CN114230958A - Low-density high-performance scratch-resistant polypropylene material for automobiles and preparation method thereof - Google Patents
Low-density high-performance scratch-resistant polypropylene material for automobiles and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 86
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 53
- -1 polypropylene Polymers 0.000 title claims abstract description 38
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 31
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 229920000098 polyolefin Polymers 0.000 claims abstract description 4
- 239000012745 toughening agent Substances 0.000 claims abstract description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 20
- 229920001903 high density polyethylene Polymers 0.000 claims description 18
- 239000004700 high-density polyethylene Substances 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 10
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 6
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-N 0.000 claims description 2
- 238000012661 block copolymerization Methods 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000000806 elastomer Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 2
- 239000013585 weight reducing agent Substances 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007790 scraping Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000008187 granular material Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000009966 trimming Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a low-density high-performance scratch-resistant polypropylene material for automobiles and a preparation method thereof, wherein the polypropylene material comprises the following components in percentage by mass: 65-90% of polypropylene, 0-10% of polyethylene, 5-10% of filler, 5-15% of toughening agent, 0-1% of coupling agent, 0-2% of scratch-resistant auxiliary agent, 0-1% of toner and 0-1% of other functional auxiliary agents. According to the invention, through the filling of the modified special mineral and the toughening of a proper amount of elastomer, the modified polypropylene material has the characteristics of high modulus, high toughness, high fluidity, excellent scratch resistance and the like, and meanwhile, the material has low density, and compared with the common talcum powder filled modified polypropylene material, the weight reduction range can exceed more than 10%, and the material can be widely applied to the design requirements of lightweight and thin-walled parts. In addition, the method adds the granular polyolefin material and the filler into the extruder through side feeding after blending, can ensure high stability and excellent mechanical property of the product without forced feeding equipment, does not need to modify the original side feeding equipment, and is convenient to process and form.
Description
Technical Field
The invention relates to a low-density high-performance scratch-resistant polypropylene material for an automobile and a preparation method thereof.
Background
Polypropylene is one of general plastics, has excellent performance, and products thereof are related to aspects such as household appliance industry, agricultural film industry, building industry, automobile industry and interior and exterior trimming parts. In the automobile industry, the average consumption of plastics of a workpiece of each automobile is more than hundreds of kilograms, wherein the modified PP material is further applied to different parts such as inner decorations, such as main and auxiliary instrument panels, door panels, upright posts and the like, and outer decorations, such as bumpers, wheel covers and the like.
With the social development and the gradual improvement of environmental awareness of people, the light weight of the automobile is not always in the gear. The automobile light weight can be realized by reducing the material density and carrying out thin-wall design on parts. The modified PP material for the automobile is usually a talcum powder modified PP material, and when the density of the material is reduced, the using amount of talcum powder is usually required to be reduced, so that the modulus strength and the like of the material are greatly reduced, and when the modified PP material is applied to the same part, the serious deformation and other consequences of the part can be caused. Therefore, the density of the material is reduced, and simultaneously, the mechanical property of the material is ensured to be kept to the condition which is mainly met by the lightweight automobile material at ordinary times. The thin-wall design directly reduces the wall thickness of the part, and if the same modified material is used, the melt is difficult to fill the mold, so that the thin-wall design has another requirement on the material that the melt flow rate is high. Therefore, the materials for realizing the lightweight of the automobile must meet the synchronous requirements of the parts on the mechanical property of the materials and the melt flow rate. At present, more PP + EPDM-T20 is generally used for automobile interior and exterior trimming parts, and most of the performance requirements of the automobile interior and exterior trimming parts are that the bending modulus is 1800MPa, the impact strength of a simply supported beam notch is 20kJ/m2, and the melt flow rate is about 20g/10 min. Chinese patent CN 110003572A discloses a polypropylene-basic magnesium sulfate whisker composite material for thin-wall automobile products, which adopts basic magnesium sulfate whisker master batches to prepare polypropylene materials with melt flow rate of 30g/10min, notch impact strength of 25kJ/m2 and bending modulus of about 1800 MPa. Chinese patent CN 106273350A discloses a high-rigidity high-toughness polypropylene composite material for automobiles and a preparation method thereof, and modified polypropylene material with excellent performance is prepared by feeding different contents of compounded whisker and talcum powder from the main side and the side of an extruder. The filler in the patent is close to 20 parts, and the influence of the modified filler on the scratch resistance of the material is not discussed. In view of the actual requirements, a modified polypropylene material with convenient blanking and excellent performance needs to be prepared.
Disclosure of Invention
Based on the above, the invention provides a low-density high-performance scratch-resistant polypropylene material for automobiles and a preparation method thereof. The method is simple and effective, is suitable for manufacturers to quickly adjust the formula according to the performance requirements of the material, and does not need to additionally increase the cost of modifying screw forced feeding equipment. The prepared material has low density and excellent mechanical property, and compared with a talcum powder modified PP material with the same mechanical property, the weight reduction amplitude exceeds 10 percent.
The invention is realized by the following technical scheme:
the low-density high-performance scratch-resistant polypropylene material for the automobile is prepared from the following raw materials in percentage by mass:
in the low-density high-performance scratch-resistant polypropylene material for automobiles,
the polypropylene is block copolymerization polypropylene, the appearance is granular, the melt flow rate is 30-100g/10min, and the impact strength of a simple beam notch is more than 3kJ/m at room temperature2。
The polyethylene is one or the combination of linear low density polyethylene, low density polyethylene and high density polyethylene, the appearance of the polyethylene is granular, and the melt flow rate is 0.2-10g/10 min.
The filler is one or the combination of basic calcium sulfate and basic magnesium sulfate whisker.
The crystal whisker has the diameter less than 1um, the length of 10-30um and the bulk density more than 0.2.
The toughening agent is one or a combination of polyolefin elastomer (POE) and styrene thermoplastic elastomer (TPS).
The melt flow rate of the POE and the TPS is more than 2g/10 min.
The coupling agent is a silane coupling agent.
The scratch-resistant auxiliary agent is one or the combination of erucamide, stearyl erucamide and polysiloxane.
The functional auxiliary agent is a combination of a phenol main antioxidant, a phosphite auxiliary antioxidant and a hindered amine light stabilizer, and the mass ratio of the phenol main antioxidant to the phosphite auxiliary antioxidant to the hindered amine light stabilizer is 2: 1: 2.
the preparation method of the low-density high-performance scratch-resistant polypropylene material for the automobile comprises the following steps:
step 1: the whiskers are modified with a silane coupling agent. Weighing the silane coupling agent and the crystal whisker according to the material ratio. Mixing a coupling agent and a 50 wt% ethanol solution according to a volume ratio of 1: stirring and dispersing for 10min, placing the crystal whisker in a stirrer after the coupling agent is dispersed uniformly, simultaneously spraying the coupling agent solution into the crystal whisker powder by a spraying device, continuously stirring for 10min, heating and drying to volatilize the solvent, and finally repeatedly stirring for 2min to disperse the powder and collect.
Step 2: and (3) uniformly blending the modified whiskers obtained in the step (1) with 5-10 parts of polyolefin, and adding the mixture through a side feeding port. And the rest materials enter through the main feeding port of the double-screw extruder, are melted and then are mixed with the materials entering through the side feeding port, and then are extruded, granulated, dried and the like to obtain the finished product material. The technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 60-180 ℃, the temperature of the second zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the whisker is modified, so that the dispersion of the whisker in the matrix material can be improved, and the excellent mechanical property of the modified PP material is maintained. Meanwhile, the scratch resistant effect of the material is greatly improved after modification of the whisker, the dosage of the scratch assistant in the system can be reduced, the cost of the assistant is saved, and the adverse effects of precipitation, stickiness and the like of the scratch assistant in the long-term use process are reduced.
According to the invention, modified whiskers and a small amount of polyolefin granules are blended and fed into the double-screw extruder through side feeding, so that the difficulty in feeding caused by a bridging effect of the whiskers due to low self-stacking density and large length-diameter ratio at a feed inlet can be effectively overcome, the operation stability and the finished product performance stability of the whiskers in the production process are improved, the shearing action and the complicated carrier replacement process when the whiskers are made into master batches are avoided, the excellent mechanical property of the material is ensured, the operation is convenient and efficient, the high-cost forced feeding modification of the double-screw extruder is not required, and the modified whisker is suitable for most downstream modification manufacturers.
Detailed description of the invention
The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
The main raw materials used in the examples and comparative examples are as follows:
| type (B) | Number plate | Manufacturer of the product |
| PP | BX39-20 | Korea SK |
| HDPE | 8008 | Solitary mountain petrochemicals |
| Filler | W40-S | Yingkoukang medicine |
| Toughening agent | 7467 | Chemistry of Dow |
Examples and comparative examples thereof, density was tested according to ISO 1183; melt flow rate was tested according to ISO 1133; the tensile strength is tested according to ISO527, and the testing speed is 50 mm/min; the flexural modulus is tested according to SO178, the testing speed is 2mm/min, and the span is 64 mm; notched impact strength was tested according to ISO179 at 23 ℃; scratch resistance the data size of Δ L was evaluated on a leather-grain board (Stipple 002) according to the PV3952 method under a load of 10N.
Example 1
The raw materials comprise the following components in parts by mass: 10 parts of basic magnesium sulfate whisker WS-40, PP BX392070 part, 5 parts of high-density polyethylene HDPE, 746713 parts of toughening elastomer POE, no scraping auxiliary agent is added, the toner is 20140.4 parts of carbot carbon black, 0.5 part of functional auxiliary agent is the combination of phenol main antioxidant 1010, phosphite auxiliary antioxidant 168 and hindered amine light stabilizer UV531, and the mass ratio is 2: 1: 2.
the preparation method comprises the following steps: weighing 10 parts of whisker, blending with 5 parts of HDPE uniformly without modification by a silane coupling agent, then feeding the mixture through a side feeding inlet, blending all the other materials, then feeding the mixture through a main feeding port of a double-screw extruder, and melting, blending, extruding and granulating the main feeding material and the side feeding port material after the main feeding material is melted. Wherein the temperature of the first zone is 60-180 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃. Then, the granules are injected into a standard test sample strip by an injection molding machine, and the performance is tested;
example 2
The raw materials comprise the following components in parts by mass: 10 parts of basic magnesium sulfate whisker WS-40, PPBX392070, 5 parts of high-density polyethylene HDPE, 746713 parts of toughening elastomer POE, KH5500.2 parts of coupling agent, no scraping auxiliary agent, 20140.4 parts of carbot carbon black as toner, 0.5 part of functional auxiliary agent is the combination of phenol main antioxidant 1010, phosphite auxiliary antioxidant 168 and hindered amine light stabilizer UV531, and the mass ratio is 2: 1: 2.
the preparation method comprises the following steps: weighing 10 parts of whisker, modifying by 0.2 part of silane coupling agent, uniformly blending with 5 parts of HDPE, feeding through a side feeding inlet, blending all the other materials, feeding through a main feeding inlet of a double-screw extruder, melting and blending the main feeding material and the side feeding inlet material after melting, and extruding and granulating. Wherein the temperature of the first zone is 60-180 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃. Then, the granules are injected into a standard test sample strip by an injection molding machine, and the performance is tested;
example 3
The raw materials comprise the following components in parts by mass: 10 parts of basic magnesium sulfate whisker WS-40, PP BX392070, 5 parts of high-density polyethylene HDPE, 746713 parts of toughening elastomer POE, KH5500.2 parts of coupling agent, 0.3 part of erucamide as a scraping auxiliary agent, 20140.4 parts of toner, 0.5 part of functional auxiliary agent which is a combination of phenol main antioxidant 1010, phosphite auxiliary antioxidant 168 and hindered amine light stabilizer UV531, wherein the mass ratio of the components is 2: 1: 2.
the preparation method comprises the following steps: weighing 10 parts of whisker, modifying by 0.2 part of silane coupling agent, uniformly blending with 5 parts of HDPE, feeding through a side feeding inlet, blending all the other materials, feeding through a main feeding inlet of a double-screw extruder, melting and blending the main feeding material and the side feeding inlet material after melting, and extruding and granulating. Wherein the temperature of the first zone is 60-180 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃. Then, the granules are injected into a standard test sample strip by an injection molding machine, and the performance is tested;
example 4
The raw materials comprise the following components in parts by mass: 10 parts of basic magnesium sulfate whisker WS-40, PP BX 392075 parts, toughened elastomer POE 746713 parts, coupling agent KH5500.2 parts, scraping auxiliary agent which is erucamide 0.3 parts, toner which is carbon black 2014 dye 0.4 parts, functional auxiliary agent which is the combination of phenol main antioxidant 1010, phosphite auxiliary antioxidant 168 and hindered amine light stabilizer UV531, wherein the mass ratio of the components is 2: 1: 2.
the preparation method comprises the following steps: weighing 10 parts of whisker, modifying by 0.2 part of silane coupling agent, uniformly blending with 5 parts of BX3920, feeding through a side feeding inlet, blending all the other materials, feeding through a main feeding port of a double-screw extruder, melting and blending the main feeding material and the side feeding port material after melting, and extruding and granulating. Wherein the temperature of the first zone is 60-180 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃. Then, the granules are injected into a standard test sample strip by an injection molding machine, and the performance is tested;
comparative example 1
The raw materials comprise the following components in parts by mass: 10 parts of talcum powder, 0 part of PP BX392070 part, 5 parts of high-density polyethylene HDPE, 746713 parts of toughening elastomer POE, 0.3 part of coupling agent KH5500.2 parts of scraping auxiliary agent, 0.3 part of erucamide, 20140.4 parts of toner of cabot carbon black, 0.5 part of functional auxiliary agent which is a combination of phenol main antioxidant 1010, phosphite auxiliary antioxidant 168 and hindered amine light stabilizer UV531, wherein the mass ratio of the functional auxiliary agent to the phenolic main antioxidant is 2: 1: 2.
the preparation method comprises the following steps: weighing talcum powder Cimbar 61010 parts, modifying by 0.2 part of silane coupling agent, uniformly blending with 5 parts of HDPE, then entering through a side feeding inlet, blending all the other materials, entering through a main feeding inlet of a double-screw extruder, melting and blending the main feeding material and the side feeding inlet material after melting, extruding and granulating. Wherein the temperature of the first zone is 60-180 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃. Then, the granules are injected into a standard test sample strip by an injection molding machine, and the performance is tested;
comparative example 2
The raw materials comprise the following components in parts by mass: 10 parts of basic magnesium sulfate whisker WS-40, PP BX392070, 5 parts of high-density polyethylene HDPE, 746713 parts of toughening elastomer POE, KH5500.2 parts of coupling agent, 0.3 part of erucamide as a scraping auxiliary agent, 20140.4 parts of cabot carbon black as a toner, and 0.5 part of functional auxiliary agent, wherein the mass ratio of the functional auxiliary agent to the basic magnesium sulfate whisker WS-40 to the functional auxiliary agent UV53l is 2: 1: 2.
The preparation method comprises the following steps: weighing 10 parts of whisker, modifying by 0.2 part of silane coupling agent, entering through a side feeding inlet, blending all the other materials, entering through a main feeding port of a double-screw extruder, melting and blending the main feeding material and the side feeding port material after melting, and extruding and granulating. Wherein the temperature of the first zone is 60-180 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃. Then, the granules are injected into a standard test sample strip by an injection molding machine, and the performance is tested;
the properties of examples 1-4 and comparative examples 1-2 are shown in Table 1 below;
TABLE 1 comparison of formulations and Properties in the samples
| Test item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Melt flow Rate (g/10min) | 41.5 | 42.5 | 41.7 | 45.3 | 40.5 | 43.1 |
| Density (g/cra)-3) | 0.96 | 0.96 | 0.96 | 0.96 | 0.98 | 0.95 |
| Tensile Strength (MPa) | 24 | 24.8 | 24.3 | 25 | 20 | 23.1 |
| Flexural modulus (MPa) | 2379 | 2453 | 2421 | 2497 | 1526 | 2261 |
| Notched impact strength (kJ/m)2) | 27 | 28 | 27 | 25 | 24 | 25 |
| Cross scrape/Δ L | 2.7 | 2 | 1.3 | 1.6 | 1.9 | 1.5 |
As can be seen from the above examples 1-4 and comparative example 1, the overall mechanical properties of the whisker modified PP material are greatly superior to those of talcum powder modified PP with the same filling amount. Meanwhile, if the flexural modulus is more than 2000MPa, the notch impact strength is more than 20kJ/m2, the material is basically selected from PP + EPDM-T20 type material, the density of the material is about 1.06, and therefore, the PP modified by the crystal whisker can effectively reduce the density of the modified PP material on the basis of maintaining high performance.
In examples 1 to 3, whether the silane coupling agent is used or not has a large influence on the mechanical properties and scratch resistance of the material under the conditions of the same material ratio and the same blanking mode. The silane coupling agent enhances the interface acting force between the whisker and the PP matrix, and the coupling agent coats the whisker to effectively reduce the whole surface friction coefficient of the material, so that the whisker modified PP material has excellent mechanical property and scratch resistance. At present, the standard basic requirement of a cross scraping evaluation method is that the change of an L value is less than 2.0, so that the mechanical property of the crystal whisker is enhanced by modifying the crystal whisker by a silane coupling agent, and the excellent scraping resistance can be achieved by matching with a small amount of micromolecule scraping auxiliaries.
It can be seen from examples 1-4 and comparative example 2 that the densities of examples 1-4 which are obtained by blending HDPE and PP with whiskers and enter through side feeding are uniform, and the densities of single whiskers slightly decrease when entering through side feeding, which indicates that when particles and whiskers are uniformly blended and enter through a side feeding port, the difficulty in blanking caused by long length-diameter ratio and light weight of whiskers can be effectively overcome, so that the operation process of whiskers entering a screw extruder is stable and reliable, and the repeatability is strong.
In the embodiment, the PP base material and the elastomer can be replaced according to the performance of actual needs, the limitation of whisker master batch carriers is avoided, more complex forced feeding equipment is not needed, the operation process is convenient and reliable, and the method is suitable for most downstream modification factories.
Claims (10)
1. The low-density high-performance scratch-resistant polypropylene material for the automobile is characterized by comprising the following components in parts by weight: the material is prepared from the following raw materials in percentage by mass:
2. the low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the polypropylene is block copolymerization polypropylene, the appearance is granular, the melt flow rate is 30-100g/10min, and the impact strength of a simple beam notch is more than 3kJ/m at room temperature2。
3. The low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the polyethylene is one or the combination of linear low density polyethylene, low density polyethylene and high density polyethylene, the appearance of the polyethylene is granular, and the melt flow rate is 0.2-10g/10 min.
4. The low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the filler is one or the combination of basic calcium sulfate and basic magnesium sulfate whisker.
5. The low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the crystal whisker has the diameter less than 1um, the length of 10-30um and the bulk density more than 0.2.
6. The low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the toughening agent is one or a combination of polyolefin elastomer (POE) and styrene thermoplastic elastomer (TPS).
7. The low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the melt flow rate of the POE and the TPS is more than 2g/10 min.
8. The low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the coupling agent is a silane coupling agent; the scratch-resistant auxiliary agent is one or the combination of erucamide, stearyl erucamide and polysiloxane.
9. The low-density high-performance scratch-resistant polypropylene material for the automobiles according to claim 1, wherein: the functional auxiliary agent is a combination of a phenol main antioxidant, a phosphite auxiliary antioxidant and a hindered amine light stabilizer, and the mass ratio of the phenol main antioxidant to the phosphite auxiliary antioxidant to the hindered amine light stabilizer is 2: 1: 2.
10. the method for preparing the low-density high-performance scratch-resistant polypropylene material for the automobile as claimed in any one of claims 1 to 9, wherein the method comprises the following steps: the method comprises the following steps:
(1) the whiskers are modified with a silane coupling agent. Weighing the silane coupling agent and the crystal whisker according to the material ratio. Mixing a coupling agent and a 50 wt% ethanol solution according to a volume ratio of 1: stirring and dispersing for 10min, placing the crystal whisker in a stirrer after the coupling agent is uniformly dispersed, simultaneously uniformly scattering a coupling agent solution into the crystal whisker powder by using a spraying device, continuously stirring for 10min, heating and drying to volatilize the solvent, and finally repeatedly stirring for 2min to disperse the powder and collect the powder;
(2) and (3) uniformly blending the modified whiskers obtained in the step (1) with 5-10 parts of polyolefin, and adding the mixture through a side feeding port. And the rest materials enter through the main feeding port of the double-screw extruder, are melted and then are mixed with the materials entering through the side feeding port, and then are extruded, granulated, dried and the like to obtain the finished product material. The technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 60-180 ℃, the temperature of the second zone is 180-210 ℃, and the extrusion temperature is 200 +/-10 ℃.
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