CN109320762A - Utilize the method for microwave recycling waste thermosetting resin - Google Patents

Utilize the method for microwave recycling waste thermosetting resin Download PDF

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CN109320762A
CN109320762A CN201811120341.7A CN201811120341A CN109320762A CN 109320762 A CN109320762 A CN 109320762A CN 201811120341 A CN201811120341 A CN 201811120341A CN 109320762 A CN109320762 A CN 109320762A
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resin
thermosetting resin
microwave
microwave heating
waste
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CN109320762B (en
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王玉忠
田飞
徐世美
王雄雷
杨洋
安文丽
赵旭
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Sichuan University
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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
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • 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
    • 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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters
    • 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

The present invention provides the methods using microwave recycling waste thermosetting resin, steps are as follows: (1) waste thermosetting resin being immersed in boiling point and be at least in 100 DEG C of polar solvent, microwave heating is swollen thermosetting resin, the temperature for controlling microwave heating is no more than the thermal decomposition temperature of thermosetting resin, washs to the thermosetting resin after swelling；(2) microwave treatment method one: is carried out to the thermosetting resin after swelling and washing to improve the internal pore structure of thermosetting resin and increase surface roughness；Alternatively, method two: the thermosetting resin after swelling and washing is dry, chemical degradation is carried out to the thermosetting resin after drying using existing chemical degradation method.The direct functional modification that waste thermosetting resin can be achieved in the present invention utilizes, can also be effectively shortened under the conditions of mild chemical degradation waste thermosetting resin recycling it is time-consuming.

Description

Utilize the method for microwave recycling waste thermosetting resin
Technical field
The invention belongs to the recovery technology fields of polymeric scrap material, are related to the side of microwave recycling waste thermosetting resin Method.
Background technique
Thermosetting resin has excellent mechanical performance and insoluble, not properties such as molten, high temperature resistant, resistant to chemical etching, extensively It is general to be applied to the industries such as electronic apparatus, automobile, space flight, coating.After these products reach life cycle, become to discard thermosetting One of the main source of property resin；Many leftover pieces and defect ware can be also generated in the process of production and processing, become discarded thermosetting Another main source of property resin.The resin waste of these curing moldings is due to forming three-dimensional netted figure between strand Structure can not dissolve in a solvent, can only be corroded by strong oxidizer and decompose or be swollen in certain solvents, thus recycle Difficulty is larger.Currently, waste thermosetting resin is mainly used landfill disposal or is destroyed in the form of burning, rough processing side The arable land that formula causes large area is destroyed, and the harmful substance in resin be easy to cause secondary pollution, seriously endangers environment.In addition, It is that raw material is prepared, therefore seeks effectively useless that resin, which is largely using non-renewable resources such as petroleum, fossil feedstocks, The recycling and reuse method for abandoning thermosetting resin may be implemented to economize on resources and mitigate the dual purpose of environmental pollution, to promotion Sustainable development has a very important significance, and meets the struggle that China is building a resource-conserving and environment-friendly society Target.
Currently, the recycling and reusing method of waste thermosetting resin mainly includes physical recovering method, the recycling of thermal energy method and changes Method recycles three kinds.Physical recovering method be usually in the case where not destroying the chemical structure and composition of thermosetting resin, will be hot Filler after thermosetting resin and its compound mechanical crushing as wood-based plate, pitch or concrete etc. in building.To tentatively it add The broken material of the resin of work further crushes or is milled into fine grained or fine powder, and the substitute that can be used as calcium carbonate is used for newly The filler of same with thermosetting compound material.This method belongs to open loop recycling, without separating the glass fibre in composite material, calcium carbonate And polymer, cost is relatively low, and removal process is fairly simple.But regenerant is only used for the lower field of material performance requirement, Application surface is narrow, economic value is lower, and removal process can generate the pollution environment such as a large amount of dust, also compares the loss of recycling tool Seriously, additional cost recovery is increased.
The recycling of thermal energy method utilizes the heat generated in combustion process mainly by combustion technology.But the method utilization rate is low, The problem of there is also secondary pollutions.High temperature pyrolytic cracking (HTP) is that the another way of thermal energy method recycling makes thermosetting property under the high temperature conditions Macromolecule polyalcohol chain rupture in resin generates small molecule compound, including liquid oil, gas, coke etc., and oil is through air-distillation Available light naphthar, heavy naphtha etc. afterwards, heat production of burning, gas and solid can be used as the heating and power generation of daily life Material.Generally speaking, thermal energy method recovery technology has certain social and economic benefit, but the skill of pyrolysis processing thermosetting resin Art content is high, and equipment investment is high, and operational risk is big, and heat utilization ratio is low, a large amount of particulate matters for releasing during processing, again Metal and SO2、CO2、NOxEqual pernicious gases, it is easy to pollute environment, also contain the heavy metals such as lead, cadmium in waste residue, if disposition It is improper to be also easy to cause secondary pollution to ambient enviroment.The inorganic material such as the metal inside resin will cause its energy release value It reduces, mass energy is caused to lose.In addition, only when being collected into a large amount of accessible thermosetting property waste materials, this way of recycling Just there is economic benefit, therefore really to realize that the also many work of industrial applications will be done.
Chemical recovering method is typically referred to through chemical reagent, such as ethylene glycol, ammonium hydroxide, nitric acid, with cooperateing with for high-temperature heating Effect disconnects the chemical bonds such as C-N, C-O in resin, forms a series of product.Prior art discloses a variety of chemical methods The method for recycling thermosetting resin utilizes water as Liu et al. people (Green Chemistry, 2017,19,4364-4372) discloses It is the method that catalyst recycles acid anhydride curable epoxy resin for solvent, phosphotungstic acid.Since the catalytic effect of catalyst is just for ester Base, therefore this method has certain limitation, and reaction product needs to dissolve in acetone, removal process is relative complex, no It is suitble to industrialized production.Dang et al. (Polymer, 2005,46,1905-1912) is disclosed using nitric acid as catalyst, 80 The method of DEG C degradation thermosetting resin, by the catabolite of the degradation available 60% of 450h, although this method condition is more Mildly, but reaction time is too long, and resin catabolite utilization rate is low.CN104672488A discloses degradation recycling thermoset epoxy The method of resin material is solvent using the mixed liquor of low carbon organic acid and water, and metal ion is catalyst, at 100-280 DEG C Degradation selectivity is carried out to thermosetting resin, generates small organic molecule.Because this method needs to carry out in a kettle, it is desirable that one Fixed high pressure, the high requirements on the equipment, and catalyst are mostly metal ion, can be caused damages to environment, limit its industrialization and answer With.There is scholar to attempt to utilize green reagents substituted metal and the organic solvents, such as CN104327303A such as overcritical or subcritical water It discloses the method for carbon fiber enhancement resin base composite material of degrading at supercritical conditions: being in 300 DEG C of reaction temperature, pressure Degrade 60min under conditions of 15MPa, and the epoxy resin ingredient of 80wt% or more is degraded in composite material.Although this method makes Degradation system is environmentally protective, but requirement of the high temperature and pressure degradation condition to equipment is high.Some scholars use ionic liquid Degrade to thermosetting resin, as CN102516594A disclose thermosetting epoxy resin and ionic liquid are placed in it is organic molten In agent, it is heated to 130-300 DEG C, epoxy resin is degraded under the catalytic action of ionic liquid.Although the method has higher Degradation efficiency, but use a large amount of expensive ionic liquids, it is at high cost, be difficult to promote and apply in practice.
The way of recycling of above-mentioned several thermosetting resins is comprehensively compared, it can be seen that existing recovery technology mostly exists back Receipt part is harsh, and the high requirements on the equipment is at high cost, and recovery product added value is low, removal process the disadvantages of time-consuming, and there are two The risk of secondary pollution, practical Difficulty.In consideration of it, if mild condition can be used, directly by waste thermosetting resin function Energyization is modified to be utilized, or is efficiently degraded using mild condition and recycled waste thermosetting resin, is effectively shortened and is recycled consumption When, this will undoubtedly generate important application value.
Summary of the invention
For existing waste thermosetting resin recovery technology there are the drawbacks of, an object of the present invention be to provide microwave return The method for receiving waste thermosetting resin preparation water-oil separating material, to realize the direct functional modification benefit of waste thermosetting resin With the second object of the present invention is to provide the method for recycling waste thermosetting resin by microwave assisted chemical degradation, in temperature The recycling that effectively shortens under the conditions of the chemical degradation of sum is time-consuming.
Method provided by the invention using microwave recycling waste thermosetting resin, steps are as follows:
(1) waste thermosetting resin is immersed in boiling point to be at least in 100 DEG C of polar solvent, microwave heating makes thermosetting property Resin swelling, the temperature for controlling microwave heating are no more than the thermal decomposition temperature of thermosetting resin, the heat after swelling is then demultiplex out Thermosetting resin simultaneously washs；
(2) microwave heating method one: is carried out to improve in thermosetting resin to the thermosetting resin after swelling and washing Portion's pore structure and increase surface roughness, that is, complete the recycling of waste thermosetting resin；
Alternatively, method two: the thermosetting resin after swelling and washing is dry, using existing chemical degradation method to drying after Thermosetting resin carry out chemical degradation；
When step (2) are using method a period of time, the microwave heating condition of rate-determining steps (1) avoids thermosetting resin from breaking Damage, the microwave heating condition of rate-determining steps (2) avoid thermosetting resin from being charred.
In the above-mentioned method using microwave recycling waste thermosetting resin, when step (2) are using method a period of time, completion is discarded The obtained material of recycling of thermosetting resin has the micron or nano-porous structure being mutually communicated, and the material is in no external world Water-oil separating can be carried out to oil-water mixture and oil hydrosol under pressure condition, i.e., when step (2) use method to discard for the moment Thermosetting resin is transformed to the oil with the micron or nano-porous structure being mutually communicated after the processing of step (1) (2) Water separation material.
In the above-mentioned method using microwave recycling waste thermosetting resin, when step (2) use method two, heat can be accelerated The degradation speed and reduction degradation conditions of thermosetting resin.
In the above-mentioned method using microwave recycling waste thermosetting resin, when step (2) are using method a period of time, in order to prepare Water-oil separating material is obtained, preferably uses blocky or sheet waste thermosetting resin as raw material in step (1)；Work as step (2) when using method two, in order to promote the chemical degradation of waste thermosetting resin, the waste thermosetting tree used in step (1) Rouge is smashed thermosetting resin, and the crushing of waste thermosetting resin is more advantageous to microwave heating swelling and promotes step (2) Chemical degradation, crush thinner, be more conducive to chemical degradation, but crush cost and will increase, waste thermosetting when practical application The grinding particle size of resin is determined according to actual needs, is usually ground into granular waste thermosetting resin, such as Waste thermosetting resin can be ground into the particle no more than 5mm.
In the above-mentioned method using microwave recycling waste thermosetting resin, step (1) is by adjusting microwave heating condition, example Such as microwave power, microwave heating time, the temperature of microwave heating, the degree of swelling of adjustable thermosetting resin；Meanwhile thermosetting The degree of swelling of property resin also suffers from the shadow of these factors of waste thermosetting resin and the polar solvent of use to be recycled It rings.When step (2) are using method a period of time, step (1) should make thermosetting property on the basis of guaranteeing that thermosetting resin breakage does not occur The swelling ratio of resin is at least up to 10%, such as 10%~40% swelling ratio can be used.When step (2) use method two, The swelling ratio of thermosetting resin is higher in step (1), is more conducive to the chemical degradation of step (2), most basicly, should make thermosetting property The swelling ratio of resin is at least up to 10%.
In the above-mentioned method using microwave recycling waste thermosetting resin, the polar solvent is cyclohexanone, 2,4- diformazan Base-propione, N-Methyl pyrrolidone, butyrolactone, dimethyl sulfoxide, hexamethylphosphoramide, formamide, acetamide, diformazan In base formamide, dimethyl acetamide, N-METHYLFORMAMIDE, o-dichlorohenzene, ortho-chlorotolu'ene, m-chlorotoluene and p-chlorotoluene extremely Few one kind.The dosage of polar solvent is being totally submerged waste thermosetting resin for principle.
In the step of above-mentioned method for recycling waste thermosetting resin using microwave (1), the washing refers to washing removal The polar solvent in thermosetting resin after swelling.
In the step of above-mentioned method for recycling waste thermosetting resin using microwave (1), the equipment of microwave heating be can be used Microwave power is the equipment of frequency conversion or fixed-frequency-type, and the temperature for controlling microwave heating is at least 50 DEG C and is no more than thermosetting resin Thermal decomposition temperature.
In the above-mentioned method using microwave recycling waste thermosetting resin, when step (2) using method for the moment, it is described discarded Thermosetting resin be epoxy resin, unsaturated polyester resin, phenolic resin, melamine resin or furane resins, or with Thermosetting resin based on epoxy resin, unsaturated polyester resin, phenolic resin, melamine resin or furane resins.
In the above-mentioned method using microwave recycling waste thermosetting resin, after method a pair of step (2) is swollen and washs Thermosetting resin carry out microwave heating purpose be improve thermosetting resin internal pore structure and increase surface roughness, by After washing removes solvent, the pore structure of thermosetting resin is in metastable state, again by microwave heating, pore structure can be made to become In stabilization and uniformly, and surface smoothness is made to change, advantageously forms rough surface.As long as in general, controlling the step Microwave heating condition, including microwave power, temperature and heating time make to be swollen under the premise of avoiding thermosetting resin from being charred And the surface of the thermosetting resin after washing becomes rougher, the specific increase degree of surface roughness is according to practical grease The application of separation material is determined, for example, when the step uses heat of the microwave power of 100~1000W to swelling after When thermosetting resin carries out microwave heating, the microwave heating time of 1~20min usually can be used.
It is described discarded when step (2) use method two in the above-mentioned method using microwave recycling waste thermosetting resin Thermosetting resin is epoxy resin, unsaturated polyester resin or phenolic resin, or with epoxy resin, unsaturated polyester resin Or the thermosetting resin based on phenolic resin.When waste thermosetting resin is unsaturated polyester resin, or for unsaturation When thermosetting resin based on polyester resin, the thermosetting resin after swelling is placed in potassium carbonate or potassium hydroxide by step (2) Chemical degradation is carried out in solution；When waste thermosetting resin is epoxy resin or phenolic resin, or for epoxy resin or phenol When thermosetting resin based on urea formaldehyde, the thermosetting resin after swelling is placed in nitric acid solution or dioxygen by step (2) Chemical degradation is carried out in the mixed solution of water and phosphoric acid.Used nitric acid, hydrogen peroxide and phosphoric acid when chemical degradation, potassium carbonate or The concentration of potassium hydroxide is determined with dosage referring to the prior art, and used chemical degradation temperature and heating method can also be with It is determined referring to the prior art, in general, the temperature of chemical degradation is no more than 100 DEG C, generally 40~90 in rate-determining steps (2) ℃。
In the above-mentioned method using microwave recycling waste thermosetting resin, in order to reduce cost and make method of the invention more Add it is environmentally protective, isolate swelling after thermosetting resin after, isolated polar solvent can be recycled, when When using single polar solvent, it can directly recycle polar solvent and recycle, be mixed when using the conduct of various polarity solvent When solvent, it can directly recycle mixed solvent and recycle, it can also be by the mixed solvent of recycling using separation means such as distillation, fractionation It is recycled after separation.
In the step of above-mentioned method for recycling waste thermosetting resin using microwave (1), make thermosetting property tree in microwave heating During liposoluble is swollen, the reflux that needs to cooperate condensation reflux unit to realize polar solvent.
The present invention realizes the base that waste thermosetting resin functional modification utilizes using microwave recycling waste thermosetting resin Plinth is, step (1) carries out physical modification to waste thermosetting resin using microwave heating, microwave heating condition appropriate and just When polar solvent cooperation, can effectively facilitate the close three-dimensional net structure of waste thermosetting resin realize it is appropriate loose.? On the basis of this, the internal pore structure of thermosetting resin can be improved by microwave heating and increase surface roughness.With waste epoxy For resin, before and after step (2) carries out microwave heating to the resin after swelling, the scanning electron microscope (SEM) photograph in resin section such as Fig. 1,2 institutes Show, after step (2) carries out microwave heating, the pore structure inside resin is more obvious, and aperture is increased, and is formed inside resin Aperture uniform nano-pore, observes by the naked eye resin surface, it is seen that resin surface rough degree increases.The present invention is by discarded heat After thermosetting resin is prepared into water-oil separating material, the functional group of resin itself does not change, illustrates only to carry out resin Physical modification, meanwhile, the thermal stability of water-oil separating material obtained is without significant change (see Fig. 3,4).
The present invention realizes waste thermosetting resin under mild conditions using microwave-assisted recycling waste thermosetting resin The basis of fast degradation is that step (1) uses microwave heating and carries out physical modification to smashed waste thermosetting resin, Microwave heating condition appropriate and appropriate polar solvent cooperate, and can become the close three-dimensional net structure of waste thermosetting resin It obtains looser.On this basis, the present invention can effectively facilitate waste thermosetting resin under the temperate condition no more than 100 DEG C Degradation.
Compared with prior art, present invention produces technical effects beneficial below:
1. the method provided by the invention using microwave recycling waste thermosetting resin, by waste thermosetting resin entirety function Water-oil separating material is made in energyization modification, realizes the complete recycling of waste thermosetting resin, or be swollen in microwave After carry out chemical degradation, can significantly promote chemical degradation of waste thermosetting resin under the conditions of normal pressure and relatively mild temperature Efficiency.The present invention provides new thinking for the recycling of waste thermosetting resin, while being also quick in a mild condition Degradation recycling waste thermosetting resin provides new means, has in the recycling field of waste thermosetting resin important Application value.
2. the reaction condition that the method for the invention uses is mild, it can be realized in normal pressure and lower temperature, do not have to equipment There is particular/special requirement, avoids using expensive corrosion resistant apparatus；Microwave heating is easy to operate, safe, and microwave heating is molten The from a wealth of sources, cheap of the polar solvent used when swollen, boiling point be high, difficult volatilization, nontoxicity, recyclable；It returns The scheme of waste thermosetting resin preparation water-oil separating material is received without using catalyst, advantageously reduces cost.Institute of the present invention The method of stating has the characteristics that popularization and application safe and environment-friendly, inexpensive and easy to accomplish.
3. discarded thermosetting resin is prepared into water-oil separating material by the present invention, the three dimensional network of resin itself is made full use of Shape structure, and do not change resin thermal stability, it ensure that the excellent mechanical performance of material, using water-oil separating material obtained Efficient separation can be realized in oil-water separation mixed liquor and lotion, the gravity relied solely on itself, this is conducive to grease material and is answering Used time saves energy consumption, reduces water-oil separating cost.
Detailed description of the invention
Fig. 1 is molten using step (1) microwave when method recycling waste epoxy resin preparation water-oil separating material of the invention The scanning electron microscope (SEM) photograph in the section of the resin after swollen.
Fig. 2 is the scanning electricity using the section of the water-oil separating material of method recycling waste epoxy resin preparation of the invention Mirror figure.
Fig. 3 is the infrared spectroscopy that water-oil separating material and epoxy resin made from waste epoxy resin are recycled in embodiment Figure.
Fig. 4 is the thermogravimetric curve differential map of the waste epoxy resin that embodiment 23 uses and water-oil separating material obtained.
Fig. 5 is the photo that water-oil separating experiment is carried out in application examples 4.
Specific embodiment
The method provided by the invention using microwave recycling waste thermosetting resin is made by the following examples further Explanation.It is necessary to note that following embodiment is served only for, the invention will be further described, should not be understood as protecting model to the present invention The limitation enclosed, one of ordinary skill in the art make some nonessential modifications and adaptations according to foregoing invention content, to the present invention It is embodied, still falls within the scope of protection of the invention.It is worth noting that in following embodiment and comparative example:
(1) number of material used in is mass parts.
(2) liquid separation is simply mixed to grease in thermosetting resin and lotion separation is carried out by the gravity of liquid itself Separation.
(3) oily permeation flux is obtained by being calculated by the following formula:
Total volume/(effective surface area × time of penetration of resin) that permeation flux=penetrating fluid passes through resin
(4) grease is simply mixed liquid and is matched by the chloroform of oil red O stain and the water of methylene blue staining by the volume ratio of 1:1 It sets.It is obtained by being calculated by the following formula that liquid separative efficiency, which is simply mixed, in grease:
Liquid separative efficiency=(quality of water before quality/separation of water after separation) × 100% is simply mixed in grease
(5) configuration of lotion is 100g chloroform to be added in the Span 80 of 0.4g, adds 1.5g water, is obtained through emulsification micro- Receive the oil hydrosol of partial size.The content of W/O is measured using karl Fischer instrument, and lotion separative efficiency is by following public affairs Formula is calculated:
Lotion separative efficiency=(content of W/O after content-separation of W/O before separating)/W/O before separating Content × 100%
It (6) is the sheet waste thermosetting resin for being about 1~5mm using thickness when preparing water-oil separating material, it is right The waste thermosetting resin that waste thermosetting resin use when chemical degradation is the particle for crushing and crossing 0.2~5mm sieve Shape waste thermosetting resin.
(7) swelling ratio that waste thermosetting resin is controlled by control microwave heating condition, especially by control microwave Power, microwave heating time and temperature adjust the swelling ratio of waste thermosetting resin, for particular types waste thermosetting tree The polar solvent that uses when rouge and swelling, be determined by experiment first the thermosetting resin swelling ratio reach 10% it is minimum Microwave condition, to ensure that the swelling ratio after the heating of step (1) of the waste thermosetting resin in each embodiment can at least reach 10%, while when step (2) are using method a period of time, step (1) needs to pay attention to observation in microwave heating process, while paying attention to controlling The microwave heating condition of step (1) processed avoids occurring in microwave heating thermosetting resin damaged.When step (1) using 100~ When the microwave power of 3500W, the microwave heating time of 10s~1000min can be used.
(8) test method of the swelling ratio of thermosetting resin: taking waste thermosetting resin, and it is molten to be subsequently placed in polarity for weighing Progress microwave heating certain time is swollen in agent, is then taken out and is placed 5min on stainless (steel) wire, is weighed.According to following public affairs Formula calculates swelling ratio:
Thermosetting property before swelling ratio=(quality of thermosetting resin before quality-swelling of thermosetting resin after swelling)/swelling Quality × 100% of resin
(9) in following embodiment and comparative example, the waste and old thermosetting resin of use is that thermosetting resin product reaches life It is generated after period, thermosetting resin waste material is the leftover pieces and defect ware generated in the process of production and processing.
Embodiment 1
(1) 100 parts of waste and old unsaturated polyester resins are immersed in 100 parts of cyclohexanone, are subsequently placed in variable frequency microwave reaction In device, add reflux unit, microwave heating 120min is swollen resin sufficiently, sets the temperature of microwave heating as 120 DEG C, microwave adds Microwave power automatically adjusts in the range of being no more than 500W with reaction temperature in thermal process, the resin after filtering to isolate swelling And removal cyclohexanone is washed under ultrasound condition using acetone, filtering gained cyclohexanone is directly recycled.
(2) by the resin after swelling and washing, microwave heating 7min, i.e. completion are useless under conditions of microwave power is 500W The recycling of old unsaturated polyester resin, obtains water-oil separating material.
Embodiment 2
(1) 100 parts of waste epoxy resins are immersed in 50 parts of N-Methyl pyrrolidones, are subsequently placed in variable frequency microwave reaction In device, add reflux unit, microwave heating 420min is swollen resin sufficiently, sets microwave heating temperature as 60 DEG C, microwave heating Microwave power automatically adjusts in the range of being no more than 800W with reaction temperature in the process, and the resin after filtering to isolate swelling is simultaneously Removal N-Methyl pyrrolidone is washed under ultrasound condition using ethyl acetate, filtering gained N-Methyl pyrrolidone is directly returned It receives and utilizes.
(2) by the resin after swelling and washing, microwave heating 15min, i.e. completion are useless under conditions of microwave power is 200W The recycling of old epoxy resin, obtains water-oil separating material.
Embodiment 3
(1) 100 parts of waste and old furane resins are immersed in 200 parts of ortho-chlorotolu'enes, are subsequently placed in variable frequency microwave reactor, Add reflux unit, sets microwave heating temperature as 100 DEG C, microwave heating 300min is swollen resin sufficiently, microwave heating process Middle microwave power automatically adjusts in the range of being no more than 400W with reaction temperature, resin and use after filtering to isolate swelling Ethyl alcohol washs removal ortho-chlorotolu'ene under ultrasound condition, and filtering gained ortho-chlorotolu'ene is directly recycled.
(2) by the resin after swelling and washing, microwave heating 2min, i.e. completion are useless under conditions of microwave power is 400W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 4
(1) 100 parts of waste and old carbon-fibre reinforced epoxy resins are immersed in 300 parts of 2,4- dimethyl-propiones, are then set In variable frequency microwave reactor, add reflux unit, sets microwave heating temperature as 80 DEG C, microwave heating 1000min fills resin Dividing swelling, microwave power automatically adjusts in the range of being no more than 850W with reaction temperature in microwave heating process, then filter, It uses ethyl acetate to be washed the resin after swelling to remove 2,4- dimethyl-propione under ultrasound condition, will filter Gained 2,4- dimethyl-propione directly recycle.
(2) by the resin after swelling and washing, microwave heating 10min, i.e. completion are useless under conditions of microwave power is 400W The recycling of old carbon-fibre reinforced epoxy resin, obtains water-oil separating material.
Embodiment 5
(1) 100 parts of post-consumer glass fiber reinforced epoxy resins are immersed in 300 parts of p-chlorotoluenes, are subsequently placed in frequency conversion In microwave reactor, adding reflux unit, sets microwave heating temperature as 120 DEG C, microwave heating 300min is swollen resin sufficiently, Microwave power automatically adjusts in the range of being no more than 700W with reaction temperature in microwave heating process, after filtering to isolate swelling Resin and using ethyl alcohol wash under ultrasound condition removal p-chlorotoluene, will filtering obtained by p-chlorotoluene directly recycle.
(2) by the resin after swelling and washing, microwave heating 1min, i.e. completion are useless under conditions of microwave power is 800W The recycling of old glass fiber reinforced epoxy resin, obtains water-oil separating material.
Embodiment 6
(1) 100 parts of waste epoxy resins are immersed in 500 parts of dimethyl sulfoxides, are subsequently placed in microwave reactor, add Reflux unit, heating 10s makes resin swelling under conditions of microwave power is 3500W, measures immediately after microwave heating molten The temperature of agent dimethyl sulfoxide is 160 DEG C, filters to isolate the resin after being swollen and is washed under ultrasound condition using ethyl alcohol and is gone Except dimethyl sulfoxide, filtering gained dimethyl sulfoxide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 17min, i.e. completion are useless under conditions of microwave power is 300W The recycling of old epoxy resin, obtains water-oil separating material.
Embodiment 7
(1) 100 parts of waste and old furane resins are immersed in 500 parts of butyrolactone, are subsequently placed in variable frequency microwave reactor, add Reflux unit sets microwave heating temperature as 90 DEG C, and microwave heating 720min is swollen resin sufficiently, micro- in microwave heating process Wave power automatically adjusts in the range of being no more than 1000W with reaction temperature, and the resin after filtering to isolate swelling simultaneously uses second Alcohol washs removal butyrolactone under ultrasound condition, and filtering gained butyrolactone is directly recycled.
(2) by the resin after swelling and washing, microwave heating 20min, i.e. completion are useless under conditions of microwave power is 300W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 8
(1) 100 parts of post-consumer glass fiber reinforced epoxy resins are immersed in 50 parts of m-chlorotoluenes, it is micro- is subsequently placed in frequency conversion In wave reactor, add reflux unit, sets microwave heating temperature as 180 DEG C, microwave heating 60min is swollen resin sufficiently, micro- Microwave power automatically adjusts in the range of being no more than 1000W with reaction temperature during Wave heating, after filtering to isolate swelling Resin and using ethyl alcohol wash under ultrasound condition removal m-chlorotoluene, will filtering obtained by m-chlorotoluene directly recycle.
(2) by the resin after swelling and washing, microwave heating 1min, i.e. completion are useless under conditions of microwave power is 900W The recycling of old glass fiber reinforced epoxy resin, obtains water-oil separating material.
Embodiment 9
(1) 100 parts of waste and old carbon fiber reinforced phenol formaldehyde resins are immersed in 300 parts of hexamethylphosphoramide, are subsequently placed in In variable frequency microwave reactor, add reflux unit, sets microwave heating temperature as 130 DEG C, microwave heating 90min keeps resin sufficiently molten Swollen, microwave power automatically adjusts in the range of being no more than 900W with reaction temperature in microwave heating process, filters to isolate molten Resin and use ethyl alcohol after swollen remove hexamethylphosphoramide to the resin washing after swelling under ultrasound condition, by filtering Hexamethylphosphoramide is obtained directly to recycle.
(2) by the resin after swelling and washing, microwave heating 15min, i.e. completion are useless under conditions of microwave power is 150W The recycling of old carbon fiber reinforced phenol formaldehyde resin, obtains water-oil separating material.
Embodiment 10
(1) 100 parts of waste and old unsaturated polyester resins are immersed in 400 parts of acetamides, are subsequently placed in variable frequency microwave reaction In device, add reflux unit, sets microwave heating temperature as 180 DEG C, microwave heating 500min is swollen resin sufficiently, microwave heating Microwave power automatically adjusts in the range of being no more than 900W with reaction temperature in the process, and the resin after filtering to isolate swelling is simultaneously Removal acetamide is washed under ultrasound condition using ethyl alcohol, filtering gained acetamide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 18min, i.e. completion are useless under conditions of microwave power is 100W The recycling of old carbon fiber reinforced phenol formaldehyde resin, obtains water-oil separating material.
Embodiment 11
(1) 100 parts of waste and old melamine resins are immersed in 100 parts of N-Methyl pyrrolidones, it is anti-is subsequently placed in microwave It answers in device, adds reflux unit, heating 25s makes resin swelling under conditions of microwave power is 2700W, stands after microwave heating The temperature for measuring solvent N-methyl pyrilidone is 120 DEG C, and the resin after filtering to isolate swelling simultaneously uses ethyl alcohol in ultrasound Under the conditions of washing removal N-Methyl pyrrolidone, will filtering gained N-Methyl pyrrolidone directly recycle.
(2) by the resin after swelling and washing, microwave heating 15min, i.e. completion are useless under conditions of microwave power is 150W The recycling of old melamine resin, obtains water-oil separating material.
Embodiment 12
(1) 100 parts of waste and old unsaturated polyester resins are immersed in 200 parts of formamides, are subsequently placed in variable frequency microwave reaction In device, add reflux unit, sets microwave heating temperature as 60 DEG C, microwave heating 300min is swollen resin sufficiently, microwave heating Microwave power automatically adjusts in the range of being no more than 850W with reaction temperature in the process, and the resin after filtering to isolate swelling is simultaneously Removal formamide is washed under ultrasound condition using ethyl alcohol, filtering gained formamide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 4min, i.e. completion are useless under conditions of microwave power is 700W The recycling of old unsaturated polyester resin, obtains water-oil separating material.
Embodiment 13
(1) 100 parts of post-consumer glass fibre reinforced phenolic resins are immersed in 100 parts of dimethyl acetamides, are subsequently placed in In variable frequency microwave reactor, add reflux unit, sets microwave heating temperature as 180 DEG C, microwave heating 360min keeps resin abundant It is swollen, microwave power automatically adjusts in the range of being no more than 500W with reaction temperature in microwave heating process, filters to isolate Resin and use ethyl alcohol after swelling wash removal dimethyl acetamide under ultrasound condition, will filtering gained dimethyl acetamide Directly recycle.
(2) by the resin after swelling and washing, microwave heating 3min, i.e. completion are useless under conditions of microwave power is 850W The recycling of old glass fibre-reinforced phenolic resin, obtains water-oil separating material.
Embodiment 14
(1) 100 parts of waste and old furane resins are immersed in 300 parts of dimethyl sulfoxides, are subsequently placed in microwave reactor, add Reflux unit, heating 30s makes resin swelling under conditions of microwave power is 2700W, measures immediately after microwave heating molten The temperature of agent dimethyl sulfoxide is 150 DEG C, filters to isolate the resin after being swollen and is washed under ultrasound condition using ethyl alcohol and is gone Except dimethyl sulfoxide, filtering gained dimethyl sulfoxide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 8min, i.e. completion are useless under conditions of microwave power is 600W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 15
(1) 100 parts of phenolic resin wastes are immersed in 50 parts of o-dichlorohenzenes, are subsequently placed in variable frequency microwave reactor, Add reflux unit, sets microwave heating temperature as 120 DEG C, microwave heating 420min is swollen resin sufficiently, microwave heating process Middle microwave power automatically adjusts in the range of being no more than 350W with reaction temperature, resin and use after filtering to isolate swelling Ethyl alcohol washs removal o-dichlorohenzene under ultrasound condition, and filtering gained o-dichlorohenzene is directly recycled.
(2) by the resin after swelling and washing microwave power be 650W under conditions of microwave heating 12min, i.e., completion phenol The recycling of urea formaldehyde waste material, obtains water-oil separating material.
Embodiment 16
(1) 100 parts of carbon fiber reinforced phenol formaldehyde resin waste materials are immersed in 300 parts of N-METHYLFORMAMIDEs, are subsequently placed in change In frequency microwave reactor, add reflux unit, sets microwave heating temperature as 50 DEG C, microwave heating 1000min keeps resin sufficiently molten Swollen, microwave power automatically adjusts in the range of being no more than 900W with reaction temperature in microwave heating process, filters to isolate molten Resin after swollen simultaneously carries out washing removal N-METHYLFORMAMIDE using acetone under ultrasound condition, will filtering gained N- methyl formyl Amine directly recycles.
(2) by the resin after swelling and washing microwave power be 200W under conditions of microwave heating 16min, i.e., completion carbon The recycling of fibre reinforced phenolic resin waste material, obtains water-oil separating material.
Embodiment 17
(1) 100 parts of unsaturated polyester resin wastes are immersed in 450 parts of ortho-chlorotolu'enes, are subsequently placed in microwave reactor In, add reflux unit, heating 45s makes resin swelling under conditions of microwave power is 1800W, surveys immediately after microwave heating Determine the temperature of solvent ortho-chlorotolu'ene, be 140 DEG C, the resin after filtering to isolate swelling is simultaneously washed under ultrasound condition using acetone Ortho-chlorotolu'ene is removed, filtering gained ortho-chlorotolu'ene is directly recycled.
(2) by the resin after swelling and washing microwave power be 100W under conditions of microwave heating 16min, that is, complete not The recycling of saturated polyester resin waste material, obtains water-oil separating material.
Embodiment 18
(1) 100 parts of melamine resin waste materials are immersed in 250 parts of dimethylformamides, are subsequently placed in variable frequency microwave In reactor, add reflux unit, sets microwave heating temperature as 180 DEG C, microwave heating 5min is swollen resin sufficiently, and microwave adds Microwave power automatically adjusts in the range of being no more than 1000W with reaction temperature in thermal process, the tree after filtering to isolate swelling Rouge simultaneously washs removal dimethylformamide using ethyl alcohol under ultrasound condition, and filtering gained dimethylformamide is directly recycled benefit With.
(2) by the resin after swelling and washing microwave power be 800W under conditions of microwave heating 7min, that is, complete three The recycling of cymel waste material, obtains water-oil separating material.
Embodiment 19
(1) 100 parts of carbon-fibre reinforced epoxy resin waste materials are immersed in 100 parts of dimethyl sulfoxides, are subsequently placed in frequency conversion In microwave reactor, adding reflux unit, sets microwave heating temperature as 120 DEG C, microwave heating 360min is swollen resin sufficiently, Microwave power automatically adjusts in the range of being no more than 800W with reaction temperature in microwave heating process, after filtering to isolate swelling Resin and using ethyl alcohol wash under ultrasound condition removal dimethyl sulfoxide, will filtering obtained by dimethyl sulfoxide directly recycle benefit With.
(2) by the resin after swelling and washing microwave power be 900W under conditions of microwave heating 2min, i.e., completion carbon The recycling of fiber reinforced epoxy resin waste material, obtains water-oil separating material.
Embodiment 20
(1) 100 parts of carbon unsaturated polyester resin wastes are immersed in 300 parts of N-Methyl pyrrolidones, are subsequently placed in change In frequency microwave reactor, add reflux unit, sets microwave heating temperature as 200 DEG C, microwave heating 60min keeps resin sufficiently molten Swollen, microwave power automatically adjusts in the range of being no more than 400W with reaction temperature in microwave heating process, filters to isolate molten Resin after swollen simultaneously uses acetone to be washed under ultrasound condition to remove N-Methyl pyrrolidone, will filtering gained N- methylpyrrole Alkanone directly recycles.
(2) by the resin after swelling and washing microwave power be 600W under conditions of microwave heating 13min, i.e., completion carbon The recycling of unsaturated polyester resin waste, obtains water-oil separating material.
Embodiment 21
(1) 100 parts of phenolic resin wastes are immersed in 500 parts of cyclohexanone, are subsequently placed in microwave reactor, add-back stream Device, heating 30s makes resin swelling under conditions of microwave power is 1800W, measures solvent ring after microwave heating immediately The temperature of hexanone is 100 DEG C, and the resin after filtering to isolate swelling simultaneously washs removal hexamethylene using acetone under ultrasound condition Ketone directly recycles filtering gained cyclohexanone.
(2) by the resin after swelling and washing microwave power be 500W under conditions of microwave heating 14min, i.e., completion phenol The recycling of urea formaldehyde waste material, obtains water-oil separating material.
Embodiment 22
(1) 100 parts of waste and old carbon fiber reinforced phenol formaldehyde resins are immersed in 100 parts of formamides, are subsequently placed in variable frequency microwave In reactor, add reflux unit, sets microwave heating temperature as 80 DEG C, microwave heating 300min is swollen resin sufficiently, microwave Microwave power automatically adjusts in the range of being no more than 300W with reaction temperature in heating process, the tree after filtering to isolate swelling Rouge simultaneously uses ethyl acetate to be washed under ultrasound condition to remove formamide, and filtering gained formamide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 2min, i.e. completion are useless under conditions of microwave power is 1000W The recycling of old carbon fiber reinforced phenol formaldehyde resin, obtains water-oil separating material.
Embodiment 23
(1) 100 parts of waste epoxy resins are immersed in 50 parts of dimethylformamides, are subsequently placed in variable frequency microwave reactor In, add reflux unit, sets the temperature of microwave heating as 50 DEG C, microwave heating 800min is swollen resin sufficiently, microwave heating Microwave power automatically adjusts in the range of being no more than 300W with reaction temperature in the process, and the resin after filtering to isolate swelling is simultaneously Washing removal dimethylformamide is carried out under ultrasound condition using ethyl alcohol, filtering gained dimethylformamide is directly recycled into benefit With.
(2) by the resin after swelling and washing, microwave heating 20min, i.e. completion are useless under conditions of microwave power is 100W The recycling of old epoxy resin, obtains water-oil separating material.
Embodiment 24
(1) 100 parts of waste and old furane resins are immersed in 100 parts of m-chlorotoluenes, are subsequently placed in variable frequency microwave reactor, Add reflux unit, sets the temperature of microwave heating as 300 DEG C, microwave heating 150min is swollen resin sufficiently, microwave heating Microwave power automatically adjusts in the range of being no more than 400W with reaction temperature in journey, and the resin after filtering to isolate swelling is simultaneously adopted Removal m-chlorotoluene is washed under ultrasound condition with ethyl alcohol, filtering gained m-chlorotoluene is directly recycled.
(2) by the resin after swelling and washing, microwave heating 12min, i.e. completion are useless under conditions of microwave power is 300W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 25
(1) 100 parts of waste and old phenolic resin are immersed in 150 parts of dimethyl acetamides, are subsequently placed in microwave reactor, Add reflux unit, heating 60s makes resin swelling under conditions of microwave power is 1800W, measures immediately after microwave heating The temperature of solvent dimethyl acetamide is 190 DEG C, and the resin after filtering to isolate swelling is simultaneously washed under ultrasound condition using ethyl alcohol Removal dimethyl acetamide is washed, filtering gained dimethyl acetamide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 10min, i.e. completion are useless under conditions of microwave power is 400W The recycling of old phenolic resin, obtains water-oil separating material.
Embodiment 26
(1) 100 parts of waste and old unsaturated polyester resins are immersed in 30 parts of dimethyl sulfoxides, it is anti-is subsequently placed in variable frequency microwave It answers in device, adds reflux unit, set the temperature of microwave heating as 180 DEG C, microwave heating 50min is swollen resin sufficiently, microwave Microwave power automatically adjusts in the range of being no more than 600W with reaction temperature in heating process, the tree after filtering to isolate swelling Rouge simultaneously washs removal dimethyl sulfoxide using ethyl alcohol under ultrasound condition, and filtering gained dimethyl sulfoxide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 18min, i.e. completion are useless under conditions of microwave power is 200W The recycling of old unsaturated polyester resin, obtains water-oil separating material.
Embodiment 27
(1) 100 parts of waste and old melamine resins are immersed in 300 parts of butyrolactone, are subsequently placed in variable frequency microwave reactor In, add reflux unit, sets microwave heating temperature as 100 DEG C, microwave heating 600min is swollen resin sufficiently, microwave heating Microwave power automatically adjusts in the range of being no more than 1000W with reaction temperature in journey, and the resin after filtering to isolate swelling is simultaneously Removal butyrolactone is washed under ultrasound condition using acetone, filtering gained butyrolactone is directly recycled.
(2) by the resin after swelling and washing, microwave heating 10min, i.e. completion are useless under conditions of microwave power is 500W The recycling of old melamine resin, obtains water-oil separating material.
Embodiment 28
(1) 100 parts of waste epoxy resins are immersed in 500 parts of N-METHYLFORMAMIDEs, are subsequently placed in variable frequency microwave reaction In device, add reflux unit, sets the temperature of microwave heating as 300 DEG C, microwave heating 180min is swollen resin sufficiently, and microwave adds Microwave power automatically adjusts in the range of being no more than 800W with reaction temperature in thermal process, the resin after filtering to isolate swelling And removal N-METHYLFORMAMIDE is washed under ultrasound condition using ethyl alcohol, filtering gained N-METHYLFORMAMIDE is directly recycled into benefit With.
(2) by the resin after swelling and washing, microwave heating 13min, i.e. completion are useless under conditions of microwave power is 200W The recycling of old epoxy resin, obtains water-oil separating material.
Embodiment 29
(1) 100 parts of phenolic resin wastes are immersed in 50 parts of butyrolactone, are subsequently placed in variable frequency microwave reactor, add Reflux unit sets microwave heating temperature as 200 DEG C, and microwave heating 20min is swollen resin sufficiently, micro- in microwave heating process Wave power automatically adjusts in the range of being no more than 300W with reaction temperature, and the resin after filtering to isolate swelling simultaneously uses acetic acid Ethyl ester washs removal butyrolactone under ultrasound condition, and filtering gained butyrolactone is directly recycled.
(2) by the resin after swelling and washing microwave power be 100W under conditions of microwave heating 15min, i.e., completion phenol The recycling of urea formaldehyde waste material, obtains water-oil separating material.
Embodiment 30
(1) 100 parts of unsaturated polyester resin wastes are immersed in 250 parts of hexamethylphosphoramide, are subsequently placed in microwave In reactor, add reflux unit, heating 12s makes resin swelling under conditions of microwave power is 3500W, after microwave heating The temperature for measuring solvent hexamethylphosphoramide immediately is 180 DEG C, and the resin after filtering to isolate swelling simultaneously uses ethyl acetate The washing removal hexamethylphosphoramide under ultrasound condition directly recycles filtering gained hexamethylphosphoramide.
(2) by the resin after swelling and washing microwave power be 500W under conditions of microwave heating 5min, that is, complete not The recycling of saturated polyester resin waste material, obtains water-oil separating material.
Embodiment 31
(1) 100 parts of waste and old melamine resins are immersed in 200 parts of ortho-chlorotolu'enes, are subsequently placed in variable frequency microwave reaction In device, add reflux unit, sets microwave heating temperature as 50 DEG C, microwave heating 1000min is swollen resin sufficiently, microwave heating Microwave power automatically adjusts in the range of being no more than 900W with reaction temperature in the process, and the resin after filtering to isolate swelling is simultaneously Removal ortho-chlorotolu'ene is washed under ultrasound condition using acetone, filtering gained ortho-chlorotolu'ene is directly recycled.
(2) by the resin after swelling and washing, microwave heating 2min, i.e. completion are useless under conditions of microwave power is 800W The recycling of old melamine resin, obtains water-oil separating material.
Embodiment 32
(1) 100 parts of post-consumer glass fiber reinforced epoxy resins are immersed in 400 parts of N-Methyl pyrrolidones, are then set In variable frequency microwave reactor, add reflux unit, sets microwave heating temperature as 120 DEG C, microwave heating 120min fills resin Divide swelling, microwave power automatically adjusts in the range of being no more than 400W with reaction temperature in microwave heating process, is separated by filtration Out be swollen after resin and using ethyl alcohol wash under ultrasound condition removal N-Methyl pyrrolidone, will filtering obtained by N- methyl pyrrole Pyrrolidone directly recycles.
(2) by the resin after swelling and washing, microwave heating 7min, i.e. completion are useless under conditions of microwave power is 600W The recycling of old glass fiber reinforced epoxy resin, obtains water-oil separating material.
Embodiment 33
(1) 100 parts of waste and old phenolic resin are immersed in 500 parts of acetamides, are subsequently placed in variable frequency microwave reactor, add Reflux unit sets the temperature of microwave heating as 60 DEG C, and microwave heating 720min is swollen resin sufficiently, in microwave heating process Microwave power automatically adjusts in the range of being no more than 300W with reaction temperature, and the resin after filtering to isolate swelling simultaneously uses second Alcohol washs removal acetamide in ultrasound condition, and filtering gained acetamide is directly recycled.
(2) by the resin after swelling and washing, microwave heating 15min, i.e. completion are useless under conditions of microwave power is 200W The recycling of old phenolic resin, obtains water-oil separating material.
Embodiment 34
(1) 100 parts of waste and old melamine resins are immersed in 300 parts of formamides, are subsequently placed in microwave reactor, add Reflux unit, heating 10s makes resin swelling under conditions of microwave power is 3500W, measures immediately after microwave heating molten The temperature of agent formamide is 150 DEG C, and the resin after filtering to isolate swelling simultaneously washs removal first using ethyl alcohol under ultrasound condition Amide directly recycles filtering gained formamide.
(2) by the resin after swelling and washing, microwave heating 5min, i.e. completion are useless under conditions of microwave power is 700W The recycling of old melamine resin, obtains water-oil separating material.
Embodiment 35
(1) 100 parts of waste and old furane resins are immersed in 150 parts of 2,4- dimethyl-propiones, are subsequently placed in variable frequency microwave In reactor, add reflux unit, sets microwave heating temperature as 120 DEG C, microwave heating 360min is swollen resin sufficiently, microwave Microwave power automatically adjusts in the range of being no more than 1000W with reaction temperature in heating process, after filtering to isolate swelling Resin simultaneously washs removal 2,4- dimethyl-propione using ethyl alcohol under ultrasound condition, by filtering gained 2,4- dimethyl -3- penta Ketone directly recycles.
(2) by the resin after swelling and washing, microwave heating 10min, i.e. completion are useless under conditions of microwave power is 500W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 36
(1) 100 parts of waste and old furane resins are immersed in 100 parts of N-METHYLFORMAMIDEs, are subsequently placed in variable frequency microwave reaction In device, add reflux unit, sets microwave heating temperature as 200 DEG C, microwave heating 10min is swollen resin sufficiently, microwave heating Microwave power automatically adjusts in the range of being no more than 1000W with reaction temperature in the process, the resin after filtering to isolate swelling And removal N-METHYLFORMAMIDE is washed under ultrasound condition using ethyl alcohol, filtering gained N-METHYLFORMAMIDE is directly recycled into benefit With.
(2) by the resin after swelling and washing, microwave heating 17min, i.e. completion are useless under conditions of microwave power is 200W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 37
(1) 100 parts of phenolic resin wastes are immersed in 400 parts of p-chlorotoluenes, are subsequently placed in variable frequency microwave reactor, Add reflux unit, sets microwave heating temperature as 100 DEG C, microwave heating 800min is swollen resin sufficiently, microwave heating process Middle microwave power automatically adjusts in the range of being no more than 300W with reaction temperature, resin and use after filtering to isolate swelling Ethyl alcohol washs removal p-chlorotoluene under ultrasound condition, and filtering gained p-chlorotoluene is directly recycled.
(2) by the resin after swelling and washing microwave power be 600W under conditions of microwave heating 5min, i.e., completion phenol The recycling of urea formaldehyde waste material, obtains water-oil separating material.
Embodiment 38
(1) 100 parts of waste epoxy resins are immersed in the mixed solvent, mixed solvent by 30 parts of N-Methyl pyrrolidones and 30 parts of dimethyl acetamides composition, is subsequently placed in variable frequency microwave reactor, adds reflux unit, set microwave heating temperature as 150 DEG C, microwave heating 120min is swollen resin sufficiently, and microwave power is in the range for being no more than 1000W in microwave heating process It is interior to be automatically adjusted with reaction temperature, it filters to isolate the resin after being swollen and removal mixing is washed under ultrasound condition using acetone Solvent will recycle after filtering gained mixed solvent distillation.
(2) by the resin after swelling and washing, microwave heating 3min, i.e. completion are useless under conditions of microwave power is 1000W The recycling of old epoxy resin, obtains water-oil separating material.
Embodiment 39
(1) 100 parts of waste and old furane resins are immersed in the mixed solvent, mixed solvent is by 50 parts of formamides and 50 parts of neighbours two Chlorobenzene composition, is subsequently placed in variable frequency microwave reactor, adds reflux unit, sets microwave heating temperature as 50 DEG C, microwave heating 500min is swollen resin sufficiently, and microwave power is automatic with reaction temperature in the range of being no more than 200W in microwave heating process It adjusts, the resin after filtering to isolate swelling simultaneously washs removal mixed solvent using ethyl alcohol under ultrasound condition, by filtering gained It is recycled after mixed solvent fractionation.
(2) by the resin after swelling and washing, microwave heating 9min, i.e. completion are useless under conditions of microwave power is 600W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 40
(1) 100 parts of waste and old melamine resins are immersed in the mixed solvent, mixed solvent is by 150 parts of dimethylacetamides Amine and 200 parts of ortho-chlorotolu'ene compositions, are subsequently placed in microwave reactor, add reflux unit, in the condition that microwave power is 2700W Lower heating 30s makes resin swelling, measures the temperature of mixed solvent after microwave heating immediately, is 180 DEG C, filters to isolate molten Resin after swollen simultaneously wash removal mixed solvent using ethyl alcohol under ultrasound condition, will filtering gained mixed solvent be fractionated after recycle It utilizes.
(2) by the resin after swelling and washing, microwave heating 1min, i.e. completion are useless under conditions of microwave power is 900W The recycling of old melamine resin, obtains water-oil separating material.
Embodiment 41
(1) 100 parts of unsaturated polyester resin wastes are immersed in the mixed solvent, mixed solvent by 50 parts of acetamides and 100 parts of ortho-chlorotolu'enes composition, is subsequently placed in variable frequency microwave reactor, adds reflux unit, sets microwave heating temperature as 70 DEG C, Microwave heating 300min is swollen resin sufficiently, and microwave power is in the range of being no more than 300W with reaction in microwave heating process Temperature automatic adjustment filters to isolate the resin after being swollen and washs removal mixed solvent under ultrasound condition using acetone, will It is recycled after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing microwave power be 450W under conditions of microwave heating 4min, that is, complete not The recycling of saturated polyester resin waste material, obtains water-oil separating material.
Embodiment 42
(1) 100 parts of waste and old fibre reinforced unsaturated polyester resins are immersed in the mixed solvent, mixed solvent is by 200 2,4- of part dimethyl-propione and 200 parts of butyrolactone compositions, are subsequently placed in variable frequency microwave reactor, add reflux unit, set Microwave heating temperature is 120 DEG C, and microwave heating 10min is swollen resin sufficiently, and microwave power is not surpassing in microwave heating process It crosses in the range of 600W and is automatically adjusted with reaction temperature, the resin after filtering to isolate swelling is simultaneously using ethyl alcohol under ultrasound condition Washing removal mixed solvent will recycle after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing, microwave heating 3min, i.e. completion are useless under conditions of microwave power is 900W The recycling of old fibre reinforced unsaturated polyester resin, obtains water-oil separating material.
Embodiment 43
(1) 100 parts of waste and old phenolic resin are immersed in the mixed solvent, mixed solvent by 300 parts of dimethyl acetamides and 100 parts of dimethyl sulfoxide compositions, are subsequently placed in microwave reactor, add reflux unit, under conditions of microwave power is 3500W Heating 10s makes resin swelling, measures the temperature of mixed solvent after microwave heating immediately, is 160 DEG C, filters to isolate swelling Rear resin simultaneously wash removal mixed solvent using acetone under ultrasound condition, will after filtering gained mixed solvent fractionation recycling it is sharp With.
(2) by the resin after swelling and washing, microwave heating 6min, i.e. completion are useless under conditions of microwave power is 800W The recycling of old phenolic resin, obtains water-oil separating material.
Embodiment 44
(1) 100 parts of waste and old furane resins are immersed in the mixed solvent, mixed solvent is by 100 parts of N-Methyl pyrrolidones Formed with 100 parts of dimethyl sulfoxides, be subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave heating temperature as 90 DEG C, microwave heating 360min is swollen resin sufficiently, and microwave power is in the range of being no more than 900W in microwave heating process It is automatically adjusted with reaction temperature, filter to isolate the resin after being swollen and removal mixing is washed under ultrasound condition using ethyl alcohol and is molten Agent will recycle after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing, microwave heating 7min, i.e. completion are useless under conditions of microwave power is 300W The recycling of old furane resins, obtains water-oil separating material.
Embodiment 45
(1) 100 parts of waste and old unsaturated polyester resins are immersed in the mixed solvent, mixed solvent is by 150 parts of N- methyl pyrroles Pyrrolidone and 100 parts of formamide compositions, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave heating temperature It is 50 DEG C, microwave heating 1000min is swollen resin sufficiently, and microwave power is in the range for being no more than 600W in microwave heating process It is interior to be automatically adjusted with reaction temperature, it filters to isolate the resin after being swollen and removal mixing is washed under ultrasound condition using ethyl alcohol Solvent will recycle after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing, microwave heating 8min, i.e. completion are useless under conditions of microwave power is 500W The recycling of old unsaturated polyester resin, obtains water-oil separating material.
Embodiment 46
(1) 100 parts of carbon fiber reinforced phenol formaldehyde resin waste materials are immersed in the mixed solvent, mixed solvent is by 50 parts of formamides Formed with 50 parts of dimethyl sulfoxides, be subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave heating temperature as 150 DEG C, microwave heating 300min is swollen resin sufficiently, and microwave power is in the range of being no more than 450W in microwave heating process It is automatically adjusted with reaction temperature, filter to isolate the resin after being swollen and removal is washed under ultrasound condition using ethyl acetate and is mixed Bonding solvent will recycle after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing microwave power be 700W under conditions of microwave heating 5min, i.e., completion carbon The recycling of fibre reinforced phenolic resin waste material, obtains water-oil separating material.
Embodiment 47
(1) 100 parts of epoxy resin waste materials are immersed in the mixed solvent, mixed solvent is by 300 parts of p-chlorotoluenes and 200 parts Formamide composition, is subsequently placed in variable frequency microwave reactor, adds reflux unit, set microwave heating temperature as 200 DEG C, microwave adds Hot 8min is swollen resin sufficiently, in microwave heating process microwave power be no more than 1000W in the range of with reaction temperature from It is dynamic to adjust, it filters to isolate the resin after being swollen and removal mixed solvent is washed under ultrasound condition using ethyl acetate, incited somebody to action It is recycled after filter gained mixed solvent fractionation.
(2) by the resin after swelling and washing microwave power be 700W under conditions of microwave heating 5min, i.e., completion ring The recycling of oxygen resin waste, obtains water-oil separating material.
Embodiment 48
(1) 100 parts of unsaturated polyester resin wastes are immersed in the mixed solvent, mixed solvent by 100 parts of formamides and 100 parts of butyrolactone composition, is subsequently placed in variable frequency microwave reactor, adds reflux unit, sets microwave heating temperature as 100 DEG C, Microwave heating 60min is swollen resin sufficiently, and microwave power is in the range of being no more than 400W with reaction in microwave heating process Temperature automatic adjustment filters to isolate the resin after being swollen and washs removal mixed solvent under ultrasound condition using ethyl alcohol, will It is recycled after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing microwave power be 150W under conditions of microwave heating 15min, that is, complete not The recycling of saturated polyester resin waste material, obtains water-oil separating material.
Embodiment 49
(1) 100 parts of melamine resin waste materials are immersed in the mixed solvent, mixed solvent is by 50 parts of cyclohexanone and 50 parts Dimethyl sulfoxide composition, is subsequently placed in microwave reactor, adds reflux unit, heats under conditions of microwave power is 1800W 30s makes resin swelling, measures the temperature of mixed solvent after microwave heating immediately, is 120 DEG C, after filtering to isolate swelling Resin simultaneously washs removal mixed solvent using ethyl alcohol under ultrasound condition, will recycle after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing microwave power be 850W under conditions of microwave heating 1min, that is, complete three The recycling of cymel waste material, obtains water-oil separating material.
Embodiment 50
(1) 100 parts of phenolic resin wastes are immersed in the mixed solvent, mixed solvent is by 100 parts of dimethyl sulfoxides and 300 Part hexamethylphosphoramide composition, is subsequently placed in variable frequency microwave reactor, adds reflux unit, set microwave heating temperature as 160 DEG C, microwave heating 10min is swollen resin sufficiently, and microwave power is in the range of being no more than 200W in microwave heating process It is automatically adjusted with reaction temperature, filter to isolate the resin after being swollen and removal mixing is washed under ultrasound condition using acetone and is molten Agent will recycle after filtering gained mixed solvent fractionation.
(2) by the resin after swelling and washing microwave power be 100W under conditions of microwave heating 18min, i.e., completion phenol The recycling of urea formaldehyde waste material, obtains water-oil separating material.
Embodiment 51
(1) 100 parts of waste epoxy resins are immersed in the mixed solvent, mixed solvent is by 5 parts of acetamides and 5 parts of dimethyl Formamide solution composition, is subsequently placed in variable frequency microwave reactor, adds reflux unit, set microwave heating temperature as 180 DEG C, micro- Wave heating 240min is swollen resin sufficiently, and microwave power is in the range of being no more than 600W with reaction temperature in microwave heating process Degree automatic adjustment filters to isolate the resin after being swollen and washs removal mixed solvent under ultrasound condition using ethyl alcohol, incited somebody to action It is recycled after filter gained mixed solvent distillation.
(2) by the resin after swelling and washing, microwave heating 7min, i.e. completion are useless under conditions of microwave power is 600W The recycling of old epoxy resin, obtains water-oil separating material.
In order to investigate the present invention using the water-oil separating material of microwave recycling waste thermosetting resin preparation to oily wastewater pollution The separating effect of object, application examples below carry out water-oil separating reality using the water-oil separating material of above section embodiment preparation It tests, tests the separative efficiency and oil flux to simple oil-water mixture and lotion of water-oil separating material.
Application examples 1
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 2, the results showed that, oil Water is simply mixed liquid separative efficiency and has reached 98.7%, and oily flux is 2128.7L/ (m2H), lotion separative efficiency reaches 97.9% or more, lotion flux is 1986.7L/ (m2h)。
Application examples 2
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 7, the results showed that, oil Water is simply mixed liquid separative efficiency and has reached 99.9%, and oily flux is 2630.3L/ (m2H), lotion separative efficiency reaches 99.8% or more, lotion flux is 2607.3L/ (m2h)。
Application examples 3
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 10, the results showed that, Grease is simply mixed liquid separative efficiency and has reached 99.7%, and oily flux is 3069.6L/ (m2H), lotion separative efficiency reaches 99.9% or more, lotion flux is 3158.2L/ (m2h)。
Application examples 4
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 12, the results showed that, Grease is simply mixed liquid separative efficiency and has reached 98.2%, and oily flux is 3856.4L/ (m2H), lotion separative efficiency reaches 97.1% or more, lotion flux is 3695.2L/ (m2h)。
Fig. 5 is the photo that the application example carries out water-oil separating experiment using water-oil separating material made from embodiment 12, In (A) figure be to pour into the grease simple mixtures of configuration in separator, show that oil can be quickly by grease point in (B) figure From material, water is then retained in the graduated cylinder above water-oil separating material.
Application examples 5
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 19, the results showed that, Grease is simply mixed liquid separative efficiency and has reached 99.9%, and oily flux is 3018.2L/ (m2H), lotion separative efficiency reaches 98.9% or more, lotion flux is 2958.1L/ (m2h)。
Application examples 6
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 22, the results showed that oil Water is simply mixed liquid separative efficiency and has reached 98.8%, and oily flux is 2507.5L/ (m2H), lotion separative efficiency reaches 97.1% or more, lotion flux is 2468.1L/ (m2h)。
Application examples 7
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 28, the results showed that, Grease is simply mixed liquid separative efficiency and has reached 98.4%, and oily flux is 2546.1L/ (m2H), lotion separative efficiency reaches 98.3% or more, lotion flux is 2045.2L/ (m2h)。
Application examples 8
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 32, the results showed that, Grease is simply mixed liquid separative efficiency and has reached 98.8%, and oily flux is 3152.0L/ (m2H), lotion separative efficiency reaches 97.7% or more, lotion flux is 2952.5L/ (m2h)。
Application examples 9
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 38, as a result table Bright, grease is simply mixed liquid separative efficiency and has reached 95.7%, and oily flux is 2537.1L/ (m2H), lotion separative efficiency reaches 92.8% or more, lotion flux is 2498.6L/ (m2h)。
Application examples 10
Water-oil separating and lotion separating experiment are carried out using water-oil separating material obtained in embodiment 44, the results showed that, Grease is simply mixed liquid separative efficiency and has reached 99.5%, and oily flux is 2845.9L/ (m2H), lotion separative efficiency reaches 98.8% or more, lotion flux is 2796.2L/ (m2h)。
Comparative example 1
100 parts of waste and old phenolic resin are added in 200 parts of glacial acetic acid solutions, is subsequently placed in variable frequency microwave reactor, adds Reflux unit sets microwave heating temperature as 100 DEG C, microwave heating 180min, and microwave power is not surpassing in microwave heating process It crosses in the range of 400W and is automatically adjusted with reaction temperature, the resin after filtering to isolate swelling is simultaneously using ethyl alcohol under ultrasound condition It washs, then microwave heating 10min under conditions of microwave power is 500W.
Using by this comparative example, treated that waste and old phenolic resin carries out water-oil separating experiment, the results showed that, by this Treated that waste and old phenolic resin does not have oil-water separation for comparative example.
Comparative example 2
100 parts of waste epoxy resins are added in 100 parts of naphthanes, are subsequently placed in variable frequency microwave reactor, add-back stream Device sets the temperature of microwave heating as 150 DEG C, microwave heating 120min, and microwave power is being no more than in microwave heating process It is automatically adjusted in the range of 600W with reaction temperature, the resin after filtering to isolate swelling is simultaneously washed under ultrasound condition using acetone It washs, then microwave heating 2min under conditions of microwave power is 400W.
Water-oil separating experiment is carried out using by this comparative example treated waste epoxy resin, the results showed that, by this Treated that waste epoxy resin does not have oil-water separation for comparative example.In conjunction with above embodiments, application examples and comparative example 1~ 2 it is found that prepare water-oil separating material using method recycling waste thermosetting resin of the invention, need to rely on specific solvent Just it is able to achieve.
Comparative example 3
100 parts of waste epoxy resins are added in 50 parts of dimethyl sulfoxides, are subsequently placed in conventional heating reactor, add-back Device is flowed, temperature programming heats 300min to 120 DEG C, takes out resin, is washed under ultrasound condition using ethyl alcohol, then In the condition microwave heating 10min that microwave power is 500W.
Water-oil separating experiment is carried out using by this comparative example treated waste epoxy resin, the results showed that, by this Treated that waste epoxy resin does not have oil-water separation for comparative example.It can in conjunction with above embodiments, application examples and this comparative example Know, water-oil separating material prepared using method recycling waste thermosetting resin of the invention, need to rely on microwave heating this Specific heating method is just able to achieve.
Embodiment 52
(1) waste epoxy resin is crushed, the sieve that aperture is 0.9mm is crossed, by the waste and old asphalt mixtures modified by epoxy resin after crushing and sieving 100 parts of rouge are immersed in 100 parts of N-Methyl pyrrolidones, are subsequently placed in variable frequency microwave reactor, add reflux unit, set micro- Wave heating temperature is 120 DEG C, and microwave heating 30min is swollen resin sufficiently, and microwave power is being no more than in microwave heating process It is automatically adjusted in the range of 400W with reaction temperature, the resin after filtering to isolate swelling is simultaneously washed under ultrasound condition using ethyl alcohol Removal N-Methyl pyrrolidone is washed, filtering gained N-Methyl pyrrolidone is directly recycled.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 300 parts of concentration and is In the nitric acid solution of 18wt.%, heating water bath carries out chemical degradation to resin, and control bath temperature is 60 DEG C, heating water bath 3h When, resin degradation yield has reached 99.8%.
Embodiment 53
(1) waste epoxy resin is crushed, the sieve that aperture is 5mm is crossed, by the waste epoxy resin after crushing and sieving 100 parts are immersed in 500 parts of dimethyl sulfoxides, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave heating Temperature is 150 DEG C, and microwave heating 120min is swollen resin sufficiently, and microwave power is no more than 100W's in microwave heating process It is automatically adjusted in range with reaction temperature, the resin after filtering to isolate swelling simultaneously washs removal using ethyl alcohol under ultrasound condition Dimethyl sulfoxide directly recycles filtering gained dimethyl sulfoxide.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 50 parts of concentration and is In the nitric acid solution of 18wt.%, heating water bath carries out chemical degradation to resin, and control bath temperature is 90 DEG C, heating water bath 1h When, resin degradation yield has reached 93.2%.
Embodiment 54
(1) waste epoxy resin is crushed, the sieve that aperture is 3mm is crossed, by the waste epoxy resin after crushing and sieving 100 parts are immersed in 50 parts of N-Methyl pyrrolidones, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave Heating temperature is 120 DEG C, and microwave heating 60min is swollen resin sufficiently, and microwave power is being no more than in microwave heating process It is automatically adjusted in the range of 800W with reaction temperature, the resin after filtering to isolate swelling is simultaneously washed under ultrasound condition using ethyl alcohol Removal N-Methyl pyrrolidone is washed, filtering gained N-Methyl pyrrolidone is directly recycled.
(2) by the resin drying by step (1) processing, 100 parts of resins is taken to put into the dioxygen that 20 parts of concentration are 30wt.% Water and 100 parts of concentration are in the mixed liquor of phosphoric acid solution of 85wt.%, and heating water bath carries out chemical degradation to resin, controls water Bath temperature is 90 DEG C, when heating water bath 500min, and resin degradation yield has reached 97.8%.
Embodiment 55
(1) waste epoxy resin is crushed, the sieve that aperture is 0.2mm is crossed, by the waste and old asphalt mixtures modified by epoxy resin after crushing and sieving 100 parts of rouge are immersed in 500 parts of formamides, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave heating temperature Degree is 90 DEG C, and microwave heating 120min is swollen resin sufficiently, and microwave power is in the model for being no more than 600W in microwave heating process It is automatically adjusted in enclosing with reaction temperature, the resin after filtering to isolate swelling simultaneously washs removal first using ethyl alcohol under ultrasound condition Amide directly recycles filtering gained formamide.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 1 part of concentration and is The hydrogen peroxide of 30wt.% and 100 parts of concentration are in the mixed liquor of phosphoric acid solution of 85wt.%, and heating water bath is to resin Degradation is learned, control bath temperature is 50 DEG C, when heating water bath 120min, and resin degradation yield has reached 90.8%.
Embodiment 56
(1) waste and old unsaturated polyester resin is crushed, crosses the sieve that aperture is 0.45mm, it will be waste and old after crushing and sieving 100 parts of unsaturated polyester resin are immersed in 500 parts of dimethylformamides, are subsequently placed in variable frequency microwave reactor, add-back stream Device sets microwave heating temperature as 120 DEG C, and microwave heating 60min is swollen resin sufficiently, microwave function in microwave heating process Rate automatically adjusts in the range of being no more than 800W with reaction temperature, and the resin after filtering to isolate swelling is simultaneously being surpassed using ethyl alcohol Washing removal dimethylformamide under the conditions of sound directly recycles filtering gained dimethylformamide.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 50 parts of concentration and is In the solution of potassium carbonate of 30wt.%, heating water bath carries out chemical degradation to resin, and control bath temperature is 80 DEG C, heating water bath When 1.5h, resin degradation yield has reached 92.1%.
Embodiment 57
(1) waste and old unsaturated polyester resin is crushed, cross aperture be 5mm sieve, by after crushing and sieving it is waste and old not 100 parts of saturated polyester resin are immersed in 150 parts of dimethyl acetamides, are subsequently placed in variable frequency microwave reactor, add-back stream dress It sets, sets microwave heating temperature as 200 DEG C, microwave heating 30min is swollen resin sufficiently, microwave power in microwave heating process It is automatically adjusted in the range of being no more than 300W with reaction temperature, the resin after filtering to isolate swelling simultaneously uses ethyl alcohol in ultrasound Under the conditions of washing removal dimethyl acetamide, will filtering gained dimethyl acetamide directly recycle.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 600 parts of concentration and is In the potassium hydroxide solution of 20wt.%, heating water bath carries out chemical degradation to resin, and control bath temperature is 40 DEG C, and water-bath adds When hot 4h, resin degradation yield has reached 94.6%.
Embodiment 58
(1) waste and old phenolic resin is crushed, the sieve that aperture is 0.2mm is crossed, by the waste and old phenolic aldehyde tree after crushing and sieving 100 parts of rouge are immersed in 500 parts of formamides, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave heating temperature Degree is 150 DEG C, and microwave heating 90min is swollen resin sufficiently, and microwave power is in the model for being no more than 200W in microwave heating process It is automatically adjusted in enclosing with reaction temperature, the resin after filtering to isolate swelling simultaneously washs removal first using ethyl alcohol under ultrasound condition Amide directly recycles filtering gained formamide.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 300 parts of concentration and is In the nitric acid solution of 18wt.%, heating water bath carries out chemical degradation to resin, and control bath temperature is 90 DEG C, heating water bath 12h When, resin degradation yield has reached 61.4%.
Embodiment 59
(1) waste epoxy resin is crushed, crosses the sieve that aperture is 0.9mm, the waste epoxy resin that will be crushed and be sieved 100 parts are immersed in 400 parts of N-Methyl pyrrolidones, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave Heating temperature is 60 DEG C, and microwave heating 30min is swollen resin sufficiently, and microwave power is being no more than 300W in microwave heating process In the range of automatically adjusted with reaction temperature, the resin after filtering to isolate swelling is simultaneously washed under ultrasound condition and is gone using ethyl alcohol Except N-Methyl pyrrolidone, filtering gained N-Methyl pyrrolidone is directly recycled.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 100 parts of concentration and is In the nitric acid solution of 18wt.%, microwave heating carries out chemical degradation to resin, and the temperature for controlling microwave heating is 60 DEG C, microwave Heating temperature is 400W, and when microwave heating 30min, resin degradation yield has reached 98.9%.
Embodiment 60
(1) waste epoxy resin is crushed, the sieve that aperture is 0.9mm is crossed, by the waste and old asphalt mixtures modified by epoxy resin after crushing and sieving 100 parts of rouge are immersed in 250 parts of dimethyl acetamides, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave Heating temperature is 80 DEG C, and microwave heating 360min is swollen resin sufficiently, and microwave power is being no more than in microwave heating process It is automatically adjusted in the range of 400W with reaction temperature, the resin after filtering to isolate swelling is simultaneously washed under ultrasound condition using ethyl alcohol Removal dimethyl acetamide is washed, filtering gained dimethyl acetamide is directly recycled.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 100 parts of concentration and is The hydrogen peroxide of 30wt.% and 200 parts of concentration are in the mixed liquor of phosphoric acid solution of 85wt.%, and microwave heating is to resin Degradation is learned, when the temperature for controlling microwave heating is 60 DEG C, microwave heating temperature 800W, microwave heating 30min, resin degradation is produced Rate has reached 88.9%.
Embodiment 61
(1) waste and old unsaturated polyester resin is crushed, crosses the sieve that aperture is 0.45mm, it will be waste and old after crushing and sieving 100 parts of unsaturated polyester resin are immersed in 100 parts of dimethylformamides, are subsequently placed in variable frequency microwave reactor, add-back stream Device sets microwave heating temperature as 150 DEG C, and microwave heating 360min is swollen resin sufficiently, microwave in microwave heating process Power automatically adjusts in the range of being no more than 100W with reaction temperature, and the resin after filtering to isolate swelling is simultaneously existed using ethyl alcohol Washing removal dimethylformamide under ultrasound condition directly recycles filtering gained dimethylformamide.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 200 parts of concentration and is In 30wt.% solution of potassium carbonate, microwave heating carries out chemical degradation to resin, and the temperature for controlling microwave heating is 90 DEG C, microwave Heating temperature is 400W, and when microwave heating 50min, resin degradation yield has reached 96.6%.
Embodiment 62
(1) waste and old phenolic resin is crushed, crosses the sieve that aperture is 0.2mm, the waste and old phenolic resin that will be crushed and be sieved 100 parts are immersed in 50 parts of formamides, are subsequently placed in variable frequency microwave reactor, add reflux unit, set microwave heating temperature It is 120 DEG C, microwave heating 240min is swollen resin sufficiently, and microwave power is in the model for being no more than 1000W in microwave heating process It is automatically adjusted in enclosing with reaction temperature, the resin after filtering to isolate swelling simultaneously washs removal first using ethyl alcohol under ultrasound condition Amide directly recycles filtering gained formamide.
(2) by the resin drying by step (1) processing, the resin after taking 100 parts of drying puts into 50 parts of concentration and is In the nitric acid solution of 18wt.%, microwave heating carries out chemical degradation to resin, and the temperature for controlling microwave heating is 80 DEG C, microwave Heating temperature is 900W, and when microwave heating 8h, resin degradation yield has reached 75.9%.
Comparative example 4
Waste epoxy resin is crushed, the sieve that aperture is 0.9mm, the waste epoxy resin 100 that will be crushed and be sieved are crossed Part is immersed in the nitric acid solution that 300 parts of concentration are 18wt.%, and heating water bath carries out chemical degradation to resin, controls water-bath temperature Degree is 80 DEG C, when heating water bath 12h, and resin yield of degrading is 0.
Comparative example 5
Waste epoxy resin is crushed, the sieve that aperture is 0.9mm, the waste epoxy resin 100 that will be crushed and be sieved are crossed In the mixed liquor for the phosphoric acid solution that the hydrogen peroxide and 200 parts of concentration that part 100 parts of concentration of investment are 30wt.% are 85wt.%, microwave Heating carries out chemical degradation to resin, and the temperature for controlling microwave heating is 90 DEG C, and the power of microwave heating is 800W, microwave heating When 240min, resin degradation yield is 0.2%.
In conjunction with comparative example 4 and embodiment 52, comparative example 5 and embodiment 60 it is found that method of the invention to waste and old asphalt mixtures modified by epoxy resin After rouge carries out microwave swelling, the degradation speed of waste epoxy resin can be dramatically speeded up, and reduce degrading waste epoxy resin Reaction condition.

Claims (9)

1. a kind of method using microwave recycling waste thermosetting resin, it is characterised in that steps are as follows:
(1) waste thermosetting resin is immersed in boiling point to be at least in 100 DEG C of polar solvent, microwave heating makes thermosetting resin Swelling, the temperature for controlling microwave heating are no more than the thermal decomposition temperature of thermosetting resin, the thermosetting property after swelling is then demultiplex out Resin simultaneously washs；
(2) microwave heating method one: is carried out to improve the internal holes of thermosetting resin to the thermosetting resin after swelling and washing Structure and increase surface roughness, that is, complete the recycling of waste thermosetting resin；
Alternatively, method two: the thermosetting resin after swelling and washing is dry, using existing chemical degradation method to the heat after drying Thermosetting resin carries out chemical degradation；
When step (2) are using method a period of time, it is damaged that the microwave heating condition of rate-determining steps (1) avoids thermosetting resin from occurring, control The microwave heating condition of step (2) processed avoids thermosetting resin from being charred.
2. utilizing the method for microwave recycling waste thermosetting resin according to claim 1, which is characterized in that when step (2) For the moment using method, the obtained material of recycling for completing waste thermosetting resin has the micron or nanoporous being mutually communicated Structure, the material can carry out water-oil separating to oil-water mixture and oil hydrosol under the conditions of no ambient pressure.
3. utilizing the method for microwave recycling waste thermosetting resin according to claim 1, which is characterized in that when step (2) When using method two, the degradation speed of thermosetting resin can be accelerated and reduce degradation conditions.
4. special according to claim 1 to the method for utilizing microwave recycling waste thermosetting resin described in any claim in 3 Sign is that control microwave heating condition makes the swelling ratio of thermosetting resin be at least up to 10% in step (1).
5. special according to claim 1 to the method for utilizing microwave recycling waste thermosetting resin described in any claim in 3 Sign is that polar solvent is cyclohexanone, 2,4- dimethyl-propione, N-Methyl pyrrolidone, butyrolactone, dimethyl sulfoxide, six Methyl phosphoric triamide, formamide, acetamide, dimethylformamide, dimethyl acetamide, N-METHYLFORMAMIDE, o-dichlorohenzene, neighbour At least one of chlorotoluene, m-chlorotoluene and p-chlorotoluene.
6. special according to claim 1 to the method for utilizing microwave recycling waste thermosetting resin described in any claim in 3 Sign is that the temperature of control microwave heating is at least 50 DEG C in step (1).
7. special according to claim 1 to the method for utilizing microwave recycling waste thermosetting resin described in any claim in 3 Sign is that, when step (2) are using method a period of time, the waste thermosetting resin is epoxy resin, unsaturated polyester resin, phenolic aldehyde Resin, melamine resin or furane resins, or with epoxy resin, unsaturated polyester resin, phenolic resin, melamine Thermosetting resin based on resin or furane resins.
8. special according to claim 1 to the method for utilizing microwave recycling waste thermosetting resin described in any claim in 3 Sign is, when step (2) use method two, the waste thermosetting resin is epoxy resin, unsaturated polyester resin or phenol Urea formaldehyde, or the thermosetting resin based on epoxy resin, unsaturated polyester resin or phenolic resin.
9. utilizing the method for microwave recycling waste thermosetting resin according to claim 8, which is characterized in that when discarded thermosetting Property resin be unsaturated polyester resin, or when for thermosetting resin based on unsaturated polyester resin, step (2) will be molten Thermosetting resin after swollen, which is placed in potassium carbonate or potassium hydroxide solution, carries out chemical degradation；When waste thermosetting resin is epoxy Resin or phenolic resin, or when for thermosetting resin based on epoxy resin or phenolic resin, after step (2) will be swollen Thermosetting resin be placed in nitric acid solution or the mixed solution of hydrogen peroxide and phosphoric acid in carry out chemical degradation.
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CN113321201B (en) * 2021-06-11 2022-12-16 同济大学 Porous carbon material based on waste recovered epoxy resin and preparation method and application thereof
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