CN111087703A - High-brightness black scratch-resistant thin-walled polypropylene composite material and preparation method thereof - Google Patents
High-brightness black scratch-resistant thin-walled polypropylene composite material and preparation method thereof Download PDFInfo
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- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
Abstract
The invention discloses a high-brightness black scratch-resistant thin-walled polypropylene composite material and a preparation method thereof, wherein the polypropylene composite material comprises the following raw materials in parts by weight: polypropylene: 63.4-79.8; talc powder: 10-20 parts of; elastomer: 6-10; highlight black master batch: 1-3; scratch-resistant auxiliary agent: 0.2-0.6; antioxidant: 0 to 1; other auxiliary agents: 0 to 3; the ultra-fine particle size carbon black in the high-brightness black master batch has extremely strong coloring effect, and the polypropylene composite material achieves stable and uniform high-brightness black aesthetic effect due to the strong dispersion effect of the hyperdispersant; meanwhile, an organic silicon polymer with a special structure is introduced, so that the polypropylene composite material has good scratch resistance, has long-acting property and durability compared with the traditional silicone scratch-resistant auxiliary agent under the condition of adding a small amount of the silicone scratch-resistant auxiliary agent, can obviously improve the scratch resistance of the surface of the polypropylene material and reduce the surface friction coefficient, and can play a synergistic effect with polyethylene wax in high-brightness black master batches to improve the scratch resistance of the polypropylene composite material.
Description
Technical Field
The invention belongs to the technical field of polymer modification and processing, and relates to a high-brightness black scratch-resistant thin-walled polypropylene composite material and a preparation method thereof.
Background
With the rapid development of the automobile industry, a large amount of natural resources are consumed for manufacturing automobiles, the environmental and energy problems caused by the automobile industry are increasingly severe, and the development and application of the automobile lightweight technology become the mainstream trend of the development of the automobile industry at present. Polypropylene is used as general plastic, has very wide application in automobiles due to the characteristics of low density, excellent price and the like, and a thin-walled polypropylene composite material which is one of automobile lightweight technical means is used for inner and outer ornaments of automobile columns, door panels, instrument panels, grids, bumpers and the like. Along with the experience and upgrade of automobile consumers, the materials with high brightness and black are gradually favored by various automobile modified material manufacturers for pursuing the brightness of the interior and exterior ornaments of the automobile, and are particularly applied to the grille and bumper materials of the automobile exterior trim.
The polypropylene material is not scratch-resistant due to lower rigidity and hardness, and the scratch phenomenon is easy to occur in the using process. Because the exterior trimming part has higher requirements on appearance, the surface scratch resistance of the exterior trimming part prepared from the polypropylene material is also concerned while the exterior trimming part has good appearance. Therefore, with the wide application of the thin-walled polypropylene composite material in the interior and exterior trim parts of the automobile, how to obtain the polypropylene material with the high bright black effect on the surface and the scratch resistance is very important.
Disclosure of Invention
The invention aims to provide a polypropylene composite material with high brightness, black color, scratch resistance and thin wall and a preparation method thereof. The method mainly introduces a master batch with high bright black function and a scratch resistant auxiliary agent into a thin-walled polypropylene material system to ensure that the master batch has the aesthetic effect of high bright black and the scratch resistant performance; the high-brightness black functional master batch is composed of carbon black, a hyper-dispersant, polyethylene wax and the like. The carbon black is selected from carbon black with superfine particle size, the particle size is 10-15nm, the smaller the particle size, the more obvious the coloring effect of the carbon black is, and the higher the represented blackness value is; a hyper-dispersant pentaerythritol stearate; the polyethylene wax has low molecular weight (molecular weight of 700-1000), and the low molecular weight polyethylene wax is beneficial to the dispersion of carbon black and filling substances in the polypropylene material and can also reduce the surface friction coefficient of the material; the scratch-resistant auxiliary agent is selected from an organic silicon polymer with a special structure, has long-acting property and durability, can obviously improve the scratch resistance of the surface of the polypropylene material and reduce the surface friction coefficient compared with the traditional silicone scratch-resistant auxiliary agent when a small amount of the scratch-resistant auxiliary agent is added, can play a synergistic effect with polyethylene wax in high-brightness black master batches, and improves the scratch resistance of the polypropylene composite material.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
a high-brightness black scratch-resistant thin-walled polypropylene composite material comprises the following raw materials in parts by weight:
polypropylene: 63.4-79.8;
talc powder: 10-20 parts of;
elastomer: 6-10;
highlight black master batch: 1-3;
scratch-resistant auxiliary agent: 0.2-0.6;
antioxidant: 0 to 1;
other auxiliary agents: 0-3.
Wherein the polypropylene matrix resin is copolymerized polypropylene, and the melt index (230 ℃, 2.16KG) is about 25g-100g/10 min.
The talcum powder is 5000-mesh talcum powder material.
The elastomer is one or two mixture of ethylene and butylene copolymer and ethylene and octene copolymer, and its density is 0.86-0.90g/cm3The melt index is 0.5-6g/10 min.
The highlight black master batch is prepared from the following components in parts by weight: 60 parts of carbon black with superfine particle size, 10 parts of hyperdispersant and 30 parts of polyethylene wax; wherein the particle size of the superfine carbon black is 10-15nm, and the hyper-dispersant pentaerythritol stearate and the polyethylene wax are low molecular weight polyethylene wax, and the molecular weight of the polyethylene wax is 700-1000.
The scratch-resistant auxiliary agent is an organic silicon polymer with a special structure, and is selected from AST-3018.
The antioxidant is considered by a person skilled in the art to be required, and mainly comprises one or more of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), stearyl thiodipropionate (antioxidant DSTP), and n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076).
The other auxiliary agents are one or a combination of several of various light stabilizers, processing aids, odor absorbers and the like which are considered to be needed by the technical personnel in the field.
The preparation method of the high-brightness black scratch-resistant thin-walled polypropylene composite material comprises the following steps:
(1) preparing highlight black master batch:
adding the carbon black, the hyper-dispersant and the polyethylene wax into a low-speed mixer together according to the weight components, uniformly mixing, then transferring into a mixing chamber of an internal mixer for high-speed internal mixing, then transferring the internally mixed blocky materials to a double-wrist feeding port for feeding, and extruding, air cooling and granulating the materials by a single-screw extruder to prepare the master batch with the extinction function. Wherein the temperature of the mixing chamber in the internal mixer is set at 140-160 ℃, the diameter of the single screw is 70mm, the length-diameter ratio is 12, the temperature of the single screw extruder is controlled by three sections, and the temperature of each section from the feeding port to the machine head is 180 ℃, 200 ℃ and 215 ℃ in turn.
(2) High-brightness black, scratch-resistant and thin-walled polypropylene composite material and preparation thereof:
(1) the components are weighed according to the mass ratio;
(2) placing the polypropylene, the high-brightness black master batch, the scratch-resistant auxiliary agent, the elastomer, the antioxidant, other auxiliary agents and the like in a high-speed mixer, and mixing for 5-10min at high speed;
(3) adding the uniformly mixed raw materials into a double-screw extruder from a main feeding port, adding talcum powder into the double-screw extruder from a lateral feeding port in the middle of the double-screw extruder, performing melt extrusion, bracing, cooling and granulation, and performing material drying treatment to prepare the high-brightness black, scratch-resistant and thin-walled polypropylene composite material, wherein the processing process temperature of each area of the double-screw extruder is respectively as follows: a first area: 185-200 deg.C, 200-210 deg.C, 210-215 deg.C, 205-210 deg.C. The time of the whole extrusion process is about 2 minutes, the pressure is 12-18Mpa, the rotating speed of a main screw is 500-600r/min, the temperature of a water tank is 30-60 ℃, double-vacuum pumping devices are added on two sides of a double-screw extruder, the vacuum degree of the double vacuum is-0.07 MPa-0.08 MPa, and a new material drying process is adopted for material drying treatment: storing in a tank A, drying in a tank B, cooling in a tank C, wherein the drying process in the tank B comprises the following steps: 130 ℃ 4H.
The invention has the advantages that:
according to the invention, the highlight black master batch is added on the basis of the traditional thin-walled polypropylene composite material, the ultra-fine particle size carbon black in the highlight black master batch has a strong coloring effect, and the strong dispersion effect of the hyperdispersant is added, so that the polypropylene composite material achieves a stable and uniform aesthetic effect of highlight black; meanwhile, an organic silicon polymer with a special structure is introduced, so that the polypropylene composite material has good scratch resistance, has long-acting property and durability compared with the traditional silicone scratch-resistant auxiliary agent under the condition of adding a small amount of the silicone scratch-resistant auxiliary agent, can obviously improve the scratch resistance of the surface of the polypropylene material and reduce the surface friction coefficient, and can play a synergistic effect with polyethylene wax in high-brightness black master batches to improve the scratch resistance of the polypropylene composite material; by adding the talc powder into the polypropylene material through side feeding, the thin-walled polypropylene material has high brightness, black and scratch resistance effects and retains the high performance characteristics of high melt index, high rigidity and high toughness; meanwhile, the preparation process of the high-brightness black scratch-resistant thin-walled polypropylene composite material provided by the invention is simple, and the production cost is low.
Detailed Description
The present invention will be described in detail with reference to specific examples. Except for specific indications, the components in the examples are in parts by weight.
The examples of the present invention and the comparative examples contain the respective component contents shown in Table 1.
TABLE 1
The contents (mass%) of the respective main components in examples and comparative examples
The polypropylene in the examples and comparative examples in Table 1 is a copolymer polypropylene prepared by compounding PP511 and BX3920 at a ratio of 1:1, the PP511 is produced by Mitsubishi corporation, the melt flow rates are respectively 30g/10min, the BX3920 is produced by Korea SK corporation, the talc has a melt flow rate of 100g/10min, the talc has a mesh number of about 5000 meshes, the elastomer is a thermoplastic POE elastomer produced by LG corporation, the LC670 is a carbon black in the high-brightness black master batch has a particle size of 10-15nm, the BR-3CF is produced by Tianjin Borui chemical Limited company, the hyper-dispersant pentaerythritol stearate has a mark of PETS-4, the polyolefin wax has a molecular weight of 700-1000, the scratch-resistant assistant has a mark of 700-3018, the common black master batch produced by philosophy corporation, the commercial silicone oil has a molecular weight of 700-3018, the silicone oil has a molecular weight of 85MB-855, the silicone oil is a di-tert-butyl antioxidant produced by DSTP 1010-352, the antioxidant produced by DSTP-352, and the antioxidant produced by DSTP antioxidant (DSTP-3) and the other antioxidant produced by Ciba antioxidant (DSTP antioxidant) produced by Ciba antioxidant).
The specific implementation is developed as follows:
A. preparing highlight black master batch:
adding the carbon black, the hyper-dispersant and the polyethylene wax into a low-speed mixer together according to the weight components, uniformly mixing, then transferring into a mixing chamber of an internal mixer for high-speed internal mixing, then transferring the internally mixed blocky materials to a double-wrist feeding port for feeding, and extruding, air cooling and granulating the materials by a single-screw extruder to prepare the master batch with the extinction function. Wherein the temperature of the mixing chamber in the internal mixer is set at 140-160 ℃, the diameter of the single screw is 70mm, the length-diameter ratio is 12, the temperature of the single screw extruder is controlled by three sections, and the temperature of each section from the feeding port to the machine head is 180 ℃, 200 ℃ and 215 ℃ in turn.
B. High-brightness black, scratch-resistant and thin-walled polypropylene composite material and preparation thereof:
(1) the components are weighed according to the mass ratio;
(2) placing the polypropylene, the high-brightness black master batch, the scratch-resistant auxiliary agent, the elastomer, the antioxidant, other auxiliary agents and the like in a high-speed mixer, and mixing for 5-10min at high speed;
(3) adding the uniformly mixed raw materials into a double-screw extruder from a main feeding port, adding talcum powder into the double-screw extruder from a lateral feeding port in the middle of the double-screw extruder, performing melt extrusion, bracing, cooling and granulation, and performing material drying treatment to prepare the high-brightness black, scratch-resistant and thin-walled polypropylene composite material, wherein the processing process temperature of each area of the double-screw extruder is respectively as follows: a first area: 185-200 deg.C, 200-210 deg.C, 210-215 deg.C, 205-210 deg.C. The time of the whole extrusion process is about 2 minutes, the pressure is 12-18Mpa, the rotating speed of a main screw is 500-600r/min, the temperature of a water tank is 30-60 ℃, double-vacuum pumping devices are added on two sides of a double-screw extruder, the vacuum degree of the double vacuum is-0.07 MPa-0.08 MPa, and a new material drying process is adopted for material drying treatment: storing in a tank A, drying in a tank B, cooling in a tank C, wherein the drying process in the tank B comprises the following steps: 130 ℃ 4H.
C. The composite particles prepared as described above were dried in a forced air oven at 80-100 ℃ for 2 hours, and then the dried particles were injection molded on an injection molding machine, followed by performance testing.
D. And (3) testing basic mechanical properties: the density was measured according to ISO1183-1, the melt index was measured according to ISO1133-1, the test temperature was 230 ℃, the load was 2.16kg, the tensile strength was tested according to ISO527-2, the specimen size was 170 × 10 × 4mm, the tensile speed was 50mm/min, the flexural modulus was tested according to ISO178, the specimen size was 80 × 10 × 4mm, the span was 64mm, the flexural speed was 2mm/min, the simple beam notched impact strength was tested according to ISO179-1, the specimen size was 80 × 10 × 4mm, and the notched depth was one fifth of the specimen width. The gloss was measured according to ISO2813 with a test angle of 60 ° and a test specimen of highlight. The L value test was evaluated with a Meinenda 2500C. The scratch resistance was tested according to the PV3952 method, K3A dermatoglyph, load 10N.
Data of material property test in examples and comparative examples
From the data results of the examples and comparative examples in the above tables, it can be found that the performance of the materials prepared by the examples and comparative examples can meet the performance requirements of the thin-walled materials. It can be found from examples 1-2, 4-5 and comparative examples 3-4 that the L value of the thin-walled polypropylene composite material system after adding the high brightness black master batch is significantly reduced, and the L value of the material added with 1 part of the high brightness black master batch is lower than the L value of the material added with 2 parts of the common black master batch, which is caused by the extremely strong coloring effect of the ultra-fine particle size carbon black in the high brightness black master batch; from examples 3, 6 and 7, it can be found that the increase of the content of the highlight black master batch can endow the polypropylene composite material system with better highlight black aesthetic effect. Compared with the comparative examples 1-2, the scratch-resistant auxiliary agent in the embodiment 3 can provide a composite material system with better scratch resistance under the condition that the addition amount of the scratch-resistant auxiliary agent is less than that of the traditional silicone master batch, and the scratch resistance of a high-brightness black polypropylene composite material system can be remarkably improved by introducing the scratch-resistant auxiliary agent of the organic silicon polymer with a special structure. By adding the talcum powder in the side feeding way, the thin-walled polypropylene material has the effects of high brightness, black and scratch resistance, and simultaneously retains the comprehensive properties of high melt index, high rigidity and high toughness.
Claims (10)
1. A high-brightness black scratch-resistant thin-walled polypropylene composite material is characterized in that: the composite material comprises the following raw materials in parts by weight:
polypropylene: 63.4-79.8;
talc powder: 10-20 parts of;
elastomer: 6-10;
highlight black master batch: 1-3;
scratch-resistant auxiliary agent: 0.2-0.6;
antioxidant: 0 to 1;
other auxiliary agents: 0-3.
2. The highlight black, scratch resistant, thin-walled polypropylene composite of claim 1, wherein: the polypropylene matrix resin is copolymerized polypropylene, and the melt index (230 ℃, 2.16KG) is about 25g-100g/10 min.
3. The highlight black, scratch resistant, thin-walled polypropylene composite of claim 1, wherein: the talcum powder is 5000-mesh talcum powder material.
4. The highlight black, scratch resistant, thin-walled polypropylene composite of claim 1, wherein: the elastomer is one or two mixture of ethylene and butylene copolymer and ethylene and octene copolymer, and its density is 0.86-0.90g/cm3The melt index is 0.5-6g/10 min.
5. The highlight black, scratch resistant, thin-walled polypropylene composite of claim 1, wherein: the highlight black master batch is prepared from the following components in parts by weight: 60 parts of carbon black with superfine particle size, 10 parts of hyperdispersant and 30 parts of polyethylene wax.
6. The highlight black, scratch resistant, thin-walled polypropylene composite of claim 5, wherein: the particle size of the superfine carbon black is 10-15nm, and the hyper-dispersant pentaerythritol stearate and the polyethylene wax are low molecular weight polyethylene wax, and the molecular weight of the polyethylene wax is 700-1000.
7. The highlight black, scratch resistant, thin-walled polypropylene composite of claim 1, wherein: the scratch-resistant auxiliary agent is an organic silicon polymer with a special structure, and is selected from AST-3018.
8. The polypropylene composite material as claimed in claim 1, wherein the antioxidant is one or more of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), stearyl thiodipropionate (antioxidant DSTP), and n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076).
9. The highlight black, scratch resistant, thin-walled polypropylene composite of claim 1, wherein: the other auxiliary agents are one or a combination of several of various light stabilizers, processing aids, odor absorbers and the like which are considered to be needed by the technical personnel in the field.
10. A method for preparing the high-brightness black, scratch-resistant and thin-walled polypropylene composite material as claimed in any one of claims 1 to 9, wherein: the method comprises the following steps:
(1) preparing highlight black master batch:
adding the carbon black, the hyper-dispersant and the polyethylene wax into a low-speed mixer together according to the weight components, uniformly mixing, then transferring into a mixing chamber of an internal mixer for high-speed internal mixing, then transferring the internally mixed blocky materials to a double-wrist feeding port for feeding, and extruding, air cooling and granulating the materials by a single-screw extruder to prepare the master batch with the extinction function. Wherein the temperature of an internal mixing chamber in the internal mixer is set at 140-160 ℃, the diameter of a single screw is 70mm, the length-diameter ratio is 12, the temperature of the single screw extruder is controlled by three sections, and the temperature of each section from a feeding port to a machine head is 180 ℃, 200 ℃ and 215 ℃ in turn;
(2) high-brightness black, scratch-resistant and thin-walled polypropylene composite material and preparation thereof:
(1) the components are weighed according to the mass ratio;
(2) placing the polypropylene, the high-brightness black master batch, the scratch-resistant auxiliary agent, the elastomer, the antioxidant, other auxiliary agents and the like in a high-speed mixer, and mixing for 5-10min at high speed;
(3) adding the uniformly mixed raw materials into a double-screw extruder from a main feeding port, adding talcum powder into the double-screw extruder from a lateral feeding port in the middle of the double-screw extruder, performing melt extrusion, bracing, cooling and granulation, and performing material drying treatment to prepare the high-brightness black, scratch-resistant and thin-walled polypropylene composite material, wherein the processing process temperature of each area of the double-screw extruder is respectively as follows: a first area: 185-200 ℃, 200-210 ℃ in the second region, 210-215 ℃ in the third region, and 210-210 ℃ in the fourth region; the time of the whole extrusion process is about 2 minutes, the pressure is 12-18Mpa, the rotating speed of a main screw is 500-600r/min, the temperature of a water tank is 30-60 ℃, double-vacuum pumping devices are added on two sides of a double-screw extruder, the vacuum degree of the double vacuum is-0.07 MPa-0.08 MPa, and a new material drying process is adopted for material drying treatment: storing in a tank A, drying in a tank B, cooling in a tank C, wherein the drying process in the tank B comprises the following steps: 130 ℃ 4H.
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| CN113583341A (en) * | 2021-07-28 | 2021-11-02 | 金发科技股份有限公司 | High-blue-phase high-heat-resistance polypropylene composition and preparation method and application thereof |
| CN115637004A (en) * | 2022-10-28 | 2023-01-24 | 金发科技股份有限公司 | High-adhesion scratch-resistant master batch and preparation method and application thereof |
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| CN115637004A (en) * | 2022-10-28 | 2023-01-24 | 金发科技股份有限公司 | High-adhesion scratch-resistant master batch and preparation method and application thereof |
| CN115637004B (en) * | 2022-10-28 | 2023-08-22 | 金发科技股份有限公司 | High-adhesion scratch-resistant master batch as well as preparation method and application thereof |
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