A 1, 4; 3, 6-diglycidyl hexanehexol polycarbonate copolymer as well as preparation method and application thereof

Abstract

The invention provides a room-temperature self-repairing high-bonding-strength 1, 4; the invention discloses a 1, 3, 6-diglycidyl hexanehexol polycarbonate copolymer and a preparation method thereof. In order to solve the problems of complex molecular structure design and multiple synthesis steps of multifunctional macromolecules, the bulk copolymer with room-temperature self-repairing and high bonding strength is prepared by a simple melt polycondensation method, and the polymerization method is simple and is beneficial to subsequent industrial amplification.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and specifically relates to a room temperature self-repairing high bonding strength 1,4;3,6-hexanedipyrol polycarbonate copolymer and a preparation method and application thereof. Background Art

[0002] In the modern society with rapid development of science and technology, people have higher requirements for the environmental friendliness of materials, and at the same time, they also hope that materials will become smarter and have multiple functions to meet a wide range of application needs. For example, properties such as high ductility, processability, self-healing, adhesion, biodegradability, biocompatibility and recyclability are widely concerned, and combining several of these properties is a hot topic for researchers. In order to meet multifunctionality, it is inevitable that the molecular structure design will be more complicated, and there will be problems with many synthesis steps.

[0003] In the application of artificial intelligence wearable devices, new materials that can self-repair at room temperature and have strong adhesive properties have received widespread attention from researchers in recent years. Self-repairing properties can not only extend the service life of the material, but also make the material more stable during use. However, most materials that have both of these properties are gel materials, and their performance will be significantly affected by the volatility of the solvent during use. Therefore, the preparation of a bulk room temperature self-repairing high adhesive strength copolymer is a problem that is of great concern and needs to be solved urgently.

[0004] In summary, in view of the difficulties of complex molecular structure design and multiple synthesis steps of multifunctional polymers, how to prepare bulk copolymers with high bonding strength and self-healing properties at room temperature through simple methods is an urgent problem to be solved. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention provides a room temperature self-repairing high bonding strength 1,4;3,6-dihydrohexanedol polycarbonate copolymer and a preparation method thereof. The present invention uses bio-based 1,4;3,6-dihydrohexanedol as a raw material, and uses a melt polycondensation method to achieve micro-crosslinking of the copolymer using the ring-opening characteristics of 1,4;3,6-dihydrohexanedol to obtain a multifunctional copolymer, which effectively overcomes the difficulties of complex molecular structure design and multiple synthesis steps of multifunctional polymers. The polymerization method of this method is simple and is conducive to subsequent industrial scale-up.

[0006] The technical solution of the present invention is as follows:

[0007] A 1,4;3,6-dihydrohexanedol polycarbonate copolymer, which is prepared by copolymerization of a polycarbonate prepolymer represented by formula I and a polyester prepolymer represented by formula II;

[0008]

[0009] Among them, R 1 are the same or different and are independently selected from the following groups which are unsubstituted or optionally substituted by one, two or more Ra: C 1-12 Alkyl or C 6-20 Aryl;

[0010] L is selected from the following groups which are unsubstituted or optionally substituted by one, two or more Rb: 1-12 Alkyl or C 6-20 Aryl;

[0011] R is selected from C which is unsubstituted or optionally substituted by one, two or more Rc 1-12 alkyl;

[0012] Ra, Rb, Rc are the same or different and are independently selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy.

[0013] According to an embodiment of the present invention, R 1 Same, selected from C 1-6 Alkyl or C 6-14 Aryl; the aryl group is optionally C 1-6 Alkyl substituted; L is selected from C 2-10 Alkyl or C 6-14 Aryl; R is selected from C 2-10 alkyl.

[0014] According to an embodiment of the present invention, R 1 Selected from methyl, ethyl, propyl, butyl, phenyl, methyl-substituted phenyl or naphthyl.

[0015] According to an embodiment of the present invention, R is selected from ethyl, propyl, butyl, pentyl, hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl.

[0016] According to an embodiment of the present invention, L is selected from ethyl, propyl, butyl, pentyl, hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl.

[0017] According to an embodiment of the present invention, based on the total mass of the copolymer, the mass fraction of the polycarbonate prepolymer of formula I is 60-90%, and the mass fraction of the polyester prepolymer of formula II is 10-40%.

[0018] According to an embodiment of the present invention, a small amount of 1,4;3,6-dihydrohexanedol polycarbonate copolymer chain segment The ring will open, so that the copolymer forms a micro-crosslinked structure, and the crosslinking degree of the copolymer is below 10%, preferably below 8%, and further preferably below 5%, for example 0.1-4.6%.

[0019] According to an embodiment of the present invention, the intrinsic viscosity of the 1,4;3,6-hexadecyl polycarbonate copolymer is 0.5 to 1.2 dL / g; preferably, the intrinsic viscosity is 0.5 to 0.9 dL / g.

[0020] According to an embodiment of the present invention, the self-healing efficiency of the 1,4;3,6-hexadecyl polycarbonate copolymer is 60 to 95%, such as 70 to 90%, preferably 80 to 90%.

[0021] According to an embodiment of the present invention, the bonding strength of the 1,4;3,6-hexadecyl polycarbonate copolymer is 0.4 to 1.1 MPa, preferably 0.5 to 0.9 MPa.

[0022] The present invention also provides a method for preparing the above-mentioned 1,4;3,6-dihydrohexanedol polycarbonate copolymer, comprising the following steps:

[0023] (1) Transesterification reaction of polycarbonate: a carbonic acid diester represented by formula A and 1,4;3,6-dihydrohexanedol are mixed and subjected to transesterification reaction to obtain a polycarbonate prepolymer represented by formula I;

[0024] The 1,4;3,6-dihydrohexanedol is selected from at least one of isosorbide, isomannide and isoidide:

[0025]

[0026] Formula A: R 1 O-CO-OR 1 , where R 1 Having the above definition;

[0027] (2) Esterification / transesterification reaction of polyester: the compound represented by formula B and the aliphatic diol represented by formula C are mixed and subjected to esterification reaction and / or transesterification reaction to obtain a polyester prepolymer represented by formula II;

[0028] Formula B: R 2 OOC-L-COOR 2

[0029] Formula C: HO-R-OH

[0030] Wherein, L and R have the above definitions; R 2 The same or different, independently selected from H, unsubstituted or optionally substituted by one, two or more Rd: C 1-12 Alkyl or C 6-20 Aryl;

[0031] Rd is selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy;

[0032] (3) Melt polycondensation reaction: The prepolymers represented by formula I and formula II are mixed and subjected to polycondensation reaction.

[0033] According to an embodiment of the present invention, the compound R 1 O-CO-OR 1 It represents a mixture of one or two dibasic esters.

[0034] According to an embodiment of the present invention, the compound R shown in formula B 2 OOC-L-COOR 2 Represents dibasic acids and / or dibasic esters, for example, the compound shown in formula B represents one dibasic acid, one dibasic ester, two or more dibasic acids, two or more dibasic esters, or a mixture of one or more dibasic acids and one or more dibasic esters. By analogy, the diol HO-R-OH shown in formula C can be a mixture of one or more dibasic alcohols. According to an embodiment of the present invention, the carbonic acid diester shown in formula A is selected from any one or a mixture of several of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ditolyl carbonate, and dinaphthyl carbonate; preferably at least one of dimethyl carbonate, diethyl carbonate, and diphenyl carbonate.

[0035] According to an embodiment of the present invention, the aliphatic diol shown in formula C is selected from at least one of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, preferably 1,4-butanediol.

[0036] According to an embodiment of the present invention, the inert gas atmosphere refers to a nitrogen atmosphere.

[0037] According to an embodiment of the present invention, R 2 Selected from H, C 1-10 Alkyl or C 6-14 Aryl; for example R 2 selected from H, methyl, ethyl, propyl, butyl, n-octyl or phenyl; for example, the compound represented by formula B is selected from succinic acid, dimethyl succinate, glutaric acid, adipic acid, pimelic acid, suberic acid, diethyl p-succinate, dipropyl succinate, dibutyl succinate, dioctyl succinate, diphenyl succinate, dimethyl glutarate, dipropyl glutarate, dibutyl glutarate, dioctyl glutarate, diphenyl glutarate, dimethyl adipate, dipropyl adipate, dibutyl adipate ester, dioctyl adipate, diphenyl adipate, dimethyl pimelate, diethyl pimelate, dipropyl pimelate, dibutyl pimelate, dioctyl pimelate, diphenyl pimelate, dimethyl suberate, diethyl suberate, dipropyl suberate, dibutyl suberate, dioctyl suberate, and diphenyl suberate, preferably at least one of succinic acid, dimethyl succinate, adipic acid, glutaric acid, pimelic acid, diethyl succinate, and dimethyl glutarate.

[0038] According to an embodiment of the present invention, in step (1), the molar ratio of the carbonic acid diester represented by formula A to 1,4;3,6-dihydrohexanedol is 10:1 to 1.5:1, preferably 5:1 to 2:1.

[0039] According to an embodiment of the present invention, in step (1), the transesterification reaction is carried out under normal pressure, the reaction temperature of the transesterification reaction is 60 to 200°C, preferably 70 to 170°C; the total time of the transesterification reaction is 2 to 20 hours, preferably 3 to 10 hours.

[0040] According to an embodiment of the present invention, step (1) is carried out in the presence of an ester exchange catalyst 1, and the ester exchange catalyst 1 is selected from at least one of metal hydrides, hydroxides, metal oxides, metal acetylacetonate complexes, titanium organic compounds, tin organic compounds, alkoxy metal compounds, metal carbonates, metal bicarbonates, metal phosphites, inorganic acids, organic acids, tertiary amines, metal acetates and metal halides.

[0041] The transesterification catalyst 1 is preferably at least one of lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium oxide, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, zinc acetylacetonate, calcium acetylacetonate, tetraethoxytitanium, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, stannous octoate, dibutyltin dilaurate, lithium methoxide, sodium methoxide, potassium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphite, potassium phosphite, phosphoric acid, acetic acid, p-toluenesulfonic acid, m-toluenesulfonic acid, benzenesulfonic acid, trimethylamine, triethylamine, dimethylaminopyridine, lithium acetate, sodium acetate, potassium acetate, zinc acetate, magnesium acetate, manganese acetate, lithium chloride, sodium chloride, potassium chloride, and cesium chloride.

[0042] According to an embodiment of the present invention, step (1) further comprises a post-treatment step, wherein the post-treatment step is to remove by-products in the reaction to obtain a prepolymer of polycarbonate.

[0043] According to an embodiment of the present invention, in step (2), the molar ratio of the compound represented by formula B to the aliphatic diol represented by formula C is 1:1-4, preferably 1:1.1-2.5, for example 1:1.1-2.

[0044] According to an embodiment of the present invention, in step (2), the esterification reaction is carried out under high temperature and high pressure, the reaction temperature is 160-200°C, preferably 165-190°C; the reaction pressure is 200-400KPa, preferably 200-330KPa; the total time of the esterification reaction is 2-20 hours, preferably 3-10 hours.

[0045] According to an embodiment of the present invention, in step (2), the transesterification reaction is carried out under normal pressure, the reaction temperature of the transesterification reaction is 150 to 200°C, preferably 160 to 190°C; the total time of the transesterification reaction is 2 to 20 hours, preferably 3 to 10 hours.

[0046] According to an embodiment of the present invention, the purity of the 1,4:3,6-hexadecene is 99.0% or more, preferably 99.5% or more.

[0047] According to an embodiment of the present invention, step (2) is carried out in the presence of an ester exchange catalyst 2, and the added ester exchange catalyst 2 is at least one of metal oxides, metal hydroxides, alkoxy metal compounds, metal phosphates, metal sulfates, metal acetylacetone complexes, metal acetates and metal halides containing magnesium, zinc, manganese, aluminum, cobalt and tin.

[0048] Preferably, the transesterification catalyst 2 is at least one of magnesium oxide, magnesium hydroxide, magnesium stearate, magnesium sulfate, magnesium acetate, magnesium chloride hexahydrate, zinc oxide, zinc hydroxide, zinc stearate, zinc phosphate, zinc sulfate, zinc acetate, manganese oxide, manganese acetylacetonate, manganese sulfate, manganese acetate, manganese chloride, aluminum oxide, aluminum hydroxide, aluminum phosphate, aluminum sulfate, aluminum acetate, cobalt oxide, cobalt acetylacetonate, cobalt acetate, cobalt acetate tetrahydrate, dibutyltin oxide, dibutyltin dichloride, tributyltin acetate, tributyltin chloride, and trimethyltin chloride.

[0049] According to an embodiment of the present invention, step (2) further comprises a post-treatment step, wherein the post-treatment step is to remove by-products in the reaction to obtain a polyester prepolymer.

[0050] According to an embodiment of the present invention, step (3) is carried out in the presence of a condensation polymerization catalyst, and the condensation polymerization catalyst is at least one of an organic metal compound or oxide or complex containing titanium, antimony, silicon, germanium or zirconium; preferably at least one of titanium dioxide, silicon dioxide / titanium dioxide composite, zirconium dioxide / titanium dioxide composite, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, antimony glycol, antimony acetate, germanium dioxide and germanium acetate.

[0051] According to an embodiment of the present invention, in step (3), the amount of the polycondensation catalyst added is 0.001 wt.% to 0.05 wt.%, preferably 0.011 wt.% to 0.04 wt.%, of the theoretical yield of the polycarbonate copolymer.

[0052] According to an embodiment of the present invention, in step (3), the temperature of the polycondensation reaction is 200-260°C, preferably 200-240°C; the time of the polycondensation reaction is 1-48 hours, preferably 3-12 hours. The pressure of the reaction system during the polycondensation reaction is less than 200Pa, for example 30-190Pa, preferably not more than 110Pa.

[0053] The present invention also provides the use of the 1,4;3,6-hexadecyl polycarbonate copolymer as an adhesive.

[0054] Beneficial Effects of the Invention

[0055] The present invention provides a room temperature self-repairing high bonding strength 1,4;3,6-dihydrohexanedol polycarbonate copolymer and a preparation method thereof. Aiming at the problem of complex molecular structure design and many synthesis steps of multifunctional polymers, the present invention prepares a bulk copolymer with room temperature self-repairing high bonding strength by a simple melt polycondensation method. The polymerization method is simple and is conducive to subsequent industrial scale-up.

[0056] The copolymer obtained by the method of the present invention is a transparent colorless solid with an intrinsic viscosity of 0.5 to 1.2 dL / g. The copolymer has room temperature self-healing properties and high bonding strength, can be used as a high-performance adhesive, and the content of each component in the main chain of the copolymer is controllable, which is convenient for performance regulation.

[0057] Definition and explanation of terms

[0058] The term "halogen" means fluorine, chlorine, bromine and / or iodine. Accordingly, the term "halo" refers to fluoro, chloro, bromo and / or iodo. Within the scope of this document, when an atom, residue, group or moiety is halogenated, the atom at the halogenated position may be monosubstituted, disubstituted or polysubstituted up to full substitution by halogen atoms, for example, "halo C 1-12 Alkyl" and "halogenated C 1-12 Alkoxy" etc.

[0059] The term "C 1-12 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. 1-6 Alkyl, the "C 1-6 The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or the like or isomers thereof.

[0060] The term "C 6-20 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 The term "C 6-14 The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0061] The term "halogenated C 1-12 "Alkyl" means C 1-12 In the case where the H on the alkyl group is optionally substituted by 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 halogens, the term “halo” and “C 1-12 "Alkyl" has the above definition. The substitution is on the same carbon atom or on different carbon atoms. 1-6 Alkyl". The "halogenated C 1-12 "Alkyl" is, for example, trifluoromethyl.

[0062] The term "C 1-12 "Alkoxy" means C 1-12 In the case where 1, 2 or 3 carbon atoms in the alkyl group are replaced by O, the above and "C 1-12 "Alkyl" has the above definition. Optionally "C 1-6 Alkoxy". The "C 1-12 "Alkoxy" is, for example, methoxy, ethoxy or propoxy. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 This is the NMR spectrum of the polyester polycarbonate copolymer obtained in Example 1. DETAILED DESCRIPTION

[0064] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0065] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0066] The performance parameters in the following examples are measured according to the following methods.

[0067] Intrinsic viscosity: 0.125 g of the copolymer was dissolved in 25 mL of phenol tetrachloroethane solution, and the intrinsic viscosity of the polymer was measured using an Ubbelohde viscometer in a thermostat at 25°C.

[0068] Self-healing performance test: first use a molding machine to mold, and then cut into rectangular splines with a sample size of 25×10×1.5mm. The splines are cut into sections and then repaired by butt-jointing. The repair temperature is 30°C and the repair time is 12h. The tensile strength of the splines before and after repair is tested respectively. The self-healing efficiency is the ratio of the tensile strength of the spline after repair to that before repair.

[0069] Bonding strength test: The sample is first formed by a molding machine, cut into certain specifications, and then clamped between two base plates for bonding. The overlapping part is 25mm long, 12.5mm wide, 100mm apart, the tensile speed is 10mm / min, the thickness of the adhesive is about 0.1mm, and the measured tensile strength is its bonding strength.

[0070] Cross-linking degree test: measured using a Soxhlet extractor, the solvent is chloroform. Weigh 0.2g of sample and wrap it with filter paper, and then weigh the total mass of the sample and filter paper. Then extract at 60°C for 48h, and bake the residue in a vacuum oven at 50°C for 8h, then weigh the total mass of the sample and filter paper to obtain the residual gel mass. The cross-linking degree is calculated by the following formula:

[0071] X=W r / W o

[0072] In the formula, X represents the degree of crosslinking, W r and W o represent the initial masses of the residue and sample, respectively.

[0073] Example 1

[0074] (1) At room temperature, in a 500 mL glass flask, 58.4 g (0.4 mol) of isosorbide, 72.0 g (0.8 mol) of dimethyl carbonate and 0.0016 g of ester exchange catalyst sodium methoxide were added under nitrogen atmosphere (the molar ratio of isosorbide to dimethyl carbonate was 1:2), stirred at 70°C, and then gradually heated to 165°C and reacted for 3.5 hours. The by-product methanol produced by the reaction was completely evaporated to obtain prepolymer I-1.

[0075] (2) In a 500 mL glass flask, 59.0 g (0.5 mol) of succinic acid and 90.0 g (1.0 mol) of 1,4-butanediol (the molar ratio of dibasic acid to diol is 1:2) were added under a nitrogen atmosphere. At a pressure of 230 kPa, the system temperature was gradually increased to 175°C and the reaction was carried out for 3.6 hours. The by-product water produced by the reaction was completely evaporated to obtain prepolymer II-1.

[0076] (3) 60 g of prepolymer I-1 and 40 g of prepolymer II-1 were added to a 250 mL glass flask, 0.015 wt% of polycondensation catalyst antimony acetate was added, vacuum was gradually established to 90 Pa, and the reaction was carried out at 230° C. for 3.6 hours to obtain a polyester polycarbonate copolymer. Its NMR spectrum is as follows Figure 1 shown.

[0077] After testing, the copolymer has an intrinsic viscosity of 0.66 g / dL, a self-healing efficiency of 70%, a bonding strength of 0.58 MPa, and a cross-linking degree of 0.8%.

[0078] Example 2

[0079] (1) At room temperature, in a 500 mL glass flask, 43.8 g (0.3 mol) of isosorbide, 106.2 g (0.9 mol) of diethyl carbonate and 0.0021 g of ester exchange catalyst lithium acetylacetonate were added under nitrogen atmosphere (the molar ratio of isosorbide to diethyl carbonate was 1:3), stirred at 60° C., then gradually heated to 178° C., reacted for 3 hours, and the by-product ethanol produced by the reaction was completely evaporated to obtain prepolymer I-2.

[0080] (2) In a 500 mL glass flask, 66.0 g (0.5 mol) of glutaric acid and 90.0 g (1.0 mol) of 1,4-butanediol (the molar ratio of dibasic acid to diol is 1:2) were added under a nitrogen atmosphere. At a pressure of 260 kPa, the system temperature was gradually increased to 167°C and the reaction was carried out for 2.9 hours. The by-product water produced by the reaction was completely evaporated to obtain prepolymer II-2.

[0081] (3) 70 g of prepolymer I-2 and 30 g of prepolymer II-2 were added to a 250 mL glass flask, 0.015 wt % of polycondensation catalyst tetrabutyl titanate was added, vacuum was gradually established to 80 Pa, and the mixture was reacted at 225° C. for 4 hours to obtain a polyester polycarbonate copolymer.

[0082] After testing, the copolymer has a characteristic viscosity of 0.69 g / dL, a self-healing efficiency of 74%, a bonding strength of 0.63 MPa, and a cross-linking degree of 1.5%.

[0083] Example 3

[0084] (1) At room temperature, in a 500 mL glass flask, 58.4 g (0.4 mol) of isosorbide, 90.0 g (1.0 mol) of dimethyl carbonate and 0.0031 g of ester exchange catalyst lithium methoxide were added under nitrogen atmosphere (the molar ratio of isosorbide to dimethyl carbonate was 1:2.5), stirred at 70°C, then gradually heated to 165°C, reacted for 3.8 hours, and the by-product methanol produced by the reaction was completely evaporated to obtain prepolymer I-3.

[0085] (2) In a 500 mL glass flask, 116.8 g (0.8 mol) of adipic acid and 99.84 g (0.96 mol) of 1,5-pentanediol (the molar ratio of dibasic acid to diol is 1:1.2) were added under a nitrogen atmosphere. At a pressure of 270 kPa, the system temperature was gradually increased to 180°C and reacted for 3 hours. The by-product water produced by the reaction was completely evaporated to obtain prepolymer II-3.

[0086] (3) 80 g of prepolymer I-3 and 20 g of prepolymer II-3 were added to a 250 mL glass flask, 0.015 wt % of polycondensation catalyst germanium dioxide was added, vacuum was gradually established to 100 Pa, and the mixture was reacted at 240° C. for 4.5 hours to obtain a polyester polycarbonate copolymer.

[0087] After testing, the copolymer has a characteristic viscosity of 0.71 g / dL, a self-healing efficiency of 80%, a bonding strength of 0.67 MPa, and a cross-linking degree of 2.2%.

[0088] Example 4

[0089] (1) At room temperature, in a 500 mL glass flask, 58.4 g (0.4 mol) of isosorbide, 214.0 g (1.0 mol) of diphenyl carbonate and 0.0018 g of ester exchange catalyst tetraethoxytitanium (the molar ratio of isosorbide to diphenyl carbonate is 1:2.5) were added under nitrogen atmosphere, and the mixture was stirred at 80° C., then gradually heated to 185° C. and reacted for 4 hours. The by-product phenol produced by the reaction was completely evaporated to obtain prepolymer I-4.

[0090] (2) In a 500 mL glass flask, 87.0 g (0.5 mol) of suberic acid and 60.8 g (0.8 mol) of 1,2-propylene glycol (the molar ratio of dibasic acid to diol is 1:1.6) were added under a nitrogen atmosphere. At a pressure of 280 kPa, the system temperature was gradually increased to 166°C and the reaction was carried out for 2.9 hours. The by-product water produced by the reaction was completely evaporated to obtain prepolymer II-4.

[0091] (3) 90 g of prepolymer I-4 and 10 g of prepolymer II-4 were added to a 250 mL glass flask, 0.015 wt % of a polycondensation catalyst, a silica / titanium dioxide composite, was added, and a vacuum was gradually established to 70 Pa. The mixture was reacted at 238° C. for 4.7 hours to obtain a polyester polycarbonate copolymer.

[0092] After testing, the copolymer has a characteristic viscosity of 0.75 g / dL, a self-healing efficiency of 88%, a bonding strength of 0.83 MPa, and a cross-linking degree of 3.0%.

[0093] Example 5

[0094] (1) At room temperature, 58.4 g (0.4 mol) of isosorbide, 144.0 g (1.6 mol) of dimethyl carbonate and 0.0036 g of ester exchange catalyst magnesium acetylacetonate were added to a 500 mL glass flask under a nitrogen atmosphere (the molar ratio of isosorbide to dimethyl carbonate was 1:4), stirred at 70° C., then gradually heated to 171° C., reacted for 3.3 hours, and the by-product methanol produced by the reaction was completely evaporated to obtain prepolymer I-5

[0095] (2) In a 500 mL glass flask, 73.0 g (0.5 mol) of dimethyl succinate, 90.0 g (1.0 mol) of butanediol (the molar ratio of dibasic acid ester to diol is 1:2), and 0.0022 g of ester exchange catalyst magnesium acetate were added under nitrogen atmosphere, and the system temperature was gradually increased to 175 ° C. The reaction was carried out for 3.8 hours, and the by-product methanol produced by the reaction was completely evaporated to obtain prepolymer II-5.

[0096] (3) 90 g of prepolymer I-5 and 10 g of prepolymer II-5 were added to a 250 mL glass flask, 0.015 wt % of antimony trioxide as a polycondensation catalyst was added, vacuum was gradually established to 100 Pa, and the mixture was reacted at 226° C. for 5 hours to obtain a polyester polycarbonate copolymer.

[0097] After testing, the copolymer has a characteristic viscosity of 0.78 g / dL, a self-healing efficiency of 84%, a bonding strength of 0.77 MPa, and a cross-linking degree of 4.6%.

[0098] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A 1,4;3,6-dihydrohexanedol polycarbonate copolymer, characterized in that: It is prepared by copolymerization of a polycarbonate prepolymer represented by formula I and a polyester prepolymer represented by formula II; Among them, R 1 are the same or different and are independently selected from the following groups which are unsubstituted or optionally substituted by one, two or more Ra: C 1-12 Alkyl or C 6-20 Aryl; L is selected from the following groups which are unsubstituted or optionally substituted by one, two or more Rb: 1-12 Alkyl or C 6-20 Aryl; R is selected from C which is unsubstituted or optionally substituted with one, two or more Rc 1-12 alkyl; Ra, Rb, Rc are the same or different and are independently selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy.

2. The 1,4;3,6-dihydrohexanedol polycarbonate copolymer according to claim 1, characterized in that: R 1 Same, selected from C 1-6 Alkyl or C 6-14 Aryl; the aryl group is optionally C 1-6 Alkyl substituted; L is selected from C 2-10 Alkyl or C 6-14 Aryl; R is selected from C 2-10 alkyl.

3. The 1,4;3,6-dihydrohexanedol polycarbonate copolymer according to claim 1 or 2, characterized in that: R 1 Selected from methyl, ethyl, propyl, butyl, phenyl, methyl-substituted phenyl or naphthyl. Preferably, R is selected from ethyl, propyl, butyl, pentyl, hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl. Preferably, L is selected from ethyl, propyl, butyl, pentyl, hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl.

4. The 1,4;3,6-dihydrohexanedol polycarbonate copolymer according to any one of claims 1 to 3, characterized in that: Based on the total mass of the copolymer, the mass fraction of the polycarbonate prepolymer of formula I is 60-90%, and the mass fraction of the polyester prepolymer of formula II is 10-40%.

5. The 1,4;3,6-dihydrohexanedol polycarbonate copolymer according to any one of claims 1 to 4, characterized in that: A small amount of the 1,4;3,6-dihydrohexanedol polycarbonate copolymer chain segment The ring will open, so that the copolymer forms a micro-crosslinked structure, and the crosslinking degree of the copolymer is less than 10%.

6. The 1,4;3,6-dihydrohexanedol polycarbonate copolymer according to any one of claims 1 to 5, characterized in that: The intrinsic viscosity of the 1,4;3,6-dihydrohexanedol polycarbonate copolymer is 0.5 to 1.2 dL / g; Preferably, the self-healing efficiency of the 1,4;3,6-dihydrohexanedol polycarbonate copolymer is 60 to 95%; Preferably, the bonding strength of the 1,4;3,6-diglycol polycarbonate copolymer is 0.4-1.1 MPa.

7. The method for preparing the 1,4;3,6-dihydrohexanedol polycarbonate copolymer according to any one of claims 1 to 6, characterized in that: The steps include: (1) Transesterification reaction of polycarbonate: a carbonic acid diester represented by formula A and 1,4;3,6-dihydrohexanedol are mixed and subjected to transesterification reaction to obtain a polycarbonate prepolymer represented by formula I; The 1,4;3,6-dihydrohexanedol is selected from at least one of isosorbide, isomannide and isoidide: Formula A: R 1 O-CO-OR 1 , where R 1 Having the definition as described in any one of claims 1 to 3; (2) Esterification / transesterification reaction of polyester: the compound represented by formula B and the aliphatic diol represented by formula C are mixed and subjected to esterification reaction and / or transesterification reaction to obtain a polyester prepolymer represented by formula II; Formula B: R 2 OOC-L-COOR 2 Formula C: HO-R-OH Wherein, L and R have the definitions as described in any one of claims 1 to 3; R 2 The same or different, independently selected from H, unsubstituted or optionally substituted by one, two or more Rd: C 1-12 Alkyl or C 6-20 Aryl; Rd is selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy; (3) Melt polycondensation reaction: The prepolymers represented by formula I and formula II are mixed and subjected to polycondensation reaction.

8. The preparation method according to claim 7, characterized in that: In step (1), the molar ratio of the carbonic acid diester represented by formula A to 1,4;3,6-dihydrohexanedol is 10:1 to 1.5:

1. Preferably, step (1) is carried out in the presence of an ester exchange catalyst 1, wherein the ester exchange catalyst 1 is selected from at least one of metal hydrides, hydroxides, metal oxides, metal acetylacetonate complexes, titanium organic compounds, tin organic compounds, alkoxy metal compounds, metal carbonates, metal bicarbonates, metal phosphites, inorganic acids, organic acids, tertiary amines, metal acetates and metal halides.

9. The preparation method according to claim 7 or 8, characterized in that: In step (2), the molar ratio of the compound represented by formula B to the aliphatic diol represented by formula C is 1:1-4. Preferably, step (2) is carried out in the presence of an ester exchange catalyst 2, and the added ester exchange catalyst 2 is at least one of metal oxides, metal hydroxides, alkoxy metal compounds, metal phosphates, metal sulfates, metal acetylacetonate complexes, metal acetates and metal halides containing magnesium, zinc, manganese, aluminum, cobalt and tin. Preferably, step (3) is carried out in the presence of a condensation polymerization catalyst, wherein the condensation polymerization catalyst is at least one of an organic metal compound, oxide or complex containing titanium, antimony, silicon, germanium or zirconium; preferably at least one of titanium dioxide, silicon dioxide / titanium dioxide composite, zirconium dioxide / titanium dioxide composite, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, antimony glycol, antimony acetate, germanium dioxide and germanium acetate.

10. Use of the 1,4;3,6-dihydrohexanedol polycarbonate copolymer according to any one of claims 1 to 6 as an adhesive.

Images