CN109438847B - High-impact-resistance and wear-resistance PP/PA composite material and preparation method thereof - Google Patents
High-impact-resistance and wear-resistance PP/PA composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 239000004743 Polypropylene Substances 0.000 claims description 85
- 229920001155 polypropylene Polymers 0.000 claims description 73
- 239000004952 Polyamide Substances 0.000 claims description 62
- 229920002647 polyamide Polymers 0.000 claims description 62
- 229920001971 elastomer Polymers 0.000 claims description 39
- 239000000806 elastomer Substances 0.000 claims description 39
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims description 38
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 36
- 239000004793 Polystyrene Substances 0.000 claims description 36
- 229920002223 polystyrene Polymers 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- -1 beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl Chemical group 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 17
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 229960000892 attapulgite Drugs 0.000 claims description 14
- 229910052625 palygorskite Inorganic materials 0.000 claims description 14
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 14
- 238000005299 abrasion Methods 0.000 claims description 11
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- ISLKXKUKTKLXLM-UHFFFAOYSA-N ethanol triethoxy(phenyl)silane Chemical compound C(C)O.C1(=CC=CC=C1)[Si](OCC)(OCC)OCC ISLKXKUKTKLXLM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 229940116351 sebacate Drugs 0.000 claims description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000005936 piperidyl group Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000009736 wetting Methods 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
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- 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)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a high-impact-resistance wear-resistance PP/PA composite material and a preparation method thereof, wherein the high-impact-resistance wear-resistance PP/PA composite material is composed of 100 parts of PP, 30-40 parts of PA, 10-15 parts of compatilizer, 0.2-0.5 part of antioxidant, 0.2-0.5 part of stabilizer, 0.2-0.5 part of lubricant and 10-15 parts of self-made filler, the PP/PA composite material is uniformly mixed by a high-speed mixer according to a proportion and then added into a double-screw extruder for melt extrusion granulation, and the prepared PP/PA composite material has excellent impact property, wear resistance at low temperature and the like. The high-impact-resistance wear-resistance PP/PA composite material prepared by the invention is used in the fields of automobiles, electronic appliances and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-impact-resistance wear-resistance PP/PA composite material and a preparation method thereof.
Background
Polypropylene (PP), which is a thermoplastic resin obtained by polymerizing propylene, is classified into isotactic polypropylene (isotatic polypropylene), atactic polypropylene (atactic polypropylene) and syndiotactic polypropylene (syndiotactic polypropylene) according to the methyl arrangement position. The polyethylene has the advantages of no toxicity, no smell, small density, strength, rigidity, hardness and heat resistance superior to low-pressure polyethylene, can be used at about 100 ℃, has good dielectric property and high-frequency insulation property, is not influenced by humidity, but becomes brittle at low temperature, is not wear-resistant and is easy to age. Polypropylene has poor impact resistance, and abrasion resistance cannot meet the requirement of high strength loss, thus severely limiting the application range of the polypropylene.
Polyamide (PA) refers to a high polymer whose main chain contains polar amide groups (-CO-NH-). PA has good combination properties: excellent mechanical property, high mechanical strength and good toughness of the nylon; has good wetting property and friction resistance. The nylon has good self-lubricating property and small friction coefficient, so that the nylon is used as a transmission part and has long service life; excellent heat resistance, such as high-crystallinity nylon such as nylon 46, has high heat distortion temperature and can be used for a long time at 150 ℃; the nylon has high volume resistance and high breakdown voltage resistance, and is an excellent electrical and electrical appliance insulating material; excellent weatherability; the water absorption is high, the saturated water can reach more than 3 percent, and the dimensional stability of a workpiece is influenced to a certain degree.
The method for improving the impact property of the PP composite material has good toughness effect in a PP/elastomer binary blending system, but the strength and the rigidity of the material are often reduced; according to the traditional method for improving the wear resistance of the PP composite material, the wear-resistant agent PTFE or molybdenum disulfide is added into the PP composite material and is compounded with mineral substances, but the toughness and the impact resistance of the material obtained by the method are poor, and the product is easy to catalyze and break in a low-temperature environment.
The impact performance can be improved by blending PP/PA, but PP is a non-polar polymer, PA is a polar polymer, and the compatibility of the PP and the PA is poor.
Disclosure of Invention
A high impact resistant and wear resistant PP/PA composite material is characterized in that: the composition is prepared from the following components in parts by weight:
the compatilizer is maleic anhydride grafted polyolefin elastomer and oxazoline functionalized polystyrene, and the dosage ratio of the maleic anhydride grafted polyolefin elastomer to the oxazoline functionalized polystyrene is 7: 3.
A high impact resistant and wear resistant PP/PA composite material is characterized in that: the components also comprise 10-15 parts of self-made filler, wherein the self-made filler is obtained by calcining attapulgite and pyrophyllite at the temperature of 400-450 ℃ for 3 hours, cooling to room temperature, grinding for 2H in a ball mill, sieving with a 2500-mesh sieve, and performing surface treatment by using 8-10% phenyltriethoxysilane ethanol solution, wherein the ratio of the attapulgite to the pyrophyllite is 5: 2.
The maleic anhydride grafted polyolefin elastomer is grafted by 0.9-1.2%.
The grafting rate of the oxazoline functionalized polystyrene is 1.1-1.6%.
The grafting rate of the maleic anhydride grafted polyolefin elastomer is 1.0 percent, and the grafting rate of the oxazoline functionalized polystyrene is 1.3 percent.
The antioxidant is beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) n-octadecyl propionate and dilauryl thiodipropionate.
The lubricant is one or more of calcium stearate, zinc stearate and paraffin.
The stabilizer is one or more of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole, bis-2, 2,6, 6-tetramethylpiperidyl sebacate and N, N-bis (2,2,6, 6-tetramethyl-4-piperidyl) -N, N-diformaldehyde hexamethylene diamine.
A preparation method of a high-impact-resistance wear-resistance PP/PA composite material comprises the following steps:
(1) pouring PP, PA and compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding an antioxidant, a lubricant or a self-made filler, and mixing for 15 minutes to obtain a premix, wherein the temperature of the mixer is 90-100 ℃, and the rotating speed is 800 revolutions per minute.
(2) Feeding the premix prepared in the step (1) into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material; wherein the temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
The invention has the beneficial effects
1. According to the invention, the compatilizer maleic anhydride grafted polyolefin elastomer and oxazoline functionalized polystyrene are compounded according to the ratio of 7:3, so that compared with the single use of the maleic anhydride grafted polyolefin elastomer or the single use of the oxazoline functionalized polystyrene, the mechanical property of the material is greatly improved, the maximum tensile strength is improved by 24%, the maximum bending strength is improved by 27%, the maximum notch impact strength is improved by 38%, and the maximum low-temperature notch impact strength is improved by 68%. When the grafting rate of the maleic anhydride grafted polyolefin elastomer is 1.0 percent and the grafting rate of the oxazoline functionalized polystyrene is 1.3 percent, the mechanical property of the material reaches the best.
2. The self-made filler is added to improve the wear resistance of the material, and the mechanical properties such as notch impact property are greatly improved and are obviously superior to those of the added common wear-resistant agent. The tensile strength is improved by 32 percent at most, the bending strength is improved by 49 percent, the notch impact strength is improved by 82 percent, and the low-temperature notch impact strength is 97 percent and the abrasion is reduced by 26 percent.
Detailed Description
The invention is further illustrated by the following specific examples which are intended to be illustrative only and not to be limiting of the invention, the following examples, unless otherwise specified, are intended to illustrate the invention as defined in the claims.
The test method of the material comprises the following steps: the tensile strength is ISO527, the bending strength is ISO178, the notch impact strength is ISO180, the normal temperature is 23 ℃, the low temperature is-40 ℃, the abrasion is ASTMD1044, and the friction coefficient is ASTMD 1894.
Example 1
100 parts of PP (polypropylene), 35 parts of PA (polyamide), 7 parts of maleic anhydride grafted polyolefin elastomer, 3 parts of oxazoline functionalized polystyrene, 0.2 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate, 0.2 part of calcium stearate and 0.3 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 95 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and preparing the PP/PA composite material with high impact resistance and wear resistance through extrusion, water cooling, grain cutting and drying; wherein the temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Comparative example 1
100 parts of PP (polypropylene), 35 parts of PA (polyamide), 10 parts of maleic anhydride grafted polyolefin elastomer, 0.2 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate, 0.2 part of calcium stearate and 0.3 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 95 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and preparing the high-impact-resistance and wear-resistance PP/PA composite material by extrusion, water cooling, grain cutting and drying, wherein the temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Comparative example 2
100 parts of PP, 35 parts of PA, 10 parts of oxazoline functionalized polystyrene, 0.2 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate, 0.2 part of calcium stearate and 0.3 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole.
Pouring PP, PA and compatilizer into a high-speed mixer according to the proportion and mixing for 10 minutes; and adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain a premix, wherein the temperature of the mixer is 95 ℃, and the rotating speed is 800 revolutions per minute.
Feeding the premix into a double-screw extruder, and preparing the PP/PA composite material with high impact resistance and wear resistance through extrusion, water cooling, grain cutting and drying; wherein the temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Comparative example 3
100 parts of PP (polypropylene), 40 parts of PA (polyamide), 5 parts of maleic anhydride grafted polyolefin elastomer, 3 parts of oxazoline functionalized polystyrene, 0.2 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate, 0.2 part of calcium stearate and 0.3 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 90 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and preparing the high-impact-resistance and wear-resistance PP/PA composite material by extrusion, water cooling, grain cutting and drying, wherein the temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
TABLE 1
According to the embodiment 1, the comparative example 1 and the comparative example 2, the compatilizer maleic anhydride grafted polyolefin elastomer and oxazoline functionalized polystyrene are compounded, so that the mechanical properties of the material are greatly improved, the maximum tensile strength is improved by 24%, the maximum bending strength is improved by 27%, the maximum notched impact strength is improved by 38%, and the maximum low-temperature notched impact strength is improved by 68% compared with the single use of the maleic anhydride grafted polyolefin elastomer or the single use of the oxazoline functionalized polystyrene. Also, from example 1 and comparative example 3, it can be seen that the best technical result is obtained when the maleic anhydride grafted polyolefin elastomer of the present invention and the oxazoline functionalized polystyrene are used in an amount of 7: 3.
Example 2
100 parts of PP, 40 parts of PA, 7.7 parts of maleic anhydride grafted polyolefin elastomer, 3.3 parts of oxazoline functionalized polystyrene, 0.4 part of N, N-bis (2,2,6,6, -tetramethyl-4 piperidyl) -N, N-dicarboxylhexanediamine, 0.1 part of beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) N-octadecyl propionate, 0.2 part of dilauryl thiodipropionate and 0.3 part of paraffin, wherein the grafting ratio of the maleic anhydride grafted polyolefin elastomer is 1.2 percent, and the grafting ratio of the oxazoline functionalized polystyrene is 1.6 percent.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 90 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Example 3
100 parts of PP (polypropylene), 30 parts of PA (polyamide), 8.4 parts of maleic anhydride grafted polyolefin elastomer, 3.6 parts of oxazoline functionalized polystyrene, 0.3 part of bis-2, 2,6, 6-tetramethylpiperidinol sebacate, 0.3 part of beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) n-octadecyl propionate, 0.2 part of dilauryl thiodipropionate and 0.2 part of zinc stearate, wherein the grafting ratio of the maleic anhydride grafted polyolefin elastomer is 1.2 percent, and the grafting ratio of the oxazoline functionalized polystyrene is 1.1 percent.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 100 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Example 4
100 parts of PP (polypropylene), 37 parts of PA (polyamide), 10.5 parts of maleic anhydride grafted polyolefin elastomer, 4.5 parts of oxazoline functionalized polystyrene, 0.1 part of bis-2, 2,6, 6-tetramethylpiperidinol sebacate, 0.1 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole, 0.1 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate and 0.2 part of zinc stearate, wherein the grafting ratio of the maleic anhydride grafted polyolefin elastomer is 0.9 percent, and the grafting ratio of the oxazoline functionalized polystyrene is 1.5 percent.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 100 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Example 5
100 parts of PP (polypropylene), 33 parts of PA (polyamide), 9.1 parts of maleic anhydride grafted polyolefin elastomer, 3.9 parts of oxazoline functionalized polystyrene, 0.3 part of bis-2, 2,6, 6-tetramethylpiperidinol sebacate, 0.2 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole, 0.1 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate and 0.3 part of zinc stearate. 0.2 part of paraffin, the grafting rate of the maleic anhydride grafted polyolefin elastomer is 1.0 percent, and the grafting rate of the oxazoline functionalized polystyrene is 1.3 percent.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 100 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
TABLE 2
Examples 2-5 show that when the maleic anhydride grafted polyolefin elastomer graft ratio is 1.0%, and the oxazoline functionalized polystyrene graft ratio is 1.3%, the mechanical properties of the material are optimal.
Example 6
100 parts of PP, 30 parts of PA, 10.5 parts of maleic anhydride grafted polyolefin elastomer, 4.5 parts of oxazoline functionalized polystyrene, 12 parts of self-made filler, 0.2 part of bis-2, 2,6, 6-tetramethylpiperidinol sebacate, 0.1 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-4 hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate and 0.2 part of paraffin.
The self-made filler is prepared by calcining attapulgite and pyrophyllite at 400 ℃ for 3 hours, cooling to room temperature, grinding for 2H in a ball mill, sieving with a 2500-mesh sieve, and performing surface treatment by using a 10% phenyltriethoxysilane ethanol solution, wherein the ratio of the attapulgite to the pyrophyllite is 5: 2.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the self-made filler, the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 100 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Comparative example 4
100 parts of PP, 30 parts of PA, 15 parts of maleic anhydride grafted polyolefin elastomer, 12 parts of wear-resistant agent polytetrafluoroethylene, 0.2 part of bis-2, 2,6, 6-tetramethylpiperidinol sebacate, 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 0.1 part of dilauryl thiodipropionate and 0.2 part of paraffin.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the polytetrafluoroethylene, the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 100 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
TABLE 3
As can be seen from Table 3, the addition of the self-made filler of the present invention improves the wear resistance of the material, and the mechanical properties such as notch impact performance are greatly improved, which is obviously superior to the addition of a common wear-resistant agent. The tensile strength is improved by 32 percent at most, the bending strength is improved by 49 percent, the notch impact strength is improved by 82 percent, and the low-temperature notch impact strength is 97 percent and the abrasion is reduced by 26 percent.
Comparative example 5
100 parts of PP, 40 parts of PA, 13 parts of maleic anhydride grafted polyolefin elastomer, 10 parts of filler, 0.5 part of N, N-bis (2,2,6, 6-tetramethyl-4 piperidyl) -N, N-dialdehyde hexamethylene diamine, 0.1 part of N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate and 0.5 part of zinc stearate. The grafting rate of the maleic anhydride grafted polyolefin elastomer is 0.9 percent, and the grafting rate of the oxazoline functionalized polystyrene is 1.6 percent.
The filler is obtained by mixing attapulgite and pyrophyllite, grinding into powder, sieving with a 500-mesh sieve, and performing surface treatment with 5% phenyltriethoxysilane ethanol solution, wherein the ratio of the attapulgite to the pyrophyllite is 1: 2.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the filler, the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 100 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Example 7
100 parts of PP, 40 parts of PA, 9.1 parts of maleic anhydride grafted polyolefin elastomer, 3.9 parts of oxazoline functionalized polystyrene, 10 parts of self-made filler, 0.5 part of N, N-bis (2,2,6,6, -tetramethyl-4 piperidyl) -N, N-dialdehyde hexamethylene diamine, 0.1 part of N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate and 0.5 part of zinc stearate. The grafting rate of the maleic anhydride grafted polyolefin elastomer is 0.9 percent, and the grafting rate of the oxazoline functionalized polystyrene is 1.6 percent.
The self-made filler is prepared by calcining attapulgite and pyrophyllite at 400 ℃ for 3 hours, cooling to room temperature, grinding for 2H in a ball mill, sieving with a 2500-mesh sieve, and performing surface treatment by using 8% phenyltriethoxysilane ethanol solution, wherein the ratio of the attapulgite to the pyrophyllite is 5: 2.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the self-made filler, the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 90 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Example 8
100 parts of PP, 35 parts of PA, 8.4 parts of maleic anhydride grafted polyolefin elastomer, 3.6 parts of oxazoline functionalized polystyrene, 15 parts of self-made filler, 0.3 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole, 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 0.2 part of dilauryl thiodipropionate and 0.3 part of zinc stearate. The grafting rate of the maleic anhydride grafted polyolefin elastomer is 1.2 percent, and the grafting rate of the oxazoline functionalized polystyrene is 1.1 percent.
The self-made filler is prepared by calcining attapulgite and pyrophyllite at 450 ℃ for 3 hours, cooling to room temperature, grinding for 2H in a ball mill, sieving with a 2500-mesh sieve, and performing surface treatment by using a 10% phenyltriethoxysilane ethanol solution, wherein the ratio of the attapulgite to the pyrophyllite is 5: 2.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the self-made filler, the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 95 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
Example 9
100 parts of PP, 34 parts of PA, 7 parts of maleic anhydride grafted polyolefin elastomer, 3 parts of oxazoline functionalized polystyrene, 11 parts of self-made filler, 0.3 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole, 0.3 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 0.2 part of dilauryl thiodipropionate, 0.1 part of calcium stearate and 0.1 part of paraffin. The grafting rate of the maleic anhydride grafted polyolefin elastomer is 1.0 percent, and the grafting rate of the oxazoline functionalized polystyrene is 1.3 percent.
The self-made filler is prepared by calcining attapulgite and pyrophyllite at 450 ℃ for 3 hours, cooling to room temperature, grinding for 2H in a ball mill, sieving with a 2500-mesh sieve, and performing surface treatment by using 9% phenyltriethoxysilane ethanol solution, wherein the ratio of the attapulgite to the pyrophyllite is 5: 2.
And pouring the PP, the PA and the compatilizer into a high-speed mixer according to the proportion, mixing for 10 minutes, adding the self-made filler, the antioxidant, the lubricant and the stabilizer, and mixing for 15 minutes to obtain the premix. The mixer temperature was 100 ℃ and the rotational speed was 800 rpm.
Feeding the premix into a double-screw extruder, and performing extrusion, water cooling, grain cutting and drying to obtain the high-impact-resistance and wear-resistance PP/PA composite material. The temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, and the rotating speed of the double-screw extruder is 220 r/min at the head temperature of 220 ℃.
TABLE 4
According to table 4, compared with the filler prepared by the specific process, the wear of the filler prepared by the specific process is reduced by 24%, the notch impact strength is improved by 44%, and the low-temperature notch impact strength is improved by 47%. The grafting rate of the maleic anhydride grafted polyolefin elastomer is 1.0 percent, the grafting rate of the oxazoline functionalized polystyrene is 1.3 percent, and the performance of the material reaches the best.
Claims (9)
1. A high impact resistant and wear resistant PP/PA composite material is characterized in that: the paint is prepared from the following components in parts by weight:
PP100 parts
30-40 parts of PA
10-15 parts of compatilizer
0.2 to 0.5 portion of antioxidant
0.2 to 0.5 portion of stabilizer
0.2 to 0.5 portion of lubricant
The compatilizer is maleic anhydride grafted polyolefin elastomer and oxazoline functionalized polystyrene, and the dosage ratio of the maleic anhydride grafted polyolefin elastomer to the oxazoline functionalized polystyrene is 7: 3.
2. The high impact, abrasion resistant PP/PA composite according to claim 1, wherein: the components also comprise 10-15 parts of self-made filler, the self-made filler is obtained by calcining attapulgite and pyrophyllite at the temperature of 400-450 ℃ for 3 hours, cooling to room temperature, grinding for 2H in a ball mill, sieving with a 2500-mesh sieve, and performing surface treatment by using 8-10% phenyltriethoxysilane ethanol solution, wherein the ratio of the attapulgite to the pyrophyllite is 5: 2.
3. A high impact, abrasion resistant PP/PA composite according to claim 1 or 2, characterized in that: the grafting rate of the maleic anhydride grafted polyolefin elastomer is 0.9-1.2%.
4. A high impact, abrasion resistant PP/PA composite according to claim 1 or 2, characterized in that: the grafting rate of the oxazoline functionalized polystyrene is 1.1-1.6%.
5. A high impact, abrasion resistant PP/PA composite according to claim 1 or 2, characterized in that: the grafting rate of the maleic anhydride grafted polyolefin elastomer is 1.0 percent, and the grafting rate of the oxazoline functionalized polystyrene is 1.3 percent.
6. A high impact, abrasion resistant PP/PA composite according to claim 1 or 2, characterized in that: the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and dilauryl thiodipropionate.
7. A high impact, abrasion resistant PP/PA composite according to claim 1 or 2, characterized in that: the lubricant is one or more of calcium stearate, zinc stearate and paraffin.
8. A high impact, abrasion resistant PP/PA composite according to claim 1 or 2, characterized in that: the stabilizer is one or more of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole, bis-2, 2,6, 6-tetramethylpiperidyl sebacate and N, N '-bis (2,2,6, 6-tetramethyl-4-piperidyl) -N, N' -dialdehyde hexamethylenediamine.
9. A preparation method of a high-impact-resistance wear-resistance PP/PA composite material comprises the following steps:
(1) 100 parts of PP (polypropylene), 35 parts of PA (polyamide), 7 parts of maleic anhydride grafted polyolefin elastomer, 3 parts of oxazoline functionalized polystyrene, 0.2 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.1 part of dilauryl thiodipropionate, 0.2 part of calcium stearate and 0.3 part of 2- (2-hydroxy-3, 5-di-tert-amyl) benzotriazole;
(2) pouring PP, PA and a compatilizer into a high-speed mixer according to a ratio, mixing for 10 minutes, adding an antioxidant, a lubricant and a stabilizer, and mixing for 15 minutes to obtain a premix, wherein the temperature of the mixer is 95 ℃, and the rotating speed is 800 revolutions per minute;
(3) feeding the premix into a double-screw extruder, and preparing the PP/PA composite material with high impact resistance and wear resistance through extrusion, water cooling, grain cutting and drying; wherein the temperature of each zone of the double-screw extruder is as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 210 ℃, the temperature of a machine head is 220 ℃, and the rotating speed of the double-screw extruder is 220 rpm.
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Effective date of registration: 20231130 Address after: 315000 Gulin Village, Gulin Town, Haishu District, Ningbo City, Zhejiang Province Patentee after: Ningbo Haishu Hongwei Plastic Co.,Ltd. Address before: 230000, Building 204, Phase 1, E-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province, China Patentee before: HEFEI WEILANHUA GREEN ENGINEERING CO.,LTD. Effective date of registration: 20231130 Address after: 230000, Building 204, Phase 1, E-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province, China Patentee after: HEFEI WEILANHUA GREEN ENGINEERING CO.,LTD. Address before: 239000 no.2188 fengle Avenue, Chuzhou City, Anhui Province Patentee before: CHUZHOU VOCATIONAL AND TECHNICAL College |