CN111718515B - Method for degrading epoxy resin cured by catalytic anhydride - Google Patents

Method for degrading epoxy resin cured by catalytic anhydride Download PDF

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CN111718515B
CN111718515B CN202010652768.2A CN202010652768A CN111718515B CN 111718515 B CN111718515 B CN 111718515B CN 202010652768 A CN202010652768 A CN 202010652768A CN 111718515 B CN111718515 B CN 111718515B
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epoxy resin
degradation
anhydride
reaction
acid
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CN111718515A (en
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邓天昇
张宁
侯相林
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Shanxi Institute of Coal Chemistry of CAS
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    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
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    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/26—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

本发明属于固体废弃物材料回收技术领域，具体涉及一种催化酸酐固化的环氧树脂降解的方法。本发明主要解决了目前降解酸酐固化的环氧树脂方法中存在的催化剂成本高，降解反应温度高、条件苛刻等问题。本发明一种催化酸酐固化的环氧树脂降解的方法通过将酸酐固化的环氧树脂与反应溶剂、有机酸催化剂配制成降解体系，进行降解反应；降解完成后向体系中加入热水，充分溶解并过滤；滤液蒸出回收得到反应溶剂、固化剂和有机酸催化剂；滤饼为有机相环氧树脂降解产物。本发明具有回收成本低、反应条件温和、易于分离得到高附加值产品的优点。

Figure 202010652768

The invention belongs to the technical field of solid waste material recovery, and in particular relates to a method for degrading epoxy resin cured by catalyzing acid anhydride. The invention mainly solves the problems of high catalyst cost, high degradation reaction temperature, harsh conditions and the like existing in the current method for degrading acid anhydride-cured epoxy resin. The present invention is a method for catalyzing the degradation of acid anhydride-cured epoxy resin by formulating the acid anhydride-cured epoxy resin, a reaction solvent and an organic acid catalyst into a degradation system to carry out a degradation reaction; after the degradation is completed, add hot water to the system to fully dissolve and filtering; the filtrate is evaporated and recovered to obtain a reaction solvent, a curing agent and an organic acid catalyst; the filter cake is a degradation product of the organic phase epoxy resin. The invention has the advantages of low recovery cost, mild reaction conditions and easy separation to obtain high value-added products.

Figure 202010652768

Description

Method for degrading epoxy resin cured by catalytic anhydride
Technical Field
The invention belongs to the technical field of solid waste material recovery, and particularly relates to a method for degrading anhydride-cured epoxy resin.
Background
Epoxy resins refer to a large class of reactive compounds containing two or more epoxy groups in the molecule. Compared with other thermosetting resins, the cured epoxy resin has the advantages of excellent mechanical property, good dimensional stability, excellent chemical stability, good bonding property, excellent insulating property and the like, is often used as a cementing agent, a coating, a repairing material, an insulating material, a composite material, matrix resin and the like, and is widely applied to various fields of aerospace, ships, automobiles, buildings, electronics and electricity and the like. The cured epoxy resin is difficult to degrade in nature, so that a large amount of leftover materials generated in production and life cannot be recycled well, which not only wastes resources, but also causes the problem of environmental pollution.
In addition to physical recovery and heat recovery, the current epoxy resin recovery method is the most effective recovery method due to mild recovery conditions and high recovery rate. Patent CN 105153461a discloses a process for recovering epoxy resin composite material, which comprises mixing absolute ethyl alcohol and p-toluic acid to prepare an organic solvent, and adding ionic liquid into the organic solvent to degrade epoxy resin. The ionic liquid has high cost and complex degradation process. Patent CN 108779286a discloses a method for treating a cured thermosetting resin, which comprises treating and contacting a cured epoxy resin or an acid anhydride-cured epoxy resin with an alcohol solvent containing an alkali metal hydroxide to decompose and dissolve the cured thermosetting resin. Patent CN 107365429a discloses the use of heteropoly acid and lewis acid as catalysts in the degradation of thermosetting resins, and anhydride-curable epoxy resins can be degraded by using heteropoly acid and lewis acid as catalysts and water, ethanol, methanol, butanol, propanol, acetic acid, acetone or tetrahydrofuran as solvents. Although heteropoly acids have high catalytic activity, heteropoly acids have redox properties, and therefore the catalyst changes before and after the reaction and cannot be recycled. In summary, the existing degradation recovery method for anhydride cured epoxy resin has the problems of difficult catalyst recovery, low degradation activity, high cost of degradation solvent and the like.
Disclosure of Invention
Aiming at the problems existing in the degradation of the existing anhydride-cured epoxy resin, the invention provides a method for catalyzing the degradation of the anhydride-cured epoxy resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of catalyzing the degradation of an anhydride-cured epoxy resin, comprising the steps of: preparing the anhydride-cured epoxy resin, a reaction solvent and an organic acid catalyst into a degradation system for degradation reaction; adding hot water into the system after degradation is completed, fully dissolving and filtering; evaporating and recovering the filtrate to obtain a reaction solvent, a curing agent and an organic acid catalyst; the filter cake is an organic phase epoxy resin degradation product.
The organic acid catalyst is an organic protonic acid catalyst, hydrogen ions can be combined with carbonyl oxygen of ester bonds, so that the ester bonds in the anhydride curing epoxy resin are selectively broken, in addition, in the catalytic degradation process of the epoxy resin, the swelling process is critical to the degradation efficiency, and the organic protonic acid not only has an acidic group with a catalytic function, but also contains a lipophilic group, so that the organic protonic acid catalyst can more easily enter a resin body, and catalytic chemical bonds are selectively opened, so that the organic protonic acid catalyst has higher catalytic activity compared with a metal ion catalyst.
Further, the reaction solvent is any one of water, glacial acetic acid, an acetic acid-water mixed solvent, a tetrahydrofuran-water mixed solvent, a 1, 4-dioxane-water mixed solvent or an acetone-water mixed solvent. The reaction solvent not only can provide an active end group which reacts with an ester bond in the anhydride cured epoxy resin, but also has a good swelling effect on the anhydride cured epoxy resin under certain conditions, so that a catalyst can conveniently enter a resin body.
Further, the mass fraction of water in the acetic acid-water mixed solvent, the tetrahydrofuran-water mixed solvent, the 1, 4-dioxane-water mixed solvent or the acetone-water mixed solvent is 1-70%. The reaction solvent with the proportion has good swelling effect on the epoxy resin solidified by anhydride, is beneficial to the catalyst to enter a three-dimensional network structure of the cross-linked resin, can ensure the action of sufficient moisture and ester bonds, and can quickly generate catalytic degradation reaction.
Further, the organic acid catalyst is an organic strong acid which can ionize hydrogen ions and contains sulfonic acid groups and carboxyl groups.
Still further, the organic acid catalyst is any one of dodecylbenzene sulfonic acid, p-toluenesulfonic acid, methane sulfonic acid, trichloroacetic acid, trifluoroacetic acid and squaric acid. The organic acid belongs to strong acid or super acid, has good solubility in a degradation system, and is beneficial to exerting a catalytic effect.
Further, the mass ratio of the anhydride-cured epoxy resin to the reaction solvent to the organic acid catalyst is 10: 50-500: 1 to 10. When the mass ratio of the anhydride-cured epoxy resin to the reaction solvent is too large, the reaction solvent cannot fully swell the resin, so that the catalyst is not favorable for entering a three-dimensional network structure of the resin, and the catalytic effect is reduced; when the mass ratio of the anhydride-cured epoxy resin to the reaction solvent is too small, the amount of the solvent used is large, the relative content of degradation products is low, the subsequent separation is not facilitated, and the economical efficiency is not good. When the mass ratio of the anhydride-cured epoxy resin to the organic acid catalyst is lower than 10:1, the concentration of the organic acid catalyst is too low to exert the catalytic effect; when the mass ratio of the acid anhydride-cured epoxy resin to the organic acid catalyst is higher than 10:10, the organic acid catalyst is excessive, causing unnecessary waste, and side reactions occur, which are not favorable for the subsequent separation step.
Further, the temperature of the degradation reaction is 80-250 ℃, and the reaction time is 10 min-48 h. When the reaction temperature is lower than 100 ℃, the degradation reaction does not substantially occur, and when it is higher than 250 ℃, a side reaction occurs. When the reaction time is less than 10min, the degradation reaction is insufficient; when the reaction time is more than 48h, other chemical bonds in the resin are broken, and controllable degradation cannot be realized.
Further, the temperature of the hot water is 50-90 ℃. The water in the temperature range can fully dissolve the degraded curing agent components, so that the curing agent can be better separated.
The epoxy resin is glycidyl ether, glycidyl ester, glycidyl amine, alicyclic epoxy resin, epoxidized olefin, novel epoxy resin, etc., and preferably one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and hydrogenated bisphenol A type epoxy resin.
The epoxy resin curing agent is linear aliphatic anhydride, aromatic anhydride, alicyclic anhydride, etc., and preferably one of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and maleic anhydride.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst used in the invention has the advantages of low dosage, low price and high catalytic efficiency;
(2) the degradation product and the catalyst are convenient to separate, and the recovery cost can be reduced;
(3) the reaction solvent used in the invention has low cost and low boiling point, and is easy to separate and recycle;
(4) under the degradation condition of the invention, the degradation rate can reach 80-100%;
(5) the method can selectively break ester bonds in the anhydride-cured epoxy resin, and realize the recovery of high value-added products.
Drawings
FIG. 1 shows the degradation products of the aqueous phase13C-NMR spectrum;
FIG. 2 shows organic phase degradation products13C-NMR spectrum.
Detailed Description
Example 1
10g of phthalic anhydride cured bisphenol F type epoxy resin, 230g of water and 6.5g of methane sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out for 16 hours at 250 ℃. After degradation, adding hot water of 50 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain water, phthalic acid (figure 1) and methane sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product (fig. 2). The degradation rate reaches 95 percent.
Example 2
10g of bisphenol S epoxy resin cured by tetrahydrophthalic anhydride, 180g of water and 4.5g of p-toluenesulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction at 240 ℃ for 20 h. After degradation, adding hot water of 90 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain water, tetrahydrophthalic acid and p-toluenesulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 93 percent.
Example 3
10g of hexahydrophthalic anhydride cured hydrogenated bisphenol A epoxy resin, 330g of water and 8.5g of dodecylbenzene sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out for 46 hours at 200 ℃. After degradation, adding 60 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain water, hexahydrophthalic acid and dodecylbenzene sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 90 percent.
Example 4
10g of maleic anhydride cured bisphenol A epoxy resin, 250g of water and 8g of trichloroacetic acid are prepared into a degradation system, and the degradation reaction is carried out for 26 hours at 170 ℃. After degradation, adding 70 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain water, maleic acid and trichloroacetic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 95 percent.
Example 5
10g of phthalic anhydride cured bisphenol A type epoxy resin, 50g of glacial acetic acid and 1g of trifluoroacetic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction for 48 hours at 80 ℃. After degradation, adding 70 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, phthalic acid and trifluoroacetic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 80 percent.
Example 6
10g of bisphenol F type epoxy resin solidified by tetrahydrophthalic anhydride, 120g of glacial acetic acid and 3g of squaric acid are prepared into a degradation system, and the degradation reaction is carried out for 40h at 120 ℃. After degradation, adding hot water of 90 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, tetrahydrophthalic acid and a squaric acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 90 percent.
Example 7
10g of hexahydrophthalic anhydride cured bisphenol S type epoxy resin, 350g of glacial acetic acid and 2g of methane sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction is carried out for 15h at 150 ℃. After degradation, adding hot water of 50 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, hexahydrophthalic acid and methane sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 96 percent.
Example 8
10g of maleic anhydride cured hydrogenated bisphenol A epoxy resin, 200g of glacial acetic acid and 2g of methane sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out for 12 hours at 180 ℃. After degradation, adding 60 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, maleic acid and methane sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 98 percent.
Example 9
10g of phthalic anhydride cured bisphenol S type epoxy resin, 500g of acetic acid water mixed solvent with the acetic acid content of 99 wt% and 10g of p-toluenesulfonic acid are prepared into a degradation system, and the degradation reaction is carried out for 10min at 250 ℃. After degradation, adding hot water of 80 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, phthalic acid and a p-toluenesulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 100 percent.
Example 10
10g of hydrogenated bisphenol A epoxy resin solidified by tetrahydrophthalic anhydride, 150g of acetic acid-water mixed solvent with the acetic acid content of 85 wt% and 5g of methane sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction at 160 ℃ for 20 hours. After degradation, adding hot water of 90 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, tetrahydrophthalic acid and a methane sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 97 percent.
Example 11
10g of hexahydrophthalic anhydride cured bisphenol A epoxy resin, 250g of acetic acid water mixed solvent with the acetic acid content of 90 wt% and 4g of dodecylbenzene sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction at 140 ℃ for 30 hours. After degradation, adding hot water of 80 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, hexahydrophthalic acid and a dodecylbenzene sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 88 percent.
Example 12
10g of bisphenol F type epoxy resin solidified by maleic anhydride, 300g of acetic acid water mixed solvent with the acetic acid content of 85 wt% and 9g of p-toluenesulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction at 160 ℃ for 20 hours. After degradation, adding 70 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetic acid aqueous solution, maleic acid and a p-toluenesulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 100 percent.
Example 13
10g of phthalic anhydride cured hydrogenated bisphenol A epoxy resin, 100g of tetrahydrofuran water mixed solvent with the tetrahydrofuran content of 30 wt% and 5g of methane sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction at 240 ℃ for 1 hour. After degradation, adding 60 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain a tetrahydrofuran aqueous solution, phthalic acid and methane sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 95 percent.
Example 14
10g of bisphenol A epoxy resin cured by tetrahydrophthalic anhydride, 400g of tetrahydrofuran water mixed solvent with tetrahydrofuran content of 60 wt% and 6g of trifluoroacetic acid are prepared into a degradation system, and the degradation reaction is carried out after 15 hours of reaction at 180 ℃. After degradation, adding hot water of 50 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain a tetrahydrofuran aqueous solution, tetrahydrophthalic acid and trifluoroacetic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 94 percent.
Example 15
10g of hexahydrophthalic anhydride cured hydrogenated bisphenol F epoxy resin, 440g of tetrahydrofuran water mixed solvent with the tetrahydrofuran content of 70 wt% and 6g of dodecylbenzene sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after 15 hours of reaction at 180 ℃. After degradation, adding hot water of 55 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain a tetrahydrofuran aqueous solution, hexahydrophthalic acid and dodecylbenzene sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 88 percent.
Example 16
10g of bisphenol S epoxy resin solidified by maleic anhydride, 100g of tetrahydrofuran water mixed solvent with tetrahydrofuran content of 85 wt% and 5g of trichloroacetic acid are prepared into a degradation system, and the degradation reaction is carried out for 35 hours at 120 ℃. After degradation, adding 65 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain tetrahydrofuran aqueous solution, maleic acid and trichloroacetic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 95 percent.
Example 17
10g of phthalic anhydride cured bisphenol A type epoxy resin, 200g of 1, 1, 4-dioxane water mixed solvent with the content of 40 wt% of 4-dioxane and 8g of dodecylbenzene sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction is carried out for 5 hours at 230 ℃. After the degradation is finished, adding 75 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain 1, 4-dioxane aqueous solution, phthalic acid and dodecylbenzene sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 90 percent.
Example 18
10g of bisphenol F type epoxy resin cured by tetrahydrophthalic anhydride, 300g of 1, 1, 4-dioxane water mixed solvent with the content of 50 wt% of 4-dioxane and 7g of p-toluenesulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction is carried out for 10 hours at 200 ℃. After degradation, adding hot water of 85 ℃ into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain a 1, 4-dioxane aqueous solution, tetrahydrophthalic acid and a p-toluenesulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 85 percent.
Example 19
10g of hexahydrophthalic anhydride cured bisphenol S type epoxy resin, 380g of 1, 1, 4-dioxane water mixed solvent with the content of 40 wt% of 4-dioxane and 7g of methane sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction is carried out for 2 hours at 250 ℃. Adding 88 ℃ hot water into the system after degradation is finished, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain 1, 4-dioxane aqueous solution, hexahydrophthalic acid and methane sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 85 percent.
Example 20
10g of maleic anhydride cured hydrogenated bisphenol A epoxy resin, 280g of 1, 4-dioxane water mixed solvent with the content of 80 wt% of 1, 4-dioxane and 6g of dodecylbenzene sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction is carried out for 10 hours at 230 ℃. After degradation, adding 77 ℃ hot water into the system, fully dissolving, filtering, evaporating the filtrate at 110 ℃ to remove the reaction solvent, and recovering to obtain 1, 4-dioxane aqueous solution, maleic acid and dodecylbenzene sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 98 percent.
Example 21
10g of phthalic anhydride cured bisphenol S type epoxy resin, 500g of acetone-water mixed solvent with acetone content of 95 wt% and 10g of squaric acid are prepared into a degradation system, and the degradation reaction is carried out for 10min at 250 ℃. Adding hot water of 64 ℃ into the system after degradation is finished, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetone aqueous solution, phthalic acid and a squaric acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 80 percent.
Example 22
10g of hydrogenated bisphenol A epoxy resin cured by tetrahydrophthalic anhydride, 150g of acetone-water mixed solvent with acetone content of 85 wt% and 5g of methane sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out after the reaction at 160 ℃ for 20 hours. Adding hot water of 58 ℃ into the system after degradation is finished, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetone aqueous solution, tetrahydrophthalic acid and a methane sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 93 percent.
Example 23
10g of hexahydrophthalic anhydride cured bisphenol A epoxy resin, 250g of acetone-water mixed solvent with acetone content of 90 wt% and 4g of dodecylbenzene sulfonic acid are prepared into a degradation system, and the degradation reaction is carried out for 30 hours at 140 ℃. Adding hot water at 68 ℃ into the system after degradation is finished, fully dissolving, filtering, evaporating the filtrate at 130 ℃ to remove the reaction solvent, and recovering to obtain an acetone aqueous solution, hexahydrophthalic acid and dodecylbenzene sulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 90 percent.
Example 24
10g of maleic anhydride cured bisphenol F type epoxy resin, 300g of acetone-water mixed solvent with acetone content of 85 wt% and 9g of p-toluenesulfonic acid are prepared into a degradation system, and the degradation reaction is carried out for 20 hours at 160 ℃. After degradation, adding hot water of 80 ℃ into the system, fully dissolving, filtering, evaporating the reaction solvent from the filtrate at 130 ℃ and recovering to obtain an acetone aqueous solution, maleic acid and a p-toluenesulfonic acid catalyst; the filter cake is an organic phase epoxy resin degradation product. The degradation rate reaches 98 percent.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.

Claims (7)

1. A method of catalyzing the degradation of an anhydride-cured epoxy resin, comprising: the method comprises the following steps: preparing the anhydride-cured epoxy resin, a reaction solvent and an organic acid catalyst into a degradation system for degradation reaction; adding hot water into the system after degradation is completed, fully dissolving and filtering; evaporating and recovering the filtrate to obtain a reaction solvent, a curing agent and an organic acid catalyst; the filter cake is an organic phase epoxy resin degradation product;
the reaction solvent is any one of water, glacial acetic acid, an acetic acid-water mixed solvent, a tetrahydrofuran-water mixed solvent, a 1, 4-dioxane-water mixed solvent or an acetone-water mixed solvent;
the mass fraction of water in the acetic acid water mixed solvent, the tetrahydrofuran water mixed solvent, the 1, 4-dioxane water mixed solvent or the acetone water mixed solvent is 1-70%;
the mass ratio of the anhydride-cured epoxy resin to the reaction solvent to the organic acid catalyst is 10: 50-500: 1-10;
the organic acid catalyst is organic strong acid which can ionize hydrogen ions and contains sulfonic acid groups or carboxyl groups;
the temperature of the degradation reaction is 80-250 ℃, and the reaction time is 10 min-48 h.
2. The method of catalyzing the degradation of an anhydride cured epoxy resin of claim 1, wherein: the organic acid catalyst is any one of dodecyl benzene sulfonic acid, p-toluenesulfonic acid, methane sulfonic acid, trichloroacetic acid, trifluoroacetic acid and squaric acid.
3. The method of catalyzing the degradation of an anhydride cured epoxy resin of claim 1, wherein: the temperature of the hot water is 50-90 ℃.
4. The method of catalyzing the degradation of an anhydride cured epoxy resin of claim 1, wherein: the epoxy resin is any one of glycidyl ether, glycidyl ester, glycidyl amine, alicyclic epoxy resin and epoxidized olefin.
5. The method of catalyzing the degradation of an anhydride cured epoxy resin of claim 1, wherein: the epoxy resin is specifically any one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and hydrogenated bisphenol A epoxy resin.
6. The method of catalyzing the degradation of an anhydride cured epoxy resin of claim 1, wherein: the epoxy resin curing agent is any one of linear aliphatic anhydride, aromatic anhydride and alicyclic anhydride.
7. The method of catalyzing the degradation of an anhydride cured epoxy resin of claim 1, wherein: the epoxy resin curing agent specifically comprises: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and maleic anhydride.
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CN113845493A (en) * 2021-09-17 2021-12-28 中国科学院山西煤炭化学研究所 A kind of method of degrading acid anhydride curing epoxy resin material to prepare aromatic polyol
CN113956428A (en) * 2021-10-28 2022-01-21 中国科学院山西煤炭化学研究所 Novel polyurethane material and preparation method thereof
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CN114479176B (en) * 2022-02-20 2024-04-05 中国科学院山西煤炭化学研究所 Method for degrading amine-cured epoxy resin and composite material thereof through DES
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