CN113717349A - Trehalose bio-based epoxy resin condensate and preparation method thereof - Google Patents
Trehalose bio-based epoxy resin condensate and preparation method thereof Download PDFInfo
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- CN113717349A CN113717349A CN202111218471.6A CN202111218471A CN113717349A CN 113717349 A CN113717349 A CN 113717349A CN 202111218471 A CN202111218471 A CN 202111218471A CN 113717349 A CN113717349 A CN 113717349A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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Abstract
The invention provides a trehalose bio-based epoxy resin condensate and a preparation method thereof, which are applied to the fields of high polymers and composite materials, and the preparation method comprises the following steps: performing prepolymerization reaction on carboxyl-derived trehalose, aliphatic epoxy resin, a curing agent and a solvent to obtain a trehalose bio-based epoxy resin prepolymer solution; and curing the trehalose bio-based epoxy resin prepolymer solution to obtain the trehalose bio-based epoxy resin cured product. The trehalose bio-based epoxy resin condensate prepared by the invention introduces an ester group structure into the main chain structure of the traditional epoxy resin, and due to the existence of the ester group structure, the cured epoxy resin cross-linked network is easy to open from the position of the ester group structure under mild alkaline conditions, so that the epoxy resin cross-linked network is degraded into a degradation product with smaller molecular weight, and the degradation product is dissolved in the traditional solvent to complete the degradation of the trehalose bio-based epoxy resin condensate.
Description
Technical Field
The invention relates to the field of high polymers and composite materials, and particularly relates to a trehalose bio-based epoxy resin cured product and a preparation method thereof.
Background
The epoxy resin is a unique high-performance thermosetting material, and can form an irreversible crosslinking material with excellent performance after being cured. These materials are known for their high mechanical strength, excellent adhesion to various substrates, and high heat and chemical resistance. However, the monomers of epoxy resins are all obtained from non-renewable petroleum-based raw materials, and the highly chemically crosslinked three-dimensional network structure of the epoxy resins also makes the waste management problem of the epoxy resins increasingly prominent. Therefore, there is an urgent need to develop a novel epoxy resin cured product which is environmentally sustainable and degradable.
Disclosure of Invention
The embodiment of the invention provides a trehalose bio-based epoxy resin cured product and a preparation method thereof, and can provide a degradable green and environment-friendly epoxy resin cured product which can be degraded under mild alkaline conditions.
In a first aspect, the present invention provides a preparation method of a trehalose bio-based epoxy resin cured product, comprising the following steps:
(1) performing prepolymerization reaction on carboxyl-derived trehalose, aliphatic epoxy resin, a curing agent and a solvent to obtain a trehalose bio-based epoxy resin prepolymer solution;
(2) and curing the trehalose bio-based epoxy resin prepolymer solution to obtain the trehalose bio-based epoxy resin cured product.
Preferably, the trehalose bio-based epoxy resin prepolymer solution comprises the following raw materials in parts by weight: 50-150 parts of carboxyl derived trehalose, 100 parts of aliphatic epoxy resin, 5-20 parts of curing agent and 10-30 parts of solvent.
Preferably, in step (1), the carboxyl-derivatized trehalose is prepared from trehalose and an organic acid anhydride by a ring-opening reaction;
the preparation method of the carboxyl-derivatized trehalose comprises the following substeps:
(1.1) stirring trehalose, organic acid anhydride and N, N-dimethylformamide to obtain a mixed solution;
(1.2) adding anhydrous pyridine and 4-dimethylaminopyridine into the mixed solution, and stirring to obtain a reaction solution;
(1.3) carrying out rotary evaporation treatment on the reaction solution, then dropwise adding ethyl acetate for dilution, and further carrying out quenching reaction to obtain an organic phase diluted solution;
and (1.4) adding a hydrochloric acid aqueous solution into the diluted solution for extraction treatment, taking an upper layer organic phase solution, and sequentially performing drying treatment, filtering treatment and secondary rotary evaporation treatment to obtain the carboxyl-derivatized trehalose.
Preferably, the organic anhydride is succinic anhydride, glutaric anhydride or adipic anhydride;
the molar ratio of the trehalose to the organic acid anhydride is 1 (8-12).
Preferably, the preparation of the carboxyl-derivatized trehalose comprises the following raw materials in parts by mass: 10 parts of trehalose, 90-110 parts of N, N-dimethylformamide, 25-35 parts of anhydrous pyridine, 1-3 parts of 4-dimethylaminopyridine, 400-500 parts of ethyl acetate and 400-500 parts of hydrochloric acid aqueous solution.
Preferably, the stirring temperature is 80-100 ℃, and the rotating speed is 500-700 r/min;
in the step (1.1), the stirring time is 5-10 min;
in the step (1.2), the stirring time is 45-55 h;
in the step (1.3), the temperature of the rotary evaporation treatment is 35-45 ℃, and the rotary evaporation time is 15-30 min.
Preferably, in the step (1.4), the drying treatment is drying with anhydrous sodium sulfate or anhydrous magnesium sulfate; the temperature of the secondary rotary evaporation treatment is 20-30 ℃, and the rotary evaporation time is 5-10 min.
Preferably, the structural general formula of the carboxyl-derivatized trehalose is
Wherein n is 2, 3 or 4.
Preferably, in the step (1), the aliphatic epoxy resin is at least one of trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and 1, 4-cyclohexanedimethanol diglycidyl ether.
The curing agent is at least one of ammonium chloride, ammonium nitrate, ammonium bromide, aromatic diamine and aliphatic diamine.
The solvent is at least one of dichloromethane, chloroform, acetone and ethyl acetate.
Preferably, the reaction time of the prepolymerization is 8-12 min.
Preferably, the method further comprises the step of sequentially performing rotary steaming treatment and drying treatment on the trehalose bio-based epoxy resin prepolymer solution before the step (2);
the temperature of the rotary evaporation treatment is 20-30 ℃, and the rotary evaporation time is 5-10 min;
the drying treatment is drying for 25-35 min under the conditions of vacuum environment, vacuum degree of-0.085 MPa and temperature of 35-45 ℃.
Preferably, in step (2), the curing process is a staged curing: curing for 1.5-2.5 h at 110-130 ℃, and then curing for 1.5-2.5 h at 155-175 ℃.
In a second aspect, the invention provides a trehalose bio-based epoxy resin cured product prepared by the preparation method of any one of the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the trehalose bio-based epoxy resin cured product introduces an ester group structure in the main chain structure of the traditional epoxy resin, and due to the existence of the ester group structure, the cured epoxy resin cross-linked network is easily opened from the position of the ester group structure under the mild alkaline condition, so that the epoxy resin cross-linked network is degraded into a degradation product with smaller molecular weight, and the degradation product is dissolved in the traditional solvent to complete the degradation of the trehalose bio-based epoxy resin cured product.
(2) The invention introduces the bio-based material carboxyl-derived trehalose, can ensure the mechanical property of the traditional epoxy resin and simultaneously consider green and environmental protection, and reduces the use of petrochemical products.
(3) The preparation method of the trehalose bio-based epoxy resin condensate prepared by the invention is simple, strong in operability, easy to implement and beneficial to large-scale industrial production.
(4) The carbon fiber composite material prepared from the trehalose bio-based epoxy resin condensate and the carbon fiber bidirectional plain cloth can degrade the carbon fiber composite material through a weak alkaline aqueous solution and recover the carbon fiber bidirectional plain cloth, and the recovered carbon fiber bidirectional plain cloth still keeps excellent monofilament tensile strength.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
In the prior art, the patent CN109280153A utilizes spiral cyclic acetal diphenol to transform epoxy resin, so that epoxy cured substances can be degraded under mild conditions, and the fiber composite material prepared by the epoxy cured substances is easy to recover fibers in the fiber composite material. However, the method disclosed in the patent has limitations that all raw materials for preparing the epoxy resin are derived from petrochemical products, and the raw materials cannot be degradable and simultaneously are environmentally friendly. The invention realizes the degradable function of the epoxy resin and gives consideration to the green and environment-friendly raw materials by introducing the bio-based material.
The invention provides a preparation method of a trehalose bio-based epoxy resin cured product, which comprises the following steps:
(1) performing polymerization reaction on carboxyl-derived trehalose, aliphatic epoxy resin, a curing agent and a solvent to obtain a trehalose bio-based epoxy resin prepolymer solution;
(2) and curing the trehalose bio-based epoxy resin prepolymer solution to obtain the trehalose bio-based epoxy resin cured product.
In the invention, an ester group structure is introduced into the main chain structure of the traditional epoxy resin, and due to the existence of the ester group structure, the cured epoxy resin cross-linked network is easily opened from the position of the ester group structure under a mild alkaline condition, so that the cured epoxy resin cross-linked network is degraded into a degradation product with a smaller molecular weight, and further can be dissolved in the traditional solvent, and the cured trehalose bio-based epoxy resin has degradability.
In addition, the bio-based material is introduced, so that the excellent mechanical property of the traditional epoxy resin is ensured, the environment is protected, and the use of petrochemical products is reduced.
According to some preferred embodiments, the trehalose bio-based epoxy resin prepolymer solution comprises the following raw materials in parts by weight: 50-150 parts (for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150 parts) of the carboxyl-derivatized trehalose, 100 parts of the aliphatic epoxy resin, 5-20 parts (for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts) of the curing agent, and 10-30 parts (for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 parts) of the solvent.
The mass part ratio of the carboxyl-derivatized trehalose to the aliphatic epoxy resin is obtained according to the molar ratio of the functional groups of the carboxyl-derivatized trehalose to the aliphatic epoxy resin, specifically according to the fact that the molar ratio of the epoxy functional groups in the aliphatic epoxy resin to the carboxyl functional groups in the carboxyl-derivatized trehalose is 1: (0.8 to 1.2) (for example, 1: 0.8, 1: 0.85, 1: 0.9, 1: 0.95, 1:1, 1: 1.05, 1: 1.1, 1: 1.15 or 1: 1.2). Thus, the epoxy functional group in the aliphatic epoxy resin and the carboxyl functional group in the carboxyl derived trehalose are subjected to ring-opening polymerization reaction to form an ester group, so that the degradable function of the cured trehalose bio-based epoxy resin is realized.
Experiments prove that if the ratio of the epoxy functional groups to the carboxyl functional groups is more than 1: 0.8, the proportion of the ester group structure in the main chain structure of the prepared trehalose bio-based epoxy resin cured product is low, so that the degradation speed is influenced, and even the degradation cannot be realized. If the ratio of the above epoxy functional groups to the carboxyl functional groups is less than 1: 1.2, excessive carboxyl-derived trehalose can affect the mechanical properties of trehalose bio-based epoxy resin cured products.
According to some preferred embodiments, in step (1), the carboxyl-derivatized trehalose is prepared from trehalose and an organic acid anhydride by a ring-opening reaction;
the preparation method of the carboxyl-derivatized trehalose comprises the following substeps:
(1.1) stirring trehalose, organic acid anhydride and N, N-dimethylformamide to obtain a mixed solution;
(1.2) adding anhydrous pyridine and 4-dimethylaminopyridine into the mixed solution, and stirring to obtain a reaction solution;
(1.3) carrying out rotary evaporation treatment on the reaction solution, then dropwise adding ethyl acetate for dilution, and further carrying out quenching reaction to obtain an organic phase diluted solution;
and (1.4) adding a hydrochloric acid aqueous solution into the diluted solution for extraction treatment, taking an upper layer organic phase solution, and sequentially performing drying treatment, filtering treatment and secondary rotary evaporation treatment to obtain the carboxyl-derivatized trehalose.
In the present invention, since the hydroxyl group in trehalose has low reactivity with the epoxy functional group in the aliphatic epoxy resin, the trehalose molecule is modified into carboxyl-derivatized trehalose having high reactivity by a ring-opening reaction of trehalose with an organic acid anhydride. In the ring-opening reaction, an anhydride group of the organic acid anhydride is connected with a part of hydroxyl groups in the trehalose in an ester group structure to obtain carboxyl, so that the trehalose is provided with the carboxyl, and the subsequent polymerization reaction with the epoxy resin is facilitated.
In the step (1.3) of the present invention, most of the solvent in the reaction solution was removed by rotary evaporation treatment, and then ethyl acetate was added to the rotary evaporated reaction solution to stop the quenching of the reaction.
According to some more preferred embodiments, after quenching the reaction in step (1.3), the method further comprises extracting and washing the quenched solution with 1.8-2.2M hydrochloric acid aqueous solution, and taking the upper organic phase solution through a separating funnel.
According to some preferred embodiments, the organic anhydride is succinic anhydride, glutaric anhydride, or adipic anhydride;
the molar ratio of the trehalose to the organic acid anhydride is 1 (8-12) (for example, 1: 8, 1: 8.5, 1: 9, 1: 9.5, 1:10, 1: 10.5, 1: 11, 1: 11.5 or 1: 12);
experiments prove that because hydroxyl groups in the trehalose can not be completely reacted with organic acid anhydride to form carboxyl groups, the inventor obtains that the molar ratio of the trehalose to the organic acid anhydride is within 1 (8-12) and the content of the carboxyl groups in the prepared carboxyl-derived trehalose is the highest (wherein the content of unreacted hydroxyl groups is 5-10%) through a large amount of change of the feeding ratio experiments. If the molar ratio of the trehalose to the organic acid anhydride is more than 1: 8, the carboxyl content in the obtained carboxyl-derived trehalose is low, and the degradation performance of the trehalose bio-based epoxy resin cured product can be influenced; if the molar ratio of the trehalose to the organic acid anhydride is less than 1: 12, the carboxyl content of the obtained carboxyl-derivatized trehalose is not obviously increased along with the increase of the organic acid anhydride, and the organic acid anhydride is remained, so that the subsequent solvent removal and quenching reaction are influenced.
According to some preferred embodiments, the carboxyl-derivatized trehalose is prepared by the following steps of: 10 parts of trehalose, 90-110 parts of N, N-dimethylformamide (for example, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110 parts of anhydrous pyridine), 25-35 parts of anhydrous pyridine (for example, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 parts of anhydrous pyridine), 1-3 parts of 4-dimethylaminopyridine (for example, 1, 2 or 3 parts of anhydrous pyridine), 400-500 parts of ethyl acetate (for example, 400, 450 or 500 parts of anhydrous pyridine), and 400-500 parts of aqueous hydrochloric acid (for example, 400, 450 or 500 parts of anhydrous pyridine).
In the invention, N, N-dimethylformamide is used as an organic solvent, and anhydrous pyridine provides a weak alkaline environment required by the reaction of carboxyl derivatization trehalose and organic acid anhydride, so that 4-dimethylaminopyridine is used as a catalyst to increase the reaction rate.
According to some preferred embodiments, the stirring temperature is 80 to 100 ℃ (for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃) and the rotation speed is 500 to 700r/min (for example, 500r/min, 550r/min, 600r/min, 650r/min or 700 r/min);
in the step (1.1), the stirring time is 5-10 min (for example, 5min, 6min, 7min, 8min, 9min or 10 min);
in the step (1.2), the stirring time is 45-55 h (for example, 45h, 46h, 47h, 48h, 49h, 50h, 51h, 52h, 53h, 54h or 55 h).
In the invention, the stirring in the step (1.1) enables all components to be fully dissolved to obtain a uniform and transparent solution; the stirring in step (1.2) allows the reactants to react well.
According to some preferred embodiments, in the step (1.3), the temperature of the rotary evaporation treatment is 35 to 45 ℃ (for example, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃ or 45 ℃), and the rotary evaporation time is 15 to 30min (for example, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30 min).
In the present invention, the solvent in the reaction solution can be removed by the rotary evaporation treatment in step (1.3).
According to some preferred embodiments, in step (1.4), the drying treatment is drying with anhydrous sodium sulfate or anhydrous magnesium sulfate; the temperature of the secondary rotary evaporation treatment is 20-30 ℃ (for example, 20 ℃, 25 ℃ or 30 ℃), and the rotary evaporation time is 5-10 min (for example, 5min, 6min, 7min, 8min, 9min or 10 min).
In the present invention, residual water in the organic phase is removed by drying treatment, and ethyl acetate in the organic phase is removed by rotary evaporation treatment.
According to some preferred embodiments, the carboxyl-derivatized trehalose has the general structural formula
Wherein n is 2, 3 or 4.
In addition, the hydroxyl groups in trehalose cannot be completely reacted with the organic acid anhydride, and some hydroxyl groups are not reacted, so that the carboxyl-derived trehalose formula is formed. In the above molar ratio range of trehalose to organic acid anhydride, the higher the proportion of organic acid anhydride, the higher the content of carboxyl groups in the formed carboxyl group-derivatized trehalose.
In the present invention, when the organic acid anhydride is succinic anhydride, n in the above general structural formula is 2; when the organic acid anhydride is glutaric anhydride, n in the structural general formula is 3; when the organic acid anhydride is adipic anhydride, n in the structural general formula is 4.
According to some preferred embodiments, in step (1), the aliphatic epoxy resin is at least one of trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and 1, 4-cyclohexanedimethanol diglycidyl ether.
In the present invention, the aliphatic epoxy resin has an epoxy group which is not bound by a rigid aromatic ring and can rotate relatively freely, and has a higher reactivity with a carboxyl group and can form an ester group more rapidly than bisphenol a type epoxy resins. In addition, the aliphatic epoxy resin has excellent thermal stability, weather resistance, manufacturability and electrical insulation, and can provide excellent thermal stability, weather resistance, manufacturability and electrical insulation for the trehalose bio-based epoxy resin cured product.
According to some preferred embodiments, the curing agent is at least one of ammonium chloride, ammonium nitrate, ammonium bromide, an aromatic diamine, an aliphatic diamine.
In the present invention, the curing agent is selected from the group consisting of, but not limited to, the above agents, and may be inorganic ammonium, but not limited to, ammonium chloride, ammonium nitrate, ammonium bromide.
According to some preferred embodiments, the solvent is at least one of dichloromethane, chloroform, acetone, ethyl acetate.
In the invention, the selected organic solvent has a low boiling point, and the organic solvent with the low boiling point can be used for dissolving the aliphatic epoxy resin, the curing agent and the carboxyl-derived trehalose at room temperature (25 ℃) to obtain a stable and uniform transparent solution and is easy to spin-evaporate and remove.
According to some preferred embodiments, the polymerization reaction has a reaction time of 8 to 12min (e.g., 8min, 9min, 10min, 11min, or 12min) and a reaction temperature of 20 to 30 ℃ (e.g., 20 ℃, 25 ℃, or 30 ℃).
In the present invention, according to some more preferred embodiments, the solution is continuously stirred during the polymerization reaction at a speed of 500 to 700r/min (for example, 500r/min, 550r/min, 600r/min, 650r/min or 700 r/min).
According to some preferred embodiments, before the step (2), the method further comprises the steps of sequentially performing rotary evaporation treatment and drying treatment on the trehalose bio-based epoxy resin prepolymer solution;
the temperature of the rotary steaming treatment is 20-30 ℃ (for example, 20 ℃, 25 ℃ or 30 ℃), and the rotary steaming time is 5-10 min (for example, 5min, 6min, 7min, 8min, 9min or 10 min);
the drying treatment is carried out in a vacuum environment at a vacuum degree of-0.085 MPa and at a temperature of 35-45 deg.C (for example, 35 deg.C, 36 deg.C, 37 deg.C, 38 deg.C, 39 deg.C, 40 deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C or 45 deg.C) for 25-35 min (for example, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35 min).
In the invention, the solvent in the solution can be removed by reduced pressure rotary evaporation, and the pressure of the vacuum environment is-0.085 MPa. All the rotary evaporation treatment mentioned in the invention is reduced pressure rotary evaporation, and the conventional reduced pressure method is adopted.
According to some preferred embodiments, in step (2), the curing process is a staged curing: curing the mixture for 1.5 to 2.5 hours (for example, 1.5 hours, 2 hours or 2.5 hours) at 110 to 130 ℃ (for example, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃), and then curing the mixture for 1.5 to 2.5 hours (for example, 1.5 hours, 2 hours or 2.5 hours) at 155 to 175 ℃ (for example, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or 175 ℃).
It should be noted that the curing reaction of the epoxy resin includes the addition reaction between small molecules and the crosslinking reaction between chain segments, the addition reaction speed is faster in the early stage, and the crosslinking reaction of the polymer chain segments mainly forms a three-dimensional network stereo structure in the later stage, so that the structure has excellent hardness and strength. However, the segmental reactivity decreases with an increase in molecular weight, and in order to further increase the degree of reaction, it is necessary to increase the temperature in stages for curing, and to continue the temperature in the second stage to increase the segmental reactivity.
The invention provides a trehalose bio-based epoxy resin cured product which is prepared by the preparation method provided by the invention.
In the invention, the preparation method of the trehalose bio-based epoxy resin condensate is simple, strong in operability, easy to implement and beneficial to large-scale industrial production.
In order to more clearly illustrate the technical scheme and advantages of the present invention, a trehalose bio-based epoxy resin cured product and a preparation method thereof are described in detail by using several examples.
Example 1:
(1) 10g of trehalose and 30g of succinic anhydride (molar ratio of 1:10) were added to a round-bottom flask, and then 100g N, N-dimethylformamide was added and stirred until completely dissolved for 8 min. Then, 30g of anhydrous pyridine and 2g of 4-dimethylaminopyridine were added to the solution, and the mixture was further stirred for 48 hours to obtain a reaction solution. The stirring temperature is 90 ℃ and the speed is 600 r/min. The reaction solution was subjected to rotary evaporation treatment (rotary evaporation at 40 ℃ C. for 15min) to remove most of the solvent, and the reaction solution from which the solvent was removed was slowly dropped into 500g of ethyl acetate to be quenched. The quenched reaction solution was washed with an aqueous hydrochloric acid solution (2M), and an upper organic phase was taken out through a separatory funnel. The organic phase was then dried over anhydrous sodium sulfate and again rotoevaporated (8 min at 25 ℃) to give the carboxylic acid derivatized trehalose (hydroxyl or carboxyl content as%):
in this example, succinic anhydride was used as a raw material, and n in the above formula was 2.
(2) Dissolving 100g of trimethylolpropane triglycidyl ether (0.99mol of epoxy functional group), 140g of carboxylic acid-derived trehalose (0.99mol of carboxyl functional group) and 5g of tetrabutylammonium bromide in 19.6g of acetone, and stirring at room temperature for 10min to complete a polymerization reaction to obtain a trehalose bio-based epoxy resin prepolymer solution; and then carrying out rotary evaporation treatment (rotary evaporation at 25 ℃ for 8min) on the reacted solution to remove the solvent, drying the reaction solution after the solvent is removed under vacuum for 30min (-0.085MPa, 40 ℃) to obtain viscous liquid, pouring the viscous liquid into a forming mold, curing for 2h at 120 ℃, curing for 2h at 165 ℃, and demolding to obtain the trehalose bio-based epoxy resin condensate sample.
Example 2:
example 2 is essentially the same as example 1, except that:
in step (2), 100g of neopentyl glycol diglycidyl ether (0.92mol of epoxy functional group) was selected instead of trimethylolpropane triglycidyl ether, and the mass of carboxylic acid-derivatized trehalose was adjusted to 130g (0.92mol of carboxyl functional group).
Example 3:
example 3 is essentially the same as example 1, except that:
in step (2), 100g of propylene glycol diglycidyl ether (0.81mol of epoxy functional group) was selected instead of trimethylolpropane triglycidyl ether, and the mass of carboxylic acid-derivatized trehalose was adjusted to 120g (0.81mol of carboxyl functional group).
Example 4:
example 4 is essentially the same as example 1, except that:
in step (2), 100g of 1, 4-cyclohexanedimethanol diglycidyl ether (0.78mol of epoxy functional group) was selected instead of trimethylolpropane triglycidyl ether, and the mass of carboxylic acid-derivatized trehalose was adjusted to 115g (0.78mol of carboxyl functional group).
Comparative example 1:
dissolving 100g of trimethylolpropane triglycidyl ether and 5g of tetrabutylammonium bromide in 19.6g of acetone, stirring for 10min at room temperature for full reaction, carrying out rotary evaporation treatment (rotary evaporation at 25 ℃ for 8min) on the solution after reaction to remove the solvent, drying the reaction solution after the solvent is removed under vacuum for 30min (-0.085MPa, 40 ℃) to obtain viscous liquid, pouring the viscous liquid into a forming mold, curing at 120 ℃ for 2h, curing at 165 ℃ for 2h, and demolding to obtain the epoxy resin cured product sample strip.
Comparative example 2:
dissolving 100g of trimethylolpropane triglycidyl ether, 140g of trehalose and 5g of tetrabutylammonium bromide in 19.6g of acetone, stirring for 10min at room temperature for full reaction, carrying out rotary evaporation treatment (rotary evaporation is carried out for 8min at 25 ℃) on the solution after the reaction to remove the solvent, drying the reaction solution after the solvent is removed for 30min (20KPa and DEG C) under vacuum to obtain viscous liquid, pouring the viscous liquid into a forming mold, curing for 2h at 120 ℃, curing for 2h at 165 ℃ and then demolding to obtain the epoxy resin cured product sample strip.
Comparative example 3:
comparative example 3 is substantially the same as example 1 except that:
in the step (2), the mass of the carboxylic acid-derivatized trehalose was adjusted to 70g (0.49mol of carboxyl functional group)
Application example:
(1) 10g of trehalose and 30g of succinic anhydride (molar ratio of 1:10) were added to a round-bottom flask, and then 100g N, N-dimethylformamide was added and stirred until completely dissolved for 8 min. Then, 30g of anhydrous pyridine and 2g of 4-dimethylaminopyridine were added to the solution, and stirring was continued for 48 hours to obtain a reaction solution. The stirring temperature is 90 ℃ and the speed is 600 r/min. The reaction solution was subjected to rotary evaporation treatment (rotary evaporation at 40 ℃ C. for 15min) to remove most of the solvent, and the reaction solution from which the solvent was removed was slowly added to 500g of ethyl acetate to quench. The quenched reaction solution was washed with an aqueous hydrochloric acid solution (2M), and an upper organic phase was taken out through a separatory funnel. The organic phase was then dried over anhydrous sodium sulfate and again rotovaped (8 min at 25 ℃) to give carboxylic acid-derivatized trehalose (8% hydroxyl content):
in this example, succinic anhydride was used as a raw material, and n in the above formula was 2.
(2) Dissolving 100g of trimethylolpropane triglycidyl ether (0.99mol of epoxy functional group), 140g of carboxylic acid-derived trehalose (0.99mol of carboxyl functional group) and 5g of tetrabutylammonium bromide in 19.6g of acetone, and stirring at room temperature for 10min to complete prepolymerization reaction to obtain a trehalose bio-based epoxy resin prepolymer solution; and then carrying out rotary evaporation treatment (rotary evaporation at 25 ℃ for 8min) on the reacted solution to remove the solvent, drying the reaction solution after the solvent is removed under vacuum for 30min (-0.085MPa, 40 ℃) to obtain viscous liquid, pouring the viscous liquid into a forming mold, curing the viscous liquid at 80 ℃ for 30min, placing the viscous liquid on a compression roller, preparing a carbon fiber prepreg with 200g of carbon fiber bidirectional plain cloth, curing the carbon fiber prepreg at 120 ℃ for 1h, post-curing the carbon fiber prepreg at 165 ℃ for 2h, and demolding to obtain the carbon fiber composite material.
(3) Soaking the obtained carbon fiber composite material in 1M NaOH aqueous solution for 4 hours, then completely degrading, and recycling after washing to obtain carbon fiber bidirectional plain cloth; the monofilament tensile strength of the recycled carbon fiber bidirectional plain cloth is 2.56GPa, and the monofilament tensile strength of the original carbon fiber is 2.63 GPa.
According to the application examples, the carbon fiber composite material prepared by treating the trehalose bio-based epoxy resin condensate and the carbon fiber bidirectional plain cloth through the compression roller can degrade the epoxy resin in the carbon fiber composite material through a weak alkaline aqueous solution, so that the carbon fiber is recycled, and the recycled carbon fiber still maintains excellent monofilament tensile strength.
The cured epoxy resin specimens obtained in examples 1 to 4 and comparative examples 1 to 3 were subjected to the performance test, and the results are shown in Table 1 below:
TABLE 1
As can be seen from Table 1, the cured epoxy resin specimens prepared according to the scheme of the present invention (examples 1 to 4) all degraded within 4 hours, and had good thermal properties and mechanical properties.
As can be seen from comparative example 1, the cured product prepared from the conventional epoxy resin was not degraded in a short time.
As can be seen from comparative example 2, the reaction activity of ordinary trehalose with aliphatic epoxy resin is low, the formation of ester group structure by the reaction product is small, and the formed cured product is difficult to degrade completely.
As shown in comparative example 3, when the carboxyl group-derivatized trehalose is less than the epoxy group of the aliphatic epoxy resin, the epoxy resin cured product finally formed has a lower ester group content and a lower degradation rate.
According to examples 1 to 3, it can be seen that the mechanical and thermal properties of the cured trehalose bio-based epoxy resin gradually decrease as the epoxy group content decreases, and therefore, it is preferable to select an epoxy resin having a high epoxy value for high load applications.
Comparing example 3 with example 4, it can be seen that the rigid six-membered ring structure of the cycloaliphatic (example 4) epoxy resin possesses better mechanical properties than the simple aliphatic chain structure (example 3) with substantially equivalent epoxy group content.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the trehalose bio-based epoxy resin cured product is characterized by comprising the following steps:
(1) performing prepolymerization reaction on carboxyl-derived trehalose, aliphatic epoxy resin, a curing agent and a solvent to obtain a trehalose bio-based epoxy resin prepolymer solution;
(2) and curing the trehalose bio-based epoxy prepolymer resin solution to obtain the trehalose bio-based epoxy resin cured product.
2. The method of claim 1, wherein:
the trehalose biological epoxy resin prepolymer solution comprises the following raw materials in parts by weight: 50-150 parts of carboxyl derived trehalose, 100 parts of aliphatic epoxy resin, 5-20 parts of curing agent and 10-30 parts of solvent.
3. The production method according to claim 1, wherein in step (1):
the carboxyl-derived trehalose is prepared from trehalose and organic acid anhydride through a ring-opening reaction;
the preparation method of the carboxyl-derivatized trehalose comprises the following substeps:
(1.1) stirring trehalose, organic acid anhydride and N, N-dimethylformamide to obtain a mixed solution;
(1.2) adding anhydrous pyridine and 4-dimethylaminopyridine into the mixed solution, and stirring to obtain a reaction solution;
(1.3) carrying out rotary evaporation treatment on the reaction solution, adding ethyl acetate for dilution, and further carrying out quenching reaction to obtain a diluted solution;
and (1.4) adding a hydrochloric acid aqueous solution into the diluted solution for extraction treatment, taking an upper layer organic phase solution, and sequentially performing drying treatment, filtering treatment and secondary rotary evaporation treatment to obtain the carboxyl-derivatized trehalose.
4. The production method according to claim 3, characterized in that:
the organic acid anhydride is succinic anhydride, glutaric anhydride or adipic anhydride;
the molar ratio of the trehalose to the organic acid anhydride is 1 (8-12); and/or
The preparation method of the carboxyl-derived trehalose comprises the following steps of: 10 parts of trehalose, 90-110 parts of N, N-dimethylformamide, 25-35 parts of anhydrous pyridine, 1-3 parts of 4-dimethylaminopyridine, 400-500 parts of ethyl acetate and 400-500 parts of hydrochloric acid aqueous solution.
5. The production method according to claim 3, characterized in that:
the stirring temperature is 80-100 ℃, and the rotating speed is 500-700 r/min;
in the step (1.1), the stirring time is 5-10 min;
in the step (1.2), the stirring time is 45-55 h;
in the step (1.3), the temperature of the rotary evaporation treatment is 35-45 ℃, and the rotary evaporation time is 15-30 min; and/or
In the step (1.4), the drying treatment is drying by using anhydrous sodium sulfate or anhydrous magnesium sulfate; the temperature of the secondary rotary evaporation treatment is 20-30 ℃, and the rotary evaporation time is 5-10 min.
6. The production method according to claim 1 or 3, characterized in that:
the structural general formula of the carboxyl-derived trehalose is shown as
Wherein n is 2, 3 or 4.
7. The production method according to claim 1, wherein in step (1):
the aliphatic epoxy resin is at least one of trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether and 1, 4-cyclohexanedimethanol diglycidyl ether;
the curing agent is at least one of ammonium chloride, ammonium nitrate, ammonium bromide, aromatic diamine and aliphatic diamine;
the solvent is at least one of dichloromethane, chloroform, acetone and ethyl acetate; and/or
The reaction time of the prepolymerization is 8-12 min.
8. The method of claim 1, wherein:
before the step (2), the steps of sequentially carrying out rotary steaming treatment and drying treatment on the trehalose bio-based epoxy resin prepolymer solution are also included;
the temperature of the rotary evaporation treatment is 20-30 ℃, and the rotary evaporation time is 5-10 min;
the drying treatment is drying for 25-35 min under the conditions of vacuum environment, vacuum degree of-0.085 MPa and temperature of 35-45 ℃.
9. The method of claim 1, wherein:
in step (2), the curing process is a staged curing: curing for 1.5-2.5 h at 110-130 ℃, and then curing for 1.5-2.5 h at 155-175 ℃.
10. A trehalose bio-based epoxy resin cured product, characterized by being produced by the production method according to any one of claims 1 to 9.
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