CN115141363A - Method for preparing regenerated cationic polyester by using waste polyester - Google Patents
Method for preparing regenerated cationic polyester by using waste polyester Download PDFInfo
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- CN115141363A CN115141363A CN202110338653.0A CN202110338653A CN115141363A CN 115141363 A CN115141363 A CN 115141363A CN 202110338653 A CN202110338653 A CN 202110338653A CN 115141363 A CN115141363 A CN 115141363A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 103
- 239000002699 waste material Substances 0.000 title claims abstract description 54
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 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 abstract description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract 2
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical group [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 150000002148 esters Chemical group 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-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 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical group O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRDBXTBGGXLZHD-UHFFFAOYSA-N benzene-1,4-dicarboperoxoic acid Chemical compound OOC(=O)C1=CC=C(C(=O)OO)C=C1 RRDBXTBGGXLZHD-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for preparing regenerated cationic polyester by using waste polyester, which comprises the following steps: carrying out crushing, washing and drying pretreatment on the waste polyester; carrying out alcoholysis on the pretreated waste polyester in ethylene glycol to obtain BHET alcoholysis liquid; purifying the BHET alcoholysis solution to obtain a high-purity BHET monomer; high-purity BHET monomer and m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate are subjected to pre-polycondensation reaction and final polycondensation reaction under the action of a catalyst to obtain the regenerated cationic polyester. The method can directly purify to obtain the high-purity BHET monomer, so that the high-purity regenerated cationic polyester can be prepared by carrying out polycondensation with the comonomer without ester exchange, thereby simplifying the recovery and regeneration process of waste polyester, obviously reducing the use of organic solvent, obviously reducing the energy consumption and cost, obtaining the regenerated cationic polyester product which is comparable to various indexes of the original cationic polyester, and being easy to realize large-scale production.
Description
Technical Field
The invention relates to a method for preparing regenerated cationic polyester by using waste polyester, belonging to the technical field of waste polyester recycling.
Background
Polyesters (i.e., polyethylene terephthalate) are saturated polyesters obtained by Polymerizing Terephthalic Acid (PTA) or dimethyl terephthalate (DMT) with Ethylene Glycol (EG), and have been widely used in the fields of food packaging, film sheets, electronic devices, mechanical devices, etc. because of their excellent physicochemical properties. According to statistics, china becomes the first major country for producing and consuming polyester in the world in 2008, the yield accounts for more than half of the world, the yield of polyester in China reaches 3530 ten thousand tons in 2015, the yield of polyester in China reaches 5006 ten thousand tons in 2019, the amplification reaches 41.8 percent, and the yield of polyester in China is expected to reach 5327 ten thousand tons in 2020. Most of polyester products become waste products after one-time use, and thus, with the rapid development of the polyester industry, the yield of waste polyester is increasing. However, polyester has strong chemical inertness, and is difficult to degrade or be decomposed by microorganisms after being naturally stored, which not only causes huge resource waste, but also generates serious environmental pollution, so how to realize the virtuous cycle of recycling and reusing the waste polyester has become an important subject which cannot be avoided and needs to be solved urgently in the development of the current polyester industry.
In the prior art, technical reports of preparing regenerated cationic polyester by using waste polyester are reported, such as: CN201710841873.9, the Chinese invention patent discloses a method for preparing regenerated cationic dye dyeable polyester by alcoholysis of waste polyester by an ethylene glycol method, which comprises the steps of firstly using an ethylene glycol method to alcoholyze the waste polyester to obtain an alcoholysis product containing ethylene terephthalate and oligomers, and then carrying out polycondensation with an added comonomer to finally obtain the regenerated cationic dye dyeable polyester, wherein although the patent can realize high-valued recycling of the waste polyester, the problems of the regenerated cationic polyester, such as color difference, large fluctuation of a byproduct diethylene glycol (DEG), difficulty in controlling a melting point and the like, exist in the method of the patent (as shown in table 1 in the patent specification, the intrinsic viscosity of the obtained regenerated polyester particles is 0.55-0.65 dl/g, the melting point is 220-230 ℃, the content of the diethylene glycol is 5.5 +/-0.3%, and the chroma b value is 7-8), so that the application grade of the regenerated polyester is limited. In addition, chinese patent application CN201911162169.6 discloses a method for producing recycled regenerated cationic chips, which comprises the steps of alcoholysis of dihydroxy terephthalate (BHET) with Ethylene Glycol (EG) in waste polyester, transesterification in methanol to obtain crude dimethyl terephthalate (DMT) solution and ethylene glycol, crystallization, separation, rectification and purification to obtain DMT monomer, and transesterification in ethylene glycol to obtain BHET, which is used for preparing regenerated cationic polyesters.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing regenerated cationic polyester by using waste polyester, which has the advantages of simple process, low energy consumption, high safety and easiness in large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing regenerated cationic polyester by using waste polyester comprises the following specific steps:
a) Carrying out crushing, washing and drying pretreatment on the waste polyester;
b) Carrying out alcoholysis on the pretreated waste polyester in ethylene glycol to obtain BHET alcoholysis liquid;
c) Purifying the BHET alcoholysis solution to obtain a high-purity BHET monomer with the HPLC purity of more than 99.0%;
d) Carrying out pre-polycondensation reaction and final polycondensation reaction on a high-purity BHET monomer and sodium bis (hydroxyethyl) isophthalate-5-Sulfonate (SIPE) under the action of a catalyst to obtain regenerated cationic polyester;
wherein the purification treatment in step C) comprises the following operations:
c1 Filtering the BHET alcoholysis solution obtained in the step B) to remove insoluble substances in the solution;
c2 Adding the filtrate obtained in the step C1) into a film evaporator I, and carrying out reduced pressure concentration at the temperature of 150-180 ℃ and the pressure of 1-10 KPa;
c3 The concentrated solution after the reduced pressure concentration in the step C2) is added into a film evaporator II, and the reduced pressure evaporation is carried out at the temperature of 150-180 ℃ and the pressure of 0.1-1 KPa;
c4 Adding the residue obtained after the reduced pressure evaporation in the step C3) into a short-path distiller, rectifying at the temperature of 180-230 ℃ and the pressure of 1-10 Pa, and crystallizing the collected fraction at normal temperature to obtain a white solid, namely the high-purity BHET monomer with the HPLC purity of more than 99.0%.
In a preferable scheme, the drying in the step A) means that the water content of the waste polyester is 1-3%.
In one embodiment, the alcoholysis process of step B) is as follows:
putting Ethylene Glycol (EG) and the pretreated waste polyester particles into an alcoholysis reaction kettle according to the mass ratio of (1-3) to 1, then putting a zinc acetate catalyst with the mass being 0.1-0.5% of the mass of the waste polyester particles, heating to 190-230 ℃, controlling the pressure in the alcoholysis reaction kettle to be 0.1-0.5 MPa, and carrying out alcoholysis reaction for 2-6 hours.
In one embodiment, in step D), the amount of sodium bis (hydroxyethyl) isophthalate-5-Sulfonate (SIPE) added is 1-2% of the mass of the high purity BHET monomer.
In one embodiment, in step D), the catalyst is ethylene glycol antimony, and the amount of the catalyst added is 0.01% to 0.03% of the mass of the high-purity BHET monomer.
In one embodiment, the conditions of the prepolycondensation reaction in step D) are: firstly, stirring and reacting for 1-1.5 hours at 265-270 ℃ and under the pressure of 8-12 KPa in the kettle, and then stirring and reacting for 2-2.5 hours at 272-275 ℃ and under the pressure of 1-1.5 KPa in the kettle.
In one embodiment, the conditions of the final polycondensation reaction in step D) are: stirring and reacting for 2-2.5 hours at 278-282 ℃ and the pressure in the kettle of 100-400 Pa.
In one embodiment, the waste polyester comprises polyester production waste and waste polyester products.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a purification treatment method combining reduced pressure evaporation in a 2-level film evaporator and rectification in a short-path distiller to creatively carry out alcoholysis solution on BHET, directly obtains a high-purity BHET monomer with the HPLC purity of 99.8 percent, and can directly carry out polycondensation with a comonomer to prepare high-purity regenerated cationic polyester without ester exchange, thereby simplifying the recovery and regeneration process of waste polyester, obviously reducing the use of organic solvent, obviously reducing the energy consumption and cost, breaking through the bottleneck that BHET is difficult to decolor and purify, and enabling the color value b of the regenerated cationic polyester to be within 4 +/-2; the melting point of the prepared regenerated cationic polyester is controllable (within the range of 248 +/-2 ℃), and the content fluctuation of the diethylene glycol is small (about 3.28 +/-0.1%); in addition, the detection analysis can also know that: the method can obtain the regenerated cationic polyester product which is comparable to the original cationic polyester in each index; in a word, the method has low requirement on the source of the waste polyester raw material, is easy to realize large-scale production, and the obtained regenerated cationic polyester product can be used for preparing cationic dye dyeable polyester filaments, has important significance and value for realizing the regeneration circulation of the waste polyester in the true sense, and has significant progress compared with the prior art.
Drawings
FIG. 1 is a HPLC analysis spectrum of the residue after reduced pressure evaporation in step C3); in the figure: the peak at retention time 3.504min is BHET, the peak at retention time 4.618min is BHET dimer, and the peak at retention time 7.091min is BHET trimer;
FIG. 2 is a HPLC analysis spectrum of the high purity BHET monomer obtained in the example; in the figure: the peak with retention time of 3.465min is BHET monomer;
FIG. 3 is a nuclear magnetic resonance analysis spectrum of the high purity BHET monomer obtained in the example; in the figure: δ =0ppm is a solvent peak of tetramethylsilane as an internal standard, δ =7.26ppm is a solvent peak of deuterated chloroform, δ =8.13ppm is a proton peak corresponding to hydrogen on a benzene ring in BHET, δ =4.51ppm is a proton peak of four hydrogen atoms on two methylene groups connected to an oxygen atom, and δ =4.00ppm is a proton peak of four hydrogen atoms on two methylene groups connected to a hydroxyl group.
FIG. 4 is an FTIR analysis spectrum of the high purity BHET monomer obtained in the example; in the figure: 3446cm -1 2963cm corresponding to the stretching vibration absorption peak of-OH -1 And 2880cm -1 Corresponding to the stretching vibration absorption peak of-CH 2-, 1716cm -1 1411cm corresponding to the characteristic absorption peak of C = O in ester group of stretching vibration -1 The peak near the position is the vibration absorption peak of the benzene ring skeleton, 1134cm -1 And 1282cm -1 Corresponding to the characteristic peak of C-O stretching vibration in ester group, 874cm -1 Is a characteristic absorption peak of para-substitution of a benzene ring.
Detailed Description
The technical scheme of the invention is further detailed and completely explained by combining the embodiment.
The HPLC analysis conditions were as follows:
an Agilent-1100 type high performance liquid chromatograph, wherein the specifications of chromatographic columns are Benetnach C18, 5 μm and 4.6 x 150mm, acetonitrile is selected as a solvent, the detection wavelength is 254nm, the mobile phase is acetonitrile-water (70, 30V/V), the flow rate is 0.5mL/min, and the sample introduction amount is 20 μ L;
the nmr analysis conditions were as follows: an AVANCE III HD 400 nuclear magnetic resonance spectrometer performs 1H NMR test on a product under the condition of 400 MHz;
the FTIR analysis conditions were as follows: tabletting the sample powder with potassium bromide, and scanning with Nicolet IS5 Fourier infrared spectrometer at 400-4000cm wavelength -1 。
Examples
A method for preparing regenerated cationic polyester by using waste polyester comprises the following specific steps:
a) Crushing waste polyester (including polyester production waste and waste polyester products), cleaning and dehydrating to obtain waste polyester particles with the water content of 1-3%;
b) Measuring 1 ton of pretreated waste polyester particles, conveying the waste polyester particles to an alcoholysis reaction kettle, adding 2 tons of EG and 3kg of zinc acetate catalyst, heating to 200 ℃ and controlling the pressure in the alcoholysis reaction kettle to be 0.1MPa, and carrying out alcoholysis reaction for 3 hours to obtain BHET alcoholysis solution;
c) Purifying BHET alcoholysis liquid, namely:
c1 B) filtering the BHET alcoholysis solution obtained in the step B) by using a filter with 50-150 meshes to remove insoluble substances in the BHET alcoholysis solution;
c2 Adding the filtrate obtained in the step C1) into a thin film evaporator I, and carrying out reduced pressure concentration at the temperature of 150-180 ℃ and the pressure of 1-10 KPa;
c3 C) adding the concentrated solution subjected to the reduced pressure concentration in the step C2) into a film evaporator II, and carrying out reduced pressure evaporation at the temperature of 150-180 ℃ and the pressure of 0.1-1 KPa;
c4 The residue after the reduced pressure evaporation in the step C3) (FIG. 1 is an HPLC analysis spectrogram of the residue, as shown in FIG. 1, the residue contains BHET monomer, BHET dimer and BHET trimer), the residue is added into a short-path distiller, the distillation is carried out at the temperature of 180-230 ℃ and the pressure of 1-10 Pa, the collected fraction is colorless transparent liquid, the crystallization is carried out at normal temperature to obtain white solid which is high-purity BHET monomer (the color value L is 97.24, the b value is 1.21, the HPLC purity is 99.8 percent, and the HPLC analysis spectrogram shown in FIG. 2 is detailed; moreover, the obtained white solid is BHET monomer as can be proved by the nuclear magnetic resonance analysis spectrum shown in figure 3 and the FTIR analysis spectrum shown in figure 4);
d) Firstly, adding a high-purity BHET monomer into a pre-polycondensation reaction kettle I, adding 1.5% (mass percent of the high-purity BHET monomer) SIPE monomer and 0.01-0.03% (mass percent of the high-purity BHET monomer) ethylene glycol antimony catalyst, stirring and reacting for 1-1.5 hours at 265-270 ℃ and under the pressure of 8 KPa-12 KPa, then introducing a reaction solution into a pre-polycondensation reaction kettle II, stirring and reacting for 2-2.5 hours at 272-275 ℃ and under the pressure of 1 KPa-1.5 KPa, finally introducing the reaction solution into a final polycondensation reaction kettle, stirring and reacting for 2-2.5 hours at 278-282 ℃ and under the pressure of 100 Pa-400 Pa to obtain a regenerated cationic polyester melt, and cooling, granulating and drying to obtain the high-purity regenerated cationic polyester slice.
Referring to the detection and analysis method of the virgin cationic polyester chip, the detection results of the recycled cationic polyester chip obtained by the invention are shown in the following table:
the results of the above table test show that: the method can obtain the regenerated cationic polyester product which is comparable to various indexes of the primary cationic polyester, can be used in the application with high requirement and high added value, has important significance and value for realizing the regeneration cycle of the waste polyester in the true sense, and has significant progress compared with the prior art.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.
Claims (8)
1. A method for preparing regenerated cationic polyester by using waste polyester is characterized by comprising the following specific steps:
a) Carrying out crushing, washing and drying pretreatment on the waste polyester;
b) Carrying out alcoholysis on the pretreated waste polyester in ethylene glycol to obtain BHET alcoholysis liquid;
c) Purifying the BHET alcoholysis solution to obtain a high-purity BHET monomer with the HPLC purity of more than 99.0%;
d) Carrying out pre-polycondensation reaction and final polycondensation reaction on a high-purity BHET monomer and sodium dihydroxy ethyl isophthalate-5-sulfonate under the action of a catalyst to obtain regenerated cationic polyester;
wherein the purification treatment in step C) comprises the following operations:
c1 Filtering the BHET alcoholysis solution obtained in the step B) to remove insoluble substances in the BHET alcoholysis solution;
c2 Adding the filtrate obtained in the step C1) into a thin film evaporator I, and carrying out reduced pressure concentration at the temperature of 150-180 ℃ and the pressure of 1-10 KPa;
c3 The concentrated solution after the reduced pressure concentration in the step C2) is added into a film evaporator II, and the reduced pressure evaporation is carried out at the temperature of 150-180 ℃ and the pressure of 0.1-1 KPa;
c4 Adding the residue obtained after the reduced pressure evaporation in the step C3) into a short-path distiller, rectifying at the temperature of 180-230 ℃ and the pressure of 1-10 Pa, and crystallizing the collected fraction at normal temperature to obtain a white solid, namely the high-purity BHET monomer with the HPLC purity of more than 99.0%.
2. The method for preparing recycled cationic polyester using waste polyester according to claim 1, wherein: the drying in the step A) means that the water content of the waste polyester is 1-3 percent.
3. The method for preparing recycled cationic polyester by using waste polyester according to claim 1, wherein the alcoholysis in step B) is carried out by the following steps:
putting ethylene glycol and the pretreated waste polyester particles into an alcoholysis reaction kettle according to the mass ratio of (1-3) to 1, then putting a zinc acetate catalyst with the mass being 0.1-0.5% of the mass of the waste polyester particles, heating to 190-230 ℃, controlling the pressure in the alcoholysis reaction kettle to be 0.1-0.5 MPa, and carrying out alcoholysis reaction for 2-6 hours.
4. The method for preparing recycled cationic polyester using waste polyester according to claim 1, wherein: in the step D), the addition amount of the m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate is 1 to 2 percent of the mass of the high-purity BHET monomer.
5. The method for preparing recycled cationic polyester using waste polyester according to claim 1, wherein: in the step D), the catalyst is ethylene glycol antimony, and the addition amount of the catalyst is 0.01-0.03% of the mass of the high-purity BHET monomer.
6. The method for preparing recycled cationic polyester using waste polyester according to claim 1, wherein the condition of the pre-polycondensation reaction in the step D) is: firstly, stirring and reacting for 1-1.5 hours at 265-270 ℃ and under the pressure of 8-12 KPa in the kettle, and then stirring and reacting for 2-2.5 hours at 272-275 ℃ and under the pressure of 1-1.5 KPa in the kettle.
7. The method for preparing recycled cationic polyesters from waste polyesters according to claim 1, characterized in that the conditions of the final polycondensation reaction in step D) are: stirring and reacting for 2-2.5 hours at 278-282 ℃ and under the pressure of 100-400 Pa in the kettle.
8. The method for preparing recycled cationic polyester using waste polyester according to claim 1, wherein: the waste polyester comprises polyester production waste and waste polyester products.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024045639A1 (en) * | 2022-08-31 | 2024-03-07 | 科泽新材料股份有限公司 | Method for preparing pent copolyester |
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