CN104592546B - A kind of method for recycling waste and old carbon fiber/epoxy resin composite material - Google Patents

A kind of method for recycling waste and old carbon fiber/epoxy resin composite material Download PDF

Info

Publication number
CN104592546B
CN104592546B CN201410834413.XA CN201410834413A CN104592546B CN 104592546 B CN104592546 B CN 104592546B CN 201410834413 A CN201410834413 A CN 201410834413A CN 104592546 B CN104592546 B CN 104592546B
Authority
CN
China
Prior art keywords
epoxy resin
carbon fiber
acid
waste
resin composite
Prior art date
Application number
CN201410834413.XA
Other languages
Chinese (zh)
Other versions
CN104592546A (en
Inventor
秦岩
许亚丰
邹镇岳
李洋
陈林锴
Original Assignee
武汉理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 武汉理工大学 filed Critical 武汉理工大学
Priority to CN201410834413.XA priority Critical patent/CN104592546B/en
Publication of CN104592546A publication Critical patent/CN104592546A/en
Application granted granted Critical
Publication of CN104592546B publication Critical patent/CN104592546B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J11/00Recovery or working-up of waste materials
    • C08J11/04Recovery or working-up of waste materials of polymers
    • C08J11/10Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/24Thermosetting resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • Y02W30/705

Abstract

The method of the waste and old carbon fiber/epoxy resin composite material of recycling provided by the invention, it is that one kind recycles waste and old carbon fiber/epoxy resin composite material using solvent method combination pressure method, overall process only needs a step, with inorganic acid and the composite acid of organic acid, the combination solvent of organic solvent and combine oxidant and handle waste and old carbon fiber/epoxy resin composite material at high temperature under high pressure, the few carbon fiber of the cull of isolated surface no significant defect.The method of the present invention step is succinct efficiently, clean environment firendly.

Description

A kind of method for recycling waste and old carbon fiber/epoxy resin composite material

Technical field

The invention belongs to macromolecule recovery technology field, is related to a kind of method for recycling same with thermosetting compound material, especially relates to And be a kind of method that solvent method combination pressure method recycles waste and old carbon fiber/epoxy resin composite material.

Background technology

Carbon fiber/epoxy resin composite material be widely used in national defence, military project, aerospace, building, communications and transportation with The multiple fields such as the energy, and emerging field is constantly extended to, such as:In hydrogen storage method, the full wound composite of high pressure Cylinder is to apply most common selection at present.As application of such composite material in these high frontiers increases rapidly, institute The junk of generation is growing day by day, but the recycling and reuse present situation to carbon fiber epoxy based composites is not allowed to find pleasure in See, if without recycling huge pollution will be brought to environment.In addition, containing big in carbon fiber/epoxy resin composite material Expensive carbon fiber is measured, the recycling work for carrying out waste and old CF/EP composite materials has larger economic implications, its time Renewable resources are received gradually to attract attention.

At present, domestic and international traditional processing same with thermosetting compound material has following three kinds of approach:

(1) Material Physics crushes, its waste material recycled is included into the composite material of a new generation;

(2) then chemical recovery (such as passing through pyrolysis), the wherein recycling of polymer can use as organic compound As a kind of chemical raw material;

(3) energy regenerating, is effectively utilized the calorie in composite material by way of burning.It is wherein traditional The main method of Treatment of Carbon reinforced epoxy discarded object is burial and burning, mechanical crushing absorption method.Attempt pyrolysismethod, Degrading solvent method (such as:Solidified resin can be dissolved in organic solvent by acid treatment, and Dang et al. has found Bisphenol F epoxy Resin can decompose in salpeter solution completely, and the product of decomposition polymerize generation regenerating resin again with epoxy resin and curing agent) Deng.

Above-mentioned three kinds of methods are cumbersome there are technique, and return period is longer, high energy consumption, the carbon fiber of recycling there are length compared with Small, the shortcomings of surface residue is more, performance loss is larger.

The content of the invention

The technical problems to be solved by the invention are:A kind of solvent method combination pressure method is provided and recycles waste and old carbon fiber/ring The method of epoxy resin composite material, one step of this method are completed, and can overcome above-mentioned the deficiencies in the prior art.

The present invention solves its technical problem and uses following technical solution:

The method of the waste and old carbon fiber/epoxy resin composite material of recycling provided by the invention, is that one kind utilizes solvent method group Combined pressure force method receives waste and old carbon fiber/epoxy resin composite material back and forth, and overall process only needs a step, with the group of inorganic acid and organic acid It is compound that conjunction acid, the combination solvent of organic solvent and combination oxidant handle waste and old carbon fiber/epoxy resin at high temperature under high pressure Material, obtains separable carbon fiber and degradation solution.

The method of the waste and old carbon fiber/epoxy resin composite material of recycling, comprises the following steps:

(1) waste and old carbon fiber/epoxy resin composite material is cut into suitable size, it is spare;

(2) it is put into reaction kettle, adds inorganic acid and the composite acid of organic acid, the combination solvent of organic solvent and combine Oxidant, 1.0-2.5h is heated in the case where temperature is 80-180 DEG C, pressure is 1.0-1.4Mp;

(3) centrifuge separation carbon fiber and solution are utilized;

(4) carbon fiber washed, be dried to obtain recovery product.

In step (1), in the waste and old carbon fiber/epoxy resin composite material, reinforcement carbon fiber is fine for PAN bases carbon One kind in dimension, viscose base carbon fibre, asphalt base carbon fiber.

In step (1), in the waste and old carbon fiber/epoxy resin composite material, matrix epoxy resin is sweet using shrinking Oily ether type epoxy resins, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic same clan asphalt mixtures modified by epoxy resin One kind in fat, finger ring same clan epoxy resin.

In step (1), in the waste and old carbon fiber/epoxy resin composite material, using curing agent to matrix asphalt mixtures modified by epoxy resin Fat carry out crosslinking curing, the curing agent using diethylenetriamine, triethylene tetramine, polyethylene polyamine, N, N- diethylaminopropylamines, One kind in polyetheramine, polyamide, or several mixtures.

In step (2), the inorganic acid is using one kind in nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid.

In step (2), the organic acid is using one kind in carboxylic acid, sulfonic acid, sulfinic acid, thionothiolic acid.

In step (2), the combination solvent of the organic solvent is using in toluene, dimethylbenzene, acetone, ethers, alcohols Two or more.

In step (2), the combination oxidant is using in hydrogen peroxide, nitrate, more nitro compounds, potassium permanganate Two or more.

The obtained recovery product of the method for the present invention, the degradation rate of its epoxy resin is >=90%.

The method that the present invention recycles waste and old carbon fiber/epoxy resin composite material using solvent method combination pressure method, with biography System other methods, which are compared, to be had the advantage that:

1. it is the waste and old carbon fiber/epoxy resin composite material processing time is short of recycling, efficient, before there are industrial applications Scape.

2. one-step method is completed, technique is simple.

3. the degradation rate of resin is high (up to more than 90%).

4. recycling obtained carbon fiber strength retains high, surface no significant defect.

In short, the method for the present invention step is succinct efficiently, clean environment firendly, it is ensured that isolated surface no significant defect The few carbon fiber of cull.

Embodiment

The present invention uses solvent method combination pressure method, it is with the combination of inorganic acid and the composite acid, organic solvent of organic acid Solvent and combination oxidant handle waste and old carbon fiber/epoxy resin composite material at high temperature under high pressure, obtain separable carbon Fiber and degradation solution.The method adds high pressure on the basis of degrading solvent method, reduces the reaction time, improves degraded effect Fruit, it is possible to increase the treating capacity of waste and old composite material, recycles more complete carbon fiber (the surface resin drop for the carbon fiber that recycling obtains Solution rate can reach more than 90%, and fibre strength is more than the 90% of pristine fibre, can be compound again with epoxy resin).

With reference to example, the present invention is further elaborated, but present disclosure is not limited solely to following implementation and shows Example.

Embodiment 1:

Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare;It is put into 200ml reaction kettles In, 20ml volume fractions are added as 70% aqueous acetic acid, 20ml concentrated phosphoric acids, 20ml acetone, 20ml benzene, 20ml30% peroxidating Hydrogen, 20g dibastic sodium phosphates;Degrade 2.5h under 180 DEG C, 1.4Mp;Carbon fiber and solution are separated by filtration, by solid product acetone Wash, be then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the degradation rate of epoxy resin is 93.13%.

Embodiment 2:

Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare;It is put into 200ml reaction kettles In, 20ml volume fractions are added as 70% aqueous acetic acid, 20m concentrated phosphoric acids, 20ml dimethyl ether, 20ml benzene, 20ml30% peroxides Change hydrogen, 20g sodium nitrate;Degrade 2.5h under 180 DEG C, 1.4Mp;Carbon fiber and solution are separated by filtration, by solid product acetone Wash, be then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the degradation rate of epoxy resin is 90.78%.

Embodiment 3:

Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare;It is put into 200ml reaction kettles In, 20ml volume fractions are added as 70% aqueous acetic acid, the 20ml concentrated sulfuric acids, 20ml acetone, 20ml benzene, 20ml30% peroxidating Hydrogen, 20g sodium nitrate;Degrade 2h under 120 DEG C, 1.0Mp;Carbon fiber and solution are separated by filtration, solid product is washed with acetone, It is then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the degradation rate of epoxy resin is 88.34%.

Embodiment 4:

Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare;It is put into 200ml reaction kettles In, add 20ml concentrated nitric acids, 20ml mass fractions are 37% hydrochloric acid, 20ml acetone, 20ml benzene, 20ml30% hydrogen peroxide, 20g Dibastic sodium phosphate;Degrade 1.5h under 180 DEG C, 1.0Mp;Carbon fiber and solution are separated by filtration, solid product is washed with acetone, so The carbon fiber that dry 12h is recycled at 80 DEG C of baking oven is put into afterwards.By test, the degradation rate of epoxy resin is 83.89%.

Embodiment 5:

Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare;It is put into 200ml reaction kettles In, addition 20ml volume fractions are 70% aqueous acetic acid, 20ml mass fractions are 37% hydrochloric acid, 20ml acetone, 20ml diformazans Ether, 20g sodium nitrate, 20g dibastic sodium phosphates;Degrade 2h under 120 DEG C, 1.0Mp;Carbon fiber and solution are separated by filtration, solid is produced Thing is washed with acetone, is then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the drop of epoxy resin Solution rate is 83.67%.

Claims (6)

  1. A kind of 1. method for recycling waste and old carbon fiber/epoxy resin composite material, it is characterized in that a kind of utilize solvent method combination pressure Force method recycles waste and old carbon fiber/epoxy resin composite material, and overall process only needs a step, with the combination of inorganic acid and organic acid Acid, the combination solvent of organic solvent and combination oxidant handle waste and old carbon fiber/epoxy resin composite wood at high temperature under high pressure Material, obtains separable carbon fiber and degradation solution;The combination oxidant is using hydrogen peroxide, nitrate, more nitro compounds Two or more in thing, potassium permanganate;
    In the waste and old carbon fiber/epoxy resin composite material, reinforcement carbon fiber is PAN base carbon fibres, viscose base carbon is fine One kind in dimension, asphalt base carbon fiber;
    In the waste and old carbon fiber/epoxy resin composite material, matrix epoxy resin using glycidyl ether type epoxy resin, Glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic same clan epoxy resin, alicyclic ring same clan asphalt mixtures modified by epoxy resin One kind in fat;
    In the waste and old carbon fiber/epoxy resin composite material, crosslinking curing is carried out to matrix epoxy resin using curing agent, The curing agent is using diethylenetriamine, triethylene tetramine, polyethylene polyamine, N, in N- diethylaminopropylamines, polyetheramine, polyamide One kind, or several mixture.
  2. 2. according to the method described in claim 1, it is characterized in that comprise the following steps:
    (1) waste and old carbon fiber/epoxy resin composite material is cut into suitable size, it is spare;
    (2) it is put into reaction kettle, adds inorganic acid and the composite acid of organic acid, the combination solvent of organic solvent and combine oxidation Agent, 1.0-2.5h is heated in the case where temperature is 80-180 DEG C, pressure is 1.0-1.4Mp;
    (3) centrifuge separation carbon fiber and solution are utilized;
    (4) carbon fiber washed, be dried to obtain recovery product.
  3. 3. according to the method described in claim 2, it is characterized in that in step (2), the inorganic acid is using nitric acid, phosphoric acid, salt One kind in acid, sulfuric acid.
  4. 4. according to the method described in claim 2, it is characterized in that in step (2), the organic acid is using carboxylic acid, sulfonic acid, Asia One kind in sulfonic acid, thionothiolic acid.
  5. 5. according to the method described in claim 2, it is characterized in that in step (2), the combination solvent of the organic solvent uses Two or more in toluene, dimethylbenzene, acetone, ethers, alcohols.
  6. 6. according to the method described in claim 2, it is characterized in that obtained recovery product, the degradation rate of its epoxy resin are >=90%.
CN201410834413.XA 2014-12-29 2014-12-29 A kind of method for recycling waste and old carbon fiber/epoxy resin composite material CN104592546B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410834413.XA CN104592546B (en) 2014-12-29 2014-12-29 A kind of method for recycling waste and old carbon fiber/epoxy resin composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410834413.XA CN104592546B (en) 2014-12-29 2014-12-29 A kind of method for recycling waste and old carbon fiber/epoxy resin composite material

Publications (2)

Publication Number Publication Date
CN104592546A CN104592546A (en) 2015-05-06
CN104592546B true CN104592546B (en) 2018-04-27

Family

ID=53118631

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410834413.XA CN104592546B (en) 2014-12-29 2014-12-29 A kind of method for recycling waste and old carbon fiber/epoxy resin composite material

Country Status (1)

Country Link
CN (1) CN104592546B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016177305A1 (en) * 2015-05-01 2016-11-10 Adesso Advanced Materials Wuxi Co., Ltd. Methods for degrading and recycling cross-linked polymers and reinforced polymer composites
KR101801788B1 (en) * 2015-12-11 2017-11-28 한국과학기술연구원 Method and apparatus for recovering fiber assembly from thermosetting resin composite materials and recovered fiber assembly
CN107082557A (en) * 2016-02-15 2017-08-22 山东理工大学 A kind of glass fibre reinforced composion castoff regenerative glass fibre method
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
CN107082584A (en) * 2016-02-15 2017-08-22 山东理工大学 A kind of carbon fibre reinforced composite castoff regenerative carbon fiber method
CN107082582A (en) * 2016-02-15 2017-08-22 山东理工大学 A kind of method that fiberglass fibers waste silk prepares electroconductive glass fibre
CN107082626A (en) * 2016-02-15 2017-08-22 山东理工大学 A kind of method for comprehensively utilizing carbon fibre reinforced composite and red mud discarded object
CN107082581A (en) * 2016-02-15 2017-08-22 山东理工大学 A kind of method of glass fiber waste silk or product normal temperature and pressure repeat glass fiber
CN108359233A (en) * 2017-07-28 2018-08-03 安徽旭升新材料有限公司 A kind of waste material continuously enhances thermoplastic carbon fiber composite wood and preparation method thereof
CN108640699A (en) * 2018-04-28 2018-10-12 中国人民解放军国防科技大学 A kind of method that carbon fiber enhancement resin base composite material recycling prepares carbon/carbon preform
CN109897216A (en) * 2019-03-15 2019-06-18 四川大学 A kind of recoverying and utilizing method of waste and old thermosetting resin and its composite material
CN110757682A (en) * 2019-10-29 2020-02-07 中国科学院山西煤炭化学研究所 Method for recycling waste circuit boards in full-component mode through two-step method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391543A (en) * 2011-09-02 2012-03-28 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
CN102558603A (en) * 2012-01-13 2012-07-11 同济大学 Method for one-step recovery and modification of carbon fiber
CN102731821A (en) * 2012-07-06 2012-10-17 中国科学院宁波材料技术与工程研究所 Recovery method of carbon-fiber reinforced epoxy composites

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391543A (en) * 2011-09-02 2012-03-28 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
CN102558603A (en) * 2012-01-13 2012-07-11 同济大学 Method for one-step recovery and modification of carbon fiber
CN102731821A (en) * 2012-07-06 2012-10-17 中国科学院宁波材料技术与工程研究所 Recovery method of carbon-fiber reinforced epoxy composites

Also Published As

Publication number Publication date
CN104592546A (en) 2015-05-06

Similar Documents

Publication Publication Date Title
Piñero-Hernanz et al. Chemical recycling of carbon fibre reinforced composites in nearcritical and supercritical water
CN102399201B (en) Method for preparing 5-hydroxymethylfurfural by solid acid catalysis
Zhang et al. Preparation of a lignin-based vitrimer material and its potential use for recoverable adhesives
Morin et al. Near-and supercritical solvolysis of carbon fibre reinforced polymers (CFRPs) for recycling carbon fibers as a valuable resource: State of the art
CN102275200B (en) A kind of manufacture method of bamboo-fiber composite section
CN101633225B (en) Method for preparing composite board by waste thermosetting foamed plastics
CA2426803C (en) Method for extracting nylon from waste materials
CN100365068C (en) Environment friendly lignin resin of high water absorbence and its preparation method
Kuang et al. Recycling of epoxy thermoset and composites via good solvent assisted and small molecules participated exchange reactions
Yuyan et al. Recycling of carbon fibre reinforced composites using water in subcritical conditions
WO2008023040A3 (en) Acrylic acid based on renewable raw materials, water-absorbing polymer structures, and method for the production thereof by means of dehydration
CN102795873A (en) Method for interface modification of carbon/carbon composite material by graphene/polymer coating
Liu et al. Mild chemical recycling of aerospace fiber/epoxy composite wastes and utilization of the decomposed resin
CN104045986B (en) Unsaturated polyester resin composite material for furniture and preparation method thereof
CN1927443A (en) Ureaformaldehyde resin coating epoxy microcapsule for material self-repair and preparing method thereof
Liu et al. Chemical recycling of carbon fibre reinforced epoxy resin composites in subcritical water: synergistic effect of phenol and KOH on the decomposition efficiency
CN107189354B (en) A kind of preparation method of graphene nanometer sheet enhancing carbon fibre composite
CN103951830B (en) A kind of preparation method of hyper-branched polyester graft modification sisal cellulose crystallite
CN103897213B (en) A kind of carbon fiber enhancement resin base composite material recovery method with pretreatment mode
CN102181160A (en) Environmentally-friendly biomass compound rubber regenerant and preparation method thereof
WO2014143657A1 (en) Method of converting lignin and uses thereof
CN105622983B (en) A kind of preparation method of heat-conducting plastic special graphite alkene microplate
CN103665427B (en) The method of carbon fiber is reclaimed in a kind of waste carbon fibre composite cracking
CN105152674A (en) Preparation method of pantograph slide plate made of graphene modified carbon/carbon composite material
Nie et al. Decomposition of waste carbon fiber reinforced epoxy resin composites in molten potassium hydroxide

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
GR01 Patent grant