CN109438847A - A kind of high-impact, wear-resisting PP/PA composite material and preparation method - Google Patents
A kind of high-impact, wear-resisting PP/PA composite material and preparation method Download PDFInfo
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- CN109438847A CN109438847A CN201811337117.3A CN201811337117A CN109438847A CN 109438847 A CN109438847 A CN 109438847A CN 201811337117 A CN201811337117 A CN 201811337117A CN 109438847 A CN109438847 A CN 109438847A
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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 7
- 239000000314 lubricant Substances 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 34
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 34
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 33
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 32
- 239000004793 Polystyrene Substances 0.000 claims description 30
- 229920002223 polystyrene Polymers 0.000 claims description 30
- -1 propionic acid n-octadecyl alcohol ester Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005453 pelletization Methods 0.000 claims description 16
- 235000019260 propionic acid Nutrition 0.000 claims description 16
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 15
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 15
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 14
- 229960000892 attapulgite Drugs 0.000 claims description 13
- 229910052625 palygorskite Inorganic materials 0.000 claims description 13
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 10
- 239000012964 benzotriazole Substances 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 6
- 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 6
- 238000000227 grinding Methods 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000005936 piperidyl group Chemical group 0.000 claims description 5
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 49
- 229920001155 polypropylene Polymers 0.000 description 49
- 239000004952 Polyamide Substances 0.000 description 41
- 229920002647 polyamide Polymers 0.000 description 41
- 239000000463 material Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 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
- 230000035939 shock Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
Landscapes
- 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 kind of high-impacts, wear-resisting PP/PA composite material and preparation method, a kind of high-impact-resistance wear-resistant PP, PA composite material is made of PP100 parts, 30-40 parts of PA, 10-15 parts of compatilizer, 0.2-0.5 parts of antioxidant, 0.2-0.5 parts of stabilizer, 0.2-0.5 parts of lubricant, 10-15 parts of self-made fill, it is passed through to high-speed mixer according to the proportion, double screw extruder melting extrusion granulation is added after mixing, the PP/PA composite material of preparation has excellent impact property is excellent, low temperature impact properties are wear-resisting etc..High-impact prepared by the present invention, wear-resisting PP/PA composite material are for fields such as automobile, electronic apparatus.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of high-impact-resistance wear-resistant PP/PA composite material and its system
Preparation Method.
Background technique
Polypropylene (PP) is the thermoplastic resin as prepared by propylene polymerization, is divided into isotactic poly- third by methyl arrangement position
Alkene (isotactic polypropylene), random polypropylene (atactic polypropylene) and syndiotactic polypropylene
Three kinds of (syndiotactic polypropylene).Nontoxic, tasteless, density is small, and intensity, rigidity, hardness heat resistance are superior to
Low pressure polyethylene can be used at 100 DEG C or so, had good dielectric properties and high-frequency insulation and do not influenced by humidity, but
Become fragile when low temperature, it is not wear-resisting, easy to aging.Polyacrylic shock resistance is poor, and wearability is not able to satisfy the demand of high-intensitive loss,
Seriously limit its application range.
Polyamide (PA) refers to that master link contains the high polymer of polar amide groups (- CO-NH one).PA has good comprehensive
Close performance: excellent mechanical property, the high mechanical strength of nylon, good toughness；Lubricant nature, rub resistance are good.Nylon has good
Self-lubricity, coefficient of friction is small, thus, as its long service life of transmission parts；Excellent heat resistance, such as nylon 46 are highly crystalline
Property nylon heat distortion temperature it is very high, can at 150 DEG C long-term phase use；Different electrical insulation capability, the volume resistance of nylon is very
Height, breakdown voltage resistant height are excellent electrical, electrical apparatus insulation material；Excellent against weather；Water imbibition is big, and saturated water is reachable
To 3% or more, in the dimensional stability for influencing product to a certain degree.
Though the method for improving PP composite impact performance has good toughness to imitate in PP/ elastomer binary blends
Fruit, but often reduce the strength and stiffness of material；The traditional method of PP composite-material abrasive is improved in PP composite material
Anti-wear agent PTFE is added or molybdenum disulfide is compound with minerals simultaneously, but this approach obtains toughness of material and resistance
Can be poor, product is easy catalysis, is crushed in low temperature environment.
It being blended using PP/PA, can improve impact property, but PP is non-polar high polymer, PA is polarity macromolecule, two
Person's compatibility is very poor, and the application does not reduce the stiffness and strength of material, significantly by addition compounding compatilizer and self-made fill
Improve the impact property and wear-resisting property of PP/PA composite material, especially low temperature impact properties.
Summary of the invention
A kind of high-impact, wear-resisting PP/PA composite material, it is characterised in that: be prepared by weight by following components:
The compatilizer is maleic anhydride stem grafting polyolefin elastomer and oxazoline functionalized polystyrene, the two dosage
Than for 7:3.
A kind of high-impact, wear-resisting PP/PA composite material, it is characterised in that: it further include 10-15 parts of self-made fills in component,
The self-made fill is calcined 3 hours by attapulgite and pyrophyllite by 400-450 DEG C, is cooled to room temperature, in the ball mill
After grinding 2H, 2500 meshes are crossed, carry out surface treatment acquisition using 8-10% phenyl triethoxysilane ethanol solution, it is concave-convex
The ratio of stick soil and pyrophyllite is 5:2.
The maleic anhydride stem grafting polyolefin elastomer graft 0.9-1.2%.
The oxazoline functionalized polystyrene grafting rate 1.1-1.6%.
The maleic anhydride stem grafting polyolefin elastomer graft rate 1.0%, oxazoline functionalized polystyrene grafting rate
1.3%.
The antioxidant is β-(3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid n-octadecyl alcohol ester and thio dipropyl
Sour dilauryl.
The lubricant is one of calcium stearate, zinc stearate, paraffin or and several.
The stabilizer is 2- (bis- tertiary pentyl of 2- hydroxyl -3,5-) benzotriazole, decanedioic acid double -2,2,6,6- tetramethyls
Piperidines alcohol ester, N, N- bis- (2,2,6,6, -4 piperidyl of-tetramethyl)-N are one or several kinds of in N- dialdehyde-based hexamethylene diamine.
A kind of high-impact, wear-resisting PP/PA composite material and preparation method thereof, the steps include:
(1) PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and is mixed 10 minutes, add antioxidant, lubrication
Agent or self-made fill, which mix, obtains premix for 15 minutes, and the temperature of the mixing machine is 90-100 DEG C, and revolving speed is 800 revs/min.
(2) by premix feeding double screw extruder prepared in (1), by extrusion, water cooling, pelletizing and drying,
High-impact, wear-resisting PP/PA composite material is made；Wherein each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, 2nd area
190 DEG C of temperature, three 190 DEG C of area temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, head temperature 220
The revolving speed of DEG C double screw extruder is 220 revs/min.
Beneficial effect of the present invention
1, the present invention by compatilizer maleic anhydride stem grafting polyolefin elastomer and oxazoline functionalized polystyrene according to
7:3 compounding, than maleic anhydride stem grafting polyolefin elastomer is used alone or oxazoline functionalized polystyrene, material is used alone
The mechanical property of material is significantly promoted, and tensile strength highest promotes 24%, and bending strength highest promotes 27%, notch punching
Hit intensity highest promotes 38%, and low temperature notched impact strength highest improves 68%.When maleic anhydride stem grafting polyolefin elastomer
Grafting rate 1.0%, oxazoline functionalized polystyrene grafting rate 1.3%, the mechanical property of material reaches best.
2, the homemade filler of the addition present invention improves the wear-resisting property of material, while mechanical property such as notched impact properties is big
Amplitude is promoted, hence it is evident that better than the general anti-wear agent of addition.Tensile strength highest promotes 32%, and bending strength promotes 49%, notch punching
Hit intensity promotes 82%, and the abrasion of low temperature notched impact strength 97% reduce by 26%.
Specific embodiment
Below by specific embodiment, the present invention is further described, but the embodiment be merely to illustrate the present invention without
It is limitation of the present invention, if following embodiment each component is not specifically noted, is limited using the claims in the present invention
Range.
The test method of material: tensile strength uses ISO527, and bending strength uses ISO178, and notch impact strength uses
ISO180,23 DEG C of normal temperature condition, -40 DEG C of cryogenic conditions, abrasion use ASTMD1044, and coefficient of friction uses ASTMD1894.
Embodiment 1
PP100 parts, PA35 parts, 7 parts of maleic anhydride stem grafting polyolefin elastomer, 3 parts of oxazoline functionalized polystyrene, β-
0.2 part of (3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid n-octadecyl alcohol ester and 0.1 part of dilauryl thiodipropionate, tristearin
0.2 part of sour calcium, 0.3 part of benzotriazole of 2- (bis- tertiary pentyl of 2- hydroxyl -3,5-).
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, add antioxidant, lubricant,
Stabilizer mixes 15 minutes and obtains premix.The temperature of mixing machine is 95 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material；Wherein each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, 3rd area
190 DEG C of temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature
Revolving speed be 220 revs/min.
Comparative example 1
PP100 parts, PA35 parts, 10 parts of maleic anhydride stem grafting polyolefin elastomer, β-(3,5- di-t-butyl -4-4 hydroxy benzenes
Base) 0.2 part of propionic acid n-octadecyl alcohol ester and 0.1 part of dilauryl thiodipropionate, 0.2 part of calcium stearate, 2- (hydroxyl -3 2-,
Bis- tertiary pentyl of 5-) 0.3 part of benzotriazole.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, add antioxidant, lubricant,
Stabilizer mixes 15 minutes and obtains premix.The temperature of mixing machine is 95 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material, wherein each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, 3rd area
190 DEG C of temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature
Revolving speed be 220 revs/min.
Comparative example 2
PP100 parts, PA35 parts, 10 parts of oxazoline functionalized polystyrene, β-(3,5- di-t-butyl -4-4 hydroxy phenyl)
0.2 part of propionic acid n-octadecyl alcohol ester and 0.1 part of dilauryl thiodipropionate, 0.2 part of calcium stearate, 2- (2- hydroxyl -3,5- bis-
Tertiary pentyl) 0.3 part of benzotriazole.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes；Add antioxidant, lubricant,
Stabilizer, which mixes, obtains premix for 15 minutes, and the temperature of mixing machine is 95 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material；Wherein each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, 3rd area
190 DEG C of temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature
Revolving speed be 220 revs/min.
Comparative example 3
PP100 parts, PA40 parts, 5 parts of maleic anhydride stem grafting polyolefin elastomer, 3 parts of oxazoline functionalized polystyrene, β-
0.2 part of (3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid n-octadecyl alcohol ester and 0.1 part of dilauryl thiodipropionate, tristearin
0.2 part of sour calcium, 0.3 part of benzotriazole of 2- (bis- tertiary pentyl of 2- hydroxyl -3,5-).
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, add antioxidant, lubricant,
Stabilizer mixes 15 minutes and obtains premix.The temperature of mixing machine is 90 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material, wherein each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, 3rd area
190 DEG C of temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature
Revolving speed be 220 revs/min.
Table 1
According to embodiment 1 and comparative example 1, comparative example 2 it is found that the present invention passes through compatilizer maleic anhydride stem grafting polyolefin bullet
Property body compounded with oxazoline functionalized polystyrene, than maleic anhydride stem grafting polyolefin elastomer or exclusive use is used alone
The mechanical property of oxazoline functionalized polystyrene, material is significantly promoted, and tensile strength highest promotes 24%, bending
Intensity highest promotes 27%, and notch impact strength highest promotes 38%, and low temperature notched impact strength highest improves 68%.And
And according to embodiment 1 and comparative example 3 it is found that maleic anhydride stem grafting polyolefin elastomer of the present invention and oxazoline functionalized polyphenylene
Ethylene usage obtains optimal technical effect in 7:3.
Embodiment 2
PP100 parts, PA40 parts, 7.7 parts of maleic anhydride stem grafting polyolefin elastomer, oxazoline functionalized polystyrene 3.3
Part, N, bis- (2,2,6,6, -4 piperidyl of-the tetramethyl)-N of N-, 0.4 part of N- dialdehyde-based hexamethylene diamine, β-(3,5- di-t-butyl -4-4
Hydroxy phenyl) 0.1 part of propionic acid n-octadecyl alcohol ester and 0.2 part of dilauryl thiodipropionate, 0.3 part of paraffin, maleic anhydride connects
Branch polyolefin elastomer grafting rate 1.2%, oxazoline functionalized polystyrene grafting rate 1.6%.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, add antioxidant, lubricant,
Stabilizer mixes 15 minutes and obtains premix.The temperature of mixing machine is 90 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Embodiment 3
PP100 parts, PA30 parts, 8.4 parts of maleic anhydride stem grafting polyolefin elastomer, oxazoline functionalized polystyrene 3.6
Part, the double 0.3 part of -2,2,6,6- tetramethyl piperidine alcohol esters of decanedioic acid, β-(3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid positive ten
Eight 0.3 part of carbon alcohol esters and 0.2 part of dilauryl thiodipropionate, 0.2 part of zinc stearate, maleic anhydride stem grafting polyolefin elastomer
Grafting rate 1.2%, oxazoline functionalized polystyrene grafting rate 1.1%.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, add antioxidant, lubricant,
Stabilizer mixes 15 minutes and obtains premix.The temperature of mixing machine is 100 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Embodiment 4
PP100 parts, PA37 parts, 10.5 parts of maleic anhydride stem grafting polyolefin elastomer, oxazoline functionalized polystyrene 4.5
Part, double -2,2,6,6- 0.1 part of the tetramethyl piperidine alcohol esters of decanedioic acid, 2- (bis- tertiary pentyl of 2- hydroxyl -3,5-) 0.1 part of benzotriazole,
It is 0.1 part of 0.1 part of β-(3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid n-octadecyl alcohol ester and dilauryl thiodipropionate, hard
0.2 part of resin acid zinc, maleic anhydride stem grafting polyolefin elastomer graft rate 0.9%, oxazoline functionalized polystyrene grafting rate
1.5%.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, add antioxidant, lubricant,
Stabilizer mixes 15 minutes and obtains premix.The temperature of mixing machine is 100 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Embodiment 5
PP100 parts, PA33 parts, 9.1 parts of maleic anhydride stem grafting polyolefin elastomer, oxazoline functionalized polystyrene 3.9
Part, double -2,2,6,6- 0.3 part of the tetramethyl piperidine alcohol esters of decanedioic acid, 2- (bis- tertiary pentyl of 2- hydroxyl -3,5-) 0.2 part of benzotriazole,
It is 0.1 part of 0.1 part of β-(3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid n-octadecyl alcohol ester and dilauryl thiodipropionate, hard
0.3 part of resin acid zinc.0.2 part in paraffin, maleic anhydride stem grafting polyolefin elastomer graft rate 1.0%, oxazoline functionalized polyphenylene
Vinyl Graft rate 1.3%.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, add antioxidant, lubricant,
Stabilizer mixes 15 minutes and obtains premix.The temperature of mixing machine is 100 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Table 2
Embodiment 2-5 is it is found that work as maleic anhydride stem grafting polyolefin elastomer graft rate 1.0%, oxazoline functionalized polyphenylene
Vinyl Graft rate 1.3%, the mechanical property of material reach best.
Embodiment 6
PP100 parts, PA30 parts, 10.5 parts of maleic anhydride stem grafting polyolefin elastomer, oxazoline functionalized polystyrene 4.5
Part, 12 parts of self-made fill, 0.2 part of tetramethyl piperidine alcohol ester of decanedioic acid double -2,2,6,6-, β-(3,5- di-t-butyl -4-4 hydroxyls
Phenyl) 0.1 part of propionic acid n-octadecyl alcohol ester and 0.1 part of dilauryl thiodipropionate, 0.2 part of paraffin.
Self-made fill is calcined 3 hours by attapulgite and pyrophyllite by 400 DEG C, is cooled to room temperature, is ground in the ball mill
After grinding 2H, 2500 meshes are crossed, carry out surface treatment acquisition, attapulgite using 10% phenyl triethoxysilane ethanol solution
Ratio with pyrophyllite is 5:2.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, self-made fill, antioxygen are added
Agent, lubricant, stabilizer, which mix 15 minutes, obtains premix.The temperature of mixing machine is 100 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Comparative example 4
PP100 parts, PA30 parts, 15 parts of maleic anhydride stem grafting polyolefin elastomer, 12 parts of anti-wear agent polytetrafluoroethylene (PTFE), the last of the ten Heavenly stems two
Sour double 0.2 part of alcohol ester of -2,2,6,6- tetramethyl piperidines, β-(3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid n-octadecyl alcohol ester
0.1 part and 0.1 part of dilauryl thiodipropionate, 0.2 part of paraffin.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, polytetrafluoroethylene (PTFE) is added, resists
Oxygen agent, lubricant, stabilizer, which mix 15 minutes, obtains premix.The temperature of mixing machine is 100 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Table 3
According to table 3 as can be seen that the homemade filler of the addition present invention improves the wear-resisting property of material, while mechanical property is such as
Notched impact properties is significantly promoted, hence it is evident that better than the general anti-wear agent of addition.Tensile strength highest promotes 32%, and bending strength mentions
49% is risen, notch impact strength promotes 82%, and the abrasion of low temperature notched impact strength 97% reduce by 26%.
Comparative example 5
PP100 parts, PA40 parts, 13 parts of maleic anhydride stem grafting polyolefin elastomer, 10 parts of filler, N, N- it is bis- (2,2,6,6 ,-
- 4 piperidyl of tetramethyl)-N, 0.5 part of N- dialdehyde-based hexamethylene diamine, β-(3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid positive 18
0.1 part of carbon alcohol ester and 0.1 part of dilauryl thiodipropionate, 0.5 part of zinc stearate.Maleic anhydride stem grafting polyolefin elastomer connects
Branch rate 0.9%, oxazoline functionalized polystyrene grafting rate 1.6%.
Filler is mixed by attapulgite and pyrophyllite, is pulverized, and 500 meshes is crossed, using 5% phenyltriethoxy silane
Alkane ethanol solution carries out surface treatment acquisition, and the ratio of attapulgite and pyrophyllite is 1:2.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, filler, antioxidant, profit are added
Lubrication prescription, stabilizer, which mix 15 minutes, obtains premix.The temperature of mixing machine is 100 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Embodiment 7
PP100 parts, PA40 parts, 9.1 parts of maleic anhydride stem grafting polyolefin elastomer, oxazoline functionalized polystyrene 3.9
Part, 10 parts of self-made fill, bis- (2,2,6,6, -4 piperidyl of-the tetramethyl)-N of N, N-, 0.5 part of N- dialdehyde-based hexamethylene diamine, β-(3,5-
Di-t-butyl -4-4 hydroxy phenyl) 0.1 part of propionic acid n-octadecyl alcohol ester and 0.1 part of dilauryl thiodipropionate, zinc stearate
0.5 part.Maleic anhydride stem grafting polyolefin elastomer graft rate 0.9%, oxazoline functionalized polystyrene grafting rate 1.6%.
Self-made fill is calcined 3 hours by attapulgite and pyrophyllite by 400 DEG C, is cooled to room temperature, is ground in the ball mill
After grinding 2H, 2500 meshes are crossed, carry out surface treatment acquisition, attapulgite using 8% phenyl triethoxysilane ethanol solution
Ratio with pyrophyllite is 5:2.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, self-made fill, antioxygen are added
Agent, lubricant, stabilizer, which mix 15 minutes, obtains premix.The temperature of mixing machine is 90 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Embodiment 8
PP100 parts, PA35 parts, 8.4 parts of maleic anhydride stem grafting polyolefin elastomer, oxazoline functionalized polystyrene 3.6
Part, 15 parts of self-made fill, 0.3 part of benzotriazole of 2- (bis- tertiary pentyl of 2- hydroxyl -3,5-), β-(3,5- di-t-butyl -4-4 hydroxyls
Phenyl) 0.1 part of propionic acid n-octadecyl alcohol ester and 0.2 part of dilauryl thiodipropionate, 0.3 part of zinc stearate.Maleic anhydride connects
Branch polyolefin elastomer grafting rate 1.2%, oxazoline functionalized polystyrene grafting rate 1.1%.
Self-made fill is calcined 3 hours by attapulgite and pyrophyllite by 450 DEG C, is cooled to room temperature, is ground in the ball mill
After grinding 2H, 2500 meshes are crossed, carry out surface treatment acquisition, attapulgite using 10% phenyl triethoxysilane ethanol solution
Ratio with pyrophyllite is 5:2.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, self-made fill, antioxygen are added
Agent, lubricant, stabilizer, which mix 15 minutes, obtains premix.The temperature of mixing machine is 95 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Embodiment 9
PP100 parts, PA34 parts, 7 parts of maleic anhydride stem grafting polyolefin elastomer, 3 parts of oxazoline functionalized polystyrene, from
11 parts of filler processed, 0.3 part of benzotriazole of 2- (bis- tertiary pentyl of 2- hydroxyl -3,5-), β-(3,5- di-t-butyl -4-4 hydroxy phenyl)
0.3 part of propionic acid n-octadecyl alcohol ester and 0.2 part of dilauryl thiodipropionate, 0.1 part of calcium stearate, 0.1 part of paraffin.Maleic acid
Acid anhydride graft polyolefin elastomer graft rate 1.0%, oxazoline functionalized polystyrene grafting rate 1.3%.
Self-made fill is calcined 3 hours by attapulgite and pyrophyllite by 450 DEG C, is cooled to room temperature, is ground in the ball mill
After grinding 2H, 2500 meshes are crossed, carry out surface treatment acquisition, attapulgite using 9% phenyl triethoxysilane ethanol solution
Ratio with pyrophyllite is 5:2.
PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and mixed 10 minutes, self-made fill, antioxygen are added
Agent, lubricant, stabilizer, which mix 15 minutes, obtains premix.The temperature of mixing machine is 100 DEG C, and revolving speed is 800 revs/min.
Premix is fed in double screw extruder, by extrusion, water cooling, pelletizing and drying, high-impact, wear-resisting is made
PP/PA composite material.Each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two 190 DEG C of area's temperature, three 190 DEG C of areas
Temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of double screw extruders of head temperature turn
Speed is 220 revs/min.
Table 4
According to table 4, using the homemade filler of the application special process than the filler under other process conditions, abrasion are reduced
24%, notch impact strength promotes 44%, and low temperature notched impact strength promotes 47%.Maleic anhydride stem grafting polyolefin elastomer connects
Branch rate 1.0%, oxazoline functionalized polystyrene grafting rate 1.3%, the performance of material reaches best.
Claims (9)
1. a kind of high-impact, wear-resisting PP/PA composite material, it is characterised in that: be prepared by weight by following components:
The compatilizer is maleic anhydride stem grafting polyolefin elastomer and oxazoline functionalized polystyrene, and the two amount ratio is
7:3。
2. a kind of high-impact according to claim 1, wear-resisting PP/PA composite material, it is characterised in that: further include in component
10-15 parts of self-made fills, the self-made fill are calcined 3 hours by 400-450 DEG C by attapulgite and pyrophyllite, are cooled to
Room temperature, after grinding 2H in the ball mill, crosses 2500 meshes, carries out table using 8-10% phenyl triethoxysilane ethanol solution
Surface treatment obtains, and the ratio of attapulgite and pyrophyllite is 5:2.
3. -2 described kinds of high-impacts, wear-resisting PP/PA composite material according to claim 1, it is characterised in that: the maleic anhydride
Graft polyolefin elastomer graft 0.9-1.2%.
4. -2 described kinds of high-impacts, wear-resisting PP/PA composite material according to claim 1, it is characterised in that: the oxazoline official
Polystyrene graft rate 1.1-1.6% can be changed.
5. -2 described kinds of high-impacts, wear-resisting PP/PA composite material according to claim 1, it is characterised in that: the maleic anhydride
Graft polyolefin elastomer graft rate 1.0%, oxazoline functionalized polystyrene grafting rate 1.3%.
6. according to high-impact, wear-resisting PP/PA composite material is planted described in claim 1-2, it is characterised in that: the antioxidant is β-
(3,5- di-t-butyl -4-4 hydroxy phenyl) propionic acid n-octadecyl alcohol ester and dilauryl thiodipropionate.
7. according to claimed in claims 1-2 kind of high-impact, wear-resisting PP/PA composite material, it is characterised in that: the lubricant is
One of calcium stearate, zinc stearate, paraffin are and several.
8. according to high-impact, wear-resisting PP/PA composite material is planted described in claim 1-2, it is characterised in that: the stabilizer is 2-
(bis- tertiary pentyl of 2- hydroxyl -3,5-) benzotriazole, decanedioic acid double -2,2,6,6- tetramethyl piperidine alcohol esters, N, N- it is bis- (2,2,6,
6, -4 piperidyl of-tetramethyl)-N, it is one or several kinds of in N- dialdehyde-based hexamethylene diamine.
9. a kind of high-impact, wear-resisting PP/PA composite material and preparation method thereof described in claim 1-7, the steps include:
(1) PP, PA, compatilizer are poured into according to the proportion in high-speed mixer and is mixed 10 minutes；Add antioxidant, lubricant or
Person's self-made fill, which mixes, obtains premix for 15 minutes, and the temperature of the mixing machine is 90-100 DEG C, and revolving speed is 800 revs/min.
(2) it by the premix feeding double screw extruder prepared in (1), by extrusion, water cooling, pelletizing and drying, is made
High-impact, wear-resisting PP/PA composite material；Wherein each area's temperature of double screw extruder are as follows: 185 DEG C of area's temperature, two area's temperature
190 DEG C, three 190 DEG C of area temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 210 DEG C of area's temperature, 220 DEG C of head temperature double
The revolving speed of screw extruder is 220 revs/min.
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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 |