CN109897282B - Polypropylene composite material and preparation method and application thereof - Google Patents
Polypropylene composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of high polymer materials, and particularly discloses a polypropylene composite material and a preparation method and application thereof. The polypropylene composite material comprises 100 (10-15) parts by weight of polypropylene, K glue and aramid fibers, and 1-5 parts by weight of aramid fibers. The polypropylene composite material provided by the invention has excellent and lasting excellent scratch resistance, does not cause poor appearance of polypropylene, and has great industrial application prospect.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly discloses a polypropylene composite material and a preparation method and application thereof.
Background
Polypropylene is a semi-crystalline thermoplastic, has the characteristics of strong impact resistance and corrosion resistance and excellent processability, and has very wide application in the industry. However, polypropylene has poor scratch resistance, and when it is used in some products with high requirements on appearance, the polypropylene is often worn or scratched, which seriously affects the beauty and service life of the products.
The existing modification of the scratch resistance of polypropylene is mainly realized by adding an inorganic mineral modifier or adding amide, silicone and other micromolecular lubricants into a polypropylene material. However, most inorganic mineral modifiers have poor compatibility with polypropylene matrix, which often results in poor appearance of polypropylene; the small molecular lubricant has a non-lasting modification effect, and is easy to cause problems of discoloration, fogging, stickiness and the like on the surface of a product.
In addition, the requirement of the spraying-free polypropylene material on the appearance of the product is more severe than that of the common polypropylene material, so that the improvement on the scratch resistance of the spraying-free polypropylene material is more urgent.
Disclosure of Invention
The invention aims to overcome the defects of modification of the friction resistance of a polypropylene material by adding an inorganic mineral modifier or a micromolecular lubricant in the prior art, and provides a polypropylene composite material capable of effectively and durably improving the friction resistance of polypropylene, and a preparation method and application thereof.
The polypropylene composite material comprises polypropylene, K glue and aramid fibers in a weight ratio of 100 (10-15) to 1-5.
Further, the melt index of the polypropylene under the test conditions of 230 ℃ and 2.16kg is 3-100 g/10 min.
Furthermore, the content of the butadiene structural unit in the K glue is 20-40 wt%.
Further, the melt index of the K glue at 200 ℃ under the test condition of 5kg is 5-15 g/10 min.
Furthermore, the aramid fiber is meta-aramid fiber.
Further, the length of the aramid fiber is 2-10 mm.
Further, the polypropylene composite material also contains an aluminum pigment.
Further, the aluminum pigment is an aluminum silver strip.
Further, the content of the aluminum pigment is 1 to 5 parts by weight relative to 100 parts by weight of polypropylene.
Further, the polypropylene composite material also contains a compatilizer.
Further, the compatilizer is polypropylene grafted maleic anhydride.
Further, the grafting rate of the polypropylene grafted maleic anhydride is 1.2-3 wt%.
Further, the content of the compatibilizer is 1 to 5 parts by weight relative to 100 parts by weight of the polypropylene.
Further, the polypropylene composite material also contains at least one of a coupling agent, an antioxidant and a lubricant.
Further, the coupling agent is selected from at least one of 3-aminopropyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and isopropyl tris (dodecylbenzenesulfonyl) titanate.
Further, the antioxidant is a compound of an antioxidant 1010 and an antioxidant 168 according to a mass ratio (0.5-2) to 1.
Further, the lubricant is an ester lubricant and/or a fatty acid lubricant.
Further, relative to 100 parts by weight of polypropylene, the content of the coupling agent is 0.1-0.5 part by weight, the content of the antioxidant is 0.2-1 part by weight, and the content of the lubricant is 0.1-2 parts by weight.
Further, the polypropylene composite material is composed of polypropylene, K glue, aramid fibers, an aluminum pigment, a compatilizer, a coupling agent, an antioxidant and a lubricant, wherein the content of the K glue is 10-15 parts by weight, the content of the aramid fibers is 1-5 parts by weight, the content of the aluminum pigment is 1-5 parts by weight, the content of the compatilizer is 1-5 parts by weight, the content of the coupling agent is 0.1-0.5 part by weight, the content of the antioxidant is 0.2-1 part by weight, and the content of the lubricant is 0.1-2 parts by weight, relative to 100 parts by weight of the polypropylene.
The invention also provides a preparation method of the polypropylene composite material, wherein the method comprises the step of uniformly mixing the polypropylene, the K glue, the aramid fiber and optional aluminum pigment, compatilizer, coupling agent, antioxidant and lubricant to obtain the polypropylene composite material.
In addition, the invention also provides application of the polypropylene composite material as a scratch-resistant material.
The key point of the invention is that polypropylene, K glue and aramid fiber in a specific proportion are used in a matching way, when the formed polypropylene composite material is subjected to injection molding, as the polypropylene has an exclusive effect during crystallization, part of the K glue can migrate to the surface of the material to form a protective layer, meanwhile, the aramid fiber is dispersed in the composite material, a good reinforcing effect can be achieved on a polypropylene matrix, the polypropylene matrix is acted through the cooperation of the K glue and the aramid fiber, and the scratch resistance of the polypropylene can be obviously and durably improved. In addition, the polypropylene has good compatibility with the K glue and the aramid fiber, and the appearance of the polypropylene cannot be deteriorated.
In addition, the polypropylene composite material provided by the invention adopts a resin compounding mode to improve the scratch resistance of polypropylene, and does not contain inorganic filler, so that the density of the material cannot be obviously improved, and the requirement of light weight of an automobile can be met.
Detailed Description
The present invention will be described in detail below.
The polypropylene composite material provided by the invention contains polypropylene, K glue and aramid fiber. The weight ratio of the polypropylene to the K glue is 100 (10-15), for example, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15 and the like. The weight ratio of the polypropylene to the aramid fiber is 100 (1-5), such as 100:1, 100:2, 100:3, 100:4, 100:5 and the like.
The polypropylene can be homopolymerized polypropylene or copolymerized polypropylene. The polypropylene copolymer may be a copolymer of propylene and at least one of ethylene, vinyl chloride, acrylic acid, and the like. Wherein, the content of the polypropylene structural unit in the copolymerized polypropylene is preferably more than 50 wt%. In addition, the melt index of the polypropylene under the test conditions of 230 ℃ and 2.16kg is preferably 3-100 g/10 min.
The K glue is a styrene-butadiene copolymer, belongs to an amorphous polymer, and has high transparency, good glossiness, impact resistance and good processability. The content of the butadiene structural unit in the K glue is preferably 20-40 wt%. The melt index of the K glue is preferably 5-15 g/10min under the test conditions of 200 ℃ and 5 kg.
The aramid fiber is poly phenylene terephthalamide. The aramid fiber can be para-aramid fiber, meta-aramid fiber or a mixture of the para-aramid fiber and the meta-aramid fiber, and particularly preferred is meta-aramid fiber. In addition, the length of the aramid fiber is preferably 2-10 mm.
In the present invention, the polypropylene composite material preferably further contains an aluminum pigment, and the addition of the aluminum pigment can enhance the metallic texture of the polypropylene composite material. The aluminum pigment may be at least one of aluminum silver stripes, aluminum silver paste, aluminum silver powder, mirror silver, and the like, and aluminum silver stripes are particularly preferable. The particle size of the aluminum powder in the aluminum silver strip is preferably 10-200 mu m. In addition, on one hand, a certain metal texture can be obtained by adding a small amount of aluminum pigment, and the metal texture is correspondingly enhanced along with the increase of the adding amount; on the other hand, an excessive amount of the aluminum pigment may cause difficulty in material processing and a decrease in mechanical strength, and therefore, the amount of the aluminum pigment is preferably 1 to 5 parts by weight based on 100 parts by weight of polypropylene, in consideration of the above.
In the present invention, the polypropylene composite material preferably further contains a compatibilizer, and the addition of the compatibilizer can further improve the friction resistance and enhance the surface texture of the polypropylene composite material. The compatilizer can be various existing substances capable of improving the compatibility of the polypropylene and other components such as K glue, aramid fiber, aluminum silver strips and other auxiliary agents, and particularly polypropylene grafted maleic anhydride (PP-g-MAH) is preferred. The grafting rate of the polypropylene grafted maleic anhydride is preferably 1.2-3 wt%. The content of the compatibilizer is preferably 1 to 5 parts by weight with respect to 100 parts by weight of polypropylene.
In the present invention, the polypropylene composite may further contain at least one of a coupling agent, an antioxidant and a lubricant. Specific examples of the coupling agent include, but are not limited to: at least one of 3-aminopropyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and isopropyltris (dodecylbenzenesulfonyl) titanate. The content of the coupling agent is preferably 0.1 to 0.5 part by weight with respect to 100 parts by weight of polypropylene. The antioxidant can be at least one of 1010, 1076, CA, 164, 168, DNP, DLTP, MB, 264 and the like, preferably is a compound of the antioxidant 1010 and the antioxidant 168, and more preferably is a compound of the antioxidant 1010 and the antioxidant 168 according to the mass ratio of (0.5-2): 1. The content of the antioxidant is preferably 0.2 to 1 part by weight relative to 100 parts by weight of polypropylene. The lubricant may be an ester lubricant and/or a fatty acid lubricant, and may be specifically selected from at least one of PP wax, white oil, stearate, and the like. The content of the lubricant is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of polypropylene.
According to the most preferred embodiment of the invention, the polypropylene composite material is composed of polypropylene, K glue, aramid fiber, aluminum pigment, a compatilizer, a coupling agent, an antioxidant and a lubricant, wherein the content of the K glue is 10-15 parts by weight, the content of the aramid fiber is 1-5 parts by weight, the content of the aluminum pigment is 1-5 parts by weight, the content of the compatilizer is 1-5 parts by weight, the content of the coupling agent is 0.1-0.5 part by weight, the content of the antioxidant is 0.2-1 part by weight and the content of the lubricant is 0.1-2 parts by weight relative to 100 parts by weight of the polypropylene, and at the moment, the corresponding polypropylene composite material has excellent and durable friction resistance and very good metal texture.
The invention also provides a preparation method of the polypropylene composite material, wherein the method comprises the step of uniformly mixing the polypropylene, the K glue, the aramid fiber and optional aluminum pigment, compatilizer, coupling agent, antioxidant and lubricant to obtain the polypropylene composite material. The mixing may be performed by manually stirring or in various existing mixing apparatuses. The mixing conditions are such that the above components form a homogeneous system. In the mixing process, the above components can be mixed in any order, for example, the above components can be added into a mixing container one by one in any order for mixing, or any two or more of the above components can be uniformly mixed and then the other components can be added for continuous uniform mixing. According to a specific embodiment of the invention, the mixing is carried out in a double-screw extruder with a double-side feeding system, in the mixing process, firstly (1/10-1/5) polypropylene, K glue and aramid fiber and optional aluminum pigment, compatilizer, coupling agent, antioxidant and lubricant are stirred and mixed in a high-speed stirrer at the rotating speed of 80-120 rpm for 5-10 minutes, then the obtained premix is added into the double-screw extruder from a side feeding port, the rest polypropylene is added into the double-screw extruder from a main feeding port, the temperature of each section of the double-screw extruder is controlled at 170-210 ℃, the rotating speed is controlled at 400-500 rpm, and the polypropylene composite material granules are obtained after extrusion and granulation.
In addition, the invention also provides application of the polypropylene composite material as a scratch-resistant material. Wherein the scratch-resistant material comprises automobile external decorations such as instrument panels/instrument boards, door interior trimming panels, automobile bumpers and the like.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following examples and comparative examples: the polypropylene is named petrochemical Z30S, and the melt index is 25 +/-3.0 g/10min under the test conditions of 230 ℃ and 2.16 kg; the K glue is Phillips KR-03, the content of a butadiene structural unit is 20-40 wt%, and the melt index is 8g/10min under the test conditions of 200 ℃ and 5 kg; the aramid fiber is emperor TWARON 1488, the meta-aramid fiber, and the length is 6 mm.
Example 1
Stirring and mixing 10 parts by weight of polypropylene (PP), K glue, aramid fiber, aluminum silver strips (the particle size is 10-200 mu m), PP-g-MAH (the grafting ratio is 1.2 wt%), a coupling agent (3-aminopropyltriethoxysilane), an antioxidant and a lubricant (PP wax) in a high-speed stirrer at the rotating speed of 100rpm for 8 minutes, adding the obtained premix into a double-screw extruder from a side feeding port, adding the rest polypropylene into the double-screw extruder from a main feeding port, controlling the temperature of each section of the double-screw extruder at 170-210 ℃ and the rotating speed at 400-500 rpm, and performing extrusion granulation to obtain the polypropylene composite material. Wherein, the dosage of each component is shown in table 1, and the performance of the obtained polypropylene composite material is shown in table 2.
Example 2
10 parts by weight of polypropylene, K glue, aramid fiber, aluminum silver strips (the particle size is 10-200 mu m), PP-g-MAH (the grafting ratio is 3 wt%), a coupling agent (3- (methacryloyloxy) propyltrimethoxysilane), an antioxidant and a lubricant (sodium stearate) are stirred and mixed for 8 minutes in a high-speed stirrer at the rotating speed of 100rpm, then the obtained premix is added into a double-screw extruder from a side feeding port, the rest polypropylene is added into the double-screw extruder from a main feeding port, the temperature of each section of the double-screw extruder is controlled at 170-210 ℃, the rotating speed is controlled at 400-500 rpm, and the polypropylene composite material is obtained after extrusion granulation. Wherein, the dosage of each component is shown in table 1, and the performance of the obtained polypropylene composite material is shown in table 2.
Example 3
10 parts by weight of polypropylene, K glue, aramid fiber, aluminum silver strips (the particle size is 10-200 mu m), PP-g-MAH (the grafting rate is 2.1 wt%), a coupling agent (isopropyl tris (dodecyl benzenesulfonyl) titanate), an antioxidant and a lubricant (white oil) are stirred and mixed in a high-speed stirrer at the rotating speed of 100rpm for 8 minutes, then the obtained premix is added into a double-screw extruder from a side feeding port, the rest polypropylene is added into the double-screw extruder from a main feeding port, the temperature of each section of the double-screw extruder is controlled at 170-210 ℃, the rotating speed is controlled at 400-500 rpm, and the polypropylene composite material is obtained after extrusion and granulation. Wherein, the dosage of each component is shown in table 1, and the performance of the obtained polypropylene composite material is shown in table 2.
Example 4
A polypropylene composite was prepared in the same manner as in example 2 except that the aluminum pigment was not added, according to the method of example 2, to obtain a polypropylene composite. Wherein, the dosage of each component is shown in table 1, and the performance of the obtained polypropylene composite material is shown in table 2.
Example 5
A polypropylene composite was prepared in the same manner as in example 2 except that the compatibilizer PP-g-MAH was not added in the preparation of the polypropylene composite according to the method of example 4. Wherein, the dosage of each component is shown in table 1, and the performance of the obtained polypropylene composite material is shown in table 2.
Comparative example 1
A polypropylene composite was prepared according to the method of example 2, except that the K-gum and aramid fiber were not added, and the rest was the same as in example 2, to obtain a reference polypropylene composite. Wherein the amounts of the components are shown in table 1, and the properties of the obtained reference polypropylene composite material are shown in table 2.
Comparative example 2
A polypropylene composite was prepared according to the method of example 2, except that aramid fiber was not added, and the rest was the same as in example 2, to obtain a reference polypropylene composite. Wherein the amounts of the components are shown in table 1, and the properties of the obtained reference polypropylene composite material are shown in table 2.
Comparative example 3
A polypropylene composite was prepared according to the method of example 2, except that the K-gel was not added, and the rest was the same as in example 2, to obtain a reference polypropylene composite. Wherein the amounts of the components are shown in table 1, and the properties of the obtained reference polypropylene composite material are shown in table 2.
TABLE 1 (amounts of the components, in parts by weight)
TABLE 2
Note: in table 2, the scratch resistance was tested according to the popular PV3952 scratch resistance test standard, wherein the test samples were obtained by placing smooth-surfaced samples prepared from the polypropylene composites obtained in examples 1 to 5 and the reference polypropylene composites obtained in comparative examples 1 to 3 for 5 days: the composite material was injection molded into a small flat plate having a size of 80X 2.0mm by an injection molding machine. The test conditions included: the contact force was 5N and the scoring speed was 1000 mm/min.
As can be seen from the results in table 2, the polypropylene composite material provided by the present invention combines polypropylene, K-size, aramid fiber and optionally aluminum pigment, compatibilizer, coupling agent, antioxidant and lubricant in a specific ratio, so that the obtained polypropylene composite material has excellent and durable scratch resistance and good metal texture. In addition, as can be seen from the comparison of example 2 with examples 4 to 5, the addition of the aluminum pigment can enhance the metallic texture of the polypropylene composite material, and the addition of the compatibilizer can further improve the friction resistance and enhance the surface texture of the polypropylene composite material. As can be seen from comparison between the example 1 and the comparative examples 1-3, the obvious synergistic effect exists between the K glue and the aramid fiber, the scratch resistance of the polypropylene material can be obviously improved, and the two are not optional, wherein the K glue is not added in the comparative example 3, the improvement range of the scratch resistance of the polypropylene material is small, and the aramid fiber is mainly distributed in the matrix and is small in addition amount, and the aramid fiber can be rarely migrated to the surface of the polypropylene material, so that the improvement range of the scratch resistance of the product is small when the aramid fiber is singly used.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (16)
1. The polypropylene composite material is characterized by comprising polypropylene, K glue and aramid fiber in a weight ratio of 100 (10-15) to 1-5;
the melt index of the polypropylene is 3-100 g/10min under the test conditions of 230 ℃ and 2.16 kg.
2. The polypropylene composite material according to claim 1, wherein the content of butadiene structural units in the K glue is 20-40 wt%; the melt index of the K glue under the test conditions of 200 ℃ and 5kg is 5-15 g/10 min.
3. The polypropylene composite of claim 1, wherein the aramid fiber is meta-aramid fiber; the length of the aramid fiber is 2-10 mm.
4. The polypropylene composite according to any one of claims 1 to 3, wherein the polypropylene composite further comprises an aluminum pigment.
5. The polypropylene composite according to claim 4, wherein the aluminum pigment is aluminum silver strips.
6. The polypropylene composite according to claim 4, wherein the aluminum pigment is contained in an amount of 1 to 5 parts by weight, relative to 100 parts by weight of the polypropylene.
7. The polypropylene composite according to any one of claims 1 to 3, further comprising a compatibilizer.
8. The polypropylene composite of claim 7, wherein the compatibilizer is polypropylene grafted maleic anhydride.
9. The polypropylene composite material according to claim 8, wherein the grafting ratio of the polypropylene grafted with maleic anhydride is 1.2 to 3 wt%.
10. The polypropylene composite according to claim 7, wherein the compatibilizer is contained in an amount of 1 to 5 parts by weight with respect to 100 parts by weight of the polypropylene.
11. The polypropylene composite according to any one of claims 1 to 3, further comprising at least one of a coupling agent, an antioxidant and a lubricant.
12. The polypropylene composite material according to claim 11, wherein the coupling agent is at least one selected from 3-aminopropyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane and isopropyltris (dodecylbenzenesulfonyl) titanate, the antioxidant is a compound of an antioxidant 1010 and an antioxidant 168 in a mass ratio of (0.5-2): 1, and the lubricant is an ester lubricant and/or a fatty acid lubricant.
13. The polypropylene composite material according to claim 11, wherein the coupling agent is contained in an amount of 0.1 to 0.5 parts by weight, the antioxidant is contained in an amount of 0.2 to 1 part by weight, and the lubricant is contained in an amount of 0.1 to 2 parts by weight, based on 100 parts by weight of the polypropylene.
14. The polypropylene composite material according to any one of claims 1 to 3, wherein the polypropylene composite material comprises polypropylene, K glue, aramid fiber, aluminum pigment, a compatilizer, a coupling agent, an antioxidant and a lubricant, and relative to 100 parts by weight of polypropylene, the content of the K glue is 10 to 15 parts by weight, the content of the aramid fiber is 1 to 5 parts by weight, the content of the aluminum pigment is 1 to 5 parts by weight, the content of the compatilizer is 1 to 5 parts by weight, the content of the coupling agent is 0.1 to 0.5 part by weight, the content of the antioxidant is 0.2 to 1 part by weight, and the content of the lubricant is 0.1 to 2 parts by weight.
15. The preparation method of the polypropylene composite material as claimed in any one of claims 1 to 14, which comprises uniformly mixing the polypropylene, the K-gum and the aramid fiber and optionally an aluminum pigment, a compatilizer, a coupling agent, an antioxidant and a lubricant to obtain the polypropylene composite material.
16. Use of a polypropylene composite according to any one of claims 1 to 14 as a scratch resistant material.
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| CN103374180A (en) * | 2012-04-26 | 2013-10-30 | 滁州格美特科技有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN104608304A (en) * | 2014-12-09 | 2015-05-13 | 虞洋 | Preparation method for long aramid fiber polypropylene composite material |
| CN105482256A (en) * | 2016-01-05 | 2016-04-13 | 苏州润佳工程塑料股份有限公司 | Low-sink-mark polypropylene composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103374180A (en) * | 2012-04-26 | 2013-10-30 | 滁州格美特科技有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN104608304A (en) * | 2014-12-09 | 2015-05-13 | 虞洋 | Preparation method for long aramid fiber polypropylene composite material |
| CN105482256A (en) * | 2016-01-05 | 2016-04-13 | 苏州润佳工程塑料股份有限公司 | Low-sink-mark polypropylene composite material and preparation method thereof |
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