CN220008479U - Preparation system for recyclable material of heat-shrinkable film - Google Patents
Preparation system for recyclable material of heat-shrinkable film Download PDFInfo
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- CN220008479U CN220008479U CN202321505067.1U CN202321505067U CN220008479U CN 220008479 U CN220008479 U CN 220008479U CN 202321505067 U CN202321505067 U CN 202321505067U CN 220008479 U CN220008479 U CN 220008479U
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 229920000728 polyester Polymers 0.000 claims abstract description 93
- 239000002245 particle Substances 0.000 claims abstract description 73
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 70
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000004064 recycling Methods 0.000 claims abstract description 33
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 28
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 28
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 22
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims abstract description 13
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940087291 tridecyl alcohol Drugs 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 238000007605 air drying Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 description 30
- 239000005020 polyethylene terephthalate Substances 0.000 description 30
- 239000010410 layer Substances 0.000 description 23
- 238000004140 cleaning Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- -1 cyclic ester Chemical class 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 235000013361 beverage Nutrition 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 5
- 238000005188 flotation Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- XRBXGZZMKCBTFP-UHFFFAOYSA-N 4-(2,2-dihydroxyethoxycarbonyl)benzoic acid Chemical compound OC(O)COC(=O)C1=CC=C(C(O)=O)C=C1 XRBXGZZMKCBTFP-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 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 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- NXDJCCBHUGWQPG-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;terephthalic acid Chemical compound OCC1CCC(CO)CC1.OC(=O)C1=CC=C(C(O)=O)C=C1 NXDJCCBHUGWQPG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The utility model provides a preparation system of a recyclable material of a heat-shrinkable film, which comprises a functional master batch preparation device, a polyester recycling particle preparation device and a mixing preparation device; the functional master batch preparation device comprises a polyester carrier dryer, a magnesium carbonate dryer, a sodium dodecyl benzene sulfonate dryer and a high-speed mixer; the high-speed mixer is respectively connected with an ester carrier dryer, a magnesium carbonate dryer, a sodium dodecyl benzene sulfonate dryer, a diethyl phenylphosphonate conveying pipe and a tridecyl alcohol stearate conveying pipe through input pipelines; the high-speed mixer is connected with the extruder through an output pipeline, and the output end of the extruder is connected with the water-cooled granulator. The preparation system provided by the utility model can be used for preparing a recyclable material suitable for a recyclable heat-shrinkable film, and the recyclable material can be singly or mixed with other polyester raw materials to prepare the heat-shrinkable film, and the prepared heat-shrinkable film has excellent performance and can meet the environmental protection requirement.
Description
Technical Field
The utility model relates to a preparation system of a recyclable material of a heat-shrinkable film.
Background
The plastic products are difficult to degrade and easily cause environmental pollution. Waste plastic products, such as recycled PET bottles and the like, are classified and recycled in a large amount, but most of the recycled PET bottles are crushed and recycled as raw materials of low-grade products, so that the waste plastic products are difficult to apply to the fields with high requirements on appearance and environmental protection. For example, heat-shrinkable films are an outer packaging material that can be significantly reduced in size after heating, and are widely used as outer packages for various consumer and industrial goods. Heat-shrinkable films as outer packaging materials are generally required to have good mechanical properties, a large transverse stretching ratio, high transparency, and fire resistance. The common recycled plastics have the problems of aging and color change due to different sources and larger component difference of different plastic products, and are difficult to be used as raw materials for preparing the heat-shrinkable film.
Disclosure of Invention
The technical problem to be solved by the utility model is to provide a preparation system of recyclable materials for heat shrinkable films, so as to reduce or avoid the problems.
In order to solve the technical problems, the utility model provides a preparation system of a recyclable material for a heat-shrinkable film, which comprises a functional master batch preparation device, a polyester recycling particle preparation device and a mixing preparation device for preparing the recyclable material by mixing the functional master batch prepared by the functional master batch preparation device and the polyester recycling particles prepared by the polyester recycling particle preparation device; wherein the functional master batch preparation device comprises a polyester carrier dryer, a magnesium carbonate dryer, a sodium dodecyl benzene sulfonate dryer and a high-speed mixer; the high-speed mixer is respectively connected with an ester carrier dryer, a magnesium carbonate dryer, a sodium dodecyl benzene sulfonate dryer, a diethyl phenylphosphonate conveying pipe and a tridecyl alcohol stearate conveying pipe through input pipelines; the high-speed mixer is connected with the extruder through an output pipeline, and the output end of the extruder is connected with the water-cooled granulator.
Preferably, the polyester recycling particle preparation device comprises a pulverizer, an air-drying winnowing machine, a decoloring cleaning machine and a recycling particle dryer, wherein the pulverizer is used for pulverizing a recycled PET bottle or a thermal shrinkage film label, the output end of the pulverizer is connected with the air-drying winnowing machine, the output end of the air-drying winnowing machine is connected with the decoloring cleaning machine, and the output end of the decoloring cleaning machine is connected with the recycling particle dryer.
Preferably, the mixing preparation device comprises a mixing extruder, a reclaimed material water-cooling granulator and a reclaimed material dryer, wherein the input end of the mixing extruder is respectively connected with the output ends of the functional master batch preparation device and the polyester reclaimed particle preparation device, the output end of the mixing extruder is connected with the reclaimed material water-cooling granulator, and the output end of the reclaimed material water-cooling granulator is connected with the reclaimed material dryer.
Preferably, the input end of the magnesium carbonate dryer is further connected with a magnesium carbonate pulverizer.
Preferably, the output end of the water-cooled granulator is further connected with a master batch dryer.
The utility model can be used for preparing the recyclable material suitable for the recyclable heat-shrinkable film, and can be singly or mixed with other polyester raw materials to prepare the heat-shrinkable film, and the prepared heat-shrinkable film has excellent performance and can meet the environmental protection requirement.
Drawings
The following drawings are only for purposes of illustration and explanation of the present utility model and are not intended to limit the scope of the utility model.
FIG. 1 is a schematic diagram showing the structure of the system for preparing a recyclable material for heat shrinkable films according to the present utility model.
Fig. 2 shows a schematic structural diagram of a functional masterbatch preparation apparatus of the present utility model.
Detailed Description
Specific embodiments of the present utility model will now be described in detail for a clearer understanding of the technical features, objects and effects of the present utility model.
In order to solve the defect that the recycled PET bottle cannot be used for directly preparing a high-quality heat-shrinkable film in the prior art, the utility model provides a heat-shrinkable film recyclable material, which is prepared by carrying out melting modification treatment on polyester recycling particles in a mode of adding functional master batch into the polyester recycling particles, and the heat-shrinkable film with the recyclable material can be produced by adding a certain proportion of the recyclable material, for example, 5-95% by weight of the total mass, into the heat-shrinkable film raw material. Wherein, the polyester recovery particles can be transparent particles obtained by crushing, decoloring and cleaning the recovered PET bottle or the heat-shrinkable film label, and the particle size of the polyester recovery particles is preferably 50-200 mu m.
Wherein, the heat-shrinkable film can be produced by selecting any existing preparation process and raw material formulation suitable for preparing the heat-shrinkable film. For example, the recyclable material prepared by the method can be selectively applied to a preparation method of a heat-shrinkable copolyester film disclosed in CN 103172990B proposed by the applicant, wherein multicomponent dibasic acid and multicomponent dihydric alcohol are subjected to esterification and polycondensation reaction in the presence of a catalyst, a stabilizer, an antistatic agent, a chain extender, an anti-adhesive or a modifier to prepare multicomponent copolyester; the multi-component copolyester slice is prepared through the procedures of melt extrusion, stretching and granulation; and then the heat-shrinkable copolyester film is prepared through the procedures of melt extrusion, die casting, transverse far infrared stretching, cooling shaping, rolling and slitting. The recyclable material can be selectively fed in the esterification reaction stage or in the polycondensation reaction stage. The multicomponent copolyester slice prepared by melt extrusion meets the recovery rate of environmental protection requirements, can be directly drawn into a heat-shrinkable film with a single-layer structure by melt extrusion, and can also be used for preparing a surface layer, a core layer or a bottom layer of the heat-shrinkable film with a multilayer composite structure by multilayer coextrusion.
Alternatively, the recyclable material prepared by the utility model can be selectively applied to a heat-shrinkable polyester film disclosed in CN 112297555B provided by the applicant, wherein the heat-shrinkable polyester film comprises a layer A, a layer B and a layer C, the layer A and the layer C are respectively arranged on two sides of the layer B, the layer A and the layer C are a polyester surface layer and a polyester bottom layer which contain functional material slices, and the layer B is a polyester core layer which does not contain functional material slices; the polyester of the layer A and the layer C has the same component as the polyester of the layer B. The recyclable material can be applied to the middle layer, namely the B layer, of the heat-shrinkable polyester film with the three-layer structure, so that the components of the existing surface layer and the existing bottom layer do not need to be adjusted, the recycling rate required by environmental protection is met, the production process does not need to be excessively adjusted, the process is simple, and the quality of the original heat-shrinkable film can be basically maintained. Of course, those skilled in the art can also use the recyclable materials to prepare the top and bottom layers of the three-layer heat-shrinkable polyester film.
As can be seen from the above examples of application of the recyclable material of the present utility model, the recyclable material of the present utility model is an intermediate product obtained by melt-modifying polyester recycled particles, which contains a functional master batch, and the recyclable material containing the functional master batch can be prepared alone into a layer structure of a heat-shrinkable film, or can be mixed with other polyester raw materials to prepare a heat-shrinkable film of a single layer structure or one layer of a heat-shrinkable film of a multilayer structure. The utility model preferably mixes the recyclable material with other polyester raw materials to avoid the performance deficiency of the recyclable material as much as possible.
In a specific embodiment, the recyclable material of the heat-shrinkable film is prepared by mixing 60-80 wt% of polyester recycling particles and 20-40 wt% of functional master batch, wherein the polyester recycling particles are prepared by recycling PET bottles or heat-shrinkable film labels, and the functional master batch consists of a polyester carrier, diethyl phenylphosphonate, sodium dodecyl benzene sulfonate, tridecyl alcohol stearate and magnesium carbonate. In one embodiment, the recyclable material of the present utility model can be prepared by the following method: transparent particles obtained by crushing, decoloring and cleaning a recovered PET bottle or a thermal shrinkage film label are used as polyester recovered particles, the polyester recovered particles with the average particle size of 100-150 mu m are selected to be uniformly mixed with the prepared functional master batch, and then the polyester recovered particles are subjected to melt extrusion and granulating by an extruder to obtain recyclable materials.
The functional master batch can be prepared by the following method: the granular polyester carrier, diethyl phenylphosphonate, sodium dodecyl benzene sulfonate, tridecyl alcohol stearate and magnesium carbonate are uniformly mixed, and then are melted and extruded by an extruder and granulated, thus obtaining the functional master batch of the utility model. The content of each component in the functional master batch is preferably as follows: 100-150 parts of polyester carrier, 25-30 parts of diethyl phenylphosphonate, 5-10 parts of sodium dodecyl benzene sulfonate, 15-20 parts of tridecyl alcohol stearate and 5-10 parts of magnesium carbonate.
The polyester carrier in the functional master batch of the utility model can be formed by polycondensation of dibasic acid and dihydric alcohol, and can also be formed by hydroxy carboxylic acid and ester-forming derivative or cyclic ester thereof. In one embodiment, the polyester carrier used in the present utility model is preferably polyethylene terephthalate (PET), polybutylene terephthalate, polytrimethylene terephthalate, poly (1, 4-cyclohexanedimethanol terephthalate) (PCT), polyethylene naphthalate, polybutylene naphthalate, polytrimethylene naphthalate and copolymers thereof. Polyethylene terephthalate (PET) and its copolymers are particularly preferred.
In one embodiment of the utility model, the functional masterbatch of the utility model may optionally be obtained simultaneously with the preparation of the polyester carrier. For example, taking PET as a polyester carrier, the preparation method of the functional master batch of the utility model can comprise the following steps: firstly, the dihydroxyethyl terephthalate is prepared by esterification reaction of terephthalic acid or dimethyl terephthalate and ethylene glycol. Then, the catalyst is used for polycondensation reaction under the high temperature and vacuum condition, and the dihydroxyethyl terephthalate is polycondensed into the PET polyester carrier. In the above step, other components than the polyester carrier may be selectively charged into the functional masterbatch in the esterification reaction stage or in the polycondensation reaction stage. Finally, the melt of the functional master batch containing the PET polyester carrier and other components is produced, and the functional master batch can be obtained through extrusion and granulating of the melt. In this embodiment, terephthalic acid, ethylene glycol, cyclohexanedimethanol, a catalyst and a heat stabilizer may be used as raw materials for the esterification reaction; or using terephthalic acid, ethylene glycol, isophthalic acid, a catalyst and a heat stabilizer as raw materials for esterification reaction. The catalyst can be any one compound of Ti/Si series non-heavy metal catalyst and antimonous oxide, and the addition amount of the catalyst is 0.01-0.09% of the mass of the polyester. The heat stabilizer can be any one of phosphoric acid compounds such as phosphoric acid, phosphorous acid, polyphosphoric acid, trimethyl phosphate, triphenyl phosphate and triethyl phosphate, and the addition amount of the heat stabilizer is 0.0003-0.030% of the mass of the polyester.
In another embodiment of the present utility model, the functional masterbatch of the present utility model may be optionally prepared by: adding terephthalic acid, ethylene glycol and germanium dioxide into a general polymerization reaction kettle, carrying out esterification reaction at 230-265 ℃ and 0.2-0.3 Mpa (gauge pressure), decompressing to normal pressure after esterification, adding triphenyl phosphate and other components except a polyester carrier in the functional master batch, stirring for 10 minutes at normal pressure, heating and decompressing to below 280 ℃ and the pressure is lower than 100Pa, carrying out reaction for 1-3 hours, and finally extruding, granulating and drying to obtain the functional master batch.
As mentioned above, in a preferred embodiment of the present utility model, the functional masterbatch of the present utility model may be optionally prepared by the following method: uniformly mixing the granular polyester carrier with diethyl phenylphosphonate, sodium dodecyl benzene sulfonate, tridecyl alcohol stearate and magnesium carbonate, and then carrying out melt extrusion and granulating by an extruder to obtain the functional master batch.
More specifically, the preparation steps of the functional master batch of the present utility model include: firstly, 100 to 150 parts by weight of polyester carrier is dried at 65 to 75 ℃ for 4 hours, 5 to 10 parts by weight of magnesium carbonate is ground to have the particle size of 0.3 to 0.5 mu m, and is dried at 65 to 75 ℃ for 4 hours, and 5 to 10 parts by weight of sodium dodecyl benzene sulfonate is dried at 65 to 75 ℃ for 4 hours. And adding the dried polyester carrier, magnesium carbonate, sodium dodecyl benzene sulfonate, 25-30 parts by weight of diethyl phenylphosphonate, 5-10 parts by weight of sodium dodecyl benzene sulfonate and 15-20 parts by weight of tridecyl alcohol stearate into a high-speed mixer for pre-dispersion mixing at the rotating speed of 1000-1500 rpm for 15-30 minutes to form a mixture. And then, carrying out melt extrusion on the mixture by a single screw extruder, wherein the temperature of a heating area of the extruder is 265-275 ℃, and then carrying out water cooling granulation. Finally, the functional master batch can be obtained.
As described above, the recyclable material of the present utility model is prepared by mixing 60 to 80wt% of the polyester recycled particles with 20 to 40wt% of the functional master batch, and thus the preparation method of the recyclable material comprises the steps of preparing the polyester recycled particles and the step of preparing the recyclable material by mixing with the functional master batch in addition to the step of preparing the functional master batch as described above.
For example, the polyester recovery particles of the present utility model are prepared by the steps of: and (3) taking transparent particles obtained after crushing, decoloring and cleaning the recovered PET bottle or the thermal shrinkage film label as polyester recovery particles. The PET beverage bottles are usually provided with labels, most of the PET beverage bottles are heat shrinkage film labels tightly combined with the bottle body, and the small part of the PET beverage bottles are adhered easily-torn type labels, so that the PET beverage bottles are very small in density and easy to sort and reject after being crushed. The recovered PET bottle needs to be removed from the bottle cap, and only the bottle body is utilized. The bottleneck part of most of the existing PET beverage bottles is usually made of an integrated molding process, and the bottleneck part is made of the same material as the bottle body. Some special fields, such as injection bottles in medical fields, have different materials for the mouth and body parts and may have germs, and need to be removed.
Thus, the preparation step of the polyester recycled particles of the present utility model further comprises: and crushing the recovered PET bottle or the thermal shrinkage film label, drying in the air while crushing, and removing impurities with low density and high density through winnowing after the air drying. Because liquid may remain in the beverage bottle, it is necessary to perform an air-drying operation while pulverizing the beverage bottle to avoid the difficulty in drying the particulate matter, and the dried material is easily subjected to an air separation operation.
The material after winnowing is decolorized by a solvent. For example, a decoloring solvent commonly used in the art may be selected for the decoloring treatment. In one embodiment, the decolorizing agent may be prepared from 20-30 wt% propylene glycol diacetate, 50-60 wt% dimethyl sulfoxide, and 10-30 wt% activated carbon. The materials and the decoloring agent are soaked for 10 to 24 hours according to the volume ratio of 1:2, and are continuously stirred at the speed of 20 to 30 revolutions per minute.
And discharging liquid after the decoloring treatment, injecting clear water, standing, and removing active carbon through floatation cleaning. The mass ratio of the materials to the clean water is preferably 1:3-1:5. The activated carbon adsorbed with the liquid has high density and is sunk into the water bottom, and the PET particles have low density and float on the upper layer, so the PET particles are easily fished out through floatation, and the activated carbon is removed. In addition, the high-density impurities which are not removed by the prior air separation can be further removed by flotation. The flotation process also has a cleaning effect and can be repeatedly operated for a plurality of times (the number of times of flotation can be selected according to the observed condition because the activated carbon is dark or not to be completely seen).
During flotation, as the materials are repeatedly cleaned, preferably sodium hydroxide with the total mass of 1.5-3% of the clean water and ethanolamine with the total mass of 0.5-1.0% of the clean water are added into the injected clean water, so that the materials are subjected to surface treatment, the attached solvent is removed as much as possible, and meanwhile, the surface properties of the materials are changed, so that the subsequent modification treatment is facilitated.
The material after flotation and cleaning is required to be dried, and polyester recovered particles with the particle size of 100-150 mu m are separated for standby. The water content of the polyester recovered particles prepared by detection is required to be lower than 0.1%.
Finally, the step of mixing the polyester recycling particles with the functional master batch to prepare the recyclable material comprises the following steps: uniformly mixing the prepared polyester recovered particles with the average particle size of 100-150 mu m with the prepared functional master batch according to a proportion, then inputting the mixture into a single screw extruder, removing impurities through melt filtration, extruding the mixture, carrying out water cooling granulation after the temperature of a heating area of the extruder is 265-275 ℃, and finally preparing the recoverable material.
Examples 1 to 3
The functional master batch 1-3 is prepared from the raw materials in parts by weight shown in the following table.
| Example 1 | Example 2 | Example 3 | |
| Polyester carrier | 100(PET) | 125(PETG) | 150(PET) |
| Phenylphosphonic acid diethyl ester | 25 | 28 | 30 |
| Sodium dodecyl benzene sulfonate | 5 | 7 | 10 |
| Tridecyl alcohol stearate | 15 | 18 | 20 |
| Magnesium carbonate | 5 | 8 | 10 |
Drying the polyester carrier in the embodiment at 65-75 ℃ for 4 hours, grinding magnesium carbonate to the grain size of 0.3-0.5 mu m, drying at 65-75 ℃ for 4 hours, drying sodium dodecyl benzene sulfonate at 65-75 ℃ for 4 hours, adding the dried polyester carrier, magnesium carbonate and sodium dodecyl benzene sulfonate and other components in the embodiment into a high-speed mixer for pre-dispersion mixing, wherein the rotating speed is 1000-1500 rpm, and mixing for 15-30 minutes to form a mixture; and then carrying out melt extrusion on the mixture by a single screw extruder, wherein the temperature of a heating area of the extruder is 265-275 ℃, and then carrying out water cooling granulation to finally prepare the functional master batch 1-3 respectively.
Examples 4 to 6
And uniformly mixing the prepared polyester recovery particles with the average particle size of 100-150 mu m with the functional master batches 1-3 respectively, inputting the mixture into an extruder, removing impurities through melt filtration, and then extruding and granulating to obtain the recoverable material.
And (3) carrying out melt coextrusion, die casting, transverse far infrared stretching, cooling shaping, rolling and slitting on the recyclable material, and stretching to obtain the heat-shrinkable film with the thickness of 50 mu m.
In example 4, polyester reclaimed particles were mixed with the functional master batch 1 in a weight ratio of 4:1 to prepare a heat shrinkable film 4. In example 5, polyester reclaimed particles were mixed with the functional master batch 2 in a weight ratio of 3:1 to prepare a heat shrinkable film 5. In example 6, polyester reclaimed particles were mixed with the functional master batch 3 in a weight ratio of 7:3 to prepare a heat shrinkable film 6. The prepared heat-shrinkable film 4-6 has no obvious peculiar smell after being stored for a week at room temperature in a sealing way.
The performance parameters of the heat-shrinkable films 4 to 6 were measured separately and are shown in the table.
According to the performance parameters, the recycled polyester particles can be directly used for preparing the heat-shrinkable film by adding the functional master batch disclosed by the utility model into the recycled polyester particles and performing melt modification treatment, the prepared heat-shrinkable film has excellent performance, the recycling rate required by environmental protection is met, excessive adjustment on the existing production process is not needed, the process is simple, and the quality of the original heat-shrinkable film can be basically maintained.
Comparative examples 1 to 3
For comparison, functional master batches 1-3 were prepared from the raw materials in the proportions by weight shown in the following table.
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Polyester carrier | 100(PET) | 125(PETG) | 150(PET) |
| Phenylphosphonic acid diethyl ester | 0 | 40 | 43 |
| Sodium dodecyl benzene sulfonate | 8 | 0 | 14 |
| Tridecyl alcohol stearate | 25 | 28 | 0 |
| Magnesium carbonate | 5 | 8 | 10 |
Comparative examples 4 to 7
Comparative heat-shrinkable films 4 to 6 having a thickness of 50 μm were prepared by the same procedure. In comparative example 4, polyester reclaimed particles were mixed with comparative functional master batch 1 in a weight ratio of 4:1 to prepare comparative heat-shrinkable film 4. In comparative example 5, polyester reclaimed particles were mixed with comparative functional master batch 2 at a weight ratio of 3:1 to prepare comparative heat-shrinkable film 5. In comparative example 6, polyester reclaimed particles were mixed with comparative functional masterbatch 3 in a weight ratio of 7:3 to prepare comparative heat-shrinkable film 6. Comparative heat-shrinkable film 7 was directly produced from polyester reclaimed particles without adding any functional masterbatch in comparative example 7. The prepared comparative heat-shrinkable film 4-7 is stored at room temperature for one week in a sealing manner, and obvious peculiar smell can be perceived.
The performance parameters of comparative heat-shrinkable films 4 to 7 are measured separately and are shown in the table.
Comparative examples 8 to 10
Comparative heat-shrinkable films 8 to 10 having a thickness of 50 μm were prepared by the same process. Wherein, only sodium hydroxide is added during the sorting and cleaning of the polyester recovered particles in comparative example 8, only ethanolamine is added during the sorting and cleaning of the polyester recovered particles in comparative example 9, and sodium hydroxide and ethanolamine are not added during the sorting and cleaning of the polyester recovered particles in comparative example 10. Similar to the foregoing examples 1 to 3, in comparative example 8, polyester reclaimed particles were mixed with the functional master batch 1 in a weight ratio of 4:1 to prepare a comparative heat-shrinkable film 8. In comparative example 9, polyester reclaimed particles were mixed with the functional master batch 2 in a weight ratio of 3:1 to prepare a comparative heat-shrinkable film 9. In comparative example 10, polyester reclaimed particles were mixed with the functional master batch 3 at a weight ratio of 7:3 to prepare a comparative heat-shrinkable film 10.
By comparison, the performance of the heat-shrinkable film can be properly improved by adding sodium hydroxide and ethanolamine in the cleaning process.
The system for preparing the recyclable material for heat shrinkable films according to the present utility model is described in further detail below with reference to the accompanying drawings.
As shown in fig. 1, the system for preparing a recyclable material for a heat shrinkable film of the present utility model includes a functional master batch preparing apparatus 100, a polyester recycling granule preparing apparatus 200, and a mixing preparing apparatus 300 for mixing the functional master batch prepared by the functional master batch preparing apparatus 100 and the polyester recycling granule prepared by the polyester recycling granule preparing apparatus 200 to prepare a recyclable material.
Wherein, as shown in fig. 2, the functional masterbatch preparation apparatus 100 includes a polyester carrier dryer 10, a magnesium carbonate dryer 20, a sodium dodecylbenzenesulfonate dryer 30, and a high-speed mixer 60; the high-speed mixer 60 is respectively connected with the ester carrier dryer 10, the magnesium carbonate dryer 20, the sodium dodecyl benzene sulfonate dryer 30, the diethyl phenylphosphonate conveying pipe 40 and the tridecyl alcohol stearate conveying pipe 50 through an input pipeline 61; the high-speed mixer 60 is connected with an extruder 70 through an output pipeline 62, and the output end of the extruder 70 is connected with a water-cooled granulator 71.
When the functional master batch preparation device 100 works, a polyester carrier is input into a polyester carrier dryer 10 to be dried at 65-75 ℃ for 4 hours, magnesium carbonate particles are input into a magnesium carbonate dryer 20 to be dried at 65-75 ℃ for 4 hours, sodium dodecyl benzene sulfonate is input into a sodium dodecyl benzene sulfonate dryer 30 to be dried at 65-75 ℃ for 4 hours, the dried polyester carrier, magnesium carbonate and sodium dodecyl benzene sulfonate are input into a high-speed mixer 60 through an input pipeline 61 of the high-speed mixer 60, and simultaneously diethyl phenylphosphonate and tridecyl alcohol stearate are also respectively input into the high-speed mixer 60 through a diethyl phenylphosphonate conveying pipeline 40 and a tridecyl alcohol stearate conveying pipeline 50 through an input pipeline 61. The high-speed mixer 60 pre-disperses and mixes the input raw materials at a rotation speed of 1000-1500 rpm for 15-30 minutes to form a mixture. The mixture is fed into an extruder 70 through an output pipeline 62 of the high-speed mixer 60, and is melt extruded through the extruder 70, wherein the temperature of a heating zone of the extruder is 265-275 ℃. The molten master batch extruded by the extruder 70 is finally fed into a water-cooled granulator 71, and a functional master batch is prepared by water-cooling granulation.
Further, the input end of the magnesium carbonate dryer 20 may be connected to a magnesium carbonate pulverizer 21 for pulverizing magnesium carbonate to a particle size of 0.3 to 0.5 μm for the next drying process.
In addition, the output end of the water-cooled granulator 71 can be further connected with a master batch dryer 72 for drying the master batch particles, so as to facilitate long-term storage of the master batch.
The polyester recycling particle preparation device 200 comprises a crusher 201, an air-drying winnowing machine 202, a decoloring cleaner 203 and a recycling particle dryer 204, wherein the crusher 201 is used for crushing recycled PET bottles or heat-shrinkable film labels, the output end of the crusher 201 is connected with the air-drying winnowing machine 202, the output end of the air-drying winnowing machine 202 is connected with the decoloring cleaner 203, and the output end of the decoloring cleaner 203 is connected with the recycling particle dryer 204.
When the polyester recycling particle preparation device 200 works, the crusher 201 firstly crushes the recycled PET bottles or the heat shrinkage film labels, then enters the air-drying winnowing machine 202 for air drying and winnowing, enters the decoloring and cleaning machine 203 for decoloring and cleaning operation after the winnowing, and finally enters the recycling particle dryer 204 for drying treatment.
The functional master batch prepared by the functional master batch preparation device 100 and the polyester reclaimed particles prepared by the polyester reclaimed particle preparation device 200 are finally input into the mixing preparation device 300 to prepare recyclable materials.
The mixing preparation device 300 comprises a mixing extruder 301, a reclaimed material water-cooled granulator 302 and a reclaimed material dryer 303. The input end of the mixing extruder 301 is respectively connected with the output ends of the functional master batch preparation device 100 and the polyester recycling granule preparation device 200, the output end of the mixing extruder 301 is connected with the recycling water-cooling granulator 302, and the output end of the recycling water-cooling granulator 302 is connected with the recycling dryer 303.
When the mixing preparation device 300 works, functional master batch and polyester recovery particles are respectively input into the mixing extruder 301 from the output ends of the functional master batch preparation device 100 and the polyester recovery particle preparation device 200, are mixed and melt extruded by the mixing extruder 301, then enter the water-cooled granulator 302 for water-cooling granulation, and finally are input into the recovery material dryer 303 for drying treatment for later storage and use.
In summary, the preparation system of the utility model can be used for preparing the recyclable material suitable for the recyclable heat shrinkable film, and the recyclable material can be singly mixed with other polyester raw materials to prepare the heat shrinkable film, and the prepared heat shrinkable film has excellent performance and can meet the environmental protection requirement.
The foregoing is illustrative of the present utility model and is not to be construed as limiting the scope of the utility model. Any equivalent alterations, modifications and combinations thereof will be effected by those skilled in the art without departing from the spirit and principles of this utility model, and it is intended to be within the scope of the utility model.
Claims (5)
1. The heat-shrinkable film recyclable material preparation system is characterized by comprising a functional master batch preparation device (100), a polyester recycling particle preparation device (200) and a mixing preparation device (300) for preparing recyclable materials by mixing the functional master batch prepared by the functional master batch preparation device (100) and polyester recycling particles prepared by the polyester recycling particle preparation device (200); wherein the functional master batch preparation device (100) comprises a polyester carrier dryer (10), a magnesium carbonate dryer (20), a sodium dodecyl benzene sulfonate dryer (30) and a high-speed mixer (60); the high-speed mixer (60) is respectively connected with an ester carrier dryer (10), a magnesium carbonate dryer (20), a sodium dodecyl benzene sulfonate dryer (30), a diethyl phenylphosphonate conveying pipe (40) and a tridecyl alcohol stearate conveying pipe (50) through an input pipeline (61); the high-speed mixer (60) is connected with the extruder (70) through the output pipeline (62), and the output end of the extruder (70) is connected with the water-cooled granulator (71).
2. The preparation system of claim 1, wherein the polyester recycling particle preparation device (200) comprises a crusher (201), an air drying winnowing machine (202), a decoloring cleaner (203) and a recycling particle dryer (204), wherein the crusher (201) is used for crushing recycled PET bottles or heat-shrinkable film labels, an output end of the crusher (201) is connected with the air drying winnowing machine (202), an output end of the air drying winnowing machine (202) is connected with the decoloring cleaner (203), and an output end of the decoloring cleaner (203) is connected with the recycling particle dryer (204).
3. The preparation system of claim 2, wherein the mixing preparation device (300) comprises a mixing extruder (301), a reclaimed material water-cooled granulator (302) and a reclaimed material dryer (303), wherein the input end of the mixing extruder (301) is respectively connected with the output ends of the functional master batch preparation device (100) and the polyester reclaimed particle preparation device (200), the output end of the mixing extruder (301) is connected with the reclaimed material water-cooled granulator (302), and the output end of the reclaimed material water-cooled granulator (302) is connected with the reclaimed material dryer (303).
4. A preparation system as claimed in claim 3, characterized in that the input of the magnesium carbonate dryer (20) is further connected with a magnesium carbonate pulverizer (21).
5. The preparation system according to claim 4, characterized in that the output end of the water-cooled granulator (71) is further connected with a masterbatch dryer (72).
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| CN202321505067.1U CN220008479U (en) | 2023-06-13 | 2023-06-13 | Preparation system for recyclable material of heat-shrinkable film |
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