CN114369359A - High-wear-resistance and good-appearance long glass fiber reinforced polyamide composite material and preparation method thereof - Google Patents
High-wear-resistance and good-appearance long glass fiber reinforced polyamide composite material and preparation method thereof Download PDFInfo
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- CN114369359A CN114369359A CN202111630609.3A CN202111630609A CN114369359A CN 114369359 A CN114369359 A CN 114369359A CN 202111630609 A CN202111630609 A CN 202111630609A CN 114369359 A CN114369359 A CN 114369359A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 64
- 239000004952 Polyamide Substances 0.000 title claims abstract description 56
- 229920002647 polyamide Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 51
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 16
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 13
- 229910052961 molybdenite Inorganic materials 0.000 claims description 13
- 230000009471 action Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000012768 molten material Substances 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 claims 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 23
- 238000001746 injection moulding Methods 0.000 description 13
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
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- 238000009472 formulation Methods 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920000426 Microplastic Polymers 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- 239000011159 matrix material Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical compound S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 229940052288 arsenic trisulfide Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 230000000007 visual effect Effects 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention discloses a long glass fiber reinforced polyamide composite material with high wear resistance and good appearance and a preparation method thereof, wherein the composition is calculated according to the mass percentage, wherein the polyamide PA 639-54%, the wear-resistant high-dispersion master batch 10-20%, the continuous long glass fiber 30-40%, the maleic anhydride graft 1-5%, and the antioxidant and other auxiliary agent master batches 2-5%. The invention is characterized in that the wear-resistant high-dispersion master batch is introduced into a formula system of the long glass fiber reinforced polyamide, thereby improving the wear resistance of the composite material and playing a role in dispersion; compared with the conventional long glass fiber reinforced polyamide material, the material cost is reduced, the wear resistance and the appearance are obviously improved, and the original mechanical properties, high heat resistance, high rigidity and the like are maintained; the excellent characteristics enable the material to have wider application value in the fields of electric driving, sports, automobiles, aerospace and the like.
Description
Technical Field
The invention relates to a preparation method of a long glass fiber reinforced polyamide composite material. In particular to a preparation method of a long glass fiber reinforced polyamide composite material with high wear resistance and good appearance
Background
The long glass fiber reinforced polyamide composite material is commonly used in the fields of electromotion, sports, automobiles, aerospace and the like due to excellent mechanical property, high hardness, high heat resistance, excellent creep resistance and the like. Because nylon has the defects of high cost, easy hydrolysis, poor wear resistance and the like, and when the addition amount of the glass fiber is large, the surface appearance of the product is poor, the product is modified usually so as to meet the requirements of larger marketization.
Some parts such as electric equipment, seat pulley, gear require to be higher to wear resistance. At present, wear-resistant materials in the market mainly comprise molybdenum disulfide, arsenic trisulfide, glass fiber, graphite, carbon fiber, phenolic resin and the like, and have the defects of serious wear loss, short service life and influence on the mechanical property of the materials when the addition amount is large. Other automobile instruments, seat peripheral parts, shell exposed parts, structural parts and the like have certain requirements on the appearance of the polyamide composite material.
In view of the above, there is still a need to develop a long glass fiber reinforced polyamide composite material with improved wear resistance, hydrolysis resistance and appearance state, and better maintained original performance.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of easy hydrolysis, poor wear resistance and poor product appearance of the polyamide composite material in the prior art; the invention provides a long glass fiber reinforced polyamide composite material with high wear resistance and good appearance and a preparation method thereof, which have the excellent characteristics of high wear resistance, good appearance and the like while maintaining the original material performance; meanwhile, the material has certain advantages in cost. Has wider application prospect.
The purpose of the invention is realized by the following technical scheme:
the long glass fiber reinforced polyamide composite material with high wear resistance and good appearance is prepared from the following raw materials in percentage by weight:
in a long glass fiber reinforced polyamide composite material system:
the polyamide PA6 is characterized by low molecular weight and viscosity of 2.2, and the high fluidity of the polyamide PA6 can realize effective infiltration of glass fiber monofilaments, so that the risk of glass fiber agglomeration of parts is avoided.
The wear-resistant high-dispersion master batch is prepared from the following raw materials in percentage by weight:
60-70% of homopolymerized polypropylene;
2-5% of hyperbranched polymer;
MoS2 20-30％；
1-5% of compatilizer.
In the wear-resistant high-dispersion master batch: the homopolymerized polypropylene resin is characterized by high fluidity and high crystallization, the melt index is 20-25g/10min, and the tensile strength is 45-50 MPa. MoS2 is a conventional commercial chemical. The hyperbranched polymer is hyperbranched polyamide/polyimide polymer and is derived from CN 112724529A. Under the shearing action of the screw, the polypropylene resin modified by the polyolefin maleic anhydride graft and the hyperbranched polyamide/polyimide polymer is covalently and chemically combined with the MoS2 particles modified by the coupling agent to form a star-shaped binding site.
In a long glass fiber reinforced polyamide composite material system:
the diameter of the continuous long glass fiber monofilament is about 15 mu m, and the linear density is 1200tex or 2400 tex. Before entering the impregnation tank, the continuous long glass fiber is coated with a layer of silicone auxiliary agent and polyolefin sizing agent, so that a good interface layer is formed between the glass fiber and the resin.
The compatilizer is maleic anhydride graft, the grafting rate is 1.2%, and the compatilizer plays a role in compatibilization in a system and is beneficial to improving the distribution of a dispersed phase in the system.
The antioxidant is a compound mixture of a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant adopts hindered phenol antioxidants, and the auxiliary antioxidant adopts thioesters and phosphites.
The lubricant is ethylene bis stearamide or silicone master batch.
The black master batch has good dispersibility and dark color, and can improve the luster and the grade of a product.
The preparation method of the long glass fiber reinforced polyamide composite material comprises the following steps:
(1) the preparation method of the wear-resistant high-dispersion master batch comprises the following steps: weighing the polypropylene, the hyperbranched polymer, the MoS2, the compatilizer and the coupling agent according to the proportion, and uniformly mixing according to the corresponding proportion, wherein the parameter of the stirrer is set to be 10min, and the rotating speed is 600 r/min. Then adding the mixture into a double-screw extrusion feeding port, wherein the processing temperature of an extruder is 110-;
(2) putting polyamide PA6, wear-resistant high-dispersion master batch, compatilizer, antioxidant, light stabilizer and black master batch into a stirrer according to corresponding mass proportion, wherein the equipment parameters of the stirrer are set to 10min and the rotating speed is 800 r/min. Pouring the uniform mixture into a feed opening of a double-screw extruder, and allowing the materials to flow into a dipping tank at a constant conveying speed after the materials are sheared, plasticized and homogenized by double screws. At the other end of the impregnation device, the continuous long glass fibers can finally enter the impregnation tank through the yarn guide roller and the die cavity under the action of the traction device. The glass fiber in the device is dispersed into monofilaments under the action of the yarn guide roller, the monofilaments are coated with the molten resin and leave the impregnation tank at a certain moving speed to form a molten material strip. And cooling the material strips by a water tank, air-drying and granulating to finally form the long glass fiber reinforced polyamide granules.
In the step (2), the melting temperature of the plastic extruder is 235 ℃.
In the step (2), the temperature of the dipping tank is set to be 280 ℃.
In the step (2), the grain cutting length of the long glass fiber reinforced polyamide is 10-12 mm.
The mechanism of the invention is as follows:
according to the invention, the self-made wear-resistant high-dispersion master batch is selected to carry out blending modification on the polyamide composite material, so that the long glass fiber reinforced polyamide composite material with high wear resistance and good appearance is prepared, and the wear-resistant high-dispersion master batch modified by the hyperbranched polymer can be used as a star-shaped binding site, can be well dispersed in a PA6 matrix, and can play a role in interface compatibilization. The wear resistance and hydrolysis resistance of the composite material can be effectively improved; meanwhile, due to the high dispersion effect, the risk of floating fiber agglomeration of the appearance of the product can be reduced. Is a potential polyamide composite material with excellent performance. The material can be widely applied to the fields of electromotion, sports, automobiles, aerospace and the like.
Compared with the prior art, the invention has the following advantages: (1) the wear resistance and hydrolysis resistance of the polyamide material are improved, and the material cost is reduced; (2) through formula optimization, the appearance state of the glass fiber reinforced material product is improved while the material performance is ensured.
Detailed Description
The present invention will be further illustrated by the following examples and comparative examples, but the present invention should not be limited to the contents specifically illustrated in the following experimental examples without departing from the gist of the present invention.
The raw materials used in the examples were as follows:
polyamide PA 6: viscosity 2.2;
polypropylene: melt index 22g/10min, test conditions 230 ℃ 2.16Kg
Hyperbranched polymer: source CN112724529A
MoS 2: commercially available chemical, CAS 1317-33-5
Coupling agent: KH550, commercially available chemical, CAS 919-30-2
Continuous glass fiber: erwins Kening (European Union)
A compatilizer: maleic anhydride grafted polypropylene: 200A commercially available
Antioxidant: 1010; hindered phenolic antioxidants, CIBA, Switzerland
Antioxidant: 619F; thiodipropionic acid distearate; is commercially available
Antioxidant: DSTP; a phosphite ester antioxidant; is commercially available
Lubricant: silicone masterbatches, commercially available
Black masterbatch: e320, commercially available
The product performance testing method comprises the following steps:
melt mass flow index (melt index): test conditions according to ISO 1133: 230 ℃ 2.16kg
Density: ISO 1183; spline size: 80mm 10mm 4mm
Tensile property: ISO 527, spline size: 170mm 10mm 4 mm; and (3) testing conditions are as follows: 5mm/min
Bending property: ISO 178, spline size: 80mm by 10mm by 4 mm; and (3) testing conditions are as follows: 2mm/min notched impact strength: ISO 179, spline size: 80mm by 10mm by 4 mm; and (3) testing conditions are as follows: 4J
Heat distortion temperature: ISO 75-2, spline size: 80mm by 10mm by 4 mm; and (3) testing conditions are as follows: 1.8MPa, 120 ℃/h
Hydrolysis resistance test: placing the injection molding sample into a pressure kettle, injecting cooling liquid (ethylene glycol: water is 1:1) into the container, setting the temperature at 130 deg.C, observing the state of the sample after 1000 hr
Apparent mass: panel size according to visual appearance assessment: 355mm 100mm 3.2mm
Surface friction coefficient test: GB/T3960, spline size: 30mm by 7mm by 6 mm; and (3) testing conditions are as follows: 200r/min, 196N
Example 1
The preparation method of the wear-resistant high-dispersion master batch comprises the following steps: 65kg of homopolymerized polypropylene, 3kg of hyperbranched polymer, 30kg of MoS2 and 2kg of compatilizer are put into a high-speed stirrer, the rotating speed of the stirrer is set to 600r/min, the time is 10min, the mixture is uniformly mixed and then put into a discharge port of a double-screw extruder, wherein the processing temperature of the extruder is 110-220 ℃, the rotating speed of a main machine is 350-450rpm, and after melt blending, the mixture is extruded, cooled and granulated to obtain the wear-resistant high-dispersion master batch with the length of about 2-4 mm.
Putting 54kg of polyamide PA6, 10kg of wear-resistant high-dispersion master batch, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch into a high-speed stirrer, setting the rotating speed of the stirrer to be 800r/min, keeping the time for 10min, uniformly mixing, putting the mixture into a feed opening of a double-screw extruder, finally conveying the materials into a dipping tank through a conveying section, a compression section and an extrusion section, simultaneously conveying continuous long glass fibers into the dipping tank through a yarn guide roller and a mold cavity under the action of traction equipment, and penetrating out from the other end of the dipping tank at a constant moving speed,
solidifying the melt when meeting cold water, air-drying, granulating and drying to obtain the long glass fiber reinforced polyamide granules, wherein the length of the plastic particles is 10-12 mm, and the content of the glass fiber is controlled at 30%. And pouring the dried particles into a feed opening of an injection molding machine, performing injection molding according to specified process parameters to form corresponding sample strips and templates, and testing the relevant performance of the composite material. The formulations and test results are shown in table 1.
Example 2
The preparation method of the wear-resistant high-dispersion master batch comprises the following steps: 65kg of homopolymerized polypropylene, 3kg of hyperbranched polymer, 30kg of MoS2 and 2kg of compatilizer are put into a high-speed stirrer, the rotating speed of the stirrer is set to 600r/min, the time is 10min, the mixture is uniformly mixed and then put into a discharge port of a double-screw extruder, wherein the processing temperature of the extruder is 110-220 ℃, the rotating speed of a main machine is 350-450rpm, and after melt blending, the mixture is extruded, cooled and granulated to obtain the wear-resistant high-dispersion master batch with the length of about 2-4 mm.
49kg of polyamide PA6, 15kg of wear-resistant high-dispersion master batch, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is uniformly mixed and then put into a feed opening of a double-screw extruder, the material is finally conveyed into a dipping tank through a conveying section, a compression section and an extrusion section, meanwhile, continuous long glass fiber enters the dipping tank through a yarn guide roller and a die cavity under the action of traction equipment and penetrates out from the other end of the dipping tank at a constant moving speed, a melt is solidified after meeting cold water, and long glass fiber reinforced polyamide granules can be obtained after air drying, grain cutting and drying, wherein the length of the plastic granules is 10mm-12mm, and the content of the glass fiber is controlled at 30%. And pouring the dried particles into a feed opening of an injection molding machine, performing injection molding according to specified process parameters to form corresponding sample strips and templates, and testing the relevant performance of the composite material. The formulations and test results are shown in table 1.
Example 3
The preparation method of the wear-resistant high-dispersion master batch comprises the following steps: 65kg of homopolymerized polypropylene, 3kg of hyperbranched polymer, 30kg of MoS2 and 2kg of compatilizer are put into a high-speed stirrer, the rotating speed of the stirrer is set to 600r/min, the time is 10min, the mixture is uniformly mixed and then put into a discharge port of a double-screw extruder, wherein the processing temperature of the extruder is 110-220 ℃, the rotating speed of a main machine is 350-450rpm, and after melt blending, the mixture is extruded, cooled and granulated to obtain the wear-resistant high-dispersion master batch with the length of about 2-4 mm.
44kg of polyamide PA6, 20kg of wear-resistant high-dispersion master batch, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is uniformly mixed and then put into a feed opening of a double-screw extruder, the material is finally conveyed into a dipping tank through a conveying section, a compression section and an extrusion section, meanwhile, continuous long glass fiber enters the dipping tank through a yarn guide roller and a die cavity under the action of traction equipment and penetrates out from the other end of the dipping tank at a constant moving speed, a melt is solidified after meeting cold water, and long glass fiber reinforced polyamide granules can be obtained after air drying, grain cutting and drying, wherein the length of the plastic granules is 10mm-12mm, and the content of the glass fiber is controlled at 30%. And pouring the dried particles into a feed opening of an injection molding machine, performing injection molding according to specified process parameters to form corresponding sample strips and templates, and testing the relevant performance of the composite material. The formulations and test results are shown in table 1.
Comparative example 1
The preparation method of the wear-resistant high-dispersion master batch comprises the following steps: 65kg of homopolymerized polypropylene, 3kg of hyperbranched polymer, 30kg of MoS2 and 2kg of compatilizer are put into a high-speed stirrer, the rotating speed of the stirrer is set to 600r/min, the time is 10min, the mixture is uniformly mixed and then put into a discharge port of a double-screw extruder, wherein the processing temperature of the extruder is 110-220 ℃, the rotating speed of a main machine is 350-450rpm, and after melt blending, the mixture is extruded, cooled and granulated to obtain the wear-resistant high-dispersion master batch with the length of about 2-4 mm.
Putting 64kg of polyamide PA6, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch into a high-speed stirrer, setting the rotating speed of the stirrer to be 800r/min, and the stirring time to be 10min, uniformly mixing, then putting the mixture into a feed opening of a double-screw extruder, finally conveying the materials into a dipping tank through a conveying section, a compression section and an extrusion section, simultaneously conveying continuous long glass fibers into the dipping tank through a yarn guide roller and a mold cavity under the action of traction equipment, penetrating out from the other end of the dipping tank at a constant moving speed, solidifying the molten glass fibers after meeting cold water, air drying, cutting into granules, and drying to obtain long glass fiber reinforced polyamide granules, wherein the length of the plastic granules is 10mm-12mm, and the content is controlled at 30%. And pouring the dried particles into a feed opening of an injection molding machine, performing injection molding according to specified process parameters to form corresponding sample strips and templates, and testing the relevant performance of the composite material. The formulations and test results are shown in table 1.
Comparative example 2
The preparation method of the wear-resistant high-dispersion master batch comprises the following steps: 65kg of homopolymerized polypropylene, 3kg of hyperbranched polymer, 30kg of MoS2 and 2kg of compatilizer are put into a high-speed stirrer, the rotating speed of the stirrer is set to 600r/min, the time is 10min, the mixture is uniformly mixed and then put into a discharge port of a double-screw extruder, wherein the processing temperature of the extruder is 110-220 ℃, the rotating speed of a main machine is 350-450rpm, and after melt blending, the mixture is extruded, cooled and granulated to obtain the wear-resistant high-dispersion master batch with the length of about 2-4 mm.
39kg of polyamide PA6, 15kg of wear-resistant high-dispersion master batch, 3kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is uniformly mixed and then put into a feed opening of a double-screw extruder, the material is finally conveyed into a dipping tank through a conveying section, a compression section and an extrusion section, meanwhile, continuous long glass fiber enters the dipping tank through a yarn guide roller and a die cavity under the action of traction equipment and penetrates out from the other end of the dipping tank at a constant moving speed, a melt is solidified after meeting cold water, and long glass fiber reinforced polyamide granules can be obtained after air drying, grain cutting and drying, wherein the length of the plastic granules is 10mm-12mm, and the content of the glass fiber is controlled at 40%. And pouring the dried particles into a feed opening of an injection molding machine, performing injection molding according to specified process parameters to form corresponding sample strips and templates, and testing the relevant performance of the composite material. The formulations and test results are shown in table 1.
Comparative example 3
The preparation method of the wear-resistant high-dispersion master batch comprises the following steps: 65kg of homopolymerized polypropylene, 3kg of hyperbranched polymer, 30kg of MoS2 and 2kg of compatilizer are put into a high-speed stirrer, the rotating speed of the stirrer is set to 600r/min, the time is 10min, the mixture is uniformly mixed and then put into a discharge port of a double-screw extruder, wherein the processing temperature of the extruder is 110-220 ℃, the rotating speed of a main machine is 350-450rpm, and after melt blending, the mixture is extruded, cooled and granulated to obtain the wear-resistant high-dispersion master batch with the length of about 2-4 mm.
51kg of polyamide PA6, 15kg of wear-resistant high-dispersion master batch, 1kg of compatilizer, 1.5kg of antioxidant, 0.5kg of lubricating master batch and 1kg of black master batch are put into a high-speed stirrer, the rotating speed of the stirrer is set to 800r/min, the time is 10min, the mixture is uniformly mixed and then put into a feed opening of a double-screw extruder, the material is finally conveyed into a dipping tank through a conveying section, a compression section and an extrusion section, meanwhile, continuous long glass fiber enters the dipping tank through a yarn guide roller and a die cavity under the action of traction equipment and penetrates out from the other end of the dipping tank at a constant moving speed, a melt is solidified after meeting cold water, and long glass fiber reinforced polyamide granules can be obtained after air drying, grain cutting and drying, wherein the length of the plastic granules is 10mm-12mm, and the content of the glass fiber is controlled at 30%. And pouring the dried particles into a feed opening of an injection molding machine, performing injection molding according to specified process parameters to form corresponding sample strips and templates, and testing the relevant performance of the composite material. The formulations and test results are shown in table 1.
Table 1: results of Performance testing
From the data shown in table 1, the addition of the wear-resistant high-dispersion master batch can effectively improve the wear resistance and hydrolysis resistance of the long fiber reinforced polyamide composite material, and the appearance can be improved; referring to comparative example 1, when 15 parts of the wear-resistant high-dispersion master batch was added in example 2, the wear resistance was the best, and the properties and thermal deformation were not significantly changed. As the content continues to increase, the wear resistance decreases, possibly due to: the wear-resistant master batch has a saturation effect in a matrix, and is not easy to disperse due to too much quantity; referring to the comparative example 2, the wear-resistant high-dispersion master batch with the increased glass fiber fraction can also achieve a good effect; referring to comparative example 3, the reduction of the content of the graft, the wear resistance and the hydrolysis resistance, which still did not decrease, and the appearance state OK, which can be provided as a cost reduction scheme; therefore, the addition of the wear-resistant high-dispersion master batch can effectively improve the wear resistance, hydrolysis resistance and appearance state of the long fiber reinforced polyamide composite material, and simultaneously the original performance can be maintained. The long glass fiber reinforced polyamide composite material prepared by the invention has the advantages of high strength, high wear resistance, high heat resistance, good appearance and the like, can be widely applied to the fields of electromotion, sports, automobiles, aerospace and the like, is particularly suitable for the field of pulley gear type electric sports influenced by multiple factors such as humidity, heat, wear resistance and the like, and is a polymer-based long glass fiber composite material with excellent comprehensive performance, high cost performance and suitability for wear resistance.
Claims (10)
1. The long glass fiber reinforced polyamide composite material with high wear resistance and good appearance is characterized in that: the material is prepared from the following raw materials in percentage by weight:
2. the high abrasion resistance and good appearance long glass fiber reinforced polyamide composite material as claimed in claim 1, wherein: the polyamide PA6 is characterized by a low molecular weight and a viscosity of 2.2.
3. The high abrasion resistance and good appearance long glass fiber reinforced polyamide composite material as claimed in claim 1, wherein: the wear-resistant high-dispersion master batch is prepared from the following raw materials in percentage by weight:
4. the high abrasion resistance and good appearance long glass fiber reinforced polyamide composite material as claimed in claim 3, wherein: the melt index of the homopolymerized polypropylene resin is 20-25g/10min, and the tensile strength is 45-50 MPa.
5. The high abrasion resistance and good appearance long glass fiber reinforced polyamide composite material as claimed in claim 3, wherein: MoS2 is a conventional commercial chemical; the hyperbranched polymer is hyperbranched polyamide/polyimide polymer and is derived from CN 112724529A; under the shearing action of the screw, the polypropylene resin modified by the polyolefin maleic anhydride graft and the hyperbranched polyamide/polyimide polymer is covalently and chemically combined with the MoS2 particles modified by the coupling agent to form a star-shaped binding site.
6. The high abrasion resistance and good appearance long glass fiber reinforced polyamide composite material as claimed in claim 1, wherein: the diameter of the continuous long glass fiber monofilament is about 15 mu m, and the linear density is 1200tex or 2400 tex.
7. The high abrasion resistance and good appearance long glass fiber reinforced polyamide composite material as claimed in claim 1, wherein: the compatilizer is maleic anhydride graft, and the grafting rate is 1.2%.
8. The high abrasion resistance and good appearance long glass fiber reinforced polyamide composite material as claimed in claim 1, wherein: the antioxidant is a compound mixture of a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant adopts hindered phenol antioxidants, and the auxiliary antioxidant adopts thioesters and phosphites; the lubricant is ethylene bis stearamide or silicone master batch.
9. The method for preparing the high-wear-resistance and good-appearance long glass fiber reinforced polyamide composite material according to any one of claims 1 to 8, wherein the method comprises the following steps: the method comprises the following steps:
(1) the preparation method of the wear-resistant high-dispersion master batch comprises the following steps: weighing the polypropylene, the hyperbranched polymer, the MoS2, the compatilizer and the coupling agent according to the proportion, and uniformly mixing according to the corresponding proportion, wherein the parameter of the stirrer is set to be 10min, and the rotating speed is 600 r/min. Then adding the mixture into a double-screw extrusion feeding port, wherein the processing temperature of an extruder is 110-;
(2) putting polyamide PA6, wear-resistant high-dispersion master batch, compatilizer, antioxidant, light stabilizer and black master batch into a stirrer according to corresponding mass proportion, wherein the equipment parameters of the stirrer are set to 10min and the rotating speed is 800 r/min; pouring the uniform mixture into a feed opening of a double-screw extruder, and allowing the materials to flow into a dipping tank at a constant conveying speed after the materials are sheared, plasticized and homogenized by double screws; at the other end of the impregnation device, the continuous long glass fibers can finally enter the impregnation tank through the yarn guide roller and the die cavity under the action of the traction device. The glass fiber in the device is dispersed into monofilaments under the action of a yarn guide roller, the monofilaments are coated with molten resin and leave an impregnation tank at a certain moving speed to form a molten material strip; and cooling the material strips by a water tank, air-drying and granulating to finally form the long glass fiber reinforced polyamide granules.
10. The method for preparing the high-wear-resistance and good-appearance long glass fiber reinforced polyamide composite material as claimed in claim 9, wherein the method comprises the following steps: in the step (2), the melting temperature of the plastic extruder is 235 ℃; the temperature of the dipping tank is set to be 280 ℃; the grain cutting length of the long glass fiber reinforced polyamide is 10mm-12 mm.
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| CN115991903A (en) * | 2023-03-22 | 2023-04-21 | 潍坊学院 | High heat conduction scale control functional floor heating pipe |
| CN115991903B (en) * | 2023-03-22 | 2023-06-02 | 潍坊学院 | High heat conduction scale control functional floor heating pipe |
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Application publication date: 20220419 |