CN117801360A - Method for preparing high-transparency cycloolefin copolymer from recycled plastics, high-transparency cycloolefin copolymer prepared by method and application of high-transparency cycloolefin copolymer - Google Patents
Method for preparing high-transparency cycloolefin copolymer from recycled plastics, high-transparency cycloolefin copolymer prepared by method and application of high-transparency cycloolefin copolymer Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 62
- 229920003023 plastic Polymers 0.000 title claims abstract description 58
- 239000004033 plastic Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 46
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002699 waste material Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 27
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- 238000004806 packaging method and process Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 48
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 239000012459 cleaning agent Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229920001684 low density polyethylene Polymers 0.000 claims description 15
- 239000004702 low-density polyethylene Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 9
- 229910000278 bentonite Inorganic materials 0.000 claims description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 4
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
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- 238000001125 extrusion Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- 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
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention provides a method for preparing a high-transparency cycloolefin copolymer from recycled plastics, the high-transparency cycloolefin copolymer prepared by the method and application thereof, and the method comprises the following steps: (1) Cleaning and drying the recycled plastic, and then performing cryogenic crushing treatment to obtain waste powder; (2) Mixing the waste powder obtained in the step (1) with a mixed solvent of methylcyclohexane and cyclohexane, and heating and stirring; (3) Adding an adsorbent into the mixed material in the step (2) for adsorption, and then filtering to obtain a purified cycloolefin copolymer solution; (4) Adding a precipitant into the cycloolefin copolymer solution in the step (3), stirring to perform precipitation reaction, and filtering, washing and drying to obtain the high-transparency cycloolefin copolymer. The regenerated COC product obtained by the method has excellent transparency without adding any additional auxiliary agent, has high application value, and can be used in high-end fields such as food packaging, medical packaging and the like.
Description
Technical Field
The invention relates to the fields of polymer material technology and plastic recycling, in particular to a method for preparing a high-transparency cycloolefin copolymer from recycled plastic, the high-transparency cycloolefin copolymer prepared from the high-transparency cycloolefin copolymer and application of the high-transparency cycloolefin copolymer.
Background
Cycloolefin copolymers (COC) are a type of amorphous thermoplastic resins obtained by addition polymerization of cycloolefins and α -olefins, and belong to the class of high-end polyolefin resins. Cycloolefin copolymers are widely used in many packaging fields because of their excellent properties such as water vapor barrier property, fragrance retention, and dead fold property. In addition, the polyethylene (especially low density polyethylene or linear low density polyethylene) has good compatibility, can be mixed with the polyethylene according to any proportion, and can be prepared into a film packaging material, so that the easy-tearing performance of the material can be effectively improved. Currently, the main high molecular resin components in the recycled materials of the easy-to-tear film obtained in the market are cycloolefin copolymer (COC) and Low Density Polyethylene (LDPE) or Linear Low Density Polyethylene (LLDPE).
Polyolefin materials are widely applied in the field of food packaging, and the volume of the polyolefin materials which are used and discarded each year is large, so that serious environmental pollution is caused. Therefore, the recycling of the film packaging material is the most important way for solving the plastic pollution, can save energy, reduce petrochemical energy consumption and can effectively solve the problems of environmental pollution and ecological crisis. The recovery of polyolefin-based plastics is generally carried out by a mechanical recovery method, a high-temperature chemical cracking method, and a solvent method. The mechanical recovery method is to obtain regenerated polyolefin materials after simple physical and mechanical treatments such as direct blending, melt blending, extrusion granulation and the like of waste polyolefin plastics, but the polyolefin plastics are degraded generally in the process of the scheme, so that the yellowing of the materials is obvious, the transparency is rapidly reduced, the mechanical property is seriously attenuated, and the regenerated polyolefin materials cannot be applied to the high-end field and can only be applied to the recycling of low-value products. The high-temperature chemical pyrolysis method is characterized in that polyolefin plastics are subjected to pyrolysis reaction under the action of heating and a catalyst, so that macromolecule chains are broken indiscriminately to form low-molecular substances, but few monomers are formed, the subsequent process can not be used as the monomers to participate in polyolefin synthesis again, and the chemical depolymerization method is complex in process, and meanwhile, the high-temperature condition has extremely high requirement on industrialization, and has high carbon emission, huge energy consumption and high cost.
The solvent method for recycling the polyolefin plastic avoids the problems of great attenuation of material performance, complex high-temperature cracking process and high energy consumption caused by mechanical recycling. Patent CN107810226B reports that a polyolefin-based plastic can be dissolved in a high-temperature and high-pressure state using a short-chain aliphatic hydrocarbon solvent, but the process is severe, high-temperature and high-pressure conditions are required, and the energy consumption is high; patent CN114133618B reports that the low-density polyethylene resin can be dissolved out by using a compound solvent (toluene/limonene), but COC is insoluble, and the high-purity COC reclaimed material is obtained after filtration, but toluene has high toxicity, pollutes the environment, and long-term contact can affect personnel health, so that the reclaimed COC material cannot be applied to high-end fields such as food packaging and medical packaging.
In view of the foregoing, there is a need in the art to develop a simple, efficient, green, and low energy-consuming method for purifying COC, so that a high purity regenerated COC material can be obtained, thereby meeting the requirements of high-end regenerated COC products.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, one of the purposes of the present invention is to provide a method for preparing a high transparent Cyclic Olefin Copolymer (COC) from recycled plastics, in particular to prepare a high transparent material by purifying a cyclic olefin copolymer from recycled plastics, which has the advantages of simplicity, high efficiency, green environmental protection, low energy consumption and low cost.
The second object of the present invention is to provide a highly transparent cycloolefin copolymer prepared by the above method, and the obtained regenerated cycloolefin copolymer material has excellent transparency without adding any additional auxiliary agent, and has improved application value as compared with other COC regenerated materials.
The invention also aims to provide an application of the high-transparency cycloolefin copolymer in high-end fields such as food packaging, medical packaging and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a process for preparing a highly transparent Cyclic Olefin Copolymer (COC) from recycled plastics, the steps comprising:
(1) Cleaning and drying the recycled plastic, and then performing cryogenic crushing treatment to obtain waste powder;
(2) Mixing the waste powder obtained in the step (1) with a mixed solvent of methylcyclohexane and cyclohexane, and heating and stirring;
(3) Adding an adsorbent into the mixed material in the step (2) for adsorption, and then filtering to obtain a purified cycloolefin copolymer solution;
(4) Adding a precipitant into the cycloolefin copolymer solution in the step (3), stirring to perform precipitation reaction, and filtering, washing and drying to obtain the high-transparency cycloolefin copolymer.
In the present invention, the recycled plastic of step (1) is a waste plastic comprising Cyclic Olefin Copolymer (COC);
preferably, the recycled plastic further comprises Linear Low Density Polyethylene (LLDPE) and/or Low Density Polyethylene (LDPE);
preferably, the sum of the mass of the cycloolefin copolymer and the linear low density polyethylene and/or the low density polyethylene is 98wt% or more, for example 98.1, 98.3, 98.5, 98.7, 99, 99.2, 99.5, 99.7, 99.9wt%, based on the mass percentage of the recycled plastic;
the specific source of the recycled plastic is not limited, and the recycled plastic is preferably easy-to-tear film particle recycled material for packaging.
The cleaning in the step (1) is performed by adding water to dilute the cleaning agent to a required concentration when the cleaning agent is at least one of a nonionic surfactant cleaning agent, a zwitterionic cleaning agent, an alkaline cleaning agent and a biological enzyme cleaning agent, and the cleaning agent is cleaned by water after the cleaning is finished.
In the invention, the cryogenic crushing treatment is carried out in the step (1), wherein the treatment temperature is-50 to-78 ℃, such as-50, -55, -60, -65, -70, -75 and-78 ℃;
the average particle size of the crushed waste powder is preferably 1000 μm or less, for example 1000, 900, 800, 700, 600, 500, 400, 300, 100, 50 μm, preferably 300 to 600 μm. After the recycled waste is processed into the powder with the preferable particle size, the method has higher processing efficiency in the subsequent dissolving and adsorbing processes, and simultaneously can remove small molecular impurities and insoluble matters in the waste more effectively.
In the invention, the mixed solvent of the methylcyclohexane and the cyclohexane in the step (2), wherein the volume ratio of the methylcyclohexane to the cyclohexane is 10: (0 to 5), for example, 10:0 (i.e., methylcyclohexane pure solvent), 10: 1. 10: 2. 10: 3. 10: 4. 10:5, preferably 10: (1-2);
in the case where cyclohexane is 0, that is, pure methylcyclohexane is used as the solvent, the present invention combines the above solvents into a mixed solvent, and the ratio is 0.
In the invention, the volume ratio of the mass of the waste powder in the step (2) to the mixed solvent is 1g: (3-20) mL, for example 1g:3mL, 1g:6mL, 1g:9mL, 1g:12mL, 1g:15mL, 1g:18mL, 1g:20mL, preferably 1g: (5-20) mL.
In the present invention, the heating and stirring in the step (2) are performed for 1 to 5 hours, for example, 1, 2, 3, 4, 5 hours, preferably 1 to 3 hours.
In the present invention, the temperature of the heating and stirring in step (2) is 25 to 50 ℃, for example 25, 30, 35, 40, 45, 50 ℃, preferably 30 to 50 ℃.
The cyclohexane consumption, heating temperature and time in the mixed solvent influence the waste material dissolving effect, and under the condition of the invention, the selectivity of the COC in the dissolved waste material powder can be improved, and the high-purity regenerated COC product can be obtained.
In the invention, the adsorbent in the step (3) is at least one of activated carbon, bentonite, montmorillonite, activated clay and alumina.
In the invention, the mass ratio of the adsorbent in the step (3) to the waste powder in the step (2) is 1: (5 to 50), for example, 1: 5. 1: 10. 1: 20. 1: 30. 1: 40. 1:50.
in the invention, the treatment processes of adsorption, filtration and the like in the step (3) are conventional treatment modes in the field, and the invention has no specific requirement;
preferably, the adsorption temperature is 20-70 ℃, e.g. 20, 30, 40, 50, 60, 70 ℃, and the adsorption time is 1-8 hours, e.g. 1, 3, 5, 7, 8 hours. Under the conditions, COC in the waste powder can be fully dissolved in the methylcyclohexane/cyclohexane compound solvent, and exuded or insoluble additive impurities such as antioxidants, colorants and the like can be fully removed through the adsorbent, so that the purity of the regenerated COC material is improved.
In the invention, the precipitant in the step (4) is an acidified ethanol solution;
preferably, the acids used for acidification in the acidified ethanol solution are one or more of hydrochloric acid, phosphoric acid, acetic acid and formic acid, and more preferably, the acid volume percentage content in the acidified ethanol solution is 5-15%, such as5, 7, 9, 11, 13 and 15%.
In the invention, the volume ratio of the olefin copolymer solution to the precipitant in the step (4) is 1: (3-6), for example 1: 3. 1: 4. 1: 5. 1:6.
in the invention, the treatment processes of stirring, precipitation, filtering, washing, drying and the like in the step (4) are conventional treatment modes in the field, and are conventional operation in the field, and the invention has no specific requirement;
preferably, the drying is vacuum drying, the temperature is 70-100 ℃, the vacuum degree is less than or equal to 0.1kPa, and the time is 6-12 hours.
In a second aspect, the present invention provides a highly transparent cycloolefin copolymer material produced by the above method.
The glass transition temperature Tg of the high-transparency cycloolefin copolymer is 60-180 ℃.
The high-transparency cycloolefin copolymer according to the present invention has a light transmittance of not less than 90%, for example, 90, 91, 92, 93, 94, 95, 97%.
The purity of the high-transparency cycloolefin copolymer is more than or equal to 98.5 weight percent.
In a third aspect, the present invention also provides the use of the above highly transparent cycloolefin copolymer in the field of food and medical packaging.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The invention uses the methyl cyclohexane/cyclohexane compound solvent for separating, purifying and recycling COC in plastics, wherein the solvent does not contain cancerogenic solvents such as toluene, benzene and the like, has good green environmental protection, and the obtained high-purity regenerated COC plastics can be used in high-end fields such as food, medical packaging and the like.
(2) The preparation method provided by the invention has the advantages of simple process, low energy consumption (low process temperature), few reagents, safety and environmental protection, and the obtained product has excellent transparency, high application value and wide application field under the condition of not adding extra auxiliary agents, and simultaneously, the solvent can be recycled, thereby changing waste into valuables, saving the cost and providing a solution for recycling COC plastics.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The main raw material source information used in the examples and comparative examples of the present invention are shown below, and others are obtained from common commercial sources unless specified otherwise:
easy tearing film particle reclaimed material a: COC content 85wt% (TOPAS 8007, japanese Bao's theory) with glass transition temperature Tg of 78deg.C; the low-density polyethylene content is 15wt% (the melt point is 109 ℃ in the case of the petrochemical LDPE 2420H);
and (2) recycling materials of the easily torn film particles: COC content 80wt% (TOPAS 5013, japanese Bao's theory) with glass transition temperature Tg of 134 ℃; the low-density polyethylene content is 20wt% (petrochemical LDPE 2420H with a melting point of 109 ℃;
the recycled materials a and b of the easy-to-tear film particles are self-made and are prepared by a film blowing process according to the conventional processing operation in the field and the component analysis of the existing easy-to-tear film product.
Adsorbent (activated carbon): 20-50 mesh Shanghai Miclin Biochemical technology Co., ltd;
adsorbent (bentonite): shanghai Miclin Biochemical technology Co., ltd., density of 2-3 g/cm 3 ；
Cleaning agent: SP-288, a nonionic surfactant, cantonese Sanpin technologies Co., ltd;
methylcyclohexane: analytical grade of Beijing enoki technologies Co., ltd;
cyclohexane: analytical grade, beijing enoki technologies Co.
The performance test parameters and the corresponding test methods adopted in the embodiments of the invention are as follows:
(1) The purity (wt%) of COC in the regenerated plastic is calculated as follows: determination of recycled plastics Using Bruker Avance III MHz Nuclear magnetic resonance apparatus 13 The purity of COC in the reclaimed plastic was calculated by C NMR spectrum, and the measurement temperature was 120℃with deuterated tetrachloroethane as a solvent.
(2) The calculation formula of the recovery rate (wt%) is: 100× (mass of COC in recycled plastic ≡mass of COC in waste plastic).
(3) Transmittance: with reference to GB 2410-2008, the test is performed on a light transmittance tester.
(4) And measuring the glass transition temperature Tg of the regenerated COC plastic by using a Differential Scanning Calorimeter (DSC), heating up at a rate of 10 ℃/min, cooling down at a rate of 10 ℃/min, and scanning at a range of 30-280 ℃ by using a secondary heating up curve.
Example 1
The preparation of the high transparent cycloolefin copolymer from the recycled plastic comprises the steps of:
(1) Washing 10g of easily torn film particle reclaimed material a with cleaning agent SP-288 and water, washing with clear water, drying reclaimed plastic in an oven at 80 ℃ for 10 hours (vacuum degree is less than or equal to 0.1 kPa), and crushing (liquid nitrogen cooling) at-50 to-78 ℃ by using a cryogenic crusher to obtain waste powder with average particle diameter of 400 mu m;
(2) 10g of the waste powder was added to a mixed solvent of 100mL of methylcyclohexane and 10mL of cyclohexane, and mixed, heated to 40℃and stirred for 1 hour to sufficiently dissolve COC;
(3) Then adding 1g of adsorbent bentonite to adsorb impurities, adsorbing for 5 hours at 50 ℃, and filtering to remove solid residues to obtain a purified cycloolefin copolymer solution;
(4) 120mL of purified cycloolefin copolymer solution is added into a mixed solution of 500mL of ethanol and 50mL of hydrochloric acid, the mixture is stirred for precipitation reaction, and after filtration and washing, the mixture is dried in an oven with the temperature of 70 ℃ for 8 hours (the vacuum degree is less than or equal to 0.1 kPa), and then the high-transparency cycloolefin copolymer is obtained.
Example 2
The preparation of the high transparent cycloolefin copolymer from the recycled plastic comprises the steps of:
(1) Washing 20g of easily torn film particle reclaimed material a with cleaning agent SP-288 and water, washing with clear water, drying reclaimed plastic in a 70 ℃ oven (vacuum degree is less than or equal to 0.1 kPa) for 12 hours, and crushing (liquid nitrogen cooling) at-50 to-78 ℃ by using a cryogenic crusher to obtain waste powder with average particle diameter of 300 mu m;
(2) Adding 20g of the waste powder into 300mL of methyl cyclohexane and 40mL of cyclohexane mixed solvent, mixing, heating to 30 ℃ and stirring for 2 hours to fully dissolve COC;
(3) Then adding 3g of adsorbent bentonite to adsorb impurities, adsorbing for 6 hours at 30 ℃, and filtering to remove solid residues to obtain a purified cycloolefin copolymer solution;
(4) 360mL of purified cycloolefin copolymer solution is added into a mixed solution of 1000mL of ethanol and 100mL of hydrochloric acid, stirred, subjected to precipitation reaction, filtered, washed and dried in an oven with the temperature of 70 ℃ for 8 hours (the vacuum degree is less than or equal to 0.1 kPa), and then the high-transparency cycloolefin copolymer is obtained.
Example 3
The preparation of the high transparent cycloolefin copolymer from the recycled plastic comprises the steps of:
(1) Washing 15g of recovered material b of the easily torn film particles with a cleaning agent SP-288 and water, washing with clear water, drying the recovered plastic in a 100 ℃ oven (vacuum degree is less than or equal to 0.1 kPa) for 6 hours, and crushing (liquid nitrogen cooling) the recovered plastic at-50 to-78 ℃ by using a cryogenic crusher to obtain waste powder with average particle size of 600 mu m;
(2) 15g of the waste powder was added to a mixture of 270mL of methylcyclohexane and 30mL of cyclohexane, and mixed, heated to 25℃and stirred for 3 hours to fully dissolve COC;
(3) Then adding 1g of adsorbent bentonite to adsorb impurities, adsorbing for 8 hours at 20 ℃, and filtering to remove solid residues to obtain a purified cycloolefin copolymer solution;
(4) 315mL of purified cycloolefin copolymer solution is added into 950mL of ethanol and 50mL of hydrochloric acid mixed solution, stirred, subjected to precipitation reaction, filtered, washed and dried in an oven at 80 ℃ for 9 hours (the vacuum degree is less than or equal to 0.1 kPa), and then the high-transparency cycloolefin copolymer is obtained.
Example 4
The preparation of the high transparent cycloolefin copolymer from the recycled plastic comprises the steps of:
(1) Washing 12g of easily torn film particle reclaimed material b with cleaning agent SP-288 and water, washing with clear water, drying reclaimed plastic in a 100 ℃ oven (vacuum degree is less than or equal to 0.1 kPa) for 6 hours, and crushing (liquid nitrogen cooling) at-50 to-78 ℃ by using a cryogenic crusher to obtain waste powder with average particle diameter of 500 mu m;
(2) Adding 12g of the waste powder into 50mL of methyl cyclohexane and 10mL of cyclohexane mixed solvent, mixing, heating to 50 ℃ and stirring for 1 hour to fully dissolve COC;
(3) Then adding 0.5g of adsorbent bentonite for impurity adsorption, and filtering to remove solid residues after adsorption for 2 hours at 60 ℃ to obtain a purified cycloolefin copolymer solution;
(4) Adding 72mL of purified cycloolefin copolymer solution into a mixed solution of 360mL of ethanol and 40mL of hydrochloric acid, stirring, performing precipitation reaction, filtering, washing, and drying in a 70 ℃ oven (vacuum degree is less than or equal to 0.1 kPa) for 12 hours to obtain the high-transparency cycloolefin copolymer.
Example 5
The preparation of the high transparent cycloolefin copolymer from the recycled plastic comprises the steps of:
(1) Washing 2.5g of easily torn film particle reclaimed material a with cleaning agent SP-288 and water, washing with clear water, drying reclaimed plastic in an oven at 80 ℃ for 10 hours (vacuum degree is less than or equal to 0.1 kPa), and crushing (liquid nitrogen cooling) at-50 to-78 ℃ by using a cryogenic crusher to obtain waste powder with average particle diameter of 900 mu m;
(2) Adding 2.5g of the waste powder into 10mL of methylcyclohexane solvent, mixing, heating to 45 ℃ and stirring for 3 hours to fully dissolve COC;
(3) Then adding 0.5g of adsorbent bentonite for impurity adsorption, and filtering to remove solid residues after adsorption for 1 hour at 70 ℃ to obtain a purified cycloolefin copolymer solution; the method comprises the steps of carrying out a first treatment on the surface of the
(4) Adding 12.5mL of purified cycloolefin copolymer solution into 65mL of ethanol and 10mL of hydrochloric acid mixed solution, stirring, performing precipitation reaction, filtering, washing, and drying in an oven at 80 ℃ for 8 hours (the vacuum degree is less than or equal to 0.1 kPa), thereby obtaining the high-transparency cycloolefin copolymer.
Example 6
The preparation of the high transparent cycloolefin copolymer from the recycled plastic comprises the steps of:
(1) Washing 75g of easily torn film particle reclaimed material a with cleaning agent SP-288 and water, washing with clear water, drying reclaimed plastic in a 100 ℃ oven (vacuum degree is less than or equal to 0.1 kPa) for 6 hours, and crushing (liquid nitrogen cooling) at-50 to-78 ℃ by using a cryogenic crusher to obtain waste powder with average particle diameter of 50 mu m;
(2) Adding 75g of the waste powder into 200mL of methylcyclohexane and 100mL of cyclohexane solvent, mixing, heating to 40 ℃ and stirring for 5 hours to fully dissolve COC;
(3) Then adding 1.5g of adsorbent bentonite to adsorb impurities, adsorbing for 4 hours at 60 ℃, and filtering to remove solid residues to obtain a purified cycloolefin copolymer solution;
(4) 375mL of purified cycloolefin copolymer solution is added into a mixed solution of 1500mL of ethanol and 150mL of hydrochloric acid, stirred, subjected to precipitation reaction, filtered, washed and dried in a 100 ℃ oven (vacuum degree is less than or equal to 0.1 kPa) for 12 hours, and then the high-transparency cycloolefin copolymer is obtained.
Comparative example 1
With reference to the method of example 3, the only difference is: the heating temperature in the step (2) is 90 ℃, and the conditions are unchanged.
Comparative example 2
With reference to the method of example 3, the only difference is: and (3) replacing the methylcyclohexane in the mixed solvent of the methylcyclohexane and the cyclohexane in the step (2) with the methylcyclopentane with the same amount, and keeping the other conditions unchanged.
Comparative example 3
With reference to the method of example 3, the only difference is: the methylcyclohexane in step (2) is replaced by an equivalent amount of cyclohexane pure solvent, methylcyclohexane is not adopted, and other conditions are unchanged.
Comparative example 4
The easy-tearing film particle reclaimed material a is adopted, and the reclaimed plastic is only treated by a simple extrusion processing method without being treated by the method.
The cycloolefin copolymers prepared in the examples and comparative examples described above were subjected to performance tests, and the test data are shown in Table 1:
TABLE 1 results of Performance test of cycloolefin copolymers of examples 1 to 6 and comparative examples 1 to 4
As is evident from comparative example 1, too high a heating temperature also results in an accelerated swelling of a portion of the LDPE and subsequent dissolution, resulting in a reduced purity of the recycled COC plastic.
As is evident from comparative example 2, the replacement of methylcyclohexane with methylcyclopentane results in insufficient dissolution of the COC by the solvent, resulting in a regenerated COC plastic having too low a purity.
As is evident from comparative example 3, the use of cyclohexane alone also results in insufficient dissolution of COC by the solvent, resulting in a recycled COC plastic having too low a purity.
As is evident from comparative example 4, when other methods are used to recover plastics, the low density polyethylene and COC cannot be completely separated, resulting in a recycled COC plastic having too low a purity.
Claims (10)
1. A process for preparing a highly transparent cyclic olefin copolymer from recycled plastic, characterized in that the steps comprise:
(1) Cleaning and drying the recycled plastic, and then performing cryogenic crushing treatment to obtain waste powder;
(2) Mixing the waste powder obtained in the step (1) with a mixed solvent of methylcyclohexane and cyclohexane, and heating and stirring;
(3) Adding an adsorbent into the mixed material in the step (2) for adsorption, and then filtering to obtain a purified cycloolefin copolymer solution;
(4) Adding a precipitant into the cycloolefin copolymer solution in the step (3), stirring to perform precipitation reaction, and filtering, washing and drying to obtain the high-transparency cycloolefin copolymer.
2. The method of claim 1, wherein the recycled plastic of step (1) is a waste plastic comprising a cyclic olefin copolymer; preferably, the recycled plastic further comprises linear low density polyethylene and/or low density polyethylene;
preferably, the sum of the mass of the cycloolefin copolymer and the linear low density polyethylene and/or the low density polyethylene is 98wt% or more in terms of the mass percentage of the recycled plastic;
preferably, the recycled plastic is a recycled material of the easily torn film particles for packaging.
3. The method of claim 1, wherein the cleaning of step (1) is performed using at least one of a nonionic surfactant cleaning agent, a zwitterionic cleaning agent, an alkaline cleaning agent, and a biological enzyme cleaning agent.
4. The method of claim 1, wherein the cryogenic crushing treatment of step (1) is carried out at a temperature of-50 to-78 ℃;
the average particle size of the waste powder after the crushing treatment is preferably 1000 μm or less, and more preferably 300 to 600 μm.
5. The method according to claim 1, wherein the mixed solvent of methylcyclohexane and cyclohexane in step (2) has a volume ratio of methylcyclohexane to cyclohexane of 10: (0 to 5), preferably 10: (1-2); and/or
The volume ratio of the mass of the waste powder to the mixed solvent in the step (2) is 1g: (3-20) mL, preferably 1g: (5-20) mL.
6. The method according to claim 1, wherein the heating and stirring in step (2) is carried out for a period of 1 to 5 hours, preferably 1 to 3 hours; and/or
The heating and stirring in the step (2) are carried out at a temperature of 25-50 ℃, preferably 30-50 ℃.
7. The method of claim 1, wherein the adsorbent of step (3) is at least one of activated carbon, bentonite, montmorillonite, activated clay, and alumina; and/or
The mass ratio of the adsorbent in the step (3) to the waste powder in the step (2) is 1: (5-50); and/or
The adsorption temperature in the step (3) is 20-70 ℃ and the adsorption time is 1-8 hours.
8. The method of claim 1, wherein the precipitant of step (4) is an acidified ethanol solution;
preferably, the acid adopted in the acidification of the acidified ethanol solution is one or more of hydrochloric acid, phosphoric acid, acetic acid and formic acid, and more preferably, the volume percentage of the acid in the acidified ethanol solution is 5-15%; and/or
The volume ratio of the olefin copolymer solution to the precipitant in the step (4) is 1: (3-6).
9. A highly transparent cyclic olefin copolymer material obtainable by the process of any one of claims 1 to 8.
10. Use of the highly transparent cycloolefin copolymer material obtainable by the process according to any of claims 1 to 8 or the highly transparent cycloolefin copolymer according to claim 9 in the field of food and medical packaging.
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| CN118027289B (en) * | 2024-04-12 | 2024-06-21 | 辽宁鲁华泓锦新材料科技有限公司 | Impurity removing refining method for cycloolefin-ethylene copolymer |
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