CN107840947A - A kind of method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material - Google Patents
A kind of method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material Download PDFInfo
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- CN107840947A CN107840947A CN201711136902.8A CN201711136902A CN107840947A CN 107840947 A CN107840947 A CN 107840947A CN 201711136902 A CN201711136902 A CN 201711136902A CN 107840947 A CN107840947 A CN 107840947A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—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
- C08J11/22—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 by treatment with organic oxygen-containing compounds
- C08J11/24—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 by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a kind of method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material, alcoholysis agent, catalyst are added to reactor, heat up and add PET composite membranes waste material under agitation and carry out alcoholysis, it is solid-state by the component that mixture after alcoholysis is cooled to functional membrane, then alcoholysate is purified by multistage filtering, unsaturated polyester (UP) is synthesized using the alcoholysate.The present invention can directly use PET composite membrane waste materials without separating treatment early stage, and be separated by follow-up multistage separation of solid and liquid to realize, greatly reduce the use of chemicals in separation cleaning, and can realize the efficient recycling of PET composite membrane waste materials.
Description
Technical field
The present invention relates to pet waste to utilize field, unsaturated poly- using the synthesis of PET composite membranes waste material more particularly to one kind
The method of ester.
Background technology
PET has good physical and chemical performance and is widely used in packaging for foodstuff, fiber, film and electrical apparatus insulation
The fields such as material, PET rapid industrial developments, annual production are gradually increasing, and wherein film ratio is also in be gradually increasing trend.Especially
In photoelectric fields such as solar cell, liquid crystal display, LED illuminations, the function membrane using PET film as substrate turns into main flow simultaneously
Extensive use, such as solar energy backboard membrane, diffusion barrier, increment film, reflectance coating etc., those function membrane are mostly by PET film
Surface adhesion functional film layer is formed.With flourishing for relevant industries, it is also more and more to be discharged into the pet waste of nature, no
But the environmental issue for causing getting worse is also the huge waste to petroleum resources.PET recycling can not only solve ring
Guarantor's problem, and can be as a kind of new resource.
At present, the method that PET recovery method can be divided into physics and chemistry.The method of physics：PET is sorted, cleans, be dry
Dry to obtain finished product, advantage processing cost is low, and efficiently, shortcoming processing bill of materials one, quality decline, product is mainly for the manufacture of fibre
Dimension, sheet material and non-edible Packaging Bottle.The method of chemistry is by PET depolymerization, then is re-used, specifically have hydrolysis, aminolysis, alcoholysis and
Pyrolysis etc., the cycling and reutilization of resource can be reached in molecular level.Disclosed in prior art and report the depolymerization to pet waste
And recycle more based on PET material single, pure after the pretreatment such as waste material separation and physical cleaning, and for PET composite membranes
Waste material, is bonded due to PET film with functional film layer by adhesive and often general thickness is smaller (generally in millimeter to micro-
Meter level is other), separation is very difficult, can not both be utilized with simple physical method, is difficult to utilize using conventional chemical method again,
Which has limited its recovery.Therefore, it is particularly important to develop a kind of chemical recovery technique suitable for PET composite membrane waste materials.
The content of the invention
The invention aims to solve the deficiency present in prior art, there is provided one kind directly utilizes PET composite membranes
The method that waste material carries out synthesis unsaturated polyester (UP) after alcoholysis, separating-purifying.
The technical scheme is that：
A kind of method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material is comprised the following steps：
1) PET composite membrane waste materials are crushed to below diameter 50mm, the PET composite membranes waste material include PET film and
It is adhered to an at least functional membrane of the PET film at least on a surface；The functional membrane is insoluble in diethylene glycol (DEG) and not anti-with diethylene glycol (DEG)
Should；
2) diethylene glycol (DEG) of 1500-2500 parts by weight and the alcoholysis catalysts of 0.5-10 parts by weight are added into reactor, is risen
Temperature adds the broken PET composite membranes waste material of 1800-3000 parts by weight under lasting stirring, is warming up to 200- to 70-90 DEG C
250 DEG C, isothermal reaction 0.5-2 hours to PET complete alcoholysis；
3) it is solid-state mixture after alcoholysis to be cooled at least part component of functional membrane, through screw filter in 3-5
Impurity is filtered out under the conditions of kilogram pressure, mesh 50-100 purposes, then temperature is maintained or is further cooled to the remnants of functional membrane
Component is solid-state, filters, obtains after purification under the conditions of 5-7 kilograms of pressure, mesh are 200-400 purposes through plate filter
Alcoholysis product；
4) alcoholysis product after purification is delivered into another reactor, is cooled to 140-150 DEG C, add cis-butenedioic anhydride, antioxidant, in
190-210 DEG C is at the uniform velocity warming up in 0.5-1 hours, esterification 1.5-2 hours, sampling detecting acid number drops to 50mg/g, opens true
It is empty 0.5~1.5 hour, it is reaction end when acid number drops to below 30mg/g, is filtered after dilution.
Optionally, the PET composite membranes waste material also includes tack coat, and the functional membrane is glued by tack coat and PET film
Connect.
Optionally, the functional membrane is at least one in polyvinyl fluoride thin film, polyvinylidene difluoride film, crosslinked EVA film
Kind.
Optionally, the tack coat is polyurethane adhesive, and the polyurethane adhesive is degraded in step 2), caused small molecule thing
Matter is drawn by condensation pipe.
Optionally, the tack coat is saturated polyester glue or acrylate glue.
Optionally, the functional membrane is by coated on the PET film surface and solidifying formed functional coating.
Optionally, the functional membrane includes solar energy backboard membrane, diffusion barrier, reflectance coating and anti-reflection film.
In step 4), after reaction to terminal, 140-160 DEG C is cooled to, adds hydroquinones, paraffin insulated and stirred 0.5-1
Hour, continue to be cooled to 100-120 DEG C, imported into the dilution kettle of styrene, mixing temperature is 70-90 DEG C, is eventually adding cycloalkanes
Copper, stir filtering blowing.
A kind of method that unsaturated polyester (UP) is synthesized using solar energy backboard membrane waste material, is comprised the following steps：
1) solar energy backboard membrane waste material is crushed to below diameter 12mm, it is thin that the solar energy backboard membrane waste material includes PET
Film and PET film is adhered to respect to the functional membrane on two surfaces；A wherein face functional membrane is that polyvinyl fluoride thin film or fluorine carbon apply
Layer, another side functional membrane is crosslinked EVA film or polyvinylidene difluoride film；
2) diethylene glycol (DEG) of 1500-2500 parts by weight and the stannous chloride of 0.5-2 parts by weight are added into reactor, is warming up to
70-90 DEG C, the broken solar energy backboard membrane waste material of 1800-3000 parts by weight is added under lasting stirring, is warming up to 200-
250 DEG C, isothermal reaction 0.5-2 hours to PET complete alcoholysis；
3) mixture after alcoholysis is cooled to 170-200 DEG C, through screw filter in 3-5 kilograms of pressure, mesh 50-
Impurity is filtered out under the conditions of 100 purposes, is then further cooled to 140-150 DEG C, through plate filter in 5-7 kilograms of pressure, net
Hole obtains alcoholysis product after purification to be filtered under the conditions of 200-400 purposes；
4) alcoholysis product after purification is delivered into another reactor, is cooled to 140-150 DEG C, add cis-butenedioic anhydride, antioxidant, in
190-210 DEG C is at the uniform velocity warming up in 0.5-1 hours, esterification 1.5-2 hours, sampling detecting acid number drops to 50mg/g, opens true
It is empty 0.5~1.5 hour, it is reaction end when acid number drops to below 30mg/g, is filtered after dilution.
Beneficial effects of the present invention are：
1st, will PET composite membranes waste material crush after directly carry out alcoholysis, control alcoholysis after mixture temperature to functional membrane group
Part is solid-state, and by multistage filtering implementation separation of solid and liquid, the alcoholysate polycondensation, dilution after separating-purifying are unsaturated poly- to synthesize
Ester, without carry out the cleaning of early stage, separation circuit and overcome interference problem of the impurity to PET alcoholysates, realize product
Farthest purifying；Solid component after separation further can be reclaimed and be used, and improve utilization rate, reached again sharp
Meaning.
2nd, need to only be transformed in the equipment of existing production unsaturated polyester (UP), cost is low, simple to operate, is easy to scale
Production, while the usage amount of chemicals in PET composite membrane waste material separation cleaning systems, more Environmental Safety are greatly reduced,
With great economic benefit and social benefit.
3rd, using diethylene glycol (DEG) as alcoholysis agent, its boiling point is higher, and the material that can dissolve each other is less, is advantageous to separating-purifying；Simultaneously
The compatibility of resin and styrene is good after polycondensation, is advantageous to subsequently synthesize unsaturated polyester (UP).
Embodiment
The present invention will be further described below, but protection scope of the present invention be not limited to it is as described below.
Embodiment one
Solar energy backboard membrane waste material is collected, the backboard membrane waste material is that PET film is two-sided by saturated polyester glue bonding layer
Polyvinyl fluoride (PVF) film functional layer is adhered to, backboard membrane waste material is crushed to below diameter 12mm.
In parts by mass, 2000 portions of diethylene glycol (DEG)s, 1 part of zinc acetate are added in 5000L reactors, stirring is warming up to 80
DEG C, the 2300 parts of backboard membrane waste materials crushed are added, stirs, heat up and control temperature between 235-240 DEG C, isothermal reaction
1.5-2 hours, simultaneously alcoholysis occurred for saturated polyester glue during this to PET complete alcoholysis.Adjust alcoholysis after mixture temperature to
180 DEG C (now PVF is solid-state), are pumped into screw solid-liquid separating machine, pressure be 5 kilograms, mesh be 60 mesh under the conditions of filter
Solid matter is removed, filtrate is pumped to plate filter, is 7 kilograms in pressure, mesh filters out for further mistake under the conditions of 300 purposes
Decontamination, alcoholysate is cooled to 140-150 DEG C after purification, adds the cis-butenedioic anhydride measured, 5 parts of antioxidant (triphenyl phosphite),
Then it is to slowly warm up to water outlet and is incubated one hour, be warming up to 190-210 DEG C, for reflux column temperature control below 105 DEG C, esterification is anti-
Answer 1.5-2 hours, sampling detecting acid number (KOH) drops to 50mg/g and opens vacuum 1 hour, when acid number drops to below 30mg/g as reaction
Terminal.Then 150 DEG C are cooled to, adds 0.1 part of hydroquinones, 0.3 part of paraffin paraffin insulated and stirred 0.5 hour.Continue to cool
To 110 DEG C, the dilution kettle of styrene is imported into, notices that mixing temperature control at 80 DEG C or so, is eventually adding cycloalkanes copper, stirring is equal
Even, performance detection is qualified, filters blowing.Product can be used for winding pipe.
Embodiment two
Solar energy backboard membrane waste material is collected, the backboard membrane waste material is that PET film is two-sided to be glued by acrylate glue tack coat
Agglomeration vinylidene (PVDF) film functional layer, backboard membrane waste material is crushed to below diameter 12mm.
In parts by mass, by 2000 portions of diethylene glycol (DEG)s, 0.8 part of stannous chloride, it is added in 5000L reactors, stirring rises
Temperature adds to 80 DEG C and crushes 2600 parts of backboard membrane waste materials, stirs, heats up and controls temperature constant temperature is anti-between 215-220 DEG C
1.5-2 hours are answered, treat PET complete alcoholysis, polyurethane adhesive can also degrade during this, small-molecule substance ammonia caused by degraded
Carbamate is drawn by condensation pipe, is reclaimed.Mixture temperature is to 160 DEG C of (now PVDF and propylene after adjusting alcoholysis
Sour glue is solid-state), by mixture after alcoholysis be pumped to screw filter pressure be 5 kilograms, mesh be 60 mesh under the conditions of filter
Solid matter is removed, filtrate is pumped to plate filter, is 7 kilograms in pressure, mesh is miscellaneous further to be filtered under the conditions of 400 purposes
Matter, alcoholysate is cooled to 140-150 DEG C after purification, adds the cis-butenedioic anhydride measured, 5 parts of antioxidant (triphenyl phosphite), then
It is to slowly warm up to water outlet and is incubated one hour, is warming up to 190-210 DEG C, reflux column temperature control is below 105 DEG C, esterification
1.5-2 hours, sampling detecting acid number (KOH) drop to 50mg/g and open vacuum 1 hour, when acid number drops to below 30mg/g to react eventually
Point.Then 150 DEG C are cooled to, adds 0.1 part of hydroquinones, 0.3 part of paraffin paraffin insulated and stirred 0.5 hour.Continue to be cooled to
110 DEG C, the dilution kettle of styrene is imported into, notices that mixing temperature control at 80 DEG C or so, is eventually adding cycloalkanes copper, stirring is equal
Even, performance detection is qualified, filters blowing.Product can be used for artificial stone.
Embodiment three
Solar energy backboard membrane waste material is collected, the backboard membrane waste material is that PET film one side is glued by polyurethane adhesive tack coat
Agglomeration PVF (PVF) film functional layer, another side adhere to crosslinked EVA film by polyurethane adhesive tack coat.Backboard membrane is given up
Material is crushed to below diameter 12mm.
In parts by mass, by 2000 portions of diethylene glycol (DEG)s, 0.8 part of stannous chloride, it is added in 5000L reactors, stirring rises
Temperature adds to 80 DEG C and crushes 2600 parts of backboard membrane waste materials, stirs, heats up and controls temperature constant temperature is anti-between 215-220 DEG C
1.5-2 hours are answered, treat PET complete alcoholysis, polyurethane adhesive can also degrade during this, small-molecule substance ammonia caused by degraded
Carbamate is drawn by condensation pipe, is reclaimed.Mixture temperature is to 180 DEG C after adjusting alcoholysis, by mixture after alcoholysis
It is 4 kilograms that screw filter, which is pumped to, in pressure, and mesh is elimination solid matter PVF under the conditions of 100 mesh, and filtrate is cooled to
140 DEG C and plate filter is pumped to, is 7 kilograms in pressure, mesh is further filtering EVA under the conditions of 300 purposes.After purification
Alcoholysate adds cis-butenedioic anhydride, 5 parts of the antioxidant (triphenyl phosphite) measured, is then to slowly warm up to water outlet and is incubated one hour,
190-210 DEG C is warming up to, reflux column temperature control is below 105 DEG C, esterification 1.5-2 hours, sampling detecting acid number (KOH) drop
Vacuum is opened to 50mg/g 1 hour, is reaction end when acid number drops to below 30mg/g.Then 150 DEG C are cooled to, adds 0.1
Part hydroquinones, 0.3 part of paraffin paraffin insulated and stirred 0.5 hour.Continue to be cooled to 110 DEG C, imported into the dilution kettle of styrene,
Notice that mixing temperature control at 80 DEG C or so, is eventually adding cycloalkanes copper, stirred, performance detection is qualified, filters blowing.Product
Available for artificial stone.
Example IV
Solar energy backboard membrane waste material is collected, the backboard membrane waste material is that PET film one side is glued by polyurethane adhesive tack coat
Agglomeration vinylidene (PVDF) film functional layer, another side adhere to crosslinked EVA film by polyurethane adhesive tack coat.By backboard membrane
Waste material is crushed to below diameter 12mm.
In parts by mass, by 2000 portions of diethylene glycol (DEG)s, 0.8 part of stannous chloride, it is added in 5000L reactors, stirring rises
Temperature adds to 80 DEG C and crushes 2800 parts of backboard membrane waste materials, stirs, heats up and controls temperature constant temperature is anti-between 215-220 DEG C
1.5-2 hours are answered, treat PET complete alcoholysis, polyurethane adhesive can also degrade during this, small-molecule substance ammonia caused by degraded
Carbamate is drawn by condensation pipe, is reclaimed.Mixture temperature is to 160 DEG C after adjusting alcoholysis, by mixture after alcoholysis
It is 5 kilograms that screw filter, which is pumped to, in pressure, and mesh is elimination solid matter PVDF under the conditions of 80 mesh, and filtrate is cooled to
140 DEG C and plate filter is pumped to, is 6 kilograms in pressure, mesh is further filtering EVA under the conditions of 300 purposes.After purification
Alcoholysate adds cis-butenedioic anhydride, 5 parts of the antioxidant (triphenyl phosphite) measured, is then to slowly warm up to water outlet and is incubated one hour,
190-210 DEG C is warming up to, reflux column temperature control is below 105 DEG C, esterification 1.5-2 hours, sampling detecting acid number (KOH) drop
Vacuum is opened to 50mg/g 1 hour, is reaction end when acid number drops to below 30mg/g.Then 150 DEG C are cooled to, adds 0.1
Part hydroquinones, 0.3 part of paraffin paraffin insulated and stirred 0.5 hour.Continue to be cooled to 110 DEG C, imported into the dilution kettle of styrene,
Notice that mixing temperature control at 80 DEG C or so, is eventually adding cycloalkanes copper, stirred, performance detection is qualified, filters blowing.Product
Available for artificial stone.
Embodiment five
Solar energy backboard membrane waste material is collected, the backboard membrane waste material is PET film dual coating F-C paint coating, by backboard
Film waste material is crushed to below diameter 12mm.
In parts by mass, by 2000 portions of diethylene glycol (DEG)s, 10 parts of zinc acetate, it is added in 5000L reactors, stirring is warming up to
80 DEG C, add and crush 2100 parts of backboard membrane waste materials, stir, heat up and control temperature between 200-210 DEG C, isothermal reaction
1.5-2 hours, treat PET complete alcoholysis.Mixture temperature is to 200 DEG C (now fluororine-carbon coating is solid-state) after adjusting alcoholysis, by alcohol
After solution mixture be pumped to screw filter pressure be 5 kilograms, mesh be 60 mesh under the conditions of filter off solid matter, filtrate pump
Deliver to plate filter, pressure be 7 kilograms, mesh be 300 purposes under the conditions of, further go the removal of impurity.Add what is measured
Cis-butenedioic anhydride, 5 parts of antioxidant (triphenyl phosphite), then it is to slowly warm up to water outlet and is incubated one hour, be warming up to 190-210 DEG C, return
Fluidization tower temperature control is below 105 DEG C, esterification 1.5-2 hours, and sampling detecting acid number (KOH) drops to 50mg/g and opens vacuum 1
Hour, it is reaction end when acid number drops to below 30mg/g.Then 150 DEG C are cooled to, adds 0.1 part of hydroquinones, paraffin 0.3
Part paraffin insulated and stirred 0.5 hour.Continue to be cooled to 110 DEG C, imported into the dilution kettle of styrene, notice that mixing temperature control exists
80 DEG C or so, cycloalkanes copper is eventually adding, is stirred, performance detection is qualified, filters blowing.Product can be used for artificial stone.
Embodiment six
Reflectance coating waste material is collected, the reflectance coating waste material is PET film surface adhesion doping acrylate glue reflecting layer, and this is mixed
Miscellaneous acrylate glue reflecting layer has cementability and reflection function simultaneously, and wherein dopant is glass fibre.Backboard membrane is given up
Material is crushed to diameter 30mm or so.
In parts by mass, by 2000 portions of diethylene glycol (DEG)s, 0.8 part of stannous chloride, it is added in 5000L reactors, stirring rises
Temperature adds to 80 DEG C and crushes 2600 parts of reflectance coating waste materials, stirs, heats up and controls temperature constant temperature is anti-between 215-220 DEG C
1.5-2 hours are answered, treat PET complete alcoholysis.Mixture after alcoholysis is pumped to spiral shell by mixture temperature to 200 DEG C after adjusting alcoholysis
Rod-type filter is 5 kilograms in pressure, and for mesh to filter off solid matter under the conditions of 60 mesh, filtrate is pumped to plate filter,
Pressure is 7 kilograms, and mesh is further impurity screening under the conditions of 400 purposes, and alcoholysate is cooled to 140-150 DEG C after purification, adds
Enter the cis-butenedioic anhydride measured, 5 parts of antioxidant (triphenyl phosphite), be then to slowly warm up to water outlet and be incubated one hour, be warming up to
190-210 DEG C, below 105 DEG C, esterification 1.5-2 hours, sampling detecting acid number (KOH) drops to reflux column temperature control
50mg/g opens vacuum 1 hour, is reaction end when acid number drops to below 30mg/g.Then 150 DEG C are cooled to, adds 0.1 part
Hydroquinones, 0.3 part of paraffin paraffin insulated and stirred 0.5 hour.Continue to be cooled to 110 DEG C, imported into the dilution kettle of styrene, note
Mixing temperature control anticipate at 80 DEG C or so, is eventually adding cycloalkanes copper, stirs, performance detection is qualified, filters blowing.Product can
For artificial stone.
In addition, those skilled in the art are, it should be understood that alcoholysis will be carried out after different types of PET composite membranes waste material co-grinding,
And by progressively adjust the temperature to different impurities component for solid-state come implement separation of solid and liquid with purified also the present invention guarantor
Within the scope of shield.
Above-described embodiment is only used for further illustrating that one kind of the present invention utilizes PET composite membranes waste material synthesis unsaturated polyester (UP)
Method, but the invention is not limited in embodiment, what every technical spirit according to the present invention was made to above example appoints
What simple modification, equivalent change and modification, each falls within the protection domain of technical solution of the present invention.
Claims (9)
- A kind of 1. method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material, it is characterised in that comprise the following steps：1) PET composite membrane waste materials are crushed to below diameter 50mm, the PET composite membranes waste material includes PET film and adhesion In an at least functional membrane of the PET film at least on a surface；The functional membrane reacts insoluble in diethylene glycol (DEG) and not with diethylene glycol (DEG)；2) diethylene glycol (DEG) of 1500-2500 parts by weight and the alcoholysis catalysts of 0.5-10 parts by weight are added into reactor, is warming up to 70-90 DEG C, the broken PET composite membranes waste material of 1800-3000 parts by weight is added under lasting stirring, is warming up to 200-250 DEG C, isothermal reaction 0.5-2 hours to PET complete alcoholysis；3) it is solid-state mixture after alcoholysis to be cooled at least part component of functional membrane, through screw filter at 3-5 kilograms Impurity is filtered out under the conditions of pressure, mesh 50-100 purposes, then temperature is maintained or is further cooled to the remaining component of functional membrane For solid-state, filtered through plate filter under the conditions of 5-7 kilograms of pressure, mesh are 200-400 purposes, obtain alcoholysis after purification Product；4) alcoholysis product after purification is delivered into another reactor, is cooled to 140-150 DEG C, cis-butenedioic anhydride, antioxidant are added, in 0.5- 190-210 DEG C is at the uniform velocity warming up in 1 hour, esterification 1.5-2 hours, sampling detecting acid number drops to 50mg/g, opens vacuum 0.5 ~1.5 hours, it is reaction end when acid number drops to below 30mg/g, is filtered after dilution.
- 2. the method according to claim 1 that unsaturated polyester (UP) is synthesized using PET composite membranes waste material, it is characterised in that：Institute Stating PET composite membranes waste material also includes tack coat, and the functional membrane is Nian Jie with PET film by tack coat.
- 3. the method according to claim 2 that unsaturated polyester (UP) is synthesized using PET composite membranes waste material, it is characterised in that：Institute Functional membrane is stated as at least one of polyvinyl fluoride thin film, polyvinylidene difluoride film, crosslinked EVA film.
- 4. the method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material according to Claims 2 or 3, it is characterised in that： The tack coat is polyurethane adhesive, and the polyurethane adhesive is degraded in step 2), and caused small-molecule substance passes through condensation pipe Draw.
- 5. the method that unsaturated polyester (UP) is synthesized using PET composite membranes waste material according to Claims 2 or 3, it is characterised in that： The tack coat is saturated polyester glue or acrylate glue.
- 6. the method according to claim 1 that unsaturated polyester (UP) is synthesized using PET composite membranes waste material, it is characterised in that：Institute Functional membrane is stated as by coated on the PET film surface and solidifying formed functional coating.
- 7. the method according to claim 1 that unsaturated polyester (UP) is synthesized using PET composite membranes waste material, it is characterised in that：Institute Stating functional membrane includes solar energy backboard membrane, diffusion barrier, reflectance coating and anti-reflection film.
- 8. the method according to claim 1 that unsaturated polyester (UP) is synthesized using PET composite membranes waste material, it is characterised in that：Step It is rapid 4) in, after reaction to terminal, be cooled to 140-160 DEG C, add hydroquinones, paraffin insulated and stirred 0.5-1 hours, continue to drop Temperature imported into the dilution kettle of styrene to 100-120 DEG C, and mixing temperature is 70-90 DEG C, is eventually adding cycloalkanes copper, stirs Filter blowing.
- A kind of 9. method that unsaturated polyester (UP) is synthesized using solar energy backboard membrane waste material, it is characterised in that comprise the following steps：1) solar energy backboard membrane waste material is crushed to below diameter 12mm, the solar energy backboard membrane waste material include PET film with And PET film is adhered to respect to the functional membrane on two surfaces；A wherein face functional membrane is polyvinyl fluoride thin film or fluororine-carbon coating, separately One face functional membrane is crosslinked EVA film or polyvinylidene difluoride film；2) diethylene glycol (DEG) of 1500-2500 parts by weight and the stannous chloride of 0.5-2 parts by weight are added into reactor, is warming up to 70- 90 DEG C, the broken solar energy backboard membrane waste material of 1800-3000 parts by weight is added under lasting stirring, is warming up to 200-250 DEG C, isothermal reaction 0.5-2 hours to PET complete alcoholysis；3) mixture after alcoholysis is cooled to 170-200 DEG C, through screw filter in 3-5 kilograms of pressure, mesh 50-100 mesh Under conditions of filter out impurity, be then further cooled to 140-150 DEG C, be in 5-7 kilograms of pressure, mesh through plate filter Filtered under the conditions of 200-400 purposes, obtain alcoholysis product after purification；4) alcoholysis product after purification is delivered into another reactor, is cooled to 140-150 DEG C, cis-butenedioic anhydride, antioxidant are added, in 0.5- 190-210 DEG C is at the uniform velocity warming up in 1 hour, esterification 1.5-2 hours, sampling detecting acid number drops to 50mg/g, opens vacuum 0.5 ~1.5 hours, it is reaction end when acid number drops to below 30mg/g, is filtered after dilution.
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| CN109181243A (en) * | 2018-08-24 | 2019-01-11 | 杭州福禧新材料有限公司 | A kind of solar cell backboard gives up the method that film and its leftover pieces recycle |
| CN110180597A (en) * | 2019-05-22 | 2019-08-30 | 漳州亚邦化学有限公司 | A kind of composite catalyst and PET biodegrading process for PET degradation |
| CN110551404A (en) * | 2019-07-06 | 2019-12-10 | 新三和石化(福建)股份公司 | Waste resin reclaimed material and preparation method thereof |
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| CN101760163A (en) * | 2010-02-08 | 2010-06-30 | 启东市鑫鑫粘合剂有限公司 | Preparation method of producing polyester hot melt adhesive based on PET waste materials |
| CN103554380A (en) * | 2013-11-08 | 2014-02-05 | 天津工业大学 | Process for preparing unsaturated polyester resin by mixed alcohol alcoholysis of RPET (recycled polyethylene terephtalate) plastic |
| CN104804698A (en) * | 2015-04-27 | 2015-07-29 | 武汉戴尔惠科技有限公司 | Bi-component composite adhesive for solar power back panel, and preparation method thereof |
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| CN101760163A (en) * | 2010-02-08 | 2010-06-30 | 启东市鑫鑫粘合剂有限公司 | Preparation method of producing polyester hot melt adhesive based on PET waste materials |
| CN103554380A (en) * | 2013-11-08 | 2014-02-05 | 天津工业大学 | Process for preparing unsaturated polyester resin by mixed alcohol alcoholysis of RPET (recycled polyethylene terephtalate) plastic |
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| CN109181243A (en) * | 2018-08-24 | 2019-01-11 | 杭州福禧新材料有限公司 | A kind of solar cell backboard gives up the method that film and its leftover pieces recycle |
| CN110180597A (en) * | 2019-05-22 | 2019-08-30 | 漳州亚邦化学有限公司 | A kind of composite catalyst and PET biodegrading process for PET degradation |
| CN110551404A (en) * | 2019-07-06 | 2019-12-10 | 新三和石化(福建)股份公司 | Waste resin reclaimed material and preparation method thereof |
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| CN107840947B (en) | 2020-09-15 |
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