CN113717349B - 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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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, wherein the preparation method comprises the following steps: performing a 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 easily opened from the position of the ester group structure under a mild alkaline condition, so that the trehalose bio-based epoxy resin condensate is degraded into degradation products with smaller molecular weight and is dissolved in the traditional solvent, and the degradation of the trehalose bio-based epoxy resin condensate is completed.
Description
Technical Field
The invention relates to the field of polymers and composite materials, in particular to a trehalose bio-based epoxy resin condensate and a preparation method thereof.
Background
Epoxy resins are unique high performance thermosets that, upon curing, form irreversibly crosslinked materials with excellent properties. 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 currently obtained from non-renewable petroleum-based raw materials, and their highly chemically crosslinked three-dimensional network structure also makes the problem of waste management of epoxy resins increasingly prominent. Therefore, development of a novel epoxy resin cured product having environmental sustainability and being degradable is urgently required.
Disclosure of Invention
The embodiment of the invention provides a trehalose bio-based epoxy resin condensate and a preparation method thereof, which can provide an epoxy resin condensate which is degradable and has environmental protection, and can be degraded under mild alkaline conditions.
In a first aspect, the invention provides a method for preparing a trehalose bio-based epoxy resin condensate, comprising the following steps:
(1) Performing a 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 anhydride by a ring-opening reaction;
the preparation method of the carboxyl-derived trehalose comprises the following substeps:
(1.1) stirring trehalose, organic anhydride and N, N-dimethylformamide to obtain a mixed solution;
(1.2) adding anhydrous pyridine and 4-dimethylaminopyridine to the mixed solution and stirring to obtain a reaction solution;
(1.3) performing rotary evaporation treatment on the reaction solution, then dropwise adding ethyl acetate for dilution, and further performing quenching reaction to obtain an organic phase dilution solution;
and (1.4) adding an aqueous solution of hydrochloric acid into the diluted solution for extraction treatment, taking an upper organic phase solution, and sequentially carrying out drying treatment, filtering treatment and secondary rotary evaporation treatment to obtain the carboxyl-derived trehalose.
Preferably, the organic acid anhydride is succinic anhydride, glutaric anhydride or adipic anhydride;
the molar ratio of the trehalose to the organic anhydride is 1 (8-12).
Preferably, the carboxyl-derivatized trehalose is prepared from 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 steaming treatment is 35-45 ℃ and the rotary steaming time is 15-30 min.
Preferably, in step (1.4), the drying treatment is drying with anhydrous sodium sulfate or anhydrous magnesium sulfate; the temperature of the secondary rotary steaming treatment is 20-30 ℃, and the rotary steaming time is 5-10 min.
Preferably, the carboxyl-derivatized trehalose has a structural formula of
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 to 12 minutes.
Preferably, the step (2) is preceded by the step of sequentially carrying out spin steaming treatment and drying treatment on the trehalose bio-based epoxy resin prepolymer solution;
the temperature of the rotary steaming treatment is 20-30 ℃, and the rotary steaming time is 5-10 min;
the drying treatment is to dry 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 in any one of the first aspects.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The trehalose bio-based epoxy resin condensate 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 easily opened from the position of the ester group structure under a mild alkaline condition, so that the trehalose bio-based epoxy resin condensate is degraded into degradation products with smaller molecular weight and is dissolved in the traditional solvent, and the degradation of the trehalose bio-based epoxy resin condensate is completed.
(2) The biological base material carboxyl derivative trehalose is introduced, so that the mechanical properties of the traditional epoxy resin are ensured, the environment is protected, and the use of petrochemical products is reduced.
(3) The trehalose bio-based epoxy resin condensate prepared by the method is simple in preparation method, strong in operability, easy to implement and beneficial to large-scale industrialized 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 the weak alkaline aqueous solution and recover the carbon fiber bidirectional plain cloth, and the recovered carbon fiber bidirectional plain cloth still maintains excellent monofilament tensile strength.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments of the present invention are all within the scope of protection of the present invention.
In the prior art, patent CN109280153A reforms epoxy resin by using spiral cyclic acetal diphenol, so that an epoxy condensate can be degraded under mild conditions, and the fiber composite material prepared by using the epoxy condensate is easy to recycle fibers in the epoxy condensate. However, the method has limitations, the raw materials for preparing the epoxy resin are all from petrochemical products, and the method cannot be degradable and has environmental protection. The invention realizes the degradable function of the epoxy resin and takes the raw materials into account in green environmental protection by introducing the biological base material.
The invention provides a preparation method of a trehalose bio-based epoxy resin condensate, 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, the trehalose bio-based epoxy resin condensate introduces an ester group structure into a traditional epoxy resin main chain structure, and due to the existence of the ester group structure, a cured epoxy resin cross-linked network is easily opened from the position of the ester group structure under a mild alkaline condition and is degraded into degradation products with smaller molecular weight, so that the trehalose bio-based epoxy resin condensate is soluble in a traditional solvent, and thus the trehalose bio-based epoxy resin condensate 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 (e.g., may be 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150 parts), 100 parts of the aliphatic epoxy resin, 5-20 parts (e.g., may be 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 (e.g., may be 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-derived trehalose to the aliphatic epoxy resin is obtained according to the molar ratio of the two functional groups, and the specific basis is that the molar ratio of the epoxy functional groups in the aliphatic epoxy resin to the carboxyl functional groups in the carboxyl-derived trehalose is 1: (0.8-1.2) (e.g., may be 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). 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 trehalose bio-based epoxy resin condensate is realized.
Experiments prove that if the ratio of the epoxy functional group to the carboxyl functional group is greater than 1: and 0.8, the proportion of the ester group structure in the main chain structure of the prepared trehalose bio-based epoxy resin is low, so that the degradation speed of the trehalose bio-based epoxy resin is influenced, and the trehalose bio-based epoxy resin cannot be degraded. If the ratio of the epoxy functional groups to the carboxyl functional groups is less than 1:1.2, the mechanical properties of the trehalose bio-based epoxy resin cured product are affected by an excessive amount of carboxyl-derivatized trehalose.
According to some preferred embodiments, in step (1), the carboxy-derivatized trehalose is prepared from trehalose and an organic anhydride by a ring-opening reaction;
the preparation method of the carboxyl-derived trehalose comprises the following substeps:
(1.1) stirring trehalose, organic anhydride and N, N-dimethylformamide to obtain a mixed solution;
(1.2) adding anhydrous pyridine and 4-dimethylaminopyridine to the mixed solution and stirring to obtain a reaction solution;
(1.3) performing rotary evaporation treatment on the reaction solution, then dropwise adding ethyl acetate for dilution, and further performing quenching reaction to obtain an organic phase dilution solution;
and (1.4) adding an aqueous solution of hydrochloric acid into the diluted solution for extraction treatment, taking an upper organic phase solution, and sequentially carrying out drying treatment, filtering treatment and secondary rotary evaporation treatment to obtain the carboxyl-derived 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 ring-opening reaction of trehalose with an organic acid anhydride. In the ring-opening reaction, the anhydride group of the organic anhydride is connected with part of hydroxyl groups of the trehalose in an ester structure, and carboxyl groups are obtained, so that the trehalose is provided with the carboxyl groups, thereby being beneficial to the subsequent polymerization reaction with the epoxy resin.
In the step (1.3) of the present invention, most of the solvent in the reaction solution was removed by spin-steaming, and then ethyl acetate was added to the spin-steamed reaction solution to stop the quenching of the reaction.
According to some more preferred embodiments, in step (1.3), after quenching the reaction, further comprising subjecting the quenched solution to extraction washing with an aqueous hydrochloric acid solution having a concentration of 1.8 to 2.2M, and obtaining an 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 trehalose to the organic anhydride is 1 (8-12) (e.g., may be 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 as hydroxyl groups in the trehalose cannot react with organic acid anhydride to form carboxyl groups, the inventor obtains that the molar ratio of the trehalose to the organic acid anhydride is in the range of 1 (8-12) through a great amount of experiments by changing the feed ratio, and the carboxyl content in the prepared carboxyl-derived trehalose is the highest (wherein the unreacted hydroxyl groups are 5-10%). If the molar ratio of trehalose to organic anhydride is greater than 1:8, the carboxyl content in the obtained carboxyl-derived trehalose is less, so that the degradation performance of the trehalose bio-based epoxy resin cured product is affected; if the molar ratio of trehalose to organic anhydride is less than 1:12, the carboxyl content in the obtained carboxyl-derived trehalose is not obviously increased along with the increase of the organic anhydride, and the organic anhydride remains, so that the subsequent solvent removal and quenching reactions are affected.
According to some preferred embodiments, the preparation of the carboxyl-derivatized trehalose comprises the following raw materials in parts by weight: 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), 25-35 parts of anhydrous pyridine (for example, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 parts), 1-3 parts of 4-dimethylaminopyridine (for example, 1, 2 or 3 parts), 400-500 parts of ethyl acetate (for example, 400, 450 or 500 parts) and 400-500 parts of aqueous hydrochloric acid (for example, 400, 450 or 500 parts).
In the present invention, N-dimethylformamide is used as an organic solvent, and anhydrous pyridine provides a weakly alkaline environment required for the reaction of carboxyl-derivatized trehalose with an organic acid anhydride, which is advantageous in that 4-dimethylaminopyridine is used as a catalyst for increasing the reaction rate.
According to some preferred embodiments, the temperature of the agitation is 80-100 ℃ (e.g., may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, or 100 ℃) at a rotational speed of 500-700 r/min (e.g., may be 500r/min, 550r/min, 600r/min, 650r/min, or 700 r/min);
in step (1.1), the stirring time is 5 to 10 minutes (for example, may be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes);
in step (1.2), the stirring time is 45 to 55 hours (for example, 45 hours, 46 hours, 47 hours, 48 hours, 49 hours, 50 hours, 51 hours, 52 hours, 53 hours, 54 hours or 55 hours may be mentioned).
In the invention, stirring in the step (1.1) enables each component to be fully dissolved, so as to obtain uniform and transparent solution; stirring in step (1.2) causes the reactants to react well.
According to some preferred embodiments, in step (1.3), the spin-steaming is performed at a temperature of 35-45 ℃ (e.g., may be 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃,40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, or 45 ℃), and the spin-steaming time is 15-30 min (e.g., may be 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 spin-steaming 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 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).
In the present invention, the residual water in the organic phase is removed by a drying process, and the ethyl acetate in the organic phase is removed by a rotary evaporation process.
According to some preferred embodiments, the carboxyl-derivatized trehalose has a structural formula of
Wherein n is 2, 3 or 4.
The hydroxyl groups in trehalose cannot react with the organic acid anhydride, and some of the hydroxyl groups are unreacted, so that the above carboxyl-derivatized 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 carboxyl group content in the formed carboxyl-derivatized trehalose.
In the invention, when the organic acid anhydride is succinic anhydride, n in the structural general formula is 2; when the organic acid anhydride is glutaric anhydride, n in the general structural formula is 3; when the organic acid anhydride is adipic acid anhydride, n in the structural 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, 1, 4-cyclohexanedimethanol diglycidyl ether.
In the invention, compared with bisphenol A epoxy resin, the epoxy group of the aliphatic epoxy resin is not limited by a rigid aromatic ring, can rotate freely, has higher reactivity with carboxyl, and can form ester groups more quickly. 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 condensate.
According to some preferred embodiments, the curing agent is at least one of ammonium chloride, ammonium nitrate, ammonium bromide, aromatic diamine, 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, and ammonium bromide.
According to some preferred embodiments, the solvent is at least one of dichloromethane, chloroform, acetone, ethyl acetate.
In the invention, the organic solvent with a low boiling point is selected, and the organic solvent with a low boiling point can dissolve 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 remove by rotary evaporation.
According to some preferred embodiments, the polymerization reaction time is 8 to 12min (e.g., may be 8min, 9min, 10min, 11min, or 12 min) and the reaction temperature is 20 to 30 ℃ (e.g., may be 20 ℃, 25 ℃, or 30 ℃).
In the present invention, according to some more preferred embodiments, the solution is continuously stirred during the polymerization 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, the method further comprises the step of sequentially performing spin steaming treatment and drying treatment on the trehalose bio-based epoxy resin prepolymer solution before the step (2);
the spin-steaming treatment is performed at a temperature of 20-30deg.C (for example, 20 deg.C, 25 deg.C or 30deg.C) for 5-10 min (for example, 5min, 6min, 7min, 8min, 9min or 10 min);
the drying treatment is performed under vacuum conditions at a vacuum degree of-0.085 MPa and a temperature of 35-45deg.C (for example, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃,40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃ or 45 ℃) 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 treatment, and the pressure of the vacuum environment is-0.085 MPa. It should be noted that all the rotary steaming treatments mentioned in the invention are decompression rotary steaming, and the existing conventional decompression mode is adopted.
According to some preferred embodiments, in step (2), the curing process is a staged curing: curing is performed at 110-130℃ (e.g., may be 110℃, 115℃, 120℃, 125℃, or 130℃) for 1.5-2.5 hours (e.g., may be 1.5 hours, 2 hours, or 2.5 hours), and then at 155-175℃ (e.g., may be 155℃, 160℃, 165℃, 170℃, or 175℃) for 1.5-2.5 hours (e.g., may be 1.5 hours, 2 hours, or 2.5 hours).
The curing reaction of the epoxy resin comprises an addition reaction between small molecules and a crosslinking reaction between chain segments, the early addition reaction is faster, and the later crosslinking reaction of the main high molecular chain segments gradually forms a three-dimensional network-shaped three-dimensional structure, so that the epoxy resin has excellent hardness and strength. However, as the molecular weight increases, the activity of the segment movement decreases, and in order to further increase the reaction degree, it is necessary to raise the temperature and cure in stages, and in the second stage, the temperature is raised continuously, thereby increasing the activity of the segment.
The invention provides a trehalose bio-based epoxy resin condensate, which is prepared by adopting the preparation method provided by the invention.
In the invention, the trehalose bio-based epoxy resin condensate has the advantages of simple preparation method, strong operability, easy implementation and contribution to large-scale industrialized production.
In order to more clearly illustrate the technical scheme and advantages of the invention, a trehalose bio-based epoxy resin cured product and a preparation method thereof are described in detail below through several examples.
Example 1:
(1) 10g of trehalose and 30g of succinic anhydride (molar ratio 1:10) are added into a round-bottomed flask, 100g of N, N-dimethylformamide are added, and stirring is carried out until complete dissolution is achieved, wherein the stirring time is 8min. 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 temperature of the stirring was 90℃and the speed was 600r/min. The reaction solution was subjected to rotary evaporation treatment (rotary evaporation at 40 ℃ C. For 15 min) to remove most of the solvent, and the solvent-removed reaction solution was slowly added dropwise to 500g of ethyl acetate for quenching. The quenched reaction solution was washed with aqueous hydrochloric acid (2M), and the upper organic phase was obtained through a separating funnel. The organic phase was then dried over anhydrous sodium sulfate and again rotary distilled (rotary distilled at 25 ℃ for 8 min) to give carboxylic acid-derivatized trehalose (hydroxyl or carboxyl content%):
in this example, succinic anhydride is used as a raw material, and n in the above general formula has a value of 2.
(2) 100g of trimethylolpropane triglycidyl ether (0.99 mol of epoxy functional group), 140g of carboxylic acid-derived trehalose (0.99 mol of carboxyl functional group), 5g of tetrabutylammonium bromide, and dissolving in 19.6g of acetone, and stirring for 10min at room temperature to complete polymerization reaction, thereby obtaining a trehalose bio-based epoxy resin prepolymer solution; then the solution after the reaction is subjected to rotary evaporation treatment (rotary evaporation at 25 ℃ for 8 min) to remove the solvent, then the reaction solution after the solvent removal is dried under vacuum for 30min (-0.085 MPa,40 ℃) to obtain viscous liquid, the viscous liquid is poured into a forming die, is cured at 120 ℃ for 2h, is cured at 165 ℃ for 2h, and is then demolded to obtain a trehalose bio-based epoxy resin cured sample strip.
Example 2:
example 2 is substantially the same as example 1 except that:
in step (2), 100g of neopentyl glycol diglycidyl ether (0.92 mol of epoxy functional group) was selected instead of trimethylolpropane triglycidyl ether, and the mass of the carboxylic acid-derivatized trehalose was adjusted to 130g (0.92 mol of carboxyl functional group).
Example 3:
example 3 is substantially the same as example 1 except that:
in step (2), 100g of propylene glycol diglycidyl ether (0.81 mol of epoxy functional group) was selected instead of trimethylolpropane triglycidyl ether, and the mass of the carboxylic acid-derivatized trehalose was adjusted to 120g (0.81 mol of carboxyl functional group).
Example 4:
example 4 is substantially the same as example 1 except that:
in step (2), 100g of 1, 4-cyclohexanedimethanol diglycidyl ether (0.78 mol of epoxy functional groups) was selected instead of trimethylolpropane triglycidyl ether, and the mass of the carboxylic acid-derivatized trehalose was adjusted to 115g (0.78 mol of carboxyl functional groups).
Comparative example 1:
100g of trimethylolpropane triglycidyl ether, 5g of tetrabutylammonium bromide are dissolved in 19.6g of acetone, stirred at room temperature for 10min for full reaction, the solvent is removed by rotary evaporation (rotary evaporation at 25 ℃ for 8 min), the reaction solution after the solvent removal is dried for 30min (-0.085 MPa,40 ℃) under vacuum, viscous liquid is obtained, the viscous liquid is poured into a forming die, the mixture is cured at 120 ℃ for 2h, the mixture is cured at 165 ℃ for 2h, and then the epoxy resin cured sample bar is obtained after demoulding.
Comparative example 2:
100g of trimethylolpropane triglycidyl ether, 140g of trehalose, 5g of tetrabutylammonium bromide are dissolved in 19.6g of acetone, stirring is carried out for 10min at room temperature for full reaction, the reacted solution is subjected to rotary evaporation treatment (rotary evaporation at 25 ℃ for 8 min) to remove the solvent, the reacted solution after the solvent removal is dried under vacuum for 30min (20 KPa and DEG C), a viscous liquid is obtained, the viscous liquid is poured into a forming die, the forming die is cured for 2h at 120 ℃, the curing is carried out for 2h at 165 ℃, and then the epoxy resin cured sample bar is obtained after demoulding.
Comparative example 3:
comparative example 3 is substantially the same as example 1 except that:
in step (2), the mass of the carboxylic acid-derivatized trehalose was adjusted to 70g (0.49 mol of carboxyl functional group)
Application example:
(1) 10g of trehalose and 30g of succinic anhydride (molar ratio 1:10) are added into a round-bottomed flask, 100g of N, N-dimethylformamide are added, and stirring is carried out until complete dissolution is achieved, wherein the stirring time is 8min. Then, 30g of anhydrous pyridine and 2g of 4-dimethylaminopyridine were added to the solution, followed by stirring for 48 hours, to obtain a reaction solution. The temperature of the stirring was 90℃and the speed was 600r/min. The reaction solution was subjected to rotary evaporation treatment (rotary evaporation at 40 ℃ C. For 15 min) to remove most of the solvent, and the solvent-removed reaction solution was slowly added to 500g of ethyl acetate for quenching. The quenched reaction solution was washed with aqueous hydrochloric acid (2M), and the upper organic phase was obtained through a separating funnel. The organic phase was then dried over anhydrous sodium sulfate and again rotary distilled (rotary distilled at 25 ℃ for 8 min) to give carboxylic acid-derivatized trehalose (hydroxyl content 8%):
in this example, succinic anhydride is used as a raw material, and n in the above general formula has a value of 2.
(2) 100g of trimethylolpropane triglycidyl ether (0.99 mol of epoxy functional group), 140g of carboxylic acid-derived trehalose (0.99 mol of carboxyl functional group), 5g of tetrabutylammonium bromide, and dissolving in 19.6g of acetone, and stirring for 10min at room temperature to complete the prepolymerization reaction to obtain a trehalose bio-based epoxy resin prepolymer solution; then the solution after the reaction is subjected to rotary evaporation treatment (rotary evaporation at 25 ℃ for 8 min) to remove the solvent, then the reaction solution after the solvent removal is dried under vacuum for 30min (-0.085 MPa,40 ℃) to obtain viscous liquid, the viscous liquid is poured into a forming die, after the viscous liquid is solidified for 30min at 80 ℃, the viscous liquid is placed on a press roll and is made into carbon fiber prepreg with 200g of carbon fiber bi-directional plain cloth, the carbon fiber prepreg is solidified for 1h at 120 ℃, then the carbon fiber prepreg is post-solidified for 2h at 165 ℃, and then the carbon fiber composite material is obtained after demoulding.
(3) Immersing the obtained carbon fiber composite material into a 1M NaOH aqueous solution, immersing for 4 hours, completely degrading, washing and recycling to obtain carbon fiber bidirectional plain cloth; the monofilament tensile strength of the recovered carbon fiber bidirectional plain cloth is 2.56GPa, and the monofilament tensile strength of the original carbon fiber is 2.63GPa.
From the application examples, the carbon fiber composite material prepared by the trehalose bio-based epoxy resin condensate and the carbon fiber bi-directional plain cloth through the compression roller treatment can degrade the epoxy resin in the carbon fiber composite material through the weak alkaline aqueous solution, so that the recovery of the carbon fiber is realized, and the recovered carbon fiber still maintains excellent monofilament tensile strength.
The epoxy resin cured product bars obtained in examples 1 to 4 and comparative examples 1 to 3 were subjected to performance test, and the results are shown in the following table 1:
TABLE 1
As can be seen from Table 1, all the epoxy resin cured product bars (examples 1 to 4) prepared by the scheme provided by the invention can be completely degraded within 4 hours, and have better thermal properties and mechanical properties.
As is clear from comparative example 1, the cured product of a conventional epoxy resin cannot be degraded in a short time.
As is clear from comparative example 2, ordinary trehalose has low reactivity with aliphatic epoxy resins, and the reaction product has less ester group structure, and the resulting cured product is less likely to be degraded entirely.
As is clear from comparative example 3, when the carboxyl group content in the carboxyl-derived trehalose is less than that of the aliphatic epoxy resin epoxy group, the finally formed epoxy resin cured product has less ester group content and lower degradation speed.
According to examples 1-3, it can be seen that the mechanical and thermal properties of the trehalose bio-based epoxy resin cured product gradually decrease as the epoxy group content decreases, so that the epoxy resin with a high epoxy value is suitable for use in the face of a high load.
Comparing examples 3 and 4, it can be seen that the rigid six-membered ring structure of the cycloaliphatic (example 4) epoxy resin has better mechanical properties than the simple aliphatic chain structure (example 3) at a substantially equivalent epoxy content.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. The preparation method of the trehalose bio-based epoxy resin condensate is characterized by comprising the following steps:
(1) Performing a 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) Solidifying the trehalose bio-based epoxy prepolymer resin solution to obtain a trehalose bio-based epoxy resin solidified substance;
the trehalose bio-based epoxy resin prepolymer solution comprises the following raw materials in parts by mass: 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;
in step (1):
the carboxyl derivatization trehalose is prepared from trehalose and organic anhydride through a ring-opening reaction;
the preparation method of the carboxyl-derived trehalose comprises the following substeps:
(1.1) stirring trehalose, organic anhydride and N, N-dimethylformamide to obtain a mixed solution;
(1.2) adding anhydrous pyridine and 4-dimethylaminopyridine to the mixed solution and stirring to obtain a reaction solution;
(1.3) carrying out rotary steaming treatment on the reaction solution, then adding ethyl acetate for dilution, and then quenching the reaction to obtain a diluted solution;
(1.4) adding an aqueous solution of hydrochloric acid into the diluted solution for extraction treatment, taking an upper organic phase solution, and sequentially carrying out drying treatment, filtering treatment and secondary rotary evaporation treatment to obtain the carboxyl-derived trehalose;
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 carboxyl derivatization trehalose is prepared from 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;
the structural general formula of the carboxyl-derived trehalose is
Wherein n is 2, 3 or 4;
in step (1):
the aliphatic epoxy resin is at least one of trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene 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 and ammonium bromide.
2. The method of manufacturing according to claim 1, 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 steaming treatment is 35-45 ℃, and the rotary steaming time is 15-30 min; and/or
In the step (1.4), the drying treatment is drying by anhydrous sodium sulfate or anhydrous magnesium sulfate; the temperature of the secondary rotary steaming treatment is 20-30 ℃, and the rotary steaming time is 5-10 min.
3. The method of claim 1, wherein in step (1):
the solvent is at least one of dichloromethane, chloroform, acetone and ethyl acetate; and/or
The reaction time of the prepolymerization reaction is 8-12 min.
4. The method of manufacturing according to claim 1, characterized in that:
the step (2) is preceded by the steps of sequentially carrying out spin steaming treatment and drying treatment on the trehalose bio-based epoxy resin prepolymer solution;
the temperature of the rotary steaming treatment is 20-30 ℃, and the rotary steaming time is 5-10 min;
the drying treatment is carried out in a vacuum environment at the vacuum degree of-0.085 MPa and the temperature of 35-45 ℃ for 25-35 min.
5. The method of manufacturing according to claim 1, characterized in that:
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 ℃.
6. A trehalose bio-based epoxy resin cured product prepared by the preparation method of any one of claims 1 to 5.
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