WO2023040734A1 - Wear-resistant high-impact polypropylene composition, preparation method therefor, and use thereof - Google Patents
Wear-resistant high-impact polypropylene composition, preparation method therefor, and use thereof Download PDFInfo
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- WO2023040734A1 WO2023040734A1 PCT/CN2022/117707 CN2022117707W WO2023040734A1 WO 2023040734 A1 WO2023040734 A1 WO 2023040734A1 CN 2022117707 W CN2022117707 W CN 2022117707W WO 2023040734 A1 WO2023040734 A1 WO 2023040734A1
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 83
- -1 polypropylene Polymers 0.000 title claims abstract description 82
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000006229 carbon black Substances 0.000 claims abstract description 52
- 238000010521 absorption reaction Methods 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 239000004611 light stabiliser Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 241000872198 Serjania polyphylla Species 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Definitions
- the invention relates to the field of polymer materials and their molding processing, in particular to a wear-resistant and high-impact polypropylene composition and its preparation method and application.
- polypropylene As a cost-effective general-purpose plastic, polypropylene has excellent mechanical properties such as high strength and toughness, chemical resistance, and high heat resistance after modification, and can be widely used in home appliances and automotive products.
- polypropylene materials For automotive interior parts made of polypropylene materials, it is usually easy to be scratched or worn by fabric shoe materials, decorations, gravel and other items, so scratch resistance and abrasion resistance are important performance requirements for automotive interior polypropylene , It is of great significance to keep the interior beautiful.
- Patent CN109721829A adds wear-resistant agents such as hexagonal boron nitride, ⁇ -alumina, zirconium boride and polytetrafluoroethylene powder, that is, uses ceramic powder to increase rigidity and PTFE powder to reduce the surface friction coefficient.
- Wear-resistant agents such as hexagonal boron nitride, ⁇ -alumina, zirconium boride and polytetrafluoroethylene powder, that is, uses ceramic powder to increase rigidity and PTFE powder to reduce the surface friction coefficient.
- Modified plastics are not a general-purpose filler, and they are used in large quantities in polypropylene systems.
- the purpose of the present invention is to provide a wear-resistant high-impact polypropylene composition.
- the present invention realizes the effective improvement of the wear resistance and impact performance of polypropylene material by adding carbon black with high oil absorption value and optimizing and optimizing polypropylene and toughening agent, and the wear-resistant and high-impact polypropylene composition can be widely used Applied to the preparation of automotive interior parts.
- Another object of the present invention is to provide a method for preparing the above-mentioned wear-resistant and high-impact polypropylene composition.
- Another object of the present invention is to provide the application of the above-mentioned wear-resistant and high-impact polypropylene composition in the preparation of interior and exterior trim parts of automobiles.
- a wear-resistant and high-impact polypropylene composition comprising the following components in parts by weight: 30-85 parts of polypropylene resin, 5-25 parts of toughening agent, 5-25 parts of filler, 5-20 parts of carbon black, 1-3 parts of lubricant, 0-0.8 parts of antioxidant, 0-0.6 parts of light stabilizer;
- the oil absorption value of the carbon black is 120-180mL/100g.
- Carbon black is an important reinforcing agent in the rubber industry. Because it improves the anti-fatigue properties of rubber, the wear resistance of materials is greatly improved. It has mature applications in the rubber industry, but no carbon black has been used to improve wear resistance in the plastics industry. In addition, the common automotive interior polypropylene is only colored with carbon black, without optimization and optimization of the addition amount, it cannot meet the use requirements of improving wear resistance.
- carbon black by selecting carbon black with a higher oil absorption value as the physical cross-linking agent, carbon black can be used to absorb and entangle polypropylene molecular chains, thereby generating physical cross-linking points to limit the surface layer of polypropylene under the abrasion test. wear; if the oil absorption value of carbon black is low, the adsorption and entanglement of carbon black to polypropylene molecular chains is less, and it is difficult to meet the requirements of improving wear resistance.
- oil absorption value of carbon black is in accordance with the ASTM D2414-09a-2017 test standard, and the specific test method is: the minimum dibutyl phthalate required for testing the gaps and surface infiltration filled with carbon black chain branches or fiber structures The amount of ester, also known as DBP oil absorption value.
- the wear-resistant and high-impact polypropylene composition includes the following components in parts by weight: 50-70 parts of polypropylene resin, 10-15 parts of toughening agent, 10-15 parts of filler, and 10-15 parts of carbon black 1.5-2.5 parts of lubricant, 0.3-0.6 part of antioxidant, 0.2-0.4 part of light stabilizer.
- the carbon black has an oil absorption value of 130-175mL/100g.
- the carbon black is furnace carbon black.
- the polypropylene resin is at least one of homopolypropylene or copolymerized polypropylene.
- the polypropylene resin is copolymerized polypropylene.
- the polypropylene resin has a melt flow rate of 60-115 g/10 min at a temperature of 230° C. and a load of 2.16 kg according to ASTM D-1238-2013 standard.
- the toughening agent is ethylene-butene copolymer or ethylene-octene copolymer (POE).
- the POE has a melt flow rate of 3-14g/10min at a temperature of 190°C and a load of 2.16Kg.
- a polypropylene resin with a higher melt flow rate is preferred, which can improve the dispersibility of carbon black in the polypropylene system, and at the same time, due to the existence of a certain amount of carbon black with high oil absorption value, it can effectively reduce the toughening agent and polypropylene resin.
- the melt flow rate of POE by optimizing the melt flow rate of POE, its dispersibility is significantly improved, so that the prepared polypropylene material can have higher impact strength at a lower elastomer content, which is conducive to further reducing The adverse effect of POE on the wear resistance of polypropylene system.
- the filler is at least one of talcum powder, calcium carbonate, barium sulfate or glass fiber.
- the lubricant is at least one of amide, amide masterbatch or silicone masterbatch.
- the antioxidant is at least one of hindered phenols or phosphites, specifically at least one of 1010, 1076, 3114, 168 or PEP-36.
- the light stabilizer is hindered amines, specifically at least one of UV-3808, LA-402XP or LA-402AF.
- the present invention also provides a method for preparing the above-mentioned wear-resistant and high-impact polypropylene composition, comprising the following steps:
- the present invention has the following beneficial effects:
- the wear resistance of the prepared wear-resistant high-impact polypropylene composition has been significantly improved, and at the same time, by optimizing polypropylene and toughening agent, to achieve It achieves high impact resistance performance under the condition of low toughening agent addition, and is suitable for automotive interior parts with wear resistance requirements.
- the preparation method of the wear-resistant and high-impact polypropylene composition prepared in the present invention is simple and easy to implement, has cost advantages, and has a high degree of freedom in design.
- melt flow rate (230°C/2.16kg) is 112g/10min
- melt flow rate (230°C/2.16kg) is 60g/10min
- melt flow rate (230°C/2.16kg) of polypropylene copolymer is 30.9g/10min
- POE 1 Model POE ENGAGE 7447 Manufacturer: Dow Chemical Melt flow rate (190°C/2.16kg) is 5g/10min;
- POE 2 Model POE ENGAGE 8137 Manufacturer: Dow Chemical Melt flow rate (190°C/2.16kg) is 13g/10min;
- POE 3 Model POE ENGAGE 7467 Manufacturer: Dow Chemical Melt flow rate (190°C/2.16kg) is 1.2g/10min;
- SEBS Model SEBS G1657 VS Manufacturer: Kraton Polymers
- Hindered phenols Model 1010 Manufacturer: Shandong Sanfeng;
- Phosphite Type 168 Manufacturer: Shandong Sanfeng;
- the polypropylene composition prepared above was injection molded into a 100mm*100mm*3mm sample piece for performance testing.
- Wear resistance test method According to the GBT 5478-2008 test standard, the material wear resistance test is carried out, the wear wheel model is CS-10/load 2.45N/cycle number 100 times/test speed 60rpm, and visual evaluation is carried out after the test; Evaluation grades: Level 1: Wear marks are very obvious; Level 2: Wear marks are relatively obvious; Level 3: Wear marks are slight but can be clearly distinguished; Level 4: Weak wear marks can be observed but not obvious; Level 5: Completely noticeable less than wear marks;
- This example provides a series of wear-resistant and high-impact polypropylene compositions, the formulations of which are shown in Table 1.
- This comparative example provides a series of polypropylene compositions, the formulations of which are shown in Table 2.
- Example 1 performance Wear resistance Notched Izod Impact Strength (KJ/m 2 ) Example 1 5 24.6 Example 2 5 15.2 Example 3 4 24.2 Example 4 4 21.5 Example 5 5 22.79 Example 6 5 24.4 Example 7 5 23.6 Example 8 5 16.5 Example 9 4 15.7 Example 10 5 21.2 Example 11 5 19.2 Example 12 5 21.8 Example 13 5 19.1 Example 14 5 20.4 Example 15 5 23.9 Example 16 4 14.6 Example 17 4 21.6 Comparative example 1 3 6.8 Comparative example 2 3 8.5 Comparative example 3 3 14.8
- the wear-resistant and high-impact polypropylene compositions prepared have a wear-resistant appearance grade ⁇ 4, and the preferred high
- the carbon black with oil absorption value can promote the dispersion of the toughening agent in the material, so that the notched Izod impact strength of the material is greater than 10KJ/m 2 .
- the oil absorption value of carbon black, polypropylene resin type, melt index, and POE melt index were optimized, and the wear resistance level and notched impact strength were further improved, reaching a wear-resistant appearance level of 5, and the notch impact strength was average. >20KJ/m 2 .
- Example 1 The comparison between Example 1 and Example 2/3 shows that the optimization of polypropylene is beneficial to further improve the wear resistance and impact resistance of the material.
- Example 1/6 The comparison between Example 1/6 and Example 7/8/12 shows that optimizing the toughening agent is beneficial to further improve the impact resistance of the material.
- Example 1 The comparison between Example 1 and Comparative Example 1/2/3 shows that by adding the preferred carbon black, compared with no carbon black and carbon black with low oil absorption value, the wear resistance and impact resistance of the material are significantly improved.
- Comparing Example 1 with Comparative Example 7 it can be known that when obtaining similar impact strength, a relatively large amount of POE needs to be added in the formula without adding carbon black, thereby causing a significant decline in the wear resistance of the material; in Comparative Example 8 , The amount of the toughening agent POE added is too small, which has no obvious effect on the wear resistance, but the impact performance of the material is seriously reduced.
- carbon black with high oil absorption value is selected as a physical crosslinking agent for polypropylene modification, and PP/POE is optimized at the same time, and the wear-resistant and high-impact polypropylene composition prepared has Excellent wear resistance and high impact performance, can be widely used in automotive interior parts.
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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)
Abstract
Disclosed in the present invention are a wear-resistant high-impact polypropylene composition, a preparation method therefor, and the use thereof. The wear-resistant high-impact polypropylene composition comprises the following components in parts by weight: 30-85 parts of a polypropylene resin, 5-25 parts of a toughening agent, 5-25 parts of a filler, 5-20 parts of carbon black, 1-3 parts of a lubricant, 0-0.8 parts of an antioxidant and 0-0.6 parts of a light stabilizer, wherein the carbon black has an oil absorption value of 120-180 mL/100 g. In the present invention, the polypropylene material is modified by selecting and adding carbon black with a high oil absorption value, and the finally prepared wear-resistant high-impact polypropylene composition has both an excellent wear resistance and an excellent impact resistance, and can be effectively used for preparing automobile interior trim parts.
Description
本发明涉及高分子材料及其成型加工领域，具体涉及一种耐磨高抗冲聚丙烯组合物及其制备方法和应用。The invention relates to the field of polymer materials and their molding processing, in particular to a wear-resistant and high-impact polypropylene composition and its preparation method and application.
聚丙烯作为一种高性价比的通用塑料，通过改性后具有高强度高韧性等优秀力学性能及耐化学、高耐热等特点，能够广泛应用于家电及汽车产品。对于聚丙烯材料制备的汽车内饰件，通常易于受到织物鞋材、装饰品、砂石以及其它物品的刮伤或者磨损，因此耐刮擦与耐磨耗是汽车内饰聚丙烯的重要性能要求，对于保持内饰美观具有重要意义。As a cost-effective general-purpose plastic, polypropylene has excellent mechanical properties such as high strength and toughness, chemical resistance, and high heat resistance after modification, and can be widely used in home appliances and automotive products. For automotive interior parts made of polypropylene materials, it is usually easy to be scratched or worn by fabric shoe materials, decorations, gravel and other items, so scratch resistance and abrasion resistance are important performance requirements for automotive interior polypropylene , It is of great significance to keep the interior beautiful.
专利CN109721829A通过添加耐磨剂如六方氮化硼、α-氧化铝、硼化锆和聚四氟乙烯微粉等，即采用陶瓷粉增刚以及PTFE微粉降低表面摩擦系数，其问题主要在于陶瓷微粉在改性塑料中并非一个通用填料，将其大量使用于聚丙烯体系当中，即使对材料耐磨性能有所改善，但其高成本的问题将限制此方案在汽车内饰聚丙烯上的使用；CN109627595A也同样是采用耐磨矿粉助剂来改善材料的耐磨性；CN103756132A则采用了添加硅酮微粉的方法，原理也是通过降低材料的表面摩擦系数来提高耐摩擦性。可知，目前在聚丙烯材料改善耐磨性上的技术手段较为单一，即通过添加陶瓷微粉或者PTFE等来改善耐磨性，且成本较高。Patent CN109721829A adds wear-resistant agents such as hexagonal boron nitride, α-alumina, zirconium boride and polytetrafluoroethylene powder, that is, uses ceramic powder to increase rigidity and PTFE powder to reduce the surface friction coefficient. Modified plastics are not a general-purpose filler, and they are used in large quantities in polypropylene systems. Even if the wear resistance of the material is improved, the problem of its high cost will limit the use of this solution on polypropylene for automotive interiors; CN109627595A Also, wear-resistant mineral powder additives are used to improve the wear resistance of the material; CN103756132A adopts the method of adding silicone micropowder, and the principle is to improve the wear resistance by reducing the surface friction coefficient of the material. It can be seen that the current technical means for improving the wear resistance of polypropylene materials is relatively single, that is, the wear resistance is improved by adding ceramic micropowder or PTFE, and the cost is relatively high.
因此，开发一种成本低且耐磨性能优异且具有良好力学性能的聚丙烯材料用于制备汽车内外饰件具有重要的研究意义和经济价值。Therefore, it is of great research significance and economic value to develop a polypropylene material with low cost, excellent wear resistance and good mechanical properties for the preparation of automotive interior and exterior trim parts.
发明内容Contents of the invention
为了克服现有技术中聚丙烯材料的耐磨改性方案单一且成本较高，本发明的目的在于提供一种耐磨高抗冲聚丙烯组合物。本发明通过添加高吸油值的炭黑以及对聚丙烯和增韧剂的优选和优化，实现了聚丙烯材料耐磨性能和冲击性能的有效改善，该耐磨高抗冲聚丙烯组合物可广泛应用于制备汽车内饰件。In order to overcome the single anti-wear modification scheme and high cost of polypropylene materials in the prior art, the purpose of the present invention is to provide a wear-resistant high-impact polypropylene composition. The present invention realizes the effective improvement of the wear resistance and impact performance of polypropylene material by adding carbon black with high oil absorption value and optimizing and optimizing polypropylene and toughening agent, and the wear-resistant and high-impact polypropylene composition can be widely used Applied to the preparation of automotive interior parts.
本发明的另一目的在于提供上述耐磨高抗冲聚丙烯组合物的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned wear-resistant and high-impact polypropylene composition.
本发明的另一目的在于提供上述耐磨高抗冲聚丙烯组合物在制备汽车内外饰件中的应用。Another object of the present invention is to provide the application of the above-mentioned wear-resistant and high-impact polypropylene composition in the preparation of interior and exterior trim parts of automobiles.
为实现上述发明目的，本发明采用如下技术方案：In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:
一种耐磨高抗冲聚丙烯组合物，包括以下重量份数的组分：聚丙烯树脂30-85份，增韧剂5-25份，填料5-25份，炭黑5-20份，润滑剂1-3份，抗氧剂0-0.8份，光稳定剂0-0.6份；A wear-resistant and high-impact polypropylene composition, comprising the following components in parts by weight: 30-85 parts of polypropylene resin, 5-25 parts of toughening agent, 5-25 parts of filler, 5-20 parts of carbon black, 1-3 parts of lubricant, 0-0.8 parts of antioxidant, 0-0.6 parts of light stabilizer;
其中，所述炭黑的吸油值为120-180mL/100g。Wherein, the oil absorption value of the carbon black is 120-180mL/100g.
炭黑作为橡胶工业上重要的补强剂，因提升了橡胶的抗疲劳特性使得材料耐磨性能大幅度提升，在橡胶工业上有成熟应用，但未见有炭黑在塑料工业上改善耐磨性的相关研究；另外常见的汽车内饰聚丙烯仅采用炭黑进行着色，未经优选以及添加量优化，达不到提升耐磨性的使用需求。Carbon black is an important reinforcing agent in the rubber industry. Because it improves the anti-fatigue properties of rubber, the wear resistance of materials is greatly improved. It has mature applications in the rubber industry, but no carbon black has been used to improve wear resistance in the plastics industry. In addition, the common automotive interior polypropylene is only colored with carbon black, without optimization and optimization of the addition amount, it cannot meet the use requirements of improving wear resistance.
本发明中，通过选用较高吸油值的炭黑作为物理交联剂，利用炭黑对于聚丙烯分子链的吸附和缠结作用，从而产生物理交联点，达到限制表层聚丙烯在磨耗测试下的磨损；如果炭黑的吸油值较低，炭黑对聚丙烯分子链的吸附和缠结较少，难以达到提升耐磨性能的要求。In the present invention, by selecting carbon black with a higher oil absorption value as the physical cross-linking agent, carbon black can be used to absorb and entangle polypropylene molecular chains, thereby generating physical cross-linking points to limit the surface layer of polypropylene under the abrasion test. wear; if the oil absorption value of carbon black is low, the adsorption and entanglement of carbon black to polypropylene molecular chains is less, and it is difficult to meet the requirements of improving wear resistance.
应当说明的是，炭黑的吸油值按照ASTM D2414-09a-2017测试标准，其具体测试方法为：测试充满炭黑链枝或者纤维结构的空隙及表面浸润所需的最低邻苯二甲酸二丁酯的量，也称DBP吸油值。It should be noted that the oil absorption value of carbon black is in accordance with the ASTM D2414-09a-2017 test standard, and the specific test method is: the minimum dibutyl phthalate required for testing the gaps and surface infiltration filled with carbon black chain branches or fiber structures The amount of ester, also known as DBP oil absorption value.
优选地，所述耐磨高抗冲聚丙烯组合物包括以下重量份数的组分：聚丙烯树脂50-70份，增韧剂10-15份，填料10-15份，炭黑10-15份，润滑剂1.5-2.5份，抗氧剂0.3-0.6份，光稳定剂0.2-0.4份。Preferably, the wear-resistant and high-impact polypropylene composition includes the following components in parts by weight: 50-70 parts of polypropylene resin, 10-15 parts of toughening agent, 10-15 parts of filler, and 10-15 parts of carbon black 1.5-2.5 parts of lubricant, 0.3-0.6 part of antioxidant, 0.2-0.4 part of light stabilizer.
优选地，所述炭黑的吸油值为130-175mL/100g。Preferably, the carbon black has an oil absorption value of 130-175mL/100g.
进一步优选地，所述炭黑为炉法炭黑。Further preferably, the carbon black is furnace carbon black.
优选地，所述聚丙烯树脂为均聚聚丙烯或共聚聚丙烯中的至少一种。Preferably, the polypropylene resin is at least one of homopolypropylene or copolymerized polypropylene.
进一步优选地，所述聚丙烯树脂为共聚聚丙烯。Further preferably, the polypropylene resin is copolymerized polypropylene.
优选地，所述聚丙烯树脂按照ASTMD-1238-2013标准，在温度为230℃、负荷为2.16kg条件下的熔体流动速率为60-115g/10min。Preferably, the polypropylene resin has a melt flow rate of 60-115 g/10 min at a temperature of 230° C. and a load of 2.16 kg according to ASTM D-1238-2013 standard.
优选地，所述增韧剂为乙烯-丁烃共聚物或乙烯-辛烯共聚物(POE)。Preferably, the toughening agent is ethylene-butene copolymer or ethylene-octene copolymer (POE).
进一步优选地，所述POE按照ASTM D-1238-2013标准，在温度为190℃、负荷为2.16Kg条件下的熔体流动速率为3-14g/10min。Further preferably, according to the ASTM D-1238-2013 standard, the POE has a melt flow rate of 3-14g/10min at a temperature of 190°C and a load of 2.16Kg.
本发明中优选较高熔体流动速率的聚丙烯树脂，能够改善炭黑在聚丙烯体系中的分散性，同时由于一定含量的高吸油值炭黑的存在，能够有效降低增韧剂与 聚丙烯的粘度比，同时通过优化POE的熔体流动速率，其分散性得到较为显著的改善，使制备得到的聚丙烯材料可以在较低的弹性体含量下具有更高的冲击强度，有利于进一步降低POE对于聚丙烯体系耐磨性能的不利影响。In the present invention, a polypropylene resin with a higher melt flow rate is preferred, which can improve the dispersibility of carbon black in the polypropylene system, and at the same time, due to the existence of a certain amount of carbon black with high oil absorption value, it can effectively reduce the toughening agent and polypropylene resin. At the same time, by optimizing the melt flow rate of POE, its dispersibility is significantly improved, so that the prepared polypropylene material can have higher impact strength at a lower elastomer content, which is conducive to further reducing The adverse effect of POE on the wear resistance of polypropylene system.
优选地，所述填料为滑石粉、碳酸钙、硫酸钡或玻璃纤维中的至少一种。Preferably, the filler is at least one of talcum powder, calcium carbonate, barium sulfate or glass fiber.
优选地，所述润滑剂为酰胺、酰胺母粒或硅酮母粒中的至少一种。Preferably, the lubricant is at least one of amide, amide masterbatch or silicone masterbatch.
优选地，所述抗氧剂为受阻酚类或亚磷酸酯类中的至少一种，具体为1010、1076、3114、168或PEP-36中的至少一种。Preferably, the antioxidant is at least one of hindered phenols or phosphites, specifically at least one of 1010, 1076, 3114, 168 or PEP-36.
优选地，所述光稳定剂为受阻胺类，具体为UV-3808、LA-402XP或LA-402AF中的至少一种。Preferably, the light stabilizer is hindered amines, specifically at least one of UV-3808, LA-402XP or LA-402AF.
本发明还提供一种上述耐磨高抗冲聚丙烯组合物的制备方法，包括以下步骤：The present invention also provides a method for preparing the above-mentioned wear-resistant and high-impact polypropylene composition, comprising the following steps:
将聚丙烯树脂、填料、增韧剂、润滑剂、抗氧剂及光稳定剂混合均匀，将混合物置于主喂料口中，从侧喂料口加入炭黑，进行熔融混炼，挤出造粒，即得所述耐磨高抗冲聚丙烯组合物。Mix polypropylene resin, filler, toughener, lubricant, antioxidant and light stabilizer evenly, place the mixture in the main feeding port, add carbon black from the side feeding port, melt and knead, and extrude pellets to obtain the wear-resistant high-impact polypropylene composition.
上述耐磨高抗冲聚丙烯组合物在制备汽车内饰件中的应用也在本发明的保护范围内。The application of the above wear-resistant and high-impact polypropylene composition in the preparation of automotive interior parts is also within the protection scope of the present invention.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明中通过选用高吸油值的炭黑，使制备得到的耐磨高抗冲聚丙烯组合物的耐磨性能得到了较为显著的改善，同时通过优化聚丙烯以及增韧剂，达到在较低增韧剂添加量条件下实现高抗冲的性能，适用于有耐磨性需求的汽车内饰件。(1) In the present invention, by selecting carbon black with high oil absorption value, the wear resistance of the prepared wear-resistant high-impact polypropylene composition has been significantly improved, and at the same time, by optimizing polypropylene and toughening agent, to achieve It achieves high impact resistance performance under the condition of low toughening agent addition, and is suitable for automotive interior parts with wear resistance requirements.
(2)本发明中所制备的耐磨高抗冲聚丙烯组合物的制备方法简单便于实行，具有成本优势，设计自由度高。(2) The preparation method of the wear-resistant and high-impact polypropylene composition prepared in the present invention is simple and easy to implement, has cost advantages, and has a high degree of freedom in design.
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。The present invention is further set forth below in conjunction with embodiment. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental method that does not indicate specific conditions in the following example embodiment, usually according to the conventional conditions in this field or according to the conditions suggested by the manufacturer; used raw materials, reagents, etc., if no special instructions, are available from commercial channels such as conventional markets Raw materials and reagents obtained. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of the present invention.
本发明各实施例及对比例选用的试剂说明如下：The reagents selected in each embodiment of the present invention and comparative examples are described as follows:
聚丙烯树脂：Polypropylene resin:
1.共聚聚丙烯：熔体流动速率(230℃/2.16kg)为112g/10min1. Copolymerized polypropylene: melt flow rate (230°C/2.16kg) is 112g/10min
型号：PDI088 厂家：埃克森美孚；Model: PDI088 Manufacturer: ExxonMobil;
2.均聚聚丙烯：熔体流动速率(230℃/2.16kg)为60g/10min2. Homopolypropylene: melt flow rate (230°C/2.16kg) is 60g/10min
型号：H9018 厂家：兰州石化；Model: H9018 Manufacturer: Lanzhou Petrochemical;
3.共聚聚丙烯 熔体流动速率(230℃/2.16kg)为30.9g/10min3. The melt flow rate (230℃/2.16kg) of polypropylene copolymer is 30.9g/10min
型号：EP548R 厂家：中海壳牌；Model: EP548R Manufacturer: China Shipping Shell;
炭黑：Carbon black:
1型号：Conductex 7055(炉法炭黑，吸油值170mL/100g)厂家：博拉炭黑；1 Model: Conductex 7055 (furnace carbon black, oil absorption value 170mL/100g) manufacturer: Birla carbon black;
2型号：Conductex SC Ultra(炉法炭黑，吸油值112mL/100g)厂家：博拉炭黑；2 Model: Conductex SC Ultra (furnace carbon black, oil absorption value 112mL/100g) manufacturer: Birla carbon black;
3型号：Conductex 7090(炉法炭黑，吸油值121mL/100g)厂家：博拉炭黑；3 Model: Conductex 7090 (furnace carbon black, oil absorption value 121mL/100g) manufacturer: Birla carbon black;
4型号：DENKA BLACK(乙炔炭黑，吸油值160mL/100g)厂家：电气化学；4 Model: DENKA BLACK (acetylene carbon black, oil absorption value 160mL/100g) Manufacturer: Electrochemical;
5型号：M717(炉法炭黑，吸油值57mL/100g)厂家：卡博特；填料：5 Model: M717 (furnace carbon black, oil absorption value 57mL/100g) manufacturer: Cabot; filler:
6型号：Conductex 7067 Ultra(炉法炭黑，吸油值140mL/100g)厂家：博拉炭黑；6 Model: Conductex 7067 Ultra (furnace carbon black, oil absorption value 140mL/100g) manufacturer: Birla carbon black;
滑石粉talcum powder
型号：TYT-777A 厂家：北海集团；Model: TYT-777A Manufacturer: Beihai Group;
碳酸钙calcium carbonate
型号：AC-05N 厂家：广东翔龙科技；Model: AC-05N Manufacturer: Guangdong Xianglong Technology;
增韧剂：Toughener:
POE 1型号：POE ENGAGE 7447 厂家：陶氏化学 熔体流动速率(190℃/2.16kg)为5g/10min；POE 1 Model: POE ENGAGE 7447 Manufacturer: Dow Chemical Melt flow rate (190℃/2.16kg) is 5g/10min;
POE 2型号：POE ENGAGE 8137 厂家：陶氏化学 熔体流动速率(190℃/2.16kg)为13g/10min；POE 2 Model: POE ENGAGE 8137 Manufacturer: Dow Chemical Melt flow rate (190℃/2.16kg) is 13g/10min;
POE 3型号：POE ENGAGE 7467 厂家：陶氏化学 熔体流动速率(190℃/2.16kg)为1.2g/10min；POE 3 Model: POE ENGAGE 7467 Manufacturer: Dow Chemical Melt flow rate (190℃/2.16kg) is 1.2g/10min;
SEBS 型号：SEBS G1657 VS 厂家：科腾聚合物；SEBS Model: SEBS G1657 VS Manufacturer: Kraton Polymers;
润滑剂：Lubricant:
硅酮母粒 型号：HMB-0221 厂家：道康宁；Silicone masterbatch Model: HMB-0221 Manufacturer: Dow Corning;
酰胺母粒 型号：GZC01 厂家：金发科技；Amide Masterbatch Model: GZC01 Manufacturer: Kingfa Technology;
抗氧剂：Antioxidant:
受阻酚类 型号：1010 厂家：山东三丰；Hindered phenols Model: 1010 Manufacturer: Shandong Sanfeng;
亚磷酸酯类 型号：168 厂家：山东三丰；Phosphite Type: 168 Manufacturer: Shandong Sanfeng;
光稳定剂：受阻胺类Light Stabilizers: Hindered Amines
型号：UV-3808 厂家：比利时索尔维。Model: UV-3808 Manufacturer: Solvay, Belgium.
本发明各实施例及对比例的聚丙烯组合物通过如下过程制备得到：The polypropylene composition of each embodiment of the present invention and comparative example is prepared by following process:
称取适当组分的聚丙烯树脂、填料、增韧剂、润滑剂、抗氧剂及光稳定剂混合均匀，将混合物置于主喂料口中，从侧喂料口加入炭黑，进行熔融共混，温度为210℃，螺杆转速为400转/分，挤出造粒，即得聚丙烯组合物；Weigh the appropriate components of polypropylene resin, filler, toughener, lubricant, antioxidant and light stabilizer and mix evenly, place the mixture in the main feeding port, add carbon black from the side feeding port, and carry out melting co- mixing, the temperature is 210°C, the screw speed is 400 rpm, extruded and granulated to obtain the polypropylene composition;
将上述所制备的聚丙烯组合物注塑成100mm*100mm*3mm样片用于性能测试。The polypropylene composition prepared above was injection molded into a 100mm*100mm*3mm sample piece for performance testing.
本发明各实施例及对比例的聚丙烯组合物的性能测试方法和标准如下：The performance testing methods and standards of the polypropylene composition of each embodiment of the present invention and comparative example are as follows:
(1)耐磨性能测试方法：按照GBT 5478-2008测试标准进行材料耐磨性测试，磨耗轮型号CS-10/载荷2.45N/循环次数100次/测试速率60rpm，测试后进行目视评价；评价等级划分：1级：磨痕非常明显；2级：磨痕比较明显；3级：磨痕轻微但能清晰分辨；4级：能观察到微弱的磨痕但不明显；5级：完全察觉不到磨痕；(1) Wear resistance test method: According to the GBT 5478-2008 test standard, the material wear resistance test is carried out, the wear wheel model is CS-10/load 2.45N/cycle number 100 times/test speed 60rpm, and visual evaluation is carried out after the test; Evaluation grades: Level 1: Wear marks are very obvious; Level 2: Wear marks are relatively obvious; Level 3: Wear marks are slight but can be clearly distinguished; Level 4: Weak wear marks can be observed but not obvious; Level 5: Completely noticeable less than wear marks;
(2)悬臂梁缺口冲击强度：按照ISO 180-2000标准进行测试。(2) Izod notched impact strength: tested according to ISO 180-2000 standard.
实施例1～17Examples 1-17
本实施例提供一系列的耐磨高抗冲聚丙烯组合物，配方如表1。This example provides a series of wear-resistant and high-impact polypropylene compositions, the formulations of which are shown in Table 1.
表1实施例1～17的配方(份)The formula (part) of table 1 embodiment 1～17
对比例1～8Comparative example 1-8
本对比例提供一系列聚丙烯组合物，其配方如表2。This comparative example provides a series of polypropylene compositions, the formulations of which are shown in Table 2.
表2对比例1～8的配方(份)The formula (part) of table 2 comparative examples 1～8
按照上述提及的方法对各实施例和对比例的聚丙烯组合物的性能进行测定，结果如表3。The properties of the polypropylene compositions of the various examples and comparative examples were measured according to the above-mentioned method, and the results are shown in Table 3.
表3各实施例和对比例的性能测试结果The performance test result of each embodiment and comparative example of table 3
| 性能performance | 耐磨性能Wear resistance | 悬臂梁缺口冲击强度(KJ/m 2) Notched Izod Impact Strength (KJ/m 2 ) |
| 实施例1Example 1 | 55 | 24.624.6 |
| 实施例2Example 2 | 55 | 15.215.2 |
| 实施例3Example 3 | 44 | 24.224.2 |
| 实施例4Example 4 | 44 | 21.521.5 |
| 实施例5Example 5 | 55 | 22.7922.79 |
| 实施例6Example 6 | 55 | 24.424.4 |
| 实施例7Example 7 | 55 | 23.623.6 |
| 实施例8Example 8 | 55 | 16.516.5 |
| 实施例9Example 9 | 44 | 15.715.7 |
| 实施例10Example 10 | 55 | 21.221.2 |
| 实施例11Example 11 | 55 | 19.219.2 |
| 实施例12Example 12 | 55 | 21.821.8 |
| 实施例13Example 13 | 55 | 19.119.1 |
| 实施例14Example 14 | 55 | 20.420.4 |
| 实施例15Example 15 | 55 | 23.923.9 |
| 实施例16Example 16 | 44 | 14.614.6 |
| 实施例17Example 17 | 44 | 21.621.6 |
| 对比例1Comparative example 1 | 33 | 6.86.8 |
| 对比例2Comparative example 2 | 33 | 8.58.5 |
| 对比例3Comparative example 3 | 33 | 14.814.8 |
| 对比例4Comparative example 4 | 33 | 7.97.9 |
| 对比例5Comparative example 5 | 33 | 17.817.8 |
| 对比例6Comparative example 6 | 22 | 42.142.1 |
| 对比例7Comparative example 7 | 22 | 23.423.4 |
| 对比例8Comparative example 8 | 55 | 8.78.7 |
由表3中的性能测试结果可知，实施例1～17中，通过添加高吸油值的炭黑，所制备耐磨高抗冲聚丙烯组合物的耐磨外观等级均≥4，同时优选的高吸油值炭黑可以促进材料当中的增韧剂分散，使得材料的悬臂梁缺口冲击强度均＞10KJ/m
2。实施例1中对炭黑的吸油值、聚丙烯树脂种类及熔指、POE熔指进行优选，耐磨等级以及缺口冲击强度都有进一步提升，达到5级的耐磨外观等级，缺口冲击强度均＞20KJ/m
2。这是由于优化了聚丙烯的流动性后促进了炭黑在材料中的分散，有利于改善聚丙烯树脂与炭黑之间的相互作用以及增加缠结位点，改善材料的耐磨性能，同时由于优选了POE的熔指，进一步降低了PP/POE的粘度比，有利于POE的进一步分散，使得材料的冲击性能等到有效提升，在此基础上实现采用较低的低POE含量来达到高的冲击强度，避免由于过量POE的加入导致材料的耐磨性能下降。
From the performance test results in Table 3, it can be seen that in Examples 1 to 17, by adding carbon black with high oil absorption value, the wear-resistant and high-impact polypropylene compositions prepared have a wear-resistant appearance grade ≥ 4, and the preferred high The carbon black with oil absorption value can promote the dispersion of the toughening agent in the material, so that the notched Izod impact strength of the material is greater than 10KJ/m 2 . In Example 1, the oil absorption value of carbon black, polypropylene resin type, melt index, and POE melt index were optimized, and the wear resistance level and notched impact strength were further improved, reaching a wear-resistant appearance level of 5, and the notch impact strength was average. >20KJ/m 2 . This is because the dispersion of carbon black in the material is promoted after optimizing the fluidity of polypropylene, which is conducive to improving the interaction between polypropylene resin and carbon black and increasing the entanglement sites, improving the wear resistance of the material, and at the same time Due to the optimization of the melt index of POE, the viscosity ratio of PP/POE is further reduced, which is conducive to the further dispersion of POE, so that the impact performance of the material can be effectively improved, and on this basis, the use of lower POE content to achieve high Impact strength, to avoid the reduction of the wear resistance of the material due to the addition of excessive POE.
实施例1与实施例2/3对比，说明通过对聚丙烯进行优选有利于进一步改善材料的耐磨性和抗冲击性能。The comparison between Example 1 and Example 2/3 shows that the optimization of polypropylene is beneficial to further improve the wear resistance and impact resistance of the material.
实施例1/6与实施例7/8/12对比，说明通过对增韧剂进行优选有利于进一步改善材料的抗冲击性能。The comparison between Example 1/6 and Example 7/8/12 shows that optimizing the toughening agent is beneficial to further improve the impact resistance of the material.
实施例1与对比例1/2/3对比说明通过添加优选的炭黑，相比于不添加炭黑、添加低吸油值的炭黑，材料的耐磨性以及抗冲击性能均有明显提升。The comparison between Example 1 and Comparative Example 1/2/3 shows that by adding the preferred carbon black, compared with no carbon black and carbon black with low oil absorption value, the wear resistance and impact resistance of the material are significantly improved.
对比例4中炭黑添加量过低，效果不明显；而对比例5中炭黑添加过量，反而会由于挤出过程中分散不良而导致材料中存在较多的团聚体缺陷点，从而导致材料的耐磨性和抗冲击性能下降。In comparative example 4, the amount of carbon black added is too low, and the effect is not obvious; while in comparative example 5, carbon black is added too much, but there will be more aggregate defect points in the material due to poor dispersion in the extrusion process, resulting in material The wear resistance and impact resistance performance is reduced.
对比例6中添加了过量的POE，虽然获取了非常高的抗冲强度，但由于POE对材料表明的软化作用，导致了材料的耐磨性显著下降。In Comparative Example 6, an excessive amount of POE was added. Although a very high impact strength was obtained, the wear resistance of the material decreased significantly due to the softening effect of POE on the material.
实施例1与对比例7相比较，可以得知在获取相近的抗冲击强度时，未添加炭黑的配方中需要添加较大量的POE，从而导致材料的耐磨性显著下降；对比 例8中，增韧剂POE的添加量过少，对耐磨性能无明显影响，但材料的冲击性能严重下降。Comparing Example 1 with Comparative Example 7, it can be known that when obtaining similar impact strength, a relatively large amount of POE needs to be added in the formula without adding carbon black, thereby causing a significant decline in the wear resistance of the material; in Comparative Example 8 , The amount of the toughening agent POE added is too small, which has no obvious effect on the wear resistance, but the impact performance of the material is seriously reduced.
综上所述，本发明中选用高吸油值的炭黑作为物理交联剂，用于聚丙烯改性，同时对PP/POE进行了优选，制备得到的耐磨高抗冲聚丙烯组合物具有优异的耐磨性能和高冲击性能，可广泛应于汽车内饰件。In summary, in the present invention, carbon black with high oil absorption value is selected as a physical crosslinking agent for polypropylene modification, and PP/POE is optimized at the same time, and the wear-resistant and high-impact polypropylene composition prepared has Excellent wear resistance and high impact performance, can be widely used in automotive interior parts.
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的说技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that Modifications or equivalent replacements can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
- 一种耐磨高抗冲聚丙烯组合物，其特征在于，包括以下重量份数的组分：聚丙烯树脂30-85份，增韧剂5-25份，填料5-25份，炭黑5-20份，润滑剂1-3份，抗氧剂0-0.8份，光稳定剂0-0.6份；A wear-resistant and high-impact polypropylene composition, characterized in that it comprises the following components in parts by weight: 30-85 parts of polypropylene resin, 5-25 parts of toughening agent, 5-25 parts of filler, 5 parts of carbon black -20 parts, lubricant 1-3 parts, antioxidant 0-0.8 parts, light stabilizer 0-0.6 parts;其中，所述炭黑的吸油值为120-180mL/100g。Wherein, the oil absorption value of the carbon black is 120-180mL/100g.
- 根据权利要求1所述耐磨高抗冲聚丙烯组合物，其特征在于，所述耐磨高抗冲聚丙烯组合物包括以下重量份数的组分：聚丙烯树脂50-70份，增韧剂10-15份，填料10-15份，炭黑10-15份，润滑剂1.5-2.5份，抗氧剂0.3-0.6份，光稳定剂0.2-0.4份。The wear-resistant and high-impact polypropylene composition according to claim 1, wherein the wear-resistant and high-impact polypropylene composition comprises the following components in parts by weight: 50-70 parts of polypropylene resin, toughened 10-15 parts of additives, 10-15 parts of fillers, 10-15 parts of carbon black, 1.5-2.5 parts of lubricants, 0.3-0.6 parts of antioxidants, and 0.2-0.4 parts of light stabilizers.
- 根据权利要求1所述耐磨高抗冲聚高抗冲聚丙烯组合物，其特征在于，所述炭黑的吸油值为130-175mL/100g。The wear-resistant high-impact polypropylene composition according to claim 1, wherein the carbon black has an oil absorption value of 130-175mL/100g.
- 根据权利要求1所述耐磨高抗冲聚高抗冲丙烯组合物，其特征在于，所述聚丙烯树脂为均聚聚丙烯或共聚聚丙烯中的至少一种；所述聚丙烯树脂按照ASTM D-1238-2013标准，在温度为230℃、负荷为2.16Kg条件下的熔体流动速率为60-115g/10min。The wear-resistant high-impact polypropylene composition according to claim 1, wherein the polypropylene resin is at least one of homopolypropylene or copolymerized polypropylene; the polypropylene resin is according to ASTM According to the D-1238-2013 standard, the melt flow rate is 60-115g/10min at a temperature of 230°C and a load of 2.16Kg.
- 根据权利要求1所述耐磨高抗冲聚丙烯组合物，其特征在于，所述增韧剂为POE；所述POE按照ASTM D-1238-2013标准，在温度为190℃、负荷为2.16kg条件下的熔体流动速率为3-14g/10min。The wear-resistant and high-impact polypropylene composition according to claim 1, wherein the toughening agent is POE; the POE is in accordance with the ASTM D-1238-2013 standard, at a temperature of 190°C and a load of 2.16kg The melt flow rate under the condition is 3-14g/10min.
- 根据权利要求1所述耐磨高抗冲聚丙烯组合物，其特征在于，所述填料为滑石粉、碳酸钙、硫酸钡或玻璃纤维中的至少一种。The wear-resistant and high-impact polypropylene composition according to claim 1, wherein the filler is at least one of talcum powder, calcium carbonate, barium sulfate or glass fiber.
- 根据权利要求1所述耐磨高抗冲聚丙烯组合物，其特征在于，所述润滑剂为酰胺、酰胺母粒或硅酮母粒中的至少一种。The wear-resistant and high-impact polypropylene composition according to claim 1, wherein the lubricant is at least one of amide, amide masterbatch or silicone masterbatch.
- 根据权利要求1所述耐磨高抗冲聚丙烯组合物，其特征在于，所述抗氧剂为受阻酚类或亚磷酸酯类中的至少一种；所述光稳定剂为受阻胺类。The wear-resistant and high-impact polypropylene composition according to claim 1, wherein the antioxidant is at least one of hindered phenols or phosphites; and the light stabilizer is hindered amines.
- 权利要求1～8中任一所述耐磨高抗冲聚丙烯组合物的制备方法，其特征在于，包括以下步骤：The preparation method of the wear-resistant and high-impact polypropylene composition described in any one of claims 1 to 8, characterized in that it comprises the following steps:将聚丙烯树脂、填料、增韧剂、润滑剂、抗氧剂及光稳定剂混合均匀，将混合物置于主喂料口中，从侧喂料口加入炭黑，进行熔融混炼，挤出造粒，即得所述耐磨高抗冲聚丙烯组合物。Mix polypropylene resin, filler, toughener, lubricant, antioxidant and light stabilizer evenly, place the mixture in the main feeding port, add carbon black from the side feeding port, melt and knead, and extrude pellets to obtain the wear-resistant high-impact polypropylene composition.
- 权利要求1～8中任一所述耐磨高抗冲聚丙烯组合物在制备汽车内饰件 中的应用。The application of any one of the wear-resistant high-impact polypropylene composition in claims 1 to 8 in the preparation of automotive interior parts.
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