CN112608452B - High-performance recyclable and easily-repaired epoxy resin and preparation method thereof - Google Patents
High-performance recyclable and easily-repaired epoxy resin and preparation method thereof Download PDFInfo
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- CN112608452B CN112608452B CN202011330625.6A CN202011330625A CN112608452B CN 112608452 B CN112608452 B CN 112608452B CN 202011330625 A CN202011330625 A CN 202011330625A CN 112608452 B CN112608452 B CN 112608452B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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Abstract
The invention relates to a high-performance recyclable and easily-repaired epoxy resin and a preparation method thereof. The recyclable and easily-repaired epoxy resin is prepared by carrying out curing reaction on epoxy resin, a curing agent and an accelerant, wherein the curing agent is bridged by a dynamic boric acid ester bondA modified polyamine curing agent comprising at least the following segments per repeating unit:
Description
Technical Field
The invention particularly relates to a high-performance recyclable and easily-repaired epoxy resin and a preparation method thereof, belonging to the field of high-performance resins.
Background
Epoxy resin is widely applied in various fields due to excellent performance, and a large amount of epoxy waste is urgently required to be recycled every year. However, due to the irreversible chemical crosslinking structure of the thermosetting epoxy resin, on one hand, when the material is damaged in the using process, the in-situ body repair is difficult to carry out, and the maintenance cost is greatly increased; on the other hand, thermosetting resins are insoluble and infusible once cured and molded, and a large amount of waste resins and composite materials cannot be effectively reprocessed and recycled, so that environmental pollution and energy waste caused by the waste resins and the composite materials become prominent problems which hinder the application and development of resin-based composite materials.
In 2011, leibler et al reported an epoxy resin material based on dynamic ester exchange reaction in Science, and found that the epoxy resin material can be melt-processed at high temperature like glass, so that the epoxy resin material can be recycled in a real sense. After this work has been published, the introduction of reversibly crosslinked networks based on dynamic covalent bonds in polymer networks has received much attention as one of the important approaches to solving the problem of recycling and reprocessing thermoset polymers. At present, most dynamic covalent bond systems studied include ester exchange reaction, disulfide bond exchange reaction, olefin double decomposition reaction and the like, however, the reactions all have the problems of instability in a thermal oxygen environment or side cross-linking reaction generated at high temperature and the like, and the utilization efficiency and the performance of the resin after repair or recovery are seriously influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a recyclable and easily-repaired epoxy resin which has excellent recyclable, easily-repaired, thermal oxygen resistance and hydrolysis resistance.
The technical solution of the invention is as follows:
the recoverable easily-repaired epoxy resin is prepared by carrying out curing reaction on epoxy resin, a curing agent and an accelerator, wherein the curing agent is a modified polyamine molecule bridged by a dynamic borate bond, and each repeating unit at least comprises the following fragments:
the curing agent is a polyamine curing agent bridged by dynamic borate bonds, the borate bonds are obtained by esterification dehydration condensation reaction of phenylboronic acid groups and dihydric alcohol groups, and the curing agent has the following structural formula:
wherein R is 1 Is an arbitrary functional group, R 2 Is composed of
n≥2。
The curing agent can be prepared by reacting an organic amine molecule A1 with a phenylboronic acid group at one end with a polyhydric diol molecule B1, or reacting an organic amine molecule A2 with a single diol group at one end with a polyhydric phenylboronic acid molecule B2.
The organic amine molecule A1 with a phenylboronic acid group at one end has the following structural formula:
wherein R is 1 And may be any functional group such as a meta or para functional group.
The organic amine molecule A1 may preferably be, but is not limited to, one of the following structural formulae:
the polyglycol molecule B1 is characterized by the following structural formula:
wherein R is 1 And may be any functional group.
The polyhydric diol molecule B1 may preferably be, but is not limited to, one of the following structural formulae:
the organic amine molecule A2 having a single diol group at one end has the following structural formula:
wherein R is 1 And may be any functional group.
The organic amine molecule A2 may preferably be, but is not limited to, one of the following structural formulae:
the poly-phenylboronic acid molecule B2 has the following structural formula:
wherein, the connecting functional group can be meta or para, and n is more than or equal to 2.R 1 And may be any functional group.
The poly (phenylboronic acid) molecule B2 may preferably be, but is not limited to, one of the following structural formulas:
the invention also provides a method for preparing the high-performance recyclable and easily-repaired epoxy resin, which is realized by the following steps:
1) Mixing and dissolving organic molecules A1 and B1 or A2 and B2 in a certain proportion in an organic solvent, adding a molecular sieve or a drying agent, fully reacting at room temperature, filtering and then concentrating in vacuum to obtain a dynamic borate ester bond bridged modified polyamine curing agent; the conditions are selected to ensure that the dehydration condensation reaction is fully carried out;
2) Uniformly mixing the epoxy resin with the curing agent and the accelerator prepared in the step 1), and obtaining the epoxy resin material after the curing reaction is completed.
The organic amine molecules and the poly (phenylboronic acid) or the poly (glycol) molecules are mixed according to a molar ratio of (f): 1 (i.e. the ratio of A1 to B1, or the ratio of A2 to B2), wherein f is the number of functional groups of the polyphenylboronic acid or the polydiol monomer, and f is ≧ 2.
The accelerator is a secondary or tertiary amine small molecule containing a N atom, and can be preferably tertiary amine or pyridine.
The epoxy resin is preferably a glycidyl epoxy resin system, and can be any one or a mixture of more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin and glycidyl ammonia type epoxy resin, and is more preferably bisphenol A type epoxy resin or bisphenol F type epoxy resin.
The organic solvent can be any common organic solvent, and preferably any one or a mixture of several of tetrahydrofuran, ethyl acetate, dichloromethane and toluene.
In the step 2), the curing reaction conditions may adopt conventional epoxy resin curing conditions, and may be: and (3) placing the uniformly mixed mixture of the epoxy resin and the curing agent into a vacuum oven, vacuumizing and defoaming for 30-50min, pouring the defoamed solution into a preheated stainless steel mold, heating and curing, cooling and demolding.
The design principle of the invention is as follows:
according to the invention, the modified polyamine curing agent with borate bridging groups is synthesized, and borate cross-linking points containing N → B coordination bonds are constructed by introducing the amine curing agent and the accelerator, so that the epoxy resin based on borate double decomposition reaction is prepared. Under certain conditions, epoxy resin fragments or damaged interfaces can be fused by high molecular chain movement and rearrangement initiated by boric acid ester double decomposition reaction, so that the re-molding of the resin and the repair of the damaged interfaces are realized. The boric acid ester crosslinking point constructed by the invention has higher bond energy and good thermo-oxidative stability, and the introduction of the N → B coordination bond greatly improves the problem of non-hydrolysis resistance of the traditional boric acid ester bond and overcomes the defects of unstable thermo-oxidative stability, non-hydrolysis resistance, poor mechanical property and the like of the traditional dynamic bond crosslinking polymer.
The invention has the beneficial effects that:
according to the invention, the epoxy resin with recoverable and easily repairable performance is obtained by constructing dynamic borate crosslinking points containing N → B coordination bonds in a resin curing crosslinking network. The curing agent prepared by the invention has universality for different epoxy resins, high universality, mild reaction conditions and simple preparation process, does not need other catalysts during recovery or repair, and can realize better recovery and repair performance under certain heating conditions based on double decomposition reaction of boric acid ester. In addition, compared with other dynamic bond system cross-linked polymers, the epoxy resin prepared by the invention has excellent mechanical property, thermal-oxidative stability and hydrolysis resistance, and has important significance for promoting the practical application of the resin material in engineering.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
The epoxy resin recovery method provided by the invention comprises the steps of breaking and finely crushing the epoxy resin prepared by the method, and carrying out die pressing for 6-12 h at 100-160 ℃ and 5-10 MPa in an air atmosphere.
Example 1: the curing agent of the embodiment is prepared by reacting an organic amine molecule A2 with a single diol group at one end with a poly-phenyl boronic acid molecule B2, wherein the A2 adopts 3-amino-1, 2-propanediol, and the B2 adopts 1, 4-phenyl diboronic acid.
Step 1: under the protection of nitrogen, 1, 4-phenyl diboronic acid (16.5 g) is dissolved in 150mL tetrahydrofuran, ultrasonic treatment is carried out, stirring is carried out until the 1, 4-phenyl diboronic acid is completely dissolved, then 3-amino-1.2-propylene glycol (18.2 g) and 20mL deionized water are added for full dissolution, stirring is carried out for 2h, magnesium sulfate (20 g) is added, heating reflux reaction is carried out for 2h, filtering is carried out after the reaction is finished, filtrate is subjected to rotary evaporation and concentration to obtain white solid, and the curing agent containing borate bridging group is obtained, wherein the structural formula is as follows:
step 2: and (2) uniformly mixing 50g of bisphenol A epoxy resin solution E51, 17.5g of the prepared curing agent and 0.6g (1 wt% of mass ratio) of tertiary amine accelerator, putting the mixture into a vacuum oven, vacuumizing and defoaming for 30-50min, pouring the defoamed solution into a preheated stainless steel mold, curing at room temperature for 8h, cooling and demolding to obtain the epoxy resin.
The prepared epoxy resin is broken and finely crushed, the resin fragments are molded for 6 hours at the temperature of 110 ℃ and under the pressure of 8MPa, the recovered sample is tested for tensile property, and the recovery efficiency of the recovered epoxy resin is shown in table 1.
Example 2: the curing agent of the embodiment is prepared by reacting an organic amine molecule A1 with a phenylboronic acid group at one end with a polyhydric diol molecule B1, wherein A1 is 3-aminophenylboronic acid, and B1 is pentaerythritol.
Step 1: pentaerythritol (13.6 g) and 3-aminophenylboronic acid (27.4 g) were weighed out and dissolved in 150ml of tetrahydrofuran, and the mixture was stirred with ultrasound until it was completely dissolved. Adding 15g of magnesium sulfate, fully reacting for 24 hours at room temperature, filtering after the reaction is finished, and performing rotary evaporation and concentration on filtrate to obtain a white solid to obtain the curing agent containing the borate bridging group, wherein the structural formula is as follows:
step 2: uniformly mixing 50g of bisphenol A epoxy resin solution E51, 21.5g of the prepared curing agent and 0.7g of pyridine accelerator (1 wt% of the mass ratio), placing the mixture into a vacuum oven, vacuumizing and defoaming for 30-50min, pouring the defoamed solution into a preheated stainless steel mold, curing at 90 ℃ for 1h, curing at 130 ℃ for 6h, cooling and demolding to obtain the epoxy resin.
The prepared epoxy resin is broken and finely crushed, the resin fragments are molded for 6 hours at 140 ℃ under the pressure of 10MPa, the recovered sample is tested for tensile property, and the recovery efficiency of the recovered epoxy resin is shown in table 1.
Example 3: the curing agent of the embodiment is prepared by reacting an organic amine molecule A2 with a single diol group at one end with a poly-benzene boric acid molecule B2, wherein A2 is 4-amino-1, 2-butanediol, and B2 is 1,3, 5-benzene triboronic acid.
Step 1: under the protection of nitrogen, 1,3, 5-benzene tricarbonic acid (20.9 g) is dissolved in 300mL of toluene, ultrasonic treatment and stirring are carried out until the benzene tricarbonic acid is completely dissolved, 4-amino-1.2-butanediol (31.5 g) is added, stirring is carried out for 2h to fully dissolve and mix, 4A molecular sieve (20 g) is added, heating reflux reaction is carried out for 2h, filtering is carried out after the reaction is finished, filtrate is subjected to rotary evaporation and concentration to obtain white solid, and the curing agent containing a boric acid ester bridging group is obtained, wherein the structural formula is as follows:
step 2: uniformly mixing 51g of bisphenol F epoxy resin CYDF-170, 20.8g of the prepared curing agent and 0.7g (1 wt% of mass ratio) of tertiary amine accelerator, placing the mixture into a vacuum oven, vacuumizing and defoaming for 30-50min, pouring the defoamed solution into a preheated stainless steel mold, curing at 60 ℃ for 3h, curing at 130 ℃ for 1h, cooling and demolding to obtain the epoxy resin, and cooling and demolding to obtain the epoxy resin.
The prepared epoxy resin is broken and finely crushed, the resin fragments are molded for 6 hours at the temperature of 130 ℃ and under the pressure of 8MPa, the recovered sample is subjected to tensile property test, and the recovery efficiency of the recovered epoxy resin is shown in Table 1.
Comparative example 1:
step 1: uniformly mixing 100g of bisphenol A epoxy resin solution E51 with a curing agent diaminodiphenylmethane (DDM), placing the mixture into a vacuum oven, vacuumizing and defoaming for 30-50min, pouring the defoamed solution into a preheated stainless steel mold, curing for 4h at 60 ℃, curing for 4h after 100 ℃, cooling and demolding to obtain the epoxy resin.
Step 2: the prepared epoxy resin is broken and finely crushed, the resin fragments are molded for 6 hours at 140 ℃ under the pressure of 10MPa, the recovered sample is tested for tensile property, and the recovery efficiency of the recovered epoxy resin is shown in table 1.
TABLE 1 comparison of the Performance and recovery efficiency of epoxy resins of the invention and comparative materials
| Sample examples | Tensile Strength (MPa) | Glass transition temperature (. Degree. C.) | RecoveringEfficiency of |
| Example 1 | 78±5 | 68 | 86％ |
| Example 2 | 85±7 | 120 | 75％ |
| Example 3 | 92±6 | 92 | 79％ |
| Comparative example 1 | 82±4 | 132 | Can not be formed after recovery |
The invention has not been described in detail and is in part known to those of skill in the art.
The particular embodiments of the present invention disclosed above are illustrative only and are not intended to be limiting, since various alternatives, modifications, and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The invention should not be limited to the disclosure of the embodiments in the present specification, but the scope of the invention is defined by the appended claims.
Claims (8)
1. The recyclable and easily-repaired epoxy resin is characterized by being prepared by carrying out curing reaction on epoxy resin, a curing agent and an accelerator, wherein the curing agent is a dynamic borate ester bond bridged modified polyamine curing agent, and each repeating unit at least comprises the following fragments:
the curing agent has the following structural formula characteristics:
wherein R is 1 Is an arbitrary functional group, R 2 Is composed of
n≥2；
The curing agent is prepared by reacting an organic amine molecule A1 with a phenylboronic acid group at one end with a polyhydric diol molecule B1, or reacting an organic amine molecule A2 with a single diol group at one end with a polyhydric phenylboronic acid molecule B2;
the recyclable and easily-repaired epoxy resin is prepared by the following steps:
1) Mixing and dissolving organic molecules A1 and B1 or A2 and B2 in a certain proportion in an organic solvent, adding a molecular sieve or a drying agent, fully reacting at room temperature, filtering and then concentrating in vacuum to obtain a dynamic borate bond bridged modified polyamine curing agent;
2) Uniformly mixing epoxy resin with the curing agent and the accelerator prepared in the step 1), and obtaining an epoxy resin material after complete curing reaction; the epoxy resin is a glycidyl epoxy resin system; the accelerant is a secondary or tertiary amine micromolecule containing N atoms.
2. The recyclable, easy-to-repair epoxy resin of claim 1 wherein the organic amine molecule A1 bearing a phenylboronic acid group at one end is characterized by the following structural formula:
wherein R is 1 Is any functional group.
3. The recyclable, easy to repair epoxy resin of claim 1 wherein the polyglycol molecule B1 is characterized by the following structural formula:
wherein R is 1 Is any functional group.
4. The recyclable, easy to repair epoxy resin of claim 1 wherein the organic amine molecule A2 bearing a single diol group at one end is characterized by the following structural formula:
wherein R is 1 Is any functional group.
5. The recyclable, easy to repair epoxy resin of claim 1 wherein the poly (phenylboronic acid) molecule B2 is characterized by the following structural formula:
wherein R is 1 Is any functional group, and n is more than or equal to 2.
6. A method for preparing the recyclable and easily repairable epoxy resin of claim 1, wherein the curing agent is prepared by reacting an organic amine molecule A1 having a phenylboronic acid group at one end thereof with a polyhydric diol molecule B1 or by reacting an organic amine molecule A2 having a mono-diol group at one end thereof with a polyhydric phenylboronic acid molecule B2, the method comprising the steps of:
1) Mixing and dissolving organic molecules A1 and B1 or A2 and B2 in a certain proportion in an organic solvent, adding a molecular sieve or a drying agent, fully reacting at room temperature, filtering and then concentrating in vacuum to obtain a dynamic borate bond bridged modified polyamine curing agent;
2) Uniformly mixing the epoxy resin with the curing agent and the accelerator prepared in the step 1), and obtaining the epoxy resin material after complete curing reaction.
7. The process according to claim 6, wherein the ratio of A1 to B1 or the ratio of A2 to B2 is such that the molar ratio f:1, wherein f is the number of functional groups of the polybasic phenylboronic acid or the polybasic diol monomer, and f is not less than 2.
8. The method according to claim 6, wherein the epoxy resin is any one or a mixture of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin and glycidyl ammonia type epoxy resin; the organic solvent is one or a mixture of more of tetrahydrofuran, ethyl acetate, dichloromethane and toluene.
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