CN118240195A - Amino curing agent containing dynamic enamine bond, degradable epoxy resin and preparation, remolding and degradation methods thereof - Google Patents

Amino curing agent containing dynamic enamine bond, degradable epoxy resin and preparation, remolding and degradation methods thereof Download PDF

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Publication number
CN118240195A
CN118240195A CN202410338436.5A CN202410338436A CN118240195A CN 118240195 A CN118240195 A CN 118240195A CN 202410338436 A CN202410338436 A CN 202410338436A CN 118240195 A CN118240195 A CN 118240195A
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epoxy resin
amine
curing agent
secondary amine
degradable
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尤伟
俞炜
刘静
齐朔
王洪荣
肖红
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Swancor New Material Technology Co ltd
Shanghai Jiaotong University
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Swancor New Material Technology Co ltd
Shanghai Jiaotong University
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Abstract

The invention relates to an amino curing agent containing dynamic enamine bonds, degradable epoxy resin and preparation, remolding and degradation methods thereof, wherein the structural formula of the amino curing agent is shown as follows: The preparation method comprises the following steps: heating and stirring an amine curing agent I and a monoacetoacetic acid esterified amino compound II at 20-200 ℃ to obtain the compound; the preparation method of the degradable epoxy resin comprises the following steps: mixing an amino curing agent containing dynamic enamine bonds with epoxy resin, and heating and curing at 30-200 ℃ to obtain the epoxy resin; the remodeling method comprises the following steps: hot-pressing the degradable epoxy resin at 140-240 ℃; the degradation method comprises the following steps: placing the degradable epoxy resin into acidolysis solution, stirring for 0.5-48h at 25-180 ℃, and then sequentially neutralizing, separating solid from liquid, washing and drying to finish degradation. Compared with the prior art, the epoxy resin material containing the dynamic amide bond has the advantages of being degradable, recyclable and beneficial to promoting the industrial application of the dynamic epoxy resin in the fields of wind power generation, sports, leisure and the like.

Description

Amino curing agent containing dynamic enamine bond, degradable epoxy resin and preparation, remolding and degradation methods thereof
Technical Field
The invention belongs to the technical field of epoxy resin, and relates to an amino curing agent containing dynamic enamine bonds, a degradable epoxy resin and preparation, remodeling and degradation methods thereof.
Background
Wind energy is used as inexhaustible renewable energy, and is a renewable green energy which is developed in various countries in the world for a long time. Wind power generation is the most mature technology in wind energy utilization at present. Wind power blades are one of the most critical components in wind power generators, and are mainly made of epoxy resin and glass fiber. However, after the service life of the wind power blade is longer than that of the wind power blade, the wind power blade is not degradable, the recovery difficulty is high, and the like, so that the wind power blade not only pollutes the environment, but also wastes resources. The epoxy resin has the largest proportion in the wind power blade composite material. Therefore, developing a degradable epoxy for wind blade use is an important approach to solve the above problems.
The introduction of dynamic covalent bonds into epoxy resins to obtain dynamically crosslinked epoxy resins is one of the effective ways to solve the problem of thermosetting epoxy resin recovery. The formation of dynamic enamine linkages by in situ crosslinking of acetoacetate groups with amine-based curing agents is also one of the common methods for preparing resins containing dynamic covalent bonds (Lessard, J.J.et al catalyst-FREE VITRIMERS from Vinyl polymers. Macromolecules 2019,52,2105-2111). However, the above curing process generates water as a byproduct in situ, which adversely affects the properties of the cured resin and the industrial production. If the dynamic enamine bond can be introduced into the epoxy resin, and the generation of byproduct water in the curing and crosslinking reaction is avoided, the method has important significance for the trend of the dynamic epoxy resin material to practical application. The Chinese patent No. 114195984B discloses a degradable epoxy resin curing agent containing dynamic enamine bonds and a preparation method of recoverable epoxy resin, and the novel curing agent effectively avoids in-situ generation of water in the polymerization process of the epoxy resin monomer, thereby being beneficial to industrial application of the dynamic epoxy resin. Unlike the preparation of the curing agent containing dynamic enamine bond through modifying epoxy resin monomer in the patent, the preparation method takes amine curing agent as an initiator, prepares the curing agent containing dynamic enamine bond through introducing enamine bond into the amine curing agent, has simple preparation process and is easy to be popularized industrially.
Disclosure of Invention
The invention aims to provide an amino curing agent containing dynamic enamine bonds, degradable epoxy resin and preparation, remolding and degradation methods thereof. Compared with the traditional non-degradable epoxy resin material, the epoxy resin material containing the dynamic amide bond has the advantages of being degradable, recyclable and recyclable. And the curing reaction condition is close to that of the traditional epoxy resin, so that the method is favorable for promoting the industrial application of the dynamic epoxy resin, and especially favorable for promoting the industrial application of the dynamic epoxy resin in the fields of wind power generation, sports, leisure and the like.
The aim of the invention can be achieved by the following technical scheme:
The first aspect of the invention provides an amine-based curing agent containing dynamic enamine bonds, which has the following structural formula:
Wherein R 1 is the intermediate composition of an amine curing agent I, and the structure is one of hydrocarbylene, cycloalkylene, alkylene cycloalkylene, aromatic alkylene, secondary amine alkylene secondary amine group, secondary amine cycloalkylene secondary amine group, secondary amine heteroalkylene secondary amine group, secondary amine cycloalkenylene secondary amine group, secondary amine aromatic secondary amine group, secondary amine heteroaromatic secondary amine group, oxyalkylene oxy group, oxycycloalkylene oxy group, oxycycloalkenylene oxy group, oxyarylene oxy group;
R 2 is the intermediate composition of an alcohol amine compound II, and the structure is one of hydrocarbylene, cycloalkylene, alkylene cycloalkylene, heterocyclic alkylene, secondary amine alkylene secondary amine group, secondary amine cycloalkylene secondary amine group, secondary amine heterocycloalkylene secondary amine group, secondary amine cycloalkenylene secondary amine group, secondary amine aromatic secondary amine group, secondary amine heteroaromatic secondary amine group, oxyhydrocarbylene oxy group, oxycycloalkylene oxy group, oxyheterocycloalkylene oxy group, oxyaromatic alkylene oxy group.
The second aspect of the invention provides a method for preparing an amine-based curing agent containing dynamic enamine bonds, comprising the following steps:
s1: preparation of monoacetoacetate amine compound II:
mixing an alcohol amine compound and an acetoacetylation reagent in an organic solvent, and heating to react to obtain a monoacetoacetic acid esterified amino compound;
Wherein the alcohol amine compound is H 2N-R2 -OH; the acetoacetylating agent is divinyl ketone or a compound shown as a formula III, wherein R 3 is one of straight-chain or branched-chain alkyl, cycloalkyl, aryl, heteroaromatic group, alkylene or alkylene heteroalkylene;
S2: preparation of an amine-based curing agent containing dynamic enamine bonds:
mixing monoacetoacetic acid esterified amino compound II with amine curing agent I in an organic solvent, and stirring for reaction to obtain amine curing agent containing dynamic enamine bond;
Wherein the amine curing agent I is at least one of polyether amine curing agent, aliphatic amine curing agent, alicyclic amine curing agent and aromatic amine curing agent.
Further, in step S1, the alcohol amine compound is one of isobutanol amine, isopropanolamine, hydroxyethyl ethylenediamine, 2-aminoethanol, DL-valinol, L-phenylglycinol or diglycolamine;
the acetoacetylation reagent is at least one of diketene, ethyl acetoacetate, propyl acetoacetate, tert-butyl acetoacetate, amyl acetoacetate or heptyl acetoacetate;
In the heating reaction, the reaction temperature is 20-100 ℃, the reaction time is 1-10h, and the catalyst is at least one of sulfuric acid, hydrochloric acid or sulfonic acid;
The mol ratio of the alcohol amine compound to the acetoacetylating agent is 1 (1-3).
In step S2, the amine curing agent I is one or more of polyetheramine, aliphatic amine, alicyclic amine, and aromatic amine, and the amine curing agent is preferably polyetheramine (D230, D400, D2000), ethylenediamine, diethylenetriamine, triethylenetetramine, polyethylenepolyamine, 1, 6-hexanediamine, m-phenylenediamine, and isophorone diamine;
further, in the step S2, in the stirring reaction, the reaction temperature is 20-100 ℃, the reaction time is 1-10h, and the catalyst is at least one of sulfuric acid, hydrochloric acid or sulfonic acid;
The molar ratio of the amine curing agent I to the monoacetoacetic acid esterified amino compound II is 1 (1-6).
Further, in step S1 and step S2, the reaction solvent is at least one selected from acetone, xylene, toluene, methylene chloride, chloroform, dimethylformamide, dimethylacetamide, dioxane or tetrahydrofuran, respectively.
A third aspect of the present invention provides a method for preparing a degradable epoxy resin, comprising: mixing an amine curing agent containing dynamic enamine bonds with epoxy resin, and performing a heating curing reaction to obtain epoxy resin containing enamine bonds, namely degradable epoxy resin;
Wherein the epoxy resin is one or a mixture of several of aliphatic epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, phenolic epoxy resin or o-cresol formaldehyde epoxy resin;
the amine-based curing agent containing dynamic enamine bonds is the amine-based curing agent containing dynamic enamine bonds.
Further, the epoxy resin is at least one selected from the following types of epoxy resins :CYD-128(E-51)、CYD-128(618)、CYD-128(0164E)、CYD-127(E-54)、CYD-115、E-44(6101)、E-42、E-39D、CY-186、TDE-85、AG-80、F-44、F51、F-48.
Further, the mixing volume ratio of the amino curing agent containing dynamic enamine bond and the epoxy resin is (3-6) (1-3);
in the heating curing reaction, the reaction temperature is 30-200 ℃ and the reaction time is 1-12h.
A fourth aspect of the present invention provides a degradation method of the above degradable epoxy resin, comprising: and (3) placing the degradable epoxy resin in a mixed solution of an organic solvent and acidolysis solution, stirring, neutralizing, and carrying out solid-liquid separation to obtain degradation products.
Further, the acidolysis solution is a mixed solution composed of water and at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid, acetic acid, phosphoric acid or p-toluenesulfonic acid, and the mass concentration is preferably 1-80%;
The feeding ratio of the degradable epoxy resin to the acidolysis solution to the organic solvent is 0.5g to 10mL (50-70 mL);
The stirring temperature is 25-180 ℃, and the stirring time is 0.5-48h.
Further, the neutralizing agent 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 of the neutralization end point is 6-10.
A fifth aspect of the present invention provides a method for remolding the degradable epoxy resin described above, comprising: the degradable epoxy resin is hot pressed for 0.3 to 8 hours at 140 to 240 ℃ (preferably 160 to 240 ℃), and the reworkable epoxy resin is obtained.
According to the amine curing agent containing dynamic enamine bonds and the degradable epoxy resin thereof, the dynamic enamine bonds are selectively introduced into an epoxy resin system through molecular design, and meanwhile, the structure of partial irreversible chemical bonds is reserved. Therefore, the prepared amine curing agent containing dynamic enamine bonds and the degradable epoxy resin thereof have good mechanical properties, the amine bonds can be subjected to dynamic exchange at a certain temperature to enable the amine curing agent to have plasticity, and the enamine bonds can be selectively degraded by utilizing the unstable characteristic of the enamine bonds under an acidic condition, so that the degradation and recovery of the epoxy resin are realized.
Compared with the prior art, the invention has the following characteristics:
1) The preparation method of the amino curing agent containing dynamic enamine bonds and the degradable epoxy resin thereof has the advantages of simple process, mild condition, convenient operation and the like, and is beneficial to industrial production;
2) The degradable epoxy resin based on the amino curing agent containing dynamic enamine bonds, which is prepared by the invention, has similar curing process and similar mechanical properties as the existing epoxy resin, has the advantages of thermoplastic processing and repeated processing and forming, and is beneficial to replacing the currently applied nondegradable epoxy resin by the dynamic epoxy resin;
3) The dynamic epoxy resin containing the enamine bond prepared by the invention can be degraded and recycled in an acid solvent under the conditions of heating and stirring, solves the problem that the existing epoxy resin is difficult to recycle, and 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 current wind power generation blades are expected to be solved.
Drawings
FIG. 1 is an infrared spectrum of an amine-based curing agent containing dynamic enamine bonds in example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of an amine-based curing agent with dynamic enamine bonds in example 1.
FIG. 3 shows the results of a remolding reprocessing of a degradable epoxy resin based on an amine-based curative containing dynamic enamine linkages in example 1.
FIG. 4 is a schematic representation of the degradation of a degradable epoxy resin based on an amine-based curing agent containing dynamic enamine bonds in example 1.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
An amine-based curing agent containing dynamic enamine bonds has the following structural formula:
Wherein R 1 is the intermediate composition of an amine curing agent I, and the structure is one of hydrocarbylene, cycloalkylene, alkylene cycloalkylene, aromatic alkylene, secondary amine alkylene secondary amine group, secondary amine cycloalkylene secondary amine group, secondary amine heteroalkylene secondary amine group, secondary amine cycloalkenylene secondary amine group, secondary amine aromatic secondary amine group, secondary amine heteroaromatic secondary amine group, oxyalkylene oxy group, oxycycloalkylene oxy group, oxycycloalkenylene oxy group, oxyarylene oxy group;
R 2 is the intermediate composition of an alcohol amine compound II, and the structure is one of hydrocarbylene, cycloalkylene, alkylene cycloalkylene, heterocyclic alkylene, secondary amine alkylene secondary amine group, secondary amine cycloalkylene secondary amine group, secondary amine heterocycloalkylene secondary amine group, secondary amine cycloalkenylene secondary amine group, secondary amine aromatic secondary amine group, secondary amine heteroaromatic secondary amine group, oxyhydrocarbylene oxy group, oxycycloalkylene oxy group, oxyheterocycloalkylene oxy group, oxyaromatic alkylene oxy group.
A preparation method of an amino curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of monoacetoacetate amine compound II:
Mixing an alcohol amine compound and an acetoacetylation reagent in an organic solvent, adding a certain amount of catalyst, heating at 20-100 ℃ for reaction for 1-10h, removing the organic solvent by reduced pressure distillation, and drying to obtain a monoacetoacetic acid esterified amino compound;
wherein the alcohol amine compound is H 2N-R2 -OH, and the alcohol amine compound is preferably isobutyl alcohol amine, isopropanolamine, hydroxyethyl ethylenediamine, 2-amino ethanol, DL-valinol, L-phenylglycine alcohol and diglycolamine;
The acetoacetylating agent is divinyl ketone or a compound shown as a formula III, wherein R 3 is straight-chain or branched-chain branched alkyl, cycloalkyl, aromatic, heteroaromatic, alkylene heteroalkylene, and the acetoacetylating agent is preferably divinyl ketone, ethyl acetoacetate, propyl acetoacetate, tert-butyl acetoacetate, amyl acetoacetate or heptyl acetoacetate;
the catalyst comprises at least one of sulfuric acid, hydrochloric acid or sulfonic acid; the mol ratio of the alcohol amine compound and the acetoacetylating agent is 1 (1-3).
S2: preparation of an amine-based curing agent containing dynamic enamine bonds:
Mixing monoacetoacetic acid esterified amino compound II with amine curing agent I in organic solvent, adding a certain amount of catalyst, stirring at 20-100 ℃ for reaction for 1-10h, and carrying out reduced pressure distillation and drying to obtain the amine curing agent containing dynamic enamine bond;
wherein, the amine curing agent I is at least one of polyether amine, aliphatic amine, alicyclic amine and aromatic amine; the catalyst comprises at least one of sulfuric acid, hydrochloric acid or sulfonic acid; the molar ratio of the amine curing agent I to the monoacetoacetic acid esterified amino compound II is 1 (1-6).
The organic solvent can be at least one of acetone, xylene, toluene, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, dioxane and tetrahydrofuran.
A degradable epoxy resin based on an amine-based curing agent containing dynamic enamine bonds, which is prepared by a method comprising:
mixing an amino curing agent containing dynamic enamine bonds with epoxy resin according to the volume ratio of (3-6) (1-3), and heating and curing at 30-200 ℃ for 1-12 hours to obtain epoxy resin containing enamine bonds, namely degradable epoxy resin;
Wherein the epoxy resin is one or more of aliphatic epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, phenolic epoxy resin and o-cresol formaldehyde epoxy resin, and the epoxy resin is preferably selected from CYD-128(E-51)、CYD-128(618)、CYD-128(0164E)、CYD-127(E-54)、CYD-115、E-44(6101)、E-42、E-39D、CY-186、TDE-85、AG-80、F-44、F51、F-48.
A method of remolding the degradable epoxy resin described above, comprising: and hot-pressing the degradable epoxy resin at 140-240 ℃ for 0.3-8 hours to obtain the reworkable epoxy resin.
The 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 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 degradation products;
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 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 neutralization end point pH is 6-10; the feeding ratio of the degradable epoxy resin to the acidolysis solution to the organic solvent is 0.5g to 10mL (50-70 mL).
The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise specified, starting materials or processing techniques are indicated as being conventional commercial products or conventional processing techniques in the art.
Example 1:
A preparation method of an amino curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of monoacetoacetic acid esterified amino compound:
17g of isobutolamine and 12ml of diketene are mixed in an organic solvent, 0.6g of p-toluenesulfonic acid is added, the mixture is heated at 30 ℃ for reaction for 2 hours, the organic solvent is removed by reduced pressure distillation, and the monoacetoacetic acid esterified amino compound is obtained after drying, wherein the yield is 93%;
S2: preparation of an amine-based curing agent containing dynamic enamine bonds:
Mixing 25g of monoacetoacetic acid esterified amino compound and 80ml of polyether amine (D230) in an organic solvent, adding 0.4g of p-toluenesulfonic acid, stirring at 30 ℃ for reaction for 4 hours, and carrying out reduced pressure distillation and drying to obtain an amine curing agent containing dynamic ethylenic amine bonds, wherein the yield is 85%;
An infrared spectrum of the amine-based curing agent containing dynamic enamine bonds is shown in fig. 1, and a nuclear magnetic resonance spectrum of the amine-based curing agent containing dynamic enamine bonds is shown in fig. 2.
A degradable epoxy resin based on an amine-based curing agent containing dynamic enamine bonds, which is prepared by a method comprising:
10mL of an amine curing agent is mixed with 10mL of an epoxy monomer with the model of CYD-127 (E-54) (China petrochemical Co., ltd.) and is heated and cured for 6 hours at 80 ℃, and then heated and cured for 3 hours at 120 ℃ to obtain the epoxy resin containing the enamine bond, namely the degradable epoxy resin.
The embodiment also comprises the step of carrying out reworkability test on the degradable epoxy resin, and specifically comprises the following steps: and placing the degradable epoxy resin on a hot press at 220 ℃ for hot pressing for 0.3h to obtain remolded epoxy resin, wherein the remolded epoxy resin is shown as a figure 3, and the material has good plasticity.
The embodiment also comprises the step of carrying out the degradation performance test on the degradable epoxy resin, and specifically comprises the following steps: 1.0g of degradable epoxy resin, 20mL of sulfuric acid solution (with the concentration of 1 mol/L) and 70mL of tetrahydrofuran are taken and mixed, and stirred for 12 hours at 80 ℃ to degrade, then 10wt% of sodium hydroxide solution is used for neutralization until the pH value of the solution is 7.0, and degradation products are obtained after filtering, precipitation, washing with water and drying. As shown in FIG. 4, the block epoxy resin is evenly dispersed in the solution after acidolysis, and degradation products are precipitated after neutralization, separated and dried to obtain degradation products.
Example 2:
A preparation method of an amino curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of monoacetoacetic acid esterified amino compound:
mixing 16g of isopropanolamine and 17ml of diketene in an organic solvent, adding 0.7g of sulfuric acid, heating at 30 ℃ for reaction for 2 hours, removing the organic solvent by reduced pressure distillation, and drying to obtain a monoacetoacetic acid esterified amino compound with the yield of 94%;
S2: preparation of an amine-based curing agent containing dynamic enamine bonds:
Mixing 20g of monoacetoacetic acid esterified amino compound with 90ml of polyether amine (D400) in an organic solvent, adding 0.7g of sulfuric acid, stirring at 50 ℃ for reaction for 2 hours, and carrying out reduced pressure distillation and drying to obtain the amine curing agent with dynamic enamine bond, wherein the yield is 90%;
a degradable epoxy resin based on an amine-based curing agent containing dynamic enamine bonds, which is prepared by a method comprising:
10mL of an amine-based curing agent is mixed with 10mL of an epoxy monomer with the model of E-44 (6101), heated and cured for 5 hours at 90 ℃, and then heated and cured for 2 hours at 120 ℃ to obtain the epoxy resin containing the enamine bond, namely the degradable epoxy resin.
The embodiment also comprises the step of carrying out reworkability test on the degradable epoxy resin, and specifically comprises the following steps: and (3) placing the degradable epoxy resin on a hot press with 220 ℃ for hot pressing for 0.3h to obtain the remolded epoxy resin.
The embodiment also comprises the step of carrying out the degradation performance test on the degradable epoxy resin, and specifically comprises the following steps: 1.0g of degradable epoxy resin, 15mL of sulfuric acid solution (with the concentration of 1 mol/L) and 60mL of tetrahydrofuran are taken and mixed, and stirred for 12 hours at 90 ℃ to degrade, then 10wt% of sodium hydroxide solution is used for neutralization until the pH value of the solution is 7.0, and degradation products are obtained after filtering, precipitation, washing with water and drying.
Example 3:
A preparation method of an amino curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of monoacetoacetic acid esterified amino compound:
mixing 12g of 2-amino ethanol and 14ml of ethyl acetoacetate in an organic solvent, adding 0.5g of hydrochloric acid, heating at 50 ℃ for reaction for 2 hours, removing the organic solvent by reduced pressure distillation, and drying to obtain the monoacetoacetate esterified amino compound, wherein the yield is 92%;
S2: preparation of an amine-based curing agent containing dynamic enamine bonds:
Mixing 10g of monoacetoacetic acid esterified amino compound with 80ml of polyether amine (D2000) in an organic solvent, adding 0.7g of hydrochloric acid, stirring at 70 ℃ for reaction for 2 hours, and carrying out reduced pressure distillation and drying to obtain the amine curing agent with dynamic enamine bond, wherein the yield is 90%;
a degradable epoxy resin based on an amine-based curing agent containing dynamic enamine bonds, which is prepared by a method comprising:
7mL of an amino curing agent is mixed with 10mL of an epoxy monomer with the model of CYD-127 (E-54), heated and cured for 5 hours at 80 ℃, and then heated and cured for 2 hours at 120 ℃ to obtain the epoxy resin containing the enamine bond, namely the degradable epoxy resin.
The embodiment also comprises the step of carrying out reworkability test on the degradable epoxy resin, and specifically comprises the following steps: and (5) placing the degradable epoxy resin on a hot press at 200 ℃ for hot pressing for 0.5h to obtain the remolded epoxy resin.
The embodiment also comprises the step of carrying out the degradation performance test on the degradable epoxy resin, and specifically comprises the following steps: 1.0g of degradable epoxy resin, 20mL of sulfuric acid solution (with the concentration of 1 mol/L) and 80mL of tetrahydrofuran are taken and mixed, and stirred for 12 hours at 80 ℃ to degrade, then 10wt% of sodium hydroxide solution is used for neutralization until the pH value of the solution is 7.0, and degradation products are obtained after filtering, precipitation, washing with water and drying.
And placing the degradable epoxy resin on a hot press with 220 ℃ for hot pressing for 1h to obtain the remolded epoxy resin, which shows that the material has good reworkability.
Example 4:
A preparation method of an amino curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of monoacetoacetic acid esterified amino compound:
Mixing 10g of isobutolamine and 12ml of ethyl acetoacetate in an organic solvent, adding 0.5g of p-toluenesulfonic acid, heating at 40 ℃ for reaction for 2 hours, removing the organic solvent by reduced pressure distillation, and drying to obtain a monoacetoacetate esterified amino compound with the yield of 94%;
S2: preparation of an amine-based curing agent containing dynamic enamine bonds:
Mixing 10g of monoacetoacetic acid esterified amino compound with 28ml of polyether amine (D230) in an organic solvent, adding 0.6g of p-toluenesulfonic acid, stirring at 60 ℃ for reaction for 2 hours, and carrying out reduced pressure distillation and drying to obtain the amine curing agent with dynamic ethylenic amine bonds, wherein the yield is 90%;
a degradable epoxy resin based on an amine-based curing agent containing dynamic enamine bonds, which is prepared by a method comprising:
6mL of an amino curing agent is mixed with 11mL of an epoxy monomer with the model of CYD-128 (E-51), the mixture is heated and cured for 6 hours at 70 ℃, and then heated and cured for 4 hours at 100 ℃ to obtain the epoxy resin containing the enamine bond, namely the degradable epoxy resin.
The embodiment also comprises the step of carrying out reworkability test on the degradable epoxy resin, and specifically comprises the following steps: and (5) placing the degradable epoxy resin on a hot press with 220 ℃ for hot pressing for 0.5h to obtain the remolded epoxy resin.
The embodiment also comprises the step of carrying out the degradation performance test on the degradable epoxy resin, and specifically comprises the following steps: 1.0g of degradable epoxy resin, 10mL of sulfuric acid solution (with the concentration of 1 mol/L) and 60mL of tetrahydrofuran are taken and mixed, and stirred for 12 hours at 70 ℃ to degrade, then 10wt% of sodium hydroxide solution is used for neutralization until the pH value of the solution is 7.0, and degradation products are obtained after filtering, precipitation, washing with water and drying.
The embodiment also comprises the step of carrying out the degradation performance test on the degradable epoxy resin, and specifically comprises the following steps: mixing 0.5g of degradable epoxy resin, 10mL of hydrochloric acid solution (with the concentration of 4 mol/L) and 70mL of tetrahydrofuran, stirring for 4 hours at 120 ℃ to degrade, neutralizing with 20wt% sodium hydroxide solution until the pH of the solution is 7.0, filtering, precipitating, washing with water and drying to obtain degradation products.
Example 5:
A preparation method of an amino curing agent containing dynamic enamine bonds comprises the following steps:
s1: preparation of monoacetoacetic acid esterified amino compound:
10g of 2-amino ethanol and 15ml of tert-butyl acetoacetate are mixed in an organic solvent, 0.5g of sulfuric acid is added, the mixture is heated at 50 ℃ for reaction for 3 hours, the organic solvent is removed by reduced pressure distillation, and the monoacetoacetic acid esterified amino compound is obtained after drying, and the yield is 94%;
S2: preparation of an amine-based curing agent containing dynamic enamine bonds:
mixing 10g of monoacetoacetic acid esterified amino compound with 30ml of polyether amine (D230) in an organic solvent, adding 0.5g of sulfuric acid, stirring at 60 ℃ for reaction for 2 hours, and carrying out reduced pressure distillation and drying to obtain the amine curing agent with dynamic enamine bond, wherein the yield is 90%;
a degradable epoxy resin based on an amine-based curing agent containing dynamic enamine bonds, which is prepared by a method comprising:
7mL of an amino curing agent is mixed with 10mL of an epoxy monomer with the model of TDE-85, heated and cured for 5 hours at 80 ℃, and then heated and cured for 3 hours at 120 ℃ to obtain the epoxy resin containing the ethylenic amine groups, namely the degradable epoxy resin.
The embodiment also comprises the step of carrying out reworkability test on the degradable epoxy resin, and specifically comprises the following steps: and placing the degradable epoxy resin on a hot press with 220 ℃ for hot pressing for 1.0h to obtain the remolded epoxy resin, which shows that the material has good reworkability.
The embodiment also comprises the step of carrying out the degradation performance test on the degradable epoxy resin, and specifically comprises the following steps: mixing 0.5g of degradable epoxy resin, 10mL of sulfuric acid solution (with the concentration of 1 mol/L) and 50mL of tetrahydrofuran, stirring for 4 hours at 100 ℃ to degrade, neutralizing with 10wt% sodium hydroxide solution until the pH of the solution is 7.0, filtering, precipitating, washing with water and drying to obtain degradation products.
Comparative example
3ML of an epoxy monomer of polyetheramine D230 (Henschel chemical industry Co., ltd.) and 7mLCYD-127 (E-54) (China petrochemical Co., ltd.) was heat-cured at 80℃for 6 hours, and then at 120℃for 3 hours, to prepare an epoxy resin.
Application examples:
This example the tensile properties of the degradable epoxy resins and epoxy resins prepared in example 1 and comparative example were tested according to standard GB/T2567-2008 and the results are shown in Table 1.
TABLE 1 comparison of Properties of enamine bond containing epoxy resins with comparative resins
Resin+curing agent Tensile Strength (MPa) Elongation at break (%)
Example 1 62.5±1.2 15.5±0.5
Comparative example 1 63.4±0.6 16.1±8.0
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (10)

1. An amine-based curing agent containing dynamic enamine bonds is characterized by having the following structural formula:
Wherein R 1 is the intermediate composition of an amine curing agent I, and the structure is one of hydrocarbylene, cycloalkylene, alkylene cycloalkylene, aromatic alkylene, secondary amine alkylene secondary amine group, secondary amine cycloalkylene secondary amine group, secondary amine heteroalkylene secondary amine group, secondary amine cycloalkenylene secondary amine group, secondary amine aromatic secondary amine group, secondary amine heteroaromatic secondary amine group, oxyalkylene oxy group, oxycycloalkylene oxy group, oxycycloalkenylene oxy group, oxyarylene oxy group;
R 2 is the intermediate composition of an alcohol amine compound II, and the structure is one of hydrocarbylene, cycloalkylene, alkylene cycloalkylene, heterocyclic alkylene, secondary amine alkylene secondary amine group, secondary amine cycloalkylene secondary amine group, secondary amine heterocycloalkylene secondary amine group, secondary amine cycloalkenylene secondary amine group, secondary amine aromatic secondary amine group, secondary amine heteroaromatic secondary amine group, oxyhydrocarbylene oxy group, oxycycloalkylene oxy group, oxyheterocycloalkylene oxy group, oxyaromatic alkylene oxy group.
2. A method of preparing the dynamic enamine bond-containing amine-based curing agent according to claim 1, comprising the steps of:
s1: mixing an alcohol amine compound and an acetoacetylation reagent in an organic solvent, and heating to react to obtain a monoacetoacetic acid esterified amino compound;
Wherein the alcohol amine compound is H 2N-R2 -OH; the acetoacetylating agent is divinyl ketone or a compound shown as a formula III, wherein R 3 is one of straight-chain or branched-chain alkyl, cycloalkyl, aryl, heteroaromatic group, alkylene or alkylene heteroalkylene;
s2: mixing monoacetoacetic acid esterified amino compound II with amine curing agent I in an organic solvent, and stirring for reaction to obtain amine curing agent containing dynamic enamine bond;
Wherein the amine curing agent I is at least one of polyether amine curing agent, aliphatic amine curing agent, alicyclic amine curing agent and aromatic amine curing agent.
3. The method for preparing an amine-based curing agent containing a dynamic enamine bond according to claim 2, wherein in the step S1, the alcohol amine compound is one of isobutylamine, isopropanolamine, hydroxyethylamine, 2-aminoethanol, DL-valinol, L-phenylglycinol or diglycolamine;
the acetoacetylation reagent is at least one of diketene, ethyl acetoacetate, propyl acetoacetate, tert-butyl acetoacetate, amyl acetoacetate or heptyl acetoacetate;
In the heating reaction, the reaction temperature is 20-100 ℃, the reaction time is 1-10h, and the catalyst is at least one of sulfuric acid, hydrochloric acid or sulfonic acid;
The mol ratio of the alcohol amine compound to the acetoacetylating agent is 1 (1-3).
4. The method for preparing an amine-based curing agent containing a dynamic enamine bond according to claim 2, wherein in the step S2, the reaction temperature is 20-100 ℃ and the reaction time is 1-10h, and the catalyst is at least one of sulfuric acid, hydrochloric acid or sulfonic acid;
The molar ratio of the amine curing agent I to the monoacetoacetic acid esterified amino compound II is 1 (1-6).
5. The method for preparing an amine-based curing agent containing a dynamic enamine bond according to claim 2, wherein in the step S1 and the step S2, the reaction solvent is at least one selected from acetone, xylene, toluene, methylene chloride, chloroform, dimethylformamide, dimethylacetamide, dioxane and tetrahydrofuran.
6. A method for preparing a degradable epoxy resin, comprising: mixing an amino curing agent containing dynamic enamine bonds with epoxy resin, and performing a heating curing reaction to obtain degradable epoxy resin;
Wherein the epoxy resin is one or a mixture of several of aliphatic epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, phenolic epoxy resin or o-cresol formaldehyde epoxy resin;
The amine-based curing agent containing dynamic enamine bonds is the amine-based curing agent containing dynamic enamine bonds as claimed in claim 1.
7. The method for preparing the degradable epoxy resin according to claim 6, wherein the mixing volume ratio of the amine-based curing agent containing dynamic enamine bonds to the epoxy resin is (3-6): 1-3;
in the heating curing reaction, the reaction temperature is 30-200 ℃ and the reaction time is 1-12h.
8. A method of degrading a degradable epoxy resin prepared by the method of claim 6 or 7, comprising: and (3) placing the degradable epoxy resin in a mixed solution of an organic solvent and acidolysis solution, stirring, neutralizing, and carrying out solid-liquid separation to obtain degradation products.
9. The method for degrading a degradable epoxy resin according to claim 8, wherein the acidolysis solution is a mixed solution of water and at least one of hydrochloric acid, hydrofluoric acid, trifluoroacetic acid, sulfuric acid, acetic acid, phosphoric acid or p-toluenesulfonic acid;
The feeding ratio of the degradable epoxy resin to the acidolysis solution to the organic solvent is 0.5g to 10mL (50-70 mL);
The stirring temperature is 25-180 ℃, and the stirring time is 0.5-48h.
10. A method of remolding a degradable epoxy resin prepared by the method of claim 6 or 7, comprising: and hot-pressing the degradable epoxy resin at 140-240 ℃ for 0.3-8 hours to obtain the reworkable epoxy resin.
CN202410338436.5A 2024-03-25 2024-03-25 Amino curing agent containing dynamic enamine bond, degradable epoxy resin and preparation, remolding and degradation methods thereof Pending CN118240195A (en)

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