1,4;3,6-diepoxycyclohexane polycarbonate copolymer, and preparation method and application thereof

Abstract

The application provides a 1,4; 3,6-diepiklimarokohexanol polycarbonate copolymer with room-temperature self-repairing and high bonding strength and a preparation method thereof. In view of the problems of complex molecular structure design and multiple synthesis steps of multifunctional polymers, the body copolymer with room-temperature self-repairing and high bonding strength is prepared by a simple melt polycondensation method, and the polymerization method is simple, which is beneficial to subsequent industrial amplification.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a room temperature self-healing high adhesive strength 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer, its preparation method, and its application. Background Technology

[0002] In today's rapidly developing technological society, while demanding higher environmental standards from materials, people also hope that materials will become more intelligent and possess multiple functionalities to meet a wide range of application needs. Properties such as high ductility, processability, self-healing, adhesiveness, biodegradability, biocompatibility, and recyclability are receiving widespread attention, and combining several of these properties is a hot topic among researchers. To achieve multifunctionality, it is inevitable that molecular structure design will become more complex, and the synthesis process will involve numerous steps.

[0003] In the application of AI-powered wearable devices, novel materials with room-temperature self-healing properties and strong adhesive properties have attracted widespread attention from researchers in recent years. Self-healing not only extends the lifespan of materials but also makes them more stable during use. However, most materials possessing both of these properties are gel materials, and their performance is significantly affected by solvent evaporation during use. Therefore, the preparation of a bulk, room-temperature self-healing copolymer with high adhesive strength is a problem of great interest and urgently needs to be solved.

[0004] In summary, given the challenges of complex molecular structure design and numerous synthesis steps associated with multifunctional polymers, finding a simple method to prepare bulk copolymers with high room temperature self-healing adhesive strength is an urgent problem to be solved. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides a 1,4;3,6-diglycidylhexane polycarbonate copolymer with high adhesive strength and self-healing properties at room temperature, and its preparation method. This invention uses bio-based 1,4;3,6-diglycidylhexane as a raw material and achieves micro-crosslinking of the copolymer through melt polycondensation, utilizing the ring-opening properties of 1,4;3,6-diglycidylhexane to obtain a multifunctional copolymer. This effectively overcomes the difficulties of complex molecular structure design and numerous synthesis steps inherent in multifunctional polymers. The polymerization method is simple and beneficial for subsequent industrial scale-up.

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

[0007] A 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer is prepared by copolymerization of polycarbonate prepolymer of Formula I and polyester prepolymer of Formula II.

[0008]

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

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

[0012] Ra, Rb, and Rc may be the same or different, and they are independently selected from halogens. 1-12 Alkyl, Halogenated C 1-12 Alkyl or C 1-12 Alkyl group.

[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 substitution; 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 It is selected from methyl, ethyl, propyl, butyl, phenyl, methyl-substituted phenyl or naphthyl.

[0015] According to embodiments 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 embodiments 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, the mass fraction of the polycarbonate prepolymer of Formula I is 60-90% based on the total mass of the copolymer, 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 the 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer segments are present. The copolymer undergoes ring-opening, forming a micro-crosslinked structure. The degree of crosslinking of the copolymer is less than 10%, preferably less than 8%, and even more preferably less than 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-diglycidyl hexane 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-diglycidyl hexane polycarbonate copolymer is 60-95%, for example 70-90%, preferably 80-90%.

[0021] According to an embodiment of the present invention, the adhesive strength of the 1,4;3,6-diglycidyl hexane 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-diglycidyl hexanediol polycarbonate copolymer, comprising the following steps:

[0023] (1) Transesterification reaction of polycarbonate: The diester of formula A and 1,4;3,6-diglycidol are mixed and transesterified to obtain the polycarbonate prepolymer of formula I.

[0024] The 1,4;3,6-diglycidol is selected from at least one of isosorbide, isomannitol, and isoidulol.

[0025]

[0026] Formula A: R 1 O-CO-OR 1 , where R 1 It has the definition as described above;

[0027] (2) Esterification / transesterification of polyester: The compound shown in Formula B and the aliphatic diol shown in Formula C are mixed and subjected to esterification and / or transesterification to obtain the polyester prepolymer shown in Formula II.

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

[0029] Formula C: HO-R-OH

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

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

[0032] (3) Melt polycondensation reaction: The prepolymers shown in Formula I and Formula II are mixed and polycondensation reaction is carried out.

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

[0034] According to an embodiment of the present invention, compound R represented by formula B 2 OOC-L-COOR 2 The compounds represent diacids and / or diesters. For example, the compound shown in Formula B represents one diacid, one diester, two or more diacids, two or more diesters, or a mixture of one or more diacids and one or more diesters. Similarly, the diol HO-R-OH shown in Formula C can be a mixture of one or more diols. According to embodiments of the present invention, the 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, xylene carbonate, and dinaphthalene 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 represented by Formula C is selected from at least one of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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 The compounds are 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, octanoic 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. The ester, dioctyl adipate, diphenyl adipate, dimethyl pimecrolate, diethyl pimecrolate, dipropyl pimecrolate, dibutyl pimecrolate, dioctyl pimecrolate, diphenyl pimecrolate, dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dioctyl succinate, and diphenyl succinate are preferred to be at least one of succinic acid, dimethyl succinate, adipic acid, glutaric acid, pimecrolate, diethyl succinate, and dimethyl glutarate.

[0038] According to an embodiment of the present invention, in step (1), the molar ratio of the carbonate diester represented by formula A to 1,4;3,6-diglycidol 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 60-200°C, preferably 70-170°C, and the total time of the transesterification reaction is 2-20 hours, preferably 3-10 hours.

[0040] According to an embodiment of the present invention, step (1) is carried out in the presence of transesterification catalyst 1, wherein the transesterification catalyst 1 is selected from at least one of metal hydrides, hydroxides, metal oxides, metal acetylacetone complexes, titanium-based organic compounds, tin-based 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 includes a post-processing step, wherein the post-processing step is to remove byproducts in the reaction to obtain a polycarbonate prepolymer.

[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 to 4, preferably 1:1.1 to 2.5, for example 1:1.1 to 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℃, preferably 165-190℃; the reaction pressure is 200-400KPa, preferably 200-330KPa; and 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 150-200°C, preferably 160-190°C, and the total time of the transesterification reaction is 2-20 hours, preferably 3-10 hours.

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

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

[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 dichloro, tributyltin acetate, tributyltin chloride, and trimethyltin chloride.

[0049] According to an embodiment of the present invention, step (2) further includes a post-processing step, wherein the post-processing step is to remove byproducts 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 polycondensation catalyst, which is at least one of an organometallic compound or oxide or complex containing titanium, antimony, silicon, germanium or zirconium; preferably at least one of titanium dioxide, silicon dioxide / titanium dioxide complex, zirconium dioxide / titanium dioxide complex, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, antimony glycolate, 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.% of the theoretical yield of the polycarbonate copolymer, preferably 0.011 wt.% to 0.04 wt.%.

[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 200 Pa, for example 30–190 Pa, preferably not greater than 110 Pa.

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

[0054] Beneficial effects of the present invention

[0055] This invention provides a room-temperature self-healing, high-adhesion-strength 1,4;3,6-diglycidylhexane hexaol polycarbonate copolymer and its preparation method. Addressing the challenges of complex molecular structure design and numerous synthesis steps inherent in multifunctional polymers, this invention utilizes a simple melt polycondensation method to prepare a bulk copolymer with room-temperature self-healing high-adhesion strength. This polymerization method is simple and beneficial for 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 adhesive strength, and can be used as a high-performance adhesive. Moreover, the content of each component in the copolymer backbone is controllable, which facilitates performance regulation.

[0057] Terminology Definitions and Explanations

[0058] The term "halogen" refers to fluorine, chlorine, bromine, and / or iodine. Correspondingly, the term "halogenated" refers to fluorination, chlorination, bromination, and / or iodination. Within the scope of this document, when an atom, residue, group, or part is halogenated, the atom at the halogenated position can be monosubstituted, disubstituted, or polysubstituted up to fully substituted by the halogen atom, for example, "halogenated C..." 1-12 Alkyl and Halogenated C 1-12 Alkoxy groups, etc.

[0059] Term "C" 1-12 "Alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. Preferably C 1-6 Alkyl, the "C" 1-6 "Alkyl" means a straight-chain or branched alkyl group 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 their isomers.

[0060] Term "C" 6-20 "Aryl" should be understood to preferably represent a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6 to 20 carbon atoms and possessing monovalent aromaticity or partial aromaticity, preferably "C". 6-14 Aryl. The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”).13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20 When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0061] The term "halogenated C" 1-12 "alkyl" indicates C 1-12 The H on the alkyl group is optionally replaced by 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 halogens, as indicated by "halogenated" and "C". 1-12 "Alkyl" has the definition as described above. The substitution refers to substitution on the same carbon atom or on different carbon atoms. Optional "halogenated C" 1-6 Alkyl group. The "halogenated C" 1-12 "Alkyl" is, for example, trifluoromethyl.

[0062] Term "C" 1-12 "Alkoxy" indicates C 1-12 When one, two, or three carbons in an alkyl group are replaced by O, the case described with "C" 1-12 "alkyl" has the definition as described above. Optionally, "C" 1-6 "alkoxy". The "C" 1-12 "Alkoxy" can be, for example, methoxy, ethoxy, or propoxy. Attached Figure Description

[0063] Figure 1 The NMR spectrum of the polyester polycarbonate copolymer obtained in Example 1 is shown. Detailed Implementation

[0064] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory 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 covered within the scope of protection intended by the present invention.

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

[0066] The performance parameters in the following examples were all measured using 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 determined using an Ubbelohde viscometer in a thermostat at 25 °C.

[0068] Self-healing performance test: First, the sample was molded using a molding machine and then cut into rectangular strips with a sample size of 25×10×1.5mm. The strips were cut into sections and then butted together for repair. The repair temperature was 30℃ and the repair time was 12h. The tensile strength of the strips before and after repair was tested respectively. The self-healing efficiency is the ratio of the tensile strength of the strip after repair to that before repair.

[0069] Bond strength test: The sample was first molded using a molding machine, cut to a certain size, and then sandwiched between two base plates for bonding. The overlap length was 25mm, the width was 12.5mm, the clamp distance was 100mm, the tensile speed was 10mm / min, and the adhesive thickness was approximately 0.1mm. The measured tensile strength was its bond strength.

[0070] Crosslinking degree test: Measured using a Soxhlet extractor with chloroform as the solvent. Weigh 0.2g of sample, wrap it in filter paper, and then weigh the total mass of the sample and filter paper. Extract at 60℃ for 48h, then dry the residue in a vacuum oven at 50℃ for 8h, and finally weigh the total mass of the sample and filter paper to obtain the residual gel mass. The crosslinking degree is calculated using the following formula:

[0071] X = W r / W o

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

[0073] Example 1

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

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

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

[0077] The copolymer was tested and found to have an intrinsic viscosity of 0.66 g / dL, a self-healing efficiency of 70%, a bond strength of 0.58 MPa, and a degree of crosslinking of 0.8%.

[0078] Example 2

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

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

[0081] (3) Add 70g of prepolymer I-2 and 30g of prepolymer II-2 into a 250mL glass flask, add 0.015wt% tetrabutyl titanate as a polycondensation catalyst, gradually build up a vacuum to 80Pa, and react at 225℃ for 4 hours to obtain a polyester polycarbonate copolymer.

[0082] The copolymer was tested and found to have an intrinsic viscosity of 0.69 g / dL, a self-healing efficiency of 74%, a bond strength of 0.63 MPa, and a degree of crosslinking of 1.5%.

[0083] Example 3

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

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

[0086] (3) Add 80g of prepolymer I-3 and 20g of prepolymer II-3 to a 250mL glass flask, add 0.015wt% of condensation catalyst germanium dioxide, gradually build up a vacuum to 100Pa, and react at 240℃ for 4.5 hours to obtain polyester polycarbonate copolymer.

[0087] The copolymer was tested and found to have an intrinsic viscosity of 0.71 g / dL, a self-healing efficiency of 80%, a bond strength of 0.67 MPa, and a degree of crosslinking of 2.2%.

[0088] Example 4

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

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

[0091] (3) Add 90g of prepolymer I-4 and 10g of prepolymer II-4 to a 250mL glass flask, add 0.015wt% of polycondensation catalyst silica / titanium dioxide composite, gradually build up a vacuum to 70Pa, and react at 238℃ for 4.7 hours to obtain polyester polycarbonate copolymer.

[0092] The copolymer was tested and found to have an intrinsic viscosity of 0.75 g / dL, a self-healing efficiency of 88%, a bond strength of 0.83 MPa, and a degree of crosslinking 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 magnesium acetylacetonate transesterification catalyst were added to a 500 mL glass flask under a nitrogen atmosphere (the molar ratio of isosorbide to dimethyl carbonate was 1:4). The mixture was stirred at 70 °C, and then gradually heated to 171 °C. The reaction was carried out for 3.3 hours. The methanol byproduct produced by the reaction was completely distilled off 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 (molar ratio of ester to diol is 1:2), and 0.0022 g of magnesium acetate as an ester exchange catalyst were added. The temperature of the system was gradually increased to 175 °C and the reaction was carried out for 3.8 hours. The methanol byproduct produced by the reaction was completely distilled off to obtain prepolymer II-5.

[0096] (3) Add 90g of prepolymer I-5 and 10g of prepolymer II-5 into a 250mL glass flask, add 0.015wt% antimony trioxide condensation catalyst, gradually build up a vacuum to 100Pa, and react at 226℃ for 5 hours to obtain polyester polycarbonate copolymer.

[0097] The copolymer was tested and found to have an intrinsic viscosity of 0.78 g / dL, a self-healing efficiency of 84%, a bond strength of 0.77 MPa, and a degree of crosslinking of 4.6%.

[0098] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer, characterized in that, It is prepared by copolymerization of the polycarbonate prepolymer shown in Formula I and the polyester prepolymer shown in Formula II; Formula I Formula II Among them, R 1 They are either the same or different, and are independently selected from the following groups: C 1-10 Alkyl or C 6-14 Aryl; L is selected from C 1-10 alkyl; R is selected from C 1-10 alkyl; Based on the total mass of the copolymers, 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%. A small amount of the 1,4;3,6-diglycidyl hexane polycarbonate copolymer segments The process involves ring-opening, causing the copolymer to form a micro-crosslinked structure, wherein the degree of crosslinking of the copolymer is 0.1-10%. The self-healing efficiency of the 1,4;3,6-diglycidyl hexane polycarbonate copolymer is 60-95%; The adhesive strength of the 1,4;3,6-diglycidyl hexane polycarbonate copolymer is 0.4 to 1.1 MPa.

2. The 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer according to claim 1, characterized in that, R 1 Same, selected from C 1-6 Alkyl, phenyl, or naphthyl.

3. The 1,4;3,6-diglycidylhexane polycarbonate copolymer according to claim 1 or 2, characterized in that, R 1 It is selected from methyl, ethyl, propyl, butyl, phenyl or naphthyl.

4. The 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer according to claim 1 or 2, characterized in that, 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.

5. The 1,4;3,6-diglycidylhexane polycarbonate copolymer according to claim 1 or 2, characterized in that, 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.

6. The 1,4;3,6-diglycidylhexane polycarbonate copolymer according to claim 1 or 2, characterized in that, The degree of crosslinking of the copolymer is less than 8%.

7. The 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer according to claim 1 or 2, characterized in that, The intrinsic viscosity of the 1,4;3,6-diglycidyl hexane polycarbonate copolymer is 0.5 to 1.2 dL / g.

8. The 1,4;3,6-diglycidylhexane polycarbonate copolymer according to claim 1 or 2, characterized in that, The self-healing efficiency of the 1,4;3,6-diglycidyl hexane polycarbonate copolymer is 70-90%.

9. The 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer according to claim 1 or 2, characterized in that, The adhesive strength of the 1,4;3,6-diglycidyl hexane polycarbonate copolymer is 0.5 to 0.9 MPa.

10. The method for preparing the 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Transesterification reaction of polycarbonate: The diester of formula A and 1,4;3,6-diglycidol are mixed and transesterified to obtain the polycarbonate prepolymer of formula I. The 1,4;3,6-diglycidol is selected from at least one of isosorbide, isomannitol, and isoidulol. Formula A: R 1 O-CO-OR 1 , where R 1 It has the definition of any one of claims 1-9; (2) Esterification / transesterification of polyester: The compound shown in Formula B and the aliphatic diol shown in Formula C are mixed and subjected to esterification and / or transesterification to obtain the polyester prepolymer shown in Formula II. Formula B: R 2 OOC-L-COOR 2 Formula C: HO-R-OH Wherein, L and R have the definitions described in any one of claims 1-9; R 2 They are the same or different, and are independently selected from H or C. 1-10 alkyl; (3) Melt polycondensation reaction: The prepolymers shown in Formula I and Formula II are mixed and undergo a polycondensation reaction; In step (3), the temperature of the polycondensation reaction is 200–260 °C. o C; The pressure of the reaction system during the polycondensation reaction is less than 200 Pa.

11. The preparation method according to claim 10, characterized in that, In step (1), the molar ratio of the carbonate diester shown in formula A to 1,4;3,6-diglycidol is 10:1 to 1.5:

1.

12. The preparation method according to claim 10, characterized in that, The carbonate diester represented by Formula A is selected from any one or a mixture of several of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, dimethyl carbonate, and dinaphthalene carbonate.

13. The preparation method according to claim 10, characterized in that, The compound represented by Formula B is selected from at least one of succinic acid, dimethyl succinate, glutaric acid, adipic acid, pimelic acid, octanoic acid, diethyl 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, dioctyl adipate, diphenyl adipate, dimethyl pimelic acid, diethyl pimelic acid, dipropyl pimelic acid, dibutyl pimelic acid, and dioctyl pimelic acid.

14. The preparation method according to claim 10, characterized in that, The aliphatic diol represented by Formula C is selected from at least one of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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.

15. The preparation method according to claim 10, characterized in that, Step (1) is carried out in the presence of transesterification catalyst 1, wherein the transesterification catalyst 1 is selected from at least one of metal hydrides, hydroxides, metal oxides, metal acetylacetone complexes, titanium-based organic compounds, tin-based organic compounds, alkoxy metal compounds, metal carbonates, metal bicarbonates, metal phosphites, inorganic acids, organic acids, tertiary amines, metal acetates, and metal halides.

16. The preparation method according to claim 10, characterized in that, In step (1), the molar ratio of the carbonate diester shown in formula A to 1,4;3,6-diglycidol is 5:1 to 2:

1.

17. The preparation method according to claim 10, characterized in that, In step (2), the molar ratio of the compound shown in formula B to the aliphatic diol shown in formula C is 1:1 to 4.

18. The preparation method according to claim 10, characterized in that, Step (2) is carried out in the presence of transesterification catalyst 2, which is at least one of the following: 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, or tin.

19. The preparation method according to claim 10, characterized in that, Step (3) is carried out in the presence of a polycondensation catalyst, which is at least one of an organometallic compound or oxide or complex containing titanium, antimony, silicon, germanium or zirconium.

20. The preparation method according to claim 19, characterized in that, The polycondensation catalyst is at least one of titanium dioxide, silicon dioxide / titanium dioxide composite, zirconium dioxide / titanium dioxide composite, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, antimony glycolate, antimony acetate, germanium dioxide, and germanium acetate.

21. The preparation method according to claim 10, characterized in that, In step (3), the temperature of the polycondensation reaction is 200–240 °C. o C; The pressure of the reaction system during the polycondensation reaction is 30-190 Pa.

22. Use of the 1,4;3,6-diglycidyl hexanediol polycarbonate copolymer according to any one of claims 1-9 as an adhesive.

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