Reversible cross-linked polyolefin elastomer and preparation method thereof

Abstract

The invention belongs to the field of olefin polymers, and relates to a reversible cross-linked polyolefin elastomer and a preparation method thereof. The reversible cross-linked polyolefin elastomer is a reversible cross-linked polyolefin elastomer in which a cross-linked network is formed through three non-covalent bonds, namely hydrogen bonds, ionic bonds and coordinate bonds, and the hydrogen bonds and the cross-linked bonds account for 0.1-85% by taking the sum of the three non-covalent bonds, namely the hydrogen bonds, the ionic bonds and the coordinate bonds as 100%; the ionic crosslinking bond accounts for 0.5-90%; and the coordination crosslinking bond accounts for 9-99%. Compared with a reversible cross-linked polyolefin elastomer in the prior art, the reversible cross-linked polyolefin elastomer prepared by the invention contains hydrogen bonds, ionic bonds and coordinate bonds at the same time, and a synergistic effect is generated through combination of reversible cross-linked interaction of the coordinate bonds, the hydrogen bonds and the ionic bonds; therefore, the material has excellent physical and mechanical properties and also has recoverability and self-repairability.

Description

Technical Field

[0001] The present invention belongs to the field of olefin polymers, and specifically, relates to a reversible crosslinked polyolefin elastomer and a preparation method thereof. Background Art

[0002] The polyolefin elastomer obtained by copolymerizing ethylene with α-olefin is a special type of polyolefin material with excellent properties and wide applications. However, the polyolefin elastomer has a low glass transition temperature and is prone to molecular chain slippage under external force. It is necessary to crosslink by chemical bond vulcanization to transform the linear polymer into a three-dimensional network structure, endowing the material with high elasticity and mechanical strength. However, the crosslinking bonds in the vulcanized crosslinked network formed by high-temperature vulcanization are irreversible covalent bonds and are difficult to recycle. If an irreversible chemical vulcanization crosslinked network is replaced by a reversible crosslinked network, while improving the properties such as strength, toughness, and creep resistance of the polymer, the material is endowed with self-healing and repeat processing properties, which can extend the service life of the product and reduce waste and environmental pollution.

[0003] In the prior art, by forming one or two dynamic bonds between polymer chains, a polyolefin elastomer network containing a single reversible crosslinking bond or a polyolefin elastomer network containing a double reversible crosslinking bond can be formed. Due to different dynamic bond structures, their bond energies and dissociation temperatures are also different. Introducing different dynamic bonds into the polyolefin elastomer can form polyolefin elastomer networks with different strengths.

[0004] Polyolefin elastomer networks containing reversible crosslinking bonds mainly include: (1) Crosslinked polyolefin elastomer networks containing dynamic covalent bonds, mainly formed by the reaction of organic small molecules with functionalized side groups to form dynamic covalent bonds such as ester bonds, borate ester bonds, and imine bonds, constituting a dynamic crosslinked network. Adding a transesterification catalyst zinc acetylacetonate and a compound with an epoxy group to maleic anhydride grafted ethylene / octene copolymer can prepare a crosslinked polyolefin elastomer network containing dynamic ester bonds, or introducing borate ester bonds into ethylene / 1-octene copolymer, such as by adding a radical initiator, 1,4-benzenediboronic acid, and α-thioglycerol, and extruding and reacting at 190 °C through a twin-screw extruder to prepare a crosslinked polyolefin elastomer network containing borate ester bonds. See: CN114854162A, CN113896998B, CN114456530A, Macromolecules 2021,54,10381. However, the bond energy of the above dynamic covalent bonds is relatively low, resulting in the difficulty of meeting some usage requirements for the high-temperature resistance of the polymer crosslinked network. (2) Crosslinked polyolefin elastomer networks containing dynamic non-covalent bonds, mainly preparing a single crosslinked polymer network by forming hydrogen bonds, ionic bonds, or coordination bonds between side group-functionalized polyolefin elastomer molecules. For example, in a terpolymer of ethylene-propylene-diene rubber grafted with methacrylic acid, a single crosslinked network formed by hydrogen bonds has a tensile strength of 6.8 MPa and an elongation at break of 650%, see Macromol.Res.2016,24,261; in a copolymer of ethylene / 1-hexene / eugenol derivative, a single crosslinked network formed by coordinating bonds through the coordination of side group catechol groups with metals such as Cu(II), Ti(IV), Mn(II), Fe(III), Fe(II), Zn(II), V(III), see Angew.Chem.Int.Ed.2020,59,7953; in a maleic anhydride grafted polyolefin elastomer, adding solid zinc chloride or aluminum chloride and mixing can obtain a single coordination bond polyolefin elastomer network, see CN101402709B. (3) After reacting a functionalized ethylene / ethylidene norbornene / undecenoic acid terpolymer with an organic base, adding citric acid and ferric chloride to form a double reversible crosslinked polyolefin network of coordination bonds and hydrogen bonds, but a certain amount of citric acid is required in the preparation of this elastomer network, resulting in the decarboxylation of citric acid and the reduction of Fe 3+ to Fe 2+ under ultraviolet irradiation, changing the material network structure and reducing the physical and mechanical properties of the material, see Angew.Chem.Int.Ed.2020,59,395.

[0005] In summary, in the prior art, the mechanical properties of the reversibly crosslinked polyolefin elastomer network have been improved to a certain extent, but the improvement amplitude is limited, the heat resistance is not high enough, and the stability of the crosslinked network is relatively poor, which limits its scope of use. There has been no publicly reported polyolefin elastic network material with three different reversibly crosslinked bonds coexisting in the prior art. Summary of the Invention

[0006] To solve the problems existing in the prior art, the present invention provides a reversibly crosslinked polyolefin elastomer and a preparation method thereof. The reversibly crosslinked polyolefin elastomer contains hydrogen bonds, ionic bonds and coordination bonds at the same time. Through the combination of the reversible crosslinking interactions of coordination bonds with hydrogen bonds and ionic bonds, a synergistic effect is produced, so that the material has more excellent physical and mechanical properties while taking into account recyclability and self-healing properties.

[0007] To achieve the above object, a first aspect of the present invention provides a reversibly crosslinked polyolefin elastomer, which is a reversibly crosslinked polyolefin elastomer network formed by three non-covalent bonds of hydrogen bonds, ionic bonds and coordination bonds.

[0008] According to the present invention, preferably, based on the total crosslinking bonds of the three non-covalent bonds of hydrogen bonds, ionic bonds and coordination bonds being 100%, the hydrogen bond crosslinking bonds account for 0.1-85%, preferably 0.2-80%, more preferably 0.5-75%; the ionic crosslinking bonds account for 0.5-90%, preferably 1-80%, more preferably 2-70%; the coordination crosslinking bonds account for 9-99%, preferably 15-98%, more preferably 20-97%.

[0009] According to the present invention, preferably, the hydrogen bond crosslinking bonds are formed by at least one of carboxyl groups, hydroxyl groups, amino groups and sulfonic acid groups, and are preferably formed by carboxyl groups and / or hydroxyl groups.

[0010] According to the present invention, preferably, the ionic crosslinking bonds are formed by the interaction of at least one negative ion of carboxylate ions, sulfonate ions and halogen ions with nitrogen positive ions.

[0011] According to the present invention, preferably, the coordination crosslinking bonds are formed by coordination of carboxylate ions and / or sulfonate ions with transition metal ions. The transition metal is preferably at least one of titanium, vanadium, chromium, manganese, iron, nickel, copper and zinc, and more preferably at least one of manganese, iron, nickel, copper and zinc.

[0012] According to the present invention, preferably, the functionalized polyolefin elastomer includes ethylene structural units, α-olefin structural units and functionalized norbornene structural units.

[0013] According to the present invention, preferably, based on the total molar number of all structural units in the functionalized polyolefin elastomer, the molar content of the ethylene structural unit is 40 to 94%, preferably 45 to 90%, more preferably 55 to 88%; the molar content of the α-olefin structural unit is 5 to 60%, preferably 7 to 50%, more preferably 10 to 41%; the molar content of the functionalized norbornene structural unit is 0.1 to 8.0%, preferably 0.2 to 6.0%, more preferably 0.3 to 4.5%.

[0014] Preferably, the α-olefin is selected from at least one of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene.

[0015] Preferably, the functional group of the functionalized norbornene is selected from at least one of a carboxyl group, an amino group, a hydroxyl group, and a sulfonic acid group.

[0016] The second aspect of the present invention provides a method for preparing the reversible crosslinked polyolefin elastomer, comprising the following steps:

[0017] (1) Dissolve the functionalized polyolefin elastomer in a first solvent to obtain a functionalized polyolefin elastomer solution;

[0018] (2) Dissolve the transition metal compound in a second solvent to obtain a transition metal compound solution, mix it with the functionalized polyolefin elastomer solution obtained in step (1), and then add a base for reaction; alternatively, dissolve the transition metal compound and the base in the second solvent to obtain a mixed solution, mix it with the functionalized polyolefin elastomer solution obtained in step (1), and then carry out the reaction;

[0019] (3) After the reaction is completed, remove the solvent and dry to a constant weight to obtain the reversible crosslinked polyolefin elastomer.

[0020] According to the present invention, preferably, in the reaction system, based on 1 equivalent of the functional group of the functionalized polyolefin elastomer, the equivalent of the transition metal compound is 0.01 to 0.55, preferably 0.03 to 0.50, more preferably 0.05 to 0.45, and the equivalent of the base is 0.1 to 1.1, preferably 0.2 to 1.0, more preferably 0.3 to 0.99.

[0021] According to the present invention, preferably, the first solvent is an organic solvent, preferably selected from at least one of alkanes, cycloalkanes, halogenated alkanes, aromatic hydrocarbons, and ethers, more preferably selected from alkanes with C5 to C 20 of alkanes, cycloalkanes with C5 to C 20 of cycloalkanes, halogenated alkanes with C1 to C 20 of halogenated alkanes, aromatic hydrocarbons with C6 to C 20 of aromatic hydrocarbons, and ethers with C4 to C 20At least one of ethers, and further preferably at least one selected from pentane, hexane, heptane, octane, cyclopentane, methylcyclopentane, cyclohexane, dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, tetrahydrofuran, benzene, toluene, ethylbenzene, and xylene.

[0022] In the present invention, the concentration of the functionalized ethylene / α-olefin copolymer elastomer solution is related to the molecular weight of the polymer. Generally, the concentration of the functionalized polyolefin elastomer solution is 5 to 200 g / L, preferably 8 to 180 g / L, and more preferably 10 to 150 g / L.

[0023] According to the present invention, preferably, the second solvent is selected from at least one of water, alcohols, alkanes, cycloalkanes, halogenated alkanes, aromatic hydrocarbons, ethers, ketones, aldehydes, and esters, and is preferably selected from at least one of water, C1-C5 alcohols, C5-C 20 alkanes, C5-C 20 cycloalkanes, C1-C 20 halogenated alkanes, C4-C 20 ethers, C3-C 20 ketones, C2-C 20 aldehydes, and C2-C 20 esters, and more preferably selected from at least one of water, methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, dichloromethane, chloroform, dichloroethane, trichloroethane, tetrahydrofuran, diethyl ether, acetone, and methyl ethyl ketone.

[0024] In the present invention, when ensuring the complete dissolution of the transition metal compound, the concentration of the solution containing the transition metal compound has little influence. Different solvents have different solubilities and different concentrations of the metal compounds used. Generally, the concentration of the transition metal compound is 0.1 to 4.0 g / L, preferably 0.15 to 3.5 g / L, and more preferably 0.2 to 3.0 g / L.

[0025] According to the present invention, preferably, when adding the base later, the base is added in the form of an alkali solution, and the solvent of the alkali solution is at least one of water, alkanes, cycloalkanes, halogenated alkanes, aromatic hydrocarbons, ethers, and ketones, and is preferably water, C5-C 20 alkanes, C5-C 20 cycloalkanes, C1-C 20 halogenated alkanes, C6-C 20 aromatic hydrocarbons, C4-C 20 ethers, and C3-C 20 ketones, and more preferably at least one of water, pentane, hexane, heptane, octane, cyclopentane, methylcyclopentane, cyclohexane, dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, tetrahydrofuran, benzene, toluene, ethylbenzene, and xylene.

[0026] In the present invention, under the condition that the base can be completely dissolved, the concentration of the organic base solution has little influence. Different types of solvents have different solubilities, and different concentrations of the organic base are used. Generally, the concentration of the base is 0.1 - 30 g / L, preferably 0.5 - 20 g / L, and more preferably 0.6 - 15 g / L.

[0027] According to the present invention, preferably, the transition metal compound is selected from at least one of titanium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, nickel compounds, copper compounds, and zinc compounds, and more preferably at least one of manganese compounds, iron compounds, nickel compounds, copper compounds, and zinc compounds.

[0028] Preferably, the manganese compound is selected from one or more of manganese fluoride, manganese chloride, manganese chloride monohydrate, manganese chloride tetrahydrate, manganese perchlorate hexahydrate, manganese bromide, manganese iodide, manganese sulfate, manganese sulfate monohydrate, manganese sulfate tetrahydrate, manganese sulfide, manganese nitrate, manganese nitrate tetrahydrate, manganese nitrate hexahydrate, manganese nitrite, manganese phosphate, manganese phosphate monohydrate, manganese dihydrogen phosphate, manganese dihydrogen phosphate dihydrate, manganese hypophosphite monohydrate, manganese silicate, manganese carbonate, manganese hydroxide, manganese borate, manganese acetate, manganese acetate dihydrate, manganese oxalate, manganese oxalate dihydrate, manganese citrate, manganese cyclohexanebutyrate, manganese naphthenate, manganese stearate, manganese neodecanoate, manganese gluconate, manganese stearate, manganese 2-ethylhexanoate, tris(2,2,6,6-tetramethyl-3,5-heptanedionate) manganese, manganese trifluoromethanesulfonate, manganese disodium ethylenediaminetetraacetate, decacarbonyldimanganese, pentacarbonylbromomanganese, bis(cyclopentadienyl) manganese, bis(tetramethylcyclopentadienyl) manganese, 2-methylcyclopentadienyltricarbonyl manganese, manganese acetylacetonate, bis(isopropylcyclopentadienyl) manganese, tricarbonylcyclopentadienyl manganese, bis(2,4-pentanedionato) manganese dihydrate, bis(hexafluoroacetylacetonato) manganese trihydrate, bis(trifluoro-2,4-pentanedionato) manganese, bis(trifluoromethanesulfonyl) imide manganese, bis(pentamethylcyclopentadienyl) manganese, and preferably at least one of manganese chloride, manganese chloride monohydrate, manganese chloride tetrahydrate, manganese carbonate, manganese hydroxide, manganese acetate, manganese acetate dihydrate, and manganese acetylacetonate.

[0029] Preferably, the iron compound is selected from one or more of iron chloride, ferrous chloride, iron bromide, ferrous bromide, iron fluoride, iron iodide, iron perchlorate, iron nitrate, iron nitrate nonahydrate, iron pyrophosphate, iron phosphate, iron phosphate dihydrate, lithium iron phosphate, iron sulfate, ammonium ferrous sulfate hexahydrate, iron 2-ethylhexanoate, ferrocene-1,1'-dicarboxylic acid, iron benzoyl sulfonate, sodium iron ethylenediaminetetraacetate, iron acetate, iron acetate monohydrate, iron acetate tetrahydrate, iron oxalate pentahydrate, sodium iron oxalate trihydrate, iron acrylate, iron naphthenate, iron tartrate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)iron, iron stearate, ferrocene, iron tert-butoxide complex, and iron acetylacetonate, and preferably at least one of iron chloride, ferrous chloride, ferrous chloride tetrahydrate, iron bromide, ferrous bromide, iron phosphate, iron phosphate dihydrate, iron oxalate pentahydrate, and iron acetylacetonate.

[0030] Preferably, the nickel compound is preferably one or more of nickel fluoride, nickel chloride, nickel chloride hexahydrate, nickel chloride ethylene glycol dimethyl ether complex, nickel chloride dimethoxyethane complex, nickel bromide, nickel bromide trihydrate, nickel iodide, nickel bromide 2-methoxyethyl ether complex, nickel sulfate, nickel sulfate heptahydrate, nickel sulfite, nickel ammonium sulfate, nickel ammonium sulfate hexahydrate, nickel sulfamate, nickel sulfamide acid tetrahydrate, nickel 2-amino-5-methylbenzenesulfonate, nickel nitrate, nickel nitrate hexahydrate, nickel nitrite, nickel phosphate, nickel hypophosphite, nickel carbonate, nickel silicate, nickel borate, nickel borate hydrate, nickel tetrafluoroborate hexahydrate, nickel formate, nickel acetate, nickel acetate tetrahydrate, nickel oxalate, nickel oxalate dihydrate, nickel citrate, nickel citrate hydrate, methylallyl nickel chloride dimer, nickel lactate, nickel stearate, nickel benzoate, nickel trifluoroacetate, nickel citrate octanoate, nickel benzenesulfonate, nickel naphthenate, nickel trifluoromethanesulfonate, nickel p-toluenesulfonate, nickel cyclohexanebutyrate, nickel acetylacetonate, bis(2,4-pentanedionato)nickel, dichloro bis(trimethylphosphine)nickel, nickel glycolate, nickel disodium ethylenediaminetetraacetate, nickel 2-ethylhexanoate, nickel diethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel hydroxide, nickel trifluoroacetylacetonate, tetrakis(triphenylphosphine)nickel, bis(triphenylphosphine)dichloronickel, bis(triphenylphosphine)dibromonickel, bis(triethylphosphine)chloronickel, bis(tributylphosphine)dibromonickel, 1,2-bis(diphenylphosphino)ethane dichloronickel, chlorobis(triphenylphosphine)phenylnickel, hexaamminenickel dichloride, tris(ethylenediamine)nickel dichloride, tris(ethylenediamine)nickel chloride, bis(hexafluoroethylacetone)nickel, bis(N,N”-di-tert-butylacetamidato)nickel, bis(tricyclohexylphosphine)dichloronickel, chlorobis(dicyclohexylphenylphosphino)(2-methylphenyl)nickel, bis[1-(N,N-dimethylamino)-2-propanolato]nickel, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel; more preferably at least one of nickel chloride, nickel chloride hexahydrate, nickel chloride ethylene glycol dimethyl ether complex, nickel chloride dimethoxyethane complex, nickel bromide, nickel bromide trihydrate, nickel iodide, nickel bromide 2-methoxyethyl ether complex, nickel oxalate, nickel oxalate dihydrate, nickel acetate, nickel acetate tetrahydrate, nickel acetylacetonate, bis(2,4-pentanedionato)nickel, dichloro bis(trimethylphosphine)nickel and bis(triphenylphosphine)dichloronickel.

[0031] Preferably, the zinc compound is preferably one or more of zinc fluoride, zinc fluoride tetrahydrate, zinc chloride, zinc perchlorate, zinc perchlorate hexahydrate, zinc bromide, zinc iodide, zinc sulfide, zinc sulfate, zinc sulfate monohydrate, zinc sulfate heptahydrate, zinc phosphate, zinc phosphate tetrahydrate, zinc dihydrogen phosphate, zinc dihydrogen phosphate dihydrate, zinc nitrate, zinc nitrate hexahydrate, basic zinc carbonate, zinc borate, zinc borate trihydrate, zinc tetrafluoroborate, zinc tetrafluoroborate monohydrate, zinc trifluoromethanesulfonate, zinc formate, zinc acetate, zinc acetate dihydrate, zinc trifluoroacetate, zinc oxalate, zinc oxalate dihydrate, zinc acrylate, zinc dimethacrylate, zinc benzoate, zinc 2-ethylhexanoate, zinc naphthenate, zinc undecylenate, zinc gluconate, zinc gluconate dihydrate, zinc lactate, zinc lactate dihydrate, zinc stearate, diethylzinc, zinc L-aspartate, zinc glycinate monohydrate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc acetylacetonate, zinc acetylacetonate monohydrate, zinc ethylenediaminetetraacetate, and zinc ethylenediaminetetraacetate disodium tetrahydrate, and more preferably at least one of zinc chloride, zinc bromide, zinc iodide, zinc sulfide, zinc formate, zinc acetate, zinc acetate dihydrate, zinc oxalate, zinc oxalate dihydrate, and basic zinc carbonate.

[0032] According to the present invention, preferably, the base is ammonia and / or an organic base, and the organic base is selected from nitrogen-containing organic base compounds, preferably at least one of monofunctional, bifunctional, and polyfunctional organic amines, pyridine, substituted pyridine, imidazole, substituted imidazole, thiazole, oxazole, and ammonium hydroxide, and their general formulas are as follows:

[0033]

[0034] In each formula, R 1 -R 7 ,R 9 -R 17 ,R 19 -R 42 ,R 44 -R 54 ,which are the same or different and are each independently selected from H, an alkyl group having 1 to C 20 or an aryl group having 6 to C 20 ; R 8 、R 18 、R 43 are the same or different and are each independently selected from an alkylene group having 1 to 6 carbon atoms or an aryl group having 6 to C 20 .

[0035] Preferably, the organic base is selected from methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, tert-butylamine, isobutylamine, 1-hexylamine, aniline, 2-methylaniline, 2,4,6-trimethylaniline, N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-diisopropylamine, N,N-dibutylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylisopropylamine, N,N-dimethylbutylamine, N,N-dimethyltert-butylamine, N-methyldiethylamine, N,N-diethylpropylamine, N,N-diethylbutylamine, N,N-diethyltert-butylamine, triethylamine, trimethylamine, tripropylamine, triisopropylamine, tributylamine, trioctylamine, ethylenediamine, propylenediamine, pentamethylenediamine, hexamethylenediamine, N-benzyethylenediamine, N-hexyethylenediamine, N-methyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-propylethylenediamine, N,N-dimethylethylenediamine, N-ethyl-N'-methylethylenediamine, N,N-diethylethylenediamine, N,N'-diethyl-1,3-propanediamine, N,N'-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N,N'-triethylethylenediamine, trimethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N-tetramethylethylenediamine, N',N'-dibenzyl-N,N'-dimethylethylenediamine, N,N'-dipropylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N-dimethyl-N',N'-dimethylethyl-1,2-diamine, N,N,N′,N′-tetramethyl-p-phenylenediamine, bis(hexamethylenetriamine), diethylenetriamine, 4-dodecyldiethylenetriamine, N,N-dimethyliminodipropylamine, N,N-diethyldiethylenetriamine, N,N',N”-trihexyldiethylenetriamine, pentamethyldiethylenetriamine, N,N',N”-trimethyldiethylenetriamine, N,N,N',N'-tetraethyldiethylenetriamine, imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-hexylimidazole, 1-benzylimidazole, 1-phenylimidazole, 1-dodecylimidazole, 1-octylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-undecylimidazole, 2-phenylimidazole, 4-methylimidazole, 4-ethylimidazole, 4-propylimidazole, 4-butylimidazole, 4-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2,4-dimethylimidazole, 1,2,4,5-tetramethylimidazole, 1,At least one of 2-dimethylimidazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraamylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetra(decyl)ammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, N,N,N-trimethyl-1-adamantylammonium hydroxide, cetyltrimethylammonium hydroxide, benzethonium hydroxide, triethylmethylammonium hydroxide, benzyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, methyltripropylammonium hydroxide, and trihexyl(tetradecyl)ammonium hydroxide.,

[0036] More preferably, the organic base is selected from at least one of methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, tert-butylamine, isobutylamine, N,N-diisopropylamine, 1-hexylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylisopropylamine, N,N-dimethylbutylamine, N,N-dimethyltert-butylamine, N-methyldiethylamine, N,N-diethylpropylamine, N,N-diethylbutylamine, N,N-diethyltert-butylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, trioctylamine, ethylenediamine, propylenediamine, pentamethylenediamine, hexamethylenediamine, tetramethyl-1,4-butanediamine, tetramethyl-1,6-hexanediamine, imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.,

[0037] According to the present invention, preferably, the dissolution temperature T1 of the functionalized polyolefin elastomer is 10 to 100 °C, preferably 12 to 80 °C, and more preferably 15 to 70 °C.,

[0038] According to the present invention, preferably, the conditions of the reaction include: the reaction temperature T2 is 10 to 100 °C, preferably 12 to 80 °C, and more preferably 15 to 70 °C; the reaction time is 1.5 h to 10 h, preferably 2 h to 8 h, and more preferably 3 h to 7 h.,

[0039] In the present invention, the dissolution temperature T1 and the reaction temperature T2 may be the same or different, and are related to the melting point of the crystalline phase of the functionalized ethylene / α-olefin copolymer elastomer. Generally, it is 10 to 100 °C, preferably 12 to 80 °C, and more preferably 15 to 70 °C.,

[0040] According to the present invention, preferably, the temperature T3 for removing the solvent is 10 to 85 °C, preferably 12 to 70 °C, and more preferably 15 to 60 °C.,

[0041] In the present invention, the temperature T3 for removing the solvent is related to the properties of the solvent used. Generally, T3 is 10 to 85 °C, preferably 12 to 70 °C, and more preferably 15 to 60 °C. A higher temperature is beneficial for the rapid removal of the solvent.,

[0042] According to the present invention, preferably, the method for preparing the functionalized polyolefin elastomer comprises the following steps:

[0043] In the presence of a vanadium-based catalyst, ethylene, an α-olefin, and ethylidene norbornene and / or vinyl norbornene are copolymerized to obtain a polyolefin elastomer, and then a functionalization reaction is carried out by a thiol-ene click reaction method or a hydroboration-oxidation method to obtain the functionalized polyolefin elastomer.

[0044] Preferably, the functionalized group of the functionalized polyolefin elastomer is at least one of a carboxyl group, a hydroxyl group, an amino group, and a sulfonic acid group.

[0045] In the present invention, the functionalized group is located on the side chain of the norbornene structural unit.

[0046] In the present invention, the preparation of the functionalized ethylene / α-olefin / norbornene copolymer elastomer with a side chain containing a functional group can refer to but is not limited to the methods described in Patent CN 202111678188.1 and the published papers Polymer Chemistry, 2021, 12: 6417 and Macromolecules, 2021, 54: 64. Commercially available functionalized polyolefin elastomers with a side chain containing a functional group are also applicable to the present invention.

[0047] The following beneficial invention effects are achieved by the method of the present invention:

[0048] By forming hydrogen bonds between some functional groups, forming ionic bonds between some functional groups and bases, and forming coordination bonds between some functional groups and transition metal compounds in the ethylene / α-olefin / functionalized norbornene copolymer elastomer, a non-covalent reversible crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds, and coordination bonds is prepared. Chemical crosslinking is not required, the preparation method is simple, and the production cost is low.

[0049] In the polymer, a dynamic bond crosslinked network is constructed by combining strong bonds and weak bonds. The weak bonds are the first to break under force and act as "sacrificial bonds" to dissipate a large amount of energy, improving the toughness of the material. The strong bonds are not easily broken and can be used to stabilize the polymer network structure and ensure the integrity of the crosslinked network, achieving the dual effects of strengthening and toughening.

[0050] The prepared non-covalent reversible cross-linked olefin-based polymer has excellent mechanical properties. Compared with polyolefin elastomers without reversible cross-linking bonds, the increase in Young's modulus can reach 5.3 times, the increase in 100% modulus at elongation can reach 2.3 times, the increase in 300% modulus at elongation can reach 13.3 times, the increase in tensile strength can reach 63.3 times, and the increase in fracture energy can reach 16.9 times. Compared with polyolefin elastomers containing a single hydrogen bond cross-linked network, the triple reversible cross-linked polyolefin elastomer network of the present invention has an increase in Young's modulus of up to 3.7 times, an increase in 100% modulus at elongation of up to 1.0 times, an increase in 300% modulus at elongation of up to 4.7 times, an increase in tensile strength of up to 4.9 times, and an increase in fracture energy of up to 20%. Compared with a double reversible cross-linked polyolefin elastomer network composed of two non-covalent bonds, hydrogen bonds and ionic bonds, the triple reversible cross-linked polyolefin elastomer network of the present invention has an increase in Young's modulus of up to 3.9 times, an increase in 100% modulus at elongation of up to 82%, an increase in 300% modulus at elongation of up to 3.8 times, an increase in tensile strength of up to 4.1 times, and an increase in fracture energy of up to 37%.

[0051] The prepared non-covalent reversible cross-linked polyolefin elastomer network has recyclable and self-healing properties.

[0052] Other features and advantages of the present invention will be described in detail in the following specific embodiments section. Specific Embodiments

[0053] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein.

[0054] Mechanical property test method for the multiple reversible cross-linked polyolefin elastomer network: Use a 4×75mm dumbbell-shaped cutter to cut the olefin-based polymer film into specimens, and test the mechanical properties of the material using a universal tensile testing machine (INSTRON3345 type) according to the test method of national standard GB / T 528-2009.

[0055] Example 1

[0056] At 25°C, add 20 mL of a tetrahydrofuran solution containing 51 mg (0.17 eq relative to carboxyl group, 0.21 mol) of NiCl2·6H2O to 50 mL of a tetrahydrofuran solution containing 2.6 g of ethylene / propylene / carboxyl-functionalized ethylidene norbornene copolymer. The content of ethylene structural units in the used terpolymer is 65.1 mol%, the content of propylene structural units is 33.1 mol%, and the content of carboxyl-functionalized ethylidene norbornene structural units is 1.8 mol%. The weight-average molecular weight (M w) is 281 kg·mol -1 , the molecular weight distribution (M w / M n ) is 3.0. Subsequently, a 10 mL tetrahydrofuran solution containing 121 mg (0.96 eq relative to carboxyl group, 1.20 mol) of triethylamine was added to the above-mentioned mixed solution of the polymer and NiCl2·6H2O. After reacting at 25 °C for 4 h, the solvent was removed at room temperature and dried under vacuum to constant weight. A triple non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds was obtained. Among them, the coordination cross-linked bonds accounted for 51%, the ionic cross-linked bonds accounted for 45%, and the hydrogen bond cross-linked bonds accounted for 4%. The obtained reversible cross-linked polyolefin elastomer network was sampled and tested. Its Young's modulus was 11.3 MPa, the 100% elongation stress was 1.8 MPa, the 300% elongation stress was 5.7 MPa, the tensile strength was 19.3 MPa, the elongation at break was 510%, and the fracture energy was 30.8 kJ / m 2 .

[0057] Compared with the polyolefin elastomer without reversible cross-linked bonds described in Comparative Example 1, the triple non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has its Young's modulus increased by 5.3 times, the 100% elongation stress increased by 2.0 times, the 300% elongation stress increased by 13.3 times, the tensile strength increased by 63.3 times, and the fracture energy increased by 17.1 times.

[0058] Compared with the reversible cross-linked polyolefin elastomer network containing a single hydrogen bond described in Comparative Example 2, the non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has its Young's modulus increased by 3.7 times, the 100% elongation stress increased by 80%, the 300% elongation stress increased by 4.7 times, the tensile strength increased by 4.9 times, and the fracture energy increased by 19%.

[0059] Compared with the double reversible cross-linked polyolefin elastomer network containing hydrogen bonds and ionic bonds described in Comparative Example 3, the triple non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has its Young's modulus increased by 3.9 times, the 100% elongation stress increased by 64%, the 300% elongation stress increased by 3.8 times, the tensile strength increased by about 4.1 times, and the fracture energy increased by 37%.

[0060] Example 2

[0061] The reaction process was as described in Example 1, except that: the polymer matrix used was 2.5 g of ethylene / butene / carboxyl-functionalized norbornene, in which the content of ethylene structural units was 83.1 mol%, the content of butene structural units was 15.9 mol%, and the content of carboxyl-functionalized norbornene structural units was 1.0 mol%, and M w was 923 kg·mol -1 , and M w / M n was 2.7. The transition metal salt used was 31 mg (0.17 eq relative to carboxyl, 0.13 mol) of NiCl2·6H2O, and the organic base used was 76 mg (0.99 eq relative to carboxyl, 0.75 mol) of triethylamine. The reaction was carried out at 55 °C for 6 h. The post-treatment method was the same as that in Example 1. A non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds was obtained, in which the coordination cross-linked bonds accounted for 51%, the ionic cross-linked bonds accounted for 48%, and the hydrogen bond cross-linked bonds accounted for 1%. The above-mentioned reversible cross-linked polyolefin elastomer network was sampled and tested. Its Young's modulus was 9.9 MPa, the 100% elongation stress was 2.3 MPa, the 300% elongation stress was 4.1 MPa, the tensile strength was 22.4 MPa, the elongation at break was 750%, and the fracture energy was 51.1 kJ / m 2 .

[0062] Compared with the polyolefin elastomer network with single hydrogen bond cross-linking described in Comparative Example 4, the triple non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example had a 27% increase in Young's modulus, a 35% increase in 100% elongation stress, a 64% increase in 300% elongation stress, a 45% increase in tensile strength, and a 24% increase in fracture energy.

[0063] Example 3

[0064] In a 0.25 mL aqueous solution containing 37 mg (0.32 eq relative to the carboxyl group, 0.15 mol) of NiCl₂·6H₂O, 48 mg (0.99 eq relative to the carboxyl group, 0.48 mol) of triethylamine was added to form a mixed solution. The above mixed solution was added to a 50 mL hexane solution containing 1.6 g of ethylene / butene / carboxyl-functionalized vinyl norbornene copolymer at 55 °C. The ethylene / butene / carboxyl-functionalized vinyl norbornene copolymer used was the same as that in Example 2. The reaction time at 55 °C was 6 h. The post-treatment method was the same as that in Example 1. A non-covalent reversible crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds, and coordination bonds was obtained, in which the coordination crosslinked bonds accounted for 96%, the ionic crosslinked bonds accounted for 3%, and the hydrogen bond crosslinked bonds accounted for 1%. The above reversible crosslinked polyolefin elastomer network was sampled and tested. Its Young's modulus was 14.6 MPa, the 100% elongation stress was 3.3 MPa, the 300% elongation stress was 5.8 MPa, the tensile strength was 29.9 MPa, the elongation at break was 810%, and the fracture energy was 77.0 kJ / m 2 。

[0065] Compared with the single hydrogen bond crosslinked polyolefin elastomer network described in Comparative Example 4, the triple non-covalent reversible crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds, and coordination bonds prepared by the method of this example had its Young's modulus increased by 87%, the 100% elongation stress increased by 94%, the 300% elongation stress increased by 1.32 times, the tensile strength increased by 93%, and the fracture energy increased by 86%.

[0066] Example 4

[0067] The reaction process was as described in Example 1, except that: the polymer used was 1.6 g of ethylene / butene / carboxyl-functionalized vinyl norbornene copolymer (the same as the polymer used in Example 4). The transition metal compound used was NiCl₂·6H₂O, and the amount used was 5 mg (0.08 eq relative to the carboxyl group, 0.02 mol). The organic base used was N-butylimidazole, and the amount used was 11 mg (0.34 eq relative to the carboxyl group, 0.09 mol). The reaction was carried out at 60 °C for 6 h. After the reaction, the solvent was removed at 18 °C to obtain a non-covalent reversible crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds, and coordination bonds, in which the coordination crosslinked bonds accounted for 24%, the ionic crosslinked bonds accounted for 10%, and the hydrogen bond crosslinked bonds accounted for 66%. The above reversible crosslinked polyolefin elastomer network was sampled and tested. Its Young's modulus was 6.0 MPa, the 100% elongation stress was 2.3 MPa, the 300% elongation stress was 3.8 MPa, the tensile strength was 15.4 MPa, the elongation at break was 840%, and the fracture energy was 48.1 kJ / m 2 。

[0068] Compared with the polyolefin elastomer network containing only hydrogen bonds in Comparative Example 5, the triple reversible non-covalent cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has a 7% increase in Young's modulus, a 44% increase in 100% modulus, a 41% increase in 300% modulus, a 34% increase in tensile strength, and a 33% increase in fracture energy.

[0069] Example 5

[0070] The reaction process was as described in Example 1, except that: the polymer matrix used was 0.8 g of ethylene / octene-carboxyl-functionalized ethylidene norbornene copolymer, in which the ethylene structural unit content was 79.4 mol%, the octene structural unit content was 17.1 mol%, and the carboxyl-functionalized ethylidene norbornene structural unit content was 3.5 mol%. The transition metal compound used was ZnCl2, with a dosage of 14 mg (0.17 eq, 0.1 mol relative to carboxyl), and the organic base was tetrabutylammonium hydroxide, with a dosage of 103 mg (0.66 eq, 0.4 mol relative to carboxyl). In the obtained non-covalent reversibly cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds, the coordination cross-links accounted for 34%, the ionic cross-links accounted for 32%, and the hydrogen bond cross-links accounted for 34%. The above-mentioned reversibly cross-linked polyolefin elastomer network was sampled and tested, and its Young's modulus was 4.9 MPa, 100% modulus was 3.3 MPa, 300% modulus was 6.2 MPa, tensile strength was 17.9 MPa, elongation at break was 658%, and fracture energy was 51.5 kJ / m 2 。

[0071] Compared with the polyolefin elastomer network containing only hydrogen bonds in Comparative Example 6, the non-covalent reversibly cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has an approximately 7.2-fold increase in Young's modulus, an approximately 3.7-fold increase in 100% modulus, an approximately 5.9-fold increase in 300% modulus, an approximately 4.8-fold increase in tensile strength, and an approximately 2.6-fold increase in fracture energy.

[0072] Example 6

[0073] The reaction process was as described in Example 1, with the differences being that the transition metal compound used was ZnCl2, with a dosage of 68 mg (0.4 eq relative to the carboxyl group, 0.50 mol), the organic base was triethylamine, with a dosage of 114 mg (0.90 eq relative to the carboxyl group, 1.13 mol). In the prepared triple non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds simultaneously, the coordination cross-linked bonds accounted for 80%, the ionic cross-linked bonds accounted for 10%, and the hydrogen bond cross-linked bonds accounted for 10%. The above reversible cross-linked polyolefin elastomer network was made into a sample for testing, with a Young's modulus of 4.5 MPa, a 100% elongation stress of 1.4 MPa, a 300% elongation stress of 2.3 MPa, a tensile strength of 10.1 MPa, an elongation at break of 780%, and a fracture energy of 27.9 kJ / m 2 。

[0074] Compared with the polyolefin elastomer network containing only hydrogen bonds in Comparative Example 2, the non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds simultaneously prepared by the method of this example had a Young's modulus increased by 88%, a 100% elongation stress increased by 40%, a 300% elongation stress increased by 1.3 times, a tensile strength increased by 2.1 times, and a fracture energy increased by 8%.

[0075] Compared with the non-covalent reversible cross-linked polyolefin elastomer network containing ionic bonds and hydrogen bonds simultaneously in Comparative Example 3, the non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds simultaneously prepared by the method of this example had a Young's modulus increased by 96%, a 100% elongation stress increased by 27%, a 300% elongation stress increased by 92%, a tensile strength increased by 1.7 times, and a fracture energy increased by 23%.

[0076] Example 7

[0077] The reaction process was as described in Example 1, with the differences being that the transition metal compound used was FeCl3, with a dosage of 35 mg (0.17 eq relative to the carboxyl group, 0.21 mol), the organic base was triethylamine, with a dosage of 76 mg (0.60 eq relative to the carboxyl group, 0.75 mol). In the prepared non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds simultaneously, the coordination cross-linked bonds accounted for 51%, the ionic cross-linked bonds accounted for 9%, and the hydrogen bond cross-linked bonds accounted for 40%. The above reversible cross-linked polyolefin elastomer network was made into a sample for testing, with a Young's modulus of 6.5 MPa, a 100% elongation stress of 2.0 MPa, a 300% elongation stress of 4.5 MPa, a tensile strength of 14.3 MPa, an elongation at break of 560%, and a fracture energy of 29.5 kJ / m 2 。

[0078] Compared with the reversibly crosslinked polyolefin elastomer network containing only hydrogen bonds in Comparative Example 2, the triple non-covalent reversibly crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has a Young's modulus increased by 1.7 times, a 100% modulus at 100% elongation increased by 1.0 times, a 300% modulus at 300% elongation increased by 3.5 times, a tensile strength increased by 3.3 times, and a fracture energy increased by 14%.

[0079] Compared with the double reversibly crosslinked polyolefin elastomer network containing ionic bonds and hydrogen bonds in Comparative Example 3, the triple non-covalent reversibly crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has a Young's modulus increased by 1.8 times, a 100% modulus at 100% elongation increased by 82%, a 300% modulus at 300% elongation increased by 2.8 times, a tensile strength increased by 2.8 times, and a fracture energy increased by 30%.

[0080] Example 8

[0081] The reaction process was as described in Example 1, except that: the amount of ZnCl2·6H2O was 28 mg (0.17 eq relative to carboxyl group, 0.20 mol), and the amount of tetrabutylammonium hydroxide was 206 mg (0.66 eq relative to carboxyl group, 0.79 mol). In the non-covalently reversibly crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared, the coordination crosslinking bonds accounted for 34%, the ionic crosslinking bonds accounted for 32%, and the hydrogen bond crosslinking bonds accounted for 34%. The above reversibly crosslinked polyolefin elastomer network was made into a sample for testing, and its Young's modulus was 5.2 MPa, the 100% modulus at 100% elongation was 1.4 MPa, the 300% modulus at 300% elongation was 2.0 MPa, the tensile strength was 10.6 MPa, the elongation at break was 810%, and the fracture energy was 28.1 kJ / m 2 。

[0082] Compared with the reversibly crosslinked polyolefin elastomer network containing only hydrogen bonds in Comparative Example 2, the triple non-covalent reversibly crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has a Young's modulus increased by 1.2 times, a 100% modulus at 100% elongation increased by 40%, a 300% modulus at 300% elongation increased by 1.0 times, a tensile strength increased by 2.2 times, and a fracture energy increased by 10%.

[0083] Compared with the reversibly crosslinked polyolefin elastomer network containing ionic bonds and hydrogen bonds in Comparative Example 3, the non-covalently reversibly crosslinked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example has a Young's modulus increased by 1.3 times, a 100% modulus at 100% elongation increased by 27%, a 300% modulus at 300% elongation increased by 67%, a tensile strength increased by about 1.8 times, and a fracture energy increased by 23%.

[0084] Example 9

[0085] The reaction process was as described in Example 1, except that: the transition metal compound used was ZnCl2, with a dosage of 13.5 mg (0.08 eq, 0.10 mol relative to the carboxyl group), the organic base was triethylamine, with a dosage of 42.6 mg (0.34 eq, 0.42 mol relative to the carboxyl group). In the simultaneously prepared triple non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds, the coordination cross-linking points accounted for 16%, the ionic bond cross-linking points accounted for 18%, and the hydrogen bond cross-linking points accounted for 66%. The above-mentioned reversible cross-linked polyolefin elastomer network was made into a sample for testing. The Young's modulus was 2.5 MPa, the 100% elongation stress was 1.5 MPa, the 300% elongation stress was 2.4 MPa, the tensile strength was 5.9 MPa, the elongation at break was 870%, and the fracture energy was 27.2 kJ / m 2 .

[0086] Compared with the polyolefin elastomer network containing only hydrogen bonds in Comparative Example 2, the non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example had a 4% increase in Young's modulus, a 50% increase in 100% elongation stress, a 1.4-fold increase in 300% elongation stress, a 78% increase in tensile strength, and a 5% increase in fracture energy.

[0087] Compared with the non-covalent reversible cross-linked polyolefin elastomer network containing ionic bonds and hydrogen bonds in Comparative Example 3, the non-covalent reversible cross-linked polyolefin elastomer network containing hydrogen bonds, ionic bonds and coordination bonds prepared by the method of this example had an 8% increase in Young's modulus, a 36% increase in 100% elongation stress, a 1.0-fold increase in 300% elongation stress, a 55% increase in tensile strength, and a 19% increase in fracture energy.

[0088] Comparative Example 1

[0089] 2.6 g of ethylene-propylene-diene monomer rubber with an ethylene structural unit content of 65.1 mol%, a propylene structural unit content of 33.1 mol%, and an ENB structural unit content of 1.8 mol% was dissolved in 50 mL of tetrahydrofuran at 25 °C to form a solution. After removing the solvent at room temperature, it was vacuum dried to constant weight to obtain a polymer film. The polymer film was made into a sample for testing. Its Young's modulus was 1.8 MPa, the 100% elongation stress was 0.6 MPa, the 300% elongation stress was 0.4 MPa, the tensile strength was 0.3 MPa, the elongation at break was 430%, and the fracture energy was 1.72 kJ / m 2 .

[0090] Comparative Example 2

[0091] Dissolve 2.6 g of the polymer used in Example 1 in 50 mL of tetrahydrofuran to prepare a polymer solution. After removing the solvent at room temperature, vacuum dry to constant weight to obtain a polymer film. Prepare a sample of the polymer film for testing. Its Young's modulus is 2.4 MPa, the 100% elongation stress is 1.0 MPa, the 300% elongation stress is 1.0 MPa, the tensile strength is 3.3 MPa, the elongation at break is 1690%, and the fracture energy is 25.8 kJ / m 2 。

[0092] Comparative Example 3

[0093] The reaction process is as described in Example 1, except that: the polymer used is 2.6 g, the polymer dissolution temperature T1 is 25 °C, the amount of all organic base triethylamine used is 63 mg, and no transition metal salt is added. After removing the solvent at room temperature, vacuum dry to constant weight to obtain a polymer film. Prepare a sample strip of the polymer film for testing. Its Young's modulus is 2.3 MPa, the 100% elongation stress is 1.1 MPa, the 300% elongation stress is 1.2 MPa, the tensile strength is 3.8 MPa, the elongation at break is 1290%, and the fracture energy is 22.7 kJ / m 2 。

[0094] Comparative Example 4

[0095] Dissolve 2.6 g of the polymer used in Example 2 in 50 mL of tetrahydrofuran at 55 °C to prepare a polymer solution. After removing the solvent at room temperature, vacuum dry to constant weight to obtain a polymer film. Prepare a sample of the polymer film for testing. Its Young's modulus is 7.8 MPa, the 100% elongation stress is 1.7 MPa, the 300% elongation stress is 2.5 MPa, the tensile strength is 15.5 MPa, the elongation at break is 910%, and the fracture energy is 41.3 kJ / m 2 。

[0096] Comparative Example 5

[0097] Dissolve 2.6 g of the polymer used in Example 4 in 50 mL of tetrahydrofuran at 60 °C to prepare a solution. After removing the solvent at room temperature, vacuum dry to constant weight to obtain a polymer film. Prepare a sample of the polymer film for testing. Its Young's modulus is 5.6 MPa, the 100% elongation stress is 1.6 MPa, the 300% elongation stress is 2.7 MPa, the tensile strength is 11.5 MPa, the elongation at break is 910%, and the fracture energy is 36.1 kJ / m 2 。

[0098] Comparative Example 6

[0099] Dissolve 0.8 g of the copolymer used in Example 5 in 20 mL of tetrahydrofuran at 25 °C to prepare a solution. After removing the solvent at room temperature, vacuum dry to constant weight to obtain a polymer film. Prepare a sample of the polymer film for testing. Its Young's modulus is 0.6 MPa, the 100% modulus at elongation is 0.7 MPa, the 300% modulus at elongation is 0.9 MPa, the tensile strength is 3.1 MPa, the elongation at break is 1000%, and the fracture energy is 14.5 kJ / m 2 。

[0100] The embodiments of the present invention have been described above. The above description is exemplary and not exhaustive, and is also not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A reversible cross-linked polyolefin elastomer, characterized in that, The reversible crosslinked polyolefin elastomer is a reversible crosslinked polyolefin elastomer that forms a crosslinked network through three non-covalent bonds: hydrogen bonds, ionic bonds, and coordination bonds.

2. The reversible crosslinked polyolefin elastomer according to claim 1, wherein, Based on the total of the crosslinking bonds of the three non-covalent bonds of hydrogen bonds, ionic bonds, and coordination bonds being 100%, the hydrogen bond crosslinking bonds account for 0.1 to 85%, preferably 0.2 to 80%, more preferably 0.5 to 75%; the ionic crosslinking bonds account for 0.5 to 90%, preferably 1 to 80%, more preferably 2 to 70%; the coordination crosslinking bonds account for 9 to 99%, preferably 15 to 98%, more preferably 20 to 97%.

3. The reversible crosslinked polyolefin elastomer according to claim 2, wherein, The hydrogen bond crosslinking bonds are formed by at least one of carboxyl groups, hydroxyl groups, amino groups, and sulfonic acid groups, and are preferably formed by carboxyl groups and / or hydroxyl groups; The ionic crosslinking bonds are formed by the interaction of at least one negative ion among carboxylate ions, sulfonate ions, and halide ions with a nitrogen positive ion; The coordination crosslinking bonds are formed by the coordination of carboxylate ions and / or sulfonate ions with transition metal ions, and the transition metals are selected from at least one of titanium, vanadium, chromium, manganese, iron, nickel, copper, and zinc, and are preferably at least one of manganese, iron, nickel, copper, and zinc.

4. The reversible crosslinked polyolefin elastomer according to claim 1, wherein The polyolefin elastomer includes ethylene structural units, α-olefin structural units, and functionalized norbornene structural units; Based on the total molar amount of all structural units in the polyolefin elastomer, the molar content of the ethylene structural units is 40 to 94%, preferably 45 to 90%, more preferably 55 to 88%; the molar content of the α-olefin structural units is 5 to 60%, preferably 7 to 50%, more preferably 10 to 41%; the molar content of the functionalized norbornene structural units is 0.1 to 8.0%, preferably 0.2 to 6.0%, more preferably 0.3 to 4.5%; Preferably, the α-olefin is selected from at least one of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. Preferably, the functional groups of the functionalized norbornene are selected from at least one of carboxyl groups, amino groups, hydroxyl groups, and sulfonic acid groups.

5. The preparation method of the reversible cross-linked polyolefin elastomer according to any one of claims 1-4, characterized in that, It includes the following steps: (1) Dissolve the functionalized polyolefin elastomer in a first solvent to obtain a functionalized polyolefin elastomer solution; (2) Dissolve the transition metal compound in a second solvent to obtain a transition metal compound solution. After mixing with the functionalized polyolefin elastomer solution obtained in step (1), add a base to react; or dissolve the transition metal compound and the base in the second solvent to obtain a mixed solution, and after mixing with the functionalized polyolefin elastomer solution obtained in step (1), react; (3) After the reaction is completed, remove the solvent and dry to constant weight to obtain the reversible crosslinked polyolefin elastomer.

6. The preparation method according to claim 5, wherein, In the reaction system, based on the functional groups of the functionalized polyolefin elastomer being 1 equivalent, the equivalent of the transition metal compound is 0.01 to 0.55, preferably 0.03 to 0.50, more preferably 0.05 to 0.45, and the equivalent of the base is 0.1 to 1.1, preferably 0.2 to 1.0, more preferably 0.3 to 0.

99.

7. The preparation method according to claim 5, wherein, The first solvent is an organic solvent, preferably selected from at least one of alkanes, cycloalkanes, halogenated alkanes, aromatic hydrocarbons, and ethers, more preferably selected from at least one of C5-C 20 alkanes, C5-C 20 cycloalkanes, C1-C 20 halogenated alkanes, C6-C 20 aromatic hydrocarbons, and C4-C 20 ethers, and further preferably selected from at least one of pentane, hexane, heptane, octane, cyclopentane, methylcyclopentane, cyclohexane, dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, tetrahydrofuran, benzene, toluene, ethylbenzene, and xylene; The second solvent is selected from at least one of water, alcohols, alkanes, cycloalkanes, halogenated alkanes, aromatic hydrocarbons, ethers, ketones, aldehydes and esters, preferably selected from at least one of water, C1-C5 alcohols, C5-C 20 alkanes, C5-C 20 cycloalkanes, C1-C 20 halogenated alkanes, C4-C 20 ethers, C3-C 20 ketones, C2-C 20 aldehydes and C2-C 20 esters, and more preferably selected from at least one of water, methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, dichloromethane, chloroform, dichloroethane, trichloroethane, tetrahydrofuran, diethyl ether, acetone and methyl ethyl ketone; When adopting the method of adding alkali later, the alkali is added in the form of an alkali solution, and the solvent of the alkali solution is at least one of water, alkane, cycloalkane, halogenated alkane, aromatic hydrocarbon, ether and ketone, preferably at least one of water, C5-C 20 alkane, C5-C 20 cycloalkane, C1-C 20 halogenated alkane, C6-C 20 aromatic hydrocarbon, C4-C 20 ether and C3-C 20 ketone, and more preferably at least one of water, pentane, hexane, heptane, octane, cyclopentane, methylcyclopentane, cyclohexane, dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, tetrahydrofuran, benzene, toluene, ethylbenzene and xylene; Preferably, the concentration of the functionalized polyolefin elastomer solution is 5 to 200 g / L, preferably 8 to 180 g / L, more preferably 10 to 150 g / L; the concentration of the transition metal compound solution is 0.1 to 4.0 g / L, preferably 0.15 to 3.5 g / L, more preferably 0.2 to 3.0 g / L; the concentration of the alkali solution is 0.1 to 30 g / L, preferably 0.5 to 20 g / L, more preferably 0.6 to 15 g / L.

8. The preparation method according to claim 4, wherein, The transition metal compound is selected from at least one of titanium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, nickel compounds, copper compounds, and zinc compounds, more preferably at least one of manganese compounds, iron compounds, nickel compounds, copper compounds, and zinc compounds; Preferably, the manganese compound is selected from one or more of manganese fluoride, manganese chloride, manganese chloride monohydrate, manganese chloride tetrahydrate, manganese perchlorate hexahydrate, manganese bromide, manganese iodide, manganese sulfate, manganese sulfate monohydrate, manganese sulfate tetrahydrate, manganese sulfide, manganese nitrate, manganese nitrate tetrahydrate, manganese nitrate hexahydrate, manganese nitrite, manganese phosphate, manganese phosphate monohydrate, manganese dihydrogen phosphate, manganese dihydrogen phosphate dihydrate, manganese hypophosphite monohydrate, manganese silicate, manganese carbonate, manganese hydroxide, manganese borate, manganese acetate, manganese acetate dihydrate, manganese oxalate, manganese oxalate dihydrate, manganese citrate, manganese cyclohexanebutyrate, manganese naphthenate, manganese stearate, manganese neodecanoate, manganese gluconate, manganese stearate, manganese 2-ethylhexanoate, tris(2,2,6,6-tetramethyl-3,5-heptanedioato)manganese, manganese trifluoromethanesulfonate, manganese disodium ethylenediaminetetraacetate, decacarbonyldimanganese, pentacarbonylbromomanganese, bis(cyclopentadienyl)manganese, bis(tetramethylcyclopentadienyl)manganese, 2-methylcyclopentadienyltricarbonylmanganese, manganese acetylacetonate, bis(isopropylcyclopentadienyl)manganese, tricarbonylcyclopentadienylmanganese, bis(2,4-pentanedionato)manganese dihydrate, bis(hexafluoroacetylacetonato)manganese trihydrate, bis(trifluoro-2,4-pentanedionato)manganese, bis(trifluoromethanesulfonyl)imide manganese, bis(pentamethylcyclopentadienyl)manganese, preferably at least one of manganese chloride, manganese chloride monohydrate, manganese chloride tetrahydrate, manganese carbonate, manganese hydroxide, manganese acetate, manganese acetate dihydrate, and manganese acetylacetonate; Preferably, the iron compound is selected from one or more of iron chloride, ferrous chloride, iron bromide, ferrous bromide, iron fluoride, iron iodide, iron perchlorate, iron nitrate, iron nitrate nonahydrate, iron pyrophosphate, iron phosphate, iron phosphate dihydrate, lithium iron phosphate, iron sulfate, ammonium ferrous sulfate hexahydrate, iron 2-ethylhexanoate, ferrocene-1,1'-dicarboxylic acid, iron benzoyl sulfonate, sodium iron ethylenediaminetetraacetate, iron acetate, iron acetate monohydrate, iron acetate tetrahydrate, iron(III) oxalate pentahydrate, sodium iron(III) oxalate trihydrate, iron acrylate, iron naphthenate, iron tartrate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)iron, iron stearate, ferrocene, iron tert-butoxide complex, and iron acetylacetonate, and preferably at least one of iron chloride, ferrous chloride, ferrous chloride tetrahydrate, iron bromide, ferrous bromide, iron phosphate, iron phosphate dihydrate, iron(III) oxalate pentahydrate, and iron acetylacetonate; Preferably, the nickel compound is preferably one or more of nickel fluoride, nickel chloride, nickel chloride hexahydrate, nickel chloride ethylene glycol dimethyl ether complex, nickel chloride dimethoxyethane complex, nickel bromide, nickel bromide trihydrate, nickel iodide, nickel bromide 2-methoxyethyl ether complex, nickel sulfate, nickel sulfate heptahydrate, nickel sulfite, nickel ammonium sulfate, nickel ammonium sulfate hexahydrate, nickel sulfamate, nickel sulfamide tetrahydrate, nickel 2-amino-5-methylbenzenesulfonate, nickel nitrate, nickel nitrate hexahydrate, nickel nitrite, nickel phosphate, nickel hypophosphite, nickel carbonate, nickel silicate, nickel borate, nickel borate hydrate, nickel tetrafluoroborate hexahydrate, nickel formate, nickel acetate, nickel acetate tetrahydrate, nickel oxalate, nickel oxalate dihydrate, nickel citrate, nickel citrate hydrate, methylallyl nickel chloride dimer, nickel lactate, nickel stearate, nickel benzoate, nickel trifluoroacetate, nickel citrate octanoate, nickel benzenesulfonate, nickel naphthenate, nickel trifluoromethanesulfonate, nickel p-toluenesulfonate, nickel cyclohexanebutyrate, nickel acetylacetonate, bis(2,4-pentanedionato)nickel, dichloro bis(trimethylphosphine)nickel, nickel glycolate, nickel disodium ethylenediaminetetraacetate, nickel 2-ethylhexanoate, nickel diethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel hydroxide, nickel trifluoroacetylacetonate, tetrakis(triphenylphosphine)nickel, bis(triphenylphosphine) nickel dichloride, bis(triphenylphosphine) nickel dibromide, bis(triethylphosphine) nickel chloride, bis(tributylphosphine) nickel dibromide, 1,2-bis(diphenylphosphino)ethane nickel chloride, chloro bis(triphenylphosphino)phenyl nickel, hexaamminenickel dichloride, tris(ethylenediamine) nickel dichloride, tris(ethylenediamine) nickel chloride, bis(hexafluoroethylacetone) nickel, bis(N,N”-di-tert-butylacetamidato)nickel, bis(tricyclohexylphosphine) nickel dichloride, chloro bis(dicyclohexylphenylphosphino)(2-methylphenyl) nickel, bis[1-(N,N-dimethylamino)-2-propanolato] nickel, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel; more preferably at least one of nickel chloride, nickel chloride hexahydrate, nickel chloride ethylene glycol dimethyl ether complex, nickel chloride dimethoxyethane complex, nickel bromide, nickel bromide trihydrate, nickel iodide, nickel bromide 2-methoxyethyl ether complex, nickel oxalate, nickel oxalate dihydrate, nickel acetate, nickel acetate tetrahydrate, nickel acetylacetonate, bis(2,4-pentanedionato)nickel, dichloro bis(trimethylphosphine)nickel and bis(triphenylphosphine) nickel dichloride; Preferably, the zinc compound is preferably one or more of zinc fluoride, zinc fluoride tetrahydrate, zinc chloride, zinc perchlorate, zinc perchlorate hexahydrate, zinc bromide, zinc iodide, zinc sulfide, zinc sulfate, zinc sulfate monohydrate, zinc sulfate heptahydrate, zinc phosphate, zinc phosphate tetrahydrate, zinc dihydrogen phosphate, zinc dihydrogen phosphate dihydrate, zinc nitrate, zinc nitrate hexahydrate, basic zinc carbonate, zinc borate, zinc borate trihydrate, zinc tetrafluoroborate, zinc tetrafluoroborate monohydrate, zinc trifluoromethanesulfonate, zinc formate, zinc acetate, zinc acetate dihydrate, zinc trifluoroacetate, zinc oxalate, zinc oxalate dihydrate, zinc acrylate, zinc dimethacrylate, zinc benzoate, zinc 2-ethylhexanoate, zinc naphthenate, zinc undecylenate, zinc gluconate, zinc gluconate dihydrate, zinc lactate, zinc lactate dihydrate, zinc stearate, diethylzinc, zinc L-aspartate, zinc glycinate monohydrate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc acetylacetonate, zinc acetylacetonate monohydrate, zinc ethylenediaminetetraacetate, zinc ethylenediaminetetraacetate disodium tetrahydrate, and more preferably at least one of zinc chloride, zinc bromide, zinc iodide, zinc sulfide, zinc formate, zinc acetate, zinc acetate dihydrate, zinc oxalate, zinc oxalate dihydrate, and basic zinc carbonate.

9. The preparation method according to claim 5, wherein, The base is ammonia water and / or an organic base, and the organic base is selected from nitrogen-containing organic base compounds, preferably at least one of monofunctional, bifunctional, and polyfunctional organic amines, pyridine, substituted pyridine, imidazole, substituted imidazole, thiazole, oxazole, and ammonium hydroxide, and its general formula is as follows: In each case, R 1 -R 7 ,R 9 -R 17 ,R 19 -R 42 ,R 44 -R 54 ,which are the same or different and each independently selected from H, an alkyl group having 1 to C 20 or an aryl group having 6 to C 20 ; R 8 , R 18 , R 43 are the same or different and each independently selected from an alkylene group having 1 to 6 carbon atoms or an aryl group having 6 to C 20 aryl; Preferably, the organic base is selected from methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, tert-butylamine, isobutylamine, 1-hexylamine, aniline, 2-methylaniline, 2,4,6-trimethylaniline, N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-diisopropylamine, N,N-dibutylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylisopropylamine, N,N-dimethylbutylamine, N,N-dimethyltert-butylamine, N-methyldiethylamine, N,N-diethylpropylamine, N,N-diethylbutylamine, N,N-diethyltert-butylamine, triethylamine, trimethylamine, tripropylamine, triisopropylamine, tributylamine, trioctylamine, ethylenediamine, propylenediamine, pentamethylenediamine, hexamethylenediamine, N-benzylethylenediamine, N-hexylethylenediamine, N-methyl-1,3-propylenediamine, N-propyl-1,3-propylenediamine, N-propylethylenediamine, N,N-dimethylethylenediamine, N-ethyl-N'-methylethylenediamine, N,N-diethylethylenediamine, N,N'-diethyl-1,3-propylenediamine, N,N'-dipropyl-1,3-propylenediamine, N,N-dibutyl-1,3-propylenediamine, N,N,N'-triethylethylenediamine, trimethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N-tetramethylethylenediamine, N',N'-dibenzyl-N,N'-dimethylethylenediamine, N,N'-dipropylethylenediamine, N,N,N',N'-tetramethyl-1,3-propylenediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N-dimethyl-N',N'-dimethyl-ethyl-1,2-diamine, N,N,N′,N′-tetramethyl-p-phenylenediamine, bis(hexamethylenetriamine), diethylenetriamine, 4-dodecyldiethylenetriamine, N,N-dimethyliminodipropylamine, N,N-diethyldiethylenetriamine, N,N',N”-trihexyldiethylenetriamine, pentamethyldiethylenetriamine, N,N',N”-trimethyldiethylenetriamine, N,N,N',N'-tetraethyldiethylenetriamine, imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-hexylimidazole, 1-benzylimidazole, 1-phenylimidazole, 1-dodecylimidazole, 1-octylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-undecylimidazole, 2-phenylimidazole, 4-methylimidazole, 4-ethylimidazole, 4-propylimidazole, 4-butylimidazole, 4-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, 2,4-dimethylimidazole, 1,2,4,5-tetramethylimidazole, 1,At least one of 2-dimethylimidazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, N,N,N-trimethyl-1-adamantylammonium hydroxide, cetyltrimethylammonium hydroxide, benzethonium hydroxide, triethylmethylammonium hydroxide, benzyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, methyltripropylammonium hydroxide, and trihexyltetradecylammonium hydroxide; More preferably, the organic base is selected from at least one of methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, tert-butylamine, isobutylamine, N,N-diisopropylamine, 1-hexylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylisopropylamine, N,N-dimethylbutylamine, N,N-dimethyltert-butylamine, N-methyldiethylamine, N,N-diethylpropylamine, N,N-diethylbutylamine, N,N-diethyltert-butylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, trioctylamine, ethylenediamine, propylenediamine, pentamethylenediamine, hexamethylenediamine, tetramethyl-1,4-butanediamine, tetramethyl-1,6-hexanediamine, imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.

10. The preparation method according to claim 5, wherein The dissolution temperature T1 of the functionalized polyolefin elastomer is 10 to 100 °C, preferably 12 to 80 °C, and more preferably 15 to 70 °C; The conditions of the reaction include: the temperature T2 is 10 to 100 °C, preferably 12 to 80 °C, and more preferably 15 to 70 °C, and the time is 1.5 h to 10 h, preferably 2 h to 8 h, and more preferably 3 h to 7 h; The temperature T3 for removing the solvent is 10 to 85 °C, preferably 12 to 70 °C, and more preferably 15 to 60 °C; Preferably, the preparation method of the functionalized polyolefin elastomer includes the following steps: In the presence of a vanadium-based catalyst, a polyolefin elastomer is prepared by copolymerizing ethylene, an α-olefin, and ethylidene norbornene and / or vinyl norbornene, and then a functionalization reaction is carried out by a thiol-ene click reaction method or a hydroboration-oxidation method to obtain the functionalized polyolefin elastomer; More preferably, the functionalized group of the functionalized polyolefin elastomer is at least one of a carboxyl group, a hydroxyl group, an amino group, and a sulfonic acid group.

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