CN106117528A - A kind of preparation method of high-performance regenerative PET G copolyesters - Google Patents
A kind of preparation method of high-performance regenerative PET G copolyesters Download PDFInfo
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- CN106117528A CN106117528A CN201610468025.3A CN201610468025A CN106117528A CN 106117528 A CN106117528 A CN 106117528A CN 201610468025 A CN201610468025 A CN 201610468025A CN 106117528 A CN106117528 A CN 106117528A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 16
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 81
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 18
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 238000010792 warming Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- NWJKPSLXLQLUTC-UHFFFAOYSA-N ethane-1,2-diol;sodium Chemical compound [Na].OCCO NWJKPSLXLQLUTC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 4
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 4
- -1 ethylene glycol aluminum compounds Chemical class 0.000 claims description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical group COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- XVBXJBGOQQLLAO-UHFFFAOYSA-J [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O Chemical compound [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O XVBXJBGOQQLLAO-UHFFFAOYSA-J 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 235000013361 beverage Nutrition 0.000 abstract description 2
- 229920006300 shrink film Polymers 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 16
- 238000011084 recovery Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000034659 glycolysis Effects 0.000 description 2
- 238000006140 methanolysis reaction Methods 0.000 description 2
- 239000003471 mutagenic agent Substances 0.000 description 2
- 231100000707 mutagenic chemical Toxicity 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- PWZUUYSISTUNDW-VAFBSOEGSA-N quinestrol Chemical compound C([C@@H]1[C@@H](C2=CC=3)CC[C@]4([C@H]1CC[C@@]4(O)C#C)C)CC2=CC=3OC1CCCC1 PWZUUYSISTUNDW-VAFBSOEGSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
Abstract
The invention discloses the preparation method of a kind of high-performance regenerative PET G copolyesters: step 1 waste PET G polyester pretreatment, step 2EG alcoholysis PETG polyester, step 3 deviates from EG, step 4 polycondensation reaction.Gained recycled polyester of the present invention can replace primary polyester to be applied to PETG section, sheet material, heat shrink films, beverage label, battery label etc..Both reached waste resource high efficiente callback to utilize, and met again enterprise and subtract the demand of this increasing profit, and met social sustainable development strategy simultaneously and use.It is suitable for waste PET G sheet material, bottle sheet and the recycling of thin film.
Description
Technical field
The present invention relates to the production technical field of waste PET G polyester reclaiming, be specifically related to one one kinds of high-performance regeneration
The preparation method of PETG copolyesters.
Background technology
PETG is a kind of amorphous high transparency engineering plastics, is widely used in articles for daily use and industrial goods, due to its nothing
Poison odorless high transparency, after making thin film, glossiness is preferable, it is easy to printing, be currently also used in carafe, packaging for foodstuff with
The TAG field such as cosmetics.According to incompletely statistics, every Year's consumption about million tons such as China's PETG sheet material, bottle sheet, thin film, therefore
There are substantial amounts of PETG goods to need to be recycled, and have leftover pieces to be also required to be recovered profit in production of polyester building-up process
With, waste polyester is reclaimed, on the one hand can alleviate the pressure of polyester synthesis raw material-this non-renewable resources of oil, simultaneously
Also enterprise's production cost is reduced；On the other hand protection and PET industry sustainable development to ecological environment all have great meaning
Justice.Waste film recovery method mainly has two kinds at present: include physiochemical mutagens and chemical recovery.Physiochemical mutagens is mainly polyester
And goods are through simple separation, cleaning, melt pelletization, obtain secondary plastic, although simple process, cost is relatively low,
But resulting product viscosity step-down, hydraulic performance decline, and secondary plastics cannot be carried out again reclaiming, and do not reach the mesh of recycling
, it is little molecule and oligomer by polymer depolymerization that chemical recovery is mainly by chemical method, through separating, purify and can obtain
Intermediate, common depolymerization method mainly includes Hydrolyze method, Methanolysis and glycolysis alcoholysis, and wherein Hydrolyze method process is complicated,
Product purifies more difficult, and process is not environmentally；Methanolysis needs to carry out at high temperature under high pressure, and equipment performance is required high, power consumption
Greatly；Glycolysis alcoholysis condition is the gentleest, and normal pressure can complete, and the intermediate obtained can carry out polycondensation reaction again, finally obtains
Recycled polyester, if pet copolyester depolymerization is complete, gained recycled polyester performance can substitute for the primary polyester synthesized by PTA method, can
With by repolymerization after polyester depolymerization being obtained high-performance regeneration copolyesters.
The patent of Publication No. CN103012758B discloses the recovery and treatment method of a kind of PET polyester, the method be by
The PET polyester reclaimed, after melting, filtering, adds the mixed liquor of ethylene glycol and catalyst in polyester fondant, carries out alcoholysis
Meeting again and react, reaction temperature 250 ~ 320 DEG C, pressure 50-1500Pa, gained polyester viscosity is only 0.62-0.68dl/g；Application number
Be 20141060131.8 patent disclose the preparation method of a kind of recycled polyester, the method first by polyester ethylene glycol with urge
Depolymerization under agent effect, ethylene glycol and polyester mass ratio are 4-50:1, and de-polymerization temperature 160-240 DEG C, depolymerization is contracted the most again
Poly-reaction, gained recycled polyester viscosity is 0.662 ~ 0.712dl/g, and not only consumption ethylene glycol amount is big, de-polymerization temperature is higher in reaction,
Power consumption is bigger.Gained polyester viscosity is only up to 0.712dl/g, it is seen that the method is gained recycled polyester in the case of high energy consumption
Performance is general.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the research design preparation side of a kind of high-performance regenerative PET G copolyesters
Method, can be prepared as multiple waste polyester raw material the copolyesters that a kind of structural homogeneity can be stable, its object is to: provide one
Low-power consumption, the preparation method of PETG copolyesters of process environment-friendly and high-performance.
The technical solution of the present invention: the preparation method of a kind of high-performance regenerative PET G copolyesters, it is characterised in that: bag
Include following steps, step 1 waste PET G polyester pretreatment: first separated by waste PET G polyester, more size-reduced machine to pulverize, and by it
It is placed in ethanol solution and is stirred washing, in 75 DEG C of air dry ovens, be then dried 24h, obtain polyester after pretreatment；
Step 2EG alcoholysis PETG polyester: take in step 1 PETG polyester 100 weight portion after pretreatment, 0. 2～0.5 weight portion alcohol
Solving catalyst, 0.01～0.03 weight portion cocatalyst, 300 weight portion ethylene glycol join in reactor, logical nitrogen, then open
Open condensate return, be warming up to 185～197 DEG C, open stirring, react after insulation backflow 0.5～4h and terminate, obtain middle product
Thing；
Step 3 deviates from EG: after depolymerization terminates, and is warming up to 240 DEG C, and abjection EG also collects；
Step 4 polycondensation reaction: join in reactor by polycondensation catalyst, stabilizer, is warming up to 260～270 DEG C, evacuation,
Insulation 2～4h, obtains recycled polyester.
Preferably, in described step 2, alcoholysis catalysts is zinc acetate or zinc acetate basic.
Preferably, the cocatalyst in described step 2 is ethylene glycol sodium.
Preferably, in described step 2, intermediate product is the mixed of diglycol terephthalate (BHET), oligomer and EG
Compound.
Preferably, one during polycondensation catalyst is titanium ethylene glycolate, antimony glycol, ethylene glycol aluminum in described step 4 or
Two kinds compound.
Preferably, in described step 4, stabilizer is dimethyl phosphate, trimethyl phosphate, dimethylphosphite, tricresyl phosphite
One or more in methyl ester.
Beneficial effects of the present invention: alcoholysis-de-ethylene glycol-repolymerization is concentrated in a reactor and carries out, without the three wastes
Produce, at ambient pressure, using compounding to alcoholysis catalysts eston and ethylene glycol sodium of novelty, when 185 DEG C, alcoholysis
PETG polyester depolymerization rate can be reached 99.6% by 0.5h；The recyclable recycling of EG of excess, the polyesters intrinsic viscosity finally given
It is up to 0.92dl/g, can substitute for primary polyester completely.Gained recycled polyester can replace primary polyester be applied to PETG section,
Sheet material, heat shrink films, beverage label, battery label etc..Both reached waste resource high efficiente callback to utilize, and met again enterprise and subtract this increasing
The demand of profit, meets social sustainable development strategy simultaneously and uses.It is suitable for waste PET G sheet material, bottle sheet and thin film
Recycling.
Detailed description of the invention:
Below in conjunction with specific embodiment, the present invention is further elaborated, its objective is to be best understood from present disclosure, therefore,
Institute's illustrated example has no effect on protection scope of the present invention.
Embodiment 1
The preparation method of a kind of high-performance regenerative PET G copolyesters, comprises the steps: the G polyester pretreatment of (1) waste PET: will
Waste PET G polyester first separates, more size-reduced machine pulverize, and be placed in ethanol solution be stirred washing, then at 75 DEG C
Air dry oven is dried 24h, obtains polyester after pretreatment；
(2) EG alcoholysis PETG polyester: take in step 1 PETG polyester 100 weight portion after pretreatment, 0.5 parts by weight acetic acid zinc, 300
Weight portion ethylene glycol, joins in reactor together, logical nitrogen, is then turned on condensate return, is warming up to 197 DEG C, opens stirring,
React after insulation backflow 4h and terminate, obtain intermediate product；
(3) abjection EG: after depolymerization terminates, be warming up to 240 DEG C, abjection EG also collect；
(4) polycondensation reaction: polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are joined in reactor, is warming up to
270 DEG C, evacuation, it is incubated 4h, obtains recycled polyester.
Gained polyester depolymerization rate is 94%, and recycled polyester intrinsic viscosity is 0.76dl/g.
Embodiment 2:
The preparation method of a kind of high-performance regenerative PET G copolyesters, comprises the steps: the G polyester pretreatment of (1) waste PET: will
Waste PET G polyester first separates, more size-reduced machine pulverize, and be placed in ethanol solution be stirred washing, then at 75 DEG C
Air dry oven is dried 24h, obtains polyester after pretreatment；
(2) EG alcoholysis PETG polyester: take in step 1 PETG polyester 100 weight portion after pretreatment, 0.2 weight portion zinc acetate basic,
300 weight portion ethylene glycol, join in reactor together, logical nitrogen, are then turned on condensate return, are warming up to 192 DEG C, and unlatching is stirred
Mix, react after insulation backflow 4h and terminate, obtain intermediate product；
(3) abjection EG: after depolymerization terminates, be warming up to 240 DEG C, abjection EG also collect；
(4) polycondensation reaction: polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are joined in reactor, is warming up to
270 DEG C, evacuation, it is incubated 4h, obtains recycled polyester.
Gained polyester depolymerization rate is 96%, and recycled polyester intrinsic viscosity is 0.78dl/g.
Embodiment 3:
The preparation method of a kind of high-performance regenerative PET G copolyesters, comprises the steps: the G polyester pretreatment of (1) waste PET: will
Waste PET G polyester first separates, more size-reduced machine pulverize, and be placed in ethanol solution be stirred washing, then at 75 DEG C
Air dry oven is dried 24h, obtains polyester after pretreatment；
(2) EG alcoholysis PETG polyester: take in step 1 PETG polyester 100 weight portion after pretreatment, 0.2 weight portion zinc acetate basic,
0.02 weight portion ethylene glycol sodium, 300 weight portion ethylene glycol, join together in reactor, logical nitrogen, be then turned on condensed water and return
Stream, is warming up to 192 DEG C, opens stirring, reacts and terminates, obtain intermediate product after insulation backflow 2h；
(3) abjection EG: after depolymerization terminates, be warming up to 240 DEG C, abjection EG also collect；
(4) polycondensation reaction: polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are joined in reactor, is warming up to
270 DEG C, evacuation, it is incubated 2h, obtains recycled polyester.
Gained polyester depolymerization rate is 99.6%, and recycled polyester intrinsic viscosity is 0.92dl/g.
Embodiment 4:
The preparation method of a kind of high-performance regenerative PET G copolyesters, comprises the steps: the G polyester pretreatment of (1) waste PET: will
Waste PET G polyester first separates, more size-reduced machine pulverize, and be placed in ethanol solution be stirred washing, then at 75 DEG C
Air dry oven is dried 24h, obtains polyester after pretreatment；
(2) EG alcoholysis PETG polyester: take in step 1 PETG polyester 100 weight portion, 0.2 weight portion alkali formula acetic acid after pretreatment
Zinc, 0.02 weight portion ethylene glycol sodium, 300 weight portion ethylene glycol, join together in reactor, logical nitrogen, be then turned on condensed water
Backflow, is warming up to 185 DEG C, opens stirring, reacts and terminates, obtain intermediate product after insulation backflow 0.5h；
(3) abjection EG: after depolymerization terminates, be warming up to 240 DEG C, abjection EG also collect；
(4) polycondensation reaction: polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are joined in reactor, is warming up to
270 DEG C, evacuation, it is incubated 2h, obtains recycled polyester.
Gained polyester depolymerization rate is 99.4%, and recycled polyester intrinsic viscosity is 0.86dl/g.
Embodiment 5:
The preparation method of a kind of high-performance regenerative PET G copolyesters, comprises the steps: the G polyester pretreatment of (1) waste PET: will
Waste PET G polyester first separates, more size-reduced machine pulverize, and be placed in ethanol solution be stirred washing, then at 75 DEG C
Air dry oven is dried 24h, obtains polyester after pretreatment；
(2) EG alcoholysis PETG polyester: take in step 1 PETG polyester 100 weight portion, 0.02 weight portion ethylene glycol sodium after pretreatment,
300 weight portion ethylene glycol, join in reactor together, logical nitrogen, are then turned on condensate return, are warming up to 192 DEG C, and unlatching is stirred
Mix, react after insulation backflow 2h and terminate, obtain intermediate product；
(3) abjection EG: after depolymerization terminates, be warming up to 240 DEG C, abjection EG also collect；
(4) polycondensation reaction: polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are joined in reactor, is warming up to
270 DEG C, evacuation, it is incubated 2h, obtains recycled polyester.
Gained polyester depolymerization rate is 90%, and recycled polyester intrinsic viscosity is 0.75dl/g.
Claims (6)
1. the preparation method of a high-performance regenerative PET G copolyesters, it is characterised in that: comprise the steps, step 1: discarded
PETG polyester pretreatment: waste PET G polyester is first separated, more size-reduced machine pulverizes, and be placed in ethanol solution and stir
Mix washing, in 75 DEG C of air dry ovens, be then dried 24h, obtain polyester after pretreatment；
Step 2:EG alcoholysis PETG polyester: take in step 1 PETG polyester 100 weight portion after pretreatment, 0. 2～0.5 weight portion alcohol
Solving catalyst, 0.01～0.03 weight portion cocatalyst, 300 weight portion ethylene glycol join in reactor, logical nitrogen, then open
Open condensate return, be warming up to 185～197 DEG C, open stirring, react after insulation backflow 0.5～4h and terminate, obtain middle product
Thing；
Step 3: abjection EG: after depolymerization terminates, be warming up to 240 DEG C, abjection EG also collect；
Step 4: polycondensation reaction: join in reactor by polycondensation catalyst, stabilizer, is warming up to 260～270 DEG C, evacuation,
Insulation 2～4h, obtains recycled polyester.
Preparation method the most according to claim 1, it is characterised in that: in described step 2 alcoholysis catalysts be zinc acetate or
Zinc acetate basic.
Preparation method the most according to claim 1, it is characterised in that: the cocatalyst in described step 2 is ethylene glycol
Sodium.
Preparation method the most according to claim 1, it is characterised in that: in described step 2, intermediate product is p-phthalic acid
Binaryglycol ester (BHET), oligomer and the mixture of EG.
Preparation method the most according to claim 1, it is characterised in that: in described step 4 polycondensation catalyst be titanium ethylene glycolate,
One or two kinds of in antimony glycol, ethylene glycol aluminum compounds.
Preparation method the most according to claim 1, it is characterised in that: in described step 4, stabilizer is dimethyl phosphate, phosphorus
Acid trimethyl, dimethylphosphite, NSC 6513 in one or more.
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| CN201610468025.3A CN106117528B (en) | 2016-06-24 | 2016-06-24 | A kind of preparation method of high-performance regenerative PET G copolyesters |
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| CN201610468025.3A CN106117528B (en) | 2016-06-24 | 2016-06-24 | A kind of preparation method of high-performance regenerative PET G copolyesters |
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| CN106117528B CN106117528B (en) | 2018-03-13 |
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| CN110606943A (en) * | 2019-09-09 | 2019-12-24 | 江苏景宏新材料科技有限公司 | Method for preparing water-soluble polyester from waste PETG |
| CN110643023A (en) * | 2019-09-09 | 2020-01-03 | 江苏景宏新材料科技有限公司 | Method for preparing unsaturated polyester resin from waste PETG |
| CN112252061A (en) * | 2020-10-29 | 2021-01-22 | 湖南金全立生物科技股份有限公司 | Environment-friendly multifunctional dye-proofing agent and preparation method thereof |
| CN113277928A (en) * | 2021-01-20 | 2021-08-20 | 银金达(上海)新材料有限公司 | Method for recovering and degrading PETG (polyethylene terephthalate glycol) |
| TWI742994B (en) * | 2021-01-29 | 2021-10-11 | 南亞塑膠工業股份有限公司 | Matte polyester film and method for manufacturing the same |
| TWI746359B (en) * | 2021-01-29 | 2021-11-11 | 南亞塑膠工業股份有限公司 | Polyester film and method for producing the same |
| CN114989400A (en) * | 2022-07-05 | 2022-09-02 | 河南源宏高分子新材料有限公司 | Preparation method of chemically regenerated PETG polyester |
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| CN107557902A (en) * | 2017-09-07 | 2018-01-09 | 江苏恒科新材料有限公司 | A kind of preparation method of cation dyeable polyester POY silks |
| CN110606943A (en) * | 2019-09-09 | 2019-12-24 | 江苏景宏新材料科技有限公司 | Method for preparing water-soluble polyester from waste PETG |
| CN110643023A (en) * | 2019-09-09 | 2020-01-03 | 江苏景宏新材料科技有限公司 | Method for preparing unsaturated polyester resin from waste PETG |
| CN110643023B (en) * | 2019-09-09 | 2021-11-19 | 江苏景宏新材料科技有限公司 | Method for preparing unsaturated polyester resin from waste PETG |
| CN112252061A (en) * | 2020-10-29 | 2021-01-22 | 湖南金全立生物科技股份有限公司 | Environment-friendly multifunctional dye-proofing agent and preparation method thereof |
| CN113277928A (en) * | 2021-01-20 | 2021-08-20 | 银金达(上海)新材料有限公司 | Method for recovering and degrading PETG (polyethylene terephthalate glycol) |
| TWI742994B (en) * | 2021-01-29 | 2021-10-11 | 南亞塑膠工業股份有限公司 | Matte polyester film and method for manufacturing the same |
| TWI746359B (en) * | 2021-01-29 | 2021-11-11 | 南亞塑膠工業股份有限公司 | Polyester film and method for producing the same |
| CN114989400A (en) * | 2022-07-05 | 2022-09-02 | 河南源宏高分子新材料有限公司 | Preparation method of chemically regenerated PETG polyester |
| CN115490839A (en) * | 2022-09-21 | 2022-12-20 | 华东理工大学 | Method for preparing PETG/PCTG copolyester by depolymerizing waste PET with mixed alcohol |
| CN115490839B (en) * | 2022-09-21 | 2024-03-22 | 华东理工大学 | Method for preparing PETG/PCTG copolyester by depolymerizing waste PET through mixed alcohol |
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