CN107400255A - Method of the organic salt as catalyst chemical degraded epoxy resin - Google Patents
Method of the organic salt as catalyst chemical degraded epoxy resin Download PDFInfo
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- CN107400255A CN107400255A CN201710770059.2A CN201710770059A CN107400255A CN 107400255 A CN107400255 A CN 107400255A CN 201710770059 A CN201710770059 A CN 201710770059A CN 107400255 A CN107400255 A CN 107400255A
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- epoxy resin
- organic salt
- catalyst
- catalyst chemical
- degraded
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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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- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of method of organic salt as catalyst chemical degraded epoxy resin, is degraded epoxy resin using organic slat solution as catalyst system and catalyzing.The present invention is using organic salt as the epoxy resin in catalyst degradation fibre reinforced composites.Compared with the inorganic salts of severe corrosive, organic salt has low-corrosiveness and being capable of efficient degradation epoxy resin.In addition, the organic anion in organic salt can promote resin to be swelled in the solution, the chemical bond in the cross-linked network and then degradative resin that are advantageous to enter cation.
Description
Technical field
The present invention relates to a kind of method of organic salt as catalyst chemical degraded epoxy resin.
Background technology
In recent years, the recycling of fibre reinforced composites is increasingly valued by people.At present, fill and burn
Burning is to handle the main method of caused leftover pieces in waste and scrap and process.If can be the fiber in composite
The destruction that will greatly improve economy and reduction to environment is reclaimed and is used with resin.However, due in composite
Thermosetting resin has the structure of stable chemistry and highdensity cross-linked network, therefore the recovery of material is a huge challenge.Change
The solution of the problem can be provided by learning edman degradation Edman.This method be by thermosetting resin be degraded to can dissolve and it is machinable small
Molecularly Imprinted Polymer, then applied the degradation polymer as resin in new composite.Fig. 1 is chemical degradation thermosetting material
The principle schematic of material.First, resin is swelled in the solution, while catalyst is entered in cross-linked network；Then, chemical bond exists
Disconnected in the presence of catalyst.The key point of the technology is to develop effectively be swelled thermosetting resin and breaking inner
Learn the catalyst system and catalyzing of key.
The chemical degradation research of early stage is often catalyst system and catalyzing degradative resin using strong acid or strong alkali aqueous solution, and its is main
Purpose is to reclaim the fiber in composite.The harmful chemicals used can cause potentially to pollute, and cause the corrosion to equipment,
It resin is degraded to the unknown small-molecule mixture of structure, cause secondary pollution.In recent years, some relatively mild methods
Left by hair so that the resin recycled in composite is possibly realized.Wherein most typically utilizing includes zinc chloride
With the inorganic salts including aluminium chloride as the chemical bond in catalyst fracture resin.Gentle condition and high degradation efficiency make it
Turn into chemical degradation recycling field promising method.However, inorganic salts have the anion containing severe corrosive mostly
（Such as：Cl-, NO2-, or SO4 2-）, easily cause the corrosion to equipment.Worse, these corrosive ions can remain in
It is difficult to remove in the resin of degraded, which greatly limits the application of degradative resin.
The content of the invention
It is an object of the invention to provide a kind of side of the good organic salt of effect as catalyst chemical degraded epoxy resin
Method.
The present invention technical solution be：
A kind of method of organic salt as catalyst chemical degraded epoxy resin, it is characterized in that：It is using organic slat solution as urging
Change system degraded epoxy resin.
The epoxy resin is present in fiber（Glass fibre and carbon fiber）, enhancing composite, epoxy coating or epoxy
In adhesive.
The organic salt is made up of cation and anion；Cation includes：Zn2+, Fe3+, Fe2+, Cu2+, Cu+,
Cr3+, Cr2+, Mn2+, Mn3+, Co3+, Ni2+, Ni3+, Sn2+, Sn4+, Pb2+, Pb4+In one or more；It is cloudy from
Attached bag includes：Acetate, formate, propionate, sad root, the one or more in oxalate and sulfonate ion.
The epoxy resin includes epoxy-amine curing system and epoxy-anhydride curing system.
The solvent used in degradation reaction is water, ethanol, methanol, propyl alcohol, butanol, ethylene glycol, acetic acid, acetone or tetrahydrochysene furan
Mutter.
Chemical degradation range of reaction temperature is 100-270 DEG C, and the reaction time is 1-15 hours.
The mass fraction of catalyst in the solution is 5wt%-50wt%.
The mass fraction of epoxy resin in the solution is 5wt%-50wt%.
Obtained degradative resin prepares new epoxy material as curing agent.
Obtained degradative resin prepares new polyurethane material as curing agent.
The present invention is using organic salt as the epoxy resin in catalyst degradation fibre reinforced composites.With severe corrosive
Inorganic salts compare, organic salt has low-corrosiveness and being capable of efficient degradation epoxy resin.In addition, in organic salt it is organic it is cloudy from
Son can promote resin to be swelled in the solution, be advantageous to make the chemistry in cross-linked network that cation enters and then degradative resin
Key.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the schematic diagram of chemical degradation thermosets.
Embodiment
（1）The epoxy-amine curing material of zinc acetate aqueous solution catalyst system and catalyzing degraded
Degradation reaction is carried out in pressure reactor.5g zinc acetates are dissolved in 20.0g water.By resulting solution and 4.0g epoxies-
Amine solidfied material is added in pressure reactor.Temperature of reactor rises to predetermined temperature and reacted 5 hours.After reaction terminates, reactor
It is cooled to room temperature, filtering reacting liquid.Filtered fluid, i.e. catalyst solution, directly it can be reused in lower secondary response.Filter
The solids arrived is degradation polymer.Degradation polymer is washed with water to remove residual catalyst, then the vacuum at 80 DEG C is dried
Dried in case.The catabolite finally given is yellow solid powder.
（2）The epoxy-amine curing material of vinegar stannous octoate aqueous solution catalytic system degraded
Degradation reaction is carried out in pressure reactor.5g stannous octoates are dissolved in 20.0g water.By resulting solution and 4.0g rings
Oxygen-amine solidfied material is added in pressure reactor.Temperature of reactor rises to predetermined temperature and reacted 5 hours.After reaction terminates, reaction
Device is cooled to room temperature, filtering reacting liquid.Filtered fluid, i.e. catalyst solution, directly it can be reused in lower secondary response.Filtering
Obtained solids is degradation polymer.Degradation polymer is washed with water to remove residual catalyst, then in 80 DEG C of vacuum
Dried in baking oven.The catabolite finally given is yellow solid powder.
（3）Ferrous acetate aqueous solution catalytic system degraded epoxy-anhydride curing materials
Degradation reaction is carried out in pressure reactor.5g ferrous acetates are dissolved in 20.0g water.By resulting solution and 4.0g rings
Oxygen-anhydride-cured thing is added in pressure reactor.Temperature of reactor rises to predetermined temperature and reacted 5 hours.After reaction terminates, instead
Device is answered to be cooled to room temperature, filtering reacting liquid.Filtered fluid, i.e. catalyst solution, directly it can be reused in lower secondary response.Cross
It is degradation polymer to filter obtained solids.Degradation polymer is washed with water to remove residual catalyst, it is then true at 80 DEG C
Dried in empty baking oven.The catabolite finally given is yellow solid powder.
（4）Zinc acetate aqueous solution catalyst system and catalyzing degraded glass fiber reinforcement epoxy composite
Degradation reaction is carried out in pressure reactor.5g zinc acetates are dissolved in 20.0g water.Resulting solution and 4.0g epoxies are answered
Condensation material is added in pressure reactor.Temperature of reactor rises to predetermined temperature and reacted 5 hours.After reaction terminates, reactor is cold
But to room temperature, filtering reacting liquid.Filtered fluid, i.e. catalyst solution, directly it can be reused in lower secondary response.It is filtrated to get
Solids be degradation polymer and glass fibre.With acetone solution degradation polymer, insoluble glass fibre is recovered by filtration.It is logical
Cross distillation and concentration and obtain degradative resin, then dried in 80 DEG C of vacuum drying oven.The degradative resin finally given is consolidated for yellow
Body powder.
（5）Zinc acetate aqueous solution catalyst system and catalyzing degradable carbon fibre enhancement epoxy composite material
Degradation reaction is carried out in pressure reactor.5g zinc acetates are dissolved in 20.0g water.Resulting solution and 4.0g epoxies are answered
Condensation material is added in pressure reactor.Temperature of reactor rises to predetermined temperature and reacted 5 hours.After reaction terminates, reactor is cold
But to room temperature, filtering reacting liquid.Filtered fluid, i.e. catalyst solution, directly it can be reused in lower secondary response.It is filtrated to get
Solids be degradation polymer and carbon fiber.With acetone solution degradation polymer, insoluble carbon fiber is recovered by filtration.Pass through steaming
Evaporate and be concentrated to give degradative resin, then dried in 80 DEG C of vacuum drying oven.The degradative resin finally given is yellow solid powder
End.
（6）The application and development of degradative resin
Under magnetic stirring, catabolite is mixed at 100 DEG C with epoxy resin.After well mixed, added at 80 DEG C solid
Agent（That Dick acid anhydrides of methyl）And accelerator（Diethylmethyl imidazoles）.After well mixed, by mixture deaeration and pour
Solidify in metal die.Use three step isothermal cure program Solidification samples：100 DEG C -2 hours, 150 DEG C -3 hours, 180 DEG C -2
Hour.After solidification, sample naturally cools to room temperature.
Claims (10)
1. a kind of method of organic salt as catalyst chemical degraded epoxy resin, it is characterized in that：Be using organic slat solution as
Catalyst system and catalyzing degraded epoxy resin.
2. method of the organic salt according to claim 1 as catalyst chemical degraded epoxy resin, it is characterized in that：It is described
Epoxy resin is present in fiber, enhancing composite, epoxy coating or epoxy adhesive.
3. method of the organic salt according to claim 1 as catalyst chemical degraded epoxy resin, it is characterized in that：Institute
Organic salt is stated to be made up of cation and anion；Cation includes：Zn2+, Fe3+, Fe2+, Cu2+, Cu+, Cr3+, Cr2 +, Mn2+, Mn3+, Co3+, Ni2+, Ni3+, Sn2+, Sn4+, Pb2+, Pb4+In one or more；Anion includes：Vinegar
Acid group, formate, propionate, sad root, the one or more in oxalate and sulfonate ion.
4. method of the organic salt according to claim 1 as catalyst chemical degraded epoxy resin, it is characterized in that：It is described
Epoxy resin includes epoxy-amine curing system and epoxy-anhydride curing system.
5. method of the organic salt as catalyst chemical degraded epoxy resin according to claim 1,2,3 or 4, its feature
It is：The solvent used in degradation reaction is water, ethanol, methanol, propyl alcohol, butanol, ethylene glycol, acetic acid, acetone or tetrahydrofuran.
6. method of the organic salt as catalyst chemical degraded epoxy resin according to claim 1,2,3 or 4, its feature
It is：Chemical degradation range of reaction temperature is 100-270 DEG C, and the reaction time is 1-15 hours.
7. method of the organic salt as catalyst chemical degraded epoxy resin according to claim 1,2,3 or 4, its feature
It is：The mass fraction of catalyst in the solution is 5wt%-50wt%.
8. method of the organic salt as catalyst chemical degraded epoxy resin according to claim 1,2,3 or 4, its feature
It is：The mass fraction of epoxy resin in the solution is 5wt%-50wt%.
9. method of the organic salt as catalyst chemical degraded epoxy resin according to claim 1,2,3 or 4, its feature
It is：Obtained degradative resin prepares new epoxy material as curing agent.
10. method of the organic salt as catalyst chemical degraded epoxy resin according to claim 1,2,3 or 4, it is special
Sign is：Obtained degradative resin prepares new polyurethane material as curing agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710770059.2A CN107400255A (en) | 2017-08-31 | 2017-08-31 | Method of the organic salt as catalyst chemical degraded epoxy resin |
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| CN201710770059.2A CN107400255A (en) | 2017-08-31 | 2017-08-31 | Method of the organic salt as catalyst chemical degraded epoxy resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718515A (en) * | 2020-07-08 | 2020-09-29 | 中国科学院山西煤炭化学研究所 | Method for degrading epoxy resin cured by catalytic anhydride |
| CN112679797A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Method for recovering carbon fiber reinforced resin matrix composite material by subcritical fluid |
| CN114573792A (en) * | 2022-03-29 | 2022-06-03 | 中海石油(中国)有限公司 | Dynamic crosslinking degradable epoxy resin, preparation method and high-temperature plugging application thereof |
| CN114835946A (en) * | 2022-05-10 | 2022-08-02 | 广东电网有限责任公司 | Method for decomposing retired composite insulator core rod by dissolution concerted catalysis |
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| CN101407596A (en) * | 2008-09-25 | 2009-04-15 | 上海第二工业大学 | Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board |
| CN101519505A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for decomposing thermosetting epoxy resin or composite material thereof by high-temperature water phase |
| CN101891902A (en) * | 2010-07-23 | 2010-11-24 | 浙江理工大学 | Method for recycling waste epoxy resin |
| CN104672488A (en) * | 2015-02-03 | 2015-06-03 | 中国科学院山西煤炭化学研究所 | Method for degrading and recycling thermosetting epoxy resin material |
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2017
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Patent Citations (4)
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|---|---|---|---|---|
| CN101407596A (en) * | 2008-09-25 | 2009-04-15 | 上海第二工业大学 | Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board |
| CN101519505A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for decomposing thermosetting epoxy resin or composite material thereof by high-temperature water phase |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679797A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Method for recovering carbon fiber reinforced resin matrix composite material by subcritical fluid |
| CN111718515A (en) * | 2020-07-08 | 2020-09-29 | 中国科学院山西煤炭化学研究所 | Method for degrading epoxy resin cured by catalytic anhydride |
| CN114573792A (en) * | 2022-03-29 | 2022-06-03 | 中海石油(中国)有限公司 | Dynamic crosslinking degradable epoxy resin, preparation method and high-temperature plugging application thereof |
| CN114573792B (en) * | 2022-03-29 | 2023-07-18 | 中海石油(中国)有限公司 | Dynamic cross-linked degradable epoxy resin, preparation method thereof and high-temperature plugging application |
| CN114835946A (en) * | 2022-05-10 | 2022-08-02 | 广东电网有限责任公司 | Method for decomposing retired composite insulator core rod by dissolution concerted catalysis |
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Application publication date: 20171128 |