CN106117528B - 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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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 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
- 239000002699 waste material Substances 0.000 claims abstract description 24
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 18
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 56
- 238000010792 warming Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 238000003756 stirring Methods 0.000 claims description 13
- 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
- 238000009413 insulation Methods 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 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical group COP(O)(=O)OC KKUKTXOBAWVSHC-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
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 235000013361 beverage Nutrition 0.000 abstract description 3
- 229920006300 shrink film Polymers 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 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
- 238000000746 purification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- -1 bottle piece Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease 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
- 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08G63/16—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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a kind of preparation method of high-performance regenerative PET G copolyesters：Step 1 waste PET G polyester pre-processes, step 2EG alcoholysis PETG polyester, step 3 abjection EG, step 4 polycondensation reaction.Gained recycled polyester of the invention can replace primary polyester to be applied to PETG sections, sheet material, heat shrink films, beverage label, battery label etc..Both waste resource high efficiente callback utilization had been reached, and had met the needs of enterprise subtracts this increasing profit again, while met that social sustainable development strategy uses.It is suitable for the recycling of waste PET G sheet materials, bottle piece and film.
Description
Technical field
The present invention relates to the production technical field of waste PET G polyester reclaimings, and in particular to an a kind 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
The odorless high transparency of poison, is made after film, and glossiness is preferable, is easy to print, be also applicable at present beverage bottle, packaging for foodstuff with
The TAG fields such as cosmetics.According to incompletely statistics, China PETG sheet materials, bottle piece, film etc. are per about million tons of Year's consumption, therefore
There are substantial amounts of PETG products to need to be recycled, and there are leftover pieces to be also required to be recovered profit in production of polyester building-up process
With being reclaimed to waste polyester, 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 the protection to ecological environment and PET industry sustainable development all have great meaning
Justice.Waste film recovery method mainly has two kinds at present：Including physiochemical mutagens and chemical recovery.Physiochemical mutagens are mainly by polyester
And its product passes through simple separation, cleaning, melt pelletization, obtains secondary plastic products, although simple process, cost is relatively low,
But resulting product viscosity step-down, hydraulic performance decline, and secondary plastics can not be reclaimed again, not reach the mesh of recycling
, polymer depolymerization is small molecule and oligomer mainly by chemical method by chemical recovery, can be obtained by separation, purification
Intermediate, common depolymerization method mainly include Hydrolyze method, Methanolysis and glycolysis alcoholysis, and wherein Hydrolyze method process is complicated,
Product purification is more difficult, and process is not environmentally；Methanolysis is needed to carry out at high temperature under high pressure, and high, power consumption is required to equipment performance
Greatly；Glycolysis alcoholysis condition is more gentle, and normal pressure can be completed, and obtained intermediate can carry out polycondensation reaction again, finally obtain
Recycled polyester, if pet copolyester depolymerization is complete, gained recycled polyester performance can replace the primary polyester synthesized by PTA methods, can
With by will polymerize to obtain high-performance regeneration copolyesters again after polyester depolymerization.
Publication No. CN103012758B patent discloses a kind of recovery and treatment method of PET polyester, this method be by
The PET polyester of recovery adds the mixed liquor of ethylene glycol and catalyst after melting, filtering in polyester fondant, carries out alcoholysis
Meet again and react, 250 ~ 320 DEG C, pressure 50-1500Pa of reaction temperature, gained polyester viscosity is only 0.62-0.68dl/g；Application number
Disclose a kind of preparation method of recycled polyester for 20141060131.8 patent, this method first by polyester in ethylene glycol with urging
The lower depolymerization of agent effect, ethylene glycol and polyester mass ratio are 4-50：1,160-240 DEG C of de-polymerization temperature, depolymerization is contracted again completely
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 for reaction,
Power consumption is larger.Gained polyester viscosity is only up to 0.712dl/g, it is seen that the method gained recycled polyester in the case of high energy consumption
Performance is general.
The content of the invention
The present invention in view of the shortcomings of the prior art, a kind of preparation side of high-performance regenerative PET G copolyesters of research and design
Method, a variety of waste polyester raw materials can be prepared into the copolyesters that a kind of structural homogeneity can be stablized, its object is to：There is provided a kind of
Low-power consumption, process environment-friendly and high-performance PETG copolyesters preparation method.
The technical solution of the present invention：A kind of preparation method of high-performance regenerative PET G copolyesters, it is characterised in that：Bag
Include following steps, the pretreatment of step 1 waste PET G polyester：Waste PET G polyester is first separated, then crushed through pulverizer, and by its
It is placed in ethanol solution and is followed by stirring and washing, 24h, polyester after being pre-processed then is dried in 75 DEG C of air dry ovens；
Step 2EG alcoholysis PETG polyester：Take the parts by weight of PETG polyester 100,0. 2~0.5 weight after being pre-processed in step 1
Part alcoholysis catalysts, 0.01~0.03 parts by weight cocatalyst, 300 parts by weight ethylene glycol are added in reactor, lead to nitrogen,
Condensate return is then turned on, is warming up to 185~197 DEG C, stirring is opened, reacts and terminate after 0.5~4h of insulation backflow, obtain centre
Product；
Step 3 deviates from EG：After depolymerization terminates, 240 DEG C are warming up to, deviates from EG and collects；
Step 4 polycondensation reaction：Polycondensation catalyst, stabilizer are added in reactor, are warming up to 260~270 DEG C, is taken out true
Sky, 2~4h is incubated, obtains recycled polyester.
Preferably, alcoholysis catalysts are zinc acetate or zinc acetate basic in the step 2.
Preferably, the cocatalyst in the step 2 is ethylene glycol sodium.
Preferably, intermediate product is diglycol terephthalate in the step 2（BHET）, oligomer and EG it is mixed
Compound.
Preferably, in the step 4 polycondensation catalyst be titanium ethylene glycolate, antimony glycol, one kind in ethylene glycol aluminium or
Two kinds of compoundings.
Preferably, stabilizer is dimethyl phosphate, trimethyl phosphate, dimethylphosphite, phosphorous acid three in the step 4
One or more in methyl esters.
Beneficial effects of the present invention：By alcoholysis ,-de- ethylene glycol-, which polymerize to concentrate in a reactor again, is carried out, three wastes
Produce, it is at ambient pressure, innovative by alcoholysis catalysts eston and ethylene glycol sodium compounding use, at 185 DEG C, alcoholysis
PETG polyester depolymerization rates can be reached 99.6% by 0.5h；The excessive recyclable recyclings of EG, the polyesters intrinsic viscosity finally given
Up to 0.92dl/g, primary polyester can be replaced completely.Gained recycled polyester can replace primary polyester be applied to PETG section,
Sheet material, heat shrink films, beverage label, battery label etc..Both waste resource high efficiente callback utilization had been reached, and had met that enterprise subtracts this increasing again
The demand of profit, while meet that social sustainable development strategy uses.It is suitable for waste PET G sheet materials, bottle piece and film
Recycling.
Embodiment：
The present invention is further elaborated with reference to specific embodiment, the purpose 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
A kind of preparation method of high-performance regenerative PET G copolyesters, comprises the following steps：（1）Waste PET G polyester is located in advance
Reason：Waste PET G polyester is first separated, then crushed through pulverizer, and is placed in ethanol solution and is followed by stirring and washing, then
24h, polyester after being pre-processed are dried in 75 DEG C of air dry ovens；
（2）EG alcoholysis PETG polyester：Take in step 1 pre-process after the parts by weight of PETG polyester 100,0.5 parts by weight acetic acid zinc,
300 parts by weight ethylene glycol, are added in reactor together, lead to nitrogen, are then turned on condensate return, are warming up to 197 DEG C, unlatching is stirred
Mix, react and terminate after insulation backflow 4h, obtain intermediate product；
（3）Deviate from EG：After depolymerization terminates, 240 DEG C are warming up to, deviates from EG and collects；
（4）Polycondensation reaction：Polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are added in reactor, risen
Temperature vacuumizes to 270 DEG C, is incubated 4h, obtains recycled polyester.
Gained polyester depolymerization rate is 94%, and recycled polyester intrinsic viscosity is 0.76dl/g.
Embodiment 2：
A kind of preparation method of high-performance regenerative PET G copolyesters, comprises the following steps：（1）Waste PET G polyester is located in advance
Reason：Waste PET G polyester is first separated, then crushed through pulverizer, and is placed in ethanol solution and is followed by stirring and washing, then
24h, polyester after being pre-processed are dried in 75 DEG C of air dry ovens；
（2）EG alcoholysis PETG polyester：Take the parts by weight of PETG polyester 100,0.2 parts by weight alkali formula vinegar after being pre-processed in step 1
Sour zinc, 300 parts by weight ethylene glycol, are added in reactor together, lead to nitrogen, are then turned on condensate return, are warming up to 192 DEG C,
Stirring is opened, reacts and terminates after insulation backflow 4h, obtain intermediate product；
（3）Deviate from EG：After depolymerization terminates, 240 DEG C are warming up to, deviates from EG and collects；
（4）Polycondensation reaction：Polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are added in reactor, risen
Temperature vacuumizes to 270 DEG C, is incubated 4h, obtains recycled polyester.
Gained polyester depolymerization rate is 96%, and recycled polyester intrinsic viscosity is 0.78dl/g.
Embodiment 3：
A kind of preparation method of high-performance regenerative PET G copolyesters, comprises the following steps：（1）Waste PET G polyester is located in advance
Reason：Waste PET G polyester is first separated, then crushed through pulverizer, and is placed in ethanol solution and is followed by stirring and washing, then
24h, polyester after being pre-processed are dried in 75 DEG C of air dry ovens；
（2）EG alcoholysis PETG polyester：Take the parts by weight of PETG polyester 100,0.2 parts by weight alkali formula vinegar after being pre-processed in step 1
Sour zinc, 0.02 parts by weight ethylene glycol sodium, 300 parts by weight ethylene glycol, are added in reactor together, lead to nitrogen, are then turned on condensing
Water flows back, and is warming up to 192 DEG C, opens stirring, reacts and terminate after insulation backflow 2h, obtain intermediate product；
（3）Deviate from EG：After depolymerization terminates, 240 DEG C are warming up to, deviates from EG and collects；
（4）Polycondensation reaction：Polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are added in reactor, risen
Temperature vacuumizes to 270 DEG C, is incubated 2h, obtains recycled polyester.
Gained polyester depolymerization rate is 99.6%, and recycled polyester intrinsic viscosity is 0.92dl/g.
Embodiment 4：
A kind of preparation method of high-performance regenerative PET G copolyesters, comprises the following steps：（1）Waste PET G polyester is located in advance
Reason：Waste PET G polyester is first separated, then crushed through pulverizer, and is placed in ethanol solution and is followed by stirring and washing, then
24h, polyester after being pre-processed are dried in 75 DEG C of air dry ovens；
（2）EG alcoholysis PETG polyester：Take the parts by weight of PETG polyester 100,0.2 parts by weight alkali formula vinegar after being pre-processed in step 1
Sour zinc, 0.02 parts by weight ethylene glycol sodium, 300 parts by weight ethylene glycol, are added in reactor together, lead to nitrogen, are then turned on condensing
Water flows back, and is warming up to 185 DEG C, opens stirring, reacts and terminate after insulation backflow 0.5h, obtain intermediate product；
（3）Deviate from EG：After depolymerization terminates, 240 DEG C are warming up to, deviates from EG and collects；
（4）Polycondensation reaction：Polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are added in reactor, risen
Temperature vacuumizes to 270 DEG C, is incubated 2h, obtains recycled polyester.
Gained polyester depolymerization rate is 99.4%, and recycled polyester intrinsic viscosity is 0.86dl/g.
Embodiment 5：
A kind of preparation method of high-performance regenerative PET G copolyesters, comprises the following steps：（1）Waste PET G polyester is located in advance
Reason：Waste PET G polyester is first separated, then crushed through pulverizer, and is placed in ethanol solution and is followed by stirring and washing, then
24h, polyester after being pre-processed are dried in 75 DEG C of air dry ovens；
（2）EG alcoholysis PETG polyester：Take the parts by weight of PETG polyester 100,0.02 parts by weight ethylene glycol after being pre-processed in step 1
Sodium, 300 parts by weight ethylene glycol, is added in reactor together, leads to nitrogen, is then turned on condensate return, is warming up to 192 DEG C, opens
Stirring is opened, reacts and terminates after insulation backflow 2h, obtain intermediate product；
（3）Deviate from EG：After depolymerization terminates, 240 DEG C are warming up to, deviates from EG and collects；
（4）Polycondensation reaction：Polycondensation catalyst antimony glycol, stabilizer dimethylphosphite are added in reactor, risen
Temperature vacuumizes to 270 DEG C, is incubated 2h, obtains recycled polyester.
Gained polyester depolymerization rate is 90%, and recycled polyester intrinsic viscosity is 0.75dl/g.
Claims (4)
- A kind of 1. preparation method of high-performance regenerative PET G copolyesters, it is characterised in that：Comprise the following steps,Step 1：Waste PET G polyester pre-processes：Waste PET G polyester is first separated, then crushed through pulverizer, and is placed on It is followed by stirring and washing in ethanol solution, 24h, polyester after being pre-processed then is dried in 75 DEG C of air dry ovens；Step 2：EG alcoholysis PETG polyester：Take the parts by weight of PETG polyester 100,0. 2~0.5 parts by weight alcohol after being pre-processed in step 1 Catalyst, 0.01~0.03 parts by weight cocatalyst are solved, 300 parts by weight ethylene glycol are added in reactor, lead to nitrogen, then open Condensate return is opened, is warming up to 185~197 DEG C, stirring is opened, reacts and terminate after 0.5~4h of insulation backflow, obtain middle production Thing；Step 3：Deviate from EG：After depolymerization terminates, 240 DEG C are warming up to, deviates from EG and collects；Step 4：Polycondensation reaction：Polycondensation catalyst, stabilizer are added in reactor, 260~270 DEG C is warming up to, vacuumizes, 2~4h is incubated, obtains recycled polyester；Alcoholysis catalysts are zinc acetate or zinc acetate basic in step 2；Cocatalyst in step 2 is ethylene glycol sodium.
- 2. preparation method according to claim 1, it is characterised in that：Intermediate product is terephthalic acid (TPA) in the step 2 The mixture of binaryglycol ester, oligomer and EG.
- 3. preparation method according to claim 1, it is characterised in that：In the step 4 polycondensation catalyst be titanium ethylene glycolate, One or two kinds of compounding in antimony glycol, ethylene glycol aluminium.
- 4. preparation method according to claim 1, it is characterised in that：Stabilizer is dimethyl phosphate, phosphorus in the step 4 One or more in sour trimethyl, dimethylphosphite, Trimethyl phosphite.
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|---|---|---|---|---|
| CN107557902B (en) * | 2017-09-07 | 2020-10-02 | 江苏恒科新材料有限公司 | Preparation method of cationic dyeable polyester POY (polyester pre-oriented yarn) |
| 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 |
| 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 |
| 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) |
| 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 |
| 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 |
| CN114989400B (en) * | 2022-07-05 | 2023-04-18 | 河南源宏高分子新材料有限公司 | Preparation method of chemically regenerated PETG polyester |
| 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 |
| CN118082028B (en) * | 2024-04-20 | 2024-08-16 | 河南银金达彩印股份有限公司 | Method for recycling waste mixed multilayer composite waste plastic film |
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| CN101805445A (en) * | 2010-01-29 | 2010-08-18 | 成强 | Chemical treating method for melt polycondensation high polymer old material regeneration |
| CN104327254A (en) * | 2014-11-03 | 2015-02-04 | 东华大学 | Preparation method of recycled polyester |
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