CN116218208B - PA/PP alloy material and preparation method and application thereof - Google Patents
PA/PP alloy material and preparation method and application thereof Download PDFInfo
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- CN116218208B CN116218208B CN202310449816.1A CN202310449816A CN116218208B CN 116218208 B CN116218208 B CN 116218208B CN 202310449816 A CN202310449816 A CN 202310449816A CN 116218208 B CN116218208 B CN 116218208B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a PA/PP alloy material, a preparation method and application thereof. The PA/PP alloy material comprises the following components in parts by weight: 40-70 parts of polyamide resin, 20-35 parts of polypropylene resin, 15-40 parts of glass fiber, 0.5-2 parts of ethylene-vinyl acetate-maleic anhydride, 1-5 parts of polyacrylamide, 5-15 parts of elastomer and 0.6-2.0 parts of auxiliary agent. The PA/PP alloy material is PA/PP-GF material with PP content more than 20%, and the melt stability and the melt strength are improved by matching the components, so that the appearance of the product has no tiger skin lines and obvious layering effect. In addition, the impact strength of the product obtained by adopting the PA/PP alloy material is obviously improved. The PA/PP alloy material provided by the invention can be used for preparing automobile structural parts, such as fans, wind protection rings, water chambers and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PA/PP alloy material and a preparation method and application thereof.
Background
The PA/PP alloy material has the advantages of simultaneously keeping the advantages of the strength, toughness and heat resistance of the PA resin, and the PP resin has the advantages of low density, no water absorption and the like, becomes a material with better comprehensive performance, and can be widely applied to automobile parts such as engine decorative covers, door handles and the like. The content of PP in the PA/PP alloy in the industry is generally less than 15 percent so as to ensure the island phase structure, so that the composite material has excellent strength, toughness and appearance. The higher the PP content is, the more obvious the weight reduction of the material is, but when the PP content is too high, the impact strength of the material is generally lower due to poor compatibility of PA and PP, and the PA/PP alloy material is layered due to lower melt strength and lower melt stability of a PA/PP system, so that tiger stripes appear on the appearance of the product. The tiger skin patterns are defects of alternate bright and dark specks on the surface of a manufactured part caused by unstable melt flow due to stretching and shearing deformation of the material in the melt flow process, and are similar to tiger patterns. The patent CN106147008A adds the polystyrene polyolefin crosslinking elastomer into the PP-TD series material, so that the occurrence of tiger stripes of the PP-TD composite material is avoided; CN105219005a adds thermoplastic polyolefin or a mixture of thermoplastic polyolefin and epoxy fatty acid methyl ester to PP-TD composite material to improve tiger skin line. All the patents improve tiger stripes in a PP-TD system, and the tiger stripes are easy to appear in a PA/PP-GF system, and the improvement of the tiger stripes is rarely reported.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a PA/PP alloy material, and a preparation method and application thereof. The PA/PP alloy material has improved melt stability and melt strength, so that the appearance of the product has no tiger skin lines and obvious layering phenomenon, and the impact strength of the material is obviously improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the PA/PP alloy material comprises the following components in parts by weight: 40-70 parts of polyamide resin, 20-35 parts of polypropylene resin, 15-40 parts of glass fiber, 0.5-2 parts of ethylene-vinyl acetate-maleic anhydride, 1-5 parts of polyacrylamide, 5-15 parts of elastomer and 0.6-2.0 parts of auxiliary agent.
Preferably, the PA/PP alloy material comprises the following components in parts by weight: 50-60 parts of polyamide resin, 18-30 parts of polypropylene resin, 20-30 parts of glass fiber, 1-1.5 parts of ethylene-vinyl acetate-maleic anhydride, 2-4 parts of polyacrylamide, 7-12 parts of elastomer and 0.8-1.6 parts of auxiliary agent.
Preferably, the polyamide resin is PA6. The PA6 has low crystallinity temperature, high fluidity and excellent appearance of injection molded parts. The relative viscosity of PA6 may be 2.0-3.0. The relative viscosity of the PA6 was tested according to ISO 307-2019 under 96% H 2 SO 4 。
Preferably, the polypropylene resin is a copolymerized polypropylene. The polypropylene copolymer contains EPR, and the EPR content of the polypropylene is 17-22%, so that the toughness of the modified alloy material is improved. The melt flow rate MFR of the copolymer polypropylene may be from 5 to 110g/10min. The melt flow rate MFR of the polypropylene copolymer was measured according to ISO 1133-2011 at 230℃under 2.16Kg.
Preferably, the elastomer is a polyamide elastomer with PA6 as the hard segment. The polyamide elastomer taking the PA6 as a hard segment has higher compatibility with polyamide resin, especially the PA6 resin, has more stable melt flow, is not easy to generate phase analysis phenomenon under high-speed shearing, and is not easy to generate tiger skin line phenomenon.
Preferably, the auxiliary agent is 0.3-1 part of antioxidant and/or 0.3-1 part of lubricant.
Preferably, the antioxidant is one or more of amines, phosphites, semi-hindered phenols and cyclic aromatics.
The lubricant is one or more of montan esters, metal soaps, stearic acid composite esters and amides.
The invention also provides a preparation method of the PA/PP alloy material, which comprises the following steps: premixing polyamide resin, polypropylene resin, polyacrylamide, elastomer, ethylene-vinyl acetate-maleic anhydride and an auxiliary agent, adding glass fiber, blending and extruding, bracing, cooling and granulating to obtain the PA/PP alloy material.
Preferably, the cooling is water cooling and then air cooling.
Preferably, the blending extrusion adopts a double screw extruder, and the extrusion temperature is 150-280 ℃.
Preferably, the extrusion temperature of the PA6 alloy is 150-170 ℃,180-200 ℃,200-215 ℃,210-225 ℃,220-230 ℃,220-240 ℃,220-240 ℃,225-245 ℃,225-245 ℃ and 225-245 ℃ respectively; the extrusion temperature of the PA66 alloy is respectively 200-220 ℃,230-250 ℃,240-255 ℃,250-260 ℃,260-280 ℃,260-280 ℃,260-280 ℃,265-280 ℃,260-280 ℃ and 260-280 ℃. The invention also provides application of the PA/PP alloy material in preparing an automobile structural member. The automobile structural member can be a fan, a wind protection ring, a water chamber and the like.
Compared with the prior art, the invention has the beneficial effects that:
the PA/PP alloy material is PA/PP-GF material with high PP content, and has no tiger skin lines and obvious layering. According to the invention, the problem of insufficient impact strength of the PA/PP alloy material is solved by adding the elastomer, and the melt stability is improved: the elastomer has high compatibility with PA, and phase separation phenomenon can not occur under the shearing action; the elastomer and the PP are incompatible due to different polarities, so that the PP phase part of the injection molding part is more difficult to form tiger stripes; by adding ethylene-vinyl acetate-maleic anhydride, the crosslinking point can be formed by reacting with amino groups at the end of the polyamide resin, so that the effect of increasing the melt strength of the material is achieved; the polyacrylamide and ethylene-vinyl acetate-maleic anhydride terpolymer are compounded to play a role in compatibilizing PA and PP resins, so that layering is avoided; the elastomer, the ethylene-vinyl acetate-maleic anhydride and the polyacrylamide are blended to form a network-shaped molecular structure formed by covalent bonds, hydrogen bonds and molecular entanglement, so that the tiger stripes on the appearance of the product are avoided.
Drawings
FIG. 1 is an external view of an article with obvious tiger stripes.
FIG. 2 is an external view of the product with the tiger stripes not apparent.
FIG. 3 is an external view of a tiger stripe-free article.
FIG. 4 is a graph showing the results of SEM analysis of a product, which shows phase separation.
FIG. 5 is a graph showing the results of SEM analysis of the product, without phase separation.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
In the following examples and comparative examples, the antioxidant and lubricant were obtained commercially, and the same antioxidant and lubricant were used in parallel experiments unless otherwise specified.
The raw materials used in the examples and comparative examples are described below:
polyamide resin 1: PA6, HY2500A, purchased from sea-sun chemical fiber;
polyamide resin 2: PA66, EP-158, from Trojan;
polypropylene resin 1: copolymerized polypropylene, EP548R, purchased from middle sea shell, EPR content 22%;
polypropylene resin 2: homo-polypropylene, N-Z30S, purchased from the Mao petrochemical industry, EPR content 0%;
polypropylene resin 3: copolymerized polypropylene, EP300M, available from liandbarsel, EPR content 17%;
polypropylene resin 4: polypropylene copolymer, PP BX3800, purchased from korea SK, EPR content 15%;
polypropylene resin 5: copolymerized polypropylene, PP K9017, purchased from bench, EPR content 27%; glass fiber: chopped glass fibers, ECS301HP-3-H, purchased from Chongqing International;
ethylene-vinyl acetate-maleic anhydride: T9307Y, purchased from alcemax, france;
polypropylene grafted maleic anhydride: CA100, a Ke Ma;
polyacrylamide: BYA9236, new material of Boyuan;
elastomer 1: polyamide elastomer, PA6 AS hard segment, AS4510, sunburn group;
elastomer 2: n406, POE-G-MAH, light available from energy;
elastomer 3: polyamide elastomer, PA12 as hard segment, pebax 2533SA01, aclamate;
an antioxidant: antioxidant 1010, commercially available;
and (3) a lubricant: erucamide, commercially available.
Examples and comparative examples
The PA/PP alloy materials of examples and comparative examples are shown in tables 1 and 2, with the components and parts by weight.
The preparation method of the low PA/PP alloy materials of the examples and the comparative examples comprises the following steps: premixing polyamide resin, polypropylene resin, polyacrylamide, elastomer, ethylene-vinyl acetate-maleic anhydride and an auxiliary agent, and feeding the premixed polyamide resin, the polypropylene resin, the polyacrylamide, the elastomer, the ethylene-vinyl acetate-maleic anhydride and the auxiliary agent into a double-screw extruder through a metering scale; feeding glass fiber into a double-screw extruder from a side feeding port through a metering scale; blending and extruding the components in a double-screw extruder, bracing, water cooling, air cooling and granulating to obtain a low PA/PP alloy material; extrusion temperature of twin screw extruder: the extrusion temperatures of the PA6 alloy are respectively as follows: 150-170 ℃,180-200 ℃,200-215 ℃,210-225 ℃,220-230 ℃,220-240 ℃,220-240 ℃,225-245 ℃,225-245 ℃ and 225-245 ℃; the extrusion temperature of the PA66 alloy is respectively 200-220 ℃,230-250 ℃,240-255 ℃,250-260 ℃,260-280 ℃,260-280 ℃,260-280 ℃,265-280 ℃,260-280 ℃ and 260-280 ℃.
Performance testing
The PA/PP alloy materials of the examples and the comparative examples are subjected to performance tests, and the specific test methods are as follows:
ball falling impact: according to the standard PV3905-2005, the material is injection molded into a square plate with the thickness of 2mm, and after being placed in a low-temperature environment with the temperature of minus 40 ℃ for 24 hours, 500g of iron balls and 40mm of falling balls are immediately used for falling impact, and whether cracks exist or not is observed.
Tiger skin lines: the material was injection molded into 2mm square plates, visually classified as obvious, not obvious, and without three conditions, see figures 1-3, respectively.
Layering: i.e. phase separation, the material was injection molded into 2mm square plates, and the sections were analyzed by SEM, with or without the two conditions, see fig. 4-5, respectively.
The test results are shown in tables 1 and 2.
TABLE 1
TABLE 2
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The PA/PP alloy material is characterized by comprising the following components in parts by weight: 40-70 parts of polyamide resin, 20-35 parts of polypropylene resin, 15-40 parts of glass fiber, 0.5-2 parts of ethylene-vinyl acetate-maleic anhydride terpolymer, 1-5 parts of polyacrylamide, 5-15 parts of elastomer and 0.6-2.0 parts of auxiliary agent;
the polypropylene resin is copolymerized polypropylene;
the elastomer is polyamide elastomer taking PA6 as a hard segment;
the EPR content of the polypropylene is 17-22%.
2. The PA/PP alloy material of claim 1, characterized by comprising the following components in parts by weight: 50-60 parts of polyamide resin, 18-30 parts of polypropylene resin, 20-30 parts of glass fiber, 1-1.5 parts of ethylene-vinyl acetate-maleic anhydride terpolymer, 2-4 parts of polyacrylamide, 7-12 parts of elastomer and 0.8-1.6 parts of auxiliary agent.
3. The PA/PP alloy material as set forth in claim 1, characterized in that,
the polyamide resin is PA6.
4. The PA/PP alloy material of claim 1, wherein the glass fiber is chopped glass fiber.
5. PA/PP alloy material according to claim 1, characterized in that the auxiliary agent is 0.3-1 part of antioxidant and/or 0.3-1 part of lubricant.
6. The PA/PP alloy material of claim 5, characterized in that,
the antioxidant is one or more of amines, phosphites and semi-hindered phenols;
and/or the lubricant is one or more of montan esters, metal soaps and amides.
7. The method for producing a PA/PP alloy material as set forth in any one of claims 1 to 6, characterized by comprising the steps of: premixing polyamide resin, polypropylene resin, polyacrylamide, elastomer, ethylene-vinyl acetate-maleic anhydride terpolymer and auxiliary agent, adding glass fiber, blending and extruding, bracing, cooling and granulating to obtain the PA/PP alloy material.
8. The method for producing a PA/PP alloy material according to claim 7, wherein,
the cooling is water cooling firstly and then air cooling secondly;
and/or, adopting a double screw extruder for blending extrusion, wherein the extrusion temperature is 150-280 ℃.
9. Use of the PA/PP alloy material of any of claims 1-6 for the manufacture of automotive structural parts.
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| CN112662106A (en) * | 2020-12-11 | 2021-04-16 | 安徽中翰高分子科技有限公司 | High-temperature-resistant oil-resistant thermoplastic vulcanized elastomer material and preparation method thereof |
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| US5140070A (en) * | 1988-11-07 | 1992-08-18 | Elf Atochem North America, Inc | Compositions comprising polymer bond flame retardants |
| US5064716A (en) * | 1989-01-26 | 1991-11-12 | E. I. Du Pont De Nemours And Company | Blends of ethylene vinyl alcohol copolymer and amorphous polyamide, and multilayer containers made therefrom |
| CN1167802A (en) * | 1996-04-19 | 1997-12-17 | 埃勒夫阿托化学有限公司 | Coextrusion binder based on mixture of cografted polyolefins |
| EP0990515A1 (en) * | 1998-09-30 | 2000-04-05 | Elf Atochem S.A. | Film comprising a polyolefin central layer and two external layers of a polyamide/polyolefin alloy |
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