阅读说明：本技术 羧酸酯/磷酸酯双重动态共价聚合物网络材料及其制法 (Carboxylate/phosphate dual dynamic covalent polymer network material and preparation method thereof ) 是由 刘艳林 马松琪 朱锦 于 2021-09-03 设计创作，主要内容包括：本发明公开了一种羧酸酯/磷酸酯双重动态共价聚合物网络材料及其制法。所述制法包括：使包含长链侧基的环状酸酐、环氧单体、含磷酸基团化合物的均匀混合反应体系进行预反应,再经固化反应,获得羧酸酯/磷酸酯双重动态共价聚合物网络材料。本发明制备的羧酸酯/磷酸酯双重动态共价聚合物网络材料不仅具有优异的热学、力学、本征阻燃和降解性能,而且能够实现自催化快速重塑加工；同时制备过程简单,可操作性强,易于实现工业化生产,有望解决现有环氧树脂易燃、难降解的难题,提高热学、力学性能与加快自催化重塑速率相矛盾的问题。(The invention discloses a carboxylate/phosphate dual dynamic covalent polymer network material and a preparation method thereof. The preparation method comprises the following steps: the carboxylate/phosphate dual dynamic covalent polymer network material is obtained by pre-reacting a uniformly mixed reaction system containing long-chain side group cyclic anhydride, epoxy monomer and phosphoric acid group-containing compound, and then carrying out curing reaction. The carboxylate/phosphate dual dynamic covalent polymer network material prepared by the invention not only has excellent thermal, mechanical and intrinsic flame retardant and degradation properties, but also can realize autocatalysis rapid remodeling processing; meanwhile, the preparation process is simple, the operability is strong, the industrial production is easy to realize, the difficult problems of flammability and difficult degradation of the existing epoxy resin are hopefully solved, and the problems of improving the thermal and mechanical properties and accelerating the self-catalytic remodeling rate are contradictory.)

1. A preparation method of a carboxylate/phosphate dual dynamic covalent polymer network material is characterized by comprising the following steps:

the carboxylate/phosphate dual dynamic covalent polymer network material is obtained by carrying out pre-reaction on a uniformly mixed reaction system containing cyclic anhydride containing long-chain side groups, epoxy monomers and a compound containing phosphoric acid groups and then carrying out curing reaction.

2. The method of claim 1, wherein: the cyclic anhydride containing long-chain side groups comprises one or the combination of more than two of dodecyl succinic anhydride, dodecenyl succinic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride and hexadecyl succinic anhydride.

3. The method of claim 1, wherein: the epoxy monomer comprises any one or the combination of more than two of bisphenol A epoxy, hydrogenated bisphenol A epoxy and hexahydrophthalic acid diglycidyl ester.

4. The method of claim 1, wherein: the phosphoric acid group-containing compound comprises any one or the combination of more than two of N- (phosphorylmethyl) glycine, glyphosine and aminotrimethylene phosphonic acid.

5. The production method according to claim 1, characterized by comprising: uniformly mixing cyclic anhydride containing long-chain side groups, epoxy monomer and a compound containing phosphoric acid groups to form a uniformly mixed reaction system;

and/or the molar ratio of the anhydride group to the phosphate group in the uniformly mixed reaction system is 1: 0.5-1: 1.5, and the molar ratio of the epoxy group to the sum of the anhydride group and the phosphate group in the uniformly mixed reaction system is 1: 1-1: 1.5.

6. The method according to claim 1, comprising: and carrying out pre-reaction on the uniformly mixed reaction system at 120 ℃ for 1-3 h.

7. The method of claim 1, wherein: the temperature of the curing reaction is 150-190 ℃, and the time is 4-6 h.

8. A carboxylate/phosphate dual dynamic covalent polymer network material prepared by the method of any one of claims 1 to 7.

9. The carboxylate/phosphate dual dynamic covalent polymer network material of claim 8, wherein: the carboxylate/phosphate dual dynamic covalent polymer network material has the glass transition temperature of 47-110 ℃, the crystallization melting temperature of 52-122 ℃, the elongation at break of 40-180%, the Young modulus of 620-2230 MPa, the tensile strength of 20.2-90.8 MPa and the limiting oxygen index of 28-33%;

and/or the degradation time of the carboxylate/phosphate dual dynamic covalent polymer network material in a 1M NaOH aqueous solution at 50 ℃ is 1.2-3.5 h.

10. Use of the carboxylate/phosphate dual dynamic covalent polymer network material according to claim 8 or 9 in the field of the preparation of remodelable thermosetting resins.

Technical Field

The invention relates to a carboxylate/phosphate dual dynamic covalent polymer network material and a preparation method thereof, in particular to a crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long-chain side groups, a preparation method and an application thereof, belonging to the technical field of preparation of sustainable thermosetting resin.

Background

Compared with thermoplastic resin, thermosetting resin has more excellent thermal and mechanical properties and dimensional stability, so that the thermosetting resin is widely applied to the fields of coatings, adhesives, composite materials, electronic packaging and the like, but the traditional thermosetting material is difficult to recover after being discarded. The dynamic covalent bond can endow the thermosetting resin with heavy plasticity, thereby solving the problem that the thermosetting resin cannot be recycled.

Among the reported dynamic covalent bonds such as ester bond, disulfide bond, borate bond, imine bond and the like, the ester exchange type remodelable thermosetting resin is one of the materials with the most application prospect, but the remodeling depends on the addition of a catalyst, so that the basic performance is sacrificed to limit the application. It is important to realize that the ester exchange type thermosetting resin can be remolded without an external catalyst, but the resin is difficult to remold without the external catalyst. There are four main methods for increasing the rate of transesterification in thermosetting resins. 1) Autocatalysis; 2) adjusting a network cross-linking structure; 3) oxime-ester dynamic bonds replace ester bonds; 4) the ortho groups participate in internal catalysis. The method for improving the remodeling rate of the ester exchange type thermosetting resin sacrifices thermal property, mechanics and stability, or raw materials are difficult to obtain compared with the traditional ester-based network. Therefore, it is of great interest to develop autocatalytically remodelable, ester-exchanged thermosetting resins that retain basic properties.

The prior document discloses a preparation method of a dynamic transfer autocatalytic ester exchange type dynamic covalent polymer network, wherein maleic anhydride (succinic anhydride) and trimethylolpropane are subjected to a mono-esterification reaction in a first step, and a synthesized polycarboxyl compound is cured to obtain bisphenol A epoxy in a second step, so that the obtained ester exchange type dynamic network realizes hot-pressing remodeling without a catalyst, but the preparation process of the method is complex and the remodeling is still slow.

Disclosure of Invention

The invention mainly aims to provide a carboxylate/phosphate dual dynamic covalent polymer network material and a preparation method thereof, thereby overcoming the defects in the prior art.

The invention also aims to provide application of the carboxylate/phosphate dual 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 a carboxylate/phosphate dual dynamic covalent polymer network material, which comprises the following steps: the carboxylate/phosphate dual dynamic covalent polymer network material is obtained by carrying out pre-reaction on a uniformly mixed reaction system containing cyclic anhydride containing long-chain side groups, epoxy monomers and a compound containing phosphoric acid groups and then carrying out curing reaction.

In some embodiments, the cyclic anhydride containing long chain pendant groups includes any one or a combination of two or more of dodecyl succinic anhydride, dodecenyl succinic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, and hexadecenyl succinic anhydride, without being limited thereto.

The embodiment of the invention also provides a carboxylate/phosphate dual dynamic covalent polymer network material prepared by the method, which has the functions of intrinsic flame retardance, degradability and autocatalysis rapid remodeling processing.

The embodiment of the invention also provides application of the carboxylate/phosphate dual dynamic covalent polymer network material in the field of preparation of remodelable thermosetting resin.

Compared with the prior art, the invention has the beneficial effects that: the invention prepares a crystallizable carboxylate/phosphate dual dynamic covalent polymer network material by introducing long-chain side groups and phosphate groups, and particularly adopts the solidification reaction of cyclic anhydride containing the long-chain side groups, an epoxy monomer and a compound containing phosphate groups, on one hand, the thermal property, the mechanical property and the stability of resin are improved by crystallization of the polymer containing the long chain, and meanwhile, the long-chain side groups can improve the segment motion capability above the glass transition temperature and the melting temperature, thereby accelerating phosphate exchange reaction and carboxylate exchange reaction and improving the remodeling efficiency; on the other hand, the introduction of phosphate groups improves the flame retardant properties and the degradation properties of the epoxy resin. The prepared crystallizable carboxylic ester/phosphate ester double dynamic covalent polymer network material containing long-chain side groups not only has excellent thermal, mechanical, intrinsic flame retardant and degradation properties, but also can realize autocatalysis rapid remodeling processing. The preparation process is simple, strong in operability, easy to implement and easy to realize industrial production, and is expected to solve the problems of flammability and difficult degradation of the existing epoxy resin and the contradiction between improvement of thermal and mechanical properties and acceleration of autocatalytic remodeling rate in the existing autocatalytic transesterification system.

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 description of the embodiments or 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 for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a picture of a crystallizable carboxylate/phosphate dual dynamic covalent network material containing long chain pendant groups obtained in example 1 of the present invention after being remolded;

FIG. 2 is a graph showing the dynamic thermo-mechanical properties of the crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long chain pendant groups obtained in example 1 of the present invention;

FIG. 3 is a schematic diagram of differential scanning calorimetry of a crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long chain pendant groups 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 introduces long-chain side groups and phosphate groups to prepare the crystallizable carboxylate/phosphate dual dynamic covalent polymer network material, has excellent thermal, mechanical and intrinsic flame retardant properties and degradation properties, can realize autocatalysis rapid remodeling processing, and is expected to solve the problems of flammability and difficult degradation of the existing epoxy resin and the problem of contradiction between thermal and mechanical properties improvement and autocatalysis remodeling speed acceleration in 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 carboxylate/phosphate dual dynamic covalent polymer network material comprises the following steps: the method comprises the steps of pre-reacting a uniformly mixed reaction system containing cyclic anhydride containing long-chain side groups, epoxy monomers and a compound containing phosphoric acid groups, and then carrying out curing reaction to obtain the carboxylate/phosphate dual dynamic covalent polymer network material (also called as a crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long-chain side groups).

The reaction mechanism of the invention is as follows: the invention provides a preparation method of a crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long-chain side groups. The invention adopts the crystallization of the polymer containing long chain, improves the thermal property, the mechanical property and the stability of the resin, and simultaneously, the long chain side group can improve the motion capability of the chain segment above the glass transition temperature and the melting temperature, thereby accelerating the phosphate ester exchange reaction and the carboxylate ester exchange reaction and improving the remodeling efficiency. In addition, the introduction of phosphate groups improves the flame retardant and degradation properties of the epoxy resin. The prepared crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long-chain side groups not only has excellent thermal, mechanical, intrinsic flame retardant and degradation properties, but also can realize autocatalytic rapid remodeling processing, and is expected to solve the problems of flammability and difficult degradation of the existing epoxy resin and the problem of contradiction between thermal and mechanical properties improvement and autocatalytic remodeling speed acceleration in the existing autocatalytic transesterification system.

In some preferred embodiments, the preparation method specifically comprises the following steps: uniformly mixing cyclic anhydride containing long-chain side groups, an epoxy monomer and a compound containing phosphoric acid groups, carrying out pre-reaction, and then carrying out gradient heating solidification to prepare the crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long-chain side groups.

In some embodiments, the cyclic anhydride containing long chain pendant groups includes any one or a combination of two or more of dodecyl succinic anhydride, dodecenyl succinic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, and hexadecenyl succinic anhydride, without being limited thereto.

In some preferred embodiments, the epoxy monomer includes any one or a combination of two or more of bisphenol a epoxy, hydrogenated bisphenol a epoxy, bis glycidyl hexahydrophthalate, and is not limited thereto.

In some preferred embodiments, the phosphorus acid group containing compound includes any one or a combination of two or more of N- (phosphorylmethyl) glycine, glyphosine, aminotrimethylene phosphonic acid, and is not limited thereto.

In some preferred embodiments, the method of preparation comprises: and uniformly mixing the cyclic anhydride containing the long-chain side group, the epoxy monomer and the compound containing the phosphoric acid group to form the uniformly mixed reaction system.

Further, the molar ratio of the anhydride group to the phosphate group in the uniformly mixed reaction system is 1: 0.5-1: 1.5, and the molar ratio of the epoxy group to the sum of the anhydride group and the phosphate group in the uniformly mixed reaction system is 1: 1-1: 1.5.

In some preferred embodiments, the method of preparation comprises: and carrying out pre-reaction on the uniformly mixed reaction system at 120 ℃ for 1-3 h.

In some preferred embodiments, the curing reaction is carried out at a temperature of 150 to 190 ℃ for 4 to 6 hours.

Further, the curing process comprises the steps of reacting at 120 ℃ for 1-3 hours, then reacting at 150 ℃ for 1-3 hours, and then reacting at 190 ℃ for 1-2 hours.

Further, the crystallizable carboxylate/phosphate dual dynamic covalent polymer network material containing long-chain side groups is prepared by curing a cyclic anhydride containing long-chain side groups, an epoxy monomer and a compound containing phosphoric acid groups in the absence of a catalyst.

In conclusion, the crystallizable carboxylic ester/phosphate ester dual dynamic covalent polymer network material containing long-chain side groups prepared by the invention has excellent thermal, mechanical, intrinsic flame retardant and degradation properties, and can realize autocatalysis rapid remodeling processing. The preparation process is simple, strong in operability, easy to implement and easy to realize industrial production, and is expected to solve the problems of flammability and difficult degradation of the existing epoxy resin and the contradiction between improvement of thermal and mechanical properties and acceleration of autocatalytic remodeling rate in the existing autocatalytic transesterification system.

As another aspect of the technical scheme, the invention relates to a carboxylate/phosphate dual dynamic covalent polymer network material prepared by the method, which has the functions of intrinsic flame retardance, degradability and autocatalytic rapid remodeling processing.

Further, the carboxylate/phosphate dual dynamic covalent polymer network material has the glass transition temperature of 47-110 ℃, the crystal melting temperature of 52-122 ℃, the elongation at break of 40-180%, the Young modulus of 620-2230 MPa, the tensile strength of 20.2-90.8 MPa and the limiting oxygen index of 28-33%.

Further, the degradation time of the carboxylate/phosphate dual dynamic covalent polymer network material in a 1M NaOH aqueous solution at 50 ℃ is 1.2-3.5 h.

In another aspect, the embodiments of the present invention further provide an application of the carboxylate/phosphate dual 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. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.

Example 1

Mixing hexahydrophthalic acid diglycidyl ester, dodecenyl succinic anhydride and N- (phosphorylmethyl) glycine in a molar ratio of 1: 1.33: 0.34 in a single-neck flask; placing the mixed system in an oil bath kettle at 120 ℃ 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 cured under vacuum condition, and the curing process comprises the steps of reacting for 2 hours at 15 ℃ and reacting for 2 hours at 190 ℃; and after natural cooling, taking out the cured product from the oven to obtain the transparent pale yellow film material (namely the crystallizable ester exchange type dynamic covalent polymer network material containing the long-chain side group).

The polymer network material prepared in this example was cut into pieces and hot-pressed at 160 ℃ for 10min using a flat-plate vulcanizer to obtain a complete material (fig. 1). The glass transition temperature of the material was 47 ℃ (FIG. 2), the crystal melting temperature was 52 ℃ (FIG. 3), the elongation at break was 180%, the Young's modulus was 620MPa, the tensile strength was 20.2MPa, the limiting oxygen index was 28%, and the degradation time in 1M NaOH aqueous solution at 50 ℃ was 3.1 h.

Example 2

Mixing hexahydrophthalic acid diglycidyl ester, dodecyl succinic anhydride and N- (phosphorylmethyl) glycine in a molar ratio of 1: 1.33: 0.34 in a single-neck flask; placing the mixed system in an oil bath kettle at 120 ℃ for pre-reaction for 2 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 cured under vacuum condition, and the curing process comprises reaction at 150 ℃ for 1h and reaction at 190 ℃ 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 130 ℃ for 20min using a flat vulcanizing machine, and the complete material was recovered, as shown in fig. 1. The glass transition temperature of the material is 55 ℃, the crystal melting temperature is 67 ℃, the breaking elongation is 150%, the Young modulus is 801MPa, the tensile strength is 22.0MPa, the limiting oxygen index is 28%, and the degradation time in a 1M NaOH aqueous solution at 50 ℃ is 3.1 h.

Example 3

Bisphenol A epoxy, hexadecyl succinic anhydride and glyphosine are mixed in a single-neck flask according to the molar ratio of 1: 1.2: 0.45, and a proper amount of ethyl acetate is added into the flask to clarify the system; placing the mixed system in a 120 ℃ oil bath for pre-reaction for 1h, 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 cured under vacuum condition, and the curing process comprises reaction at 150 ℃ for 3h and reaction at 190 ℃ 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 150 ℃ for 1 hour using a flat-plate vulcanizer, and a complete material was obtained again, as shown in fig. 1. The glass transition temperature of the material is 110 ℃, the crystal melting temperature is 122 ℃, the breaking elongation is 40%, the Young modulus is 2230MPa, the tensile strength is 90.8MPa, the limiting oxygen index is 30%, and the degradation time of the material in 1M NaOH aqueous solution at 50 ℃ is 2.6 h.

Example 4

Hydrogenated bisphenol A epoxy, tetradecenyl succinic anhydride and glyphosine are mixed in a single-neck flask according to the molar ratio of 1: 1.2: 0.45; placing the mixed system in an oil bath kettle at 120 ℃ 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 cured under the vacuum condition, and the curing process comprises the steps of reacting for 2 hours at 150 ℃ and reacting for 1 hour at 190 ℃; 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 130 ℃ for 40min using a flat-plate vulcanizing machine, and the complete material was recovered, as shown in fig. 1. The glass transition temperature of the material is 62 ℃, the crystal melting temperature is 72 ℃, the breaking elongation is 98%, the Young modulus is 1022MPa, the tensile strength is 43.2MPa, the limiting oxygen index is 31%, and the degradation time in a 1M NaOH aqueous solution at 50 ℃ is 2.2 h.

Example 5

Mixing hexahydrophthalic acid diglycidyl ester, hexadecenyl succinic anhydride and amino trimethylene phosphonic acid in a molar ratio of 1: 1.2: 0.3 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 a 120 ℃ oil bath for pre-reaction for 1h, 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 cured under vacuum condition, and the curing process comprises reaction at 150 ℃ for 2h and reaction at 190 ℃ 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 for 30min at 130 ℃ using a flat-plate vulcanizing machine, and the complete material was recovered, as shown in fig. 1. The glass transition temperature of the material is 79 ℃, the crystal melting temperature is 85 ℃, the breaking elongation is 89%, the Young modulus is 1890MPa, the tensile strength is 55.6MPa, the limiting oxygen index is 33%, and the degradation time in a 1M NaOH aqueous solution at 50 ℃ is 1.2 h.

Example 6

Mixing hexahydrophthalic acid diglycidyl ester, tetradecyl succinic anhydride and N- (phosphorylmethyl) glycine in a single-neck flask according to the molar ratio of 1: 1.33: 0.36, and placing the mixed system in an oil bath kettle at 120 ℃ for pre-reaction for 2 hours; pouring the pre-reaction product into a polytetrafluoroethylene mold, putting the mold into a vacuum oven, and vacuumizing; the system is controlled to be cured under vacuum condition, and the curing process comprises reaction at 150 ℃ for 2h and reaction at 190 ℃ 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 for 30min at 130 ℃ using a flat-plate vulcanizing machine, and the complete material was recovered, as shown in fig. 1. The glass transition temperature of the material is 57 ℃, the crystal melting temperature is 69 ℃, the breaking elongation is 130%, the Young modulus is 976MPa, the tensile strength is 24.1MPa, the limiting oxygen index is 29%, and the degradation time in a 1M NaOH aqueous solution at 50 ℃ is 2.9 h.

Example 7

Mixing hexahydrophthalic acid diglycidyl ester, tetradecenyl succinic anhydride and N- (phosphorylmethyl) glycine in a molar ratio of 1: 1.33: 0.38 in a single-neck flask; placing the mixed system in an oil bath kettle at 120 ℃ for pre-reaction for 2 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 cured under vacuum condition, and the curing process comprises reaction at 150 ℃ for 2h and reaction at 190 ℃ 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 for 30min at 130 ℃ using a flat-plate vulcanizing machine, and the complete material was recovered, as shown in fig. 1. The glass transition temperature of the material is 53 ℃, the crystal melting temperature is 61 ℃, the breaking elongation is 142%, the Young modulus is 892MPa, the tensile strength is 23.6MPa, the limiting oxygen index is 29%, and the degradation time in a 1M NaOH aqueous solution at 50 ℃ is 3.2 h.

Example 8

Mixing hexahydrophthalic acid diglycidyl ester, hexadecenyl succinic anhydride and N- (phosphorylmethyl) glycine in a molar ratio of 1: 1.33: 0.4 in a single-neck flask; placing the mixed system in an oil bath kettle at 120 ℃ for pre-reaction for 2 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 cured under vacuum condition, and the curing process comprises reaction at 150 ℃ for 2h and reaction at 190 ℃ 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 for 30min at 130 ℃ using a flat-plate vulcanizing machine, and the complete material was recovered, as shown in fig. 1. The glass transition temperature of the material is 54 ℃, the crystal melting temperature is 63 ℃, the breaking elongation is 150%, the Young modulus is 851MPa, the tensile strength is 22.9MPa, the limiting oxygen index is 28%, and the degradation time of the material in 1M NaOH aqueous solution at 50 ℃ is 3.5 h.

Comparative example 1

This comparative example differs from example 1 in that: the dodecenyl succinic anhydride is replaced by 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: dodecenyl succinic anhydride was replaced with nonenyl succinic anhydride. The finally obtained material has no crystallization phenomenon and has lower thermal and mechanical properties: the glass transition temperature was 17 ℃, the elongation at break was 90%, the Young's modulus was 336MPa, and the tensile strength was 11.0 MPa.

Comparative example 3

This comparative example differs from example 1 in that: the N- (phosphorylmethyl) glycine is replaced by citric acid, the ultimate oxygen index of the finally obtained material is 20%, and the degradation time in 1M NaOH aqueous solution at 50 ℃ is 6 h.

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.