CN116396561B - Low-gloss polypropylene composition and preparation method and application thereof - Google Patents
Low-gloss polypropylene composition and preparation method and application thereof Download PDFInfo
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- CN116396561B CN116396561B CN202310355851.7A CN202310355851A CN116396561B CN 116396561 B CN116396561 B CN 116396561B CN 202310355851 A CN202310355851 A CN 202310355851A CN 116396561 B CN116396561 B CN 116396561B
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- -1 polypropylene Polymers 0.000 title claims abstract description 86
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 78
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000012360 testing method Methods 0.000 claims abstract description 22
- 239000000155 melt Substances 0.000 claims abstract description 21
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012745 toughening agent Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 16
- 239000002861 polymer material Substances 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229920001955 polyphenylene ether Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-gloss polypropylene composition, and a preparation method and application thereof. The low-gloss polypropylene composition comprises the following components in parts by weight: 40-90 parts of polypropylene and 0.5-10 parts of polyphenyl ether; the mass flow rate of the melt of the polyphenyl ether under the test condition of 5kg at 280 ℃ is 8-20 g/10min; the melt mass flow rate of the polypropylene under the test condition of 2.16kg at 230 ℃ is 0.5-55 g/10min. The low-gloss polypropylene composition prepared by the invention can realize lower glossiness, and has good appearance, mechanical property, ageing resistance and higher heat distortion temperature.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-gloss polypropylene composition, and a preparation method and application thereof.
Background
The polypropylene (PP) has excellent processability, low density, excellent chemical stability and electrical property, good heat resistance and mechanical property, and is one of the most used general plastics. Meanwhile, polypropylene has low price and is easy to recycle, so that the polypropylene has wide application in the fields of electronic appliances, automobile industry and the like. The surface of the polypropylene material has certain glossiness, and if the polypropylene material is applied to a scene with low glossiness requirement, a certain treatment method is needed to reduce the surface glossiness of the polypropylene material. There are a number of patents disclosing methods for reducing the surface gloss and CN101173075A disclosing the addition of 0.5-5 parts of silica to polypropylene composites to reduce the gloss of the polypropylene composites. Patent CN101121799a reduces gloss by adding polyethylene, peroxide crosslinking agent to crosslink polyethylene molecules, dispersing in polypropylene to form rough surface. CN102108175A discloses a low-gloss high-rigidity and toughness polypropylene composite material and a preparation method thereof, when nano montmorillonite and PP-g-MAH are added, the glossiness of the PP composite material is continuously reduced along with the increase of the content of the nano montmorillonite and PP-g-MAH. CN109251407a discloses a method of adding two matting agents, crosslinked polyethylene powder and maleic anhydride graft, to reduce the surface gloss of polypropylene composites. In general, the gloss reduction efficiency is not high by adding inorganic powder, and the gloss reduction is not obvious by adding low amount of inorganic powder; the high addition amount can have adverse effects on the system performance.
Disclosure of Invention
The invention aims to provide a low-gloss polypropylene composition, and a preparation method and application thereof. The low-gloss polypropylene composition can realize lower glossiness, and has excellent appearance effect, good mechanical property, ageing resistance and higher heat distortion temperature.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the low-gloss polypropylene composition comprises the following components in parts by weight: 40-90 parts of polypropylene and 0.5-10 parts of polyphenyl ether;
The mass flow rate of the melt of the polyphenyl ether under the test condition of 5kg at 280 ℃ is 8-20 g/10min;
The melt mass flow rate of the polypropylene under the test condition of 2.16kg at 230 ℃ is 0.5-55g/10min. The melt mass flow rate is according to GB/T3682: the 2000 standard was tested.
Preferably, the low gloss polypropylene composition comprises the following components in parts by weight: 58-76 parts of polypropylene and 5-8 parts of polyphenyl ether.
Preferably, the polypropylene accounts for 45-94% of the total weight of the low-gloss polypropylene composition, and the polyphenylene ether accounts for 6-13% of the total weight of the low-gloss polypropylene composition.
Preferably, the polyphenylene ether includes poly (2, 6-dimethyl-1, 4-phenylene) ether, poly (2, 6-diethyl-1, 4-phenylene) ether, poly (2, 6-dipropyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, and the like.
More preferably, the polyphenylene ether is poly (2, 6-dimethyl-1, 4-phenylene) ether.
Preferably, the polypropylene is at least one of homo-polypropylene and co-polypropylene.
Preferably, the polypropylene has a density of 0.894 to 0.914g/cm 3.
Preferably, the polypropylene has a melt mass flow rate of 2 to 30g/10min at 230℃under 2.16kg test conditions.
The melt mass flow rate of the polypropylene in the invention can obviously influence the appearance of the final product, when the melt mass flow rate of the polypropylene is lower, the appearance of the product can be effectively improved, and when the melt mass flow rate of the polypropylene is higher, the polypropylene and the polyphenyl ether are mixed and incompatible, although the surface gloss of the PP is reduced, defects such as pitting, dragging and the like are generated on the surface, so that the appearance is poor. Therefore, a proper PPE/PP viscosity ratio is required to disperse the PPE well, thereby achieving the effect of reducing gloss without affecting its appearance.
In addition, the inventor also unexpectedly found that the thermal oxidative aging performance of the system can be remarkably improved by introducing a small amount of PPE resin into the PP resin system. In general, the introduction of incompatible resins into the resin system forms new interfaces, creating weak points, but the introduction of PPE does not create the above-mentioned drawbacks, but rather improves the thermo-oxidative ageing properties.
Preferably, the low gloss polypropylene composition further comprises the following components in parts by weight: 0 to 12 parts of polyethylene, 0 to 30 parts of toughening agent, 0 to 40 parts of filler and 0.2 to 1 part of processing aid.
More preferably, the low gloss polypropylene composition further comprises the following components in parts by weight: 1 to 9 parts of polyethylene, 5 to 15 parts of toughening agent, 10 to 30 parts of filler and 0.2 to 1 part of processing aid.
Preferably, the polyethylene is a high density polyethylene having a melt mass flow rate of 0.1 to 30g/10min at 190 ℃ under 2.16kg test conditions.
Preferably, the toughening agent comprises at least one of an ethylene-alpha olefin copolymer, a hydrogenated styrene-butadiene block copolymer, and an ethylene propylene diene monomer; the mass flow rate of the melt of the toughening agent under the test condition of 2.16kg at 190 ℃ is 0.1-30 g/10min.
Preferably, the filler comprises at least one of talc, whiskers, calcium carbonate, barium sulfate, wollastonite.
Preferably, the processing aid comprises at least one of a hindered amine antioxidant, a phosphite/phosphonite antioxidant, a thioether stabilizer, an ultraviolet absorber.
A method for preparing the low gloss polypropylene composition comprising the steps of:
weighing the components according to the weight ratio, mixing to obtain a premix, and then carrying out melt extrusion and granulation on the premix to obtain the low-gloss polypropylene composition.
Preferably, the rotation speed of the mixing is 1000-2000 rpm, and the mixing time is 1-3 minutes.
Preferably, the temperature of the melt extrusion is 190-230 ℃.
The application of the low-gloss polypropylene composition in automotive upholstery and home appliance shells. The automotive interior spare and household electrical appliances shell include instrument board, vice instrument board, stand, glove box, door plant, threshold, car light support etc..
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, a small amount of polyphenyl ether is added into a polypropylene system, so that the prepared polypropylene composition has excellent appearance effect and thermal oxidation aging resistance, and meanwhile, the surface glossiness of the material can be greatly reduced, but when the melt mass flow rate of the polyphenyl ether is too low, the glossiness reduction effect is poor. Meanwhile, the addition of a small amount of polyphenyl ether in the invention does not bring adverse effects to the mechanical property and the processing property of the system, and the heat distortion temperature and the ageing resistance of the system can be improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the processing aid and filler were commercially available and the same was used in parallel experiments.
The raw materials used in the examples and comparative examples are described in Table 1.
TABLE 1
Examples 1 to 10 and comparative examples 1 to 6
The low gloss polypropylene compositions of examples 1 to 10 and comparative examples 1 to 6 were as shown in tables 2 to 3 in terms of components and parts by weight.
The preparation method of the low gloss polypropylene compositions of examples 1 to 10 and comparative examples 1 to 6 comprises the steps of:
Weighing the components according to the weight ratio, mixing for 2 minutes at 1500 revolutions per minute to obtain a premix, melting the premix, extruding the premix by a double-screw extruder, and carrying out vacuum granulation at the temperature of each area of a screw at 200 ℃ to obtain the low-gloss polypropylene composition.
Table 2 the amounts (parts by weight) of the components in the examples
Table 3 amounts of the components (parts by weight) in the comparative examples
Performance testing
The low gloss polypropylene compositions prepared in examples 1 to 10 and comparative examples 1 to 6 were subjected to the relevant performance test, the test methods and standards are as follows, and the experimental results are shown in Table 4.
Tensile strength: testing was performed according to ISO 527:1993 standard;
flexural modulus: testing was performed according to ISO 178:2001 standard;
impact strength: testing according to ISO 180:2000 standard, wherein the notch type is IZOD A type notch;
melt flow rate: testing is carried out according to ISO 1133:2011 standard, wherein the testing condition is that the testing temperature is 230 ℃ and the testing load is 2.16 kg;
Surface gloss: according to ASTM D523:2014, testing the surface glossiness of a material, wherein a sample plate is a square plate with 100mm x 2mm, and the incident angle of light is 60 degrees;
HDT: according to GB1634:2004 standard, pressure: 0.45MPa; horizontally placing the sample strip;
Ageing resistance test: the heat aging test box is selected according to GB/T7141-2008 method B, the temperature of the oven is set to be 150 ℃, and the ventilation amount of the oven is controlled to be 5-20 times/h.
TABLE 4 Performance test experiment results
From the data in Table 4, it can be seen that the low gloss polypropylene composition prepared in the examples of the present invention can achieve good appearance, good mechanical properties, and aging resistance. Wherein the tensile strength can be kept between 24 and 34.2MPa, the flexural modulus can be realized between 1400 and 2133MPa, and simultaneously, the low glossiness, the high heat distortion temperature and the good aging performance can be kept, wherein the glossiness can be kept between 10.7 and 25.7, the heat distortion temperature can be realized between 98.1 and 117.9 ℃, and the aging time at 150 ℃ can be realized between 29 and 55 days. The reason that the aging time of example 5 can reach 55 days may be that the talc component is not added in example 5, and the addition of talc greatly reduces the aging time of the polypropylene composition. In the limited melt mass flow rate range, the aging resistance of the composition is not greatly influenced by the change of the melt mass flow rate of the polypropylene, and the aging resistance is mainly influenced by the added polyphenyl ether.
The polypropylene composition prepared in comparative example 1 was unable to achieve lower gloss due to too little weight part of polyphenylene ether added to the polypropylene system; the polypropylene composition obtained by adding too much polyphenylene ether in comparative example 2 has a low flexural modulus and has a pitting appearance; the polypropylene composition prepared without polyphenylene ether in comparative example 3 had higher gloss and had inferior aging resistance to the examples; the melt mass flow rate of the polyphenylene ether added in comparative examples 4 to 5 is not in the protective range, and the prepared polypropylene composition has higher glossiness and poorer ageing resistance than the examples; the polypropylene added in comparative example 6 had a melt mass flow rate too high, and the resulting polypropylene composition had problems of pitting and dragging in appearance.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The low-gloss polypropylene composition is characterized by comprising the following components in parts by weight: 40-90 parts of polypropylene, 0.5-10 parts of polyphenyl ether, 1-9 parts of polyethylene, 5-15 parts of a toughening agent, 10-30 parts of a filler and 0.2-1 part of a processing aid;
The mass flow rate of the melt of the polyphenyl ether under the test condition of 5kg at 280 ℃ is 8-20 g/10min;
The mass flow rate of the melt of the polypropylene under the test condition of 2.16kg at 230 ℃ is 0.5-55 g/10min.
2. The low gloss polypropylene composition of claim 1, comprising the following components in parts by weight: 58-76 parts of polypropylene and 5-8 parts of polyphenyl ether.
3. The low gloss polypropylene composition according to claim 1, comprising at least one of the following (1) to (3):
(1) The polypropylene is at least one of homo-polypropylene and co-polypropylene;
(2) The density of the polypropylene is 0.894-0.914 g/cm 3;
(3) The mass flow rate of the melt of the polypropylene under the test condition of 2.16kg at 230 ℃ is 2-30 g/10min.
4. The low gloss polypropylene composition according to claim 1, wherein the polyethylene is a high density polyethylene having a melt mass flow rate of from 0.1 to 30g/10min at 190 ℃ under 2.16kg test conditions.
5. The low gloss polypropylene composition according to claim 1, comprising at least one of the following (1) to (3):
(1) The toughening agent comprises at least one of ethylene-alpha olefin copolymer, hydrogenated styrene-butadiene block copolymer and ethylene propylene diene monomer;
(2) The filler comprises at least one of talcum powder, whisker, calcium carbonate, barium sulfate and wollastonite;
(3) The processing aid comprises at least one of hindered amine antioxidant, phosphite/phosphonite antioxidant, thioether stabilizer and ultraviolet absorbent.
6. A method for preparing the low gloss polypropylene composition according to any one of claims 1 to 5, comprising the steps of:
weighing the components according to the weight ratio, mixing to obtain a premix, and then carrying out melt extrusion and granulation on the premix to obtain the low-gloss polypropylene composition.
7. The preparation method according to claim 6, comprising at least one of the following (1) - (2):
(1) The rotating speed of the mixing is 1000-2000 rpm, and the mixing time is 1-3 minutes;
(2) The temperature of the melt extrusion is 190-230 ℃.
8. Use of the low gloss polypropylene composition according to any one of claims 1 to 5 in automotive upholstery and home appliance housings.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333490A (en) * | 2013-06-13 | 2013-10-02 | 江苏安格特科技发展有限公司 | Low gloss, high impact and high temperature resistance nylon alloy material and preparation method thereof |
| CN111286186A (en) * | 2020-02-29 | 2020-06-16 | 深圳远致富海智能产业有限公司 | Oil-resistant composition with good appearance and capable of being applied to electric appliance shell |
| CN113999460A (en) * | 2021-12-08 | 2022-02-01 | 青岛国恩科技股份有限公司 | Thermo-oxidative aging resistant and weather resistant PP material for household appliances and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333490A (en) * | 2013-06-13 | 2013-10-02 | 江苏安格特科技发展有限公司 | Low gloss, high impact and high temperature resistance nylon alloy material and preparation method thereof |
| CN111286186A (en) * | 2020-02-29 | 2020-06-16 | 深圳远致富海智能产业有限公司 | Oil-resistant composition with good appearance and capable of being applied to electric appliance shell |
| CN113999460A (en) * | 2021-12-08 | 2022-02-01 | 青岛国恩科技股份有限公司 | Thermo-oxidative aging resistant and weather resistant PP material for household appliances and preparation method thereof |
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