CN115678099B - Degradation recovery method of thermosetting anhydride cured epoxy resin in hydrazine hydrate - Google Patents
Degradation recovery method of thermosetting anhydride cured epoxy resin in hydrazine hydrate Download PDFInfo
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- CN115678099B CN115678099B CN202211446633.6A CN202211446633A CN115678099B CN 115678099 B CN115678099 B CN 115678099B CN 202211446633 A CN202211446633 A CN 202211446633A CN 115678099 B CN115678099 B CN 115678099B
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 title claims abstract description 39
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 31
- 238000011084 recovery Methods 0.000 title claims abstract description 28
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000007857 degradation product Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 10
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- 239000002131 composite material Substances 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004634 thermosetting polymer Substances 0.000 description 1
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- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention belongs to the field of epoxy resin recovery, and provides a degradation recovery method of thermosetting anhydride cured epoxy resin in hydrazine hydrate. According to the method, the thermosetting anhydride cured epoxy resin particles pretreated by methylene dichloride are placed in hydrazine hydrate for heating, the epoxy resin is degraded under the catalysis of the hydrazine hydrate, and the hydrazine hydrate plays the triple roles of a degradation agent, a catalyst and a solvent in the reaction process, so that the degradation system has the advantages of simple composition, high degradation efficiency, mild reaction conditions and easiness in separation and recycling of degradation products. The recovery method provided by the invention has the advantages of mild degradation conditions, simple process, low cost, less three wastes, convenient recovery and utilization of products and the like, and solves the problem of difficult recovery of the existing epoxy resin.
Description
Technical Field
The invention belongs to the field of epoxy resin recovery, and particularly relates to a degradation recovery method of thermosetting anhydride cured epoxy resin in hydrazine hydrate.
Background
Thermosetting polymers, such as epoxy resins, are widely used in the fields of electronic packaging materials, coatings, electronic devices, adhesives, composite materials, and the like due to their excellent combination of properties. The method for disposing the waste epoxy resin product is generally landfill or incineration, but the waste epoxy resin product generally contains a plurality of materials with high added value, for example: the waste printed circuit board contains noble metals such as gold, palladium, copper, rare earth and the like; the waste high-performance composite material contains carbon fiber or glass fiber and the like, so that the traditional treatment method can cause waste of resources and pollute the environment.
In recent years, as the application of epoxy resins has become more and more widespread, recycling thereof has also been attracting attention. However, the cured form of the epoxy resin is a crosslinked structure of a three-dimensional network, and cannot be remelted, and thus cannot be reformed like a thermoplastic resin, which makes recycling of the epoxy resin product difficult.
At present, the recovery method of the thermosetting epoxy resin product includes a physical recovery method, a heat recovery method, a biodegradation recovery method, a photodegradation recovery method and a chemical recovery method. The method has the advantages that the production cost is low, the treatment method is simple, but the original size of long fibers is damaged and more utilization value is lost in the process of recycling the long fiber materials. The heat energy recovery means that waste materials are directly combusted to obtain heat energy, and the method generally releases a large amount of toxic gas to cause environmental pollution, and meanwhile, the direct combustion is extremely wasteful of materials with high added value. The biodegradation recovery method is to degrade the resin matrix into micromolecular monomers or oligomers under the action of biomass catalysts such as enzyme and the like, and has mild and environment-friendly conditions, but the degradation efficiency is too low. The photodegradation recovery method is a method of causing decomposition of a resin matrix under the action of light, and has high degradation efficiency, mild degradation conditions and environmental protection, but generally requires addition of an initiator in a degradation system and has excessively high energy consumption. Chemical recovery is currently the most commonly used recovery method, which is a method of chemically degrading the resin matrix into small molecular monomers or oligomers, separating the resin from the filler. The waste materials are degraded by the solvent, so that the damage of crushing or smashing to high-added-value materials in the waste materials can be avoided, and the resin can be recycled as a raw material. Therefore, the chemical recovery method is one of research hotspots for recovering waste epoxy resin.
The prior art discloses various methods for recycling epoxy resin articles using chemical recycling methods, such as: the chinese patent document of application No. 200610151145.7 discloses a method for degrading thermosetting epoxy resin and its composite material, which is to degrade thermosetting epoxy resin by using hydrogenated aromatic compounds such as tetrahydronaphthalene or decalin. The disadvantage of this method is that the use of large amounts of organic solvents is very polluting. Another example is: chinese patent application No. 03132542.4 discloses a chemical recovery method of a thermosetting epoxy resin composite material, which degrades thermosetting epoxy resin using nitric acid solution. The chinese patent application No. 200910046524.3 discloses a method for separating thermosetting epoxy resin or its composite material with high temperature water phase, which uses heteropolyacid as catalyst to catalyze the degradation of epoxy resin. Chinese patent application No. 00819116.6 discloses a method of treating a cured product of a reduced resin by catalyzing the degradation of the epoxy resin with one or more of an alkali metal/alkali metal compound, a phosphorus acid/phosphorus acid salt, an organic acid and/or an organic salt as a catalyst. The problems of all three methods are as follows: in addition to active substances which act as degradation, additional catalysts and solvents are added into the degradation system, so that the components of degradation products are complex and difficult to recycle, and resource waste and environmental problems are caused.
Disclosure of Invention
The invention solves the technical problem of providing a method for degrading and recycling thermosetting anhydride cured epoxy resin in hydrazine hydrate, which is environment-friendly, mild in reaction condition and high in degradation efficiency.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a degradation recovery method of thermosetting anhydride cured epoxy resin in hydrazine hydrate comprises the following steps:
(1) Crushing thermosetting anhydride curing epoxy resin into particles, immersing the particles in dichloromethane with the weight being 2-10 times of the weight of the particles for 24-48 hours, filtering, putting the particles of the thermosetting anhydride curing epoxy resin pretreated by the dichloromethane into a baking oven with the temperature of 40 ℃ for drying, and putting the particles of the thermosetting anhydride curing epoxy resin into a dryer for preservation;
(2) The thermosetting anhydride curing epoxy resin particles treated by methylene dichloride are placed in hydrazine hydrate to be heated, the thermosetting anhydride curing epoxy resin particles undergo degradation reaction under the catalysis of the hydrazine hydrate, the heating temperature is 90-120 ℃, and the reaction time is 30-80 min.
(3) And adding water into the mixture obtained after the reaction, performing rotary evaporation, and removing hydrazine hydrate in the mixture through azeotrope formation to obtain the micromolecular epoxy resin degradation product.
Preferably, the weight ratio of thermosetting anhydride-cured epoxy resin particles to hydrazine hydrate is (0.1-0.5): 1.
Preferably, the mass percentage concentration of the hydrazine hydrate is 60-90 wt%.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the rapid degradation of the anhydride cured epoxy resin under the mild condition is realized without adding extra solvent and catalyst, and the hydrazine hydrate plays the triple roles of the degradation agent, the catalyst and the solvent in the degradation process, so that the separation process of the degradation mixture is simplified, the cost is low, and the degradation product is convenient to recycle; meanwhile, due to the pretreatment of dichloromethane and the high reactivity of hydrazine hydrate and ester bonds, the degradation efficiency and the degradation reaction selectivity of the degradation recovery method are far better than those of other epoxy resin degradation systems, and the epoxy resin granules pretreated by dichloromethane can be completely degraded even at 120 ℃ within 60 min.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The invention provides a degradation recovery method of thermosetting anhydride cured epoxy resin in hydrazine hydrate, which comprises the following steps:
and (3) placing the thermosetting anhydride curing epoxy resin particles pretreated by methylene dichloride into hydrazine hydrate for heating, and degrading the epoxy resin under the catalysis of the hydrazine hydrate.
According to the method provided by the invention, hydrazine hydrate is used as a degradation agent, a catalyst and a solvent, and epoxy resin is degraded in the hydrazine hydrate, so that the epoxy resin is degraded into monomer substances which are easy to separate, and the recycling of the epoxy resin is realized.
The reason why the inventors selected hydrazine hydrate to degrade anhydride cured epoxy resins is that:
the hydrazine hydrate and the ester bond structure in the anhydride curing epoxy resin have high reactivity;
the hydrazine hydrate is used for catalytic degradation, the reaction condition is mild, the reaction rate is high, and the reaction vessel is not corroded;
the hydrazine hydrate can play a triple role of a degradation agent, a catalyst and a solvent at the same time, so that a reaction system is simple and energy-saving;
the hydrazine hydrate is easy to separate from other substances, and is convenient for purifying and recycling degradation products.
The concentration of the hydrazine hydrate is preferably 60 to 90wt%, more preferably 80 to 85wt%.
In the degradation reaction process, the reaction temperature and time and the ratio of the epoxy resin particles to the hydrazine hydrate have influence on the degradation rate of the epoxy resin. The increase in reaction temperature and the increase in time contribute to the increase in the degradation rate of the epoxy resin, for which the reaction temperature is preferably set to 90℃to 120℃and more preferably 110℃to 120 ℃. The reaction time is preferably 30min to 80min, more preferably 60min to 70min. The invention also preferably controls the weight ratio of epoxy resin particles to hydrazine hydrate to be (0.1-0.5): 1, more preferably (0.1-0.2): 1.
After the degradation reaction, the epoxy resin is degraded into monomer substances which are easy to separate, so that the treated epoxy resin can be simply recovered, and the separation can be performed in a manner well known to a person skilled in the art, for example, water is added into a liquid mixture after the reaction for rotary evaporation, hydrazine hydrate and an epoxy resin degradation product are separated, and finally a micromolecular epoxy resin degradation product is obtained.
In order to further understand the present invention, the degradation recovery method of the thermosetting anhydride-cured epoxy resin provided by the present invention is described below with reference to examples, and the scope of the present invention is not limited by the following examples.
The thermosetting anhydride-cured epoxy resins used in the following examples were all prepared as follows:
bisphenol A diglycidyl ether type epoxy resin E-51 (epoxy value: 0.51) is used as an epoxy resin matrix, methyltetrahydrophthalic anhydride (MeTHPA) is used as a curing agent, 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) is used as an accelerator, the mass ratio of the bisphenol A diglycidyl ether type epoxy resin E-51 to the MeTHPA/DMP-30=100:80:1, the three materials are mixed, cured for 2 hours at 120 ℃, and then cured for 4 hours at 150 ℃ to prepare the thermosetting anhydride cured epoxy resin.
Examples 1 to 12
Adding epoxy resin particles and hydrazine hydrate into a reactor, heating to a reaction temperature at normal pressure, controlling the reaction time, taking out unreacted epoxy resin after the reaction is finished, washing the unreacted epoxy resin with ethyl acetate and acetone in sequence, drying, weighing, and calculating to obtain the degradation rate of the epoxy resin, wherein the specific reaction conditions and the degradation rate result of the epoxy resin are shown in table 1.
TABLE 1 reaction conditions and resin degradation Rate for examples 1-12
As can be seen from examples 1-4, the increase in degradation temperature favors complete degradation of the epoxy resin;
from examples 4 and 5 to 8, it is understood that the degradation rate of the epoxy resin gradually increases with the increase of the degradation reaction time;
from examples 4 and 9-12, it is seen that the mass ratio of epoxy resin particles to hydrazine hydrate also has an effect on the resin degradation rate, and the mass ratio of epoxy resin particles to hydrazine hydrate is most preferably 2:10 in consideration of the epoxy resin degradation rate and the reaction cost.
The result shows that the method provided by the invention is used for recycling the anhydride curing epoxy resin, the degradation rate of the epoxy resin is high, the reaction condition is mild, and degradation products are easy to separate and recycle.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (2)
1. The degradation recovery method of the thermosetting anhydride cured epoxy resin in the hydrazine hydrate is characterized by comprising the following steps of:
(1) Pulverizing thermosetting anhydride-cured epoxy resin into granules, immersing the granules into dichloromethane with the weight being 2-10 times of that of the granules for 24-48h, filtering, and putting the granules of the thermosetting anhydride-cured epoxy resin pretreated by the dichloromethane into the granules for 40 o Drying in a drying oven, and storing in a dryer;
(2) The method comprises the steps of placing the thermosetting anhydride curing epoxy resin particles treated by methylene dichloride into hydrazine hydrate for heating, and carrying out degradation reaction on the thermosetting anhydride curing epoxy resin particles under the catalysis of the hydrazine hydrate, wherein the weight ratio of the thermosetting anhydride curing epoxy resin particles to the hydrazine hydrate is (0.1-0.2): 1, and the heating temperature is 120% o C, reacting for 60-70 min;
(3) And adding water into the mixture obtained after the reaction, performing rotary evaporation, and removing hydrazine hydrate in the mixture through azeotrope formation to obtain the micromolecular epoxy resin degradation product.
2. The degradation recovery method according to claim 1, wherein the mass percentage concentration of the hydrazine hydrate is 60wt% -90wt%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897216A (en) * | 2019-03-15 | 2019-06-18 | 四川大学 | A kind of recoverying and utilizing method of waste and old thermosetting resin and its composite material |
| CN113621171A (en) * | 2021-09-11 | 2021-11-09 | 哈尔滨工业大学 | Method for lossless recovery of reinforcement in waste carbonyl-containing thermosetting resin under mild condition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2986590B8 (en) * | 2013-04-18 | 2018-12-19 | Adesso Advanced Materials Wuhu Co., Ltd. | Novel curing agents and degradable polymers and composites based thereon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897216A (en) * | 2019-03-15 | 2019-06-18 | 四川大学 | A kind of recoverying and utilizing method of waste and old thermosetting resin and its composite material |
| CN113621171A (en) * | 2021-09-11 | 2021-11-09 | 哈尔滨工业大学 | Method for lossless recovery of reinforcement in waste carbonyl-containing thermosetting resin under mild condition |
Non-Patent Citations (1)
| Title |
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| 降解PET聚酯瓶实验条件的研究――综合研究型实验设计;黎天浩等;大学化学(第06期);81-85 * |
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