CN107974059A - A kind of polyester material based on recycled PET and preparation method thereof - Google Patents
A kind of polyester material based on recycled PET and preparation method thereof Download PDFInfo
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- CN107974059A CN107974059A CN201711319039.XA CN201711319039A CN107974059A CN 107974059 A CN107974059 A CN 107974059A CN 201711319039 A CN201711319039 A CN 201711319039A CN 107974059 A CN107974059 A CN 107974059A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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Abstract
The present invention provides a kind of polyester material based on recycled PET, it is prepared by following raw material：The recycled PET of 90~97wt%, the pyromellitic acid anhydride of 0.5~1.5wt%, the fluoro epoxide of 0.3~0.5wt%, the anti-hydrolysis agent of 0.2~1wt%, the nucleator of 0.5~1wt%, the heat stabilizer of 0.5~3.5wt%, the lubricant of 0.5~3wt%.Present invention also provides the preparation method of the polyester material.The application by using pyromellitic acid anhydride as main chain extender, fluoro epoxide as auxiliary chain extender, simultaneously because the compounding of anti-hydrolysis agent, heat stabilizer and other auxiliary agents, makes polyester material have the antiacid alkali characteristic of preferable wet-heat resisting.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of polyester material and its system based on recycled PET
Preparation Method.
Background technology
With the sternness of petroleum resources increasingly depleted and environmental problem, the new high score of development energy-saving and environmental protection and low emission
Sub- composite material becomes an urgent demand for adapting to global low-carbon economy development.
Polyethylene terephthalate (PET) is a kind of crystalline polyester, has excellent comprehensive performance, a large amount of
For making chemical fibre, packaging material, engineering plastics etc..Particularly PET bottle (such as mineral water bottle, beverage bottle, edible oil bottle
Deng) mostly disposable, if do not recycled, the wasting of resources had both been caused, has also seriously polluted environment.Due to various PET bags
A large amount of discardings of bottling, " white pollution " problem getting worse, therefore recycled PET bottles, which recycle, can not only reduce environment dirt
Dye, but also resource can be saved, processing recycles waste polyester bottle and is asked as the key of polyester industrial sustainable development
Topic.
PET is the condensation polymer of terephthalic acid (TPA) and glycols, contains ester group in its molecular structure, causes it certain
To damp and hot very sensitive under acid-base condition and moisture existence condition, especially hydrolysis becomes apparent from more than 160 DEG C, leads
PET product surfaces are caused to tarnish, mechanical property declines rapidly, this shortcoming limits PET under soda acid and hygrothermal environment
Using.The above problem is more obvious in the regeneration process of waste PET bottle, and fracture, which occurs, for its strand causes molecular weight big
Width reduces, and ultimately results in product impact property variation etc., it is impossible to meet requirement.It is thus typically necessary to recycled PET is carried out
It is modified, to achieve the purpose that to improve material property.
Influencing the principal element of polyester hydrolysis includes carboxylic end group concentration and environmental condition (such as acid-base value, humidity, temperature),
By the concentration for reducing the active and initial end carboxyl of free end carboxyl in polyester material, it is possible to increase polyester material is in damp and hot ring
Service life in border.Furthermore it is possible to using anti-hydrolysis agent is added into polyester material, consume what it was produced in hydrolytic process
End carboxyl, controls the carboxylic end group concentration of polyester material, and then reduces the speed of its hydrolysis.
Publication No. CN101215730 Chinese patents disclose a kind of polyester fiber being modified with anti-hydrolysis agent and its production
Method, it is the anti-hydrolysis agent carbodiimides of the addition 0.1~1% in spinning screw, with 99~99.9% high-viscosity polyesters
Melt blended composite spinning forms.The Chinese patent of Publication No. CN1603357A discloses a kind of resin with ester group with resistance to
Hydrolysis stabilizer and thermoplastic resin composition, it is by being mixed into phosphorus system in synthctic fat family carbodiimide compound
Antioxidant improves Carbodiimides to hydrolysis resistance containing ester base resin, so as to prepare resistant to hydrolysis ester base resin composition.It is public
The number of opening is that the Chinese patent of CN104045980A discloses a kind of resistant to hydrolysis PET color master batch and its preparation method and application, wherein,
Resistant to hydrolysis PET color master batch is made of PET, anti-hydrolysis agent, toner and auxiliary addition agent, its each component percentage by weight is：PET 80-
96%th, anti-hydrolysis agent 2-4%, toner 0-5%, auxiliary addition agent 1-3%.The Chinese patent of Publication No. CN1936127A discloses
A kind of high anti-hydrolysis colored flat yarn and its manufacture method, it is to merge liquid carbodiimides with polyester (PET), and adds face
Rectangular monofilaments are made in material；The liquid carbodiimides addition is the 1-2wt% of polyester (PET).Publication No.
The Chinese patent of CN104356612A discloses a kind of anti-xanthochromia resistant to hydrolysis polyester blend, it is by adding one in formula
Quantitative ester exchange inhibitor and anti-hydrolysis agent, effectively solve the background color yellowing problems that ester exchange reaction produces in blend, together
When be conducive to suppress ester exchange reaction and hydrolysis in blend and cause its backbone structure to change.Japan Patent
JP9296097 is disclosed adds special carbodiimides as stabilizer in polyester plastics, assigns its preferable resistant to hydrolysis
Performance, but carbodiimides are expensive, heat endurance is poor, and process can produce harmful gas.
United States Patent (USP) US 5910363A disclose a kind of hydrolysis resistant composition, by adding polycarbodiimide energy in PCTG materials
It is enough effectively to reduce the water-disintegrable of PCTG, but cause PCTG materials to turn to be yellow, its use scope is limited, and do not solve
The problem of PCTG heat resistances are very low.The Chinese patent of Publication No. CN1312327A uses the height containing epoxy and amino group
Molecule improves the hydrolytic resistance of polyester as end-capping reagent, but the preparation process of end-capping reagent is complicated.Publication No.
The Chinese patent of CN104177789A discloses a kind of new and effective resistant to hydrolysis polyester master particle and preparation method thereof, it includes following
Component and parts by weight content：100 parts of matrix resin, 1-30 parts of anti-hydrolysis agent, 1-20 parts of calcium oxide, 1-10 parts of dispersant, antioxygen
0.1-2 parts of agent, by add calcium oxide on the basis of adding anti-hydrolysis agent, easily reacted using calcium oxide with water the characteristics of, adding
Excessive moisture during work, use inside absorbing material, suppresses the hydrolysis of material；In this method, the length of calcium oxide in itself
Phase stability problem can not ensure the long-time stability of material, and the addition of calcium oxide can influence the processing performance of material.
The various methods of above-mentioned raising ester base resin hydrolysis resistance, or by physical blending add anti-hydrolysis agent or
Person is introduced anti-hydrolysis agent using special anti-hydrolysis agent or during synthesizing polyester or uses fluorine-containing epoxidation
Compound carries out blocking modification etc. to polyester, and above-mentioned method of modifying is not easy to grasp, it is difficult to forms the hydrophobic surface for knitting state densification, changes
Kind heat resistance hydrolysis ability is limited, and involved raw material is polyester PET virgin material, and cost is higher.
The content of the invention
Present invention solves the technical problem that being to provide a kind of polyester material, the polyester material that the application provides has highly resistance
Soda acid humidity resistance.
In view of this, this application provides a kind of polyester material based on recycled PET, it is prepared by following raw material：
Preferably, the content of the recycled PET is 92~95wt%.
Preferably, the content of the pyromellitic acid anhydride is 0.6~1.2wt%.
Preferably, the fluoro epoxide is selected from double (the 3- shrinks of bis-phenol base hexafluoropropane diglycidyl ether, 1,3-
Glycerine ether phenyl tetrafluoride epoxide) -2- hydroxy propanes, double (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of 1,4-, the double (hydroxyls of 1,3-
Base hexafluoro isopropyl) benzene diglycidyl ether, the positive perfluoro propyl benzene diglycidyl ethers of 1,3- double (hydroxyl hexafluoro isopropyl), 1,
Double (hydroxyl hexafluoro isopropyl) the phenyl tetrafluoride diglycidyl ethers of 4-, 4,4 '-dihydroxy octafluorobiphenyl diglycidyl ether, 4,4 '-
Double (hydroxyl hexafluoro isopropyl) octafluorobiphenyl diglycidyl ethers, (3- trifluoromethylbenzenes) hydroquinone glycidol ether, 1,1-
Double (4- glycidols phenyl) -1- (3 '-fluoroform phenyl) -2,2,2- trifluoroethane, fluorine-containing biphenyl type epoxy resin and 4,4 ' -
Double (2,3- glycidoxies) -1- (3- fluoroforms phenyl) -2,2,2- trifluoroethane and fluorine-containing glycidol (methyl) acrylic acid
One or more in ester polymer.
Preferably, the anti-hydrolysis agent is selected from Carbodiimides, selected from dicyclohexylcarbodiimide, N, N '-diisopropyl
Base carbodiimide, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and one kind or more in polycarbodiimide
Kind.
Preferably, the nucleator is ionomer type nucleator, selected from ethylene-acrylic acid sodium ionomer, ethene-methyl-prop
Olefin(e) acid sodium ionomer, ethylene-acrylic acid calcium ionomer, ethylene-acrylic acid zinc ionomer, ethylene-methyl methacrylate calcium ionomer
With the one or more in ethylene-methyl methacrylate zinc ionomer.
Preferably, the heat stabilizer is selected from (Asia) phosphoric acid ester, selected from phosphorous acid bisphenol-A ester, four (2,4- di-t-butyls
Phenyl -4,4 '-xenyl) biphosphonate, N, N '-hexylidene -1,6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide],
Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, three (2,4- di-tert-butyl-phenyls) phosphite esters and
One or more in double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
Preferably, it is double stearic to be selected from silicone, ethylene bis stearamide, low molecular weight high polymer and ethylene for the lubricant
One or more in acid amides and its derivative.
Present invention also provides the preparation method of the polyester material, including：
By recycled PET, pyromellitic acid anhydride, anti-hydrolysis agent, nucleator, fluoro epoxide, heat stabilizer and profit
Lubrication prescription mixes in proportion, obtains mixed material；
By the mixed material successively through melting extrusion, granulation, polyester material is obtained.
Preferably, the melting extrusion is carried out using double screw extruder, and area's temperature of the double screw extruder is
160~200 DEG C, two area's temperature are 190~230 DEG C, and three area's temperature are 220~260 DEG C, and four area's temperature are 220~260 DEG C；Institute
It is 3~5min to state time of delivery of the mixed material in the screw rod of double screw extruder.
This application provides a kind of polyester material based on recycled PET, it is prepared by following raw material：90~97wt%
Recycled PET, the pyromellitic acid anhydride of 0.5~1.5wt%, the fluoro epoxide of 0.3~0.5wt%, 0.2~
The anti-hydrolysis agent of 1wt%, the nucleator of 0.5~1wt%, the heat stabilizer of 0.5~3.5wt%, the lubricant of 0.5~3wt%.
The polyester material of the application using pyromellitic acid anhydride as main chain extender, by add a small amount of fluoro epoxide be used as it is auxiliary
Co-chain extender, during making chain extension thickening, fluorine element enrichment while interpenetrating networks are formed in polyester material molecular structure
In surface, the superpower water repellency of polyester material is assigned, so that the wet-heat resisting of polyester material and antiacid alkali ability are improved, while poly-
Anti-hydrolysis agent is introduced in ester material and heat stabilizer further increases the wet-heat resisting hydrolysis property of polyester material, is made based on recycling
The polyester material of PET has superpower antiacid alkali moisture-proof thermal characteristics.
Brief description of the drawings
Fig. 1 is that the SEM before the polyester material corrosion that polyester material prepared by the embodiment of the present invention 3 is prepared with comparative example shines
Piece；
Fig. 2 is that polyester material prepared by the embodiment of the present invention 3 corrodes traversing of probe electron microscope；
Fig. 3 is that polyester material prepared by comparative example of the present invention corrodes traversing of probe electron microscope.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of polyester material based on recycled PET, it is prepared by following raw material：
The application provide based on the polyester material of recycled PET by pyromellitic acid anhydride, fluoro epoxide, water resistant
Solution agent, heat stabilizer and nucleator are rationally compounded, and improve the antiacid alkali wet-heat resisting using recycled PET as the polyester material of base
Corrosive nature.
Specifically, herein described recycled PET, mainly based on common mineral water bottle reclaimed materials, it is for polyester material
Preceding to need by the processing procedure such as crushing, washing, dry, above-mentioned processing procedure is well known to those skilled in the art, to this
Application is without particularly repeating.The content of the recycled PET is 90~97wt%, in a particular embodiment, the recycled PET
Content be 92~95wt%, more specifically, the content of the recycled PET is 92.5~94.5wt%.
Main chain extender of the pyromellitic acid anhydride as synthesizing polyester material, its content are 0.5~1.5wt%,
In specific embodiment, the content of the pyromellitic acid anhydride is 0.6~1.2wt%.
Auxiliary chain extender of the fluoro epoxide as synthesizing polyester material, it is selected from bis-phenol base hexafluoropropane two
Double (3- glycidyl ether tetrafluoros the phenoxy group) -2- hydroxy propanes of glycidol ether, 1,3-, 1,4- are double (hydroxyl hexafluoro isopropyl)
Double (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of benzene diglycidyl ether, 1,3-, 1,3- double (hydroxyl hexafluoro isopropyls) are just
Perfluoro propyl benzene diglycidyl ether, 1,4- double (hydroxyl hexafluoro isopropyl) phenyl tetrafluoride diglycidyl ether, 4,4 '-dihydroxy eight
Fluorine biphenyldiglycid ether, 4,4 '-bis- (hydroxyl hexafluoro isopropyl) octafluorobiphenyl diglycidyl ethers, (3- trifluoromethylbenzenes)
Double (4- glycidols phenyl) -1- (3 '-fluoroform phenyl) -2,2,2- trifluoroethane of hydroquinone glycidol ether, 1,1-, contain
Fluorine biphenyl type epoxy resin and 4,4 '-bis- (2,3- glycidoxies) -1- (3- fluoroforms phenyl) -2,2,2- trifluoroethane and contains
One or more in fluorine glycidol (methyl) acrylate polymer.In a particular embodiment, the fluorine-containing epoxy compound
Thing is selected from double (hydroxyl hexafluoro isopropyl) the phenyl tetrafluoride 2-glycidyls of fluorine-containing glycidol (methyl) acrylate polymer, 1,4-
Ether or bis-phenol base hexafluoropropane diglycidyl ether.The fluoro epoxide combines chain extension with pyromellitic acid anhydride,
Local inierpeneirating network structure can be formed while effectively increasing recycled PET molecular weight, increase its inherent viscosity, the interpenetrating networks
Structure can improve the antiacid alkali wet-hot aging performance of composite polyester material；The fluorine element on strand is enriched in compound poly- automatically at the same time
Ester material surface forms water resistant layer, so that composite polyester material has water repellent ability, further improves composite polyester material
Wet-hot aging performance.
According to surface thermodynamic theory, under isothermal, constant volume, what system always reduced towards Helmholtz free energys
Direction carries out, untill the Helmholtz free energys of system reach minimum value.Therefore, in chain extension viscosifies recycled PET technique
Using fluoro epoxide as auxiliary chain extender, relative to the C-C segments in PET molecular structures, section containing fluorocarbon chain has
Stronger hydrophobicity, fluoroalkyl chain make reduction in surface tension to surface migration enrichment, cause material to have lower surface energy, dredge
Water-based enhancing, further improves the antiacid alkali wet-heat resisting corrosive power of polyester granules.In this application, the fluorine-containing epoxy compound
The content of thing is 0.3~0.5wt%, in a particular embodiment, the content of the fluoro epoxide is 0.3wt%,
0.4wt% or 0.5wt%.
In this application, the anti-hydrolysis agent is Carbodiimides, specifically, dicyclohexylcarbodiimide, N are selected from,
In N '-diisopropylcarbodiimide, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and polycarbodiimide
One or more, in a particular embodiment, the anti-hydrolysis agent are selected from polycarbodiimide class, such as commercially available Stabaxol KE
7646.The content of the anti-hydrolysis agent is 0.2~1wt%, in a particular embodiment, the content of the anti-hydrolysis agent for 0.4~
0.8wt%.
The heat stabilizer is (Asia) phosphoric acid ester, selected from phosphorous acid bisphenol-A ester, four (2,4- di-tert-butyl-phenyls -4,4
'-xenyl) biphosphonate, N, N '-hexylidene -1,6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyls) phosphite esters and double (2,4- bis-
Tert-butyl-phenyl) one or more in pentaerythritol diphosphites；In a particular embodiment, the heat stabilizer is selected from Asia
Phosphoric acid bisphenol-A ester.The content of the heat stabilizer is 0.5~3.5wt%, and in a particular embodiment, the heat stabilizer contains
Measure as 1.5~2.0wt%.
Herein described nucleator is ionomer type nucleator, specifically, selected from ethylene-acrylic acid sodium ionomer, ethene-
Sodium methacrylate ionomer, ethylene-acrylic acid calcium ionomer, ethylene-acrylic acid zinc ionomer, ethylene-methyl methacrylate calcium
One or more in ionomer and ethylene-methyl methacrylate zinc ionomer；In a particular embodiment, the nucleator is selected from
Surlyn 8920.The content of the nucleator is 0.5~1wt%, and in a particular embodiment, the content of the nucleator is 0.6
~0.8wt%.The nucleator can cause the mixed material rapid crystallization that each component melted in extrusion is formed, and increase polyester
Material crystalline density simultaneously promotes fine grain size so that crystallization is more perfect, so that it is water-fast to improve the antiacid alkali of polyester material
Solution ability.
The lubricant be selected from silicone, ethylene bis stearamide, low molecular weight high polymer and ethylene bis stearamide and
One or more in its derivative；In a particular embodiment, the lubricant is ethylene bis stearamide.The lubricant
Content is 0.5~3wt%, and in a particular embodiment, the content of the lubricant is 1.5~2.5wt%.
The conjunction of the components such as above-mentioned pyromellitic acid anhydride, fluoro epoxide, anti-hydrolysis agent, heat stabilizer, nucleator
Reason compounding, improves the antiacid alkali wet-heat resisting corrosive power of recycled PET polyester granules.Wherein, fluoro epoxide is effective
It can participate in forming local inierpeneirating network structure while increasing recycled PET molecular weight, increase its inherent viscosity, at the same it is therein
Fluorine element is enriched in polyester granules surface and forms water repellent layer, so as to improve the structural stability of antiacid alkali wet-heat resisting polyester granules；
Anti-hydrolysis agent is particularly above-mentioned preferable polycarbodiimide at high temperature can be with reaction of moisture, also can be with PET resin end
Acidic-group reacts, therefore the hydrolysis of PET resin is minimized；Above-mentioned preferable heat stabilizer can make PET
Resin reduces carboxylic end group concentration during hot-melt extruded, so as to improve hydrothermal stability；Above-mentioned preferable nucleator to squeeze
The PET rapid crystallizations melted during going out, increase pellet crystallization density and promote fine grain size so that crystallization is more complete
It is kind, so as to improve the antiacid alkali hydrolysis ability of composite material.
Above-mentioned polyester material is interacted by each component of proper content scope during melting extrusion so that this hair
Bright recycled PET polyester material has excellent antiacid alkali wet-hot aging performance, so that using the recycled PET polyester material as raw material
Product can be used for a long time in soda acid hygrothermal environment.Further, the matrix resin source in the application polyester material formula
In reclaimed materials, cost is low, beneficial to environmental protection, economizes on resources at the same time, and other each components easily obtain, so that should be based on recycling
The antiacid alkali wet-heat resisting polyester material of PET has a good application prospect.
Present invention also provides the preparation method of above-mentioned polyester material, including：
By recycled PET, pyromellitic acid anhydride, anti-hydrolysis agent, nucleator, fluoro epoxide, heat stabilizer and profit
Lubrication prescription mixes in proportion, obtains mixed material；
By the mixed material successively through melting extrusion, granulation, polyester material is obtained.
During polyester material is prepared, first by recycled PET, pyromellitic acid anhydride, anti-hydrolysis agent, nucleator,
Fluoro epoxide, heat stabilizer and lubricant are mixed according to the above mentioned proportion, obtain mixed material.In the process of above-mentioned mixing
In preferably in mixer carry out high-speed stirred mixing.
After above-mentioned raw materials mixing, then by obtained mixed material successively through melting extrusion, granulation, to obtain polyester material
Material.Above-mentioned melting extrusion is technological means well known to those skilled in the art with the flow being granulated, herein without particularly saying
It is bright.In a particular embodiment, the melting extrusion is using double screw extruder, area's temperature of the double screw extruder
For 160~200 DEG C, two area's temperature are 190~230 DEG C, and three area's temperature are 220~260 DEG C, and four area's temperature are 220~260 DEG C；
Time of delivery of the mixed material in the screw rod of double screw extruder is 3~5mn；The mixed material is in twin-screw extrusion
Time of delivery in the screw rod of machine is 3~5min.
For a further understanding of the present invention, with reference to embodiment to the polyester material provided by the invention based on recycled PET
Material is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
The recipe ingredient of high acid and alkali-resistance heat resistance polyester granules percentage by weight based on recycled PET is as follows：
Recycled PET bottles material 94.5%, pyromellitic acid anhydride 0.6%, polycarbodiimide Stabaxol KE 7646
0.4%th, bis-phenol base hexafluoropropane diglycidyl ether 0.3%, phosphorous acid bisphenol-A ester 1.7%, Surlyn 8,920 0.6%, profit
Lubrication prescription ethylene bis stearamide 1.9%.
The preparation method of high acid and alkali-resistance heat resistance polyester granules based on recycled PET is as follows：
The first step：Formula according to the above-mentioned high acid and alkali-resistance heat resistance polyester granules based on recycled PET weighs each component；
Second step：By the recycled PET bottles material weighed, pyromellitic acid anhydride, polycarbodiimide, bis-phenol base hexafluoropropane
The components such as diglycidyl ether, phosphorous acid bisphenol-A ester, nucleator, lubricating auxiliary agent are placed in mixer, are mixed
Material；
3rd step：Mixed material is placed in the feed inlet of double screw extruder and fed, melted and squeeze through double screw extruder
Go out, be granulated, obtain the acid and alkali-resistance heat resistance polyester granules based on recycled PET；Wherein, double screw extruder process conditions are：One
190 DEG C of area, 210 DEG C of 2nd area, 230 DEG C of 3rd area, 250 DEG C of 4th area；The spiral shell of the mixed material and glass fibre in double screw extruder
Time of delivery is 3.5min in bar.
Embodiment 2
Preparation method with embodiment 1, difference lies in：Recycled PET bottles material 94.5%, pyromellitic acid anhydride 0.8%, poly- carbon
Change diimine Stabaxol KE 7,646 0.4%, bis-phenol base hexafluoropropane diglycidyl ether 0.5%, phosphorous acid bisphenol-A ester
1.5%th, the mixture (weight ratio 2 of nucleator Surlyn 89200.6%, lubricant ethylene bis stearamide and silicone:1)
1.7%.
Embodiment 3
Preparation method with embodiment 1, difference lies in：Recycled PET bottles material 94.5%, pyromellitic acid anhydride 1%, poly- carbonization
Diimine Stabaxol KE 7,646 0.4%, 1,4- double (hydroxyl hexafluoro isopropyl) benzene diglycidyl ether 0.3%, phosphorous acid
Bisphenol-A ester 1.5%, nucleator Surlyn8920 0.8%, the mixture (weight ratio of lubricant ethylene bis stearamide and silicone
2:1) 1.5%.
Embodiment 4
Preparation method with embodiment 1, difference lies in：Recycled PET bottles material 93%, pyromellitic acid anhydride 1.1%, poly- carbonization
Diimine Stabaxol KE 7,646 0.8%, 1,4- double (hydroxyl hexafluoro isopropyl) benzene diglycidyl ether 0.4%, phosphorous acid
Bisphenol-A ester 1.6%, nucleator Surlyn8920 0.6%, lubricating auxiliary agent ethylene bis stearamide 2.5%.
Embodiment 5
Preparation method with embodiment 1, difference lies in：Recycled PET bottles material 92.5%, pyromellitic acid anhydride 1.1%, poly- carbon
Change diimine Stabaxol KE 7,646 0.8%, the copolymerization of Hexafluorobutyl mathacrylate-co- glycidyl methacrylate
Thing 0.5%, phosphorous acid bisphenol-A ester 1.8%, nucleator Surlyn 8,920 0.8%, lubricating auxiliary agent ethylene bis stearamide
2.5%.
Comparative example 1
Comparative example polyester granules weight percentages of components is as follows：
Preparation method with embodiment 1, difference lies in：Recycled PET bottles material 94.5%, pyromellitic acid anhydride 1.3%, poly- carbon
Change diimine Stabaxol KE 7,646 0.4%, phosphorous acid bisphenol-A ester 1.5%, nucleator Surlyn 8,920 0.8%, profit
The mixture of lubrication prescription ethylene bis stearamide and silicone (weight ratio 2:1) 1.5%
The performance for the polyester material that embodiment is prepared with comparative example is detected, is detected as follows, testing result such as table 1
Shown in table 2；
Mechanics parameter test method：Pellet is molded into by dumbbell shape batten by injection molding machine, batten is placed in 50 DEG C of water-baths
2h corrosion tests are carried out under environment difference acid-base condition, using omnipotent mechanics tester, respectively refer to ASTM D256,
ASTMD638, ASTMD790 standard, mechanical property before and after test impact property, tensile property and bending property test corrosion, take
Average out to result three times；
Corrode front and rear surfaces pattern variation characteristic and use Japan Hitachi companies S-3400N (II) scanning electron microscope
Observation；As a result as shown in FIG. 1 to 3, Fig. 1 is polyester material and the polyester material of comparative example preparation prepared by the embodiment of the present invention 3
SEM photograph before material corrosion；Fig. 2 is that polyester material prepared by the embodiment of the present invention 3 corrodes traversing of probe electron microscope；Fig. 3 is this
Polyester material corrosion traversing of probe electron microscope prepared by invention comparative example.As seen from the figure, before corrosion, in embodiment 3 and comparative example
Surface of polyester it is all more smooth, without it is obvious the defects of；After acid corrosion, the material surface of embodiment 3 does not have significant change,
And there is obvious hole in the material surface in comparative example；After caustic corrosion, the material surface in embodiment 3 has least a portion of
Hole occurs, and the material surface in comparative example is by heavy corrosion.
Mechanics parameter conservation rate after the recycled PET polyester granules acid corrosion of the present invention of table 1
Mechanics parameter conservation rate after the recycled PET polyester granules caustic corrosion of the present invention of table 2
The above-mentioned polyester granules based on recycled PET bottles material, which are can be seen that, from table 1,2 data of table passes through proper content scope
Each component interacts during melting extrusion so that composite material of the present invention has excellent antiacid alkali wet-heat resisting corrosivity
Can, so that the product using the polyester granules as raw material can be used in hygrothermal environment for a long time.By the data phase in Tables 1 and 2
Than understanding, polyester granules prepared by above-described embodiment 1~5 by adjusting nucleator, anti-hydrolysis agent, fluoro epoxide,
The constituent content such as pyromellitic acid anhydride and heat stabilizer, and rationally compounded, make to form perfect interpenetrating net with matrix resin
Network, while a small amount of fluorine element priority enrichment forms water repellent layer in material surface, the acid and alkali-resistance for improving recycled PET polyester granules resists
Hot-water corrosion ability.
The explanation of above example is only intended to help to understand method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide scope caused.
Claims (10)
1. a kind of polyester material based on recycled PET, is prepared by following raw material：
2. polyester material according to claim 1, it is characterised in that the content of the recycled PET is 92~95wt%.
3. polyester material according to claim 1, it is characterised in that the content of the pyromellitic acid anhydride for 0.6~
1.2wt%.
4. polyester material according to claim 1, it is characterised in that the fluoro epoxide is selected from bis-phenol base hexafluoro
Double (3- glycidyl ether tetrafluoros the phenoxy group) -2- hydroxy propanes of propane diglycidyl ether, 1,3-, double (the hydroxyl hexafluoros of 1,4-
Isopropyl) double (hydroxyl hexafluoro is different by benzene diglycidyl ether, double (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of 1,3-, 1,3-
Propyl group) positive perfluoro propyl benzene diglycidyl ether, double (hydroxyl hexafluoro isopropyl) the phenyl tetrafluoride diglycidyl ethers of 1,4-, 4,4 '-
Dihydroxy octafluorobiphenyl diglycidyl ether, 4,4 '-bis- (hydroxyl hexafluoro isopropyl) octafluorobiphenyl diglycidyl ethers, (3- tri-
Methyl fluoride benzene) hydroquinone glycidol ether, double (4- glycidols phenyl) -1- (3 '-fluoroform phenyl) -2,2,2- three of 1,1-
Fluoroethane, fluorine-containing biphenyl type epoxy resin and 4,4 '-bis- (2,3- glycidoxies) -1- (3- fluoroforms phenyl) -2,2,2- three
One or more in fluoroethane and fluorine-containing glycidol (methyl) acrylate polymer.
5. polyester material according to claim 1, it is characterised in that the anti-hydrolysis agent is selected from Carbodiimides, choosing
From dicyclohexylcarbodiimide, N, N '-diisopropylcarbodiimide, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimide salt
One or more in hydrochlorate and polycarbodiimide.
6. polyester material according to claim 1, it is characterised in that the nucleator is ionomer type nucleator, is selected from
Ethylene-acrylic acid sodium ionomer, ethylene-methyl methacrylate sodium ionomer, ethylene-acrylic acid calcium ionomer, ethylene-acrylic acid zinc
One or more in ionomer, ethylene-methyl methacrylate calcium ionomer and ethylene-methyl methacrylate zinc ionomer.
7. polyester material according to claim 1, it is characterised in that the heat stabilizer is selected from (Asia) phosphoric acid ester, choosing
From phosphorous acid bisphenol-A ester, four (2,4- di-tert-butyl-phenyls -4,4 '-xenyl) biphosphonates, N, N '-hexylidene -1,6- two
[(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythrites
One in ester, three (2,4- di-tert-butyl-phenyls) phosphite esters and double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites
Kind is a variety of.
8. polyester material according to claim 1, it is characterised in that it is double stearic that the lubricant is selected from silicone, ethylene
One or more in acid amides, low molecular weight high polymer and ethylene bis stearamide and its derivative.
9. the preparation method of the polyester material described in claim 1, including：
By recycled PET, pyromellitic acid anhydride, anti-hydrolysis agent, nucleator, fluoro epoxide, heat stabilizer and lubricant
Mix in proportion, obtain mixed material；
By the mixed material successively through melting extrusion, granulation, polyester material is obtained.
10. preparation method according to claim 9, it is characterised in that the melting extrusion using double screw extruder into
OK, area's temperature of the double screw extruder is 160~200 DEG C, and two area's temperature are 190~230 DEG C, and three area's temperature are 220
~260 DEG C, four area's temperature are 220~260 DEG C；Time of delivery of the mixed material in the screw rod of double screw extruder is 3
~5min.
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| CN114656626A (en) * | 2020-12-22 | 2022-06-24 | 中国科学院宁波材料技术与工程研究所 | Reworkable thermosetting resin based on polyethylene terephthalate and preparation method thereof |
| CN114805775A (en) * | 2022-05-17 | 2022-07-29 | 华润化学材料科技股份有限公司 | Regenerated PET (polyethylene terephthalate) polyester, regenerated flame-retardant PET foam material and preparation method thereof |
| CN116218157A (en) * | 2022-12-28 | 2023-06-06 | 深圳市益联塑胶有限公司 | Modified injection molding grade rPET material based on recycled PET and preparation method thereof |
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