CN1213096C - Chenical recovery method for thermosetting epoxy compound material - Google Patents

Chenical recovery method for thermosetting epoxy compound material Download PDF

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Publication number
CN1213096C
CN1213096C CNB031325424A CN03132542A CN1213096C CN 1213096 C CN1213096 C CN 1213096C CN B031325424 A CNB031325424 A CN B031325424A CN 03132542 A CN03132542 A CN 03132542A CN 1213096 C CN1213096 C CN 1213096C
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CN
China
Prior art keywords
fiber
epoxy
resins
degraded
recovery
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CNB031325424A
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Chinese (zh)
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CN1483754A (en
Inventor
刘宇艳
孟令辉
黄玉东
党伟荣
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哈尔滨工业大学
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Priority to CNB031325424A priority Critical patent/CN1213096C/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/141Feedstock
    • Y02P20/143Feedstock the feedstock being recycled material, e.g. plastics
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling

Abstract

The present invention provides a chemical recovering method for waste and old composite materials of epoxy resin. The composite materials are put into nitric acid solution of 2 mol/l to 8 mol/l by the method and are heated so that the epoxy resin is decomposed under an ordinary pressure. A liquid phase is a katabolite of the epoxy resin. A solid phase is an undissolved fiber which is separated to be washed and dried. The obtained recovered fiber has the advantages of clean appearance, no defect on the surface and capability of reutilization. The present invention has the advantages of mild reaction condition, simple technology, low cost and high product recovery rate. The problem that the current composite materials of epoxy resin are recovered difficultly is solved by the present invention. The recovering method of dissolving matrix resin, recovering fibers and filtering the katabolite separated by crystallization is adopted by the present invention. The method has the advantages of simple technological flow, no courses of a high temperature and a high pressure, simple equipment and high decomposition efficiency, and can realize the 100 percent recovery of reinforced fibers.

Description

A kind of chemical recovery method of thermoset epoxy matrix material
Technical field: the present invention relates to a kind of recovery method of waste epoxy resin matrix material, particularly a kind of recovery method of amine curing agent solidified epoxy systems reinforced composite materials.
Background technology: Resins, epoxy and matrix material thereof have light weight, good corrosion resistance, electrical property excellence, material source is extensive, machine-shaping is easy, production efficiency is high and have characteristics such as material designability, be widely used in every field such as electronic industry, automotive industry, physical culture industry, aerospace, its consumption increases just year by year fast.But these materials can produce a large amount of depleted epoxy composite materials after surpassing life cycle.Epoxy composite material is molten and can not be made the difficult problem that is treated as of waste and scrap by the characteristic of microbiological degradation.And other fiber reinforced material of the carbon fiber in the matrix material and some is recycled and is worth greatly.Therefore, consider from the angle of environment protection and renewable resources, the recycle of epoxy composite material have great reality with the potential meaning.At present, the recovery method of Resins, epoxy is the physics circulation method.After being about to heat cured Resins, epoxy pulverizing, as the filler of other systems.Studies show that, compare with original Resins, epoxy, mix 20% cycle stock after, the flexural strength of material and shock strength all have significantly and reduce.S.R.Farber has studied a kind of resin extractor, can be from Resins, epoxy preimpregnation waste material mechanical separation matrix resin and fiber.Pannkoke etc. have studied the method for utilizing low temperature to reclaim Resins, epoxy preimpregnation waste material.L.Monney etc. study the possibility of electrochemical degradation epoxy resin composite material with x-ray analysis, infrared spectroscopy.After the copper of circuit card (glass fibre/epoxy) is removed by Peninsula Copper industrial, calcine to remove epoxy adhesive, obtain not having the glasscloth of resin, these fibers are cut into the staple fibre of certain-length, can be used for the enhancing body of thermosetting polyester resin.U.S. Brooklyn polytechnical university research and utilization cracking process reclaims the carbon fiber of prepreg, carries out thermo-cracking at 300~600 ℃ and reclaims raw material and carbon fiber, and the carbon fiber of recovery is as soil improvement agent, and products such as gas, oil content are as fuel.Carbon fiber is very expensive material, can recover from matrix material through three grades of chemical cycle.It is reported, the matrix material waste material or the prepreg (inefficacy) that reclaim are seated in the dull and stereotyped reactor, under heat and catalyst action, polymer can be transformed into low-molecular-weight hydrocarbon compound, obtain oily matter after removing fiber and gas, can make chemical feedstocks or monomer, also can be used as fuel.Switching process very fast (5min/200 ℃), whole process is pollution-free, and the carbon fiber that obtains is recycling.This method does not also still have widespread use, and domestic do not have this technology especially.And these methods also are not suitable for the solidified epoxy composite material.The chemical cycle method of the Resins, epoxy of research and matrix material thereof all has limitation separately at present.Most cost recovery height, the equipment complexity, recovering effect is also not ideal enough.
Summary of the invention: reclaim difficult problem for solving present epoxy resin composite material, the invention provides a kind of chemical recovery method of thermoset epoxy matrix material.The present invention carries out as follows: one, the amine curing agent solidified epoxy systems reinforced composite materials of collecting is cut and cleaned; Two, above-mentioned materials is put into the Glass Containers that has prolong, and put into the salpeter solution that concentration is 2mol/l~8mol/l in container, the ratio of above-mentioned solid material and salpeter solution is (5~20) g:100ml; Three, system is heated to 70~90 ℃, decomposes fully up to Resins, epoxy, and this moment, liquid phase was the degraded product of Resins, epoxy, and solid phase is insoluble fiber; Four, taking out fiber cleans and dries; Five, for liquid filtration, remove solid impurity, be cooled to 0~20 ℃ then, crystallization is separated out and is obtained low-molecular-weight degraded product.Adopt industrial acetone to clean fiber in said process, the remaining decomposed solution on the flush away fiber and the Resins, epoxy of degraded obtain clean fiber after the oven dry, reach the purpose of recycled fiber.The present invention adopts dissolution method that Resins, epoxy and matrix material thereof are reclaimed, and makes Resins, epoxy be degraded to the solubility oligopolymer, then with insoluble fiber separation.The present invention adopts dissolving matrix resin, recycled fiber, filtering for crystallizing to separate out the recovery method of degraded product.Present method technical process is simple, does not have the High Temperature High Pressure process, and equipment is simple, the decomposition efficiency height; Can realize that fortifying fibre 100% reclaims.
Embodiment one: the raw material of present embodiment is the glass fiber reinforcement epoxy matrix material, and resin system is EP/IPDA, and resin content is 31.6%.After the matrix material cleaning, put into the Glass tubing that diameter is 10cm, inject the 100ml aqueous nitric acid.Glass tubing is put in the water bath with thermostatic control constant temperature.Decompose recovering condition and see Table 1.Change the ratio of the temperature, concentration, matrix material and the decomposed solution that reclaim decomposed solution, it is also inequality that Resins, epoxy decomposes the required time fully.Treat that resin decomposes the back fully and takes out Glass tubing, from the solution of Glass tubing, take out fiber.Clean fiber repeatedly with industrial acetone, the remaining decomposed solution on the flush away fiber and the resin of degraded, oven dry obtains clean fiber.To liquid filtration, remove solid impurity again, be cooled to 10 ℃ then, crystallization is separated out and is obtained low-molecular-weight degraded product.Fiber after reclaiming is made scanning electron microscope test, observe the surface topography of fiber, find the fiber clean appearance of recovery, the surface does not have defective.The glass fibre that reclaims under protofibril before reclaiming and each decomposition condition of table 1 has been carried out filament stretch test (table 2), decline to some extent before the monofilament tensile strength ratio of discovery recovery back fiber reclaims, maximum strength loss is 15.14%, and is recycling.From top test as can be seen, the processing required time of test 1 is short, and glass fiber strength descends 5.19%, is top condition.
Utilize analysis technology such as infrared spectra, gas chromatography-mass spectrometry machine, liquid phase chromatogram-mass spectrometry combination machine, gel chromatography to determine the composition of Resins, epoxy degradation production.The result shows: the main component of degraded product is the low-molecular-weight nitro-compound that contains phenyl ring.
The recovering condition of table 1 glass fibre/epoxy composite material
Glass fibre monofilament tensile strength before and after table 2 reclaims
Test number Precursor ?1 ?2 ?3 ?4 ?5 ?6 ?7 ?8 ?9
Monofilament tensile strength (MPa) 3560 ?3375 ?3192 ?3036 ?3190 ?3144 ?3021 ?3237 ?3437 ?3514
Loss of strength (%) ?5.19 ?10.33 ?14.72 ?10.39 ?11.69 ?15.14 ?9.07 ?3.46 ?1.29
Embodiment two: the raw material of present embodiment is carbon-fibre reinforced O compoiste material, and resin system is EP/IPDA, and resin content is 35.6%.After the matrix material cleaning, put into Glass tubing, inject the 100ml aqueous nitric acid.Glass tubing is put in the water bath with thermostatic control constant temperature.Decompose recovering condition and see Table 3.Change the ratio of the temperature, concentration, matrix material and the decomposed solution that reclaim decomposed solution, it is also inequality that Resins, epoxy decomposes the required time fully.Treat to take out Glass tubing after the resin dissolves, from the solution of Glass tubing, take out fiber.Clean fiber repeatedly with industrial acetone, the remaining decomposed solution on the flush away fiber and the resin of degraded, oven dry obtains clean fiber.For liquid filtration, remove solid impurity again, be cooled to 12 ℃ then, crystallization is separated out and is obtained low-molecular-weight degraded product.Fiber after reclaiming is made scanning electron microscope test, observe the surface topography of fiber, find the fiber clean appearance of recovery, the surface does not have defective.The carbon fiber that reclaims under protofibril before reclaiming and each decomposition condition of table 3 has been carried out filament stretch test (table 4), decline to some extent before the monofilament tensile strength ratio of discovery recovery back fiber reclaims, maximum strength loss is 13.4%, and is recycling.From top test as can be seen, the processing required time of test 1 is short, and fibre strength drops to 1.1%, is top condition.Utilize analysis technology such as infrared spectra, gas chromatography-mass spectrometry machine, liquid phase chromatogram-mass spectrometry combination machine, gel chromatography to determine the composition of degradation production.The result shows: the main component of degraded product is the low-molecular-weight nitro-compound that contains phenyl ring.
The recovering condition of table 3 Carbon Fiber
Carbon fiber monofilament tensile strength before and after table 4 reclaims
Test number Precursor ?1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9
Monofilament tensile strength (MPa) 2610 ?2581 ????2578 ????2259 ????2531 ????2449 ????2402 ????2353 ????2283 ????2278
Loss of strength (%) ?1.1 ????1.2 ????13.4 ????3.1 ????6.2 ????8.0 ????9.8 ????12.5 ????12.7
Embodiment three: the raw material of present embodiment is carbon-fibre reinforced O compoiste material, and resin system is EP/DDM, and resin content is 34.1%.After the matrix material cleaning, put into Glass tubing, inject 8mol/l aqueous nitric acid 100ml.Glass tubing is put in the water bath with thermostatic control 90 ℃ of constant temperature.Resin decomposes fully after 24 hours, takes out fiber from the solution of Glass tubing.Clean fiber repeatedly with industrial acetone, the remaining decomposed solution on the flush away fiber and the resin of degraded, oven dry obtains clean fiber.Reclaim back fibre single thread tensile strength and descend to some extent than before reclaiming, loss of strength is 2.2%, and is recycling.

Claims (2)

1, a kind of chemical recovery method of thermoset epoxy matrix material is characterized in that carrying out as follows: one, the amine curing agent solidified epoxy systems reinforced composite materials of collecting is cut and cleaned; Two, above-mentioned materials is put into the Glass Containers that has prolong, and put into the salpeter solution that concentration is 2mol/l~8mol/l in container, the ratio of above-mentioned solid material and salpeter solution is (5~20) g:100ml; Three, system is heated to 70~90 ℃, decomposes fully up to Resins, epoxy, and this moment, liquid phase was the degraded product of Resins, epoxy, and solid phase is insoluble fiber; Four, taking out fiber cleans and dries; Five, for liquid filtration, remove solid impurity, be cooled to 0~20 ℃ then, crystallization is separated out and is obtained the low degraded product of molecular weight.
2, the chemical recovery method of a kind of thermoset epoxy matrix material according to claim 1, it is characterized in that in said process, adopting industrial acetone to clean fiber, the remaining decomposed solution on the flush away fiber and the Resins, epoxy of degraded obtain clean fiber after the oven dry.
CNB031325424A 2003-07-30 2003-07-30 Chenical recovery method for thermosetting epoxy compound material CN1213096C (en)

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649068B (en) * 2008-08-12 2011-12-14 贵州航天林泉电机有限公司 Epoxy resin dissolving agent and preparing method thereof
CN101407596B (en) * 2008-09-25 2011-08-17 上海第二工业大学 Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board
CN101519505B (en) * 2009-02-24 2011-06-08 上海大学 Method for decomposing thermosetting epoxy resin or composite material thereof by high-temperature water phase
CN101787145B (en) * 2010-03-12 2011-09-21 中国科学院长春应用化学研究所 Method for recovering fiber from epoxy resin/fiber composite material
CN101891902B (en) * 2010-07-23 2012-05-23 浙江理工大学 Method for recycling waste epoxy resin
CN102391543B (en) * 2011-09-02 2013-05-08 中国科学院宁波材料技术与工程研究所 Method for recovering carbon-fiber enhanced epoxy resin composite material
CN102416675B (en) * 2011-10-26 2014-10-08 合肥工业大学 Industrializable waste thermosetting plastic regeneration process and equipment based on mechanical and physical method
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
CN107082586A (en) * 2016-02-15 2017-08-22 山东理工大学 A kind of low energy consumption comprehensive utilizes fiberglass and the method for red mud solid waste
CN106750182B (en) * 2016-12-29 2019-06-14 广东生益科技股份有限公司 A kind of degradable resin composition and its prepreg, laminate and its recovery method of preparation
CN109365487B (en) * 2018-11-30 2020-07-07 清远市进田企业有限公司 Efficient energy-saving cleaning process for epoxy coating in waste circuit board
CN111333905A (en) * 2020-04-20 2020-06-26 中国科学院过程工程研究所 Recovery method of fiber reinforced composite material

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