CN113087873B - Ester exchange type dynamic covalent polymer network material containing non-planar ring and preparation method thereof - Google Patents
Ester exchange type dynamic covalent polymer network material containing non-planar ring and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract
The invention discloses an ester exchange type dynamic covalent polymer network material containing a non-planar ring and a preparation method thereof. The preparation method comprises the following steps: pre-reacting a uniform mixed reaction system containing an epoxy monomer containing a non-planar ring, cyclic anhydride containing the non-planar ring and a polyhydroxy compound, and then carrying out curing reaction to obtain the ester exchange type dynamic covalent polymer network material containing the non-planar ring. The one-pot preparation method provided by the invention introduces a non-planar ring structure, and accelerates chain segment movement in the remodeling process through conformation transformation of the non-planar ring, so that the prepared dynamic transfer autocatalytic transesterification type network material containing the non-planar ring not only has excellent thermal, mechanical and stable properties, but also can realize autocatalytic rapid remodeling processing, and the preparation process is simple, strong in operability, easy to implement, easy to realize industrial production, and is expected to solve the problems of poor thermal, mechanical and stable properties and slower autocatalytic remodeling of the existing autocatalytic transesterification system.
Description
Technical Field
The invention relates to an ester exchange type dynamic covalent polymer network, in particular to a preparation method and related application of an ester exchange type dynamic covalent polymer network material containing a non-planar ring, and belongs to the technical field of preparation of sustainable thermosetting resin.
Background
The thermosetting resin has excellent thermal and mechanical properties and dimensional stability, and is widely applied to the fields of coatings, adhesives, composite materials, electronic packaging and the like. However, conventional thermoset materials once formed cannot be recycled by melting or dissolving, etc. Dynamic covalent bonds are introduced into a cross-linked network, and the remodeling of the thermosetting resin is realized through the fracture and recombination of the dynamic bonds under the stimulation (heat, light, pH value and the like), so that the method is one of effective ways for solving the difficult problem of the traditional thermosetting resin recovery.
In the reported dynamic covalent bonds such as ester bonds, disulfide bonds, borate bonds, imine bonds and the like, the ester exchange type remodelable thermosetting resin is one of the materials which are most researched and have the greatest application prospect at present, however, remodeling generally depends on the addition of a large amount of catalyst (more than or equal to 5 percent), so that the performance of a matrix is damaged, and the toxicity, precipitation and inactivation of the addition type catalyst can limit the application of the matrix. In the existing catalyst-free system, the method for improving the remodeling rate of the ester exchange type thermosetting resin usually sacrifices thermal, mechanical and stable properties.
The prior document discloses a preparation method of a dynamic transfer autocatalytic ester exchange type dynamic covalent polymer network, which comprises the steps of firstly carrying out monoester reaction on maleic anhydride (succinic anhydride) and trimethylolpropane, curing bisphenol A epoxy with a synthesized polycarboxyl compound, and realizing hot-pressing remodeling of the obtained ester exchange type dynamic network without a catalyst, wherein the preparation process of the method is complex and the remodeling is still slow.
Disclosure of Invention
The invention mainly aims to provide an ester exchange type dynamic covalent polymer network material containing non-planar rings and a preparation method thereof, thereby overcoming the defects in the prior art.
The invention also aims to provide application of the non-planar ring-containing ester exchange type dynamic covalent polymer network material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of an ester exchange type dynamic covalent polymer network material containing a non-planar ring, which comprises the following steps: the method comprises the steps of pre-reacting a uniformly mixed reaction system containing an epoxy monomer containing a non-planar ring, cyclic anhydride containing a non-planar ring and a polyhydroxy compound, and then carrying out curing reaction to obtain the ester exchange type dynamic covalent polymer network material containing a non-planar ring.
In some embodiments, the non-planar ring-containing epoxy monomer includes any one or combination of two or more of hydrogenated bisphenol a epoxy, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl methylhexahydrophthalate, and the like, but is not limited thereto.
In some embodiments, the non-planar ring-containing cyclic anhydride includes any one or a combination of two or more of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, nadic anhydride, and the like, but is not limited thereto.
The embodiment of the invention also provides the ester exchange type dynamic covalent polymer network material containing the non-planar ring, which is prepared by the method and has the function of realizing the autocatalytic rapid remodeling processing.
The embodiment of the invention also provides application of the ester exchange type dynamic covalent polymer network material containing the non-planar ring in the field of preparation of remodelable thermosetting resin.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention introduces a non-planar ring to prepare an ester exchange type dynamic covalent polymer network material, and particularly adopts an epoxy monomer containing the non-planar ring and a cyclic anhydride containing the non-planar ring to accelerate chain segment movement in the remodeling process through conformation transformation of the non-planar ring, so as to accelerate network remodeling, and simultaneously can keep high thermal, mechanical and stable performances, thereby effectively solving the problem that the remodeling of the ester exchange dynamic network depends on a large amount of catalysts and the problem that the remodeling of the existing catalyst-free system sacrifices thermal, mechanical and stable performances;
2) the dynamic transfer autocatalytic ester exchange type network containing the non-planar ring prepared by the one-pot method not only has excellent thermal, mechanical and stable properties, but also can realize autocatalytic rapid remodeling processing, and the process for preparing the dynamic transfer autocatalytic ester exchange type dynamic covalent polymer network by the one-pot method has the advantages of simple preparation process, strong operability, easy implementation and easy realization of industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic diagram of the remodeling process of the non-planar ring-containing ester-exchanged dynamic covalent polymer network material obtained in example 1 of the present invention.
Detailed Description
As described above, in view of the defects of the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose a technical solution of the present invention. In order to solve the problems, the invention simplifies the process by a one-pot method on one hand, and introduces a non-planar ring structure into a dynamic transfer autocatalysis system to accelerate chain segment movement in the remodeling process on the other hand, thereby hopefully solving the problems of poor thermal, mechanical and stable properties and slow autocatalysis remodeling of the existing autocatalysis transesterification system.
The technical solution, its implementation and principles, etc. will be further explained as follows.
Specifically, as an aspect of the technical scheme of the invention, the preparation method of the ester exchange type dynamic covalent polymer network material containing the non-planar ring comprises the following steps: the method comprises the steps of pre-reacting a uniformly mixed reaction system containing an epoxy monomer containing a non-planar ring, cyclic anhydride containing a non-planar ring and a polyhydroxy compound, and then carrying out curing reaction to obtain the ester exchange type dynamic covalent polymer network material containing a non-planar ring.
The reaction mechanism of the invention is as follows: the preparation method of the ester exchange type dynamic covalent polymer network containing the non-planar ring introduces the non-planar ring structure, uniformly mixes the three reaction raw materials through the conformation transformation of the non-planar ring, and then carries out pre-reaction on a mixed system, wherein in the mixed system of the three reaction raw materials, cyclic anhydride containing the non-planar ring firstly carries out mono-esterification reaction with polyhydroxy compound to generate carboxyl, and further, the carboxyl is subjected to ring opening epoxy. According to the invention, the epoxy monomer containing the non-planar ring and the cyclic anhydride containing the non-planar ring are adopted, so that the chain segment movement in the remodeling process can be accelerated, the network remodeling is accelerated, the polymer network can keep high thermal, mechanical and stable performances, the problem that the remodeling of the ester exchange dynamic network depends on a large amount of catalysts can be effectively solved, and the problems that the remodeling of the existing catalyst-free system sacrifices thermal, mechanical and stable performances are solved.
In some preferred embodiments, the preparation method specifically comprises the following steps: mixing an epoxy monomer containing a non-planar ring, cyclic anhydride containing the non-planar ring and a polyhydroxy compound for pre-reaction, and then carrying out curing reaction to obtain the ester exchange type dynamic covalent polymer network material containing the non-planar ring.
In some embodiments, the non-planar ring-containing epoxy monomer includes any one or a combination of two or more of hydrogenated bisphenol a epoxy, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl methylhexahydrophthalate, and the like, but is not limited thereto.
In some embodiments, the non-planar ring-containing cyclic anhydride includes any one or a combination of two or more of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, nadic anhydride, and the like, but is not limited thereto.
In some embodiments, the polyol includes any one or a combination of two or more of trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, triethanolamine, and the like, but is not limited thereto.
In some embodiments, the method of making specifically comprises: uniformly mixing an epoxy monomer containing a non-planar ring, cyclic anhydride containing a non-planar ring and a polyhydroxy compound to form the uniformly mixed reaction system, wherein the molar ratio of an anhydride group to a hydroxyl group in the uniformly mixed reaction system is 1: 0.5-1: 1.5, and the molar ratio of an epoxy group to an anhydride group or a hydroxyl group in the uniformly mixed reaction system is 1: 1-1: 1.5.
In some embodiments, the temperature of the pre-reaction is 70 to 90 ℃, and the time of the pre-reaction is 1 to 5 hours.
In some embodiments, the curing reaction temperature is 120-180 ℃ and the curing time is 5-8 h.
Further, the curing process comprises the steps of reacting at 120 ℃ for 1-2 hours, then reacting at 150 ℃ for 1-2 hours, and then reacting at 180 ℃ for 1-2 hours.
In conclusion, the dynamic transfer autocatalytic ester exchange type network containing the non-planar ring prepared by the one-pot method has excellent thermal, mechanical and stable properties, and can realize autocatalytic rapid remodeling processing, and the process for preparing the dynamic transfer autocatalytic ester exchange type dynamic covalent polymer network by the one-pot method has the advantages of simple preparation process, strong operability, easy implementation and easy realization of industrial production.
As another aspect of the technical scheme, the invention relates to a non-planar ring-containing ester exchange type dynamic covalent polymer network material prepared by the method, and the material has the function of realizing the autocatalytic rapid remodeling processing.
Further, the ester exchange type dynamic covalent polymer network material containing the non-planar ring is prepared by curing the epoxy monomer containing the non-planar ring, the cyclic anhydride containing the non-planar ring and the polyhydroxy compound in the absence of a catalyst.
Further, the ester exchange type dynamic covalent polymer network material containing the non-planar ring has excellent thermal, mechanical and stable properties, and specifically, the glass transition temperature is 80-150 ℃, the elongation at break is 2.5-8.5%, the Young modulus is 2082-5512 MPa, and the tensile strength is 50.6-100.1 MPa.
In another aspect, the embodiments of the present invention further provide an application of the above-mentioned non-planar ring-containing ester-exchange type dynamic covalent polymer network material in the field of preparation of a remodelable thermosetting resin.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Mixing hexahydrophthalic acid diglycidyl ester, hexahydrophthalic anhydride and trimethylolpropane in a single-neck flask according to the molar ratio of 1: 2.5: 0.83; placing the mixed system in an oil bath kettle at 90 ℃ for pre-reaction for 5 hours; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is cured under vacuum condition, and the curing process comprises reaction at 120 ℃ for 2h, reaction at 150 ℃ for 2h and reaction at 180 ℃ for 2 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent pale yellow film material (namely the ester exchange type dynamic covalent polymer network material containing the non-planar ring).
After the polymer network material prepared in this example was cut into pieces, it was hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material is 115 ℃, the elongation at break is 4.5%, the Young modulus is 3310MPa, and the tensile strength is 78.3 MPa.
Example 2
Mixing methyl hexahydrophthalic acid diglycidyl ester, hexahydrophthalic anhydride and pentaerythritol in a molar ratio of 1: 2.5: 0.625 in a single-neck flask, and adding a proper amount of ethyl acetate into the flask to clarify a system; placing the mixed system in an oil bath kettle at 80 ℃ for pre-reaction for 5h, and volatilizing the solvent while reacting; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is cured under vacuum condition, and the curing process comprises reaction at 120 ℃ for 2h, reaction at 150 ℃ for 2h and reaction at 180 ℃ for 2 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent light yellow film material.
After the polymer network material prepared in this example was cut into pieces, it was hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material was 124 ℃, the elongation at break was 3.4%, the Young's modulus was 3583MPa, and the tensile strength was 81.5 MPa.
Example 3
Mixing tetrahydrophthalic acid diglycidyl ester, tetrahydrophthalic anhydride and dipentaerythritol in a molar ratio of 1: 2.5: 0.42 in a single-neck flask, and adding a proper amount of ethyl acetate into the flask to clarify a system; placing the mixed system in an oil bath kettle at 80 ℃ for pre-reaction for 5 hours, and volatilizing the solvent while reacting; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is cured under vacuum condition, and the curing process comprises reaction at 120 ℃ for 2h, reaction at 150 ℃ for 2h and reaction at 180 ℃ for 2 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent light yellow film material.
After the polymer network material prepared in this example was cut into pieces, it was hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material is 138 ℃, the elongation at break is 3.0%, the Young modulus is 4081MPa, and the tensile strength is 89.9 MPa.
Example 4
Mixing hydrogenated bisphenol A epoxy, methyl hexahydrophthalic anhydride and triethanolamine in a molar ratio of 1: 2.5: 0.83 in a single-neck flask; placing the mixed system in an oil bath kettle at 70 ℃ for pre-reaction for 1 h; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is controlled to be solidified under the vacuum condition, and the solidification process comprises reaction at 120 ℃ for 1h, reaction at 150 ℃ for 2h and reaction at 180 ℃ for 2 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent light yellow film material.
The polymer network material prepared in this example was cut into pieces and hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material was 125 ℃, the elongation at break was 3.9%, the Young's modulus was 3488MPa, and the tensile strength was 81.2 MPa.
Example 5
Mixing hexahydrophthalic acid diglycidyl ester, hexahydrophthalic anhydride and glycerol in a molar ratio of 1: 2.5: 0.42 in a single-neck flask; placing the mixed system in an oil bath kettle at 90 ℃ for pre-reaction for 3 h; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is controlled to be solidified under the vacuum condition, and the solidification process comprises reaction at 120 ℃ for 2h, reaction at 150 ℃ for 2h and reaction at 180 ℃ for 2 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent light yellow film material.
After the polymer network material prepared in this example was cut into pieces, it was hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material is 108 ℃, the elongation at break is 5.8%, the Young modulus is 3082MPa, and the tensile strength is 70.6 MPa.
Example 6
Mixing hexahydrophthalic acid diglycidyl ester, nadic anhydride and trimethylolpropane in a molar ratio of 1: 2.5: 0.83 in a single-neck flask, and adding a proper amount of ethyl acetate into the flask to clarify a system; placing the mixed system in an oil bath kettle at 80 ℃ for pre-reaction for 5h, and volatilizing the solvent while reacting; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is controlled to be solidified under the vacuum condition, and the solidification process comprises reaction at 120 ℃ for 2h, reaction at 150 ℃ for 2h and reaction at 180 ℃ for 2 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent light yellow film material.
After the polymer network material prepared in this example was cut into pieces, it was hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material is 122 ℃, the breaking elongation is 3.8%, the Young modulus is 3512MPa, and the tensile strength is 81.6 MPa.
Example 7
Mixing hexahydrophthalic acid diglycidyl ester, hexahydrophthalic anhydride and glycerol in a molar ratio of 1: 2: 0.83 in a single-neck flask; placing the mixed system in an oil bath kettle at 90 ℃ for pre-reaction for 3 h; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is cured under vacuum condition, and the curing process comprises reaction at 120 ℃ for 2h, reaction at 150 ℃ for 3h and reaction at 180 ℃ for 3 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent light yellow film material.
After the polymer network material prepared in this example was cut into pieces, it was hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material is 80 ℃, the breaking elongation is 8.5%, the Young modulus is 2082MPa, and the tensile strength is 50.6 MPa.
Example 8
Hydrogenated bisphenol A epoxy, nadic anhydride and dipentaerythritol are mixed in a single-neck flask according to the molar ratio of 1: 3: 0.25, and a proper amount of ethyl acetate is added into the flask to clarify the system; placing the mixed system in an oil bath kettle at 80 ℃ for pre-reaction for 5h, and volatilizing the solvent while reacting; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is cured under vacuum condition, and the curing process comprises reaction at 120 ℃ for 2h, reaction at 150 ℃ for 2h and reaction at 180 ℃ for 2 h; and after natural cooling, taking out the cured product from the oven to obtain the transparent light yellow film material.
After the polymer network material prepared in this example was cut into pieces, it was hot-pressed at 180 ℃ for 1 hour using a flat-plate vulcanizer to obtain a complete material again, as shown in fig. 1. The glass transition temperature of the material is 150 ℃, the elongation at break is 2.5%, the Young modulus is 5512MPa, and the tensile strength is 100.1 MPa.
Comparative example 1
This comparative example differs from example 1 in that: replacing hexahydrophthalic anhydride with succinic anhydride. And after the finally obtained material is cut into pieces, the material can be remolded only by hot pressing for 2 hours at 190 ℃ by a flat vulcanizing machine, and remolding is slow.
Comparative example 2
This comparative example differs from example 1 in that: the diglycidyl hexahydrophthalate was replaced with bisphenol a epoxy (DER 331). And shearing the finally obtained material, and performing hot pressing at 200 ℃ for 3 hours by using a flat vulcanizing machine to perform remodeling, wherein remodeling is slow.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (3)
1. A preparation method of an ester exchange type dynamic covalent polymer network material containing a non-planar ring is characterized by comprising the following steps:
uniformly mixing an epoxy monomer containing a non-planar ring, cyclic anhydride containing a non-planar ring and a polyhydroxy compound to form the uniformly mixed reaction system, wherein the molar ratio of an anhydride group to a hydroxyl group in the uniformly mixed reaction system is 1: 0.5-1: 1.5, and the molar ratio of an epoxy group to an anhydride group in the uniformly mixed reaction system is 1: 1-1: 1.5;
pre-reacting the uniformly mixed reaction system at 70-90 ℃ for 1-5 h, and curing at 120-180 ℃ for 5-8 h to obtain an ester exchange type dynamic covalent polymer network material containing a non-planar ring, wherein the ester exchange type dynamic covalent polymer network material containing the non-planar ring has a function of realizing self-catalysis rapid remodeling processing;
wherein the epoxy monomer containing the non-planar ring comprises any one or the combination of more than two of hydrogenated bisphenol A epoxy, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate and diglycidyl methylhexahydrophthalate;
the non-planar ring-containing cyclic anhydride comprises any one or the combination of more than two of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and nadic anhydride;
the polyhydroxy compound comprises any one or the combination of more than two of trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and triethanolamine.
2. A non-planar ring containing, interesterified, dynamic covalent polymer network material prepared by the process of claim 1, wherein: the transesterification type dynamic covalent polymer network material containing the non-planar ring has the glass transition temperature of 80-150 ℃, the elongation at break of 2.5-8.5%, the Young modulus of 2082-5512 MPa and the tensile strength of 50.6-100.1 MPa.
3. Use of the non-planar ring-containing, ester-exchanged, dynamic, covalent polymeric network material of claim 2 in the preparation of a remodelable, thermosetting resin.
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| CN113603866B (en) * | 2021-09-03 | 2023-10-24 | 中国科学院宁波材料技术与工程研究所 | Carboxylate/phosphate dual dynamic covalent polymer network material and preparation method thereof |
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