CN114195984B - Bisphenol A type epoxy curing agent containing dynamic enamine bond, degradable epoxy resin and preparation, remodeling and degradation methods thereof - Google Patents
Bisphenol A type epoxy curing agent containing dynamic enamine bond, degradable epoxy resin and preparation, remodeling and degradation methods thereof Download PDFInfo
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- CN114195984B CN114195984B CN202111588674.4A CN202111588674A CN114195984B CN 114195984 B CN114195984 B CN 114195984B CN 202111588674 A CN202111588674 A CN 202111588674A CN 114195984 B CN114195984 B CN 114195984B
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to a bisphenol A type epoxy curing agent containing dynamic enamine bonds, a degradable epoxy resin and a preparation, remodeling and degradation method thereof, wherein the structural formula of the bisphenol A type epoxy curing agent is as follows:
the preparation method comprises the following steps: heating and stirring acetoacetylated epoxy monomer and amine curing agent at 30-130 ℃ to obtain the epoxy resin; the preparation method of the degradable epoxy resin comprises the following steps: mixing an epoxy curing agent and a bisphenol A type epoxy monomer and heating and curing at 60-150 ℃ to obtain the epoxy resin; the remodeling method comprises the following steps: carrying out hot pressing on the degradable epoxy resin at 160-220 ℃ to obtain the degradable epoxy resin; the degradation method comprises the following steps: the degradable epoxy resin is placed in acidolysis solution and stirred for 0.5 to 48 hours at the temperature of between 25 and 180 ℃, and then the degradation is finished after neutralization, solid-liquid separation, washing and drying in turn. Compared with the prior art, the epoxy resin material containing the dynamic amido bond has the advantages of degradability, recovery and recycling, and is beneficial to promoting the industrial application of the dynamic epoxy resin.
Description
Technical Field
The invention belongs to the technical field of epoxy resin, and relates to a bisphenol A type epoxy curing agent containing dynamic enamine bonds, degradable epoxy resin and preparation, remodeling and degradation methods thereof.
Background
Wind energy is an inexhaustible renewable energy source and is a green energy source which is vigorously developed in various countries in the world all the time. The wind power blade material is one of key components in a wind power generator and is mainly made of epoxy resin and glass fibers. However, after the service life of the wind power blade is prolonged, the wind power blade cannot be degraded, and the recovery difficulty is high, so that the environment is polluted, and the resource waste is caused. The wind blade is dozens of meters long and several tons to dozens of tons heavy, wherein the consumption of the epoxy resin in the wind blade composite material is large. Therefore, developing degradable epoxy resins for wind turbine blades is an important approach to solve the above problems.
Polymers can be generally classified into thermoplastic materials and thermosetting materials according to their thermal properties. Thermoplastic polymers can be repeatedly processed and utilized, but often have insufficient mechanical properties; the three-dimensional crosslinked network structure of thermoset polymers provides them with good mechanical strength and solvent resistance, but cannot be processed repeatedly. And by introducing the dynamic reversible covalent bond into the polymer network, the dynamic covalent crosslinked polymer is formed, so that the polymer has the advantages of heavy plasticity of thermoplastic materials, excellent mechanical strength of thermosetting materials and the like. The recyclable epoxy resin is prepared by introducing dynamic bonds into the epoxy monomer, so that the purposes of recycling and reusing the resin material can be effectively realized.
The Chinese patent CN 110218294A discloses a degradable imine bond-containing epoxy resin curing agent and a preparation method thereof, wherein imine bonds are introduced into epoxy resin through in-situ crosslinking reaction to prepare the degradable thermosetting epoxy resin. The in situ crosslinking reaction of acetoacetate groups with amine-based curing agents to form dynamic enamine linkages is also one of the most common methods for preparing dynamic resins (Lessard, J.J.et. Al. Catalyst-Free polymers from macromolecules 2019,52, 2105-2111). However, the above curing process generates water as a by-product in situ, which adversely affects the properties of the cured resin and industrial production. If dynamic enamine bonds can be introduced into bisphenol A epoxy resin and water as a by-product generated in the curing crosslinking reaction is avoided, the method has important significance for the practical application of dynamic epoxy resin materials.
Disclosure of Invention
The invention aims to provide a bisphenol A type epoxy curing agent containing dynamic enamine bonds, a degradable epoxy resin and a preparation, remodeling and degradation method thereof. Compared with the traditional non-degradable epoxy resin material, the epoxy resin material containing the dynamic amido bond has the advantages of degradable recovery and recyclable use. In addition, the curing reaction condition is close to that of the traditional bisphenol A epoxy resin, and the industrial application of the dynamic epoxy resin is promoted.
The purpose of the invention can be realized by the following technical scheme:
a bisphenol A type epoxy curing agent containing dynamic enamine bonds has the following structural formula:
wherein R is the middle composition of the amine curing agent.
A preparation method of a bisphenol A type epoxy curing agent containing dynamic enamine bonds comprises the following steps:
mixing acetoacetylated epoxy monomer and amine curing agent in a reaction solvent, heating and stirring at 30-130 ℃ for reaction for 0.5-5h, and carrying out post-treatment to obtain the bisphenol A type epoxy curing agent containing dynamic enamine bonds.
Further, the preparation method of the acetoacetylated epoxy monomer comprises the following steps:
mixing a hydroxylated bisphenol A monomer and an acetoacetic ester compound in a solvent, heating to react for 1-5h at 30-150 ℃, and separating and purifying to obtain the acetoacetylated epoxy monomer;
wherein, the acetoacetic ester compound comprises at least one of ethyl acetoacetate, propyl acetoacetate, tert-butyl acetoacetate, amyl acetoacetate and heptyl acetoacetate;
the solvent comprises at least one of acetone, xylene, toluene, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, dioxane and tetrahydrofuran;
the charging ratio of the hydroxylated bisphenol A monomer to the acetoacetate compound is (30-40) g:100mL.
Further, the preparation method of the hydroxylated bisphenol A monomer comprises the following steps:
stirring bisphenol A type epoxy monomer and acid solution at 60-90 ℃ for reaction for 0.5-4h, and separating and purifying to obtain the hydroxylated bisphenol A monomer;
wherein, the bisphenol A epoxy monomer is at least one of the following epoxy monomers: CYD-128 (E-51), CYD-128 (618), CYD-128 (0164E), CYD-127 (E-54), CYD-115, E-44 (6101), E-42, E-39D;
the acid solution comprises a mixed solution consisting of at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid and acetic acid and water, and the mass concentration of the mixed solution is 80-98%;
the feeding ratio of the bisphenol A epoxy monomer to the acid solution is (50-60) g (3-10) mL.
Further, the amine curing agent is at least one of polyether amine, ethylenediamine, m-phenylenediamine and isophorone diamine; the dosage ratio of the acetoacetylated epoxy monomer to the amine curing agent is 40g (40-60) mL.
The preparation method of the degradable epoxy resin based on the epoxy curing agent comprises the following steps:
mixing an epoxy curing agent and a bisphenol A type epoxy monomer according to a volume ratio of (4-5) to (2-3), and heating and curing at 60-150 ℃ for 1-8h to obtain epoxy resin containing enamine bond groups, namely degradable epoxy resin;
wherein, the bisphenol A type epoxy monomer is at least one of the following epoxy monomers: CYD-128 (E-51), CYD-128 (618), CYD-128 (0164E), CYD-127 (E-54), CYD-115, E-44 (6101), E-42 and E-39D.
A remodeling method of the degradable epoxy resin comprises the following steps:
and (3) carrying out hot pressing on the degradable epoxy resin at 160-220 ℃ for 0.3-8h to obtain the remolded epoxy resin.
A degradation method of the degradable epoxy resin comprises the following steps:
placing the degradable epoxy resin into acidolysis solution, stirring for 0.5-48h at 25-180 ℃, and then sequentially performing neutralization, solid-liquid separation, washing and drying to obtain a degradation product;
the feeding ratio of the degradable epoxy resin to the acidolysis solution is 0.5g (10 mL).
Further, the acidolysis solution comprises at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid, acetic acid, phosphoric acid and p-toluenesulfonic acid.
The bisphenol A epoxy curing agent containing dynamic enamine bonds and the degradable epoxy resin thereof selectively introduce the enamine bond dynamic bonds into an epoxy resin system through molecular design, and simultaneously retain the structure of part of irreversible chemical bonds. Therefore, the prepared bisphenol A epoxy curing agent containing dynamic enamine bonds and the degradable epoxy resin thereof have good mechanical properties, the dynamic exchange characteristic of the enamine bonds at a certain temperature is utilized to enable the enamine bonds to have plasticity, and the unstable characteristic of the enamine bonds under the acidic condition is utilized to selectively degrade the enamine bonds, thereby realizing the degradation and recovery of the epoxy resin.
Compared with the prior art, the invention has the following characteristics:
1) The preparation method of the bisphenol A type epoxy hardener containing dynamic enamine bonds and the degradable epoxy resin thereof has the advantages of simple process, convenient operation and the like, and is beneficial to industrial production;
2) The degradable epoxy resin based on the bisphenol A type epoxy curing agent containing the dynamic enamine bond prepared by the invention has the curing process and the mechanical property similar to those of the existing bisphenol A type epoxy resin, and has the advantages of hot plastic processing and repeated processing and forming, thereby being beneficial to the industrial application of the dynamic epoxy resin;
2) The dynamic epoxy resin containing enamine bonds prepared by the invention can be degraded and recycled in an acid solvent under the conditions of heating and stirring, so that the problem that the existing bisphenol A epoxy resin is difficult to recycle is solved, and the epoxy resin has wide application prospect; and for the field of wind power generation blades, the problems of environmental pollution and resource waste caused by the epoxy resin of the existing wind power generation blades are expected to be solved.
Drawings
FIG. 1 is an IR spectrum of a bisphenol A type epoxy hardener in example 1 containing a dynamic enamine bond.
FIG. 2 is a nuclear magnetic hydrogen spectrum of a bisphenol A type epoxy hardener in example 1.
FIG. 3 is the result of the re-molding of a degradable epoxy resin based on a bisphenol A type epoxy curing agent containing a dynamic enamine bond in example 1.
FIG. 4 is a schematic diagram showing the degradation of a degradable epoxy resin based on a bisphenol A type epoxy hardener containing a dynamic enamine bond in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A bisphenol A type epoxy curing agent containing dynamic enamine bonds has the following structural formula:
wherein R is the middle composition of the amine curing agent.
A preparation method of a bisphenol A epoxy curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of hydroxylated bisphenol a monomer:
adding bisphenol A epoxy monomer into an organic solvent, mixing with an acidic solution, stirring and reacting for 0.5-4h at 60-90 ℃, washing with water and collecting an organic phase to obtain a hydroxylated bisphenol A monomer;
wherein the bisphenol A type epoxy monomer is at least one of the following epoxy monomers: CYD-128 (E-51), CYD-128 (618), CYD-128 (0164E), CYD-127 (E-54), CYD-115, E-44 (6101), E-42, E-39D; the acid solution comprises a mixed solution of at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid and acetic acid and water, and the mass concentration of the mixed solution is 80-98%; the feeding ratio of the bisphenol A epoxy monomer, the organic solvent and the acid solution is (50-60) g, (50-80) mL, (3-10) mL;
s2: preparation of acetoacetylated epoxy monomer:
mixing a hydroxylated bisphenol A monomer and an acetoacetate compound in an organic solvent, heating to react for 1-5h at 30-150 ℃, removing the organic solvent through reduced pressure distillation, and drying to obtain an acetoacetylated epoxy monomer;
wherein, the acetoacetic ester compound comprises at least one of ethyl acetoacetate, propyl acetoacetate, tert-butyl acetoacetate, amyl acetoacetate and heptyl acetoacetate; the charging ratio of the hydroxylated bisphenol A monomer, the organic solvent and the acetoacetate compound is (30-40) g, (50-60) mL and 100mL.
S3: preparation of bisphenol A type epoxy curing agent containing dynamic enamine bond:
mixing acetoacetylated epoxy monomer and amine curing agent in an organic solvent, heating and stirring at 30-130 ℃ for reaction for 0.5-5h, and carrying out reduced pressure distillation and drying to obtain a bisphenol A type epoxy curing agent containing dynamic enamine bonds;
wherein the amine curing agent is at least one of polyether amine (D230, D400 and D2000), ethylenediamine, m-phenylenediamine and isophorone diamine; the charge ratio of the acetoacetylated epoxy monomer, the organic solvent and the amine curing agent is 40g (40-60) mL.
The organic solvent may be at least one of acetone, xylene, toluene, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, dioxane, and tetrahydrofuran.
A degradable epoxy resin based on a bisphenol A type epoxy curing agent containing dynamic enamine bonds is prepared by the following steps:
mixing an epoxy curing agent and a bisphenol A type epoxy monomer according to a volume ratio of (4-5) to (2-3), and heating and curing at 60-150 ℃ for 1-8h to obtain epoxy resin containing enamine bond groups, namely degradable epoxy resin;
wherein, the bisphenol A type epoxy monomer is at least one of the following epoxy monomers: CYD-128 (E-51), CYD-128 (618), CYD-128 (0164E), CYD-127 (E-54), CYD-115, E-44 (6101), E-42, E-39D.
The method for remodeling the degradable epoxy resin comprises the following steps: and hot-pressing the degradable epoxy resin at 160-220 ℃ for 0.3-8h to obtain the reworkable epoxy resin.
A degradation method of the degradable epoxy resin comprises the following steps: placing the degradable epoxy resin into a mixed solution of an organic solvent and an acidolysis solution, stirring for 0.5-48h at 25-180 ℃, and then sequentially neutralizing with an alkaline reagent, carrying out solid-liquid separation, washing and drying to obtain a degradation product;
wherein the acidolysis solution comprises a mixed solution of water and at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid, acetic acid, phosphoric acid and p-toluenesulfonic acid, and the mass concentration of the mixed solution is 1-80%; the alkaline reagent is at least one of sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, potassium bicarbonate solution and ammonia water, the mass concentration is 1-50%, and the pH value of the neutralization end point is 6-10; the feeding ratio of the degradable epoxy resin, the acidolysis solution and the organic solvent is 0.5g (50-70) mL.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
a preparation method of bisphenol A type epoxy curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of hydroxylated bisphenol a monomer:
adding 50g of bisphenol A epoxy monomer of CYD-127 (E-54) (China petrochemical Co., ltd.) into 50mL of acetone, uniformly stirring, adding 3mL of trifluoroacetic acid solution with the mass fraction of 96%, stirring and reacting at 80 ℃ for 2h, washing with water for multiple times, and collecting an organic phase to obtain a hydroxylated bisphenol A monomer, wherein the yield is 93.5%;
s2: preparation of acetoacetylated epoxy monomer:
adding 40g of hydroxylated bisphenol A monomer into 60mL of dimethylbenzene, uniformly stirring, then adding 100mL of ethyl acetoacetate, heating to react for 4 hours at 30 ℃, and obtaining acetoacetylated epoxy monomer after reduced pressure distillation and drying, wherein the yield is 81.3%;
s3: preparation of bisphenol A type epoxy curing agent containing dynamic enamine bond:
40g of acetoacetylated epoxy monomer is added into 100mL of toluene and stirred uniformly, 70mL of D230 type polyetheramine (Hensman chemical trade (Shanghai) Co., ltd.) is added, the mixture is heated and reacted for 1h at the temperature of 80 ℃, and the bisphenol A type epoxy curing agent containing dynamic enamine bonds is obtained after reduced pressure distillation and drying, wherein the yield is 92.5%.
FIG. 1 shows an infrared spectrum of a bisphenol A type epoxy curing agent containing dynamic enamine bonds, and FIG. 2 shows a nuclear magnetic hydrogen spectrum of a bisphenol A type epoxy curing agent containing dynamic enamine bonds.
A degradable epoxy resin based on a bisphenol A type epoxy curing agent containing dynamic enamine bonds is prepared by the following steps:
10mL of epoxy curing agent and 5.4mL of bisphenol A type epoxy monomer of CYD-127 (E-54) (China petrochemical Co., ltd.) were mixed, and the mixture was cured by heating at 80 ℃ for 6 hours, and then cured by heating at 120 ℃ for 2 hours to obtain an enamine bond-containing epoxy resin, i.e., a degradable epoxy resin.
The embodiment further includes performing a reworkable performance test on the degradable epoxy resin, specifically including: and (3) putting the degradable epoxy resin on a hot press at 200 ℃ for hot pressing for 0.3h to obtain the remolded epoxy resin, as shown in figure 3, showing that the material has good plasticity.
This embodiment still includes to above-mentioned degradable epoxy carry out the degradable performance test, specifically includes: mixing 0.5g of degradable epoxy resin, 10mL of sulfuric acid solution (the concentration is 1 mol/L) and 50mL of tetrahydrofuran, stirring at 80 ℃ for 12h to complete degradation, neutralizing with 10wt% of sodium hydroxide solution until the pH value of the solution is 7.0, filtering, precipitating, washing with water and drying to obtain a degradation product. As shown in FIG. 4, the block epoxy resin is uniformly dispersed in the solution after acid hydrolysis, and the degradation product is precipitated after neutralization, separated and dried to obtain the degradation product.
Example 2:
a preparation method of a bisphenol A epoxy curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of hydroxylated bisphenol a monomer:
adding 50g of bisphenol A epoxy monomer of CYD-127 (E-54) (No-Sn Diesen epoxy Co., ltd.) into 60mL of acetone, uniformly stirring, adding 5mL of trifluoroacetic acid solution with the mass fraction of 98%, stirring and reacting at 90 ℃ for 1.5h, washing with water for multiple times, and collecting an organic phase to obtain a hydroxylated bisphenol A monomer with the yield of 94.2%;
s2: preparation of acetoacetylated epoxy monomer:
adding 40g of hydroxylated bisphenol A monomer into 60mL of toluene, uniformly stirring, then adding 100mL of ethyl acetoacetate, heating to react for 3 hours at 60 ℃, carrying out reduced pressure distillation, and drying to obtain an acetoacetylated epoxy monomer with the yield of 90.3%;
s3: preparation of bisphenol A type epoxy curing agent containing dynamic enamine bond:
40g of acetoacetylated epoxy monomer is added into 100mL of toluene and stirred uniformly, 60mL of D230 type polyetheramine (Basff China Co., ltd.) is added, the mixture is heated and reacted for 1 hour at 90 ℃, and the bisphenol A type epoxy curing agent containing dynamic enamine bonds is obtained after reduced pressure distillation and drying, wherein the yield is 96.2%.
A degradable epoxy resin based on a bisphenol A type epoxy curing agent containing dynamic enamine bonds is prepared by the following steps:
10mL of epoxy curing agent was mixed with 6mL of bisphenol A type epoxy monomer of CYD-127 (E-54) (No tin Diesen epoxy Co., ltd.), and cured by heating at 100 ℃ for 5 hours to obtain an epoxy resin containing an enamine bond, i.e., a degradable epoxy resin.
And (3) placing the degradable epoxy resin on a hot press at 200 ℃ for hot pressing for 1h to obtain the remolded epoxy resin, which shows that the material has good plasticity.
This embodiment still includes to above-mentioned degradable epoxy carry out the degradable performance test, specifically includes: mixing 0.5g of degradable epoxy resin, 10mL of sulfuric acid solution (the concentration is 3 mol/L) and 50mL of tetrahydrofuran, stirring at 100 ℃ for 6h to complete degradation, neutralizing with 10wt% of potassium hydroxide solution until the pH value of the solution is 7.0, filtering, precipitating, washing with water and drying to obtain a degradation product.
Example 3:
a preparation method of a bisphenol A epoxy curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of hydroxylated bisphenol a monomer:
adding 60g of bisphenol A epoxy monomer with the model number of E-44 (6101) (China petrochemical company, ltd.) into 80mL of tetrahydrofuran, uniformly stirring, adding 10mL of trifluoroacetic acid solution with the mass fraction of 90%, stirring and reacting at 70 ℃ for 2h, washing with water for multiple times, and collecting an organic phase to obtain a hydroxylated bisphenol A monomer with the yield of 92.8%;
s2: preparation of acetoacetylated epoxy monomer:
adding 30g of hydroxylated bisphenol A monomer into 50mL of dimethylbenzene, uniformly stirring, then heating 100mL of acetoacetic acid amyl ester at 140 ℃ for reaction for 4 hours, carrying out reduced pressure distillation, and drying to obtain an acetoacetylated epoxy monomer with the yield of 96.1%;
s3: preparation of bisphenol A type epoxy curing agent containing dynamic enamine bond:
40g of acetoacetylated epoxy monomer is added into 100mL of toluene and stirred uniformly, 40mL of isophorone diamine (Shanghai Yi En chemical technology Co., ltd.) is added, the mixture is heated and reacted for 1.5h at 80 ℃, and the bisphenol A type epoxy curing agent containing dynamic enamine bonds is obtained after reduced pressure distillation and drying, wherein the yield is 92.7%.
A degradable epoxy resin based on a bisphenol A type epoxy curing agent containing dynamic enamine bonds is prepared by the following steps:
8mL of epoxy curing agent and 4mL of bisphenol A epoxy monomer with the model number of E-44 (6101) (China petrochemical Co., ltd.) were mixed, and heated and cured at 80 ℃ for 6 hours to obtain epoxy resin containing enamine bond, i.e., degradable epoxy resin.
The degradable epoxy resin is placed on a hot press at 220 ℃ for hot pressing for 1.5h to obtain the remolded epoxy resin, which shows that the material has good reworkability.
This embodiment still includes to above-mentioned degradable epoxy carry out the degradable performance test, specifically includes: mixing 0.5g of degradable epoxy resin, 10mL of hydrochloric acid solution (the concentration is 3 mol/L) and 70mL of tetrahydrofuran, stirring at 120 ℃ for 4h to complete degradation, neutralizing with 20wt% of sodium hydroxide solution until the pH value of the solution is 7.5, filtering, precipitating, washing with water and drying to obtain a degradation product.
Example 4:
a preparation method of a bisphenol A epoxy curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of hydroxylated bisphenol a monomer:
adding 60g of bisphenol A epoxy monomer of CYD-127 (E-54) (Dow chemical Co., ltd.) into 80mL of acetone, uniformly stirring, adding 93% by mass of 10mL of trifluoroacetic acid solution, reacting for 2 hours at 70 ℃, washing with water for multiple times, and collecting an organic phase to obtain a hydroxylated bisphenol A monomer with the yield of 94.1%;
s2: preparation of acetoacetylated epoxy monomer:
adding 30g of hydroxylated bisphenol A monomer into 50mL of dimethylbenzene, uniformly stirring, then adding 100mL of acetoacetic acid propyl ester, heating and reacting for 4 hours at 140 ℃, and obtaining acetoacetylated epoxy monomer after reduced pressure distillation and drying, wherein the yield is 95.2%;
s3: preparation of bisphenol A type epoxy curing agent containing dynamic enamine bond:
40g of acetoacetylated epoxy monomer is added into 100mL of toluene and stirred evenly, 50mL of D400 type polyetheramine (Hensmei chemical trade (Shanghai) Co., ltd.) is added, the mixture is heated and reacted for 1.5h at 90 ℃, and after reduced pressure distillation and drying, the bisphenol A type epoxy curing agent containing dynamic enamine bonds is obtained, and the yield is 92.3%.
A degradable epoxy resin based on a bisphenol A type epoxy curing agent containing dynamic enamine bonds is prepared by the following steps:
8mL of epoxy curing agent was mixed with 4.5mL of bisphenol A type epoxy monomer of CYD-127 (E-54) (Dow chemical Co., ltd.), and cured by heating at 80 ℃ for 6 hours to obtain an epoxy resin containing an enamine bond, i.e., a degradable epoxy resin.
And (3) placing the degradable epoxy resin on a hot press at 220 ℃ for hot pressing for 1h to obtain the remolded epoxy resin, which shows that the material has good reworkability.
This embodiment still includes to above-mentioned degradable epoxy carry out the degradable performance test, specifically includes: mixing 0.5g of degradable epoxy resin, 10mL of hydrochloric acid solution (the concentration is 4 mol/L) and 70mL of tetrahydrofuran, stirring at 120 ℃ for 4h to complete degradation, neutralizing with 20wt% of sodium hydroxide solution until the pH value of the solution is 7.0, filtering, precipitating, washing with water and drying to obtain a degradation product.
Example 5:
a preparation method of bisphenol A type epoxy curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of hydroxylated bisphenol a monomer:
adding 60g of bisphenol A epoxy monomer with the model number of E-42 (Wuxi Diesen epoxy Co., ltd.) into 80mL of tetrahydrofuran, uniformly stirring, adding 10mL of trifluoroacetic acid solution with the mass fraction of 91%, stirring and reacting at 70 ℃ for 2 hours, washing for multiple times, and collecting an organic phase to obtain a hydroxylated bisphenol A monomer, wherein the yield is 93.3%;
s2: preparation of acetoacetylated epoxy monomer:
adding 30g of hydroxylated bisphenol A monomer into 50mL of dimethylbenzene, uniformly stirring, then adding 100mL of acetoacetic acid propyl ester, heating and reacting for 5 hours at 110 ℃, distilling under reduced pressure, and drying to obtain an acetoacetylated epoxy monomer with the yield of 95.2%;
s3: preparation of bisphenol A type epoxy curing agent containing dynamic enamine bond:
40g of acetoacetylated epoxy monomer is added into 100mL of toluene and stirred uniformly, 50mL of isophorone diamine (Vanhua chemical group Co., ltd.) is added, the mixture is heated and reacted for 1.5h at 90 ℃, and the bisphenol A type epoxy curing agent containing dynamic enamine bonds is obtained after reduced pressure distillation and drying, wherein the yield is 94.3%.
A degradable epoxy resin based on a bisphenol A type epoxy curing agent containing dynamic enamine bonds is prepared by the following steps:
8mL of epoxy curing agent was mixed with 5mL of bisphenol A type epoxy monomer of CYD-127 (E-54) (No tin Diesen epoxy Co., ltd.), and cured by heating at 100 ℃ for 5 hours to obtain an epoxy resin containing an enamine bond, i.e., a degradable epoxy resin.
The embodiment further includes performing a reworkable performance test on the degradable epoxy resin, specifically including: the degradable epoxy resin is placed on a hot press at 200 ℃ for hot pressing for 1.5h to obtain the remolded epoxy resin, which shows that the material has good reworkability.
This embodiment still includes to above-mentioned degradable epoxy carry out the degradable performance test, specifically includes: 0.5g of degradable epoxy resin, 10mL of sulfuric acid solution (with the concentration of 1 mol/L) and 50mL of tetrahydrofuran are mixed, stirred at 100 ℃ for 4 hours until degradation is completed, then neutralized by 10wt% of sodium hydroxide solution until the pH value of the solution is 7.0, and filtered, precipitated, washed and dried to obtain a degradation product.
Comparative example
3mL of a bisphenol A type epoxy monomer of polyetheramine D230 (Hensmei chemical trade (Shanghai) Co., ltd.) and 7mL of LCYD-127 (E-54) (China petrochemical Co., ltd.) was cured by heating at 80 ℃ for 6 hours, and then cured by heating at 120 ℃ for 2 hours to prepare a bisphenol A type epoxy resin.
The application example is as follows:
in this example, the tensile properties of the degradable epoxy resin and the bisphenol a epoxy resin prepared in example 1 and the comparative example were tested according to the standard GB/T2567-2008, and the results are shown in table 1.
TABLE 1 comparison of the Properties of bisphenol A epoxy resins containing enamine bonds with comparative resins
| Resin + curing agent | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 1 | 62.0±1.0 | 12.2±0.7 |
| Comparative example 1 | 62.9±0.9 | 16.7±9.0 |
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A bisphenol A type epoxy curing agent containing dynamic enamine bonds is characterized in that the epoxy curing agent is a compound with the following structural formula,
wherein R is the middle composition of the amine curing agent.
2. The process for preparing a bisphenol A type epoxy hardener as claimed in claim 1, which comprises:
mixing acetoacetylated epoxy monomers and amine curing agents in a reaction solvent, heating, stirring, reacting, and carrying out post-treatment to obtain a bisphenol A type epoxy curing agent containing dynamic enamine bonds;
the preparation method of the acetoacetylated epoxy monomer comprises the following steps: mixing a hydroxylated bisphenol A monomer and an acetoacetic ester compound in a solvent, heating to react for 1-5h at 30-150 ℃, and separating and purifying to obtain the acetoacetylated epoxy monomer; wherein, the acetoacetic ester compound comprises at least one of ethyl acetoacetate, propyl acetoacetate, tert-butyl acetoacetate, amyl acetoacetate and heptyl acetoacetate; the feeding ratio of the hydroxylated bisphenol A monomer to the acetoacetic ester compound is (30-40) g:100mL;
the preparation method of the hydroxylated bisphenol A monomer comprises the following steps: stirring bisphenol A type epoxy monomer and acid solution at 60-90 ℃ for reaction for 0.5-4h, and separating and purifying to obtain the hydroxylated bisphenol A monomer; wherein the charging ratio of the bisphenol A type epoxy monomer to the acid solution is (50-60) g (3-10) mL.
3. The process for preparing a bisphenol A type epoxy hardener as claimed in claim 2,
the solvent comprises at least one of acetone, xylene, toluene, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, dioxane and tetrahydrofuran.
4. The method for preparing the dynamic enamine bond-containing bisphenol A-type epoxy hardener as claimed in claim 3, wherein the bisphenol A-type epoxy monomer is at least one of the following epoxy monomers: CYD-128E-51, CYD-128 618, CYD-128 0164E, CYD-127E-54, CYD-115, E-44 6101, E-42 and E-39D; the acid solution comprises a mixed solution consisting of at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid and acetic acid and water, and the mass concentration of the mixed solution is 80-98%.
5. The method for preparing the bisphenol A epoxy hardener containing the dynamic enamine bond according to claim 2, wherein the amine hardener is at least one of polyetheramine, ethylenediamine, m-phenylenediamine and isophorone diamine; the charging ratio of the acetoacetylated epoxy monomer to the amine curing agent is 40g (40-60) mL.
6. The process for preparing a bisphenol A type epoxy hardener as claimed in claim 2, wherein the reaction temperature is 30 to 130 ℃ and the reaction time is 0.5 to 5 hours in the heating and stirring reaction.
7. A method for preparing a degradable epoxy resin based on the epoxy hardener as claimed in claim 1, comprising:
mixing an epoxy curing agent and a bisphenol A type epoxy monomer according to a volume ratio of (4-5) to (2-3), and heating and curing at 60-150 ℃ for 1-8h to obtain epoxy resin containing enamine bond groups, namely degradable epoxy resin;
wherein, the bisphenol A type epoxy monomer is at least one of the following epoxy monomers: CYD-128E-51, CYD-128 618, CYD-128 0164E, CYD-127E-54, CYD-115, E-44 6101, E-42 and E-39D.
8. A remodeling method based on the degradable epoxy resin according to claim 7, wherein the method comprises:
and (3) carrying out hot pressing on the degradable epoxy resin at 160-220 ℃ for 0.3-8h to obtain the remolded epoxy resin.
9. A degradation method based on the degradable epoxy resin of claim 7, wherein the method comprises:
placing the degradable epoxy resin into acidolysis solution, stirring for 0.5-48h at 25-180 ℃, and then sequentially performing neutralization, solid-liquid separation, washing and drying to obtain a degradation product;
the feeding ratio of the degradable epoxy resin to the acidolysis solution is 0.5g (10 mL).
10. The method of claim 9, wherein the acidolysis solution comprises at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid, acetic acid, phosphoric acid, and p-toluenesulfonic acid.
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