CN101759913A - Novel scratch-proof polypropylene material and preparation method thereof - Google Patents

Novel scratch-proof polypropylene material and preparation method thereof Download PDF

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Publication number
CN101759913A
CN101759913A CN200810203129A CN200810203129A CN101759913A CN 101759913 A CN101759913 A CN 101759913A CN 200810203129 A CN200810203129 A CN 200810203129A CN 200810203129 A CN200810203129 A CN 200810203129A CN 101759913 A CN101759913 A CN 101759913A
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China
Prior art keywords
polypropylene
proof
scratch
mar
novel scratch
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CN200810203129A
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康兴宾
张鹰
张祥福
周文
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Shanghai Pret Composites Co Ltd
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Shanghai Pret Composites Co Ltd
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Priority to CN200810203129A priority Critical patent/CN101759913A/en
Publication of CN101759913A publication Critical patent/CN101759913A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B29C48/9185Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92514Pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92561Time, e.g. start, termination, duration or interruption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

Abstract

The invention discloses novel scratch-proof polypropylene material which is prepared from the following materials by weight percent: 55-98 polypropylene, 0-35 inorganic filling, 0-20 flexibilizer POE, 0.5-10 scratch-proof additive, 0.1-2 antioxidant, 0.1-1 light stabilizer and 0-5 other additives. By adding the additive capable of effectively improving the scratch resistance in the basic ingredients of the polypropylene compound material, the invention can prepare polypropylene compound material with better scratch resistance. The invention has the advantages that: 1, appropriate amount of scratch-proof additive is added to the compound material system, so the polypropylene compound material prepared through the method has better scratch resistance; 2, the scratch resistance of the polypropylene compound material prepared through the method is ensured while the physical mechanical properties of the material are barely affected; and 3, through the method for improving the scratch resistance of the polypropylene compound material, the preparation process is simple and the production cost is low.

Description

A kind of novel scratch-proof polypropylene material and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of novel scratch-proof polypropylene matrix material, can be used for automobile and field of household appliances, belong to polymer modification and processing technique field.
Background technology
Polypropylene has good processing properties and physics, mechanics, chemical property because of it, simultaneously light weight, inexpensive thereby be widely used in inner and outer decorative parts of automobile.The shape and the condition of surface of some vitals of inside gadget such as dashboard, door-plate directly affect the attractive in appearance of car, so motor corporation has proposed corresponding requirement to the mar-proof performance of associated materials.Polypropylene has influenced its application in automotive material because of mar-proof performance is relatively poor, the mar-proof performance that therefore how to improve polypropylene material becomes the urgent problem of this class material of exploitation.
The mar-proof performance of relevant raising polypropylene has some reports, has proposed some solutions, fills as polypropylene to strengthen, and improves polyacrylic degree of crystallinity, adds the method that some contain organo-siloxane.
Foreign patent WO02051933 relates to the mar-proof performance of improving material with the method for mica instead of part talcum powder raising material hardness.Japanese patent laid-open 6-220270 is reported in the polypropylene modification and improves surface hardness by adding nucleator, reaches the purpose of improving mar-proof performance, finds to increase rubber consumption simultaneously and also can improve mar-proof performance.U.S. Pat 5585420 and US5731376 relate to the mar-proof performance that the method that adds high molecular weight siloxane improves material, and be not mentioned rubber toughened.Chinese patent CN1580115A mentions the rubber toughened technology that adopts, and adds the high molecular silicone elastomer and nucleator NA-21 makes the rigidity of material and toughness reach good balance.Adopt high-crystallinity polypropylene and talcum powder blend among the Chinese patent CN 1631959A, prepared and have the heat-stable mar-proof talc powder filled polypropylene of high rigidity height.
Summary of the invention
The purpose of this invention is to provide modified polypropylene material of a kind of mar-proof, anti-light aging and resistance toheat and preparation method thereof.
In order to improve the mar-proof performance of polypropylene composite material, technical scheme of the present invention is that a kind of fluorine of adding is mar-proof auxiliary agent in the basic components of polypropylene material, and this auxiliary agent can improve the mar-proof performance in the polypropylene composite material effectively.This fluorine is that mar-proof auxiliary agent is a kind of low-molecular-weight polytetrafluoroethylene (PTFE) white powder, has lubricated and antiwear characteristic.
This novel scratch-proof polypropylene matrix material is mixed with by following raw materials by weight percent:
Polypropylene 55~98
Mineral filler 0~35
Toughner POE 0~20
Mar-proof auxiliary agent 0.5~10
Oxidation inhibitor 0.1~2
Photostabilizer 0.1~1
Other auxiliary agents 0~5
In the polypropylene composite material system that the present invention was suitable for, described polypropylene is a melt flow rate (MFR) (test condition: 230 ℃ * 2.16kg) high crystallization homo-polypropylene or the block copolymerization propylene between 5~50g/10min, wherein the comonomer of block copolymerization propylene is common is ethene, its content is in the scope of 4~10mol%, the degree of crystallinity of high-crystallinity polypropylene is more than 70%, and degree of isotacticity is greater than 99%; Described mineral filler is talcum powder, lime carbonate, barium sulfate or their composition, and its particle size range is 1~10 micron; Described toughner POE is linear ethylene-octene copolymer, and density is 0.88~0.90g/cm 3, melting index is 0.5~15g/10min (test condition: 190 ℃ * 2.16kg); Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant can select for use hindered phenol or thioesters kind antioxidant as 3114,1010, DSTP wherein one or more; Auxiliary anti-oxidant can select for use the phosphorite kind antioxidant as 618,168 etc.; Described photostabilizer can select for use hindered amine light stabilizer as one or more the composition in 944,770.
Fluorine of the present invention is that mar-proof auxiliary agent is a kind of low-molecular-weight PTFE white powder, and diameter of particle is between 3-7 μ m.Described mar-proof auxiliary agent, its addition is weight percentage 0.5~10%, and the addition of better effects if is 1~5%.
Other auxiliary agents of the present invention comprise shades of colour additive, various ester series lubricant agent or fatty acid lubricant etc.
The preparation method of the illumination aging resisting performance of this raising polypropylene composite material is as described below:
(1) takes by weighing raw material by weight ratio;
(2) polypropylene, talcum powder, thermoplastic elastomer, mar-proof auxiliary agent, oxidation inhibitor, photostabilizer or other additives were done in super mixer mixed 3~5 minutes;
(3) raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: 190~200 ℃ in a district, 200~210 ℃ in two districts, 210~220 ℃ in three districts, 205~215 ℃ in four districts; The residence time of whole extrusion is 1~2 minute, and pressure is 12~18MPa.
The present invention adds in the basic components of polypropylene composite material a kind ofly can improve the auxiliary agent of mar-proof performance effectively, can better polypropylene composite material thereby prepare scratch-resistant.
Advantage of the present invention is:
1, the present invention uses an amount of mar-proof auxiliary agent in composite system, makes polypropylene compound material prepared have better mar-proof characteristic.
2, polypropylene compound material prepared of the present invention is when guaranteeing the mar-proof performance of material, and every physical and mechanical property of material is unaffected substantially.
3, the method preparation technology who improves the mar-proof performance of polypropylene composite material of the present invention's proposition is simple, production cost is low.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and Comparative Examples composite-material formula, described polypropylene is different mobile homo-polypropylene and block copolymerization propylene, and consumption is 50~98% (weight %).Wherein the comonomer of block copolymerization propylene is common is ethene, its content is in the scope of 4~10mol%, the degree of crystallinity of homo-polypropylene is more than 70%, degree of isotacticity is greater than 99%, polyacrylic melt flow rate (MFR) (test condition: 230 ℃ * 2.16kg) be 2~60g/10min, more commonly used is 5~30g/10min.The particle size range of described talcum powder, lime carbonate, mica or barium sulfate is 1~10 micron.Described toughner POE is linear ethylene-octene copolymer that E.I.Du Pont Company produces, and density is 0.88~0.90g/cm 3, melting index is 0.5~15g/10min (test condition: 190 ℃ * 2.16kg).Described fluorine is that mar-proof auxiliary agent is a kind of low-molecular-weight PTFE white powder, and diameter of particle is between 3-7 μ m.Described primary antioxidant is the DSTP that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester, and Ciba company produce 3114, trade names are Irganox 3114, and chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid.Auxiliary anti-oxidant is 168 of Ciba company product, and trade names are Irgafos 168, and chemical name is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Described photostabilizer is 944 of Ciba company product, and chemical name is poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] }, and Ciba company produce 770, chemical name be pairs (2,2,6, the 6-tetramethyl-piperidyl) sebate.Comprise shades of colour additive, various ester class or fatty acid lubricant etc. in addition.
Resin and various additive do to mix in super mixer 3~5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: 190~200 ℃ in a district, 200~210 ℃ in two districts, 210~220 ℃ in three districts, 205~215 ℃ in four districts; The residence time of whole extrusion is 1~2 minute, and pressure is 12~18Mpa.
Performance evaluation mode and implementation standard:
With the particulate material for preparing as stated above, drying is 2~3 hours in 90~100 ℃ convection oven, and then the particulate material that drying is good carries out the injection molding sample preparation on injection moulding machine.
Mar-proof performance test: injection molding size of sample 150 * 100 * 3.2mm, with hand-held hardness test pen load is 10N, the nib diameter is that 0.75mm carries out scratch test on the model surface, cut is 2mm at interval, each stroke of vertical and horizontal 10-20 bar line, the color and luster that grid material is drawn in the color measurement system testing of adopting Japanese Minolta company to produce changes, the Δ L value of recording materials, thereby the mar-proof performance of discriminating material.
Melt flow rate (MFR) (MFR) is measured: undertaken by the ISO1183 standard, probe temperature is 230 ℃, load 2.16kg;
The tensile property test: undertaken by ISO 527-2 standard, specimen size is 170*10*4mm, and draw speed is 50mm/min;
The bending property test: undertaken by ISO 178 standards, specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm, and modulus in flexure is undertaken by tangential direction;
The simple beam impact strength test: undertaken by ISO 179 standards, specimen size is 80*6*4mm, and notch depth is 1/3rd of a sample thickness;
Comprehensive mechanical performance is passed judgment on by the numerical value of shock strength, notched Izod impact strength, tensile strength, flexural strength and the modulus in flexure of test gained.
The mar-proof performance of material is according to the PV3952 standard code, passes judgment on the photostabilization grade according to the value of the colour-change scale Δ L of material surface.The numerical value of Δ L is more little, and the mar-proof performance of expression material is good more, and mar-proof grade is also just high more.Example formulations and every The performance test results be each table as follows:
Table 1 embodiment 1-6 material prescription and every performance test
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
??M2600R??wt% ??79.55 ??77.55 ??75.55 ??82.55 ??84.55 ??39.55
Talc 1250 order wt% ??12 ??12 ??12 ??12 ??- ??35
??POE?wt% ??5 ??5 ??5 ??- ??10 ??20
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
??PTFE?LF-100wt% ??1 ??3 ??5 ??3 ??3 ??3
??3114wt% ??0.15 ??0.15 ??0.15 ??0.15 ??0.15 ??0.15
??DSTP?wt% ??0.3 ??0.3 ??0.3 ??0.3 ??0.3 ??0.3
??168wt% ??0.2 ??0.2 ??0.2 ??0.2 ??0.2 ??0.2
??944wt% ??0.3 ??0.3 ??0.3 ??0.3 ??0.3 ??0.3
??770wt% ??0.3 ??0.3 ??0.3 ??0.3 ??0.3 ??0.3
Toner wt% ??1.2 ??1.2 ??1.2 ??1.2 ??1.2 ??1.2
Melting index (g/10min) ??24.4 ??24.2 ??24.1 ??28.2 ??23.1 ??17.4
Density (g/cm 3) ??0.982 ??0.990 ??1.001 ??0.994 ??0.915 ??1.151
Notched Izod impact strength (kJ/m 2) ??8.4 ??7.8 ??7.7 ??4.8 ??22.0 ??42
Tensile strength (MPa) ??19.0 ??19.8 ??20.3 ??24.5 ??18.0 ??15.2
Flexural strength (MPa) ??33.0 ??33.4 ??35.1 ??36.0 ??24.2 ??23.0
Mar-proof performance (Δ L) ??1.8 ??1.5 ??1.4 ??1.4 ??1.6 ??1.7
Table 2 Comparative Examples 1-4 material prescription and every performance test
Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4
??M2600R??wt% ??80.55 ??85.55 ??87.55 ??52.55
Talc 1250 order wt% ??12 ??12 ??- ??35
??POE?wt% ??5 ??- ??10 ??20
Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4
??PTFE?LF-100wt% ??- ??- ??- ??-
??3114wt% ??0.15 ??0.15 ??0.15 ??0.15
??DSTP?wt% ??0.3 ??0.3 ??0.3 ??0.3
??168wt% ??0.2 ??0.2 ??0.2 ??0.2
??944wt% ??0.3 ??0.3 ??0.3 ??0.3
??770wt% ??0.3 ??0.3 ??0.3 ??0.3
Toner wt% ??1.2 ??1.2 ??1.2 ??1.2
Melting index (g/10min) ??24.4 ??28.0 ??22.1 ??17.2
Density (g/cm3) ??0.982 ??0.990 ??0.902 ??1.140
Notched Izod impact strength (kJ/m2) ??8.5 ??4.7 ??23.0 ??43
Tensile strength (MPa) ??18.8 ??24.8 ??18.2 ??15.0
Flexural strength (MPa) ??32.0 ??36.7 ??23.8 ??22.8
Mar-proof performance (Δ L) ??2.0 ??1.8 ??1.8 ??2.1
From the contrast of embodiment 1-3 and Comparative Examples 1 and embodiment 4,5,6 respectively with the contrast of Comparative Examples 2,3,4 as can be seen, PTFE auxiliary agent LF-100 improves a lot to the mar-proof performance of the polypropylene composite material system of toughner and talcum powder filling, and the mar-proof performance to raising PP material when wherein adding 3% LF-100 is comparatively remarkable.Therefore addition be controlled at about 3% (weight %) the most suitable.At this moment, material not only possesses better mar-proof performance, and the basic physical and mechanical property of material also can keep preferably simultaneously.

Claims (11)

1. novel scratch-proof polypropylene material is mixed with by following raw materials by weight percent:
Polypropylene 55~98
Mineral filler 0~35
Toughner POE 0~20
Mar-proof auxiliary agent 0.5~10
Oxidation inhibitor 0.1~2
Photostabilizer 0.1~1
Other auxiliary agents 0~5.
2. a kind of novel scratch-proof polypropylene material according to claim 1 is characterized in that: described polypropylene is that melt flow rate (MFR) is high crystallization homo-polypropylene or the block copolymerization propylene of 5~50g/10min.
3. a kind of novel scratch-proof polypropylene material according to claim 2 is characterized in that: the comonomer of described block copolymerization propylene is an ethene, and its content is 4~10mol%.
4. a kind of novel scratch-proof polypropylene material according to claim 2, it is characterized in that: the degree of crystallinity of described high-crystallinity polypropylene is more than 70%, and degree of isotacticity is greater than 99%.
5. a kind of novel scratch-proof polypropylene material according to claim 1 is characterized in that: described mar-proof auxiliary agent is a kind of low-molecular-weight PTFE white powder, and diameter of particle is between 3-7 μ m, and the weight percent of its addition is 1~5%.
6. a kind of novel scratch-proof polypropylene material according to claim 1 is characterized in that: described mineral filler is one or more mixtures in talcum powder, lime carbonate and the barium sulfate, and its particle size range is 1~10 micron.
7. a kind of novel scratch-proof polypropylene material according to claim 1 is characterized in that: described toughner POE is linear ethylene-octene copolymer, and density is 0.88~0.90g/cm 3, melting index is 0.5~15g/10min.
8. a kind of novel scratch-proof polypropylene material according to claim 1, it is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant is hindered phenol or thioesters kind antioxidant; Auxiliary anti-oxidant is the phosphorite kind antioxidant.
9. a kind of novel scratch-proof polypropylene material according to claim 8 is characterized in that: primary antioxidant be 3114,1010 and DSTP in one or more mixing; Auxiliary anti-oxidant is as 618 and 168.
10. a kind of novel scratch-proof polypropylene material according to claim 1 is characterized in that: described photostabilizer is a hindered amine light stabilizer, as one or more the composition in 944,770.
11. a method for preparing the described novel scratch-proof polypropylene material of claim 1, its concrete steps are as follows:
(1) takes by weighing raw material by weight ratio;
(2) polypropylene, talcum powder, thermoplastic elastomer, mar-proof auxiliary agent, oxidation inhibitor, photostabilizer or other additives were done in super mixer mixed 3~5 minutes;
(3) raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: 190~200 ℃ in a district, 200~210 ℃ in two districts, 210~220 ℃ in three districts, 205~215 ℃ in four districts; The residence time of whole extrusion is 1~2 minute, and pressure is 12~18MPa.
CN200810203129A 2008-11-21 2008-11-21 Novel scratch-proof polypropylene material and preparation method thereof Pending CN101759913A (en)

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CN109721830A (en) * 2018-12-06 2019-05-07 宁波泰甬汽车零部件有限公司 High-gloss scraping-resistant extrusion grade modified polypropylene material, preparation method and outer water cut of automobile
CN109762258A (en) * 2018-12-17 2019-05-17 会通新材料股份有限公司 A kind of high scratch-proof polypropylene material and preparation method thereof
CN112048128A (en) * 2020-08-10 2020-12-08 金旸(厦门)新材料科技有限公司 Soft touch and scratch-resistant polypropylene composite material and preparation method thereof

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CN102532697A (en) * 2010-12-30 2012-07-04 合肥杰事杰新材料股份有限公司 High-toughness low-odor scratch-resistant polypropylene composition and preparation method thereof
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CN102286177A (en) * 2011-08-17 2011-12-21 金发科技股份有限公司 Polypropylene composition with low luster and excellent scratch resistance and preparation method thereof
CN102504413A (en) * 2011-11-14 2012-06-20 江门市奇德工程塑料科技有限公司 Polypropylene complex and preparation method thereof
CN102558677A (en) * 2011-12-26 2012-07-11 上海普利特复合材料股份有限公司 Novel scratch-resistant polypropylene composite material and preparation method thereof
CN103044769A (en) * 2012-12-10 2013-04-17 上海普利特复合材料股份有限公司 Polypropylene composite material with high strength and high elongation at break and preparation method thereof
CN104163990A (en) * 2013-05-16 2014-11-26 苏州御诚数码科技有限公司 Preparation method of polytetrafluoroethylene modified polypropylene composite material
CN104163987A (en) * 2013-05-16 2014-11-26 苏州御诚数码科技有限公司 Polytetrafluoroethylene modified polypropylene composite material
CN104086889A (en) * 2014-07-09 2014-10-08 安徽宁国市高新管业有限公司 Anti-aging MPP (modified polypropylene) electric tube
CN105385088A (en) * 2015-11-02 2016-03-09 金发科技股份有限公司 Polypropylene composition and preparation method thereof
CN105385088B (en) * 2015-11-02 2018-08-21 金发科技股份有限公司 A kind of polypropene composition and preparation method thereof
CN105255060A (en) * 2015-11-11 2016-01-20 深圳毅彩鸿翔新材料科技有限公司 PVC-MMA composite material and plastic product
CN105504530A (en) * 2015-12-30 2016-04-20 上海普利特复合材料股份有限公司 Wear-resistant polypropylene composite material and preparation method thereof
CN106390761A (en) * 2016-10-20 2017-02-15 合肥创想能源环境科技有限公司 Method for adopting general resin for preparing separation membranes
CN106496780A (en) * 2016-10-24 2017-03-15 珠海格力电器股份有限公司 There is high-fire resistance, the polypropylene material of strong mechanical performance, Preparation Method And The Use
CN109721830A (en) * 2018-12-06 2019-05-07 宁波泰甬汽车零部件有限公司 High-gloss scraping-resistant extrusion grade modified polypropylene material, preparation method and outer water cut of automobile
CN109762258A (en) * 2018-12-17 2019-05-17 会通新材料股份有限公司 A kind of high scratch-proof polypropylene material and preparation method thereof
CN112048128A (en) * 2020-08-10 2020-12-08 金旸(厦门)新材料科技有限公司 Soft touch and scratch-resistant polypropylene composite material and preparation method thereof

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Application publication date: 20100630