CN101544806B - Solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates and preparation method and application thereof - Google Patents
Solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates and preparation method and application thereof Download PDFInfo
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- CN101544806B CN101544806B CN2008101027595A CN200810102759A CN101544806B CN 101544806 B CN101544806 B CN 101544806B CN 2008101027595 A CN2008101027595 A CN 2008101027595A CN 200810102759 A CN200810102759 A CN 200810102759A CN 101544806 B CN101544806 B CN 101544806B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention provides a solvent-resistance polystyrene ternary alloy material used for refrigerator inner liner plates. The solvent-resistance polystyrene ternary alloy material comprises 20 to 65 percent of high-impact polystyrene, 15 to 60 percent of linear low-density polyethylene, 5 to 25 percent of ethane-butadiene-styrol copolymer compatilizer, 0.1 to 0.6 percent of antioxidant and 0.1 to 0.6 percent of calcium stearate. The invention also provides a preparation method and an application of the alloy material. The polyethylene has excellent solvent-resistance, the polystyrene has good mechanical strength, and the invention enables the polyethylene and the polythene to be mixed into an interpenetrating network structure through a special solvent polymer to form stable polymer alloy, therefore, the invention not only retains the mechanical property of the polystyrene but also has the excellent solvent-resistance of the polyethylene simultaneously, the solvent-resistance polystyrene product widely applied to the refrigerator inner liner plates is obtained, the material cost of the refrigerator inner liner plates is reduced, and the refrigerator inner liner plate material with stable supply of goods and quick delivery is provided.
Description
Technical field
The present invention relates to a kind of polystyrene alloy material, specifically, relate to a kind of solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates, its preparation method and application thereof.
Background technology
(English is Polystyrene to polystyrene, be called for short PS) be a kind of water white thermoplastics, high-impact polystyrene is by add a kind of shock proof polystyrene products that poly-isoprene-isobutylene rubber particulate way is produced in polystyrene, opaque and slightly be white in color, this polystyrene products are by adding the micron order rubber grain and the way by scion grafting links together polystyrene and rubber grain.
A distinct disadvantage of polystyrene is exactly that solvent resistance is poor, can be by multiple organic solvent dissolution, and can be corroded not anti-grease by strong acid and strong base.
Everybody is familiar with refrigerator, can be for the making material of inner container of icebox, people know little about it, and refrigerator inner liner plates requires to have very high solvent resistance, lower temperature resistance and shock resistance, this particular requirement of refrigerator plate causes raw material production technical sophistication, production difficulty big.
Inner container of icebox is after sheet material is extruded into sheet material, plastics sucking moulding is the required shape of inner bag, form a cavity with outside stainless steel casing, the processing of in cavity, foaming then, make in the cavity of foam layer injection between stainless steel casing and inner bag of loose insulation, reach the purpose of insulation.
Because the freonll-11 CFC that the conventional refrigerator production adopts is after the atmosphere high-altitude is gathered, by a series of photochemical degradation reactions, produce chlorine radical and destroy the high-altitude ozonosphere, promptly produce so-called " ozonosphere black hole " phenomenon and cause ozonosphere to keep out ultraviolet ability drop even forfeiture, therefore international environmental protection organization has cancelled the application of freonll-11, use pentamethylene C5 replacement fluorine Leon instead, but because the pentamethylene boiling point is lower, according to the manufacturing equipment actuality of present refrigerator, can't accomplish all to use pentamethylene, the actual greatly chlorodifluoroethane HCFC141b that replaces with through the approval of international environmental protection organization, yet HCFC141b p-poly-phenyl ethene, there is very big erosion action in ABS, and foamed material is to be dissolved in pentamethylene C5 and these organic solvents of fluorine ethylene dichloride HCFC141Bz, solvent in foaming process and later over a long time in remaining solvent can cause erosion to inner liner plates, the physical strength and the toughness of inner liner plates have been weakened, can use the softening forfeiture of the refrigerator inner liner plates necessary function of these material produce, thereby jeopardize final user benefit, therefore cause refrigerator inner liner plates to become chemical resistance, promptly solvent resistance requires very strict.
Present most of refrigerator producer adopts the method for the ABS extrusion board of strengthening solvent resistance.ABS is formed by vinylbenzene, the copolymerization of acrylonitrile and butadiene serum, thermotolerance own and solvent resistance are good than polystyrene all, and has glossiness, the ratio content of general vinyl cyanide is higher, its thermotolerance, rigidity and solvent resistance are better, and what wherein extensively adopt is exactly strange beautiful Polylac (R) the ABS series in Taiwan.
Regular grade ABS solvent resistance is poor, in order to adapt to the solvent resistance requirement of inner liner plates, need to adopt the ABS that strengthens solvent resistance, this ABS designs at the environment of the high solvent resistance of needs specially, kind is few, output is little, and price is very high, and general price is between 17000~18000 yuan/ton, higher 3000~4000 yuan than polystyrene price per ton, cause the material cost of refrigerator inner liner plates high, source of goods instability, Lead Time is long.
If improve the solvent resistance of polystyrene, adopt the home-made polystyrene to produce the material of refrigerator inner liner plates, the inner container of icebox material cost be can reduce greatly, and the competent source of goods and quick response Lead Time guaranteed.
Therefore improve the solvent resistance of polystyrene, the polystyrene products of developing solvent resistance seem very urgent.
Because the molecular structure and the characteristic of polystyrene and these two kinds of polymkeric substance of polyethylene itself differ greatly, cause this two kinds of high molecular polymers, under the effect that does not have compatilizer and chemical polarity key, the two is inconsistent, this point from the difference of the solubility parameters of the two also as can be seen, the solubility parameters of polystyrene is 8.9~9.4, poly solubility parameters is 7.24, the difference of the two is more than 1.5, and according to compatible thermodynamic principles, the two is incompatible on thermodynamics.
CN 1563166A discloses a kind of Anti-141b Polystyrene Refrigerator Lining Material, and this material is mainly by polystyrene 15~50%; Polyethylene 23~58%; Compatilizer (polycthylene grafted cis-butenedioic anhydride or superoxide) 7~13%; Nucleator 5~13%; Rubber elastomer 9.3~11.3%; Polyethylene wax 0.2~0.5%; Zinic stearas 0.1~0.3%; Oxidation inhibitor 0.1~0.2% is formed.Though this inner lining material can improve solvent resistance equally, but prescription more complicated, also increased production cost to a certain extent, there is the smell of irritating cis-butenedioic anhydride resistates in the compatilizer of grafting class in melted by heating extruding pelletization and extrusion board, and in fact consistency is also unstable owing to the instability of the percentage of grafting of grafts causes.
Summary of the invention
The purpose of this invention is to provide a kind of solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates, this alloy material has had the higher mechanical properties of polystyrene, good hot melt processing characteristics and poly excellent solvent-resistance energy simultaneously.
Another object of the present invention provides a kind of preparation method of solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates.
An also purpose of the present invention provides the application of a kind of polystyrene ternary alloy material in the preparation inner container of icebox.
The present invention utilizes polyethylene excellent solvent-resistance energy, select a kind of polymkeric substance of the used grafts of conventional alloy that is different from as compatilizer, polystyrene and these two kinds also incompatible polymers of polyethylene own are organically combined, form a kind of structure of interpenetrating(polymer)networks, obtain a kind of stable ternary alloy system, this alloy system has had the higher mechanical properties of polystyrene, good hot melt processing characteristics and poly excellent solvent-resistance energy simultaneously.
In order to realize the object of the invention, a kind of solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of the present invention is made up of high-impact polystyrene 20~65%, linear low density polyethylene 15~60%, ethylene-butadiene-styrene multipolymer compatilizer 5~25%, oxidation inhibitor 0.1~0.6% and calcium stearate 0.1~0.6%.
Wherein, preferably, high-impact polystyrene 35~50%, linear low density polyethylene 35~45%, ethylene-butadiene-styrene multipolymer compatilizer 10~20%, oxidation inhibitor 0.2~0.5% and calcium stearate 0.3~0.5%.
Wherein percentage composition is a weight percentage.
The melting index of high-impact polystyrene of the present invention (MI) be 4~12g/10min (200 ℃/5kg) (testing method GB3682, down with), cantilever beam impact strength is 80~150J/m (ASTM D-256).
The melting index of described linear low density polyethylene (MI) be 2~20g/10min (190 ℃/5kg).
Compatilizer used in the present invention itself is a kind of polymkeric substance, is different from existing polycthylene grafted cis-butenedioic anhydride or superoxide.Compatilizer of the present invention is a kind of ethylene-butadiene-styrene elastic block copolymer, have at least one constitute the block S that contains vinyl aromatic monomer unit in hard phase, the polymer chain with at least one constitute soft mutually, contain vinyl aromatic monomer S and the unitary elastomeric block B/S of divinyl B simultaneously in the polymer chain, the glass transition temperature Tg of block S is greater than 25 ℃, the Tg of B block/S is lower than 25 ℃, and therein ethylene content is 25~50%.
Described oxidation inhibitor is organic Hinered phenols, amine, oxidation inhibitor such as phosphorous acid esters or thioesters class, such as four [β-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid] pentaerythritol ester (abbreviation antioxidant 1010), β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid (abbreviation antioxidant 1076), 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol) (abbreviation antioxidant 300), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (being called for short oxidation inhibitor 168), triphenyl phosphite (TPP), thio-2 acid two (18) ester DSTP etc. and compound thereof.
The present invention selects polystyrene and polyethylene matrix resin, and select elastic block copolymer by melt blending technology with good together compatible of two kinds of matrix resins, obtain having the ternary alloy product of good solvent resistance.Its concrete working method is: earlier each component is joined the high-speed mixer high speed and mix after 1~3 minute, form through the twin screw extruder extruding pelletization down at 170~220 ℃ then.
Make material obtain homodisperse on the both macro and micro by high-temperature fusion and screw rod shearing in twin screw extruder, the extruded stock bar cools off in tank, is cut into the alloy product of particle diameter, length homogeneous again in dicing machine.
Solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of the present invention is compared with existing alloy material, need not add any type of rubber elastomer, need not add any type of inorganic mineral toughener and nucleator, select the good elastic block copolymer of consistency as compatilizer, and prescription is simple, cost is low, it is little that product has density, super toughness, after testing, density 0.95~1.00g/cm
3, cantilever beam impact strength reaches more than the 550J/m, and the simply supported beam notched Izod impact strength reaches 70kJ/m
2More than.
The application of solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of the present invention in the preparation inner container of icebox.
Polystyrene ternary alloy material of the present invention is processed into the thin layer of 0.1~0.5mm by expressing technique, uses as the sealing coat of inner container of icebox.After testing, this thin slice tensile yield pressure 〉=12.0MPa, resistance to impact shock 〉=85.0J/m, elongation at break 〉=30%, heat-drawn wire>75 ℃ (adopting the GB detection method), size changing rate<10% does not have cracking and any fine cracks through the cold cycling test sheets.
When making inner container of icebox, can earlier alloy material of the present invention be extruded into the thin layer (as sealing coat) of 0.1~0.5mm separately, the refrigerator inner liner plates material then can be selected cheap common high-impact extrusion grade polystyrene for use, after polystyrene also is extruded into sheet material, with alloy thin layer and polystyrene plates overlapping after, carry out plastics sucking moulding, the plastic uptake finished product is through forming a cavity with stainless steel casing after the cutting, in cavity, inject whipping agent, processings of foaming after initiator causes makes in the cavity of foam layer injection between stainless steel casing and inner bag of loose insulation.Because thin layer had both had good solvent resistance; the provide protection of solvent resistance is provided for polystyrene layer; simultaneously again because there are good compatibility performance in this alloy and polystyrene; can keep excellent contact with polystyrene layer, thereby avoid thin layer and the isolating phenomenon of polystyrene layer.
The cross section of inner container of icebox was formed by 4 layers after foaming was finished, and was respectively isolation layer and polystyrene bladder layer that metal shell layer (as stainless steel, providing outer layer protection), polyurethane foam (playing the heat-insulation and heat-preservation effect), described ternary-alloy material are made.Wherein the effect of isolation layer is exactly polyurethane foam and polystyrene layer is isolated comes, and prevents that the solvent p-poly-phenyl pvdf layer in the urethane from causing erosion effect, reaches the solvent-proof purpose of protection polystyrene.
The present invention solves the problem of the poor chemical stability of high-impact polystyrene, improve the solvent resistance of high-impact polystyrene, reach and directly contact with pentamethylene, a fluorine ethylene dichloride equal solvent and keep self physical strength and flexible purpose, go thereby the polystyrene with excellent solvent-resistance can be applied in the refrigerator inner liner plates production on a large scale.Solvent resistance is meant the swelling that plastics opposing solvent causes, dissolving, the ability of be full of cracks or deformation.Solvent resistance characterizes with the elongation at break velocity of variation before and after the ESCR experiment, elongation at break before ESCR=(elongation at break before experiment back elongation at break-experiment)/experiment, the solvent resistance of alloy material of the present invention is pressed ESCR result more than 100%, and HIPS and ABS are generally 60~70%.
In the present invention, the polyethylene of selecting has excellent solvent-resistance, and polystyrene has excellent mechanical intensity, is an inierpeneirating network structure by extraordinary compatible polymeric with the two blend, form the stabilization of polymer alloy, thereby the mechanical property that had both kept polystyrene, also had poly excellent solvent-resistance simultaneously, obtained to be widely used in the solvent-resistance polystyrene product of refrigerator inner liner plates, reduced the material cost of refrigerator inner liner plates, the source of goods refrigerator inner liner plates material rapidly of stablizing, supply is provided.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of present embodiment is made up of 65% high-impact polystyrene, 20% linear low density polyethylene, 14% ethylene-butadiene-styrene multipolymer compatilizer, 0.5% antioxidant 1010 and 0.5% calcium stearate.
Wherein, high-impact polystyrene is the 495F that BASF AG produces, MI be 12g/10min (200 ℃/5kg), cantilever beam impact strength be 110J/m, linear low density polyethylene MI be 9g/10min (190 ℃/5kg), the ethylene-butadiene-styrene multipolymer is a segmented copolymer, and therein ethylene content is 25%.
The solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of present embodiment adopts and earlier each component is joined in proportion the mixing of high-speed mixer high speed after 3 minutes; extrude through twin screw extruder down at 200 ± 10 ℃ then; the material bar cools off in tank, is cut into the alloy product of particle diameter, length homogeneous again in dicing machine.
Polystyrene ternary alloy material of the present invention is extruded the thin layer that is processed into 0.1~0.5mm by forcing machine, uses as the sealing coat of inner container of icebox.
When making inner container of icebox, can earlier alloy material of the present invention be extruded into the thin layer (as sealing coat) of 0.1~0.5mm separately, the refrigerator inner liner plates material then can be selected cheap common high-impact extrusion grade polystyrene for use, after polystyrene also is extruded into sheet material, with alloy thin layer and polystyrene plates overlapping after, carry out plastics sucking moulding, the plastic uptake finished product is through forming a cavity with stainless steel casing after the cutting, in cavity, inject whipping agent, processings of foaming after initiator causes makes in the cavity of foam layer injection between stainless steel casing and inner bag of loose insulation.The cross section of inner container of icebox was formed by 4 layers after foaming was finished, and was respectively isolation layer and polystyrene bladder layer that stainless steel casing layer (outer layer protection is provided), polyurethane foam (playing the heat-insulation and heat-preservation effect), described ternary-alloy material are made.
Embodiment 2
The solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of present embodiment is made up of 35% high-impact polystyrene, 40% linear low density polyethylene, 24.3% ethylene-butadiene-styrene multipolymer compatilizer, 0.1% oxidation inhibitor 168 and 0.6% calcium stearate.
Wherein, high-impact polystyrene is 1300 of a LG-DOW product, MI be 7.5g/10min (200 ℃/5kg), cantilever beam impact strength be 100J/m, linear low density polyethylene MI be 6g/10min (190 ℃/5kg), the ethylene-butadiene-styrene multipolymer is a segmented copolymer, and therein ethylene content is 35%.
The solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of present embodiment adopts and earlier each component is joined in proportion the mixing of high-speed mixer high speed after 2 minutes; extrude through twin screw extruder down at 180 ± 10 ℃ then; the material bar cools off in tank, is cut into the alloy product of particle diameter, length homogeneous again in dicing machine.
Embodiment 3
The solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of present embodiment is made up of 55% high-impact polystyrene, 35% linear low density polyethylene, 9.5% ethylene-butadiene-styrene multipolymer compatilizer, 0.2% antioxidant 1076 and 0.3% calcium stearate.
Wherein, high-impact polystyrene is the 476L that BASF produces, MI be 4g/10min (200 ℃/5kg), cantilever beam impact strength be 80J/m, linear low density polyethylene MI be 2g/10min (190 ℃/5kg), the ethylene-butadiene-styrene multipolymer is a segmented copolymer, and therein ethylene content is 30%.
The solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of present embodiment adopts and earlier each component is joined in proportion the mixing of high-speed mixer high speed after 1 minute; extrude through twin screw extruder down at 210 ± 10 ℃ then; the material bar cools off in tank, is cut into the alloy product of particle diameter, length homogeneous again in dicing machine.
Embodiment 4-6
The set of dispense of the solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of embodiment 4-6 is such as following:
Test example 1
Alloy product with embodiment 1-6 detects respectively, and the thin slice performance of simultaneously alloy material being made as isolation layer detects, and the results are shown in Table 1 and table 2.
The performance test results of table 1 embodiment 1-6 alloy product
The performance test results of table 2 thin slice
Simultaneously the solvent resistance of alloy material of the present invention is tested, solvent resistance characterizes with the elongation at break velocity of variation before and after the ESCR experiment, elongation at break (testing method ISO4599) before ESCR=(elongation at break before experiment back elongation at break-experiment)/experiment.ESCR is big more, illustrates that solvent resistance is good more.Result such as table 3 after testing.
Table 3 alloy material ESCR of the present invention (141B solvent) test-results
This shows that the solvent resistance of alloy material of the present invention is pressed ESCR and measured, the result is equal more than 100%.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates, it is characterized in that this alloy material is made up of following components in weight percentage content: high-impact polystyrene 20~65%, linear low density polyethylene 15~60%, ethylene-butadiene-styrene multipolymer compatilizer 5~25%, oxidation inhibitor 0.1~0.6% and calcium stearate 0.1~0.6%.
2. solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates according to claim 1, it is characterized in that described alloy material is made up of following components in weight percentage content: high-impact polystyrene 35~50%, linear low density polyethylene 35~45%, ethylene-butadiene-styrene multipolymer compatilizer 10~20%, oxidation inhibitor 0.2~0.5% and calcium stearate 0.3~0.5%.
3. solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates according to claim 1 and 2, it is characterized in that, the melting index of described high-impact polystyrene is determined as 4~12g/10min under 200 ℃, 5kg, cantilever beam impact strength is 80~150J/m.
4. solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates according to claim 1 and 2 is characterized in that, the melting index of described linear low density polyethylene is determined as 2~20g/10min under 190 ℃, 5kg.
5. according to claim 1 or 2 described solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates, it is characterized in that the weight percentage of ethene is 25~50% in the described ethylene-butadiene-styrene multipolymer.
6. according to claim 1 or 2 described solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates, it is characterized in that described oxidation inhibitor is organic Hinered phenols, amine, phosphorous acid esters, thioesters kind antioxidant.
7. prepare the method for any described solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of claim 1-6, it is characterized in that, comprise the steps:
Earlier each component is joined the high-speed mixer high speed and mix after 1~3 minute, form through the twin screw extruder extruding pelletization down at 170~220 ℃ then.
8. the application of any described solvent-resistance polystyrene ternary alloy material for refrigerator inner liner plates of claim 1-6 in the preparation inner container of icebox.
9. application according to claim 8 is characterized in that, the cross section of described inner container of icebox is formed by 4 layers, is respectively isolation layer and polystyrene bladder layer that metal shell layer, polyurethane foam, described ternary-alloy material are made.
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TWI509011B (en) * | 2013-12-26 | 2015-11-21 | Chi Mei Corp | High impact styrene-based polymer composition for plate of refrigerator and plate of refrigerator |
CN103951925B (en) * | 2014-04-18 | 2016-10-05 | 合肥华凌股份有限公司 | HIPS material, composite board and there is the refrigeration plant of this composite board |
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WO2018224272A1 (en) * | 2017-06-07 | 2018-12-13 | Arcelik Anonim Sirketi | Thermoformable polystyrene sheet composition of high chemical durability and high gloss |
CN112143153A (en) * | 2020-09-30 | 2020-12-29 | 海信容声(广东)冰箱有限公司 | Refrigerator liner, refrigerator liner material and preparation method thereof |
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