SH), which was confirmed by extensional rheology data shown in Figure 5. SH is described by the upturn in the extensional viscosity from the common line descnbed by the data measured at various extensional rates. Figure 5 compared the extensional viscosity of the neat polymer and the vitrimer sample VMX-V5, measured at 120°C. The neat sample (VMX 6100) showed the typical absence of SH observed in linear polymers measured way above their Tg. In contrast, the vitrimer samples VMX-V5 showed very strong SH. Overall the vitrimers showed superior processability properties (melt strength, shear thinning and SH) compared to the neat Vistamaxx sample.

OTHER EMBODIMENTS [0150] 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.

Claims

What is claimed is:

1. A polyolefin elastomer vitrimer, which is formed from the polyolefin elastomer and at least one compound (1) containing at least one reversible borate moiety or derivative thereof and at least two free-radically polymerizable groups. wherein there is a reversible borate moiety or derivative thereof between any two free- radically poly merizable groups in compound (1), and 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.

2. The polyolefin elastomer vitrimer according to claim 1, wherein the reversible borate moiety or derivative thereof has a structure of Formula (I):

wherein each Q is independently an element of the sixth main group or oxygen or sulfur.

3. The polyolefin elastomer vitrimer according to claim 2, wherein 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.

4. The polyolefin elastomer vitrimer according to claim 3, wherein 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 or oxygen or sulfur.

5. The polyolefin elastomer vitrimer according to any of claims 1 to 4, wherein compound (1) contains 1 to 3 reversible borate moieties or derivative thereof and 2 to 4 free-radically polymerizable groups.

6. The polyolefin elastomer vitrimer according to any of claims 1 to 5, wherein compound (1) is selected from at least one compound having following structure:

FP is a free-radically polymerizable group; 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.

7. The polyolefin elastomer vitrimer according to claim 6, wherein each Ri is independently a direct bond or a divalent hydrocarbyl having 1 to 12 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 divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; each R2 is independently a direct bond or a linear or branched 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 hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; C4-Cs-cycloalkyl, Cs-Cio-cycloalkenyl, Ce-Cio aryl, Ce-Cio aryl-Ce-Cio aryl, C4-C10 heterocycloalkyl, C4-C10 heterocycloalkenyl, C4-C10 hetaryl or C4-C10 hetaryl-C4-Cio hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 heteroatoms selected from N, O, and S; and wherein the valence of R2 corresponds to the value of n;

FP is a free-radically polymerizable group; each A is independently a ring having 5 or 6 ring members; each Q is oxygen; and n is 2 or 3.

8. The polyolefin elastomer vitrimer according to claim 6 or 7, wherein each Ri is C2-C12 alkylene, which can optionally be interrupted by one or more nonadj acent oxygen atoms, and/or one or more non adjacent carbon atoms in the C2-C12 alkylene can optionally be replaced with -(CO)-O- and/or CO; and each R2 is independently a direct bond, divalent or trivalent C1-C12 alkyl, divalent or trivalent Cr-Cs-cycloalkyl, divalent or trivalent Cs-Cio-cycloalkenyl, divalent or trivalent

Cs-Cio aryl, divalent ortrivalent Cs-Cio aryl-Cs-Cio aryl, divalent or trivalent C4-C10 heterocycloalkyl, divalent or trivalent C4-C10 heterocycloalkenyl, divalent or trivalent C4-C10 hetaryl, divalent or trivalent C4-C10 hetaiyl-C4-Cio hetaryl, wherein the heterocycloalkyl, heterocycloalkenyl and hetaryl contain 1 to 3 heteroatoms selected from N, O, and S, wherein the divalent or trivalent C1-C12 alkyl 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

C1-C12 alkyl can optionally be replaced with -(CO)-O- and/or CO.

9. The polyolefin elastomer vitrimer according to claim 6 or 7, wherein each Ri is independently a R11-O-R12, wherein Rn is a divalent hydrocarbyl having 1 to 12 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; and

R12 is a direct bond or a divalent hydrocarbyl having 1 to 12 carbon atoms, which can optionally be interrupted by one or more nonadjacent oxygen atoms, and/or one or more nonadjacent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO.

10. The polyolefin elastomer vitrimer according to claim 9, wherein R12 is -C(O)-RB, wherein RB is a direct bond or a divalent hydrocarbyl having 1 to 11 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.

11. The polyolefin elastomer vitrimer according to any of claims 1 to 10, wherein the free- radically polymerizable group is selected from allyl, vinyl, acrylate, methacrylate, acryloxy, methacryloxy, aciylamido, methacrylamido or acetylenyl.

12. The polyolefin elastomer vitrimer according to any of claims 1 to 11, wherein the elastic modulus of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of 10‘²⁹ rad/s is at least 1.5, or at least 2 orders of magnitude larger than that of the neat polyolefin elastomer.

13. The polyolefin elastomer vitrimer according to any of claims 1 to 12, wherein the viscosity of the polyolefin elastomer vitrimer tested at 120°C and at a frequency of 10‘²⁹ rad/s is at least 1, or at least 1.5 orders of magnitude larger than that of the neat polyolefin elastomer.

14. The polyolefin elastomer vitrimer according to any of claims 1 to 13, wherein the polyolefin elastomer vitrimer shows improved shear-thinning behavior comparing with the neat polyolefin elastomer.

15. The polyolefin elastomer vitrimer according to any of claims 1 to 14, wherein the polyolefin elastomer vitrimer displays extensional strain hardening.

16. The polyolefin elastomer vitrimer according to any of claims 1 to 15, wherein the amount of the moiety derived from compound (1) is in the range from about 0.1 wt% to about 8 wt%, or from about 0.15 wt% to about 5 wt%, based on the weight of the polyolefin elastomer.

17. A process for preparing the polyolefin elastomer vitrimers according to any of claims 1 to 16 comprising reacting the polyolefin elastomer with at least one compound (1) as defined in any of claims 1 to 16 in the presence of a free-radical polymerization initiator.

18. The process according to claim 17, wherein the amount of the at least one compound (1) is in the range from about 0. 1 wt% to about 8 wt%, or about 0. 15 wt% to about 5 wt%, based on the weight of the polyolefin elastomer.

19. A process for preparing compound of Formula (B),

wherein R2 is as defined in claim 6 or 7 or 8;

Q is oxygen; each Ri is independently R11-O-R12; wherein Rn is a divalent hydrocarbyl having 1 to 12 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;

R12 is a direct bond or a divalent hydrocarbyl having 1 to 12 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 divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; n is 2, 3 or 4; and

FP is a free-radically polymerizable group; wherein the process comprises

(1) reacting a compound of Formula (Bl)

(B2)

(B2’) wherein Rn is as defined above, to obtain a compound of Formula (B3)

wherein R2, Rn, Q and n are as defined above, and

(ii) reacting the compound of Formula (B3) with a compound of Formula (B4)

X - R12-FP (B4) wherein x is halogen; and

R12 and FP are as defined above; to obtain the compound of Formula (B).

20. A process for preparing compound of Formula (D),

wherein R2 is as defined in claim 6 or 7 or 8;

Q is oxygen; each A is independently a ring having 5 to 10 ring members, or each A is independently a ring having 5 or 6 ring members; each Ri is independently R11-O-R12; wherein Rn is a divalent hydrocarbyl having 1 to 12 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;

R12 is a direct bond or a divalent hydrocarbyl having 1 to 12 carbon atoms, which can optionally be interrupted by one or more nonadjacent oxygen atoms, and/or one or more nonadjacent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO;

FP is a free-radically polymerizable group; and n is 2, 3 or 4; wherein the process comprises

(i) reacting a compound of Formula (Bl)

(Bl), wherein R2, Q and n are as defined above, with a compound of Formula (D2) or a compound of Formula (D2'J

(D2)

(D2’)

wherein A and Rn are as defined above, to obtain a compound of Formula (D3)

wherein R2, Rn, A, Q and n are as defined above, and

(ii) reacting the compound of Formula (D3) with a compound of Formula (B4)

X Ri2^— FP (B4) wherein x is halogen; and

R12 and FP are as defined above; to obtain the compound of Formula (D).

21. A process for preparing compound of Formula (F)

wherein R2 is as defined in claim 6 or 7 or 8;

R12 is a direct bond or a divalent hydrocarbyl having 1 to 12 carbon atoms, which can optionally be interrupted by one or more nonadjacent oxygen atoms, and/or one or more nonadjacent carbon atoms in the divalent hydrocarbyl can optionally be replaced with -(CO)-O- and/or CO; n is 2, 3 or 4; and

FP is a free-radically polymerizable group; wherein the process comprises

(i) reacting a compound of Formula (B l)

(Bl), wherein R2, Q and n are as defined above, with a compound of Formula (F2) or a compound of Formula (F2’)

wherein Rn is as defined above, to obtain a compound of Formula (F3)

wherein R2, Rn, Q and n are as defined above, and

(11) reacting the compound of Formula (F3) with a compound of Formula (B4) x— R12-FP _(B4) wherein x is halogen; and

R12 and FP are as defined above; to obtain the compound of Formula (F).

A process for preparing compound of Formula (H)

wherein R2 is as defined in claim 6 or 7 or 8;

FP is a free-radically polymerizable group; wherein the process comprises

(i) reacting a compound of Formula (Bl)

(Bl), wherein R2, Q and n are as defined above, with a compound of Formula (H2) or a compound of Fomrula (H2’)

(H2)

(H2’) wherein A and R11 are as defined above, to obtain a compound of Formula (H3)

X Ri2^_FP (B4) wherein x is halogen; and R12 and FP are as defined above; to obtain the compound of Formula (H).

23. The process according to any of claims 19 to 22, wherein R12 is -C(O)-RB, wherein R13 is a direct bond or a divalent hy drocarbyl having 1 to 11 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.

24. A composition comprising the polyolefin elastomer vitrimer according to any of claims 1 to 16 and at least one additive. 25. An article comprising the polyolefin elastomer vitrimers according to any of claims 1 to 16 or the composition according to claim 24.