CN114605740A - Long glass fiber reinforced polypropylene material and preparation method and application thereof - Google Patents
Long glass fiber reinforced polypropylene material and preparation method and application thereof Download PDFInfo
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- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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Abstract
The invention discloses a long glass fiber reinforced polypropylene material and a preparation method and application thereof, wherein the material comprises the following components: polypropylene resin, polyamide resin, a compatilizer, a nylon elastomer, long glass fiber, aluminum powder and an auxiliary agent. According to the invention, the uniform metal scintillation effect is realized by the long glass fiber and the aluminum powder compounded with different particle sizes; aluminum powder is distributed on the surface of the workpiece, and floating fibers are covered; the long glass fibers are mutually interpenetrated, so that the performance reduction of the material caused by adding aluminum powder is avoided; the scratch resistance and the impact resistance are improved by adding the polyamide and nylon elastomers. The material is suitable for appearance structural members, is free from spraying and has wide application prospect.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a long glass fiber reinforced polypropylene material and a preparation method and application thereof.
Background
The spraying-free material is an environment-friendly product, can avoid the step of spraying paint, and can enhance the competitiveness of the product under the policy of carbon neutralization and carbon peak reaching.
CN201710383662 provides a spraying-free PP material with metallic luster, which comprises 90-97% of PP, 1-5% of aluminum silver strips, 0.2-0.3% of antioxidant, 0.1-0.2% of anti-UV auxiliary agent and 0.1-0.5% of wax powder. The spraying-free PP material is prepared from the aluminum silver strips with good dispersibility and the matrix resin PP material, the prepared spraying-free PP material has high reflectivity, the aluminum silver strips (with the particle size of 30-35 mu m) are uniformly dispersed in the PP material, and the metal glossiness is high.
CN102942742A provides a spray-free PP material with a metal glittering effect, which comprises 97-99% of random PP, 0.2-0.8% of antioxidant, 0.1-1% of lubricant and 0.3-1.5% of effect pigment. The spraying-free PP material can obtain good high gloss, pearly luster and metal spraying effect without spraying and direct injection molding, has good appearance, saves cost compared with a spraying process, and avoids the paint removal problem in the using process of a product.
CN106279971A discloses a spray-free high-gloss PP material, which comprises 6 to 9 percent of tetrahydrofuran, 0.1 to 0.3 percent of palladium tetrakistriphenylphosphine, 1 to 2 percent of pearl powder, 1 to 2 percent of toner, 0.3 to 0.5 percent of lubricant, 0.3 to 0.5 percent of nucleating agent, 0.3 to 0.5 percent of liquid-shaped de-graining brightening agent, 0.5 to 0.8 percent of liquid-shaped flow modifier, 0.3 to 0.8 percent of liquid-shaped phase solvent and the balance of PP powder. The product has good surface highlight effect, forms a uniform and continuous pearl powder layer on the surface of the product, and has no flow lines and strong texture.
The spraying-free polypropylene material belongs to a spraying-free material without a reinforcing system, because the aluminum powder and the glass fiber are easily sheared and broken by the glass fiber in the process of melting and blending the aluminum powder and the glass fiber by the double screws, and the original surface metallic luster cannot be maintained. In addition, part of the metal powder or the pearl powder is easy to disperse unevenly, so that accumulation is formed in a resin system, the color of a product is uneven, and the metal powder or the pearl powder can reduce the tensile property and the toughness of the material. Meanwhile, the scratch resistant effect of the system material is poor.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a long glass fiber reinforced polypropylene material and a preparation method and application thereof. The material is free from spraying, has an excellent metal effect, and simultaneously has good tensile property, scratch resistance and high toughness.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the long glass fiber reinforced polypropylene material comprises the following components in parts by weight: 12.8-78.2 parts of polypropylene resin, 5-20 parts of polyamide resin, 3-5 parts of compatilizer, 3-10 parts of nylon elastomer, 10-40 parts of long glass fiber, 0.2-5 parts of aluminum powder and 0-0.7 part of assistant.
Preferably, the long glass fiber reinforced polypropylene material comprises the following components in parts by weight: 28-70 parts of polypropylene resin, 10-15 parts of polyamide resin, 3-5 parts of compatilizer, 4-6 parts of nylon elastomer, 30-40 parts of long glass fiber, 2-4 parts of aluminum powder and 0.2-0.5 part of assistant.
Preferably, the polypropylene resin has a melt flow rate of 10 to 150g/10min (test conditions 230 ℃, 2.16kg, test standard ISO 1133). When the melt flow rate of the polypropylene resin is less than 10g/10min, the glass fibers cannot be fully impregnated by the resin, and the impregnation die head is serious in material return or strip breakage, so that smooth production cannot be realized.
Preferably, the polyamide resin is at least one of polyamide 6(PA6), polyamide 610(PA610), and polyamide 612(PA 612).
Preferably, the compatibilizer is polypropylene grafted maleic anhydride (PP-G-MAH).
Preferably, the nylon elastomer is a copolymer which takes PA6 as a hard segment and takes propylene oxide polyether as a soft segment.
Preferably, the long glass fiber is provided with coarse twisted sand, and the diameter of each single fiber is 7-18 mu m.
Preferably, the aluminum powder is a mixture of 55-100 mu m particle size (D50) aluminum powder and 5-15 mu m particle size aluminum powder; more preferably, the mass ratio of the aluminum powder with the particle diameter of 55-100 μm to the aluminum powder with the particle diameter of 5-15 μm is (3-8): 1, compounding.
Preferably, the auxiliary agent is at least one of an antioxidant and a lubricant.
The preparation method of the long glass fiber reinforced polypropylene material comprises the following steps: the polypropylene resin, the polyamide resin, the compatilizer, the nylon elastomer, the aluminum powder and the auxiliary agent are uniformly mixed, and are melted, plasticized and homogenized under the conditions of 275-temperature and 330-temperature and 400-temperature and 800r/min, so that the obtained resin auxiliary agent melt is used for infiltrating the long glass fiber at the temperature of 320-temperature and 350-temperature, and the long glass fiber reinforced polypropylene material is obtained.
Preferably, the long glass fiber reinforced polypropylene material is cooled, shaped and granulated to obtain a finished product.
Preferably, the pellets are cut to a length of 6 ± 3mm or 10 ± 3 mm.
Preferably, the melt plastification homogenization is achieved using a twin screw extruder. By adopting the LFT pultrusion process, aluminum powder and glass fiber cannot be simultaneously present in the double-screw extruder, and the metal aluminum powder is prevented from being excessively damaged by strong shearing of glass fiber in the extruder to influence the metal effect.
Preferably, the infiltration is realized by adopting an infiltration die head, the resin additive melt passes through the infiltration die head, and the traction equipment pulls the long glass fiber to pass through the infiltration die head, so that the long glass fiber is infiltrated by the resin additive melt.
Preferably, the speed of said traction is between 40 and 90 m/min.
The long glass fiber reinforced polypropylene material is applied to preparing an appearance structural member with scratch resistance and impact resistance. The appearance structural part can be parts such as an automobile lower guard plate, a foot support, an electric tool handle, a traffic joint, an automobile door handle, a rearview mirror bracket and the like.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the long glass fiber and the aluminum powder compounded with different particle sizes are used to realize the metal scintillation effect of the material: the large-particle-size aluminum powder is oriented along with the flow direction of the melt and part of the long glass fibers to provide a uniform metal effect, and the small-particle-size aluminum powder is inserted into the long glass fiber skeleton structure to provide a flickering metal dot effect. And secondly, the aluminum powder is distributed on the surface of the workpiece to cover the floating fibers. Moreover, the long glass fibers are mutually interpenetrated, so that a glass fiber three-dimensional skeleton structure inside the injection molding part is provided, and the reduction of material performance caused by adding aluminum powder is avoided. The material adopts a spraying-free process to obtain gorgeous metal effect on the surface of a product, so that the reject ratio of the product is reduced, the pollution is reduced, especially the carbon emission is reduced, and the energy consumption is reduced. The surface hardness of the material is improved by adding polyamide, and the scratch resistance of the composite material is improved. The nylon elastomer improves the impact resistance, especially the low-temperature impact toughness of the modified material. The material disclosed by the invention has an excellent metal effect, and meanwhile, has good scratch resistance, tensile property and high toughness.
Drawings
FIG. 1 is a diagram showing the effect of a long glass fiber reinforced polypropylene material product without flow marks and floating fibers.
FIG. 2 is a diagram showing the effect of a long glass fiber reinforced polypropylene material product with severe flow marks and obvious fiber floating.
FIG. 3 is a diagram showing the effect of a long glass fiber reinforced polypropylene material product with flow marks and no floating fibers.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following detailed description and accompanying drawings.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
The materials used in the examples and comparative examples are now described below, but are not limited to these materials:
polypropylene resin 1: plastic table, K9026; a melt flow rate of 26g/10min measured according to ISO1133 standard using a 2.16kg weight at a temperature of 230 ℃;
polypropylene resin 2: LG, MH 7900; a melt flow rate of 150g/10min measured according to ISO1133 standard using a 2.16kg weight at a temperature of 230 ℃;
polypropylene resin 3: marine petrochemical, PP PPH-T03; a melt flow rate of 4g/10min measured according to ISO1133 standard using a 2.16kg weight at a temperature of 230 ℃;
polyamide resin 1: PA6, haiyang chemical fiber, HY 2500A;
polyamide resin 2: PA610, shandong wide whole boundless new materials limited, F120;
polyamide resin 3: PA612, Shanghai Yingkungkui engineering Co., Ltd., A150;
polypropylene grafted maleic anhydride: arkema, CA 100;
nylon elastomer: atochem, 5512 MNOO; a copolymer which is composed of PA6 as a hard segment and propylene oxide polyether as a soft segment;
polyolefin elastomer: POE ENGAGE8137, dow;
long glass fiber: chongqing International composite Co., Ltd, ER 4301R-2400; the coarse twisting sand is arranged, and the diameters of the single wires are respectively 17 mu m;
short wave fiber: chongqing International composite materials, Inc., ECS301 HP-3-H;
aluminum powder 1: mixing the Asahi Yang, TH5390 (particle size 85 +/-2 μm) and XYC710 (particle size 10 +/-2 μm) according to the mass ratio of 3: 1, compounding;
aluminum powder 2: the fertilizer comprises the following components in percentage by mass of 2: 1, compounding;
aluminum powder 3: mixing the Asahi Yang, TH5390 (particle size 85 +/-2 μm) and XYC710 (particle size 10 +/-2 μm) according to a mass ratio of 9: 1, compounding;
aluminum powder 4: mixing the Asahi Yang, TH5390 (particle size 85 +/-2 μm) and XYC710 (particle size 10 +/-2 μm) according to the mass ratio of 8: 1, compounding;
auxiliary agent: antioxidant, 1010, commercially available; lubricants, erucamide, commercially available; the mass ratio of the antioxidant to the lubricant is 1: 1.
examples 1 to 8 and comparative examples 1 to 12
The components and parts by weight of the long glass fiber reinforced polypropylene materials of examples 1 to 8 and comparative examples 1 to 12 are shown in tables 1 and 2. The preparation method of the polypropylene composite materials of examples 1 to 8 and comparative examples 1 to 12 comprises the following steps: the polypropylene resin, the polyamide resin, the compatilizer, the nylon elastomer aluminum powder and the auxiliary agent are uniformly mixed and fed into a double-screw extruder by a weigher for melting, plasticizing and homogenizing, wherein the temperature of the double-screw extruder is set to 290 ℃, and the rotating speed is 600 r/min. And conveying the obtained resin auxiliary agent melt to an infiltration die head, wherein the temperature of the infiltration die head is set to be 340 ℃. The drawing equipment draws the long glass fiber to pass through the infiltration die head at a drawing speed of 50m/min, so that the long glass fiber is infiltrated by the resin additive melt. And (3) obtaining the material strips of the long glass fiber reinforced polypropylene material after the complete infiltration, and obtaining a finished product with the length of 10mm through cooling, shaping and granulating.
Raw material components and parts by weight in the examples of Table 1
Table 2 raw material components and parts by weight in comparative examples
Effect example Performance test
The long glass fiber reinforced polypropylene materials prepared in examples 1 to 8 and comparative examples 1 to 12 were subjected to the following specific performance tests:
the mechanical property test evaluation method comprises the following steps: the tensile strength of the bars is measured at 23 ℃ according to ISO527-1/2 standard; the specimens were tested for notched impact strength at 23 ℃ according to ISO179/1eA standard.
The low-temperature falling ball impact performance test evaluation method comprises the following steps: the material is injected into a 2mm square plate and stored for 24h in a-40 ℃ environment, and whether cracks exist is observed by using 500g of iron balls and 40mm falling balls for falling impact.
The metal effect evaluation method comprises the following steps: whether the metal effect is even or not is observed, whether the flicker effect is obvious or not is observed, and whether the defects of flow marks and floating fibers exist or not is judged: the more uniform the metal effect, the more obvious the flicker effect, the better the spraying effect, the more the visual effect, the better the effect.
Method for evaluating scratch resistance: and (4) scratching according to a PV3952 standard under a 15N force, and testing the scratch resistance effect delta L value.
Fiber floating and flow mark rating method: and (5) visual inspection. The state without floating fiber and without flow mark is shown in fig. 1, the state with severe flow mark and obvious flow mark is shown in fig. 2, and the state without floating fiber and with flow mark is shown in fig. 3.
Table 3 results of performance testing of examples
Table 4 results of performance testing of comparative examples
The invention adds polyamide and nylon elastomer to improve the scratch resistance and impact resistance of the modified material, especially the low-temperature impact toughness. The aluminum powder is added in a proper proportion, so that the impact strength of the material, the metal scintillation effect and the metal uniformity effect are improved, and a finished piece has no flow mark and floating fiber. The material disclosed by the invention has excellent metal effect, tensile property, scratch resistance and high toughness. FIG. 1 is a graph showing the effect of the long glass fiber reinforced polypropylene material of example 3, and it can be seen that the material exhibits uniform metal effect, has glittering metal dot effect, well covers floating fibers, and has no flow mark. Examples 1, 2 and 7 used less long glass fibers, but the tensile strength and room temperature notched impact strength were still at relatively high levels.
The data in table 4 show that: comparative example 1, the chopped glass fiber has poor toughness, very poor metal effect, severe flow marks and obvious fiber floating; comparative example 2: no polyamide, good metal effect, poor toughness, poor appearance and poor scratch resistance; comparative example 3: no aluminum powder is added, so that the metal effect cannot be realized; comparative example 4: no nylon elastomer, poor toughness; comparative example 5: the aluminum powder consumption is too small, the metal effect is poor, flow marks exist, and the scintillation effect is poor; comparative example 6: excessive aluminum powder consumption, flow marks and poor scintillation effect; comparative example 7: the proportion of the small-particle-size aluminum powder is too large, the metal uniformity effect is poor, and flow marks exist; comparative example 8: the large-particle-size aluminum powder has too large proportion, poor scintillation effect and flow marks; comparative example 9: the glass fiber can not be fully impregnated by the resin, the material return or strip breakage of an impregnation die head is serious, and smooth production can not be realized; comparative example 10: the metal effect and the scintillation effect are poor, and the low-temperature falling ball impact strength is poor; comparative example 11: the metal effect and the scintillation effect are poor, the low-temperature falling ball impact strength is poor, and floating fibers exist; comparative example 12: the polyolefin elastomer is poor in metal effect and glittering effect, and poor in low-temperature ball drop impact strength.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The long glass fiber reinforced polypropylene material is characterized by comprising the following components in parts by weight: 12.8-78.2 parts of polypropylene resin, 5-20 parts of polyamide resin, 3-5 parts of compatilizer, 3-10 parts of nylon elastomer, 10-40 parts of long glass fiber, 0.2-5 parts of aluminum powder and 0-0.7 part of assistant.
2. The long glass fiber reinforced polypropylene material of claim 1, wherein the long glass fiber reinforced polypropylene material comprises the following components in parts by weight: 28-70 parts of polypropylene resin, 10-15 parts of polyamide resin, 3-5 parts of compatilizer, 4-6 parts of nylon elastomer, 30-40 parts of long glass fiber, 2-4 parts of aluminum powder and 0.2-0.5 part of assistant.
3. The long glass fiber reinforced polypropylene material according to claim 1,
the polyamide resin is at least one of PA6, PA610 and PA 612;
the compatilizer is polypropylene grafted maleic anhydride;
the nylon elastomer is a copolymer which is composed of PA6 as a hard segment and propylene oxide polyether as a soft segment.
4. The long glass fiber reinforced polypropylene material of claim 1, wherein the polypropylene resin has a melt flow rate of 10-150g/10min at 230 ℃ under a 2.16kg test condition.
5. The long glass fiber reinforced polypropylene material of claim 1, wherein the long glass fibers are coarse twisted sand and have a filament diameter of 7-18 μm.
6. The long glass fiber reinforced polypropylene material of claim 1, wherein the aluminum powder is a mixture of aluminum powder with a particle size of 55-100 μm and aluminum powder with a particle size of 5-15 μm.
7. The long glass fiber reinforced polypropylene material of claim 6, wherein the mass ratio of the aluminum powder with the particle size of 55-100 μm to the aluminum powder with the particle size of 5-15 μm is (3-8): 1, compounding.
8. The long glass fiber reinforced polypropylene material of claim 1, wherein the auxiliary agent is at least one of an antioxidant and a lubricant.
9. The process for preparing the long glass fiber reinforced polypropylene material of any one of claims 1 to 8, comprising the steps of: uniformly mixing polypropylene resin, polyamide resin, a compatilizer, a nylon elastomer, aluminum powder and an auxiliary agent, and melting, plasticizing and homogenizing under the conditions of 275-;
cooling, shaping and dicing the long glass fiber reinforced polypropylene material to obtain a finished product;
the melting plasticizing homogenization is realized by adopting a double-screw extruder;
the infiltration is realized by adopting an infiltration die head.
10. Use of the long glass fiber reinforced polypropylene material according to any one of claims 1 to 8 for the production of scratch-resistant, impact-resistant structural parts with an appearance.
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| CN202210321085.8A CN114605740B (en) | 2022-03-29 | 2022-03-29 | Long glass fiber reinforced polypropylene material and preparation method and application thereof |
| PCT/CN2023/082077 WO2023185504A1 (en) | 2022-03-29 | 2023-03-17 | Long glass fiber reinforced polypropylene material and preparation method therefor and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449157A (en) * | 2022-09-30 | 2022-12-09 | 江苏金发科技新材料有限公司 | Long glass fiber reinforced polypropylene material and preparation method and application thereof |
| WO2023185504A1 (en) * | 2022-03-29 | 2023-10-05 | 江苏金发科技新材料有限公司 | Long glass fiber reinforced polypropylene material and preparation method therefor and application thereof |
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| CN115449157A (en) * | 2022-09-30 | 2022-12-09 | 江苏金发科技新材料有限公司 | Long glass fiber reinforced polypropylene material and preparation method and application thereof |
| CN115449157B (en) * | 2022-09-30 | 2023-12-19 | 江苏金发科技新材料有限公司 | Long glass fiber reinforced polypropylene material and preparation method and application thereof |
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| CN114605740B (en) | 2023-10-03 |
| WO2023185504A1 (en) | 2023-10-05 |
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