CN112406148A - Method for preparing PETG shrink film by using PET waste bottles and application - Google Patents
Method for preparing PETG shrink film by using PET waste bottles and application Download PDFInfo
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- CN112406148A CN112406148A CN202011259202.XA CN202011259202A CN112406148A CN 112406148 A CN112406148 A CN 112406148A CN 202011259202 A CN202011259202 A CN 202011259202A CN 112406148 A CN112406148 A CN 112406148A
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- petg
- bhet
- surface layer
- shrink film
- propanediol
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- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 title claims abstract description 100
- 229920006300 shrink film Polymers 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- 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 113
- 239000002344 surface layer Substances 0.000 claims abstract description 56
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 30
- 239000012792 core layer Substances 0.000 claims abstract description 28
- 239000000155 melt Substances 0.000 claims abstract description 24
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 17
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 16
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 16
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 15
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000012634 fragment Substances 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 238000004513 sizing Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 40
- 239000003921 oil Substances 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000003381 stabilizer Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 21
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 11
- 239000011654 magnesium acetate Substances 0.000 claims description 11
- 229940069446 magnesium acetate Drugs 0.000 claims description 11
- 235000011285 magnesium acetate Nutrition 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 235000011056 potassium acetate Nutrition 0.000 claims description 9
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009998 heat setting Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 235000013904 zinc acetate Nutrition 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003712 decolorant Substances 0.000 claims description 2
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 22
- 239000005020 polyethylene terephthalate Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 8
- 230000032050 esterification Effects 0.000 description 6
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- 229920006257 Heat-shrinkable film Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000021586 packaging of beverage Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for preparing a PETG shrink film by using PET waste bottles and application, and relates to the technical field of high polymer materials. The PETG shrink film is prepared by the following method: s1, crushing the PET waste bottle into fragments, and carrying out alcoholysis, crystallization, decoloration and purification to obtain BHET crystals; s2, mixing the BHET crystal with 2, 2-dimethyl-1, 3-propylene glycol and 1, 3-propylene glycol, and reacting to obtain a PETG melt; s3, mixing the BHET crystal with 2, 2-dimethyl-1, 3-propanediol and 1, 3-propanediol, mixing with silicon dioxide, reacting, and granulating to obtain a PETG master batch; s4, enabling the PETG melt to pass through a melt metering pump and enter a core layer of the adapter; melting and plasticizing the PETG master batch, and feeding the PETG master batch into an inner surface layer and an outer surface layer of a dispenser through a melt metering pump; and superposing and flowing out the melts of the inner surface layer, the core layer and the outer surface layer on a die lip, cooling to form a casting sheet, and stretching, sizing and cooling to obtain the PETG shrink film. The PETG shrink film of the invention has high shrinkage characteristics and good printing characteristics.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for preparing a PETG shrink film by using PET waste bottles and application thereof.
Background
The heat-shrinkable film has a property of being easily shrinkable by heating, and is widely used for shrink packaging of beverage bottles, milk bottles, daily chemical bottles, and the like. Currently, heat shrinkable film materials on the face mainly comprise three types: polyvinyl chloride (PVC), Polystyrene (PS) and copolyester (PETG). When the polyvinyl chloride shrink film is burnt, international primary carcinogens such as dioxin and the like can be generated, the recycling rate is low, and the consumption is gradually reduced at present. Polystyrene shrink films, which have poor chemical resistance, must use an ink having a specific composition when printed, and may spontaneously shrink at room temperature and change in size, are used in a relatively small amount. The copolyester shrink film has good chemical resistance, strong printing adaptability and strong environmental protection property, and is considered as a main material for replacing PVC shrink films.
In beverages such as milk and daily chemical products such as shampoo and emulsion, PET (polyethylene terephthalate) bottles are generally used for filling. Due to the requirements of filling content, appearance design and the like, various pigments or blocking agents are added in the manufacturing process of many PET bottles. When the colored PET bottles are recycled, the colored PET bottles are usually recycled by a physical method, degraded and used, and used as low-end products such as black yarns or isolation belts, and have no high-value application. Until now, no report has been made on the production of PETG high-shrinkage films from colored PET waste bottles in household garbage.
Disclosure of Invention
Therefore, it is necessary to provide a method for preparing a PETG shrink film by using PET waste bottles aiming at the problem of high-value use of colored PET waste bottles of household garbage, the method can efficiently remove impurities such as pigments in recovered products of the PET waste bottles to obtain high-purity products, and the high-purity products are applied to the preparation of the PETG shrink film, and the obtained PETG shrink film has high shrink characteristics and good printing characteristics.
A method for preparing PETG shrink film by using PET waste bottles comprises the following steps:
s1, crushing PET waste bottles into fragments, adding alcohol and a catalyst for alcoholysis, filtering to remove impurities, cooling for crystallization, squeezing for purification, adding a composite decolorant for decoloration and purification, and evaporating to remove redundant water, alcohol and oligomers to obtain BHET (BHET) crystals;
s2, mixing the BHET crystal with 2, 2-dimethyl-1, 3-propanediol and 1, 3-propanediol, adding a catalyst and a stabilizer, and performing esterification reaction and polycondensation reaction to obtain a PETG melt;
s3, mixing the BHET crystal with 2, 2-dimethyl-1, 3-propanediol and 1, 3-propanediol, mixing with silicon dioxide, adding a catalyst and a stabilizer, performing esterification reaction and polycondensation reaction, and underwater pelletizing to obtain a PETG master batch;
s4, enabling the PETG melt to pass through a melt metering pump and enter a core layer of the adapter; melting and plasticizing the PETG master batch, and feeding the PETG master batch into an inner surface layer and an outer surface layer of the adapter through a melt metering pump; and superposing and flowing out the melts of the inner surface layer, the core layer and the outer surface layer on a die lip, cooling to form a casting sheet, and stretching, sizing and cooling to obtain the PETG shrink film.
The method has the advantages that BHET in the PET waste bottle is efficiently recovered, the purity of the obtained BHET crystal reaches more than 99.5%, the BHET crystal is used as a raw material to prepare the PETG melt and the PETG master batch, and the PETG shrink film is prepared by utilizing direct melting and three-layer co-extrusion technologies.
In one embodiment, the step S1 specifically includes:
1) crushing PET waste bottles into fragments with the width of 3-5 cm, adding an alcohol solution and a catalyst, and carrying out primary alcoholysis reaction for 1.5-2.5 hours at 190-220 ℃ to obtain a primary BHET solution;
2) filtering the primary BHET solution, wherein a filtering screen is 100-500 meshes, and removing insoluble impurities and part of oligomers to obtain a primary BHET solution containing oil;
3) adding an alcohol solution and a catalyst into the product obtained in the step 2), and carrying out a final alcoholysis reaction at 190-220 ℃ for 1.5-2.5 h to obtain a monopolymer BHET solution containing oil;
4) cooling the product obtained in the step 3) to 80-100 ℃, then cooling to 10-30 ℃, and crystallizing to obtain a monopolymer BHET crystal containing the oil;
5) squeezing and purifying the product obtained in the step 4), adding a composite decoloring agent, and decoloring and purifying to obtain a BHET material block;
6) and melting the BHET material block, and evaporating excessive water, alcohol and oligomer to obtain the BHET crystal.
The purity of the BHET crystal obtained by the method is as high as 99.6%, and the particle size is 50-200 mu m.
In one embodiment, the number of times of pressing and purifying in the step 5) is 2-4.
In one embodiment, the alcohol solution in step S1 is an ethylene glycol solution, and the catalyst used in alcoholysis is selected from the group consisting of: one or more of zinc acetate, potassium acetate and magnesium acetate.
In one embodiment, the catalyst in steps S2 and S3 is selected from: one or more of tetrabutyl titanate, germanium dioxide, ethylene glycol antimony, antimony trioxide, potassium acetate, magnesium acetate and zinc acetate; the dosage of the catalyst is 200-500 ppm of the weight of BHET in the reaction system.
In one embodiment, the stabilizing agent in steps S2 and S3 is selected from: one or more of trimethyl phosphate, dimethyl phosphate, tributyl phosphate and triphenyl phosphate; the amount of the stabilizer is 100-500 ppm of the weight of BHET in the reaction system.
In one embodiment, the D50 particle size of the silica in the step S3 is 0.8 to 1.2 μm.
In one embodiment, in the step S2, the mass ratio of the BHET crystal, the 2, 2-dimethyl-1, 3-propanediol and the 1, 3-propanediol is (80-90): (7-18): (1-6). The intrinsic viscosity of the PETG melt is 0.70-0.85dl/g, and 75-80% of high shrinkage characteristic can be realized.
In one embodiment, in the step S3, the mass ratio of the BHET crystal, the 2, 2-dimethyl-1, 3-propanediol, the 1, 3-propanediol and the silicon dioxide is (80-90): (7-18): (1-6): (0.1-0.3). The PETG master batch has a melting point of 180-210 ℃ and an intrinsic viscosity of 0.70-0.85 dl/g.
In one embodiment, the step S4 specifically includes: enabling the PETG melt to pass through a melt metering pump, enter a disc type filter with the diameter of 20-60 mu m, enter a core layer of a three-layer adapter and reach a core layer of a die head; melting and plasticizing the PETG master batch by a double-screw extruder, feeding the PETG master batch into a disc type filter with the diameter of 20-60 mu m by a melt metering pump, and then feeding the PETG master batch into the inner surface layer and the outer surface layer of the layer adapter to reach the surface layer and the outer surface layer of the die head; superposing and flowing out the melts of the inner surface layer, the core layer and the outer surface layer at a die lip, and cooling by a quenching roller at 10-30 ℃ under the action of a force field of an electrostatic adsorption device at 9-12 kV to form a cast sheet with the thickness of 50-360 mu m; preheating the casting sheet, transversely stretching 4.5-5.2 times at 80-88 ℃, and carrying out heat setting and cooling to form the PETG shrink film.
The invention also provides a PETG shrink film which is prepared by the method, the PETG shrink film is formed by sequentially laminating an inner surface layer, a core layer and an outer surface layer, and the thickness ratio of the inner surface layer to the core layer to the outer surface layer is (5-15): (70-90): (5-15), wherein the thickness of the PETG shrink film is 10-80 mu m. The PETG shrinkage film has a transverse shrinkage rate of 75-80% in a water bath at 95 ℃ for 10s, and a longitudinal shrinkage rate of 0-5% in a water bath at 95 ℃ for 10 s. Moreover, the PETG shrink film does not lose ink dots during the light screen printing process.
The invention also provides application of the PETG shrink film in packaging plastic bottles. In particular to the application in the packaging of milk bottles, beverage bottles and daily chemical articles.
Compared with the prior art, the invention has the following beneficial effects:
the method of the invention efficiently recovers BHET in PET waste bottles, the purity of the obtained BHET crystal reaches more than 99.5%, the BHET crystal is used as a raw material to prepare PETG melt and PETG master batch, and direct melting and three-layer co-extrusion technology is utilized to prepare the PETG shrink film, the preparation method is simple, the processing and the forming are easy, the large-scale production is convenient, the obtained PETG has high shrinkage characteristic, the transverse shrinkage rate is 75-80%, the longitudinal shrinkage rate is less than 5%, the printing property is good, the printing ink does not lose points in the process of shallow screen printing, and the product has wide application prospect.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the preferred embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
A PETG shrink film is prepared by the following method:
s1, preparing BHET crystal by using PET waste bottle:
(1) crushing the colored PET waste bottle into 3-5 cm fragments by using a crusher, adding a catalyst zinc acetate into a 220 ℃ ethylene glycol solution, and carrying out a primary alcoholysis reaction for 1.5 hours to obtain a primary BHET solution containing insoluble impurities and a colored oil;
(2) separating insoluble impurities and part of oligomer impurities from the primary BHET solution by using a 400-mesh coarse filtering device, and then feeding the solution into a buffer tank to obtain a primary BHET solution containing oil;
(3) adding the primary BHET solution containing the oil of color into an ethylene glycol solution at 220 ℃, adding zinc acetate as a catalyst, and carrying out a final alcoholysis reaction for 1.5 hours to obtain a monomeric BHET solution containing the oil of color;
(4) inputting the monopolymer BHET solution containing the color oil into a three-stage pure water tank, cooling to 80 ℃ to obtain a cooled monopolymer BHET solution containing the color oil, inputting the cooled monopolymer BHET solution containing the color oil into a three-stage crystallization tank, and gradually cooling to 10 ℃ to obtain monopolymer BHET crystals containing the color oil;
(5) squeezing and purifying the monopolymer BHET crystal containing the oil at room temperature, and separating to obtain a BHET primary material block containing the oil;
(6) adding the BHET primary material block containing the color oil into a deionized water tank containing a composite decoloring agent, decoloring and purifying, repeating for 2 times, and squeezing to obtain a BHET secondary material block;
(7) and melting the BHET secondary material block, adding the melted BHET secondary material block into an evaporator, and removing excessive water, glycol and oligomer step by step to obtain BHET white crystals, wherein the BHET white crystals have the particle size of 50-100 mu m and the purity of 99.6%.
S2, preparing a core layer raw material PETG melt:
the above BHET crystals were mixed with 2, 2-dimethyl-1, 3 propanediol (NPG) and 1,3 Propanediol (PDO) in 80: 15: 5, adding a catalyst and a stabilizer, and performing esterification and polycondensation reaction to obtain a PETG melt; the catalyst is a mixture of tetrabutyl titanate, potassium acetate, magnesium acetate and zinc acetate, and the dosage of the catalyst is 500ppm based on the total weight of BHET in the reaction system; the stabilizer is a mixture of trimethyl phosphate and triphenyl phosphate, and the dosage of the stabilizer is 500ppm based on the total weight of BHET in the reaction system; the PETG melt had an intrinsic viscosity of 0.85 dl/g.
S3, preparing a PETG master batch as the raw materials of the inner surface layer and the outer surface layer:
the above BHET crystals were mixed with a mixture of 2, 2-dimethyl-1, 3 propanediol (NPG) and 1,3 Propanediol (PDO) and silica in a ratio of 80: 14.85: 4.95: 0.2, adding a catalyst and a stabilizer, carrying out esterification and polycondensation reactions, and carrying out underwater granulation to obtain a PETG master batch; the catalyst is a mixture of tetrabutyl titanate, potassium acetate, magnesium acetate and zinc acetate, and the dosage of the catalyst is 500ppm based on the total weight of BHET in the reaction system; the stabilizer is a mixture of trimethyl phosphate and triphenyl phosphate, and the dosage of the stabilizer is 500ppm based on the total weight of BHET in the reaction system; the PETG master batch has a melting point of 180 ℃ and an intrinsic viscosity of 0.85 dl/g.
S4 preparation of PETG shrink film
(1) The PETG melt in the step S2 is metered by a melt metering pump, enters a 30-micron disc type filter, passes through the disc type filter, enters a core layer of a three-layer adapter, and then reaches the core layer of a 'clothes hanger type' die head;
(2) adding the PETG master batch in the step S3 into a double-screw extruder, performing melt plasticization, metering by a melt metering pump, feeding into a 30-micron disc type filter, feeding into the inner surface layer and the outer surface layer of a three-layer adapter, and then feeding into the inner surface layer and the outer surface layer of a clothes rack type die head;
(3) the melt of the inner surface layer, the core layer and the outer surface layer is prepared at the die lip position of the die head according to the following ratio of 10: 80: 10, and cooling the mixture in a quenching roller at 30 ℃ to form 135 mu m cast pieces under the action of a force field of a 9kV electrostatic adsorption device;
(4) preheating the cast sheet at 95-90 deg.c, transversely stretching at 79-79 deg.c to 79 deg.c by 4.5 times, heat setting at 50-50 deg.c and cooling to form 30 micron PETG high shrinkage polyester film.
Example 2
A PETG shrink film is prepared by the following method:
s1, preparing BHET crystal by using PET waste bottle:
(1) crushing the colored PET waste bottle into 3-5 cm fragments by using a crusher, adding a catalyst zinc acetate into a 205 ℃ ethylene glycol solution, and carrying out a primary alcoholysis reaction for 1.5 hours to obtain a primary BHET solution containing insoluble impurities and a colored oil;
(2) separating insoluble impurities and part of oligomer impurities from the primary BHET solution by using a coarse filtering device with 300 meshes, and then feeding the solution into a buffer tank to obtain a primary BHET solution containing oil;
(3) adding the primary BHET solution containing the oil of color into an ethylene glycol solution at 210 ℃, adding zinc acetate as a catalyst, and carrying out a final alcoholysis reaction for 2.0 hours to obtain a monomeric BHET solution containing the oil of color;
(4) inputting the monopolymer BHET solution containing the color oil into a three-stage pure water tank, cooling to 85 ℃ to obtain a cooled monopolymer BHET solution containing the color oil, inputting the cooled monopolymer BHET solution containing the color oil into a three-stage crystallization tank, and gradually cooling to 30 ℃ to obtain monopolymer BHET crystals containing the color oil;
(5) squeezing and purifying the monopolymer BHET crystal containing the oil at room temperature, and separating to obtain a BHET primary material block containing the oil;
(6) adding the BHET primary material block containing the color oil into a deionized water tank containing a composite decoloring agent, decoloring and purifying, repeating for 3 times, and squeezing to obtain a BHET secondary material block;
(7) and melting the BHET secondary material block, adding the melted BHET secondary material block into an evaporator, and removing excessive water, glycol and oligomer step by step to obtain BHET white crystals, wherein the BHET white crystals have the particle size of 100-120 mu m and the purity of 99.7%.
S2, preparing a core layer raw material PETG melt:
the above BHET crystals were mixed with 2, 2-dimethyl-1, 3 propanediol (NPG) and 1,3 Propanediol (PDO) in an 85: 12: 3, adding a catalyst and a stabilizer, and performing esterification and polycondensation reaction to obtain a PETG melt; the catalyst is a mixture of ethylene glycol antimony, potassium acetate and magnesium acetate, and the dosage of the catalyst is 350ppm based on the total weight of BHET in the reaction system; the stabilizer is trimethyl phosphate, and the dosage of the stabilizer is 300ppm based on the total weight of BHET in the reaction system; the PETG melt had an intrinsic viscosity of 0.80 dl/g.
S3, preparing a PETG master batch as the raw materials of the inner surface layer and the outer surface layer:
the above BHET crystals were mixed with a mixture of 2, 2-dimethyl-1, 3 propanediol (NPG) and 1,3 Propanediol (PDO) and silica in a ratio of 85: 11.76: 2.94: 0.3, adding a catalyst and a stabilizer, carrying out esterification and polycondensation reactions, and carrying out underwater granulation to obtain a PETG master batch; the catalyst is a mixture of tetrabutyl titanate and ethylene glycol antimony, and the dosage of the catalyst is 350ppm based on the total weight of BHET in the reaction system; the stabilizer is trimethyl phosphate, and the dosage of the stabilizer is 300ppm based on the total weight of BHET in the reaction system; the PETG masterbatch had a melting point of 195 ℃ and an intrinsic viscosity of 0.80 dl/g.
S4, preparing a PETG shrink film:
(1) the PETG melt in the step S2 is metered by a melt metering pump, enters a disc type filter with the diameter of 40 mu m, enters a core layer of a three-layer adapter after passing through the disc type filter, and then reaches the core layer of a clothes rack type die head;
(2) adding the PETG master batch in the step S3 into a double-screw extruder, performing melt plasticization, metering by a melt metering pump, feeding into a 40-micron disc type filter, feeding into the inner surface layer and the outer surface layer of a three-layer adapter, and then feeding into the inner surface layer and the outer surface layer of a clothes rack type die head;
(3) and the melt of the inner surface layer, the core layer and the outer surface layer is molten at the die lip position of the die head according to the ratio of 7.5: 85: 7.5, and cooling by a quenching roller at 20 ℃ under the action of a force field of a 10kV electrostatic adsorption device to form a casting sheet with the diameter of 200 mu m;
(4) preheating the cast sheet at 100-95-90 deg.c, transversely stretching at 81-81 deg.c by 5.0 times, heat setting at 60-50 deg.c and cooling to form high shrinkage PETG polyester film of 40 micron size.
Example 3
A PETG shrink film is prepared by the following method:
s1, preparing BHET crystal by using PET waste bottle:
(1) crushing the colored PET waste bottles into 3-5 cm fragments by using a crusher, adding a catalyst magnesium acetate into a 195 ℃ ethylene glycol solution, and carrying out a primary alcoholysis reaction for 2.0 hours to obtain a primary BHET solution containing insoluble impurities and a colored oil;
(2) separating insoluble impurities and part of oligomer impurities from the primary BHET solution by using a coarse filtering device with 200 meshes, and then feeding the solution into a buffer tank to obtain a primary BHET solution containing oil;
(3) adding the primary BHET solution containing the oil of color into an ethylene glycol solution at 200 ℃, adding magnesium acetate as a catalyst to perform a final alcoholysis reaction for 2.5 hours to obtain a monomeric BHET solution containing the oil of color;
(4) inputting the monopolymer BHET solution containing the color oil into a three-stage pure water tank, cooling to 90 ℃ to obtain a cooled monopolymer BHET solution containing the color oil, inputting the cooled monopolymer BHET solution containing the color oil into a three-stage crystallization tank, and gradually cooling to 20 ℃ to obtain monopolymer BHET crystals containing the color oil;
(5) squeezing and purifying the monopolymer BHET crystal containing the oil at room temperature, and separating to obtain a BHET primary material block containing the oil;
(6) adding the BHET primary material block containing the color oil into a deionized water tank containing a composite decoloring agent, decoloring and purifying, repeating for 4 times, and squeezing to obtain a BHET secondary material block;
(7) and melting the BHET secondary material block, adding the melted BHET secondary material block into an evaporator, and removing excessive water, glycol and oligomer step by step to obtain BHET white crystals, wherein the BHET white crystals have the particle size of 150-120 mu m and the purity of 99.9%.
S2, preparing a core layer raw material PETG melt:
the above BHET crystals were mixed with a mixture of 2, 2-dimethyl-1, 3 propanediol (NPG) and 1,3 Propanediol (PDO) at a ratio of 90: 9: 1, adding a catalyst and a stabilizer, and performing esterification and polycondensation reaction to obtain a PETG melt; the catalyst is a mixture of ethylene glycol antimony, potassium acetate and magnesium acetate, and the dosage of the catalyst is 300ppm based on the total weight of BHET in the reaction system; the stabilizer is trimethyl phosphate, and the dosage of the stabilizer is 400ppm based on the total weight of BHET in the reaction system; the intrinsic viscosity of the PETG melt was 0.78 dl/g.
S3, preparing a PETG master batch as the raw materials of the inner surface layer and the outer surface layer:
the above BHET crystals were mixed with a mixture of 2, 2-dimethyl-1, 3 propanediol (NPG) and 1,3 Propanediol (PDO) and silica in a ratio of 90: 8.91: 0.99: 0.1, adding a catalyst and a stabilizer, carrying out esterification and polycondensation reactions, and carrying out underwater granulation to obtain a PETG master batch; the catalyst is a mixture of ethylene glycol antimony, potassium acetate and magnesium acetate, and the dosage of the catalyst is 300ppm based on the total weight of BHET in the reaction system; the stabilizer is trimethyl phosphate, and the dosage of the stabilizer is 400ppm based on the total weight of BHET in the reaction system; the PETG masterbatch has a melting point of 210 ℃ and an intrinsic viscosity of 0.78 dl/g.
S4, preparing a PETG shrink film:
(1) the PETG melt in the step S2 is metered by a melt metering pump, enters a disc filter with the diameter of 20 mu m, enters a core layer of a three-layer adapter after passing through the disc filter, and then reaches the core layer of a clothes-hanger type die head;
(2) adding the PETG master batch in the step S3 into a double-screw extruder, performing melt plasticization, metering by a melt metering pump, feeding into a 60-micrometer disc type filter, feeding into an inner surface layer and an outer surface layer of a three-layer adapter, and then feeding into the inner surface layer and the outer surface layer of a clothes rack type die head;
(3) and the melt of the inner surface layer, the core layer and the outer surface layer is prepared at the die lip position of the die head according to the following steps of 5: 90: 5, and cooling the mixture to form a 200-micron cast piece by a quenching roller at 15 ℃ under the action of a force field of a 12kV electrostatic adsorption device;
(4) preheating the casting sheet at 105-98-92 deg.c, transversely stretching at 80-80 deg.c by 4.8 times, heat setting at 70-60 deg.c and cooling to form high shrinkage PETG polyester film of 45 micron size.
Comparative example 1
A petroleum-based PETG film is prepared by the following method:
selecting a PETG slice of SK chemical industry type SK2012 and an open master batch of Sukano type MB13, mixing the PETG slice and the open master batch according to a proportion of 99/1, then feeding the PETG slice and the open master batch into a double-screw extruder for melting and plasticizing, feeding the PETG slice and the open master batch into a die head through a metering pump and a 40-micron disc type filter, flowing out, cooling on a quenching roller at 40 ℃ to form a cast slice, preheating in hot air at 105-95-85 ℃, transversely stretching 5.2 times at 80-80 ℃, and forming a PETG shrink film through heat setting at 75-75 ℃ and cooling at 60-40 ℃.
Test examples
The PETG shrink films of the examples and comparative examples were subjected to performance testing and the results are shown in Table 1.
Table 1 results of performance test of PETG shrink films of examples and comparative examples
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for preparing a PETG shrink film by using PET waste bottles is characterized by comprising the following steps:
s1, crushing the PET waste bottles into fragments, adding alcohol and a catalyst for alcoholysis, filtering to remove impurities, cooling for crystallization, squeezing for purification, adding a composite decolorant for decoloration and purification, and evaporating to remove redundant water, alcohol and oligomers to obtain BHET crystals;
s2, mixing the BHET crystal with 2, 2-dimethyl-1, 3-propanediol and 1, 3-propanediol, adding a catalyst and a stabilizer, and performing esterification reaction and polycondensation reaction to obtain a PETG melt;
s3, mixing the BHET crystal with 2, 2-dimethyl-1, 3-propanediol and 1, 3-propanediol, mixing with silicon dioxide, adding a catalyst and a stabilizer, performing esterification reaction and polycondensation reaction, and underwater pelletizing to obtain a PETG master batch;
s4, enabling the PETG melt to pass through a melt metering pump and enter a core layer of the adapter; melting and plasticizing the PETG master batch, and feeding the PETG master batch into an inner surface layer and an outer surface layer of the adapter through a melt metering pump; and superposing and flowing out the melts of the inner surface layer, the core layer and the outer surface layer on a die lip, cooling to form a casting sheet, and stretching, sizing and cooling to obtain the PETG shrink film.
2. The method according to claim 1, wherein the step S1 specifically includes:
1) crushing PET waste bottles into fragments with the width of 3-5 cm, adding an alcohol solution and a catalyst, and carrying out primary alcoholysis reaction for 1.5-2.5 hours at 190-220 ℃ to obtain a primary BHET solution;
2) filtering the primary BHET solution, wherein a filtering screen is 100-500 meshes, and removing insoluble impurities and part of oligomers to obtain a primary BHET solution containing oil;
3) adding an alcohol solution and a catalyst into the product obtained in the step 2), and carrying out a final alcoholysis reaction at 190-220 ℃ for 1.5-2.5 h to obtain a monopolymer BHET solution containing oil;
4) cooling the product obtained in the step 3) to 80-100 ℃, then cooling to 10-30 ℃, and crystallizing to obtain a monopolymer BHET crystal containing the oil;
5) squeezing and purifying the product obtained in the step 4), adding a composite decoloring agent, and decoloring and purifying to obtain a BHET material block;
6) and melting the BHET material block, and evaporating excessive water, alcohol and oligomer to obtain the BHET crystal.
3. The method according to claim 1 or 2, wherein the alcoholic solution in step S1 is an ethylene glycol solution, and the catalyst for alcoholysis is selected from the group consisting of: one or more of zinc acetate, potassium acetate and magnesium acetate.
4. The method of claim 1, wherein the catalyst in steps S2 and S3 is selected from the group consisting of: one or more of tetrabutyl titanate, germanium dioxide, ethylene glycol antimony, antimony trioxide, potassium acetate, magnesium acetate and zinc acetate; the dosage of the catalyst is 200-500 ppm of the weight of BHET in the reaction system.
5. The method according to claim 1 or 4, wherein the stabilizer in steps S2 and S3 is selected from: one or more of trimethyl phosphate, dimethyl phosphate, tributyl phosphate and triphenyl phosphate; the amount of the stabilizer is 100-500 ppm of the weight of BHET in the reaction system.
6. The method as claimed in claim 1, wherein the silica in the step S3 has a D50 particle size of 0.8-1.2 μm.
7. The method according to claim 1, wherein in step S2, the mass ratio of BHET crystal, 2-dimethyl-1, 3-propanediol and 1, 3-propanediol is (80-90): (7-18): (1-6);
in the step S3, the mass ratio of the BHET crystal, the 2, 2-dimethyl-1, 3-propanediol, the 1, 3-propanediol and the silicon dioxide is (80-90): (7-18): (1-6): (0.1-0.3).
8. The method according to claim 1, wherein the step S4 specifically includes: enabling the PETG melt to pass through a melt metering pump, enter a disc type filter with the diameter of 20-60 mu m, enter a core layer of a three-layer adapter and reach a core layer of a die head; melting and plasticizing the PETG master batch by a double-screw extruder, feeding the PETG master batch into a disc type filter with the diameter of 20-60 mu m by a melt metering pump, and then feeding the PETG master batch into the inner surface layer and the outer surface layer of the layer adapter to reach the surface layer and the outer surface layer of the die head; superposing and flowing out the melts of the inner surface layer, the core layer and the outer surface layer at a die lip, and cooling by a quenching roller at 10-30 ℃ under the action of a force field of an electrostatic adsorption device at 9-12 kV to form a cast sheet with the thickness of 50-360 mu m; preheating the casting sheet, transversely stretching 4.5-5.2 times at 80-88 ℃, and carrying out heat setting and cooling to form the PETG shrink film.
9. The PETG shrink film is characterized by being prepared by the method of any one of claims 1 to 8, and is formed by sequentially laminating an inner surface layer, a core layer and an outer surface layer, wherein the thickness ratio of the inner surface layer to the core layer to the outer surface layer is (5-15): (70-90): (5-15), wherein the thickness of the PETG shrink film is 10-80 mu m.
10. Use of the PETG shrink film of claim 9 in packaging plastic bottles.
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Denomination of invention: A Method and Application of Preparing PETG Shrinkage Film Using PET Waste Bottles Effective date of registration: 20230714 Granted publication date: 20230203 Pledgee: Guangzhou Xinxi Technology Co.,Ltd. Pledgor: SHUYE ENVIRONMENTAL TECHNOLOGY Co.,Ltd. Registration number: Y2023980048456 |
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Inventor after: Dong Xingguang Inventor after: Lin Shuguang Inventor after: Yuan Haoran Inventor before: Dong Xingguang Inventor before: Lin Shuguang |