CN101519505B - Method for decomposing thermosetting epoxy resin or composite material thereof by high-temperature water phase - Google Patents
Method for decomposing thermosetting epoxy resin or composite material thereof by high-temperature water phase Download PDFInfo
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- CN101519505B CN101519505B CN2009100465243A CN200910046524A CN101519505B CN 101519505 B CN101519505 B CN 101519505B CN 2009100465243 A CN2009100465243 A CN 2009100465243A CN 200910046524 A CN200910046524 A CN 200910046524A CN 101519505 B CN101519505 B CN 101519505B
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- epoxy resin
- thermosetting epoxy
- temperature
- matrix material
- decomposing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to a method for decomposing a thermosetting epoxy resin or a composite material thereof by high-temperature water phases, which belongs to the technical field of regenerative utilization of waste resin materials or treatment of industrial wastes. The method is characterized by comprising the following steps: putting certain amount of thermosetting epoxy resin sheets or granules, and deionization and catalyst heteropolyacid into a high-temperature high-pressure stainless steel reaction kettle; heating the reaction kettle to raise the temperature to a temperature of 250 and370 DEG C for 30 to 120 hours; and decomposing the water diversion phase so that the decomposed product becomes an oligomer or a single substance which cannot be dissolved in liquid phase and is easy to separate. The method mainly adopts heteropoly acid, phosphotungstic acid, tungstosilicic acid, or molybdenum phosphoric acid as a catalyst, the addition of the catalyst is 0.1 to 3.0 percent of th at of deionized water, and a higher decomposition rate of the epoxy resin can be obtained finally. The method does not need to use an organic solvent as a decomposing liquid, but uses water as the decomposing liquid, thus the method has low cost and is pollution-free to the environment; and the method can achieve the aims of waste regeneration and utilization as well as environmental protection.
Description
Technical field
The present invention relates to the method for a kind of high-temperature water phase decomposition thermosetting epoxy resin or its matrix material, belong to waste resin material regeneration or trade waste processing technology field.
Background technology
Along with the widespread use of electronic product and the high speed development of corresponding industry thereof, the waste and old electric product comprises waste material, the waste product that produces in waste computer, signal equipment, household electrical appliance, other various electronic instruments that are eliminated and the Industrial processes, has become new environment hidden danger.The consumption and the turnout of China's electronic product all are in prostatitis, the world at present, and the electron wastes problem of environment pollution caused is also outstanding day by day.Waste printed circuit board (PCB) is eliminated with electronic product, it (is example with the computer that its discarded amount also grows at top speed with the increase of electron wastes total amount, PCB account for the computer gross weight about 8%), and also containing a large amount of useless PCB in a large amount of waste materials that in the course of processing, produce of electronic product, waste leftover material, the therefore discarded formed electronic pollution of PCB has become severe environmental problem.
Be mainly thermosetting epoxy resin composite material in the board substrate.The thermosetting epoxy resin of thermosetting epoxy resin and adding filler (glass fibre etc.) has good corrosion resistance, and light weight is easy to characteristics such as machine-shaping.But, cause that thermosetting epoxy resin material and glass fibre etc. are nonmetal not to carry out development and utilization preferably as yet because thermosetting epoxy resin is not molten, insoluble and the characteristic that is difficult for being decomposed.At present, the recycling disposal method of waste printed circuit board epoxy resin composite material mainly contains pyrolysis absorption method, physical recovery method, solvent pyrolytic decomposition recovery method.Pyrolysis method is the traditional processing polymeric scrap material and the common method of polymer composite.But because mineral filler such as a lot of glass fibre is arranged in the epoxy resin composite material in the board substrate, can incendiary organic content and few, behind incineration disposal, still have a large amount of slags to need ultimate disposal.Simultaneously contained brominated flame retardant etc. easily produces hazardous and noxious substances such as dioxin in the epoxy resin composite material in combustion processes, if furnace temperature is not enough or exhaust gas treating method is improper, can cause secondary pollution.Also there is certain problem in the physics absorption method in the recycling disposal process, by the application number of Xu Zhenming, the Li Jia of Shanghai Communications University application be: 200510023786.X " manufacture method of the base plate material granules regeneration plate of waste and old printed circuit board " is exactly to belong to physical recovery method.The incomplete same character of Resins, epoxy composition as board substrate is variant, can influence the performance of reconstituted product to a certain extent; The useless Resins, epoxy that reclaims can not use separately usually, can only mix use as additive and new same type of material or other materials, and usage quantity and use range have certain limitation.Solvent pyrolytic decomposition recovery method is put into organic solvent or water with thermosetting material, adds catalyzer, decomposes under the comparatively high temps pressure condition, and this method decomposition efficiency is higher.Application number as Liu Yuyan, Meng Linghui application is 200610151145.7 " method of decomposing thermoset epoxy resin and matrix material thereof ", and decomposed solution is naphthane or perhydronaphthalene; Catalyzer is magnesium, aluminium, ferric oxide, lime carbonate or yellow soda ash; The degradation production that obtains at last is dissolved in the decomposed solution.Though this decomposition method can decomposing thermoset epoxy resin and matrix material thereof, also have many defectives: decomposed solution is an organic solvent, and the catalyst activity is not high, and degradation production is dissolved in the decomposed solution, and is not easily separated.The application number of Liu Yuyan, Li Li application is 200710144538.X " method of water-phase decomposition thermoset epoxy resin and matrix material thereof ", used decomposed solution is a water, but catalyzer is Indian red, sodium hydroxide solution, the vitriol oil, hydrogen peroxide, ammonium chloride, the catalyst activity is not high or corrodibility is bigger, and is not easy to operate; And the catalyzer add-on accounts for the 10%-30% of thermosetting epoxy resin and matrix material quality thereof, and catalyst levels is too big.
Summary of the invention
The method that the purpose of this invention is to provide a kind of high-temperature water phase decomposition thermosetting epoxy resin or its matrix material.
The method of the present invention's a kind of high-temperature water phase decomposition thermosetting epoxy resin or its matrix material is characterized in that having following process and step:
A. at first thermosetting epoxy resin or its matrix material are ground into the sheet stock or the particulate material of a certain size size, a certain amount of thermosetting epoxy resin or its matrix material are added in the High Temperature High Pressure stainless steel cauldron with deionized water, add a certain amount of catalyzer subsequently; The weight ratio of thermosetting epoxy resin or its matrix material and deionized water add-on is 1: 1～1: 10; Described catalyzer is 12-phospho-wolframic acid or 12-tungstosilicic acid or the 12-copper molybdophosphate in the heteropllyacids; Perhaps above-mentioned heteropolyacid salt; The add-on of catalyzer heteropolyacid is 0.1～3.0% of a deionized water add-on;
B. will put into heating kettle after the aforesaid reaction vessel sealing, heat temperature raising, Heating temperature is 250～370 ℃, the reacting by heating time is 30～120 minutes; Make its abundant water decomposition reaction; What degradation production is become be insoluble to liquid phase is easy to isolating oligopolymer or monomeric substance.
The characteristics of the inventive method are to have adopted heteropolyacid as catalyzer.Heteropolyacid is the polyacid that contains different acid anhydrides.Be the verdant shape, cage is to pile up by oxo bridge with 12 molybdenums or tungsten to form, and the cage center is the non-metallic atom (as phosphorus, arsenic, silicon etc.) of another kind of acid anhydrides; This non-metallic element is connected with all around molybdenum or tungsten by oxo bridge again.For example 12-tungstophosphoric acid, 12-tungstosilicic acid, 12-molybdophosphate etc.The acidity of heteropolyacid is better than traditional inorganic acids, and has oxidation-reduction quality, by changing molecular composition, can regulate strength of acid and redox property, is a kind of multifunctional novel catalyzer.The heteropolyacid good stability, low temperature high activity can be made homogeneous phase and inhomogeneous reaction, even can make phase-transfer catalyst, and environmentally safe is the coming green catalyst of a class.Their molecular formula is:
The molecular formula of 12-phospho-wolframic acid is H
3PO
412WO
3X H
2O, or H
3[P (W
12O
40)] X H
2O;
The molecular formula of 12-tungstosilicic acid is H
4SiO
412WO
3X H
2O, or H
4[Si (W
12O
40)] X H
2O;
The molecular formula of 12-molybdophosphate is H
3PO
412MoO
3X H
2O, or H
3[P (Wo
12O
40)] X H
2O;
The advantage of the inventive method is as described below: high-temperature water phase decomposition thermosetting epoxy resin of the present invention or its matrix material, with an organic solvent do not do decomposed solution, and water is as decomposed solution, and cost is low, environmentally safe; The catalyzer heteropoly acid catalysis is active high, is soluble in the aqueous phase, and consumption is few, easy handling, and catalyzer is easy to separate with degradation production, and catalyzer can use repeatedly, continues to be used for decomposing thermoset epoxy resin or its matrix material; Degradation production of the present invention is insoluble to the liquid phase decomposed solution, be easy to separate, degradation production is oligopolymer or monomer, and major part is the homologue of substituted benzene or phenol, be mainly phenol, p-methyl phenol, australol, dihydroxyphenyl propane etc., can be used as industrial chemicals through separation and utilize once more; After matrix material decomposed, solid products such as glass fibre were deposited in the decomposed solution, and glass fibre is recyclable.Thermosetting epoxy resin rate of decomposition of the present invention is up to 100%, and its matrix material all decomposes except that glass fibre.Technical process of the present invention is simple, and the decomposition efficiency height is a kind of decomposition recovery thermosetting epoxy resin of high-efficiency environment friendly and the method for matrix material thereof.
Embodiment
Embodiment 1: the process and the step of present embodiment are as described below: adopt through amine curing agent solidified glycidyl ether type dihydroxyphenyl propane thermosetting epoxy resin, at first be cut to the rectangle small pieces of 1 * 1cm, take by weighing the 100 above-mentioned thermosetting epoxy resins of gram and 500 gram deionized waters are incorporated in the high temperature high voltage resistant stainless steel cauldron, add catalyzer 12-phospho-wolframic acid 2.5 gram subsequently again.To put into heating kettle after the aforesaid reaction vessel sealing, heat temperature raising, Heating temperature is 350 ℃, the reacting by heating time is 30 minutes, makes its abundant water decomposition reaction.
Adopt glass fiber reinforced epoxy resin matrix material 100 grams, going into 500 gram deionized waters and 2.5 gram catalyzer 12-phospho-wolframic acids, under above-mentioned similarity condition, do same test, then accounting for whole matrix material massfractions by Resins, epoxy is 61.7%, epoxy resin content is 61.7%, and content of glass fiber is 38.3 grams.The resin of this moment and the ratio of water are 1: 8.1.
Embodiment 2: the process and the step of present embodiment are as described below: adopt E-51/ quadrol thermosetting epoxy resin, at first be cut to the rectangle small pieces of 1 * 1cm, take by weighing the 100 above-mentioned thermosetting epoxy resins of gram and 500 gram deionized waters are incorporated in the high temperature high voltage resistant stainless steel cauldron, add catalyzer 12-phospho-wolframic acid 2.5 gram subsequently again; To put into heating kettle after the aforesaid reaction vessel sealing, heat temperature raising, Heating temperature is 250 ℃ to 370 ℃, is divided into into 8 temperature class by 20 ℃ at every interval, measures the rate of decomposition of the Resins, epoxy of each temperature spot respectively.
Measurement result is listed in the table below 1:
The Resins, epoxy rate of decomposition of each temperature spot of table 1
| Decomposition temperature/℃ | Resolving time/min | Rate of decomposition/% |
| 250 | 60 | 24.7 |
| 270 | 60 | 71.2 |
| 290 | 60 | 74.8 |
| 310 | 60 | 85.1 |
| 330 | 60 | 93.5 |
| 350 | 60 | 100 |
| 350 | 30 | 92.3 |
| 370 | 30 | 100 |
Embodiment 3
The process and the step of present embodiment are as described below:
Adopt E-51/ quadrol thermosetting epoxy resin, at first be cut to the rectangle small pieces of 1 * 1cm, take by weighing 100 the gram above-mentioned thermosetting epoxy resins and 500 the gram deionized waters be incorporated in the high temperature high voltage resistant stainless steel cauldron, add phosphate-tungstic acid 2.5 grams or tungstosilicic acid 2.5 grams or molybdophosphate 2.5 grams subsequently again, do the test of three kinds of different catalysts respectively; To put into heating kettle after the aforesaid reaction vessel sealing, heat temperature raising, Heating temperature is 270 ℃, the reacting by heating time is 30 minutes, measures the rate of decomposition of the thermosetting epoxy resin under the different catalysts condition.
Measurement result is listed in the table below 2:
Resins, epoxy rate of decomposition under the variant catalyzer condition of table 2
| Catalyst type | Rate of decomposition/% |
| Do not add catalyzer | 55.2 |
| Tungstosilicic acid | 64.9 |
| Molybdophosphate | 65.4 |
| Phospho-wolframic acid | 72.7 |
Claims (1)
1. the method for a high-temperature water phase decomposition thermosetting epoxy resin or its matrix material is characterized in that having following process and step:
A. at first thermosetting epoxy resin or its matrix material are ground into the sheet stock or the particulate material of a certain size size, a certain amount of thermosetting epoxy resin or its matrix material are added in the High Temperature High Pressure stainless steel cauldron with deionized water, add a certain amount of catalyzer subsequently; The weight ratio of thermosetting epoxy resin or its matrix material and deionized water add-on is 1: 1～1: 10; Described catalyzer is 12-phospho-wolframic acid or 12-tungstosilicic acid or the 12-copper molybdophosphate in the heteropllyacids; Perhaps above-mentioned heteropolyacid salt; The add-on of catalyzer heteropolyacid is 0.1～3.0% of a deionized water add-on;
B. will put into heating kettle after the aforesaid reaction vessel sealing, heat temperature raising, Heating temperature is 250～370 ℃, the reacting by heating time is 30～120 minutes; Make its abundant water decomposition reaction; What degradation production is become be insoluble to liquid phase is easy to isolating oligopolymer or monomeric substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100465243A CN101519505B (en) | 2009-02-24 | 2009-02-24 | Method for decomposing thermosetting epoxy resin or composite material thereof by high-temperature water phase |
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|---|---|---|---|
| CN2009100465243A CN101519505B (en) | 2009-02-24 | 2009-02-24 | Method for decomposing thermosetting epoxy resin or composite material thereof by high-temperature water phase |
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| CN101519505B true CN101519505B (en) | 2011-06-08 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928406B (en) * | 2010-09-02 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for catalytically decomposing carbon fiber-reinforced thermosetting epoxy resin composite material |
| CN102532947B (en) * | 2012-01-13 | 2013-12-04 | 同济大学 | Method for modifying nonmetallic metal powder of scrap circuit boards |
| CN103172905A (en) * | 2012-09-28 | 2013-06-26 | 上海大学 | Method for degrading thermosetting epoxide resin and composite material thereof by using phenols organic phase |
| CN103275350B (en) * | 2013-05-20 | 2016-09-28 | 中国科学院长春应用化学研究所 | The method of epoxy resin/fiber composite material pretreatment layering |
| CN104530390A (en) | 2014-12-11 | 2015-04-22 | 广东生益科技股份有限公司 | Degradable resin composition, as well as prepreg, laminated board and copper-clad plate using degradable resin composition, and degradation method of degradable resin composition |
| CN107400255A (en) * | 2017-08-31 | 2017-11-28 | 江苏中信世纪新材料有限公司 | Method of the organic salt as catalyst chemical degraded epoxy resin |
| CN109518264B (en) * | 2018-11-09 | 2020-03-10 | 深圳大学 | Electro-catalysis heterogeneous catalysis recovery device based on CFRP material and control method thereof |
Citations (2)
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|---|---|---|---|---|
| CN1483754A (en) * | 2003-07-30 | 2004-03-24 | 哈尔滨工业大学 | Chenical recovery method for thermosetting epoxy compound material |
| WO2006051663A1 (en) * | 2004-11-09 | 2006-05-18 | Sumitomo Bakelite Company Limited | Decomposition reaction apparatus, system for producing raw material for recycled resin composition, method for producing raw material for recycled resin composition, raw material for recycled resin composition, and formed article |
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2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483754A (en) * | 2003-07-30 | 2004-03-24 | 哈尔滨工业大学 | Chenical recovery method for thermosetting epoxy compound material |
| WO2006051663A1 (en) * | 2004-11-09 | 2006-05-18 | Sumitomo Bakelite Company Limited | Decomposition reaction apparatus, system for producing raw material for recycled resin composition, method for producing raw material for recycled resin composition, raw material for recycled resin composition, and formed article |
Non-Patent Citations (1)
| Title |
|---|
| 陈晋阳,金鹿江,褚燕萍,刘桂阳.杂多酸催化废尼龙水解再资源化的研究.《现代化工》.2007,第27卷243-244. * |
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