CN104326907B - A kind of degraded reclaims the method for unsaturated polyester resin material - Google Patents
A kind of degraded reclaims the method for unsaturated polyester resin material Download PDFInfo
- Publication number
- CN104326907B CN104326907B CN201410562107.5A CN201410562107A CN104326907B CN 104326907 B CN104326907 B CN 104326907B CN 201410562107 A CN201410562107 A CN 201410562107A CN 104326907 B CN104326907 B CN 104326907B
- Authority
- CN
- China
- Prior art keywords
- unsaturated polyester
- degraded
- reclaims
- structural unit
- reaction
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of method reclaiming unsaturated polyester resin material of degrading is that catalyzer and reaction solvent are made into reaction soln; Reaction soln mixes with unsaturated polyester material, is made into unsaturated polyester degraded system; The heating of the unsaturated polyester be made into degraded system degraded, in the unsaturated polyester degraded system of cooling, add separation solvent, filter, solid is fortifying fibre and catalyzer, reclaims after drying screening; Filtrate adds water and makes to separate out containing the polymer degradation component of styrol structural unit, filters, the polymer solids dried recovered containing styrol structural unit after filtration; Filtrate evaporate to dryness, the material obtained is not mainly containing the resin degradation product of styrol structural unit.It is low that the present invention has cost, and recovering condition is gentle, the advantage that degrading activity is high.
Description
Technical field
The invention belongs to MAT'L recycling field, be specifically related to a kind of degraded and reclaim the method for unsaturated polyester resin material.
Background technology
Unsaturated polyester resin is a kind of typical thermoset resin material.Thermoset unsaturated polyester resin has excellent mechanical property, electrical insulation capability and resistance to chemical corrosion, and complete processing is easy, is to develop one of kind faster in thermosetting resin.Be widely used in high performance composite at present.A large amount of corner wastes is remained in unsaturated polyester resin and composite product production process thereof, also considerable waste product can be produced in use procedure, how these inertia organism being converted into valuable fine chemicals by relaxing simple technique, is the inevitably challenge that our society faces.
Thermosetting resin and matrix material thereof all have tridimensional network, do not dissolve non-fusible, can not be decomposed by Institute of Micro-biology, and therefore its degraded is recycled and become a difficult problem urgently to be resolved hurrily.At present, mechanical process, heat energy method and the chemical method three kinds of methods that mainly contain process thermosetting resin waste.
Mechanical process be various waste and old matrix material first classified, differentiate, disintegrate, cut off, broken, then obtain rigid particles by technology such as fine-powdered, be used for filling and strengthening other materials.This method not only can be destroyed carbon fiber and glass fibre etc. in thermosetting resin and be worth higher composition, and the performance that twice-laid stuff is obtained is lower, and the added value of recycling is not high yet; Energy recovery method comprises fluidized bed combustion and pyrolytic technique, and the method utilizes high temperature by the destruction of the chemical bond non-selectivity in resin, and resultant kind is complicated, and comprises a large amount of toxic substance.Chemical method utilizes chemical process that thermosetting resin is degraded, and because degradation condition relaxes, effectively can reduce the discharge of toxic gas, and the method is considered to the method that the most promising spent high molecular material reclaims.
For the current effective degradation method of unsaturated polyester material mainly solution chemical edman degradation Edman.As national inventing patent (201210086004.7) utilizes ionic liquid to realize the recovery of unsaturated polyester through catalyst degraded; Patent of invention (201210338567.0) utilizes phenylcarbinol to utilize Tripotassium phosphate to be catalyst degradation 15-25 hour at 190 DEG C, completes the degraded to unsaturated polyester; Patent of invention (95106464.9 again) utilizes dibasic alcohol as degraded solvent, at high temperature under high pressure, is realized the degraded of unsaturated polyester by transesterification reaction.Although above technology can realize the degraded of unsaturated polyester, solvent cost is higher, and reactive behavior is not enough, and solvent boiling point is high, not easily reclaims.These all limit its application in suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of cost low, recovering condition is gentle, and the method for unsaturated polyester resin material is reclaimed in the degraded that degrading activity is high.
After general unsaturated polyester resin is mixed with vinylbenzene by the multipolymer of dibasic alcohol, monounsaturated dicarboxylic acid, unsaturated dibasic acid, heating and catalyzer effect under, the build macromole with three-dimensional net structure of formation.Unsaturated polyester resin due to containing low-pole compositions such as a large amount of phenyl ring, due to water molecules and its avidity weak, make the metal ion as catalyzer be difficult to enter resin body, limit its catalytic activity.We are through a large amount of experiments, find that unsaturated polyester is easily swelling in acetic acid, and many metal ions can be dissolved in acetic acid, particularly because acetic acid is a kind of weak ligand solvent, the metal ion be dissolved in wherein is easy to and the heteroatoms effect in resin, its degraded of catalysis, thus obtain higher degrading activity.
A kind of degraded provided by the invention reclaims the method for unsaturated polyester resin, and the method is first by unsaturated polyester resin material, catalyzer and reaction solution heat temperature raising reaction degraded, then will react degraded product Separation and Recovery.
Concrete operation step of the present invention is as follows:
(1) catalyzer and reaction solvent are made into the reaction soln that catalyst quality concentration is 5 ~ 60%;
(2) reaction soln mixes with the part by weight of unsaturated polyester material by 100:1 ~ 200, is made into unsaturated polyester degraded system;
(3) unsaturated polyester be made into degraded system is heated to 100 ~ 280 DEG C, carries out degraded 10min ~ 72h;
(4) add separation solvent in the unsaturated polyester degraded system also cooled after the reaction, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate adds water and makes to separate out containing the polymer degradation component of styrol structural unit, filters, the polymer solids dried recovered containing styrol structural unit after filtration; Filtrate evaporate to dryness, the material obtained is not mainly containing the resin degradation product of styrol structural unit.
In described (1), reaction solvent refers to be acetic acid or water content to be the acetum of mass concentration 1 ~ 80%.
In described (1), catalyzer refers to muriate, vitriol, nitrate or acetate that zine ion, magnesium ion, ferric iron, aluminum ion or bivalent cupric ion are formed.
In described (4), be separated solvent and refer to methyl acetate, tetrahydrofuran (THF), ethyl acetate, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, gamma-butyrolactone or γ-valerolactone etc.
In described (4), being separated the degrade ratio of system reaction soln of solvent and unsaturated polyester is 25 ~ 1000ml:50g.
In described (4), to add water in filtrate be the amount adding water is 0.1 ~ 10:1 with the volume ratio being separated solvent.
The structural formula of the polymer degradation component containing styrol structural unit in described (4) is as follows:
Wherein, n=1-3
Do not refer to one or several and monounsaturated dicarboxylic acid of glycol diacetate, glycol ether diacetate esters, propylene-glycol diacetate, bisphenol A propylene oxide reaction product containing the resin degradation product of styrol structural unit in described (4).
The present invention's tool compared with bipod technology has the following advantages:
1. the solvent adopted due to the present invention can swellable resins well, makes catalyzer easily immerse resin body, can efficient catalytic ester linkage breaking.
2. because catalyzer is conventional metal acid-salt, wide material sources, cheap, degraded cost recovery can be reduced further.
3. solvent for use of the present invention is with low cost, and boiling point is lower, can Separation and Recovery.
4. selectivity scission of link, becomes monomer or oligopolymer by resin degradation, the overall high value being not only applicable to thermosetting resin reclaims, and after applicable fiber reinforcement, the degraded of unsaturated polyester composite is reclaimed.
Embodiment
Degradable material
Unsaturated polyester generally becomes oligopolymer with propylene glycol, phthalic acid, butene dioic acid esterification, then forms with vinylbenzene is crosslinked.Unsaturated polyester Recipe common is at present all change slightly on this basis, and its chemical constitution is similar to, bond valence structure phase class, and the present invention produces the unsaturated polyester material of solidification as degraded raw material using following several formula:
Formula (1): propylene glycol: 2.2mol; Tetra hydro Phthalic anhydride: 1mol; MALEIC ANHYDRIDE: 1mol; Vinylbenzene: 2mol.
Formula (2): propylene glycol: 1.92mol; Tetra hydro Phthalic anhydride: 1mol; MALEIC ANHYDRIDE: 1mol; Glycol ether: 0.27mol; Vinylbenzene: 1.8mol.
Formula (3): propylene glycol: 4.3mol; Tetra hydro Phthalic anhydride: 1mol; MALEIC ANHYDRIDE: 2.9mol; Vinylbenzene: 3.5mol.
Formula (4): propylene glycol: 4.3mol; M-phthalic acid: 0.8mol; MALEIC ANHYDRIDE: 1.4mol; Hexanodioic acid: 0.8mol; Vinylbenzene: 4.7mol.
Formula (5): ethylene glycol: 2.75mol; Tetra hydro Phthalic anhydride: 0.75mol; MALEIC ANHYDRIDE: 3.5mol; Glycol ether: 2.75mol; Hexanodioic acid: 0.75mol; Vinylbenzene: 5.25mol.
Formula (6): ethylene glycol: 1mol; MALEIC ANHYDRIDE: 2.88mol; Bisphenol A propylene oxide reaction product: 2mol; Vinylbenzene: 4.4mol.
Embodiment 1
(1) it is the reaction soln of 60% that the aqueous acetic acid being 90% by zinc chloride and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material that 0.5g formula (1) synthesizes, be heated to 100 DEG C, DeR 72h;
(3) after the reaction and cool, add the acetone of 1000ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water, filter (filter cake is the polymkeric substance containing styrol structural unit, by analysis, wherein n=2), the solid drying after filtration reclaims; Filtrate evaporate to dryness, reclaim acetone and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 2
(1) it is the reaction soln of 50% that the aqueous acetic acid being 80% by magnesium chloride and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material that 5g formula (3) synthesizes, be heated to 120 DEG C, DeR 60h;
(3) after the reaction and cool, add the tetrahydrofuran (THF) of 800ml, filter, the solid catalyst after filtration, reclaims after super-dry; Filtrate adds 200ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=1); Filtrate evaporate to dryness, reclaim tetrahydrofuran (THF) and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 3
(1) it is the reaction soln of 30% that the aqueous acetic acid being 70% by iron(ic) chloride and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material that 25g formula (1) synthesizes, be heated to 140 DEG C, DeR 48h;
(3) after the reaction and cool, add the ethyl acetate of 600ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim ethyl acetate and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 4
(1) it is the reaction soln of 10% that the aqueous acetic acid being 60% by cupric chloride and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material that 40g formula (2) synthesizes, be heated to 180 DEG C, DeR 12h;
(3) after the reaction and cool, add the methyl acetate of 400ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim methyl acetate and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, glycol ether diacetate esters, phthalic acid).
Embodiment 5
(1) it is the reaction soln of 5% that the aqueous acetic acid being 50% by zinc sulfate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 60g formula (1) synthesizes, be heated to 200 DEG C, DeR 24h;
(3) after the reaction and cool, add the ethyl acetate of 200ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim ethyl acetate and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 6
(1) it is the reaction soln of 10% that the aqueous acetic acid being 40% by copper sulfate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 80g formula (1) synthesizes, be heated to 210 DEG C, DeR 72h;
(3) after the reaction and cool, add the trimethyl carbinol of 50ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 300ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim the trimethyl carbinol and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 7
(1) it is the reaction soln of 20% that the aqueous acetic acid being 30% by Tai-Ace S 150 and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of 100g formula (1) glass fiber reinforcement synthesis, be heated to 280 DEG C, DeR 1h;
(3) after the reaction and cool, add the isopropylcarbinol of 25ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 250ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim isopropylcarbinol and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 8
(1) it is the reaction soln of 20% that the aqueous acetic acid being 20% by magnesium sulfate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material that 1g formula (1) synthesizes, be heated to 260 DEG C, DeR 10min;
(3) after the reaction and cool, add the gamma-butyrolactone of 800ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim gamma-butyrolactone and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 9
(1) it is the reaction soln of 20% that the aqueous acetic acid being 99% by aluminum chloride and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 100g formula (6) synthesizes, be heated to 240 DEG C, DeR 30min;
(3) after the reaction and cool, add the propyl carbinol of 200ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim propyl carbinol and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing glycol diacetate, bisphenol A propylene oxide reaction product).
Embodiment 10
(1) it is the reaction soln of 5% that the aqueous acetic acid being 70% by ferric sulfate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 5g formula (5) synthesizes, be heated to 240 DEG C, DeR 6h;
(3) after the reaction and cool, add the tetrahydrofuran (THF) of 600ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 300ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim tetrahydrofuran (THF) and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing glycol diacetate, glycol ether diacetate esters, phthalic acid, hexanodioic acid).
Embodiment 11
(1) it is the reaction soln of 10% that the aqueous acetic acid being 99% by zinc acetate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 2g formula (4) synthesizes, be heated to 160 DEG C, DeR 24h;
(3) after the reaction and cool, add the tetrahydrofuran (THF) of 600ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 180ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=3); Filtrate evaporate to dryness, reclaim tetrahydrofuran (THF) and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, m-phthalic acid, hexanodioic acid).
Embodiment 12
(1) it is the reaction soln of 15% that the aqueous acetic acid being 99% by aluminum acetate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 5g formula (3) synthesizes, be heated to 120 DEG C, DeR 60h;
(3) after the reaction and cool, add the tetrahydrofuran (THF) of 800ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 300ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=1); Filtrate evaporate to dryness, reclaim tetrahydrofuran (THF) and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 13
(1) it is the reaction soln of 10% that the aqueous acetic acid being 95% by ironic acetate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 10g formula (2) synthesizes, be heated to 180 DEG C, DeR 12h;
(3) after the reaction and cool, add the propyl carbinol of 400ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 200ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim propyl carbinol and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, glycol ether diacetate esters, phthalic acid).
Embodiment 14
(1) it is the reaction soln of 5% that the aqueous acetic acid being 90% by venus crystals and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material of the glass fiber reinforcement that 1g formula (1) synthesizes, be heated to 150 DEG C, DeR 36h;
(3) after the reaction and cool, add the isopropylcarbinol of 100ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim isopropylcarbinol and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 15
(1) it is the reaction soln of 40% that the aqueous acetic acid being 80% by magnesium acetate and acetic acid quality concentration mixes the catalyst content being made into 50g;
(2) in reaction soln, add the unsaturated polyester material that 0.5g formula (6) synthesizes, be heated to 190 DEG C, DeR 1h;
(3) after the reaction and cool, add the trimethyl carbinol of 50ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim the trimethyl carbinol and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing glycol diacetate, bisphenol A propylene oxide reaction product).
Embodiment 16
(1) catalyst content zinc chloride and acetic acid being made into 50g is the reaction soln of 20%;
(2) in reaction soln, add the unsaturated polyester material that 80g formula (5) synthesizes, be heated to 270 DEG C, DeR 1h;
(3) after the reaction and cool, add the γ-valerolactone of 80ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 100ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim γ-valerolactone and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing glycol diacetate, glycol ether diacetate esters, phthalic acid, hexanodioic acid).
Embodiment 17
(1) catalyst content aluminum chloride and acetic acid being made into 50g is the reaction soln of 10%;
(2) in reaction soln, add the unsaturated polyester material that 100g formula (4) synthesizes, be heated to 140 DEG C, DeR 48h;
(3) after the reaction and cool, add the tetrahydrofuran (THF) of 25ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 250ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=3); Filtrate evaporate to dryness, reclaim tetrahydrofuran (THF) and acetic acid, filtration cakes torrefaction obtains machine material (mainly containing propylene-glycol diacetate, m-phthalic acid, hexanodioic acid).
Embodiment 18
(1) catalyst content zinc chloride and acetic acid being made into 50g is the reaction soln of 40%;
(2) in reaction soln, add the unsaturated polyester material that 100g formula (3) synthesizes, be heated to 100 DEG C, DeR 72h;
(3) after the reaction and cool, add the tetrahydrofuran (THF) of 90ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 300ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=1); Filtrate evaporate to dryness, reclaim tetrahydrofuran (THF) and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Embodiment 19
(1) catalyst content aluminum chloride and acetic acid being made into 50g is the reaction soln of 20%;
(2) in reaction soln, add the unsaturated polyester material that 5g formula (2) synthesizes, be heated to 110 DEG C, DeR 72h;
(3) after the reaction and cool, add the tetrahydrofuran (THF) of 200ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 150ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim tetrahydrofuran (THF) and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, glycol ether diacetate esters, phthalic acid).
Embodiment 20
(1) catalyst content aluminum acetate and acetic acid being made into 50g is the reaction soln of 30%;
(2) in reaction soln, add the unsaturated polyester material that 60g formula (1) synthesizes, be heated to 130 DEG C, DeR 60h;
(3) after the reaction and cool, add the ethyl acetate of 200ml, filter, the solid after filtration is catalyzer, reclaims after super-dry; Filtrate adds 200ml water and makes to separate out containing the degradable component of polystyrene, filters, and solid drying after filtration reclaims (containing the polymkeric substance of styrol structural unit, by analysis, wherein n=2); Filtrate evaporate to dryness, reclaim ethyl acetate and acetic acid, filtration cakes torrefaction obtains organic substance (mainly containing propylene-glycol diacetate, phthalic acid).
Claims (4)
1. degrade and reclaim a method for unsaturated polyester resin material, it is characterized in that comprising the steps:
(1) catalyzer and reaction solvent are made into the reaction soln that catalyst quality concentration is 5 ~ 60%;
(2) reaction soln mixes with the part by weight of unsaturated polyester material by 100:1 ~ 200, is made into unsaturated polyester degraded system;
(3) unsaturated polyester be made into degraded system is heated to 100 ~ 280 DEG C, carries out degraded 10min ~ 72h;
(4) add separation solvent in the unsaturated polyester degraded system also cooled after the reaction, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate adds water and makes to separate out containing the polymer degradation component of styrol structural unit, filters, the polymer solids dried recovered containing styrol structural unit after filtration; Filtrate evaporate to dryness, the material obtained is not mainly containing the resin degradation product of styrol structural unit;
In described step (1), catalyzer is muriate, vitriol, nitrate or the acetate that zine ion, magnesium ion, ferric iron, aluminum ion or bivalent cupric ion are formed;
Being separated solvent in described step (4) is methyl acetate, tetrahydrofuran (THF), ethyl acetate, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, gamma-butyrolactone or γ-valerolactone;
Being separated the degrade ratio of system reaction soln of solvent and unsaturated polyester in described step (4) is 25 ~ 1000ml:50g;
To add water in described step (4) in filtrate be the amount adding water is 0.1 ~ 10:1 with the volume ratio being separated solvent.
2. a kind of degraded as claimed in claim 1 reclaims the method for unsaturated polyester resin material, it is characterized in that reaction solvent in described step (1) to be acetic acid or water content be the acetum of mass concentration 1 ~ 80%.
3. a kind of degraded as claimed in claim 1 reclaims the method for unsaturated polyester resin material, it is characterized in that the structural formula of the polymer degradation component containing styrol structural unit in described step (4) is as follows:
Wherein, n=1-3.
4. a kind of degraded as claimed in claim 1 reclaims the method for unsaturated polyester resin material, the resin degradation product that it is characterized in that not containing in described step (4) styrol structural unit refers to one or several of glycol diacetate, glycol ether diacetate esters, propylene-glycol diacetate, bisphenol A propylene oxide reaction product, monounsaturated dicarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410562107.5A CN104326907B (en) | 2014-10-22 | 2014-10-22 | A kind of degraded reclaims the method for unsaturated polyester resin material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410562107.5A CN104326907B (en) | 2014-10-22 | 2014-10-22 | A kind of degraded reclaims the method for unsaturated polyester resin material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104326907A CN104326907A (en) | 2015-02-04 |
| CN104326907B true CN104326907B (en) | 2016-03-02 |
Family
ID=52401733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410562107.5A Active CN104326907B (en) | 2014-10-22 | 2014-10-22 | A kind of degraded reclaims the method for unsaturated polyester resin material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104326907B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175146A (en) * | 2015-09-27 | 2015-12-23 | 常州市奥普泰科光电有限公司 | Method for preparing flower nutrient soil by degrading agricultural films |
| CN106519292A (en) * | 2016-11-07 | 2017-03-22 | 中国科学院山西煤炭化学研究所 | Method for degrading and recycling polyurethane material |
| CN106807425B (en) * | 2017-04-01 | 2019-06-07 | 北京化工大学 | Discarded carbon fiber resin matrix composite pyrolysis catalysts and recycling carbon fiber method |
| US10800906B2 (en) | 2017-04-25 | 2020-10-13 | William B. Coe | Inter-penetrating elastomer network derived from ground tire rubber particles |
| WO2018200340A1 (en) | 2017-04-25 | 2018-11-01 | Coe William B | Process for regenerating a monolithic, macro-structural, inter-penetrating elastomer network morphology from ground tire rubber particles |
| CN107254021A (en) * | 2017-06-20 | 2017-10-17 | 江苏锐康新材料科技有限公司 | A kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste |
| KR20200029045A (en) | 2017-08-04 | 2020-03-17 | 윌리엄 비. 코 | Interpenetrating elastomer network derived from crushed tire rubber particles |
| MX2020006750A (en) * | 2018-01-04 | 2021-03-26 | William B Coe | Inter-penetrating elastomer network derived from ground tire rubber particles. |
| CN109666180A (en) * | 2018-12-21 | 2019-04-23 | 江苏中信世纪新材料有限公司 | A method of using organotin catalysts solution degradation unsaturated polyester material |
| CN110157038B (en) * | 2019-04-11 | 2021-03-16 | 四川大学 | Low-temperature rapid degradation and separation method of ester bond-containing high-molecular resin |
| CN110590534B (en) * | 2019-04-26 | 2020-10-27 | 中国科学院山西煤炭化学研究所 | Method for recovering unsaturated polyester resin waste through selective catalytic degradation |
| TWI744750B (en) | 2019-12-23 | 2021-11-01 | 財團法人工業技術研究院 | Method for degradating thermosetting resin, catalyst composition used therein and resin composition obtained thereby |
| CN111203202B (en) * | 2020-01-22 | 2022-09-06 | 中国工程物理研究院核物理与化学研究所 | Polymer thermal degradation catalyst and catalytic degradation method |
| CN114907211A (en) * | 2021-02-10 | 2022-08-16 | 上海科技大学 | Polyester degradation method |
| CN113354544B (en) * | 2021-06-30 | 2023-03-31 | 中国科学院山西煤炭化学研究所 | Method for preparing diaminodiphenylmethane by selectively breaking C-N bond |
| CN114589196B (en) * | 2022-03-06 | 2023-03-31 | 四川大学 | Method for recycling thermosetting resin and composite material thereof through mild oxidative degradation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232615A (en) * | 2013-05-07 | 2013-08-07 | 中国科学院山西煤炭化学研究所 | Method for degrading epoxy resin carbon fiber composite material |
| CN103910904A (en) * | 2013-01-04 | 2014-07-09 | 杨晓林 | Recycling method of unsaturated polyester material |
-
2014
- 2014-10-22 CN CN201410562107.5A patent/CN104326907B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910904A (en) * | 2013-01-04 | 2014-07-09 | 杨晓林 | Recycling method of unsaturated polyester material |
| CN103232615A (en) * | 2013-05-07 | 2013-08-07 | 中国科学院山西煤炭化学研究所 | Method for degrading epoxy resin carbon fiber composite material |
Non-Patent Citations (1)
| Title |
|---|
| 不饱和聚酯废弃物的回收利用;马洪霞;《热固性树脂》;20100331;第25卷(第2期);第38-42页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104326907A (en) | 2015-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104326907B (en) | A kind of degraded reclaims the method for unsaturated polyester resin material | |
| CN110590534B (en) | Method for recovering unsaturated polyester resin waste through selective catalytic degradation | |
| CN101407596B (en) | Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board | |
| CN104672488A (en) | Method for degrading and recycling thermosetting epoxy resin material | |
| CN103232615B (en) | A kind of method of epoxy resin carbon fiber matrix material of degrading | |
| CN102516594B (en) | Recovery method of thermosetting epoxy resin or composite material thereof | |
| Wang et al. | Revealing the dissolution mechanism of polyvinylidene fluoride of spent lithium-ion batteries in waste oil-based methyl ester solvent | |
| CN107021983B (en) | The resource recycling Application way of butyl octanol unit rhodium-containing waste liquid | |
| Zhang et al. | Removal of Zn2+ from polyethylene terephthalate (PET) glycolytic monomers by sulfonic acid cation exchange resin | |
| CN105170108B (en) | A kind of rice husk cellulose adsorbent and its preparation method and application | |
| CN111718515A (en) | Method for degrading epoxy resin cured by catalytic anhydride | |
| CN106732452B (en) | A kind of modified macroporous resin and its method for handling butyl acrylate waste water | |
| CN102153443B (en) | Method for degrading polyethylene terephthalate | |
| CN110026159A (en) | A kind of preparation method of lead adsorbent | |
| CN107399928B (en) | Glass fiber ball bundle and preparation method thereof | |
| Wang et al. | Synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by solid base catalyst derived from waste carbide slag | |
| CN102557883A (en) | Method for transforming bromine-containing plastic of waste electric equipment into phenol in subcritical fluid | |
| CN103275350B (en) | The method of epoxy resin/fiber composite material pretreatment layering | |
| CN109651645A (en) | A kind of method that wet oxidation separates glass fibre and epoxy resin in WPCB non-metal powder | |
| CN102634061B (en) | Decomposition method for epoxy resin or composite materials thereof | |
| CN103657653B (en) | A kind of solid acid catalyst C/Fe3O4The method of MWCNTs and catalyzing cellulose hydrolysis thereof | |
| CN102001655A (en) | Method for cleaning and recovering activating agent in production process of activated carbon | |
| CN102276789A (en) | Method for recovering and utilizing waste and old paper-based copper-coated board non-metallic material | |
| CN102989428A (en) | Composite absorption material capable of removing scandium ions in natural water body as well as preparation method thereof | |
| CN103464100B (en) | The method of solvent recovery active carbon adsorption material is prepared by plant acidolysis slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230407 Address after: 030001 No. 27 Taoyuan South Road, Shanxi, Taiyuan Patentee after: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee after: Wenzhou Xiangji Resource Recycling Co.,Ltd. Address before: No. 27, Taoyuan South Road, Yingze District, Taiyuan, Shanxi Patentee before: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |