CN115160550A - Method for preparing low-yellowness-value film-grade slices by using recycled organic silicon PET release film - Google Patents
Method for preparing low-yellowness-value film-grade slices by using recycled organic silicon PET release film Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 24
- 239000010703 silicon Substances 0.000 title claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- 230000000925 erythroid effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 44
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 8
- 229920002799 BoPET Polymers 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 11
- 238000005086 pumping Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000004383 yellowing Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000006136 alcoholysis reaction Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- REIDAMBAPLIATC-UHFFFAOYSA-N 4-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000034659 glycolysis Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution 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
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- 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
-
- 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
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- 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
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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)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention belongs to the field of green environmental protection recovery, and particularly relates to a method for preparing a low-yellowness-value film-grade slice by using a recovered organic silicon PET release film, which comprises the following steps: crushing the waste organic silicon PET release film, then performing enhanced drying, mixing with a catalyst, a stabilizer and a toner, then performing melting, extrusion mixing, filtering and solid phase polycondensation to prepare the low-yellowness-value film-grade slice. The slice prepared by recycling the waste PET release film has transparent appearance and low yellowness, can be directly used as a raw material for preparing the PET film, and greatly improves the value of the waste PET release film.
Description
Technical Field
The invention belongs to the field of green and environment-friendly recovery, and particularly relates to a method for preparing a low-yellowness-value film-grade slice by using a recovered organic silicon PET release film
Background
The release film is a functional film with release function formed by coating a very thin coating liquid on the surface of a base film and curing the coating liquid by heat or ultraviolet. Among them, the most widely used is silicone PET release film. Because organosilicon PET is from type the film use amount is big, and is used in the in-process protection usually, just abandons, has consequently produced huge discarded organosilicon of quantity from type the film, if handle improperly, can bring huge pressure for environmental protection. The main raw material for producing the organic silicon release film is PET, has excellent creep resistance, fatigue resistance and friction resistance, is a material with higher recycling value, and if the material is recycled, the economic benefit is considerable. Therefore, the organic silicon release film has very important social significance and economic value in recycling.
At present, two main recovery modes of the waste organic silicon release film include a chemical method and a physical method. The chemical recovery method is to depolymerize the waste organosilicon release film and convert the film into smaller molecules and intermediate raw materials or directly into monomers, so that some high-value chemical products can be obtained. Among chemical recovery techniques, the methanol alcoholysis process, the hydrolysis process, the glycolysis process and the glycol alcoholysis process are most widely used. The principle of alcoholysis of methanol is that waste polyester bottle materials are subjected to alcoholysis in a methanol solution to obtain methyl terephthalate and ethylene glycol, the alcoholysis process is simple, but the product purification is complex, and the final product quality is low. The principle of hydrolysis is to react the waste polyester bottle material with water to degrade the polyester into terephthalic acid and ethylene glycol. The process has a later separation problem. The process is carried out at high temperature and is complicated to operate. The alcoholysis method is characterized in that the waste film is degraded in the presence of glycol to obtain the glycol terephthalate and the oligomer thereof. In general, the chemical synthesis method has the defects of complex process, high purification difficulty and high cost, so that the method is rarely applied in the industry. The physical recovery process is relatively simple, mainly by a melting granulation method, and no obvious chemical reaction exists in the process. At present, the main recovery method of the waste organic silicon PET release film is physical recovery, the waste film is broken into fragments, and the fragments are dried, crystallized, plasticized, filtered and then granulated. However, since the silicone PET release film is coated with silicone, two problems exist in the process of granulation by heating, the first is very easy to yellow, the second molecular weight is greatly reduced, the original mechanical properties are lost, the molecular weight must be increased by adding a chain extender, and a part of cross-linked substances can be formed after adding the chain extender, so that the silicone PET release film can be finally used only by reducing and the like to be used as low-end injection products with low requirements on appearance, and cannot be used as a raw material of a PET film again.
Disclosure of Invention
In order to solve the problems that the current organic silicon PET release film is seriously yellowed after being recycled and granulated and is greatly degraded so as not to be used as a film-making raw material again, the invention provides a method for preparing a low-yellowness-value film-grade slice by using the recycled organic silicon PET release film.
The method for preparing the low-yellowness-value film-grade slice by using the recycled organic silicon PET release film comprises the following steps of: crushing the waste organic silicon PET release film, then performing enhanced drying, mixing with a catalyst, a stabilizer and a toner, then performing melting, extrusion mixing, filtering and solid phase polycondensation to prepare the low-yellowness-value film-grade slice.
The organic silicon PET release film comprises one or more of an off-line coating organic silicon release film and an on-line coating organic silicon release film.
The intensified drying refers to drying under nitrogen atmosphere; the drying is preferably air-blast drying; the drying temperature is preferably 120-160 ℃,120-150 ℃,120-140 ℃,120-130 ℃,130-160 ℃,130-150 ℃,130-140 ℃,140-160 ℃,140-150 ℃,150-160 ℃ and the like. The drying time is preferably 4 to 6 hours, 4 to 5 hours, 5 to 6 hours, 4.5 to 5.5 hours, 4.5 to 6 hours, or the like.
The catalyst is preferably one or more of ethylene glycol antimony, antimony trioxide, antimony acetate, germanium dioxide and zinc acetate. The dosage of the catalyst is preferably 100-400ppm,150-400ppm,200-400ppm,300-400ppm,100-350ppm, 150-300ppm,150-200ppm and the like which occupy the mass ratio of the waste organic silicon PET release film.
The stabilizer is preferably one or more of triphenyl phosphate, trimethyl phosphate and triethyl phosphate. The dosage of the stabilizer is preferably 10-100ppm,15-100ppm,20-100ppm,30-100ppm,40-100ppm,20-80ppm,20-70ppm,30-60ppm,40-50ppm and the like which occupy the mass ratio of the waste organic silicon PET release film
The toner is preferably one or more of cobalt acetate, an redness agent, and a blueness agent. The dosage of the toner is preferably 20-100ppm,30-90ppm,40-80ppm,50-70ppm,30-80ppm,30-70ppm,40-80ppm and the like which occupy the mass ratio of the waste silicone PET release film.
The reaction temperature of the solid phase polycondensation is 190-230 ℃, the vacuum degree is 30Pa or below, and the reaction time is 6-24 hours. The reaction temperature is preferably 200-230 ℃,210-230 ℃,220-230 ℃,200-220 ℃ and the like. The degree of vacuum is preferably 28Pa or less, 27Pa or less, 25Pa or less, 23Pa or less, or the like. The reaction time is preferably 7 to 23 hours, 8 to 22 hours, 9 to 21 hours, 10 to 20 hours, 11 to 19 hours, 12 to 18 hours, or the like.
Has the beneficial effects that:
the slice prepared by recycling the waste PET release film has transparent appearance and low yellowness, can be directly used as a raw material for preparing the PET film, and greatly improves the value of the waste PET release film.
The invention adopts the reclaimed materials added with the catalyst, the stabilizer and the toner to overcome the defects of serious yellowing and great degradation of the product.
Before adding the catalyst, the stabilizer and the toner, the product can be relieved from yellowing and degradation to a certain extent by drying the crushed particles of the reclaimed materials.
The catalyst used in the invention can avoid the degradation of the reclaimed materials, thereby increasing the utilization rate of the reclaimed materials. The stabilizer used in the invention can stabilize the reclaimed materials in the reaction process, thereby having influence on the degradability and color change of the product. The invention can relieve the yellowing performance of the product by using the toner.
The solid phase polycondensation temperature of the invention has great influence on the degradability of the product and also influences the yellowing performance of the product to a certain extent.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, 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. If there is a conflict, the present specification will control.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention may be commercially available or may be prepared by existing methods.
Example 1
Crushing 100 kg of PET organosilicon release film reclaimed materials into fine particles, drying for 4 hours in a 120-DEG oven in a nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 40g of ethylene glycol antimony, 10g of triphenyl phosphate and 10g of cobalt acetate by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering, granulating, and enabling the mesh number of a filter screen of the extruder to be 300 meshes. Putting the prepared particles into a vacuum oven, setting the temperature at 220 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping the pressure for 24 hours.
Example 2
Crushing 100 kg of recycled PET organosilicon release film material into fine particles, drying for 4 hours in a 120-degree oven under the nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 20g of ethylene glycol antimony, 5g of triphenyl phosphate, 7g of a blue agent and 3g of a red agent by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering and granulating, wherein the mesh number of a filter screen of the extruder is 300 meshes. Putting the prepared particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping for 6 hours.
Example 3
Crushing 100 kg of recycled PET organosilicon release film material into fine particles, drying for 4 hours in a 120-DEG oven under nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 10g of ethylene glycol antimony, 5g of triphenyl phosphate and 10g of a blue agent by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering, granulating, and enabling the mesh number of a filter screen of the extruder to be 300 meshes. Putting the manufactured particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping the pressure for 18 hours.
Example 4
Crushing 100 kg of PET organosilicon release film reclaimed materials into fine particles, drying for 4 hours in a 120-DEG oven in a nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 30g of ethylene glycol antimony, 5g of triphenyl phosphate and 10g of a red pigment by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering, granulating, and enabling the mesh number of a filter screen of the extruder to be 300 meshes. Putting the prepared particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping the pressure for 12 hours.
Comparative example 1
Crushing 100 kg of PET organosilicon release film reclaimed materials into fine particles, drying for 4 hours in a 120-DEG oven under the nitrogen atmosphere, putting the particles into a double-screw granulator, melting, extruding, filtering and granulating, wherein the mesh number of a filter screen of the extruder is 300. Putting the prepared particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping for 6 hours.
Comparative example 2
Crushing 100 kg of recycled PET organosilicon release film material into fine particles, uniformly mixing the dried PET organosilicon release film with 20g of ethylene glycol antimony, 5g of triphenyl phosphate, 7g of blue agent and 3g of red agent by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering, granulating, and enabling the mesh number of a filter screen of the extruder to be 300 meshes. Putting the prepared particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping for 6 hours.
Comparative example 3
Crushing 100 kg of recycled PET organosilicon release film material into fine particles, drying for 4 hours in a 120-degree oven under the nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 5g of triphenyl phosphate, 7g of blue agent and 3g of red agent by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering, granulating, and enabling the mesh number of a filter screen of the extruder to be 300 meshes. Putting the prepared particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping for 6 hours.
Comparative example 4
Crushing 100 kg of recycled PET organosilicon release film material into fine particles, drying for 4 hours in a 120-DEG oven under the nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 20g of ethylene glycol antimony, 7g of blue agent and 3g of red agent by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering, granulating, and enabling the mesh number of a filter screen of the extruder to be 300 meshes. Putting the prepared particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping for 6 hours.
Comparative example 5
Crushing 100 kg of PET organosilicon release film reclaimed materials into fine particles, drying for 4 hours in a 120-DEG oven in a nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 20g of ethylene glycol antimony and 5g of triphenyl phosphate by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering, granulating, and enabling the mesh number of a filter screen of the extruder to be 300 meshes. Putting the prepared particles into a vacuum oven, setting the temperature at 230 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to 30Pa, and keeping for 6 hours.
Comparative example 6
Crushing 100 kg of PET organosilicon release film reclaimed materials into fine particles, drying for 4 hours in a 120-DEG oven in a nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 20g of ethylene glycol antimony, 5g of triphenyl phosphate, 7g of a blue-degree agent and 3g of a red-degree agent by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering and granulating, wherein the mesh number of a filter screen of the extruder is 300. And putting the manufactured particles into a vacuum oven, setting the temperature to be 150 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to be 30Pa, and keeping the pressure for 6 hours.
Comparative example 7
Crushing 100 kg of PET organosilicon release film reclaimed materials into fine particles, drying for 4 hours in a 120-DEG oven in a nitrogen atmosphere, uniformly mixing the dried PET organosilicon release film with 20g of ethylene glycol antimony, 5g of triphenyl phosphate, 7g of a blue-degree agent and 3g of a red-degree agent by using a high-speed mixer, putting the mixture into a double-screw granulator together, melting, extruding, mixing, filtering and granulating, wherein the mesh number of a filter screen of the extruder is 300. And putting the manufactured particles into a vacuum oven, setting the temperature to be 270 ℃, starting a vacuum pump, forcibly pumping the pressure in the oven to be 30Pa, and keeping for 6 hours.
The products of examples and comparative examples were subjected to measurement of intrinsic viscosity (using test standard SN/T1015-2001) and whiteness value (using 3NH particle color difference meter NR20 XE), and the test results were as follows:
compared with the data of the embodiment 1 and the embodiment 2, the data of the invention adopts the recovered materials added with the catalyst, the stabilizer and the toner to overcome the defects of severe yellowing and great degradation of the product, the finished product has transparent appearance and low yellowing index, can be directly used as a raw material for preparing the PET film, and greatly improves the value of the waste PET release film.
As can be seen from comparison of the data of comparative example 2 and example 2, the drying of the crushed reclaimed material particles before the addition of the catalyst, the stabilizer and the toner can relieve the yellowing and the degradation of the product to a certain extent. It is possible that the above-mentioned effects are produced in that the drying of the recovered material can reduce the influence of impurities on the subsequent reaction.
The use of the catalyst according to the present invention can prevent the degradation of the recyclates and thus increase the utilization of the recyclates, which can be found in the data of example 2 and comparative example 3. The stabilizer used in the invention can stabilize the recycled materials in the reaction process, thereby influencing the degradability and color change of the product; the yellowing performance of the product can be relieved by using the toner; this is obtained by comparing comparative examples 4 to 5 with example 2.
The solid phase polycondensation temperature of the invention has great influence on the degradability of the product and also influences the yellowing performance of the product to a certain extent. Compared with the method in example 2, the comparative examples 6 to 7 of the invention use too low or too high polycondensation temperature to make the degradation of the product reach the negative effect, and increase the yellowing effect of the product to a certain extent.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for preparing a low-yellowness-value film-grade slice by using a recycled organic silicon PET release film is characterized by comprising the following steps of: crushing the waste organic silicon PET release film, then performing enhanced drying, mixing with a catalyst, a stabilizer and a toner, then performing melting, extrusion mixing, filtering and solid-phase polycondensation to prepare the low-yellowness-value film-grade slice.
2. The method of claim 1, wherein: the organic silicon PET release film comprises one or more of an off-line coating organic silicon release film and an on-line coating organic silicon release film.
3. The method of claim 1, wherein: the intensified drying is drying under nitrogen atmosphere; preferably, the intensive drying is preferably forced air drying; preferably, the temperature of the intensified drying is preferably 120-160 ℃; preferably, the time period for intensive drying is preferably 4 to 6 hours.
4. The method of claim 1, wherein: the catalyst is one or more of ethylene glycol antimony, antimony trioxide, antimony acetate, germanium dioxide and zinc acetate; preferably, the amount of the catalyst is 100-400ppm of the mass ratio of the waste silicone PET release film.
5. The method of claim 1, wherein: the stabilizer is one or more of triphenyl phosphate, trimethyl phosphate and triethyl phosphate; preferably, the stabilizer is used in an amount of 10-100ppm based on the mass ratio of the waste silicone PET release film.
6. The method of claim 1, wherein: the toner is preferably one or more of cobalt acetate, an erythroid agent, and a bluing agent.
7. The method of claim 1, wherein: the using amount of the toner is 20-100ppm of the mass ratio of the waste organic silicon PET release film.
8. The method of claim 1, wherein: the reaction temperature of the solid phase polycondensation is 190-230 ℃, the vacuum degree is 30Pa or below, and the reaction time is 6-24 hours.
9. The method of claim 8, wherein: the reaction temperature of the solid phase polycondensation is 210-230 ℃.
10. The preparation of low-yellowness-value film-grade slices from recycled silicone PET release films prepared by the process according to any one of claims 1 to 9.
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