CN117162618A - Recovered heat-shrinkable film and preparation method thereof - Google Patents
Recovered heat-shrinkable film and preparation method thereof Download PDFInfo
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- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 109
- 239000002245 particle Substances 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 71
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 61
- 239000010410 layer Substances 0.000 claims abstract description 59
- 238000002156 mixing Methods 0.000 claims abstract description 37
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004064 recycling Methods 0.000 claims abstract description 21
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 21
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 18
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 18
- 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
- 239000012792 core layer Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000002344 surface layer Substances 0.000 claims abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 42
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 16
- -1 polyethylene terephthalate Polymers 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 238000005188 flotation Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229920006300 shrink film Polymers 0.000 claims description 3
- 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 claims description 2
- 229940116423 propylene glycol diacetate Drugs 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000012760 heat stabilizer Substances 0.000 description 8
- 235000013361 beverage Nutrition 0.000 description 7
- 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 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013618 particulate matter Substances 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
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The recovered heat-shrinkable film consists of an extruded layer A surface layer, an extruded layer B core layer and an extruded layer C bottom layer, wherein the layer A and the extruded layer C are respectively arranged on two sides of the layer B and are made of polyester for common films, and the layer B is made of recovered materials with the weight of 5-95% of the total mass of the core layer and polyester for common films; the recycled material is prepared by mixing 60-80 wt% of polyester recycled particles and 20-40 wt% of functional master batch, the polyester recycled particles are prepared by recycling PET bottles or heat shrinkage film labels, and the functional master batch consists of a polyester carrier, diethyl phenylphosphonate, sodium dodecyl benzene sulfonate, tridecyl alcohol stearate and magnesium carbonate. According to the application, the functional master batch is added into the polyester recovered particles for melting modification treatment, so that the prepared recovered material can be directly used for preparing the heat-shrinkable film, and the prepared heat-shrinkable film has excellent performance, can meet the environmental protection requirement and has the quality equivalent to that of a common heat-shrinkable film.
Description
Technical Field
The application relates to the field of plastic product recovery, in particular to the technical field of preparing a heat-shrinkable film by utilizing waste plastic products, and particularly relates to a recovered heat-shrinkable film and a preparation method thereof.
Background
The plastic recycling is a technology for recycling waste plastic products. Because the waste plastics have different sources, the components of different plastic products are greatly different, and the problems of aging and color change exist, the plastic products which are usually lower-grade and are prepared by reclaimed materials have limited application in the consumption field with high quality requirements.
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 heat-shrinkable film prepared from the recycled waste plastics has defects such as transparency which can be identified by naked eyes, and can only be used as a low-grade packaging material in the industrial field.
For example, CN 100493903C discloses a heat-shrinkable polyester film having a multilayer structure, wherein one layer uses a PET bottle recycling material and the other layer does not contain the recycling material. In the prior art, it is considered that the cyclic raw materials of PET bottles are arbitrarily mixed raw materials of various PET having different melt viscosity, molecular weight distribution, monomer composition, crystallinity, presence or absence of additives such as polymerization catalyst, and the like, and the physical properties thereof vary greatly from one cyclic raw material to another. The heat-shrinkable film cannot be produced directly from such a recycled material, and a stable and uniform product cannot be obtained, and in addition, a film using 45 mass% or more of the recycled material cannot be provided with sufficient mechanical strength or heat shrinkability. Therefore, this prior art adopts a heat-shrinkable film of a multilayer structure, and provides desired mechanical strength and heat-shrinkability with a layer containing no recycled raw material, so as to avoid the defect of insufficient performance of the recycled raw material.
Similarly, CN 101155689B discloses a heat-shrinkable polyester film having good printability even in the case of recycling materials such as polyethylene terephthalate bottles. In the conventional art, a heat-shrinkable polyester film having a printed surface which is a layer containing no polyethylene terephthalate bottle recycling material, or a heat-shrinkable polyester film having a base layer containing 45 to 80wt% of polyethylene terephthalate bottle recycling material and a top layer containing an amorphous material as a main component is laminated on at least one side of a base layer containing polyethylene terephthalate bottle recycling material, wherein the heat shrinkage in the main shrinkage direction after immersing in warm water at 80 ℃ for 10 seconds is 30% or more and the heat shrinkage in the direction perpendicular to the main shrinkage direction is 10% or less. In addition, in this prior art, it is considered that the polyethylene terephthalate bottle recycled material has various polyethylene terephthalate bottle-constituting materials having different melt viscosities, molecular weights, molecular weight distributions, monomer compositions, crystallinity, types of polymerization catalysts, addition to the problem of mixing of impurities such as foreign materials and sand, and the like, and therefore these physical properties vary widely for each production lot of recycled material. Therefore, the film containing 40wt% or more of such a recycling material has a large quality deviation, and the heat shrinkage rate and mechanical strength required for the heat shrinkable label cannot be obtained.
The recycled plastic is used in the prior art, and recycled materials and conventional raw materials are subjected to layering treatment to cover the defects of a recycled material layer, but if the recycled material layer has the problems of color change, turbidity, peculiar smell and the like, the recycled material layer cannot be thoroughly removed, and further improvement is still needed.
Disclosure of Invention
The technical problem to be solved by the present application is to provide a recycled heat shrink film and a preparation method thereof, so as to reduce or avoid the aforementioned problems.
In order to solve the technical problems, the application provides a recovery heat-shrinkable film, which consists of an extruded A layer surface layer, a B layer core layer and a C layer bottom layer, wherein the A layer and the C layer are respectively arranged on two sides of the B layer and are made of polyester for common films, and the B layer is made of recovery materials with the total mass of the core layer being 5-95 wt% and polyester for common films; the recycled material is prepared by mixing 60-80 wt% of polyester recycled particles and 20-40 wt% of functional master batch, wherein the polyester recycled 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.
Preferably, the functional master batch comprises the following components in percentage by weight: 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.
Preferably, the polyester carrier is polyethylene terephthalate and its copolymers.
Preferably, the particle diameter of the polyester recovery particles is 50 to 200 μm.
The application also provides a preparation method of the recovered heat-shrinkable film, which comprises the following steps: metering a polyester slice for a common film by an electronic scale, mixing in a mixing bin, and then respectively putting the polyester slice into a first double-screw extruder and a third double-screw extruder; simultaneously, the recycled materials accounting for 5 to 95 weight percent of the total mass of the polyester chips and the core layer for the common film are respectively metered by an electronic scale, enter a mixing bin for mixing, and then enter a second single-screw extruder; then, the temperature of the first twin-screw extruder and the third twin-screw extruder is regulated to 270-280 ℃, and the temperature of the second single-screw extruder is regulated to 265-280 ℃; after melting, filtering, taking the materials extruded by the first and third double-screw extruders as a layer A and a layer C, taking the material extruded by the second single-screw extruder as a layer B, and preparing a three-layer composite thick sheet through a multi-layer coextrusion process; after preparing a thick sheet, preheating the thick sheet at 50-90 ℃, entering an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min to obtain a stretched sheet, wherein the longitudinal stretching multiplying power is 3.0-4.5; then preheating the stretching sheet at the temperature of 90-120 ℃, and transversely stretching at the temperature of 100-160 ℃ with the transverse stretching multiplying power of 3.0-4.5; and then shaping at 165-250 ℃, cooling at 100-50 ℃, shaping, cooling and rolling to obtain the heat-shrinkable film.
Preferably, the preparation of the reclaimed materials respectively comprises a preparation step of a functional master batch, a preparation step of polyester reclaimed particles and a preparation step of mixing the polyester reclaimed particles with the functional master batch to prepare the reclaimed materials, wherein the preparation step of the functional master batch comprises the following steps: firstly, 100 to 150 weight parts of polyester carrier is dried for 4 hours at 65 to 75 ℃,5 to 10 weight parts of magnesium carbonate is ground to the grain size of 0.3 to 0.5 mu m, and is dried for 4 hours at 65 to 75 ℃, and 5 to 10 weight parts of sodium dodecyl benzene sulfonate is dried for 4 hours at 65 to 75 ℃; then 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, 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 obtain the functional master batch.
Preferably, the preparation step of the polyester recycled particles comprises: 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.
Preferably, the preparation method further comprises the steps of: 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 by winnowing after the air drying; the material after air separation is decolorized by a solvent.
Preferably, the preparation method further comprises the steps of: discharging liquid after the decoloring treatment, injecting clear water, standing, and removing active carbon through floatation cleaning; drying the material after flotation and cleaning, and separating out polyester recovered particles with the particle size of 100-150 mu m for standby.
Preferably, the injected clear water is added with sodium hydroxide accounting for 1.5 to 3 percent of the total mass of the clear water and ethanolamine accounting for 0.5 to 1.0 percent of the total mass of the clear water.
Preferably, the step of preparing the reclaimed materials by mixing the polyester reclaimed particles with the functional master batch 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 recovered material.
According to the application, the functional master batch is added into the polyester recovered particles for melting modification treatment, so that the prepared recovered material can be directly used for preparing the heat-shrinkable film, and the prepared heat-shrinkable film has excellent performance, can meet the environmental protection requirement and has the quality equivalent to that of a common heat-shrinkable film.
Drawings
The following drawings are only for purposes of illustration and explanation of the present application and are not intended to limit the scope of the application.
Fig. 1 shows a schematic cross-sectional structure of a recovered heat-shrinkable film according to an embodiment of the present application.
Detailed Description
For a clearer understanding of technical features, objects, and effects of the present application, a specific embodiment of the present application will be described with reference to the accompanying drawings. Wherein like parts are designated by like reference numerals.
As shown in the drawing, which shows a schematic cross-sectional structure of a recycled heat-shrinkable film according to an embodiment of the present application, the heat-shrinkable film shown in the drawing is composed of an extruded a-layer surface layer, a B-layer core layer, and a C-layer bottom layer, the a-layer and the C-layer being respectively disposed on both sides of the B-layer and each being made of a polyester for a general film, and the B-layer being made of recycled material having 5 to 95wt% of the total mass of the core layer and the polyester for a general film.
Specifically, the reclaimed material is prepared from melt-modified polyester reclaimed particles, wherein the polyester reclaimed particles can be transparent particles obtained by crushing, decoloring and cleaning reclaimed PET bottles or heat-shrinkable film labels. According to the application, the polyester reclaimed particles are subjected to melting modification treatment in a mode of adding the functional master batch into the polyester reclaimed particles, so that reclaimed materials are prepared. The recovery of a proportion, for example 5% to 95% by weight of the total mass, is added to the polyester for film, which can be used to produce the core layer of the heat-shrinkable film with recovery.
In a specific embodiment, the recycling material 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 regrind of the present application may 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 the recovered material.
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 application. 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 masterbatch of the application is preferably polyethylene terephthalate (PET), polybutylene terephthalate, polypropylene terephthalate, 1, 4-cyclohexanedimethanol terephthalate (PCT), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Polyethylene terephthalate (PET) and its copolymers are particularly preferred.
The preparation method of the polyester carrier takes PET as an example. The preferred preparation method comprises the following steps: firstly, the dihydroxyethyl terephthalate is prepared by esterification or transesterification of terephthalic acid or dimethyl terephthalate and ethylene glycol. Then, a polycondensation reaction is carried out under high temperature and vacuum conditions by using a catalyst, and the dihydroxyethyl terephthalate is polycondensed into polyethylene terephthalate (PET). In a specific 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 application, the polyester carrier of the present application can be prepared by the following method: adding 5.0kg of terephthalic acid, 2.2kg of ethylene glycol and 1.10g of germanium dioxide into a 20L general polymerization reaction kettle, carrying out esterification reaction under the conditions of 230-265 ℃ and 0.2-0.3 Mpa (gauge pressure), decompressing to normal pressure when the water yield reaches 1200ml, adding 1.025g of triphenyl phosphate, stirring for 10 minutes at normal pressure, heating and decompressing to below 280 ℃ and the pressure below 100Pa, and carrying out extrusion, granulating and drying after the reaction for 1-3 hours to finally obtain the polyester carrier.
In one embodiment of the application, the functional masterbatch of the application 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 application 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 application, the functional masterbatch of the present application 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 application, the functional masterbatch of the present application 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 application 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 reclaimed material of the present application is produced by mixing 60 to 80wt% of the polyester reclaimed particles with 20 to 40wt% of the functional master batch, and thus the reclaimed material production method comprises the step of producing the polyester reclaimed particles and the step of producing the reclaimed material by mixing with the functional master batch in addition to the step of producing the functional master batch described above.
For example, the polyester recovery particles of the present application 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 application 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 preparing the reclaimed materials by mixing the polyester reclaimed particles and the functional master batch 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 recovered 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 recovery material.
And directly putting the prepared reclaimed materials into a double-screw extruder, adjusting the temperature of the double-screw extruder to 270-280 ℃, melting, filtering, and extruding thick sheets. After the thick sheet is prepared, preheating the thick sheet at 50-90 ℃, entering an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min, wherein the longitudinal stretching multiplying power is 3.0-4.5, thus obtaining the stretched sheet. Then preheating the stretch sheet at 90-120 ℃, and transversely stretching at 100-160 ℃ with a transverse stretching multiplying power of 3.0-4.5. And then shaping at 165-250 ℃, cooling at 100-50 ℃, shaping, cooling and rolling 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 are added with the functional master batch, and the recycled material obtained after the melting modification treatment can be directly used for preparing the heat-shrinkable film, so that the prepared heat-shrinkable film not only meets the environmental protection requirement, but also basically maintains the quality of the original heat-shrinkable film.
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 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 example 7 comparative heat-shrinkable film 7 having a thickness of 50 μm was directly produced from polyester reclaimed particles without adding any functional masterbatch. 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 procedure. 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 method for producing the three-layer heat shrinkable film of the present application is further described below with reference to the accompanying drawings. Specifically, the preparation method of the heat-shrinkable film comprises the following steps.
Firstly, polyester slices for common films are metered by an electronic scale and enter a mixing bin for mixing, and then are respectively put into a first double-screw extruder and a third double-screw extruder.
Simultaneously, the recycled materials accounting for 5-95 wt% of the total mass of the polyester chips and the core layer for the common film are respectively metered by an electronic scale, enter a mixing bin for mixing, and then enter a second single-screw extruder.
Then, the temperature of the first twin-screw extruder and the third twin-screw extruder is regulated to 270-280 ℃, and the temperature of the second single-screw extruder is regulated to 265-280 ℃; after melting, filtering, taking the materials extruded by the first and third double-screw extruders as a layer A and a layer C, taking the material extruded by the second single-screw extruder as a layer B, and preparing the three-layer composite thick sheet through a multilayer coextrusion process.
After the thick sheet is prepared, preheating the thick sheet at 50-90 ℃, entering an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min, wherein the longitudinal stretching multiplying power is 3.0-4.5, thus obtaining the stretched sheet. Then preheating the stretch sheet at 90-120 ℃, and transversely stretching at 100-160 ℃ with a transverse stretching multiplying power of 3.0-4.5. And then shaping at 165-250 ℃, cooling at 100-50 ℃, shaping, cooling and rolling to obtain the heat-shrinkable film.
Examples 11 to 13
The heat-shrinkable film of three-layer structure was produced by the above method, and the respective performance parameters are shown in the following table.
It should be understood by those skilled in the art that while the present application has been described in terms of several embodiments, not every embodiment contains only one independent technical solution. The description is given for clearness of understanding only, and those skilled in the art will understand the description as a whole and will recognize that the technical solutions described in the various embodiments may be combined with one another to understand the scope of the present application.
The foregoing is illustrative of the present application and is not to be construed as limiting the scope of the application. 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 application, and it is intended to be within the scope of the application.
Claims (10)
1. A recycling heat shrinkage film is formed by an extruded layer A surface layer, an extruded layer B core layer and an extruded layer C bottom layer, wherein the layer A and the extruded layer C are respectively arranged on two sides of the layer B and are made of polyester for common films, and the layer B is made of recycled materials with the weight of 5-95% of the total mass of the core layer and polyester for common films; the polyester recycling material is characterized in that the recycling material is prepared by mixing 60-80 wt% of polyester recycling particles and 20-40 wt% of functional master batch, the polyester recycling particles are prepared by recycling PET bottles or heat shrinkage film labels, and the functional master batch is composed of a polyester carrier, diethyl phenylphosphonate, sodium dodecyl benzene sulfonate, tridecyl alcohol stearate and magnesium carbonate.
2. The recycled heat shrink film of claim 1, wherein the functional masterbatch comprises the following components: 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.
3. The recycled heat shrink film of claim 1, wherein the polyester carrier is polyethylene terephthalate and copolymers thereof.
4. The recovered heat-shrinkable film of claim 1, wherein the polyester recovery particles have a particle diameter of 50 to 200 μm.
5. A method of producing the recovered heat shrinkable film of any one of claims 1 to 4, comprising the steps of: metering a polyester slice for a common film by an electronic scale, mixing in a mixing bin, and then respectively putting the polyester slice into a first double-screw extruder and a third double-screw extruder;
simultaneously, the recycled materials accounting for 5 to 95 weight percent of the total mass of the polyester chips and the core layer for the common film are respectively metered by an electronic scale, enter a mixing bin for mixing, and then enter a second single-screw extruder;
then, the temperature of the first twin-screw extruder and the third twin-screw extruder is regulated to 270-280 ℃, and the temperature of the second single-screw extruder is regulated to 265-280 ℃; after melting, filtering, taking the materials extruded by the first and third double-screw extruders as a layer A and a layer C, taking the material extruded by the second single-screw extruder as a layer B, and preparing a three-layer composite thick sheet through a multi-layer coextrusion process;
after preparing a thick sheet, preheating the thick sheet at 50-90 ℃, entering an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min to obtain a stretched sheet, wherein the longitudinal stretching multiplying power is 3.0-4.5; then preheating the stretching sheet at the temperature of 90-120 ℃, and transversely stretching at the temperature of 100-160 ℃ with the transverse stretching multiplying power of 3.0-4.5; and then shaping at 165-250 ℃, cooling at 100-50 ℃, shaping, cooling and rolling to obtain the heat-shrinkable film.
6. The method of producing a functional masterbatch according to claim 5, wherein the production of the reclaimed material includes a functional masterbatch production step, a polyester reclaimed particle production step, and a polyester reclaimed particle and functional masterbatch mixing production step, respectively, wherein the functional masterbatch production step includes: firstly, 100 to 150 weight parts of polyester carrier is dried for 4 hours at 65 to 75 ℃,5 to 10 weight parts of magnesium carbonate is ground to the grain size of 0.3 to 0.5 mu m, and is dried for 4 hours at 65 to 75 ℃, and 5 to 10 weight parts of sodium dodecyl benzene sulfonate is dried for 4 hours at 65 to 75 ℃; then 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, 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 obtain the functional master batch.
7. The method of producing according to claim 6, wherein the step of producing the polyester reclaimed particles comprises: 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.
8. The method of manufacturing according to claim 7, further comprising the steps of: 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 by winnowing after the air drying; decolorizing the winnowing material with solvent; the decoloring treatment comprises the following steps: mixing 20-30wt% of propylene glycol diacetate, 50-60wt% of dimethyl sulfoxide and 10-30wt% of activated carbon to obtain a decoloring agent; 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.
9. The method of preparation of claim 8, further comprising the steps of: discharging liquid after the decoloring treatment, injecting clear water, standing, and removing active carbon through floatation cleaning; drying the material after flotation and cleaning, and separating out polyester recovered particles with the particle size of 100-150 mu m for standby.
10. The method of any one of claims 6 to 9, wherein the step of mixing the polyester recycled particles with the functional masterbatch to produce a recycle comprises: 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 recovered material.
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| CN202310698596.6A CN117162618A (en) | 2023-06-13 | 2023-06-13 | Recovered heat-shrinkable film and preparation method thereof |
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| CN202310698596.6A CN117162618A (en) | 2023-06-13 | 2023-06-13 | Recovered heat-shrinkable film and preparation method thereof |
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