Glass-like polymer based on ring-opening polyolefin of cyclopentene

Abstract

The present disclosure relates generally to glass-like macromolecules based on ring-opened polyolefins of cyclopentene, to methods for producing glass-like macromolecules, to compounds (1) as cross-linking agents, to methods for producing compounds (1), to vulcanized glass-like macromolecules, and to methods for producing glass-like macromolecules based on ring-opened polyolefins of cyclopentene. The present invention relates to a composition comprising a glass-like polymer or a vulcanized glass-like polymer and to an article comprising a glass-like polymer or a vulcanized glass-like polymer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 478,284, filed January 3, 2023, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure generally relates to a glassy polymer (vitrimer) based on a ring-opening polyolefin of cyclopentene, to a method for preparing the glassy polymer, to a compound (1) as a crosslinking agent, to a method for preparing the compound (1), to a sulfurized glassy polymer, to a composition comprising the glassy polymer or the sulfurized glassy polymer, and to an article comprising the glassy polymer or the sulfurized glassy polymer. Background Art

[0004] Conventional rubber vulcanization methods involve cross-linking reactions that create irreversible covalent bonds between all polymer chains in the sample.

[0005] Glassy polymers are a new class of polymer materials that display dynamic cross-linked networks. The topology of such networks is not fixed because the bonds connecting the different polymer chains undergo associative exchange reactions, which allow them to "dissociate" from a given position in the network and "reassociate" at a different position. These exchange reactions are activated at temperatures above the topological freezing transition temperature (Tv). Below Tv, glassy polymers behave as solid elastic networks (i.e., behave as thermosetting or vulcanized elastomers), while above Tv, they behave as viscoelastic liquids (i.e., behave as melts). Summary of the Invention

[0006] In a first general aspect, the present disclosure provides a glass-like polymer of a cyclopentene-based ring-opened polyolefin, wherein the cyclopentene-based ring-opened polyolefin is cross-linked with a compound (1), wherein the compound (1) contains at least one reversible borate moiety or a derivative thereof and at least two cycloolefin groups; and a reversible borate moiety or a derivative thereof is present between any two cycloolefin groups in the compound (1); wherein the derivative of the borate moiety refers to a moiety in which oxygen in the borate moiety is replaced by another element of the sixth main group (e.g., sulfur).

[0007] In a second general aspect, the present disclosure provides a method for preparing the glass-like polymer of the present disclosure, comprising polymerizing cyclopentene, compound (1) of the present disclosure, and an optional comonomer via ring-opening metathesis polymerization to form the glass-like polymer in one step.

[0008] In a third general aspect, the present disclosure provides compound (1), wherein compound (1) contains at least one reversible boronate moiety or a derivative thereof and at least two cycloolefin groups; and a reversible boronate moiety or a derivative thereof is present between any two cycloolefin groups in compound (1); wherein the derivative of the boronate moiety refers to a moiety in which the oxygen in the boronate moiety is replaced by another element of the sixth main group (e.g., sulfur).

[0009] In a fourth general aspect, the present disclosure provides a method for preparing compound (1) of the present disclosure, comprising:

[0010] (i) reacting a boron (B) containing compound with a polyol type compound to form a compound containing at least one reversible borate ester moiety or derivative thereof and one hydroxyl group.

[0011] (ii) reacting the compound containing at least one reversible boronate moiety or a derivative thereof and one hydroxyl group obtained in step (i) with a compound containing a carboxyl group and a cycloolefin group to form compound (1),

[0012] wherein the boron-containing compound is selected from compounds having a structure of B(QR)3 and compounds having at least two B(QR)2 groups, wherein R is selected from H or C1-C6-alkyl and each Q is independently an element of the sixth main group, or oxygen or sulfur; and

[0013] The polyol type compound has three hydroxyl groups and two of them can form a reversible borate ester structure part or a derivative thereof with the boron-containing compound, or the polyol type compound has one hydroxyl group and one oxirane ring or oxetane ring.

[0014] In a fifth general aspect, the present disclosure provides a sulfurized glass-like polymer formed by sulfurizing the glass-like polymer of the present disclosure.

[0015] In a sixth general aspect, the present disclosure provides a composition comprising a glass-like polymer of the present disclosure or a sulfurized glass-like polymer of the present disclosure and at least one additive.

[0016] In a seventh general aspect, the present disclosure provides an article comprising a glass-like polymer of the present disclosure, a sulfurized glass-like polymer of the present disclosure, or a composition of the present disclosure.

[0017] Certain aspects of the first, second, third, fourth, fifth, sixth, and seventh general aspects may include one or more of the following features.

[0018] In some aspects, the reversible boronate moiety or derivative thereof has the structure of Formula (I):

[0019]

[0020] wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur, more preferably oxygen.

[0021] In some aspects, the -QBQ- moiety in formula (I) forms, together with 2 to 5 carbon atoms, a boron-containing ring having 5 to 8 ring members, preferably together with 2 or 3 carbon atoms, a boron-containing ring having 5 or 6 ring members, optionally fused to another ring to form a fused ring system; or two borate ester moieties can share one B atom and form a spiro ring.

[0022] In some aspects, the boron-containing ring has the following structure:

[0023]

[0024] The fused ring system containing the boron-containing ring has the following structure:

[0025]

[0026] Or two borate moieties may share one B atom and form a spirocycle; wherein A is a ring having 5 to 10 ring members, and wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur, more preferably oxygen.

[0027] In some aspects, compound (1) contains 1 to 3 reversible boronate moieties or derivatives thereof and 2 to 4 cycloolefin groups; or compound (1) contains 1 or 2 reversible boronate moieties or derivatives thereof and 2 or 3 cycloolefin groups.

[0028] In some aspects, compound (1) is selected from at least one compound having the following structure:

[0029] in:

[0030] Each R1 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; or two borate moieties may share one B atom and form a spirocycle;

[0031] OP is a cycloolefin group;

[0032] each A is independently a ring having 5 to 10 ring members;

[0033] Each Q is independently an element of the sixth main group, or oxygen or sulfur; and

[0034] n is 2, 3 or 4.

[0035] In some aspects, the variables in the compounds of Formulas (A) to (H) have the following definitions:

[0036] each R1 is independently a direct bond or a divalent hydrocarbon group having 1 to 12 carbon atoms, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group may be optionally replaced by -(CO)-O- and / or CO;

[0037] Each R2 is independently a direct bond or a linear or branched hydrocarbon group having 1 to 12 carbon atoms; or a C4-C8-cycloalkyl, C5-C 10 -cycloalkenyl, C6-C 10 Aryl, C1-C 12 Alkyl-C6-C 10 Aryl, C6-C 10 Aryl-C6-C 10 Aryl, C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, C4-C 10 Heterocycloalkyl, C4-C 10 Heterocycloalkenyl, C4-C 10 Heteroaryl or C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein the hydrocarbon group and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or the hydrocarbon group and the C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may be optionally replaced by -(CO)-O- and / or CO and wherein the heterocycloalkyl, heterocycloalkenyl and heteroaryl groups contain 1 to 3 heteroatoms selected from N, O and S; and wherein the valence of R2 corresponds to the value of n; or two borate moieties may share one B atom and form a spirocycle;

[0038] OP is a cycloolefin group;

[0039] each A is independently a ring having 5 or 6 ring members;

[0040] each Q is oxygen; and

[0041] n is 2 or 3.

[0042] In some aspects, each R1 is independently a direct bond or a C1-C 12 Alkylene, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO; and

[0043] Each R2 is independently a direct bond, a divalent or trivalent C1-C 12 Alkyl, divalent or trivalent C4-C8-cycloalkyl, divalent or trivalent C5-C 10 -cycloalkenyl, divalent or trivalent C6-C 10 Aryl, divalent or trivalent C1-C 12 Alkyl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, divalent or trivalent C4-C 10 Heterocycloalkyl, divalent or trivalent C4-C 10 Heterocycloalkenyl, divalent or trivalent C4-C 10 Heteroaryl, divalent or trivalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 heteroatoms selected from N, O and S, wherein the divalent or trivalent C1-C 12 Alkyl and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms and / or a divalent or trivalent C1-C 12 Alkyl and C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO.

[0044] In some aspects, the cycloolefin group in compound (1) is selected from 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, cyclopentene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbornene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethylnorbornene carboxylate, and norbornene-exo-2,3-carboxylic anhydride groups, preferably cyclopentene groups.

[0045] In some aspects, compound (1) is (1,4-phenylenebis(1,3,2-dioxaborolane-2,4-diyl))bis(butane-4,1-diyl)bis(cyclopent-3-ene-1-carboxylate).

[0046] In some aspects, the molar amount of the moiety derived from compound (1) is in the range of about 0.5 mol % to about 15 mol %, or about 0.6 mol % to about 10 mol %, based on the total molar amount of the repeating units of the cyclopentene-based ring-opening polyolefin.

[0047] In some aspects, the glass-like polymer is formed from cyclopentene and compound (1), or the glass-like polymer is formed from cyclopentene, compound (1) and other comonomers.

[0048] In some aspects, the glass-like polymer has a tensile stress at 1000% strain that is at least 30 times, or at least 40 times, greater than that of a pure cyclopentene-based ring-opening polyolefin.

[0049] In some aspects, the glassy polymer has an elastic modulus of at least about 180% or at least about 250% of the elastic modulus of a pure cyclopentene-based ring-opening polyolefin as tested by dynamic thermomechanical analysis at a heating rate of 2°C / min at 150°C.

[0050] Glass-like polymers can be prepared in one step by copolymerizing cyclopentene and optionally other cyclic monomers with compound (1) via cyclopentene ring-opening metathesis polymerization (ROMP) and exhibit enhanced properties, including high tensile strength and high service temperature. In addition, the incorporation of cyclopentene units into the polymer chain provides an opportunity for ideal recyclability because they can be readily converted back to monomers in high yield and high selectivity under mild conditions in the presence of a ring-closing metathesis catalyst.

[0051] These and other features and properties of the disclosed glass-like polymers of the present disclosure and their advantageous applications and / or uses will be apparent from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 Shown are the dynamic mechanical temperature runs of the CPR homopolymer and the glass-like polymers CPR-V1 and CPR-V2. The temperature ramp was performed at a heating rate of 2°C / min.

[0053] Figure 2 Shows the dynamic frequency sweeps of the CPR homopolymer and the glass-like polymers CPR-V1 and CPR-V2.

[0054] Figure 3 Shown are the tensile responses of CPR homopolymer and glassy polymers CPR-V1 and CPR-V2, (a) data for uncured samples, and (b) data for samples cured with sulfur.

[0055] Figure 4 Shown are the curing kinetics curves of CPR homopolymer and glass-like polymers CPR-V1 and CPR-V2 measured at 150°C. DETAILED DESCRIPTION

[0056] Various specific embodiments, versions, and examples are described herein; including exemplary embodiments and definitions adopted for the purpose of understanding the claimed invention. Although the following detailed description sets forth specific preferred embodiments, those skilled in the art will understand that these embodiments are exemplary only and that the invention may be practiced in other ways. For the purpose 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 recited. Any reference to the "invention" may refer to one or more, but not necessarily all, of the inventions defined by the claims.

[0057] All numerical values ​​in this detailed description and claims are modified by the "about" indication, and take into account experimental error and variations that would be expected by a person skilled in the art.

[0058] In a first general aspect, the present disclosure provides a glass-like polymer of a cyclopentene-based ring-opened polyolefin, wherein the cyclopentene-based ring-opened polyolefin is cross-linked with a compound (1), wherein the compound (1) contains at least one reversible boronate moiety or a derivative thereof and at least two cyclic olefin groups; and a reversible boronate moiety or a derivative thereof is present between any two cyclic olefin groups in the compound (1); wherein the derivative of the boronate moiety refers to a moiety in which oxygen in the boronate moiety is replaced by another element of the sixth main group (e.g., sulfur).

[0059] 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” may be S.

[0060] According to the present disclosure, the phrase “oxygen in the borate ester moiety is replaced by other elements of the sixth main group” means that oxygen in the borate ester moiety is replaced by an element of the sixth main group other than oxygen, for example, oxygen in the borate ester moiety may be replaced by S.

[0061] In an embodiment, a derivative of a boronate moiety means that the oxygen in the boronate moiety is replaced by S.

[0062] According to the present disclosure, there are no substituents on Q.

[0063] In an embodiment, two boronate moieties can share one B atom and form a spiro ring.

[0064] In an embodiment, the reversible boronate moiety or derivative thereof has the structure of Formula (I):

[0065]

[0066] wherein each Q is independently an element of the sixth main group, preferably O or S, more preferably O.

[0067] In an embodiment, the -QBQ moiety in formula (I) forms a boron-containing ring with 5 to 8 ring members together with 2 to 5 carbon atoms, preferably forms a boron-containing ring with 5 or 6 ring members together with 2 or 3 carbon atoms, optionally the boron-containing ring is fused with another ring (e.g., Ring A described below) to form a fused ring system, or two -QBQ- moieties share one B atom and form a spiro ring.

[0068] In an embodiment, the boron-containing ring has the following structure:

[0069]

[0070] The fused ring system containing the boron-containing ring has the following structure:

[0071]

[0072] or two -QBQ- moieties share one B atom and form a spirocycle; 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.

[0073] According to the present disclosure, the ring (A) fused to the boron-containing ring is a ring having 5 to 10 ring members, for example 5 to 8, or 5, 6 or 7 ring members. Ring (A) may be saturated, or partially unsaturated, or an aromatic carbocyclic or heterocyclic ring containing 1 to 4 (1, 2, 3 or 4), or 1 to 3 heteroatoms selected from N, O and S, and wherein the aforementioned carbocyclic or heterocyclic ring system may be unsubstituted or substituted, wherein the substituents on the ring may be joined to form additional rings.

[0074] Examples of the heterocyclic ring as ring (A) include one of the following:

[0075]

[0076] Examples of the aromatic ring as ring (A) include a phenyl ring or a naphthalene ring.

[0077] In an embodiment, the fused ring system containing the boron-containing ring has the following structure:

[0078]

[0079] wherein each Q is independently an element of the sixth main group, preferably oxygen or sulfur.

[0080] In an embodiment, compound (1) contains at least two (e.g., 2 or 3) reversible boronate moieties or derivatives thereof. In an embodiment, compound (1) contains 1 to 3 (e.g., 1, 2 or 3) reversible boronate moieties or derivatives thereof and 2 to 4 (e.g., 2, 3 or 4) cycloolefin groups. In an embodiment, compound (1) contains 1 to 3 (e.g., 1, 2 or 3) reversible boronate moieties or derivatives thereof and 2 cycloolefin groups. In an embodiment, compound (1) contains 1 to 3 (e.g., 1, 2 or 3) reversible boronate moieties or derivatives thereof and 3 cycloolefin groups. In an embodiment, compound (1) contains 1 or 2 reversible boronate moieties or derivatives thereof and 2 or 3 cycloolefin groups. In an embodiment, compound (1) contains 1 or 2 reversible boronate moieties or derivatives thereof and 2 cycloolefin groups. In an embodiment, compound (1) contains 2 reversible boronate moieties or derivatives thereof and 2 cycloolefin groups. In an embodiment, compound (1) contains two reversible boronate moieties and two cycloolefin groups.

[0081] In an embodiment, compound (1) is selected from at least one compound having the following structure:

[0082]

[0083]

[0084] in

[0085] Each R1 is independently a direct bond or a divalent organic group having 1 to 20 carbon atoms;

[0086] Each R2 is independently a direct bond or an organic group having 1 to 20 carbon atoms; or two -QBQ- moieties share one B atom and form a spiro ring;

[0087] OP is a cycloolefin group;

[0088] each A is independently a ring having 5 to 10 ring members;

[0089] Each Q is independently an element of the sixth main group, or oxygen or sulfur; and

[0090] n is 2, 3 or 4.

[0091] In an embodiment, each R1 is independently a direct bond or a divalent hydrocarbon group having 1 to 12 carbon atoms (e.g., 1 to 6 carbon atoms, or 1 to 4 carbon atoms), which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group may be optionally replaced by -(CO)-O- and / or CO.

[0092] In an embodiment, each R is independently a direct bond or a cyclic alkyl group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, or 1 to 20, 1 to 16, 1 to 10, 1 to 12, 1 to 6, 2 to 20, 2 to 16, 2 to 12, 2 to 10, 2 to 6, 3 to 20, 3 to 16, 3 to 10, 3 to 12, 3 to 6, 4 to 20, 4 to 16, 4 to 10, 4 to 12, 4 to 6, 5 to 20, 5 to 16, 5 to 10, 5 to 12, 5 to 6, 6 to 20, 6 to and a 5-20-membered (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, 5-18, 5-16, 5-12 or 5-10-membered) heterocyclic ring containing 1 to 3 (e.g., 1, 2 or 3) heteroatoms selected from N, O and S, or two -QBQ- moieties share one B atom and form a spirocycle.

[0093] If two -QBQ- moieties share one B atom and form a spiro ring, R2 is absent and n is 2.

[0094] Those skilled in the art will appreciate that the valence of R2 corresponds to the value of n. For example, if n is 2, the valence of R2 is 2; if n is 3, the valence of R2 is 3; and if n is 4, the valence of R2 is 4.

[0095] Unless otherwise indicated, the terms "hydrocarbyl radical," "hydrocarbyl," and "hydrocarbyl group" are used interchangeably throughout this document. For the purposes of this disclosure, a hydrocarbyl group is defined as a C1 to C 20 Groups (e.g. C1, C2, C3, C4, C5, C6, C8, C 10 、C 12 、C 16 、C 18 or C 20 ) or C1 to C 12 Groups, C1 to C6 groups, C2 to C 12 Group, C3 to C 12 group, or C4 to C 12 group, or C5 to C 20 Group, C6 to C 20 group, or C7 to C 20 Group or C5 to C 10group, or C5 to C 10 Group or C6 to C 10 groups, which may, where appropriate, be linear, branched or cyclic (aromatic or non-aromatic, for example saturated or unsaturated); and may additionally comprise hydrocarbyl groups substituted by other hydrocarbyl groups and / or one or more functional groups.

[0096] In an embodiment, each R1 is independently a direct bond or a C1-C 12 Alkylene, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may be optionally replaced by -(CO)-O- and / or CO. In an embodiment, each R1 is independently a direct bond or a C1-C6 alkylene group, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the C1-C6 alkylene group may be optionally replaced by -(CO)-O- and / or CO. In an embodiment, R1 is methylene or ethylene.

[0097] In some aspects, each R1 is independently R 11 -(CO)-OR 12 , where R 11 is a direct bond or a divalent hydrocarbon group (e.g., alkylene) having 1 to 12, 1 to 6, or 1 to 4 carbon atoms, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group (e.g., alkylene) may be optionally replaced by -(CO)-O- and / or CO; and

[0098] R 12 is a divalent hydrocarbon group (e.g., alkylene) having 1 to 12, or 1 to 6, or 1 to 4, or 2 to 12, or 2 to 6, or 3 to 12, or 3 to 6 carbon atoms, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group (e.g., alkylene) may be optionally replaced by -(CO)-O- and / or CO,

[0099] where R 11 Connected to a cycloolefin group (OP).

[0100] In an embodiment, each R2 is independently a direct bond, a linear or branched C1-C 20A hydrocarbon group, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the hydrocarbon group may be optionally replaced by -(CO)-O- and / or CO; a saturated or partially unsaturated or aromatic carbocyclic or heterocyclic ring having 3 to 20 carbon atoms, which contains 1 to 3 (e.g., 1, 2, 3) heteroatoms selected from N, O and S; or two -QBQ- moieties share one B atom and form a spirocycle. The number of carbon atoms of the linear or branched hydrocarbon group and the number of carbon atoms of the ring are as mentioned above for the organic group.

[0101] In an embodiment, each R2 is independently a direct bond or a linear or branched hydrocarbon having 1 to 12 carbon atoms (e.g., 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); C4-C8 cycloalkyl, C5 ... 10 -cycloalkenyl, C6-C 10 Aryl, C1-C 12 Alkyl-C6-C 10 Aryl, C6-C 10 Aryl-C6-C 10 Aryl, C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, C4-C 10 Heterocycloalkyl, C4-C 10 Heterocycloalkenyl, C4-C 10 Heteroaryl, C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein the hydrocarbon group and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or the hydrocarbon group and the C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may be optionally replaced by -(CO)-O- and / or CO and wherein the heterocycloalkyl, heterocycloalkenyl and heteroaryl groups contain 1 to 3 (e.g., 1, 2, 3) heteroatoms selected from N, O and S; and wherein the valence of R2 corresponds to the value of n.

[0102] In an embodiment, each R2 is independently a direct bond, a divalent or trivalent C1-C 12 Alkyl, divalent or trivalent C4-C8-cycloalkyl, divalent or trivalent C5-C 10 -cycloalkenyl, divalent or trivalent C6-C 10 Aryl, divalent or trivalent C1-C 12 Alkyl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C6-C 10Aryl, divalent or trivalent C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, divalent or trivalent C4-C 10 Heterocycloalkyl, divalent or trivalent C4-C 10 Heterocycloalkenyl, divalent or trivalent C4-C 10 Heteroaryl, divalent or trivalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g. 1, 2, 3) heteroatoms selected from N, O and S, wherein the divalent or trivalent C1-C 12 Alkyl and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms and / or a divalent or trivalent C1-C 12 Alkyl and C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO.

[0103] With divalent or trivalent C1-C 12 Alkyl-C6-C 10 For example, aryl means C1-C 12 Alkyl-C6-C 10 The total valence of the aryl group is divalent or trivalent.

[0104] In an embodiment, each R2 is independently a direct bond, a divalent or trivalent C1-C6 alkyl group, or a divalent or trivalent C4-C8-cycloalkyl group, a divalent or trivalent C5-C 10 -cycloalkenyl, divalent or trivalent C6-C 10 Aryl, divalent or trivalent C1-C6 alkyl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C1-C6 alkylene-C6-C 10 Aryl, divalent or trivalent C4-C 10 Heterocycloalkyl, divalent or trivalent C4-C 10 Heterocycloalkenyl, divalent or trivalent C4-C 10 Heteroaryl, divalent or trivalent C4-C 10 Heteroaryl-C4-C 10Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g., 1, 2, 3) heteroatoms selected from N, O and S, wherein the divalent or trivalent C1-C6 alkyl and C1-C6 alkylene groups may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent or trivalent C1-C6 alkyl and C1-C6 alkylene groups may be optionally replaced by -(CO)-O- and / or CO.

[0105] In an embodiment, each R2 is independently a direct bond, a divalent or trivalent C4-C 12 Alkyl, or divalent or trivalent C4-C8-cycloalkyl, divalent or trivalent C5-C 10 -cycloalkenyl, divalent or trivalent C6-C 10 Aryl, divalent or trivalent C1-C6 alkyl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C1-C6 alkylene-C6-C 10 Aryl, divalent or trivalent C4-C 10 Heterocycloalkyl, divalent or trivalent C4-C 10 Heterocycloalkenyl, divalent or trivalent C4-C 10 Heteroaryl, divalent or trivalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g. 1, 2, 3) heteroatoms selected from N, O and S, wherein the divalent or trivalent C4-C 12 The alkyl and C1-C6 alkylene groups may optionally be interrupted by one or more non-adjacent oxygen atoms and / or divalent or trivalent C4-C6 12 One or more non-adjacent carbon atoms in the alkyl group and the C1-C6 alkylene group may optionally be replaced by -(CO)-O- and / or CO.

[0106] In an embodiment, each R2 is independently a direct bond, a C1-C 12 Alkylene (i.e. divalent C1-C 12 Alkyl), or divalent C4-C8 cycloalkyl, divalent C5-C 10 -cycloalkenyl, divalent C6-C 10 Aryl, divalent C1-C6 alkyl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, divalent C4-C10 Heterocycloalkyl, divalent C4-C 10 Heterocycloalkenyl, divalent C4-C 10 Heteroaryl, divalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g. 1, 2, 3) heteroatoms selected from N, O and S, wherein C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO.

[0107] In an embodiment, each R2 is independently a direct bond, a C4-C 12 Alkylene (i.e. divalent C4-C 12 Alkyl), or divalent C4-C8-cycloalkyl, divalent C5-C 10 -cycloalkenyl, divalent C6-C 10 Aryl, divalent C1-C6 alkyl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, divalent C4-C 10 Heterocycloalkyl, divalent C4-C 10 Heterocycloalkenyl, divalent C4-C 10 Heteroaryl, divalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g. 1, 2, 3) heteroatoms selected from N, O and S, wherein C4-C 12 Alkylene and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or C4-C 12 Alkylene and C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO.

[0108] In an embodiment, each R2 is independently a direct bond, a C1-C6 alkylene group (ie, a divalent C1-C6 alkyl group), or a divalent C4-C8-cycloalkyl group, a divalent C5-C6 alkyl group, or a divalent C5-C6 alkyl group. 10 -cycloalkenyl, divalent C6-C 10 Aryl, divalent C1-C6 alkyl-C6-C 10 Aryl, divalent C6-C10 Aryl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C1-C6 alkylene-C6-C 10 Aryl, divalent C4-C 10 Heterocycloalkyl, divalent C4-C 10 Heterocycloalkenyl, divalent C4-C 10 Heteroaryl or divalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g., 1, 2, 3) heteroatoms selected from N, O and S, wherein the C1-C6 alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the C1-C6 alkylene group may be optionally replaced by -(CO)-O- and / or CO.

[0109] In an embodiment, each R2 is independently a divalent C4-C8-cycloalkyl, a divalent C5-C 10 -cycloalkenyl, divalent C6-C 10 Aryl, divalent C1-C6 alkyl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C1-C6 alkylene-C6-C 10 Aryl, divalent C4-C 10 Heterocycloalkyl, divalent C4-C 10 Heterocycloalkenyl, divalent C4-C 10 Heteroaryl or divalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g. 1, 2, 3) heteroatoms selected from N, O and S, wherein C1-C6 alkylene may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in C1-C6 alkylene may be optionally replaced by -(CO)-O- and / or CO; preferably a divalent C6-C 10 Aryl, divalent C6-C 10 Aryl-C6-C 10 Aryl, divalent C4-C 10 Heteroaryl or divalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein the heteroaryl group contains 1 to 3 (e.g., 1, 2, 3) heteroatoms selected from N, O, and S.

[0110] In an embodiment, each R2 is independently phenylene, phenylene-phenylene, or a divalent thienyl group.

[0111] A is as defined above. In an embodiment, each A is independently a ring having 5 or 6 ring members.

[0112] In an embodiment, n is 2 or 3, such as 2, such as 3.

[0113] In an embodiment, Q is S or O, preferably O.

[0114] In an embodiment, the variables in the above formulas (A), (B), (C), (D), (E), (F), (G), and (H) have the following definitions:

[0115] each R1 is independently a direct bond or a divalent hydrocarbon group having 1 to 12 carbon atoms, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group may be optionally replaced by -(CO)-O- and / or CO;

[0116] Each R2 is independently a direct bond or a linear or branched hydrocarbon group having 1 to 12 carbon atoms; or a C4-C8-cycloalkyl, C5-C 10 -cycloalkenyl, C6-C 10 Aryl, C1-C 12 Alkyl-C6-C 10 Aryl, C6-C 10 Aryl-C6-C 10 Aryl, C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, C4-C 10 Heterocycloalkyl, C4-C 10 Heterocycloalkenyl, C4-C 10 Heteroaryl or C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein the hydrocarbon group and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or the hydrocarbon group and the C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may be optionally replaced by -(CO)-O- and / or CO and wherein the heterocycloalkyl, heterocycloalkenyl and heteroaryl groups contain 1 to 3 (e.g., 1, 2 or 3) heteroatoms selected from N, O and S; and wherein the valence of R2 corresponds to the value of n; or two -QBQ- moieties share one B atom and form a spirocycle;

[0117] OP is a cycloolefin group;

[0118] each A is independently a ring having 5 or 6 ring members;

[0119] each Q is oxygen; and

[0120] n is 2 or 3.

[0121] In an embodiment, the variables in the above formulas (A), (B), (C), (D), (E), (F), (G), and (H) have the following definitions:

[0122] Each R1 is independently a direct bond or a C1-C 12 Alkylene, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO;

[0123] Each R2 is independently a direct bond, a divalent or trivalent C1-C 12 Alkyl, divalent or trivalent C4-C8-cycloalkyl, divalent or trivalent C5-C 10 -cycloalkenyl, divalent or trivalent C6-C 10 Aryl, divalent or trivalent C1-C 12 Alkyl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, divalent or trivalent C4-C 10 Heterocycloalkyl, divalent or trivalent C4-C 10 Heterocycloalkenyl, divalent or trivalent C4-C 10 Heteroaryl or divalent or trivalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g. 1, 2, 3) heteroatoms selected from N, O and S, wherein the divalent or trivalent C1-C 12 Alkyl and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms and / or a divalent or trivalent C1-C 12 Alkyl and C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may be optionally replaced by -(CO)-O- and / or CO; or two -QBQ- moieties share one B atom and form a spirocycle;

[0124] OP is a cycloolefin group;

[0125] each A is independently a ring having 5 or 6 ring members;

[0126] each Q is oxygen; and

[0127] n is 2 or 3.

[0128] In an embodiment, the variables in the above formulas (A), (B), (C), (D), (E), (F), (G), and (H) have the following definitions:

[0129] each R1 is independently a direct bond or a C1-C6 alkylene group, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the C1-C6 alkylene group may be optionally replaced by -(CO)-O- and / or CO;

[0130] Each R2 is independently a direct bond, a C1-C6 alkylene group, a divalent C4-C8-cycloalkyl group, a divalent C5-C 10 -cycloalkenyl, divalent C6-C 10 Aryl, divalent C1-C6 alkyl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C1-C6 alkylene-C6-C 10 Aryl, divalent C4-C 10 Heterocycloalkyl, divalent C4-C 10 Heterocycloalkenyl, divalent C4-C 10 Heteroaryl or divalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g., 1, 2, 3) heteroatoms selected from N, O and S, wherein C1-C6 alkylene may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in C1-C6 alkylene may be optionally replaced by -(CO)-O- and / or CO; or two -QBQ- moieties share one B atom and form a spirocycle;

[0131] OP is a cycloolefin group;

[0132] each A is independently a ring having 5 or 6 ring members;

[0133] each Q is oxygen; and

[0134] n is 2.

[0135] In an embodiment, the variables in the above formulas (A), (B), (C), (D), (E), (F), (G), and (H) have the following definitions:

[0136] each R1 is independently a direct bond or a C1-C6 alkylene group, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the C1-C6 alkylene group may be optionally replaced by -(CO)-O- and / or CO;

[0137] Each R2 is independently C4-C 12 Alkylene, divalent C4-C8 cycloalkyl, divalent C5-C 10 -cycloalkenyl, divalent C6-C 10 Aryl, divalent C1-C6 alkyl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C6-C 10 Aryl, divalent C6-C 10 Aryl-C1-C6 alkylene-C6-C 10 Aryl, divalent C4-C 10 Heterocycloalkyl, divalent C4-C 10 Heterocycloalkenyl, divalent C4-C 10 Heteroaryl or divalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 (e.g. 1, 2, 3) heteroatoms selected from N, O and S, wherein C4-C 12 The alkylene and C1-C6 alkylene groups may optionally be interrupted by one or more non-adjacent oxygen atoms, and / or C4-C 12 One or more non-adjacent carbon atoms in the alkylene and C1-C6 alkylene groups may be optionally replaced by -(CO)-O- and / or CO; or two -QBQ- moieties share one B atom and form a spirocycle;

[0138] OP is a cycloolefin group;

[0139] each A is independently a ring having 5 or 6 ring members;

[0140] each Q is oxygen; and

[0141] n is 2.

[0142] In an embodiment, each R1 is independently C1-C6 alkylene, wherein one or more (eg, 1, 2, or 3) non-adjacent carbon atoms in the C1-C6 alkylene are replaced by -(CO)-O- and / or CO.

[0143] In an embodiment, the cycloolefin group (OP) is selected from 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, cyclopentene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbornene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene (e.g., 1,5-cyclooctadiene), cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethylnorbornene carboxylate, and norbornene-exo-2,3-carboxylic anhydride groups, preferably a cyclopentene group.

[0144] Specific examples of compound (1) may include, but are not limited to, (1,4-phenylenebis(1,3,2-dioxaborolane-2,4-diyl))bis(butane-4,1-diyl)bis(cyclopent-3-ene-1-carboxylate).

[0145] In the glass-like polymer, the molar amount of the structural moiety derived from compound (1) is in the range of about 0.5 mol% to about 15 mol% (e.g., about 0.6 mol%, about 0.7 mol%, about 0.8 mol%, about 0.9 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol% or about 14 mol%), or about 0.6 mol% to about 10 mol%, or about 0.6 mol% to about 8 mol%, or about 1 mol% to about 8 mol%, or about 1.5 mol% to about 6 mol%, based on the total molar amount of the repeating units of the cyclopentene-based ring-opening polyolefin.

[0146] In the present disclosure, a cyclopentene-based ring-opening polyolefin refers to a polymer comprising at least 50 wt% of C5 repeating units derived from ring-opening metathesis polymerization (ROMP) of cyclopentene. In embodiments, the cyclopentene-based ring-opening polyolefin comprises at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, or at least 95 wt% of C5 repeating units derived from ring-opening metathesis polymerization (ROMP) of cyclopentene.

[0147] In this disclosure, polypentene means a polymer derived from the ring-opening metathesis polymerization (ROMP) of cyclopentene.

[0148] In an embodiment, the glass-like polymer of the present disclosure is formed from cyclopentene and compound (1), or the glass-like polymer is formed from cyclopentene, compound (1) and other comonomers. As mentioned below, the glass-like polymer is prepared in one step by ring-opening metathesis polymerization.

[0149] Suitable comonomers can include 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbornene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene (e.g., 1,5-cyclooctadiene), cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, and norbornene-exo-2,3-carboxylic anhydride.

[0150] In the glass-like polymer of the present disclosure, the weight of the unit derived from the ring-opening metathesis polymerization of the commoner is not higher than the weight of the C5 repeating unit derived from the ring-opening metathesis polymerization of cyclopentene.

[0151] As used herein, Mn is the number average molecular weight and Mw is the weight average molecular weight. The polydispersity index (PDI) is the value of Mw divided by Mn.

[0152] The glass-like polymers of the present disclosure may have a weight average molecular weight (MW) of about 10 to about 1000 kDa (e.g., 20, 50, 80, 100, 150, 200, 300, 350, 400, 500, 600, 800, or 900 kDa), or about 20 to about 800 kDa, or about 50 to about 800 kDa, or about 80 to about 800 kDa, or about 100 to about 600 kDa. w ).

[0153] The glass-like polymers of the present disclosure may have a PDI of about 1.5 to about 4 (eg, 1.6, 1.8, 2, 2.5, 3, 3.5, or 4), or about 1.6 to about 3.5, or about 1.6 to about 3.

[0154] In the glass-like polymers of the present disclosure, each pentene repeating unit (C5 repeating unit) may have a cis or trans configuration. As used herein, the term "cis" refers to the cis configuration of the carbon-carbon double bonds of the polymer backbone. As used herein, the term "trans" refers to the trans configuration of the carbon-carbon double bonds of the polymer backbone. The molar ratio of cis to trans may be in the range of about 5:95 to about 40:60, or about 10:90 to about 30:70, or about 15:85 to about 25:75.

[0155] The glass-like polymers disclosed herein have enhanced properties, including high tensile strength, high operating temperature, and the like.

[0156] The samples used for tensile and hysteresis testing are dog-bone shaped samples (0.3 mm × 2 mm × 7 mm). For example, the samples can be prepared by compression molding in a hot press preheated at 80°C. The tensile and hysteresis tests can be performed by uniaxial stretching at a linear deformation rate of 100 microns / s at 25°C. The equipment can be a solid analysis instrument (RSA-G2, TA Instruments).

[0157] In embodiments, the glass-like polymer has a tensile stress at 1000% strain that is at least 30 times, at least 40 times, at least 50 times, at least 80 times, at least 100 times, at least 150 times, at least 200 times, at least 250 times, at least 300 times, or at least 350 times greater than that of a pure cyclopentene-based ring-opening polyolefin. In embodiments, the glass-like polymer has a tensile stress at 1000% strain that is 30 to 600 times, or 40 to 550 times, 50 to 500 times, 80 to 500 times, 100 to 450 times, 150 to 400 times, 200 to 350 times, or 250 to 350 times greater than that of a pure cyclopentene-based ring-opening polyolefin.

[0158] The glassy polymer has an elastic modulus of at least about 180%, at least about 200%, at least about 250%, at least about 300%, at least about 350%, at least about 400%, at least about 450%, at least about 500%, or at least about 550%, or at least about 600%, or at least about 700% of that of the pure cyclopentene-based ring-opening polyolefin as measured by dynamic thermomechanical analysis at a heating rate of 2°C / min at 150°C. In embodiments, the glassy polymer has an elastic modulus of from about 180% to about 1200%, or from about 200% to about 1000%, or from about 250% to about 800%, or from about 300% to about 800%, or from about 350% to about 800%, or from about 400% to about 700% of that of the pure cyclopentene-based ring-opening polyolefin as measured by dynamic thermomechanical analysis at a heating rate of 2°C / min at 150°C.

[0159] In an embodiment, the -3 rad / s, the complex viscosity of the glass-like polymer 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 greater than that of the pure cyclopentene-based ring-opening polyolefin. -3 rad / s, dynamic frequency sweep test at 120℃ and 10 -3 The viscosity of the glass-like polymer measured at a frequency of rad / s is 1 to 4.5, or 1.2 to 4, or 1.5 to 3.5, or 1.5 to 3 orders of magnitude greater than that of the pure cyclopentene-based ring-opening polyolefin.

[0160] The glass-like polymers of the present disclosure exhibit high zero shear viscosity (e.g., at 10 -3 rad / s), and low high shear viscosity (e.g. at 10 2.5 rad / s).

[0161] Unlike traditional cross-linked materials, the glass-like polymers of the present disclosure can be reshaped and reprocessed.

[0162] The glass-like polymers disclosed herein have thermoplastic properties and are preferably capable of being processed by pressing, injection molding, extrusion molding, blow molding, calendaring, foaming, solvent plasticization, mold pressing, casting, reaction molding, for example, by pelletizing and further hot pressing or extrusion. "Thermoplastic polymer(s)" means a polymer that can be melted by heat and then cooled without significant changes in solid state properties before and after heating.

[0163] In an embodiment, the glass-like polymer is reprocessed by physical means. For example, the glass-like polymer can be crushed and hot pressed, for example, at 150° C., 0.5 MPa for 5 minutes.

[0164] The glass-like polymers of the present disclosure can also be easily converted back to monomers in high yield and high selectivity under mild conditions in the presence of a ring-closing metathesis catalyst.

[0165] Preparation method of glass-like polymer

[0166] Another aspect of the present disclosure relates to a method for preparing the glass-like polymer of the present disclosure, comprising polymerizing cyclopentene, the compound (1) of the present disclosure, and an optional comonomer via ring-opening metathesis polymerization to form the glass-like polymer in one step. The compound (1) is as defined above.

[0167] In the present disclosure, the ring-opening metathesis polymerization is carried out in the presence of a catalyst.

[0168] The polymerization temperature of the present invention may be in the range of -30°C to 50°C (e.g., -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, or 50°C), or -30°C to 40°C, or -30°C to 30°C. In an embodiment, the catalyst is added at a lower temperature, for example, -30°C to -20°C, and after the catalyst is added, the temperature may be increased, for example, to 15°C to 50°C, or 20°C to 40°C, or 20°C to 30°C.

[0169] The polymerization time is typically in the range of 1 hour to 10 hours (eg, 1.5, 2, 3, 4, 5, 6, 8, or 10 hours), or 1.5 hours to 8 hours, or 1.5 hours to 5 hours.

[0170] The catalyst for the ring-opening metathesis polymerization used in the present invention is a compound that catalyzes ring-opening metathesis polymerization.

[0171] The catalyst used for ROMP may include a metal such as tungsten (W), molybdenum (Mo), rhenium (Re), ruthenium (Ru), titanium (Ti), and / or osmium (Os).

[0172] In some embodiments of the present invention, the ring-opening metathesis polymerization catalyst is represented by the formula:

[0173]

[0174] in:

[0175] M is a Group 8 metal, preferably Ru or Os, more preferably Ru;

[0176] X and X 1 are independently any anionic ligand, preferably a halogen (preferably chlorine), an alkoxy group or a triflate, or X and X 1 can be joined to form a dianionic group and can form a monocyclic ring having up to 30 non-hydrogen atoms or a polynuclear ring system having up to 30 non-hydrogen atoms;

[0177] L and L 1 are independently neutral two-electron donors, preferably phosphines or N-heterocyclic carbenes, L and L 1 can be joined to form a monocyclic ring having up to 30 non-hydrogen atoms or a polynuclear ring system having up to 30 non-hydrogen atoms;

[0178] L and X may be joined to form a polydentate monoanionic group and may form a monocyclic ring having up to 30 non-hydrogen atoms or a polynuclear ring system having up to 30 non-hydrogen atoms;

[0179] L 1 and X 1 can be joined to form a polydentate monoanionic group and can form a monocyclic ring having up to 30 non-hydrogen atoms or a polynuclear ring system having up to 30 non-hydrogen atoms;

[0180] R c and R c1 are independently hydrogen, halogen or C1 to C 20 Substituted or unsubstituted hydrocarbon group (preferably C1 to C 20 Substituted or unsubstituted alkyl or substituted or unsubstituted C6 to C 20 aryl), which may contain at least one atom selected from halogen, oxygen, nitrogen, sulfur, phosphorus and silicon atoms;

[0181] R c1 and L 1 or X 1can be joined to form a monocyclic ring having up to 30 non-hydrogen atoms or a polynuclear ring system having up to 30 non-hydrogen atoms; and

[0182] R c and L or X may be joined to form a monocyclic ring having up to 30 non-hydrogen atoms or a polynuclear ring system having up to 30 non-hydrogen atoms.

[0183] Preferred alkoxy groups include those wherein the alkyl group is C1 to C 10 Hydrocarbyl, preferably C1 to C 10 Alkyl groups, preferably those of methyl, ethyl, propyl, butyl or phenyl, or including those derived from (phenyl)phenol, substituted (phenyl)phenol (wherein the (phenyl)phenol may be replaced by up to 1, 2, 3, 4 or 5 C1 to C 12 those substituted with alkyl groups).

[0184] Preferred phosphines are of the formula PR 3 'R 4 'R 5 ' to indicate that R 3 ' is a secondary alkyl or cycloalkyl (preferably C3 to C 12 secondary alkyl or cycloalkyl), and R 4 ' and R 5 ' is aryl, C1 to C 10 Primary alkyl, secondary alkyl or cycloalkyl. 4 ' and R 5 ' can be the same or different. Preferred phosphines include P(cyclohexyl)3, P(cyclopentyl)3, and / or P(isopropyl)3.

[0185] Preferred trifluoromethanesulfonates are represented by the formula:

[0186]

[0187] where R c2 is hydrogen or C1 to C 30 Hydrocarbyl groups, preferably C1 to C 12 The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group.

[0188] Preferred N-heterocyclic carbenes are represented by the formula:

[0189]

[0190] in:

[0191] Each R c4is independently a hydrocarbyl group or a substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluoyl, chlorophenyl, (phenyl)phenol or substituted (phenyl)phenol; and

[0192] Each R c5 is hydrogen, halogen or C1 to C 12 Hydrocarbyl groups, preferably hydrogen, bromine, chloride, methyl, ethyl, propyl, butyl or phenyl. In other possible embodiments, one of the N groups bound to the carbene in these formulae can be replaced by an S, O or P atom, preferably a S atom.

[0193] Other useful N-heterocyclic carbenes include compounds described in Hermann, W. A. ​​(1996) Chem. Eur. J., Vol. 2, pp. 772 and 1627; Enders, D. et al. (1995) Angew. Chem. Int. Ed., Vol. 34, p. 1021; Alder R. W. (1996) Angew. Chem. Int. Ed., Vol. 35, p. 1121; and Bertrand, G. et al. (2000) Chem. Rev., Vol. 100, p. 39.

[0194] In embodiments, the ring-opening metathesis polymerization catalyst is one or more of the following: tricyclohexylphosphine [1,3-bis (2,4,6-trimethylphenyl) imidazole-2-ylidene] [3-phenyl-1H-indene-1-ylidene] dichlororuthenium (II), tricyclohexylphosphine [3-phenyl-1H-indene-1-ylidene] [1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydro-imidazol-2-ylidene] dichlororuthenium (II), tricyclohexylphosphine [1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene] [(phenylthio) methylene] dichlororuthenium (II), bis (tricyclohexylphosphine) -3-phenyl-1H-indene-1-ylidene dichlororuthenium (II), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(isopropyloxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylenedichlororuthenium(II), and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene] chloride, dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II) (M206). In some embodiments, the ring-opening metathesis polymerization catalyst is 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(isopropyloxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylenedichlororuthenium(II), tricyclohexylphosphine[3-phenyl-1H-indene-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]dichlororuthenium(II) and / or dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II) (M206).

[0195] The amount of ring-opening metathesis polymerization catalyst employed in the methods of the present disclosure is any amount that provides operable ring-opening metathesis polymerization. Preferably, the molar ratio of monomers added to the catalyst is generally not less than 1,000:1; not less than 5,000:1; not less than 10,000:1; not less than 25,000:1; not less than 50,000:1; not less than 75,000:1; or not less than 100,000:1. In embodiments, the molar amount of monomer added to the catalyst typically ranges from 1000:1 to 2000000:1 (e.g., 2000:1, 5000:1, 8000:1, 10000:1, 20000:1, 50000:1, 80000:1, 100000:1, 200000:1, 500000:1, 800000:1, 1000000:1, or 1500000:1), or from 5000:1 to 1000000:1 or from 8000:1 to 500000:1 or from 10000:1 to 250000:1, or from 50000:1 to 200000:1.

[0196] The polymerization of the method of the present disclosure can be carried out in an inert solvent. The term "inert solvent" means that the solvent does not react with the catalyst and can be capable of dissolving the resulting polymer. Examples of solvents for the polymerization of the method of the present invention include straight-chain and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof such as the commercially available product (Isopar TM ); aromatic compounds such as benzene, toluene, mesitylene, ethylbenzene and xylene; halogenated hydrocarbons such as dichloromethane, dichloroethane, tetrachloroethane, chlorobenzene and trichlorobenzene; ethers such as tetrahydrofuran; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide.

[0197] In some embodiments of the present disclosure, the solvent used for the polymerization of the present method may be selected from dichloromethane, tetrahydrofuran, dimethylformamide, toluene, or xylene.

[0198] In an embodiment, the polymerization of the method of the present disclosure can be carried out in the substantial absence of an inert solvent. As used herein, "substantially absent of an inert solvent" means that the amount of inert solvent is no more than 5 weight percent, or no more than 4 weight percent, or no more than 3 weight percent, or no more than 2 weight percent, based on the weight of the monomers.

[0199] At the termination of the ring-opening metathesis polymerization, a vinyl compound such as 1-butene, 1-pentene, 1-hexene, 1-octene, or an alkyl vinyl ether such as ethyl vinyl ether may be added to terminate the polymerization.

[0200] In embodiments, the glass-like polymer may undergo segregation.

[0201] In order to isolate the glass-like polymer obtained from the polymerization, the glass-like polymer can be diluted, precipitated, washed, and dried. Generally, the drying temperature does not exceed 85°C, or does not exceed 75°C, or does not exceed 65°C, for example, 40°C to 85°C, 45°C to 75°C, or 50°C to 65°C.

[0202] Preparation method of compound (1)

[0203] Another aspect of the present disclosure relates to a method for preparing compound (1) of the present disclosure, comprising:

[0204] (i) reacting a boron (B)-containing compound with a polyol-type compound to form a compound containing at least one reversible borate ester moiety or derivative thereof and one hydroxyl group;

[0205] (ii) reacting the compound containing at least one reversible boronate moiety or a derivative thereof and one hydroxyl group obtained in step (i) with a compound containing a carboxyl group and a cycloolefin group to form compound (1),

[0206] wherein the boron-containing compound is selected from compounds having a structure of B(QR)3 and compounds having at least two B(QR)2 groups, wherein R is selected from H or C1-C6-alkyl and each Q is independently an element of the sixth main group, or oxygen or sulfur; and

[0207] The polyol type compound has three hydroxyl groups and two of them can form a reversible borate ester structure part or a derivative thereof with the boron-containing compound, or the polyol type compound has one hydroxyl group and one oxirane ring or oxetane ring.

[0208] In the present disclosure, the boron-containing compound may be selected from compounds having a structure of B(QR)3 and compounds having at least two (e.g., 2, 3, or 4) B(QR)2 groups, wherein R is selected from H or C1-C6-alkyl, such as methyl, ethyl, propyl, or butyl, and each Q is independently an element of the sixth main group, or oxygen or sulfur. In an embodiment, R is H. In an embodiment, R is C1-C6-alkyl, such as methyl, ethyl, propyl, or butyl.

[0209] In an embodiment, R may be C1-C6-alkyl, such as methyl, ethyl or propyl, preferably methyl or ethyl in the structure of B(QR)3. In an embodiment, R may be H in the structure of B(QR)2.

[0210] The boron-containing compound can be selected from trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tributyl borate, tri-tert-butyl borate, benzene-1,4-diboronic acid, 2,5-diboronic acid thiophene, 4,4-biphenyldiboronic acid, polyboric acid and tetrahydroxydiboron and ((((oxybis(ethane-2,1-diyl))bis(oxy))bis(methylene))bis(4,1-phenylene))diboronic acid.

[0211] In the present disclosure, the polyol-type compound has three hydroxyl groups, two of which are capable of forming a reversible borate ester moiety or a derivative thereof with a boron-containing compound, or the polyol-type compound has one hydroxyl group and one oxirane ring or an oxetane ring. The two hydroxyl groups capable of forming a reversible borate ester moiety or a derivative thereof with a boron-containing compound have a structure in which the two carbon atoms carrying the two hydroxyl groups are in ortho positions (e.g., a 1,2-diol structure) or are interrupted by one carbon atom (e.g., a 1,3-diol structure).

[0212] In an embodiment, the polyol-type compound is selected from compounds having the formula:

[0213]

[0214]

[0215] Ring A and R 12 As defined above.

[0216] For example, R 12 is a divalent hydrocarbon group (e.g., alkylene) having 1 to 12, or 1 to 6, or 1 to 4, or 2 to 12, or 2 to 6, or 3 to 12, or 3 to 6 carbon atoms, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group (e.g., alkylene) may be optionally replaced by -(CO)-O- and / or CO.

[0217] The compound containing a carboxyl group and a cycloolefin group may be a compound having the formula

[0218] HOOC-R 11 -OP (B4)

[0219] Where OP is a cycloolefin group, and R 11 As defined above.

[0220] For example, R 11is a direct bond or a divalent hydrocarbon group (e.g., alkylene) having 1 to 12, or 1 to 6, or 1 to 4 carbon atoms, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group (e.g., alkylene) may be optionally replaced by -(CO)-O- and / or CO.

[0221] OP is a cycloolefin group. The specific definition of OP is as mentioned above.

[0222] The reaction in step (i) can be carried out in the presence of a water trapping agent (such as magnesium sulfate or molecular sieves), or by using a Dean-Stark apparatus (which allows the water formed during the condensation to be removed by distillation). Preferably, the reaction in step (i) is carried out at an elevated temperature, for example, at 105°C to 160°C or at 110°C to 150°C. The reaction in step (i) is preferably carried out under an inert atmosphere, for example, under a nitrogen atmosphere. The reaction time in step (i) can be in the range of 3 hours to 30 hours, or 5 hours to 25 hours. The reaction in step (i) can be carried out in the presence of a sulfonic acid, for example, toluenesulfonic acid. The reaction in step (i) can be carried out in the presence of a solvent, for example, an aromatic hydrocarbon (such as toluene).

[0223] The reaction in step (ii) is carried out at an elevated temperature, for example, at 105°C to 160°C, or at 110°C to 150°C. The reaction in step (ii) is preferably carried out under an inert atmosphere, for example, under a nitrogen atmosphere. The reaction time in step (ii) can be in the range of 3 hours to 30 hours, or 5 hours to 25 hours. The reaction in step (ii) can be carried out in the presence of a sulfonic acid, for example, toluenesulfonic acid. The reaction in step (ii) can be carried out in the presence of a solvent, for example, an aromatic hydrocarbon (for example, toluene).

[0224] In an embodiment, compound (1) comprises at least two (eg, 2 or 3) reversible boronate moieties or derivatives thereof.

[0225] In an embodiment, the present disclosure provides a method for preparing a compound of formula (B)

[0226]

[0227] wherein R2, Q, OP and n are as defined above, or two -QBQ- moieties share one B atom and form a spirocycle;

[0228] Each R1 is independently R 11 -(CO)-OR 12 , where R 11 and R 12 As defined above, wherein the method comprises

[0229] (i) making a compound of formula (B1)

[0230]

[0231] wherein R2, Q and n are as defined above,

[0232] Reaction with a compound of formula (B2) or a compound of formula (B2')

[0233]

[0234] where R 12 As defined above,

[0235] To obtain a compound of formula (B3)

[0236]

[0237] Among them, R2, R 12 , Q and n are as defined above, and

[0238] (ii) reacting a compound of formula (B3) with a compound of formula (B4)

[0239] HOOC-R 11 -OP (B4)

[0240] where R 11 and OP as defined above;

[0241] to obtain the compound of formula (B).

[0242] In an embodiment, the present disclosure provides a method for preparing a compound of formula (D)

[0243]

[0244] wherein ring A, R2, Q, OP and n are as defined above; or two -QBQ- moieties share one B atom and form a spirocycle,

[0245] Each R1 is independently R 11 -(CO)-OR 12 , where R 11 and R 12 As defined above, wherein the method comprises

[0246] (i) making a compound of formula (B1)

[0247]

[0248] wherein R2, Q and n are as defined above,

[0249] Reaction with a compound of formula (D2) or a compound of formula (D2')

[0250]

[0251]

[0252] Where A and R 12 As defined above,

[0253] To obtain a compound of formula (D3)

[0254]

[0255] Among them, R2, R 12 , A, Q and n are as defined above, and

[0256] (ii) reacting a compound of formula (D3) with a compound of formula (B4)

[0257] HOOC-R 11 -OP (B4)

[0258] where R 11 and OP as defined above;

[0259] to obtain the compound of formula (D).

[0260] In an embodiment, the present disclosure provides a method for preparing a compound of formula (F)

[0261]

[0262] wherein R2, Q, OP and n are as defined above; or two -QBQ- moieties share one B atom and form a spirocycle,

[0263] Each R1 is independently R 11 -(CO)-OR 12 , where R 11 and R 12 As defined above, wherein the method comprises

[0264] (i) making a compound of formula (B1)

[0265]

[0266] wherein R2, Q and n are as defined above,

[0267] Reaction with a compound of formula (F2) or a compound of formula (F2')

[0268]

[0269] where R 12 As defined above,

[0270] To obtain a compound of formula (F3)

[0271]

[0272] Among them, R2, R 12 , Q and n are as defined above, and

[0273] (ii) reacting a compound of formula (F3) with a compound of formula (B4)

[0274] HOOC-R 11 -OP (B4)

[0275] where R 11 and OP are as defined above; to obtain a compound of formula (F).

[0276] In an embodiment, the present disclosure provides a method for preparing a compound of formula (H)

[0277]

[0278] wherein ring A, R2, Q, OP and n are as defined above; or two -QBQ- moieties share a B atom and form a spirocycle, each R1 being independently R 11 -(CO)-OR 12 , where R 11 and R 12 As defined above,

[0279] The methods include

[0280] (i) making a compound of formula (B1)

[0281]

[0282] wherein R2, Q and n are as defined above, react with a compound of formula (H2) or a compound of formula (H2')

[0283]

[0284] Ring A and R 12 As defined above, to obtain a compound of formula (H3)

[0285]

[0286] Among them, R2, R 12 , Q, ring A and n are as defined above, and

[0287] (ii) reacting a compound of formula (H3) with a compound of formula (B4)

[0288] HOOC-R11 -OP (B4)

[0289] where R 11 and OP are as defined above; and to obtain a compound of formula (H).

[0290] Preferably, Q in formulae (B), (D), (F) and (H) is oxygen.

[0291] Sulfurized glassy polymer

[0292] Additional aspects of the present disclosure relate to sulfurized glass-like polymers formed by sulfurizing the glass-like polymers of the present disclosure.

[0293] The glass-like polymer of the present disclosure can be cured by adding a curing agent (such as sulfur), a metal fatty acid, an accelerator, an activator, and other reagents commonly used in the art, if necessary.

[0294] The glass-like polymers are cured (cured) by any suitable means, for example, by subjecting them to heat or radiation according to any conventional curing method. The amount of heat or radiation required is that required to achieve the curing in the present disclosure, and the present disclosure is limited to the amount of heat and method required to cure the composition herein. Typically, curing is carried out at a temperature of 100° C. to about 250° C., or 120° C. to 200° C., or 130° C. to 180° C., for 50 to 200 minutes or for 90 to 160 minutes.

[0295] The metal fatty acid may be, for example, zinc stearate or calcium stearate. The metal fatty acid may be used alone or in combination with its corresponding metal oxide, such as ZnO and CaO. The amount of the metal fatty acid may be in the range of 0.1 phr to 5 phr, for example, 0.2 phr to 2 phr.

[0296] Sulfur is the most common chemical vulcanizing agent. Sulfur vulcanization systems may contain activators to activate the sulfur, accelerators, and retarders to help control the rate of vulcanization.

[0297] General types of accelerators include amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, and combinations thereof. The amount of accelerator can range from 0.1 phr to 10 phr, or from 0.2 phr to 5 phr, or from 0.3 phr to 4 phr.

[0298] Accelerators help control the onset and rate of vulcanization, and the number and type of crosslinks formed. Retarders can be used to delay the initial onset of cure to allow sufficient time to process the unvulcanized rubber.

[0299] Many accelerators are known in the art and include, but are not limited to, the following: stearic acid, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), benzothiazyl disulfide (MBTS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), N-cyclohexyl-2-benzothiazylsulfenamide (CBS), and thiourea.

[0300] The amount of curing agent (e.g., sulfur) can range from 0.2 phr to 8 phr (e.g., 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 2, 3, 4, 5, 6, 7, or 8 phr), or 0.3 phr to 5 phr, or 0.4 phr to 2 phr, based on 100 phr of the glass-like polymer.

[0301] In embodiments, the tensile stress of the cured glassy polymer at 1000% strain is at least about 110% (e.g., 115%, 120%, 125%, 130%, 135%, 140%, 150%, or 160%), or at least about 115%, or at least about 120%, or at least about 125% of the tensile stress of the cured pure cyclopentene-based ring-opening polyolefin at 1000% strain. In embodiments, the tensile stress of the cured glassy polymer at 1000% strain is between about 110% and 160%, or between about 115% and 150%, or between about 120% and 140% of the tensile stress of the cured pure cyclopentene-based ring-opening polyolefin at 1000% strain.

[0302] Composition

[0303] Another aspect of the present disclosure relates to a composition comprising a glass-like polymer or a sulfurized glass-like polymer of the present disclosure and at least one additive. Such additives are well known in the art and may include, for example, fillers; antioxidants (e.g., hindered phenols such as IRGANOX available from Ciba-Geigy); TM 1010 or IRGANOX TM 1076); phosphites (e.g., IRGAFOS available from Ciba-Geigy); TM 168); anti-cling additives; tackifiers such as polybutene, terpene resins, aliphatic resins and aromatic hydrocarbon resins, alkali metal stearates and glyceryl stearate and hydrogenated rosin; UV stabilizers; heat stabilizers; antiblocking agents; mold release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc; modifiers, etc.

[0304] Blending and processing of glass-like polymers, sulfurized glass-like polymers and compositions

[0305] The glass-like polymers and compositions described herein can be processed or formed using conventional equipment and methods, for example, by dry blending and subsequent melt mixing of the individual components in a mixer, or by mixing the components directly together in a mixer, such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single-screw or twin-screw extruder, which may include a compounding extruder and a sidearm extruder used directly downstream of the polymerization process. Additionally, additives may be included in the glass-like polymer, the blend, in one or more components of the blend, and / or in products formed from the blend, such as films, as desired. Examples of additives are described above.

[0306] The glass-like polymer can be in any physical form. In an embodiment, reactor pellets are used, which are defined as pellets of glass-like polymer separated from a polymerization reactor prior to any processing steps. In another embodiment, the glass-like polymer is in the form of pellets formed by melt extrusion. When the glass-like polymer is used for blending with additives, it can be in the physical form mentioned above.

[0307] The components can be blended by any suitable means and are typically blended to provide an intimately mixed composition. For example, they can be blended in a static mixer, a batch mixer, an extruder, or a combination thereof sufficient to achieve adequate dispersion of the additives in the glass-like polymer.

[0308] The mixing step may include first performing dry blending using, for example, a tumble blender, wherein the glass-like polymer and the additive are first brought into contact without intimate mixing, and then melt blending may be performed in an extruder. Another method of blending the components is to melt blend the glass-like polymer pellets with the additive directly in an extruder or batch mixer. A "masterbatch" method may also be included, wherein the final additive concentration is achieved by combining the glass-like polymer with an appropriate amount of additive that has previously been prepared at a higher additive concentration. The mixing step may occur as part of a processing method for manufacturing an article, for example, on an extruder or injection molding machine or a blown film production line or a fiber production line.

[0309] In a preferred aspect of the present disclosure, the glass-like polymer and the additive are "melt blended" in an apparatus such as an extruder (single screw or twin screw) or a batch mixer. The glass-like polymer can also be "dry blended" with the additive using a roller, a double cone blender, a ribbon blender or other suitable blender. In yet another embodiment, the glass-like polymer and the additive are blended by a combination of methods, such as a roller followed by an extruder. The preferred method of blending includes a final stage of blending as part of the article manufacturing step, such as in an extruder for melting and transferring the composition (for molding steps such as injection molding or blow molding). This can include injecting the additive directly into the extruder either before or after the glass-like polymer is completely melted. Extrusion technology for polymers can be referenced, for example, in PLASTICS EXTRUSIONTECHNOLOGY 26-37 (edited by Friedhelm Hensen, Hanser Publishers, 1988).

[0310] In another aspect of the present disclosure, the compositions can be blended in solution by any suitable means using a solvent that dissolves the components to a significant degree. Blending can occur at any temperature or pressure where the additives and glass-like polymer remain in solution. In the case of a solution process, the additives are added directly to the finishing train rather than being added to the dry glass-like polymer in a separate blending step.

[0311] Thus, in the case of the manufacture of articles using a process involving an extruder, such as injection molding or blow molding, any means of combining the glass-like polymer and the additive to achieve the desired composition can be equivalent to achieving a fully formulated pre-blended pellet, since the formation process includes remelting and mixing of the raw materials; example combinations include glass-like polymer pellets and additives, glass-like polymer pellets and additives, glass-like polymer pellets and pre-blended pellets, and simple blending of glass-like polymer pellets and pre-blended pellets. Here, "pre-blended pellets" means pellets that contain a certain concentration of additives and a combination of glass-like polymers. However, in compression molding methods, little mixing of the molten components occurs, and pre-blended pellets are more preferred than simple blends of the component pellets (or pellets) and additives. Those skilled in the art will be able to determine the appropriate procedure for blending the glass-like polymer to balance the need for intimate mixing of the component ingredients with the desire for process economy.

[0312] Products

[0313] Additional aspects of the present invention relate to articles comprising the glass-like polymers, sulfurized glass-like polymers, or compositions of the present disclosure.

[0314] The article can be an extruded article, a molded article, a hose, a sheet, a film, a jacket, or a foam. For example, the article includes, but is not limited to, extruded articles such as self-sealing weatherseals, non-self-sealing weatherseals, building profiles, etc.; molded articles such as seals, gaskets, etc.; hoses such as air hoses, heating hoses, garden hoses, industrial hoses, etc.; sheets such as roofing panels; films; jackets such as cable jackets, or foams.

[0315] Example

[0316] Example 1 - Synthesis of diboronic ester dicyclopentene (DBDCP) crosslinking agent

[0317] The diboronate dicyclopentene (DBDCP, boron-containing monomer, compound 1) crosslinker was synthesized according to Scheme 1:

[0318]

[0319] Scheme 1: Synthesis of 1 from commercially available 3, 4, and 5 via a two-step sequence.

[0320]

[00155] Synthesis of 4,4'-(1,4-phenylenebis(1,3,2-dioxaborolane-2,4-diyl))bis(butan-1-ol) (2) - To a 1 L single-necked round-bottom flask equipped with a magnetic stir bar under nitrogen atmosphere were added benzene-1,4-diboronic acid 3 (50.0 g, 301.6 mmol), 1,2,6-hexanetriol 4 (85.0 g, 633.5 mmol), anhydrous toluene (500 mL) and p-toluenesulfonic acid (20 mg). The reaction mixture was refluxed at 130 °C using a Dean-Stark trap for 18 hours. The solvent was removed by rotary evaporation. Cold toluene (500 mL) was added to the same flask and the mixture was stirred at room temperature for 30 minutes before being filtered to remove any solids and concentrated brown oil. The solvent in the filtrate was removed by rotary evaporation and dried under vacuum at 60°C for 18 hours to afford a dark yellow oil 2 (86.6 g, 239.2 mmol, 79.3% yield). 1 H NMR (500 MHz, CDCl3) δ7.82 (s, 4H), 4.59 (t, 2H), 4.44 (t, 2H), 3.96 (t, 2H), 3.68 (t, 4H), 1.80-1.40 (m, 12H). 1 H NMR data exclude those labile in -OH groups.

[0321] (1,4-phenylenebis(1,3,2-dioxaborolane-2,4-diyl))bis(butane-4,1-diyl)bis(cyclopent-3-ene-1-carboxylate) (1) - Under nitrogen atmosphere, to a 250 mL single-necked round-bottom flask equipped with a magnetic stir bar was added 4,4'-(1,4-phenylenebis(1,3,2-dioxaborolane-2,4-diyl))bis(butan-1-ol) 2 (16.0 g, 46.4 mmol), 3-cyclopentene-1-carboxylic acid 5 (10.9 g, 97.4 mmol), anhydrous toluene (150 mL) and p-toluenesulfonic acid (20 mg). The reaction mixture was refluxed at 130 ° C for 18 hours using a Dean-Stark trap. After cooling to room temperature, the reaction mixture was filtered to remove floating solids in the solution. The solvent in the collected filtrate was removed by rotary evaporation to give 1 (25.0 g, 45.4 mmol, 97.9% yield) as a dark yellow oil. 1 H NMR (500MHz, CDCl3) δ7.84(s,4H),5.68(m,4H),4.59(m,2H),4.45(m,2H),4. 15(t,2H),3.96(t,2H),3.69(m,2H),3.14(m,2H),2.67(m,8H),1.64(m,12H).

[0322] Example 2 - Glass-like polymer (CPR-V1)

[0323] The Ru catalyst (dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II) (M206), 20 mg, 0.0214 mmol) was dissolved in 2 mL of DCM. The resulting solution (274 microliters, 0.00293 mmol of catalyst) was added to a reaction mixture consisting of a boron-containing monomer (4.04 g, 58.7 mmol) and cyclopentene (20 g, 294 mmol) cooled to -35°C. The cyclopentene was homemade and obtained by depolymerization of polypentene (see WO2021 / 242636) [>99.9% purity]. The mixture was stirred for 2 hours while slowly warming to 25°C. Then, a few drops of ethyl vinyl ether were added and the mixture was diluted with dichloromethane (100 mL). The product was precipitated by adding isopropanol (300 mL) containing BHT (1 g) and washed twice with isopropanol (50 mL each) and then dried in an oven at 55° C. for 3 hours. The product was isolated as a solid material (12.73 g, 53% yield). 1 H NMR analysis of cyclopentene:boron-containing monomer incorporation (145:1). cis / trans 20:80. GPC-ID: Mw 345 kDa, PDI 2.30.

[0324] The product (CPR-V1) is easily converted back to the monomer in high yield and selectivity.The method for depolymerizing the glass-like polymer is the same as that used to depolymerize polypentene.

[0325] Example 3 - Glass-like polymer (CPR-V2)

[0326] The Ru catalyst (dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II) (M206), 25 mg, 0.0268 mmol) was dissolved in 2 mL of DCM. The resulting solution (274 microliters, 0.0037 mmol of catalyst) was added to a reaction mixture consisting of a boron-containing monomer (20 g, 291 mmol) and cyclopentene (20 g, 294 mmol) cooled to -35 ° C. Cyclopentene was homemade and obtained from the depolymerization of polypentene [> 99.9% purity]. The mixture was stirred for 2 hours while slowly warming to 25 ° C. Then, a few drops of ethyl vinyl ether were added and the mixture was diluted with dichloromethane (100 mL). The product was precipitated by adding isopropanol (300 mL) containing BHT (1 g) and washed twice with isopropanol (50 mL each) and then dried in an oven at 55° C. for 3 hours. The product was isolated as a solid material (13.0 g, 33% yield). 1 H NMR analysis of cyclopentene:boron-containing monomer incorporation (29:1). cis / trans 20:80. GPC-ID: Mw 407 kDa, PDI 1.89.

[0327] The product (CPR-V2) is easily converted back to the monomer in high yield and selectivity.The method for depolymerizing the glass-like polymer is the same as that used to depolymerize polypentene.

[0328] Thermal behavior

[0329] DSC was used to measure the Tg (glass transition temperature), Tm (melting point), and heat of fusion (ΔHm) of polypentene homopolymer (CPR) and two glass-like polymers (CPR-V1 and CPR-V2) at a heating rate of 10°C / min. The results are shown in Table 1.

[0330] Table 1. Thermal properties of CPR and glass-like polymers (CPR-V1 and CPR-V2)

[0331]

[0332]

[0333] *The cis / trans molar ratio in CPR is 20 / 80.

[0334] Rheological response

[0335] The dynamic mechanical thermal analysis (DMTA) data of the CPR homopolymer and the glassy polymers are shown in Figure 1 where the temperature ramp was carried out at a heating rate of 2 °C / min. Above the melting temperature (marked by a sharp drop in modulus), the modulus of the CPR homopolymer showed a typical steady modulus drop and a crossover temperature above which G’ became less than G” (and tanδ > 1), indicating that the polymer lost its elasticity and became more “liquid-like”. This crossover was not observed in the glassy polymer samples, indicating that the samples maintained high elasticity up to a temperature of 150 °C. The results of G’ and tanδ at 150 °C are also shown in Table 2.

[0336] Table 2

[0337] Example name G'(kPa) Tanδ CPR 147 1.4 2 CPR-V1 495 0.36 3 CPR-V2 693 0.33

[0338] Figure 2 Additional evidence of network formation is provided in Figure 2 which shows the dynamic frequency sweep (DFS) measured at 50 °C of the CPR homopolymer and the glassy polymers CPR-V1 and CPR-V2. The homopolymer showed a conventional G’ and G” crossover, a G’ < G” relationship and a viscosity plateau at low frequencies corresponding to the zero shear viscosity, which corresponded to the relaxation process of the entangled polymer melt. The low frequency elastic modulus of the glassy polymer samples was one to two orders of magnitude higher than that of the homopolymer. This indicated the solid-like behavior in the glassy polymers. However, the glassy polymer samples could be reprocessed at temperatures above the melting temperature. As -3 shown in

[0339] Tensile properties

[0340] The CPR homopolymer and the glassy polymer samples were compression molded into dog-bone shaped samples (0.3 mm × 2 mm × 7 mm) in a hot press preheated at 80 °C. Tensile and hysteresis tests were carried out by uniaxial stretching at a linear strain rate of 100 μm / s at 25 °C in a solid analysis device (RSA-G2, TA Instruments). Two groups of samples were analyzed. The first group was the uncured samples. In the second group, 100 phr of the CPR or the glassy polymer was mixed with sulfur (0.5 phr), zinc stearate (0.5 phr), diphenyl guanidine (DPG, 0.2 phr) and N-cyclohexyl-2-benzothiazole-sulfenamide (CBS, 0.2 phr) and vulcanized at 150 °C for 2 hours. Figure 3(a) shows that the incorporation of DBDCP into uncured polypentene results in elastic behavior (ie, CPR-V1 and CPR-V2), and the tensile strength increases with increasing levels of incorporated DBDCP. Figure 4 It is shown that CPR homopolymers and glassy polymers can be cured with sulfur at 150°C. The final elastic modulus (G') of the cured samples increases with increasing DBDCP levels in the copolymers. Figure 3 As shown in (b), the vulcanization of the three samples enhances their elastic behavior. The elastic strength of the glassy polymer is higher than that of the CPR homopolymer. The tensile stress data at 1000% strain for the unvulcanized and vulcanized samples are summarized in Table 3.

[0341] Table 3

[0342]

[0343] The curing kinetics of CPR homopolymer and glass-like polymers CPR-V1 and CPR-V2 measured at 150 °C are shown in Figure 4 All samples contained sulfur (0.5 phr), zinc stearate (0.5 phr), diphenylguanidine (DPG, 0.2 phr), and N-cyclohexyl-2-benzothiazole-sulfenamide (CBS, 0.2 phr) in addition to 100 phr of CPR, CPR-V1, or CPR-V2.

[0344] Other implementation plans

[0345] It should be understood that although the application has been described in conjunction with its detailed description, the foregoing description is intended to illustrate rather than limit the scope of the 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

1. A glass-like polymer based on a ring-opened polyolefin of cyclopentene, wherein the ring-opened polyolefin based on cyclopentene is cross-linked with a compound (1), wherein the compound (1) contains at least one reversible borate moiety or a derivative thereof and at least two cycloolefin groups; and a reversible borate moiety or a derivative thereof is present between any two cycloolefin groups in the compound (1); The derivative of the borate moiety refers to a moiety in which oxygen in the borate moiety is replaced by another element of the sixth main group, for example, sulfur.

2. The glass-like polymer according to claim 1, wherein the reversible borate moiety or its derivative has a structure of formula (I): wherein each Q is independently an element of the sixth main group, or oxygen or sulfur.

3. The glass-like polymer according to claim 2, wherein the -QBQ- moiety in formula (I) forms, together with 2 to 5 carbon atoms, a boron-containing ring having 5 to 8 ring members, preferably, together with 2 or 3 carbon atoms, a boron-containing ring having 5 or 6 ring members, and the boron-containing ring is optionally fused with another ring to form a fused ring system; or two -QBQ- moieties share one B atom and form a spiro ring.

4. The glass-like polymer according to claim 3, wherein the boron-containing ring has the following structure: The fused ring system containing the boron-containing ring has the following structure: or two -QBQ- moieties share one B atom and form a spiro ring; wherein A is a ring having 5 to 10 ring members and wherein each Q is independently an element of the VI main group, or oxygen or sulfur.

5. The glass-like polymer according to any one of claims 1 to 4, wherein compound (1) contains 1 to 3 reversible borate moieties or derivatives thereof and 2 to 4 cycloolefin groups; or compound (1) contains 1 or 2 reversible borate moieties or derivatives thereof and 2 or 3 cycloolefin groups.

6. The glass-like polymer according to any one of claims 1 to 5, wherein compound (1) is selected from at least one compound having the following structure: in: Each R1 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; or two -QBQ- moieties share one B atom and form a spiro ring; OP is a cycloolefin 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 glass-like polymer according to claim 6, wherein the variables in the compounds of formulae (A) to (H) have the following definitions: each R1 is independently a direct bond or a divalent hydrocarbon group having 1 to 12 carbon atoms, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or one or more non-adjacent carbon atoms in the divalent hydrocarbon group may be optionally replaced by -(CO)-O- and / or CO; Each R2 is independently a direct bond or a linear or branched hydrocarbon group having 1 to 12 carbon atoms; or a C4-C8-cycloalkyl, C5-C 10 -cycloalkenyl, C6-C 10 Aryl, C1-C 12 Alkyl-C6-C 10 Aryl, C6-C 10 Aryl-C6-C 10 Aryl, C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, C4-C 10 Heterocycloalkyl, C4-C 10 Heterocycloalkenyl, C4-C 10 Heteroaryl or C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein the hydrocarbon group and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or the hydrocarbon group and the C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may be optionally replaced by -(CO)-O- and / or CO and wherein the heterocycloalkyl, heterocycloalkenyl and heteroaryl groups contain 1 to 3 heteroatoms selected from N, O and S; and wherein the valence of R2 corresponds to the value of n; or two -QBQ- moieties share one B atom and form a spirocycle; OP is a cycloolefin 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 glass-like polymer according to claim 6 or 7, wherein Each R1 is independently a direct bond or a C1-C 12 Alkylene, which may be optionally interrupted by one or more non-adjacent oxygen atoms, and / or C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO; and Each R2 is independently a direct bond, a divalent or trivalent C1-C 12 Alkyl, divalent or trivalent C4-C8-cycloalkyl, divalent or trivalent C5-C 10 -cycloalkenyl, divalent or trivalent C6-C 10 Aryl, divalent or trivalent C1-C 12 Alkyl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C6-C 10 Aryl, divalent or trivalent C6-C 10 Aryl-C1-C 12 Alkylene-C6-C 10 Aryl, divalent or trivalent C4-C 10 Heterocycloalkyl, divalent or trivalent C4-C 10 Heterocycloalkenyl, divalent or trivalent C4-C 10 Heteroaryl, divalent or trivalent C4-C 10 Heteroaryl-C4-C 10 Heteroaryl, wherein heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1 to 3 heteroatoms selected from N, O and S, wherein the divalent or trivalent C1-C 12 Alkyl and C1-C 12 The alkylene group may be optionally interrupted by one or more non-adjacent oxygen atoms and / or a divalent or trivalent C1-C 12 Alkyl and C1-C 12 One or more non-adjacent carbon atoms in the alkylene group may optionally be replaced by -(CO)-O- and / or CO.

9. The glass-like polymer according to any one of claims 1 to 8, wherein the cycloolefin group in compound (1) is selected from 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, cyclopentene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbornene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethylnorbornene carboxylate, and norbornene-exo-2,3-carboxylic anhydride groups, preferably cyclopentene groups.

10. The glass-like polymer according to any one of claims 1 to 9, wherein compound (1) is (1,4-phenylenebis(1,3,2-dioxaborolane-2,4-diyl))bis(butane-4,1-diyl)bis(cyclopent-3-ene-1-carboxylate).

11. The glass-like polymer according to any one of claims 1 to 10, wherein the molar amount of the structural portion derived from compound (1) is in the range of about 0.5 mol% to about 15 mol%, or about 0.6 mol% to about 10 mol%, based on the total molar amount of the repeating units of the cyclopentene-based ring-opening polyolefin.

12. The glass-like polymer according to any one of claims 1 to 11, wherein the glass-like polymer is formed from cyclopentene and compound (1), or the glass-like polymer is formed from cyclopentene, compound (1) and other comonomers.

13. The glass-like polymer according to any one of claims 1 to 12, wherein the tensile stress of the glass-like polymer at 1000% strain is at least 30 times, or at least 40 times, that of a pure cyclopentene-based ring-opening polyolefin.

14. The glass-like polymer according to any one of claims 1 to 13, wherein the glass-like polymer has an elastic modulus of at least about 180% or at least about 250% of the elastic modulus of a pure cyclopentene-based ring-opening polyolefin as measured by dynamic thermomechanical analysis at a heating rate of 2°C / min at 150°C.

15. A method for preparing a glass-like polymer according to any one of claims 1 to 14, comprising polymerizing cyclopentene, the compound (1) defined in any one of claims 1 to 10, and an optional comonomer via ring-opening metathesis polymerization to form a glass-like polymer in one step.

16. The compound (1) as defined in any one of claims 1 to 14, wherein the compound (1) contains at least one reversible boronate moiety or a derivative thereof and at least two cycloolefin groups; and a reversible borate ester structure moiety or a derivative thereof exists between any two cycloolefin groups in the compound (1); The derivative of the borate moiety refers to a moiety in which oxygen in the borate moiety is replaced by another element of the sixth main group, such as sulfur.

17. A method for preparing the compound (1) as defined in any one of claims 1 to 10, comprising: (i) reacting a B-containing compound with a polyol-type compound to form a compound containing at least one reversible boronate moiety or derivative thereof and one hydroxyl group; (ii) reacting the compound containing at least one reversible boronate moiety or a derivative thereof and one hydroxyl group obtained in step (i) with a compound containing a carboxyl group and a cycloolefin group to form compound (1), wherein the B-containing compound is selected from compounds having a structure of B(QR)3 and compounds having at least two B(QR)2 groups, wherein R is selected from H or C1-C6-alkyl and each Q is independently an element of the sixth main group, or oxygen or sulfur; and The polyol type compound has three hydroxyl groups and two of them can form a reversible borate ester structure part or a derivative thereof with the B-containing compound, or the polyol type compound has one hydroxyl group and one oxirane ring or oxetane ring.

18. A sulfurized glass-like polymer formed by sulfurizing the glass-like polymer defined in any one of claims 1 to 14.

19. The cured glassy polymer of claim 18, wherein the cured glassy polymer has a tensile stress at 1000% strain of at least about 110%, or at least about 120%, of the tensile stress at 1000% strain of the cured pure cyclopentene-based ring-opening polyolefin.

20. A composition comprising the glassy polymer according to any one of claims 1 to 14 or the sulfurized glassy polymer according to claim 18 or 19 and at least one additive.

21. An article comprising the glass-like polymer according to any one of claims 1 to 14 or the composition according to claim 20.

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