CN103923427B - Heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof and preparation method thereof - Google Patents
Heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof and preparation method thereof Download PDFInfo
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- CN103923427B CN103923427B CN201410182419.3A CN201410182419A CN103923427B CN 103923427 B CN103923427 B CN 103923427B CN 201410182419 A CN201410182419 A CN 201410182419A CN 103923427 B CN103923427 B CN 103923427B
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Abstract
The invention discloses heat-resisting HIPS plastic of a kind of automotive upholstery halogen-free flameproof and preparation method thereof.The heat-resisting HIPS plastic of described automotive upholstery halogen-free flameproof, comprises the component of following weight parts: HIPS resin 100 parts, fire retardant 2-15 part, heat-resistant agent 1-8 part.Preferably, described fire retardant is the mixture of one or more in ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide; Described heat-resistant agent is the mixture of one or more in Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester.Production cost of the present invention is low, good processability, flame retardant resistance and good heat resistance, environmental friendliness.The heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of the present invention, is particularly suitable for being injection molded into various automotive upholstery.
Description
Technical field
The invention belongs to chemical material technical field, be specifically related to a kind of modification HIPS plastic and preparation method thereof, particularly relate to heat-resisting HIPS plastic of a kind of automotive upholstery halogen-free flameproof and preparation method thereof.
Background technology
Impact resistant polystyrene (HIPS) is the shock proof polystyrene products of one that the way by adding poly-isoprene-isobutylene rubber particle is in polystyrene produced.This polystyrene products can be added micron order rubber grain and by the way of scion grafting, polystyrene and rubber grain be linked together.When being subject to impacting, the point stresses of crack propagation can be discharged by the rubber grain of flexible relative.Therefore the expansion of crackle is hindered, and shock resistance is improved.
Polystyrene is a kind of broad-spectrum brittle plastic.The case of computer that you are using now is exactly polystyrene.Transparent plastic cup, wrapping porous plastics is also made up of polystyrene.Polystyrene belongs to polyolefine, is formed by radical polymerization by vinylbenzene.A kind of novel polyphenyl ethene can be obtained, i.e. syndiotactic polystyrene (syndiotactic) by polymerization catalyzed by metallocene.The both sides of the main chain that the phenyl ring on syndiotactic polystyrene alternately connects, and the phenyl ring of ordinary polystyrene is randomly being connected to main chain both sides.Syndiotactic polystyrene (syndiotactic) is crystalline polymers, and fusing point reaches 270 DEG C.Add polyhutadiene in styrene polymerization system, make vinylbenzene graft polymerization on polyhutadiene main chain.Polystyrene and polyhutadiene are inconsistent, and therefore vinylbenzene and butadiene segment are assembled respectively, and generation is separated.These polyhutadiene phase regions can absorb striking energy, thus improve the opaque particle of shock strength HIPS engineering plastics oyster white of polystyrene, and density is 1.05g/cm
3, melt temperature 150 ~ 180 DEG C, heat decomposition temperature 300 DEG C, is dissolved in aromatic hydrocarbon, chlorinated hydrocarbon, ketone (except your ketone) and ester class. and the much mineral oil of ability, organic acid, alkali, salt, lower alcohol and the aqueous solution thereof, not resistance to boiling water.
HIPS is one of the most cheap engineering plastics, and ABS, PC/ABS, PC compare, and the glossiness of material is poor, over-all properties also relative mistake some.HIPS adds divinyl modification by PS and forms, because the shock strength of PS is very low, the product made is very crisp, and the toughness of divinyl is fine, and the impact property of PS can be made after adding divinyl to improve 2 ~ 3 times.Although the shock strength of HIPS exceeds a lot than the shock strength of PS, but its over-all properties is still not as ABS, the impact property of the .HIPS such as PC/ABS is lower in engineering plastics, and therefore, we should note the inspection of the impact property to material when using this material.
High impact polystyrene, in order to meet the requirement of toughness material, nineteen fifty starts to develop rubber modified polystyrene (high impact polystyrene and HIPS).By rubber is added polystyrene base material, the high impact polystyrene of the various grades with different performance can be produced.In recent years, develop the HIPS of various special grade, as anti-stress cracking level, high glossiness level, high shock strength level, glass fiber reinforcement level and low residue volatilization classification etc., they can compete mutually with the engineering resin of costliness in many Application Areass.The outstanding characteristic of High Impact Polystyrene (HIPS) is easy processing, excellent in dimensional stability, shock strength is high and have high stiffness.For HIPS just in thermotolerance.There is certain limit oxygen permeability, ultraviolet light stability and oil resistant moral character aspect.Chemistry and performance High Impact Polystyrene (HIPS) are by being dissolved in styrene monomer and obtained before polymerization by polybutadiene rubber.Although can suspension polymerization legal system HIPS be used, the mainly mass polymerization that current industrial production HIPS adopts.In bulk polymerisation process, the mixture of styrene monomer/rubber/additive is by series reaction device, and transformation efficiency reaches 70 ~ 90%.
Other key property of standard HIPS is as follows: flexural strength 13.8 ~ 55.1MPa; Tensile strength 13.8-41.4MPa; Elongation at break is 15-75%; Density 1.035-1.04g/ml; Vicat softening point 185-220 °F.
Uniquely the industrialized HIPS of mixing alloy is the blend of itself and polyphenylene oxide.The thermotolerance of this blend and toughness are all very outstanding, but product price is more much higher than the product of alone HIPS.
The development of polystyrene technology makes factory can produce the grade compared with standard level PS with more outstanding properties.Many performances of polystyrene can not be held concurrently and obtain, and as improving resistance to impact shock, just have to sacrifice glossiness etc.Some new type resins of current appearance, they have the glossiness of ABS, also have very high toughness simultaneously.Some grade, can resistance to various grease and also developing for ability Chlorofluorocarbons (CFCs) (CFC) whipping agent during rerigerator as when wrap food.Flame retardant grade (ULV-0 and UL5-V), High Impact Polystyrene (HIPS) is existing to be produced and is widely used in television cabin, business machine and electrical apparatus product.The process operation of these resins is more easier than many fire-retardant engineering resins, and price is also lower.
Shock resistance PS can process with many traditional forming methods, as shaping in injection moulding, structural foam moding, sheet material and film extrusion, thermoforming and injection blow molding etc.HIPS Resin Absorbent moisture is comparatively slow, does not therefore generally need drying.Sometimes the excess moisture of material surface can be absorbed, thus affects the visual appearance of the finished product.Under 160 °F, dry 2-3h just can remove unnecessary moisture.
The extrusion molding of film, sheet material and section bar is HIPS processing molding method with the most use.The work range of High Impact Polystyrene (HIPS) is very wide, and therefore it becomes one of resin of the easiest thermoforming.The common extrusion apparatus resin melt temperature of general use is 400-500 °F, and the melt index range of resin is 1.5-4.0g/10min.Also that often adopt rotary, series connection with pressure that is shuttle-type and vacuum thermoforming equipment.HIPS has excellent shear stability, can connect the reclaimed materials by volume, and not reduce product performance, and the reclaimed materials usage quantity in thermoforming processing can up to 60%.
Injection moulding is the processing molding method with the most use being only second to extrusion molding.The injection moulding of resin be generally length-to-diameter ratio be 16:1-24:1, compression ratio be 2.5/1-3.0/1 reciprocating-screw machine on carry out.Its melt index of resin of injection molding forming method processing is adopted to be generally 5.0 ~ 15.0g/min.Structural foam moding method is conventional technique, adopts chemistry and pneumatogen.
Although various HIPS resin is compatible by this, but want surface cleaning equipment before the procedure, to ensure good quality product, shock resistance PS and acrylonitrile one fourth Th alkene one styrol copolymer (ABS), polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE), acrylic resin and other most of plastics are all incompatible, inconsistent plastics mixture can produce separating delamination phenomenon in processing units, causes the very big decline of physicals.
Shock resistance PS has workability, good performance and low price, is therefore used to manufacture permitted multiduty goods and Industrial products.Main application fields has packaging and disposable product, instrument, household electrical appliance, toy and amusement article and building trade.
The maximum single-minded purposes of HIPS is as packaging and disposable product material, particularly packaging material for food and tableware for food and drink.Main application comprises daily packaging vessel.Vending machine is used and packing cup, various cover cap, dish, bowl etc.Disposable product such as dish class, bottle cap, safety razor, penholder etc. are also a part of purposes that HIPS consumption is large.
In recent years, Special Products becomes the emphasis of HIPS product development.HIPS product newly developed can be competed with engineering resin in some Application Areas, the used quality product of some ratios is much higher, instrument and consumer appliances are one of ever-increasing market of HIPS product, comprise miniature instrument, refrigerator inwall and internals, housing of TV set, air supply rate, business machine and recording picture recording tape cassete.HIPS resin instead of the high engineering plastics of valency in a lot of fields, but the heat-resisting and flame retardant properties of HIPS resin is not so good, and these shortcomings seriously limit the application of HIPS resin.
Halogen containing polymers or have excellent flame retardant properties with the flame-retardant mixture that halogen containing flame-retardant combines, Zeng Zuowei hinders alkene material and is widely used.
But when fire occurs, this kind of Halogen fire retardant material can produce a large amount of smog and poisonous corrosive hydrogen halides gas, cause into secondary harm.Therefore the flame-retardant system of invention Halogen, during burning, the amount of being fuming is little, does not produce poisonous, corrosive gases, has important practical significance.
Summary of the invention
For above shortcomings in prior art, technical problem to be solved by this invention is to provide the heat-resisting HIPS plastic of a kind of automotive upholstery halogen-free flameproof, has good anti-flame retardant resistance and thermotolerance, and during burning, the amount of being fuming is little, do not produce poisonous, corrosive gases, avoid secondary pollution.
The present invention seeks to be achieved through the following technical solutions:
The heat-resisting HIPS plastic of a kind of automotive upholstery halogen-free flameproof, comprises the component of following weight parts:
HIPS resin 100 parts,
Fire retardant 2-15 part,
Heat-resistant agent 1-8 part.
Preferably, the heat-resisting HIPS plastic of described automotive upholstery halogen-free flameproof comprises the component of following weight parts:
HIPS resin 100 parts,
Fire retardant 5-15 part,
Heat-resistant agent 4-8 part.
Preferably,
Described fire retardant is the mixture of one or more in ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide;
Described heat-resistant agent is the mixture of one or more in Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester;
It is preferred further,
Described fire retardant is made up of the component of following weight parts:
It is preferred further,
Described heat-resistant agent is made up of the component of following weight parts:
It is preferred,
The described heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof, is characterized in that, comprise the component of following weight parts:
Present invention also offers the preparation method of the heat-resisting HIPS plastic of above-mentioned automotive upholstery halogen-free flameproof, it comprises the following steps: take raw material by proportioning, and fully mixing, after 5-10 minute, adds twin screw extruder, at 170-200 DEG C of extruding pelletization at a high speed.
Obviously, in the present invention for improving other performances of product, other auxiliary agents can also be added adaptively, as heat-resistant agent, antiaging agent, scratch resistant agent, lubricant, photostabilizer, oxidation inhibitor, nucleator, softening agent, tinting material and static inhibitor etc.
In the present invention,
Ammonium polyphosphate, also known as ammonium polyphosphate or polycondensation ammonium phosphate, is called for short APP, English name: ammoniumpolyphosphate; Polyphosphoricacidsammoniumsalts, CAS number: 68333-79-9.The branchiess long chain polymer of ammonium polyphosphate, the polymerization degree is preferably 21-26.
Polynite, English name: Montmorillonite, No. CAS: 1318-93-0.
Melamine cyanurate, No. CAS: 37640-57-6.
Aluminium hydroxide, No. CAS: 21645-51-2.
Magnesium Stearate, No. CAS: 557-04-0.
Methyl tin three (isooctyl mercaptoacetate), No. CAS: 57583-34-3.
Dibutyl tin laurate, No. CAS: 77-58-7.
Three (4-nonyl phenyl) phosphorous acid ester, No. CAS: 3050-88-2.
Contriver is found by great many of experiments, use fire retardant of the present invention and heat-resistant agent, effectively can strengthen flame retardant properties and the resistance toheat of HIPS plastic, especially the compound flame retardant of ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide is used, there is the flame retardant effect of synergy, and not containing haloid element in compound flame retardant, during burning, the amount of being fuming is little, do not produce poisonous, corrosive gases, avoid secondary pollution.Use the composite heat-resistant agent of Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester, have collaborative heat-resisting effect, its mechanism need the further research and inquirement of contriver.Meanwhile, it draws high the conventional parameters such as intensity, flexural strength, modulus in flexure and notched Izod impact strength and all comparatively meets the demands.
The preparation technology of this product is simple, and product cost is low, and the over-all properties of product is more excellent.Automotive upholstery flame-proof heat-resistant HIPS plastic of the present invention, can be processed into the part of different shape easily, can be used for making automobile inside gadget by Shooting Technique.
Embodiment
Below in conjunction with embodiment, the invention will be further described.The HIPS resin used in the embodiment of the present invention and comparative example, buys from Shanghai Ying Fei Industrial Co., Ltd..
Embodiment 1
Take each flame retardant compositions according to embodiment 1 data corresponding in table 1, fully after mixing, obtain the compound flame retardant of embodiment 1;
Get the compound flame retardant of the HIPS resin 100 kilograms after drying treatment, Magnesium Stearate 5 kilograms and embodiment 1, fully mixing, after 10 minutes, adds the spout of twin screw extruder at a high speed; Control the rotating speed of twin screw extruder at 300rpm, temperature, at 200 DEG C, by twin screw extruder extruding pelletization, namely obtains the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 1.
The HIPS plastic flame retardant formulations list position of table 1: embodiment 1-7: kilogram
| Ammonium polyphosphate | Polynite | Melamine cyanurate | Aluminium hydroxide | |
| Embodiment 1 | 1.5 | 2 | 5 | 2 |
| Embodiment 2 | 1 | 2.5 | 4 | 3 |
| Embodiment 3 | 1.5 | 2 | 7 | / |
| Embodiment 4 | 6.5 | 2 | / | 2 |
| Embodiment 5 | 3.5 | / | 5 | 2 |
| Embodiment 6 | / | 3.5 | 5 | 2 |
| Embodiment 7 | 10.5 | / | / | / |
Embodiment 2
Take each flame retardant compositions according to embodiment 2 data corresponding in table 1, fully after mixing, obtain the compound flame retardant of embodiment 2;
According to method described in embodiment 1, obtain the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 2.
Embodiment 3
Take each flame retardant compositions according to embodiment 3 data corresponding in table 1, fully after mixing, obtain the compound flame retardant of embodiment 3;
According to method described in embodiment 1, obtain the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 3.
Embodiment 4
Take each flame retardant compositions according to embodiment 4 data corresponding in table 1, fully after mixing, obtain the compound flame retardant of embodiment 4;
According to method described in embodiment 1, obtain the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 4.
Embodiment 5
Take each flame retardant compositions according to embodiment 5 data corresponding in table 1, fully after mixing, obtain the compound flame retardant of embodiment 5;
According to method described in embodiment 1, obtain the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 5.
Embodiment 6
Take each flame retardant compositions according to embodiment 6 data corresponding in table 1, fully after mixing, obtain the compound flame retardant of embodiment 6;
According to method described in embodiment 1, obtain the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 6.
Embodiment 7
Take each flame retardant compositions according to embodiment 7 data corresponding in table 1, fully after mixing, obtain the compound flame retardant of embodiment 7;
According to method described in embodiment 1, obtain the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 7.
Test case 1
Test the flame retardant resistance of the HIPS plastic of embodiment 1-7, test result is in table 2.
The HIPS plastic flame retardant resistance test chart of table 2: embodiment 1-7
| UL-94 flame retardant rating, (1.6mm) | LOI，％ | Smoke density, m 2/kg | |
| Embodiment 1 | V0 | 32.8 | 970 |
| Embodiment 2 | V0 | 31.6 | 981 |
| Embodiment 3 | V1 | 27.4 | 1050 |
| Embodiment 4 | V0 | 29.3 | 992 |
| Embodiment 5 | V1 | 27.2 | 1024 |
| Embodiment 6 | V0 | 30.1 | 1002 |
| Embodiment 7 | V2 | 25.9 | 1195 |
The flame retardant resistance of the HIPS plastic of embodiment 1-7 is tested, found that the HIPS plastic that embodiment 1-7 obtains all has certain flame retardant resistance, especially embodiment 1-2 employs the compound flame retardant that ammonium polyphosphate, polynite, melamine cyanurate and aluminium hydroxide are made, be compared to embodiment 3-7, when adding same ratio fire retardant, oxygen index LOI value brings up to 31.6%-32.8% from 25.9%-30.1%, and smoke density is from 1195-992m
2/ kg has been reduced to 970-981m
2/ kg, clearly, the flame retardant effect especially for HIPS plastic is more excellent for flame retardant effect.
Embodiment 8
Various heat-resistant agent component is taken according to embodiment 8 data corresponding in table 3, get the compound flame retardant 10.5 kilograms of the HIPS resin 100 kilograms after drying treatment and embodiment 1, after fully mixing 10 minutes at a high speed, their spouts from twin screw extruder are added, control the rotating speed of screw extrusion press at 300rpm, temperature, at 200 DEG C, by screw extrusion press extruding pelletization, namely obtains the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof of embodiment 8.
The HIPS plastic heat-resistant agent formula table unit of table 3: embodiment 8-13: kilogram
| Magnesium Stearate | Methyl tin three (isooctyl mercaptoacetate) | Dibutyl tin laurate | Three (4-nonyl phenyl) phosphorous acid ester | |
| Embodiment 8 | 1 | 1 | 2 | 1 |
| Embodiment 9 | 1 | 1 | 3 | / |
| Embodiment 10 | 1 | 1 | / | 3 |
| Embodiment 11 | 2 | / | 2 | 1 |
| Embodiment 12 | / | 2 | 2 | 1 |
| Embodiment 13 | 5 | / | / | / |
Embodiment 9
Take various heat-resistant agent component according to embodiment 9 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant HIPS plastic of embodiment 9.
Embodiment 10
Take various heat-resistant agent component according to embodiment 10 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant HIPS plastic of embodiment 10.
Embodiment 11
Take various heat-resistant agent component according to embodiment 11 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant HIPS plastic of embodiment 11.
Embodiment 12
Take various heat-resistant agent component according to embodiment 12 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant HIPS plastic of embodiment 12.
Embodiment 13
Take various heat-resistant agent component according to embodiment 13 data corresponding in table 3, according to method described in embodiment 8, obtain the automotive upholstery flame-proof heat-resistant HIPS plastic of embodiment 13.
Test case 2
Test the resistance toheat of the HIPS plastic of embodiment 8-13, test its heat-drawn wire (HDT, 1.8MPa), test result is in table 4.
The HIPS plastic thermotolerance test chart of table 4: embodiment 8-13
| Heat-drawn wire/DEG C | |
| Embodiment 8 | 129 |
| Embodiment 9 | 109 |
| Embodiment 10 | 121 |
| Embodiment 11 | 119 |
| Embodiment 12 | 114 |
| Embodiment 13 | 102 |
By the test result in table 4, the heat-drawn wire of the HIPS plastic that embodiment 8-13 obtains is obtained for and significantly improves, especially embodiment 8 employs the composite heat-resistant agent of Magnesium Stearate, methyl tin three (isooctyl mercaptoacetate), dibutyl tin laurate and three (4-nonyl phenyl) phosphorous acid ester, be compared to embodiment 9-13, when using the heat-resistant agent of equal consumption, heat-drawn wire is higher, more significantly enhances the resistance toheat of HIPS plastic.
Therefore, the heat-resisting HIPS plastic of halogen-free flameproof of the present invention can significantly improve flame retardant resistance, thermotolerance, and preparation technology is simple, and product cost is low, and the over-all properties of product is more excellent.Other auxiliary agents can also be added adaptively, as antiaging agent, lubricant, photostabilizer, oxidation inhibitor, nucleator, softening agent, tinting material and static inhibitor etc., in order to improve other aspect performances.
Automotive upholstery flame-proof heat-resistant HIPS plastic of the present invention, can be processed into the part of different shape easily, can be used for making automobile inside gadget by Shooting Technique.
The above; be only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; any those of ordinary skill in the art are in the technical scope disclosed by the present invention; the change can expected without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (5)
1. the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof, is characterized in that, comprises the component of following weight parts:
HIPS resin 100 parts,
Fire retardant 2-15 part,
Heat-resistant agent 1-8 part;
Described fire retardant is made up of the component of following weight parts:
Described heat-resistant agent is made up of the component of following weight parts:
2. the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof as claimed in claim 1, is characterized in that, comprise the component of following weight parts:
HIPS resin 100 parts,
Fire retardant 5-15 part,
Heat-resistant agent 4-8 part.
3. the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof as claimed in claim 1, it is characterized in that, the polymerization degree of described ammonium polyphosphate is 21-26.
4. the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof as claimed in claim 1, is characterized in that, comprise the component of following weight parts:
5. the preparation method of the heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof according to any one of claim 1-4, it is characterized in that, comprise the following steps: take raw material by proportioning, after fully mixing 5-10 minute at a high speed, add twin screw extruder, at 170-200 DEG C of extruding pelletization.
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| CN105061915A (en) * | 2015-08-04 | 2015-11-18 | 金宝丽科技（苏州）有限公司 | High-heat stability antistatic polystyrene composite material and preparation method thereof |
| CN107828139A (en) * | 2017-10-12 | 2018-03-23 | 费全中 | Household electrical appliances flame-retarding HIPS plastics and its production technology |
| CN109517315B (en) * | 2018-11-16 | 2021-03-30 | 上海瀚氏科技集团有限公司 | Antibacterial plastic for automotive interior parts and production process thereof |
| CN109735017A (en) * | 2019-01-15 | 2019-05-10 | 胡敏悫 | A kind of penholder and its production technology |
| CN115181344B (en) * | 2022-07-28 | 2023-08-22 | 金发科技股份有限公司 | High heat-resistant flame-retardant HIPS material and preparation method and application thereof |
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