CN107974021A - A kind of high durable ASA film PP Pipe Compounds and preparation method and application - Google Patents
A kind of high durable ASA film PP Pipe Compounds and preparation method and application Download PDFInfo
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- CN107974021A CN107974021A CN201610932003.8A CN201610932003A CN107974021A CN 107974021 A CN107974021 A CN 107974021A CN 201610932003 A CN201610932003 A CN 201610932003A CN 107974021 A CN107974021 A CN 107974021A
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
A kind of high durable ASA film PP Pipe Compounds the present invention relates to polymeric material field and preparation method and application.The high durable ASA film PP Pipe Compounds of the present invention, include the following components in terms of parts by weight：Wherein, counted by 100 parts by weight of ASA resin dosage, each component parts by weight are as follows：Counted by 100 parts by weight of ASA resin dosage, other each component parts by weight are as follows：5~55 parts of POE, 0.2~4 part of bulking agent, 0.1~5 part of lubricant, 0.2~5 part of light stabilizer, 0.2~3 part of antioxidant, 0.5~9 part of pigment.It the described method comprises the following steps：1st, each component has been weighed according to the above ratio spare；2nd, it is first that lubricant, light stabilizer, antioxidant, pigment is first after mixing, add the components such as ASA resin and remix uniformly；3rd, by uniformly mixed material extruding pelletization, high durable ASA film PP Pipe Compounds are prepared.The present invention is compared with prior art：Have the advantages that speed of production is fast, thickness is stable, color is uniform, tearing strength is high, weather resistance is excellent.
Description
Technical field
The present invention relates to the ASA resin composition of polymeric material field, furtherly, is related to a kind of high durable ASA
Film PP Pipe Compound and preparation method and application.
Background technology
In recent years, developing rapidly with real estate industry, the PVC profile of plastic door-window develops also rapidly, mesh
Before untill, domestic annual output is more than 4,000,000 tons；As the improvement of people's living standards, former machine-made white plastic door
Window cannot meet the needs of market, and it is desirable for motley colored plastic windows and doors, the door and window shaped plastics of early stage
Material colorization is realized by entire body coloring, but the weatherability of entire body polychloroethylene section bar is extremely difficult to 6000h xenon lamp agings
Aberration is less than 5 requirement afterwards, is gradually substituted by other materials.
ASA (English names:Acrylonitrile Styrene acrylate copolymer) it is esters of acrylic acid rubber
Colloid and acrylonitrile, the copolymer of styrene, if containing double bond in high molecular polymer, double bond is easily larger by energy intensity
Sunlight in ultraviolet opened, thereby result in the degraded of high molecular polymer, and ASA is exactly with being free of unsaturated double-bond
Acrylic rubber instead of the butadiene rubber containing unsaturated double-bond in ABS, therefore, can not only draw to ultraviolet radiation resisting
Degraded, aging, the colour fading risen, while have strong guarantee to decomposing or changing colour caused by the high temperature in process, thus pole
The big anti-aging and weathering performance for improving material.According to test result, the anti-aging property of ASA is more than 10 times of ABS.
ASA is widely used in automotive field earliest, gradually pushes building materials market to later, is widely used in PVC colour section bars, synthetic resin
Watt and exterior wall cladding etc..
So far, colored PVC profile constitutes about more than half of total dosage, and developing rapidly for colour section bar, solves
The discoloration problem of white section bar in the past, but in use, because it uses ASA or its modified materials to be coextruded and prepare, it is welded
Angle is easily cracked, and causes a large amount of disputes.In addition, because coextrusion processes determine there is inevitable extrusion on the surface of section bar
The defects of trace.More advanced technique is needed to meet the needs of market, by the coating technique of ASA films, but at present
In the market, without the dedicated ASA PP Pipe Compounds of film.
The ASA that existing market is sold does not roll the PP Pipe Compound of film forming based on being mainly molded and extrude, and is extruded into
Type, in order to ensure the minimum thickness of coextruded layer, it is necessary to average thickness be far longer than minimum thickness, and co-extrusion layer thickness is thicker,
It is bigger for the Effect on Mechanical Properties of material；In addition, the product surface of coextrusion inevitably has extrusion trace, influence outside it
See, market needs ASA film PP Pipe Compounds.
It was mostly in the past individual layer PVC film in the field of Weather-proof film, because its weatherability is poor, existing its is applied indoors substantially,
In addition, also multilayer complex films such as PVC/PVDF, PMMA/PVDF, its weather resistance is excellent, but price is very expensive.Market
Be badly in need of being used in outdoor use, high durable, cost-effective film.
The Chinese patent of Application No. 201510216057.X provide a kind of ASA composite membranes that can be laminating with metal and its
Prepare and apply, it discloses a kind of acrylonitrile-styrene-acrylic ester ternary graft copolymer (ASA) that can be laminating with metal
The preparation method and applications of composite membrane.The method comprising the steps of：Hot melt adhesive by extruder heating extrusion after through salivate head
Outflow, doubling roller press together ASA films and hot melt adhesive；Doubling roller is made of guide-in roller and water chill rolls；ASA films, which overlay on, leads
Enter on roller, the movement of ASA film stretchings is driven by the rotation of guide-in roller and water chill rolls；Hot melt adhesive flow to water chill rolls through salivating head
On, ASA films and hot melt adhesive are pressed together by the rotation of guide-in roller and water chill rolls；The head temperature of extruder is 150
~190 DEG C, the temperature for salivating head is 180~195 DEG C；The water temperature of water chill rolls is 10~30 DEG C.ASA composite membranes are covered with metal
After conjunction, smooth, bubble-free, the resistance to acid and alkali of the laminating plate of metal of the ASA composite membranes with metallic plate after laminating is excellent, the stripping of ASA
Intensity is high.Its disclosed technical solution is to prepare hot melt adhesive and the composite membrane of ASA, does not provide the ASA films of single component.
The content of the invention
In order to solve the above-mentioned problems in the prior art, the present invention proposes a kind of high durable ASA film PP Pipe Compounds.Tool
Say body and be related to a kind of high durable ASA film PP Pipe Compounds and preparation method and application.The high durable ASA films of the application are special
Material, can prepare the ASA films for being as thin as 0.05mm to 0.2mm, cost performance higher, and weatherability is excellent.
One of the object of the invention is to provide a kind of high durable ASA film PP Pipe Compounds, comprising in terms of parts by weight with the following group
Point：
Wherein, counted by 100 parts by weight of ASA resin dosage, each component parts by weight are as follows：
Wherein, melt flow rate have impact on the processing performance of material, if too high, it is difficult to extrusion molding, if too low,
It is difficult to carry out the small film preparation of wide cut, thickness, and influences the thickness evenness of film.The ASA trees of the application
The melt flow rate of fat is between 6~15g/10min, between preferably 8~12g/10min.
The POE is the copolymer of ethene and alpha-olefin, and alpha-olefin can be 1- hexenes or 1- octenes or more Long carbon chain α-alkene
At least one of hydrocarbon, part by weight of the alpha-olefin in comonomer is between 20%-30%.The addition of POE, is conducive to
The casting film-forming processing of ASA.
The bulking agent is Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene to graft glycidyl methacrylate, polyethylene
It is grafted at least one of fumaric acid anhydride etc..Bulking agent is conducive to ASA and POE therebetween compatible.
The lubricant is organosilicon compound, and specific can be is selected from dimethyl silicone polymer and/or polymethyl-benzene
Radical siloxane, molecular weight is between 20 ten thousand to 100 ten thousand.Organic silicon lubricant not only can guarantee that the superficiality of the film of processing
Can, also advantageously improve anti-scratch ability.
The antioxidant is selected from least one of Hinered phenols antioxidant, phosphoric acid ester antioxidant；Or commercially available it is obstructed
The compound antioxidant of phenolic antioxidant and phosphoric acid ester antioxidant, such as the antioxidant B225 of BASF joint-stock company；Work as antioxygen
When agent is selected from the mixture of Hinered phenols antioxidant and phosphoric acid ester antioxidant, Hinered phenols antioxidant and phosphoric acid ester antioxidant
Weight ratio be preferably 1:(1~3), more preferably 1:(1.5~2.5).
The Hinered phenols antioxidant preferably is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythrites
Ester, N, N'- couples-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, (3,5- di-t-butyls -4- of 1,3,5- tri-
At least one of hydroxybenzyl) isocyanuric acid；The phosphoric acid ester antioxidant preferably is selected from three (2,4- di-tert-butyl-phenyls) Asia
At least one of phosphate, double (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites.
The light stabilizer is selected from { (6- morpholinyl -5- triazine -2,4- diyls) (the 2,2,6,6- tetramethyl piperidines of UV 3346
Base) imido grpup hexa-methylene [(2,2,6,6- tetramethyl-piperidyls)-imido grpup], (2- hydroxyl -4- n-octyloxies two of UV 531
Benzophenone), UV-5411 (2- (2 '-hydroxyl -5 '-t-octyl)-benzotriazole) or UV-770 (double (2,2,6,6- tetramethyls -4-
At least one of piperidyl) sebacate), preferably UV 3346 and/or UV-5411.
Light stabilizer and antioxidant fusing point ratio generally in the art is relatively low, and the preferably more dystectic light of the present invention is steady
Determine agent and antioxidant, fusing point is generally not less than 100 DEG C.
The pigment is one or more compoundings of titanium dioxide, iron oxide, chrome yellow, organic pigment etc., and sun-proof rank is general
More than six grades.
The two of the object of the invention are to provide a kind of preparation method of high durable ASA film PP Pipe Compounds, comprise the following steps：
Comprise the following steps：1), weigh：Each component is weighed according to the above ratio spare；2), batch mixing：First by lubricant,
Light stabilizer, antioxidant, pigment first after mixing, add the other components including ASA resin etc., are uniformly mixed；3), squeeze
Go out：The material extruding pelletization that will be uniformly mixed, to obtain the final product.Wherein, in extruding pelletization step, the abilities such as double screw extruder can be used
The common instrument in domain, from charge door to head outlet for 150~180 DEG C, 200~220 DEG C, 220~240 DEG C, 220~250 DEG C,
220~250 DEG C, 50~100rpm of screw speed, extrusion material strip is cooled down by sink, pelletizing, it is dry after that high durable ASA is made is thin
Film special material.
The three of the object of the invention are application of the high durable ASA film PP Pipe Compounds on film is prepared.
The film of thickness 0.05mm to 0.2mm can be produced using the high durable ASA films PP Pipe Compound of the present invention.Film
Preparation method be curtain coating film production process commonly used in the prior art.The one kind produced by melt salivation and then cooling and shaping
The cast film of tensionless winkler foundation, non-directional.Raw material plastifying fusion in an extruder, then melt from molding die lip constant speed,
It is cast in cooling roller surface and is cooled and shaped evenly, then winds finished product after the devices such as stripping.
Relative to coextrusion processes commonly used in the prior art, thickness is difficult to equal control, easily produces extrusion trace in addition,
Influence products appearance；The ASA film PP Pipe Compounds that the application provides, the film prepared with its extrusion curtain coating can be applied in PVC-U
The fields such as section bar, synthetic resin watt, composited steel and plastic decking, in addition, ASA surfaces easily scratch；And the application is whole by modified raising
Body weatherability, prepares individual layer high durable film, thus it is more economical, and improve scratch resistant performance.
Technical scheme is compared with prior art：With speed of production is fast, thickness is stable, color is uniform, tear
The advantages that intensity is high, weather resistance is excellent.
Embodiment
With reference to embodiment, the present invention is further illustrated.But the present invention is not restricted by the embodiments.
Embodiment 1
(1) weigh ASA resin 32.5kg, POE12.5kg, bulking agent 0.5kg, lubricant 0.4kg, light stabilizer 0.6kg,
Antioxidant 0.5kg, pigment 0.6kg (ASA resin, WE8100, Formosa Chemical ＆ Fiber Corporation, melt index 11g/
min；POE, 8411, DOW chemical companies, for ethene and the copolymer of 1- octenes；Bulking agent is Research of Grafting Malaic Anhydride Onto Polyethylene,
1040H, Guangzhou Hao Su Chemical Co., Ltd.s；Lubricant, is silicone plasties lubricant, and the triumphant outstanding plastic toughening material in Jiande City has
Limit company produces, and is dimethyl silicone polymer, molecular weight about 800,000；Light stabilizer, UV5411, U.S.'s cyanogen specialization work；Antioxidant,
B225, BASF AG；Pigment, Green410, Xue Te companies of the U.S.), and be mixed uniformly；First by lubricant, light stabilizer,
Antioxidant, pigment are uniformly mixed, and then add ASA resin, bulking agent, POE, are uniformly mixed；
(2) uniformly mixed material is transported to double screw extruder, from charge door to head outlet be 170 DEG C, 210
DEG C, 230 DEG C, 240 DEG C, 240 DEG C, screw speed 60rpm, extrusion material strip is cooled down by sink, pelletizing, it is dry after prepare high durable
ASA film PP Pipe Compounds.
Embodiment 2
(1) weigh ASA resin 37.5kg, POE7.5kg, bulking agent 0.5kg, lubricant 0.3kg, light stabilizer 0.6kg,
Lubricant, light stabilizer, antioxidant, pigment, are first uniformly mixed by antioxidant 0.5kg, pigment 0.6kg, then add ASA trees
Fat, bulking agent, POE, are uniformly mixed；
(2) uniformly mixed material is transported to double screw extruder, from charge door to head outlet be 170 DEG C, 210
DEG C, 230 DEG C, 240 DEG C, 240 DEG C, screw speed 60rpm, extrusion material strip is cooled down by sink, pelletizing, it is dry after prepare high durable
ASA film PP Pipe Compounds.
High durable ASA film PP Pipe Compound performance tests
High durable ASA films PP Pipe Compound prepared by embodiment 1 and embodiment 2 is carried out to the survey of physical property as follows
Examination, experimental result are shown in Table 1.
Melt index：Tested according to GB/T 3682-2000,220 DEG C of temperature, load 10kg；
Tensile strength：Tested according to GB/T 1040.2-2006, draw speed 50mm/min；
Bending strength and bending modulus：Tested according to GB/T 9341-2008, test speed 2mm/min；
Notch impact strength：Tested according to GB/T 1043.1-2008, using 1eA type samples；
Xenon lamp aging test condition：Carried out according to the A methods of GB/T 16422.2-1999；
Color measuring condition：CIED65 light sources, 8/d include mirror-reflection, measure aperture 19mm.
The test result of 1 high durable ASA film PP Pipe Compound physical properties of table
| Test event | Embodiment 1 | Embodiment 2 |
| Melt index, g/10min | 11.5 | 12.3 |
| Tensile strength, MPa | 41.2 | 44.6 |
| Bending strength, MPa | 68.2 | 70.1 |
| Bending modulus, MPa | 1820 | 1960 |
| Notch impact strength, kJ/m2 | 32.3 | 28.2 |
| Xenon lamp aging (6000h) | 2.5 | 2.8 |
Film performance test
High durable ASA film PP Pipe Compounds prepared by embodiment 1 and embodiment 2 are made to the film of 0.05mm thickness, test is thin
Film properties, the results are shown in Table 2.
Films test method：
Tearing strength：Tested according to QB/T 1130-1991；
Xenon lamp aging test condition：Carried out according to the A methods of GB/T 16422.2-1999；
Color measuring condition：CIED65 light sources, 8/d include mirror-reflection, measure aperture 19mm.
Wherein, the preparation method of film is：By raw material plastifying fusion in an extruder, then melt is from molding die lip
Constant speed, equably be cast to cooling roller surface on be cooled and shaped, finished product is then wound after stripping off device.The processing of casting machine
Temperature is as follows：Body temperature is 175 DEG C -200 DEG C -220 DEG C -220 DEG C -215 DEG C -220 DEG C, head temperature is respectively 225 DEG C -
230℃-225℃-230℃-225℃。
2 high durable ASA film performances of table
| Test event | 1 film of embodiment | 2 film of embodiment |
| Appearance | The defects of without extrusion trace | The defects of without extrusion trace |
| Thickness deviation, % | 2 | 2 |
| Color homogeneity | 0.1 | 0.2 |
| Tearing strength, N/mm | 113 | 126 |
| Xenon lamp aging (6000h) | 2.6 | 2.9 |
It can be seen that the film splitting intensity of preparation is high, is conducive to the application of next step, avoids in overlay film application process because opening
Split and caused by production process interruption；Weather resistance is excellent can apply indoors, outdoor various occasions；In addition, using single
Tunic technique, comparatively production finished product is lower, and product cost is high.
Claims (10)
1. a kind of high durable ASA film PP Pipe Compounds, it is characterised in that include following components in parts by weight：
Wherein, counted by 100 parts by weight of ASA resin dosage, each component parts by weight are as follows：
A kind of 2. high durable ASA film PP Pipe Compounds according to claim 1, it is characterised in that comprising in parts by weight with
Lower component：
Wherein, counted by 100 parts by weight of ASA resin dosage, each component parts by weight are as follows：
A kind of 3. high durable ASA film PP Pipe Compounds according to claim 1 or 2, it is characterised in that：
The melt flow rate of the ASA resin is between 6~15g/10min, between preferably 8~12g/10min.
A kind of 4. high durable ASA film PP Pipe Compounds according to claim 1 or 2, it is characterised in that：
The POE is the copolymer of ethene and alpha-olefin, and the alpha-olefin is selected from 1- hexenes or 1- octenes or more Long carbon chain α-alkene
At least one of hydrocarbon, part by weight of the alpha-olefin in comonomer is between 20%~30%.
A kind of 5. high durable ASA film PP Pipe Compounds according to claim 1 or 2, it is characterised in that：
The bulking agent is selected from Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene to graft glycidyl methacrylate, polyethylene and connects
At least one of branch fumaric acid anhydride.
A kind of 6. high durable ASA film PP Pipe Compounds according to claim 1 or 2, it is characterised in that：
The lubricant is organosilicon compound, and the organosilicon compound is selected from dimethyl silicone polymer and polymethyl-benzene
At least one of radical siloxane, molecular weight is between 20 ten thousand to 100 ten thousand.
A kind of 7. high durable ASA film PP Pipe Compounds according to claim 1 or 2, it is characterised in that：
The antioxidant is selected from least one of Hinered phenols antioxidant, phosphoric acid ester antioxidant；
The light stabilizer is selected from { (6- morpholinyl -5- triazine -2,4- diyls) (2,2,6,6- tetramethyl-piperidyls) imido grpup six
Methylene [(2,2,6,6- tetramethyl-piperidyls)-imido grpup] }, 2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyl-
5 '-t-octyl) at least one of-benzotriazole or double (2,2,6,6- tetramethyl -4- piperidyls) sebacates, preferably { (6-
Morpholinyl -5- triazine -2,4- diyls) (2,2,6,6- tetramethyl-piperidyls) imido grpup hexa-methylene [(2,2,6,6- tetramethyl piperazines
Piperidinyl)-imido grpup] and/or 2- (2 '-hydroxyl -5 '-t-octyl)-benzotriazole；
The pigment is selected from least one of titanium dioxide, iron oxide, chrome yellow, organic pigment.
8. according to a kind of preparation method of high durable ASA film PP Pipe Compounds of any one of them of claim 1~7, its feature
It is to comprise the following steps：
First lubricant, light stabilizer, antioxidant, pigment are uniformly mixed, then added comprising other groups including ASA resin
Point, it is uniformly mixed；The material extruding pelletization that will be uniformly mixed, to obtain the final product.
A kind of 9. preparation method of high durable ASA film PP Pipe Compounds according to claim 8, it is characterised in that：
During extruding pelletization, from charge door to head outlet for 150~180 DEG C, 200~220 DEG C, 220~240 DEG C,
220~250 DEG C, 220~250 DEG C, 50~100rpm of screw speed.
10. according to a kind of high durable ASA film PP Pipe Compounds of any one of them of claim 1~7 answering on film is prepared
With.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112080214A (en) * | 2020-09-03 | 2020-12-15 | 苏州凯伦高分子新材料科技有限公司 | Building composite film |
| CN112239633A (en) * | 2020-10-15 | 2021-01-19 | 青岛未来塑胶有限公司 | Repairing material containing ASA film for outdoor house, preparation process and film laminating method |
| CN114290778A (en) * | 2021-12-28 | 2022-04-08 | 山东结力新材料科技有限公司 | High-weather-resistance POE decorative composite film and manufacturing method thereof |
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| CN102372891A (en) * | 2010-08-22 | 2012-03-14 | 山东道恩高分子材料股份有限公司 | Special acrylonitile-styrene-acrylate color masterbatch |
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| CN112080214A (en) * | 2020-09-03 | 2020-12-15 | 苏州凯伦高分子新材料科技有限公司 | Building composite film |
| CN112239633A (en) * | 2020-10-15 | 2021-01-19 | 青岛未来塑胶有限公司 | Repairing material containing ASA film for outdoor house, preparation process and film laminating method |
| CN114290778A (en) * | 2021-12-28 | 2022-04-08 | 山东结力新材料科技有限公司 | High-weather-resistance POE decorative composite film and manufacturing method thereof |
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Application publication date: 20180501 |