CN101225203B - Cyclopentane, pentafluoropropane and dichloromonofluoroethane resistant refrigerator lining resin - Google Patents
Cyclopentane, pentafluoropropane and dichloromonofluoroethane resistant refrigerator lining resin Download PDFInfo
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- CN101225203B CN101225203B CN2007101914005A CN200710191400A CN101225203B CN 101225203 B CN101225203 B CN 101225203B CN 2007101914005 A CN2007101914005 A CN 2007101914005A CN 200710191400 A CN200710191400 A CN 200710191400A CN 101225203 B CN101225203 B CN 101225203B
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Abstract
The invention relates to an anti-chemical corrosion resin for making refrigerator liners, in particular to a refrigerator liner resin for resisting cyclopentane, pentafluoropropane, dichloropheno-fluoride ethane, which comprises polystyrene 15 to 70 percent, polyethylene 8 to 70 percent, compatilizer 5 to 25 percent, thermoplastic elastomer 5 to 18 percent, Tissuemat E 0.2 to 0.6 percent and zinc stearate 0.2 to 0.5 percent. The compatilizer comprises glycidyl methacrylate 0.1 to 3.5 percent, acrylic acid 0.1 to 3.5 percent, methyl methacrylate 0.1 to 3.5 percent, dicumyl peroxide 0.03 to 0.15 percent, antioxidant 10 or antioxidant 168 0.2 to 1.2 percent and polyethylene 2 to 15 percent, wherein, the unit is mass percent to the gross of refrigerator liner resin. The anti-chemical corrosion resin can be directly used or co-extruded together with HIPS refrigerator material. The anti-chemical corrosion resin for making refrigerator liners has the advantages of high reuse rate and good compatibility.
Description
Technical field
The invention belongs to a kind of resist chemical resin that is used to make refrigerator lining, specifically a kind of anti-pentamethylene, HFC-245FA (pentafluoropropane), HCFC-141b (dichloro one fluoroethane) refrigerator lining resin.
Background technology
Traditional refrigerator production adopts freonll-11 (CFC) refrigeration agent, because freonll-11 is after the atmosphere high-altitude is gathered, by a series of photoelectricity DeRs, produce chlorine radical and destroy high aerial ozonosphere, promptly produce so-called " black hole " and destroy existent environment of people, therefore Chinese Government is decided by on 07 01st, 2007 termination use freon refrigerant comprehensively, uses pentamethylene, the alternative freon refrigerant of HFC-245FA, HCFC-141b instead.Because pentamethylene, these substitutes of HFC-245FA, HCFC-141b have very strong chemical corrosion ability, common HIPS (polystyrene) can't bear the corrosion of these substitutes and influence the inner quality of refrigerator production product, so the refrigerator production can be destroyed the use properties of HIPS refrigerator lining material for the environmental protection refrigerant that satisfies environmental protection condition and energy-saving and cost-reducing condition and select for use.
Summary of the invention
The objective of the invention is to design a kind of refrigerator lining resin that comprises anti-pentamethylene, pentafluoropropane, dichloro one fluoroethane.This liner alloy film covered resin novel material can be avoided the corrosion to material of main part HIPS refrigerator proprietary material of pentamethylene, HFC-245FA, HCFC-141b, guarantees the refrigerator product quality of stability, and has good consistency with HIPS refrigerator proprietary material.
According to technical scheme provided by the invention, the described refrigerator lining resin that comprises anti-pentamethylene, pentafluoropropane, dichloro one fluoroethane comprises: polystyrene 15～70%; Polyethylene 8～70%; Compatilizer 5～25%; Thermoplastic elastomer 5～18%; Polyethylene wax 0.2～0.6%; Zinic stearas 0.2～0.5%;
Compatilizer wherein is to add after preparing by following proportioning raw materials in advance again, therefore is referred to as the self-control compatilizer in an embodiment;
Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 0.1～3.5%; 0.1～3.5% vinylformic acid; 0.1%～3.5% methyl methacrylate; 0.03～0.15% dicumyl peroxide; 0.2～1.2% oxidation inhibitor 10 or oxidation inhibitor 168; 2～15% polyethylene, unit are mass percent.
Also the raw material of preparation compatilizer can be added with other raw material of refrigerator lining resin, at this moment poly one-tenth branch slightly adjusts, and poly amount in the compatilizer should be merged together, and makes total amount become 10～85%.Its composition comprises: polystyrene 15～70%; Polyethylene 10～85%; Thermoplastic elastomer 5～18%; Polyethylene wax 0.2～0.6%; Zinic stearas 0.2～0.5%; Glytidyl methacrylate 0.1～3.5%; Vinylformic acid 0.1～3.5%; Methyl methacrylate 0.1%～3.5%; Dicumyl peroxide 0.03～0.15%; 0.2～1.2% oxidation inhibitor 10 or oxidation inhibitor 168, unit are mass percent.
Wherein: polystyrene is the basic material as proprietary material, helps the machine-shaping of material.
Polyethylene is the good macromolecular material of a kind of stability, has very strong resistance to chemical attack.
Anti-pentamethylene, HFC-245FA, the main materials of HCFC-141b refrigerator lining resin property:
Self-control compatilizer: because these two kinds of materials of polystyrene and polyethylene have different molecular structures and different characteristics, so these two kinds of high molecular polymers are inconsistent.Under the situation of the polarity chemical b ` that does not have compatilizer to provide, polystyrene and polyethylene can not be made alloy material.Therefore, compatilizer is only the main medium of the anti-pentamethylene of material of the present invention, HFC-245FA, HCFC-141b refrigerator lining resin material.Under the effect of compatilizer polarity chemical bond, these two kinds of molecular structures of polystyrene and polyethylene high molecular polymer all different with characteristic could organically combine makes the anti-pentamethylene of high molecule alloy material, HFC-245FA, HCFC-141b refrigerator lining resin material.Compatilizer can be polyethylene, polystyrene, thermoplastic elastomer and GMA, AA, MMA, by with DCP (dicumyl peroxide) being initiator and with oxidation inhibitor 10 or oxidation inhibitor 168, makes through traditional melt blending reaction.
Thermoplastic elastomer: because this proprietary material is mainly used in refrigerator lining and inner bag, bigger elongation at break must be arranged,, add a certain proportion of thermoplastic elastomer and help satisfying above performance requriements with resistance to low temperature preferably.The present invention mainly uses SBS and SEBS.
Polyethylene wax: play the effect of lubricant in the process of manufacture.
Zinic stearas: play lubricant and function of stabilizer in the process of manufacture.
Oxidation inhibitor: prevent the effect of macromolecular material oxidative degradation in the process of manufacture.The present invention mainly adopts oxidation inhibitor 10 and oxidation inhibitor 168 etc.
Because traditional refrigerator production adopts the refrigeration agent of freonll-11 as refrigerator, international environmental protection organization considers destruction and the Greenhouse effect of CFC for atmospheric ozone layer, in order to safeguard ball ecological environment, China's Mainland government is decided by on the July 1st, 2007 of the use of cancellation freonll-11 comprehensively according to the Kyoto Protocol of signature in 1997.But the pentamethylene of product, HFC-245FA, HCFC-141b have stronger chemical corrosivity to existing HIPS refrigerator lining proprietary material as an alternative, the author invents this product all material and is domestic production, by the scientific formula development, adopt the mixing novel low-cost multifunction alloy resin that forms of twin screw extruder.
In fact domestic some refrigerator manufacturing concern uses anti-141bABS refrigerator proprietary material, procurement cycle is long, being external large-scale petrochemical enterprise produces, price is all more than 22000 yuan/ton, having nitrile compound in the reprocessing process produces, cause environmental pollution, and use the words of anti-pentamethylene, HFC-245FA, HCFC-141b refrigerator lining resin material just can not produce the problems referred to above, and the overlay film consumption only is 5～13% just can reach the manufacturing specification of quality of refrigerator.
It is anti-pentamethylene, HFC-245FA, HCFC-141b carrier with polyethylene (PE) that the applicant has invented a kind of according to the chemical property of pentamethylene, HFC-245FA, HCFC-141b refrigeration agent and refrigerator lining (also claiming the PE/PS alloy resin) material performance requirement, form a kind of high molecule alloy material by macromolecular grafted polystyrene, have the refrigerator lining novel material resin of very strong resist chemical.
Embodiment
Embodiment one
Polystyrene 15%, polyethylene 65%, self-control compatilizer 15%, thermoplastic elastomer 10%, polyethylene wax 0.3%, Zinic stearas 0.2%, this material adding 15% is stirred the back plate squeezing with HIPS refrigerator material mixing, satisfies pentamethylene, the application of HFC-245FA refrigeration agent refrigerator plate fully.Its physical index: melting index 0.7～2.5g/10min, tensile strength is greater than 22MPa, and cantilever beam impact strength is greater than 180J/m, and heat-drawn wire is greater than 70 degrees centigrade, and elongation at break is greater than 140%, and chemical resistance is good.Described self-control compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 0.5%; 0.5% vinylformic acid; 0.15% methyl methacrylate; 0.11% dicumyl peroxide; 0.5% oxidation inhibitor 10 or oxidation inhibitor 168; 3% polyethylene, unit are mass percent.
Embodiment two
Polystyrene 20%, polyethylene 49.5%, self-control compatilizer 7%, ultra-fine ceramic fine bead 15%, thermoplastic elastomer 8%, polyethylene wax 0.5%, Zinic stearas 0.1%, this is a kind of good automotive trim plastics sucking moulding material, resistance to chemical corrosion is strong, winter hardiness is good, and physicals is good, melting index 0.7～2.5g/10min, tensile strength is greater than 23MPa, cantilever beam impact strength is greater than 450J/m, and heat-drawn wire is greater than 80 degrees centigrade, and elongation at break is greater than 120%.Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 2.2%; 2.2% vinylformic acid; 2.2% methyl methacrylate; 0.06% dicumyl peroxide; 0.6% oxidation inhibitor 168; 12% polyethylene, unit are mass percent.
Embodiment three
Polystyrene 25%, polyethylene 50%, self-control compatilizer 8%, 1200 order talcum powder 8%, thermoplastic elastomer 8.3%, polyethylene wax 0.3%, Zinic stearas 0.2%, this is a kind of PE/PS resist chemical material, and its physical index is: melting index 2.5～5.5g/10min, and tensile strength is greater than 20MPa, cantilever beam impact strength is greater than 300J/m, heat-drawn wire is greater than 80 degrees centigrade, and elongation at break is greater than 90%, is applicable to that injection moulding forming process such as extrudes.Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 0.5%; 0.5% vinylformic acid; 0.5% methyl methacrylate; 0.08% dicumyl peroxide; 0.9% oxidation inhibitor 10; 4% polyethylene, unit are mass percent.
Embodiment four
Polystyrene 35%, polyethylene 35%, self-control compatilizer 15% (perhaps GMA1.2%, DCP0.03～0.1%, stop crosslinking reaction agent 10 oxidation inhibitor 0.5% in the grafting process), styrene-ethylene-butylene-styrene segmented copolymer SEBS15%, polyethylene wax 0.2%, Zinic stearas 0.3%, this is a kind of good anti-pentamethylene, HFC-245FA, HCFC-141b refrigerator lining resin material (also being called PE/PS alloy resin overlay film material), usage ratio is: pentamethylene, HFC-245FA during as refrigerator refrigerant the peritonaeum ratio be 5%, HCFC-141b during as refrigerator refrigerant the peritonaeum ratio be 10%.Its physical index: melting index 3～7.5g/10min, tensile strength is greater than 16MPa, and cantilever beam impact strength is greater than 300J/m, and heat-drawn wire is greater than 75 degrees centigrade, elongation at break is greater than 100%, and anti-pentamethylene, HFC-245FA, HCFC-141b dissolubility are good.Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 1.5%; 1.5% vinylformic acid; 1.5% methyl methacrylate; 0.09% dicumyl peroxide; 0.5% oxidation inhibitor 168; 9% polyethylene, unit are mass percent.
Embodiment five
Polystyrene 50%, polyethylene 30%, self-control compatilizer 10%, styrene-butadiene-styrene multipolymer SBS9%, polyethylene wax 0.5%, Zinic stearas 0.3%, this is that a kind of good anti-pentamethylene, HFC-245FA refrigerator lining are resin dedicated.Its physical index is: melting index 2.5～5.5g/10min, and tensile strength is greater than 20MPa, and cantilever beam impact strength is greater than 150J/m, and heat-drawn wire is greater than 80 degrees centigrade, and elongation at break is greater than 60%, is applicable to that injection moulding forming process such as extrudes.Anti-pentamethylene, HFC-245FA, HCFC-141b dissolubility are good.Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 2.5%; 2.5% vinylformic acid; 2.5% methyl methacrylate; 0.10% dicumyl peroxide; 1.2% oxidation inhibitor 10; 7% polyethylene, unit are mass percent.
Embodiment six
Polystyrene 60%, polyethylene 20%, self-control compatilizer 11%, styrene-ethylene-butylene-styrene segmented copolymer SEBS12%, polyethylene wax 0.5%, Zinic stearas 0.3%, this is that a kind of good anti-pentamethylene, HFC-245FA refrigerator lining are resin dedicated.Its physical index is: melting index 2.5～4.5g/10min, and tensile strength is greater than 21MPa, and cantilever beam impact strength is greater than 110J/m, and heat-drawn wire is greater than 80 degrees centigrade, and elongation at break is greater than 50%, is applicable to that injection moulding forming process such as extrudes.Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 3.5%; 0.1% vinylformic acid; 3.5% methyl methacrylate; 0.15% dicumyl peroxide; 0.2% oxidation inhibitor 168; 2% polyethylene, unit are mass percent.
Embodiment seven
Polystyrene 70%, polyethylene 10%, self-control compatilizer 8%, styrene-butadiene-styrene multipolymer SBS11%, polyethylene wax 0.5%, Zinic stearas 0.3%, oxidation inhibitor 10 0.9%, this is that a kind of good anti-pentamethylene, HFC-245FA refrigerator lining are resin dedicated.Its physical index is: melting index 2.5～5.5g/10min, and tensile strength is greater than 23MPa, and cantilever beam impact strength is greater than 100J/m, and heat-drawn wire is greater than 80 degrees centigrade, and elongation at break is greater than 45%, is applicable to that injection moulding forming process such as extrudes.Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 0.1%; 3.5% vinylformic acid; 0.1% methyl methacrylate; 0.03% dicumyl peroxide; 1.2% oxidation inhibitor 10; 15% polyethylene, unit are mass percent.
Embodiment eight
Polystyrene 40%; Polyethylene 45%; Styrene-butadiene-styrene multipolymer SBS5%; Polyethylene wax 0.3%; Zinic stearas 0.4%; Glytidyl methacrylate 0.1%; Vinylformic acid 0.1%; Methyl methacrylate 0.1%; Dicumyl peroxide 0.03%; Be used for stoping the grafting process that the oxidation inhibitor 10 1.0% of crosslinking reaction takes place, unit is a mass percent.
Embodiment nine
Polystyrene 45%; Polyethylene 55%; Styrene-ethylene-butylene-styrene segmented copolymer SEBS6%; Polyethylene wax 0.25%; Zinic stearas 0.35%; Glytidyl methacrylate 3.5%; Vinylformic acid 3.5%; Methyl methacrylate 3.5%; Dicumyl peroxide 0.15%; Be used for stoping the grafting process that the oxidation inhibitor 168 1.2% of crosslinking reaction takes place, unit is a mass percent.
Embodiment ten
Polystyrene 65%; Polyethylene 65%; Styrene-butadiene-styrene multipolymer SBS7%; Polyethylene wax 0.45%; Zinic stearas 0.45%; Glytidyl methacrylate 0.25%; Vinylformic acid 0.25%; Methyl methacrylate 0.25%; Dicumyl peroxide 0.1%; Be used for stoping the grafting process that the oxidation inhibitor 10 1.1% of crosslinking reaction takes place, unit is a mass percent.
Embodiment 11
Polystyrene 68%; Polyethylene 75%; Styrene-ethylene-butylene-styrene segmented copolymer SEBS10%; Polyethylene wax 0.38%; Zinic stearas 0.38%; Glytidyl methacrylate 0.5%; Vinylformic acid 2.5%; Methyl methacrylate 2.2%; Dicumyl peroxide 0.08%; Be used for stoping the grafting process that the oxidation inhibitor 168 0.25% of crosslinking reaction takes place, unit is a mass percent.
Embodiment 12
Polystyrene 18%; Polyethylene 85%; Styrene-butadiene-styrene multipolymer SBS13%; Polyethylene wax 0.45%; Zinic stearas 0.45%; Glytidyl methacrylate 0.7%; Vinylformic acid 0.9%; Methyl methacrylate 1.6%; Dicumyl peroxide 0.09%; Be used for stoping the grafting process that the oxidation inhibitor 10 0.35% of crosslinking reaction takes place, unit is a mass percent.
When utilizing material of the present invention to make the refrigerator lining material, all manufacture crafts need not to change with to utilize original material to make the used technology of refrigerator lining identical.
Claims (2)
1. comprise the refrigerator lining resin of anti-pentamethylene, pentafluoropropane, dichloro one fluoroethane, it is characterized in that this refrigerator lining resin comprises: polystyrene 15～70%; Polyethylene 8～70%; Compatilizer 5～25%; Thermoplastic elastomer 5～18%; Polyethylene wax 0.2～0.6%; Zinic stearas 0.2～0.5%;
Described compatilizer comprises the glytidyl methacrylate that accounts for refrigerator lining resin total amount 0.1～3.5%; 0.1～3.5% vinylformic acid; 0.1%～3.5% methyl methacrylate; 0.03～0.15% dicumyl peroxide; 0.2～1.2% oxidation inhibitor 10 or oxidation inhibitor 168; 2～15% polyethylene, unit are mass percent;
Described thermoplastic elastomer is the styrene-ethylene-butylene-styrene segmented copolymer.
2. comprise the refrigerator lining resin of anti-pentamethylene, pentafluoropropane, dichloro one fluoroethane, it is characterized in that this refrigerator lining resin comprises: polystyrene 15～70%; Polyethylene 10～85%; Thermoplastic elastomer 5～18%; Polyethylene wax 0.2～0.6%; Zinic stearas 0.2～0.5%; Glytidyl methacrylate 0.1～3.5%; Vinylformic acid 0.1～3.5%; Methyl methacrylate 0.1%～3.5%; Dicumyl peroxide 0.03～0.15%; 0.2～1.2% oxidation inhibitor 10 or oxidation inhibitor 168, unit are mass percent;
Described thermoplastic elastomer is the styrene-ethylene-butylene-styrene segmented copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101914005A CN101225203B (en) | 2007-12-14 | 2007-12-14 | Cyclopentane, pentafluoropropane and dichloromonofluoroethane resistant refrigerator lining resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101914005A CN101225203B (en) | 2007-12-14 | 2007-12-14 | Cyclopentane, pentafluoropropane and dichloromonofluoroethane resistant refrigerator lining resin |
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| Publication Number | Publication Date |
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| CN101225203A CN101225203A (en) | 2008-07-23 |
| CN101225203B true CN101225203B (en) | 2010-08-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101914005A Expired - Fee Related CN101225203B (en) | 2007-12-14 | 2007-12-14 | Cyclopentane, pentafluoropropane and dichloromonofluoroethane resistant refrigerator lining resin |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104371205A (en) * | 2014-10-30 | 2015-02-25 | 六安索伊电器制造有限公司 | Polystyrene refrigerator liner material and preparation method thereof |
| CN107868374A (en) * | 2017-12-06 | 2018-04-03 | 博维恩冷冻科技（苏州）有限公司 | A kind of refrigeration plant of low noise |
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Assignee: Wuxi Zhongke Fubang modified engineering plastics Co., Ltd. Assignor: Wu Nansong Contract record no.: 2011320000294 Denomination of invention: Cyclopentane, pentafluoropropane and dichloromonofluoroethane resistant refrigerator lining resin Granted publication date: 20100825 License type: Exclusive License Open date: 20080723 Record date: 20110316 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100825 Termination date: 20171214 |
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| CF01 | Termination of patent right due to non-payment of annual fee |