CN111925598A - Scratch-resistant polypropylene composite material and preparation method thereof - Google Patents
Scratch-resistant polypropylene composite material and preparation method thereof Download PDFInfo
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention relates to a scratch-resistant polypropylene composite material and a preparation method thereof, wherein the scratch-resistant polypropylene composite material comprises the following raw material components: polypropylene, toughening elastomer, talcum powder, scratch resistance agent, black seeds, antioxidant and weather resistance agent. By adding the scratch resistant agent, the composite material can keep good scratch resistance at normal temperature, has no loss of the scratch resistance after being stored at high temperature, can still keep good scratch resistance, can also keep good comprehensive performance, and can be widely applied to large interior parts such as automobile instrument panels, door panels and the like.
Description
Technical Field
The invention belongs to the field of polypropylene composite materials, and particularly relates to a scratch-resistant polypropylene composite material and a preparation method thereof.
Background
Compared with other general thermoplastic resins, the polypropylene resin has the advantages of small relative density, low price, good processability, good comprehensive performance and the like, but the polypropylene also has the defects of poor rigidity, large molding shrinkage and the like. Fillers such as talcum powder are often added for modification, the rigidity of polypropylene is improved, the shrinkage rate is reduced, but the scratch resistance of the material is poor due to the addition of the talcum powder, and a solution is urgently needed in the automobile industry with more and more attention paid to customer experience.
The automobile decorative parts are subjected to high-temperature storage experiments, and in practical use, a high-temperature environment exists, so that the scratch resistance of the material is obviously reduced after the automobile decorative parts are stored for a certain time at a certain temperature. In general, the conventional scratch resistant agent is added to achieve a better scratch resistant effect at normal temperature, but the scratch resistant effect after high-temperature storage is not improved.
CN109749249A discloses a scratch-resistant polypropylene composite material and a preparation method thereof, and discloses that the scratch resistance of the material needs to be improved by fatty acid ester in cooperation with a silicone type scratch-resistant agent, so that good scratch resistance effect of polypropylene at normal temperature can be realized, but the scratch resistance effect after high-temperature storage is not realized.
Disclosure of Invention
The invention aims to solve the technical problem of providing a scratch-resistant polypropylene composite material and a preparation method thereof, and overcoming the defect of poor scratch-resistant effect after high-temperature storage in the prior art.
The invention provides a polypropylene composite material, which comprises the following raw material components in percentage by weight:
40% -75% of polypropylene;
5% -10% of toughened elastomer;
10-30% of talcum powder;
5 to 10 percent of scratch resistant agent;
1% -1.5% of black seeds;
0.2 to 0.4 percent of antioxidant;
0.2 to 0.4 percent of weather resistant agent;
the scratch resistant agent is prepared from high-density polyethylene, linear low-density polyethylene and silicone scratch resistant agent through extrusion and granulation.
The polypropylene is copolymerized polypropylene, the melt mass flow rate is 40-60g/10min, and the test conditions are 230 ℃ and 2.16 kg; the toughening elastomer is one or more of polybutadiene rubber, ethylene-butylene copolymer, ethylene-octene copolymer and ethylene-propylene-diene rubber.
The particle size of the talcum powder is 1-50 mu m, and the weight percentage content of the silicon dioxide is 60-90%; the black seeds are carbon black with the particle size of 10-1000 nm.
The antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri (2, 4-di-tert-butylphenyl) phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Preferably, the antioxidant is a compound of two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further preferably, the antioxidant is a compound of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite.
The weather resisting agent is at least one of hindered amine, benzotriazole, benzophenone and triazine benzylidene malonate light stabilizer.
Further, the weather resisting agent is UV-3808PP 5.
The silicone scratch resistant agent is silicone grafted polypropylene scratch resistant agent, wherein the mass grafting rate of silicone is 30-70%.
The mass ratio of the high-density polyethylene to the linear low-density polyethylene to the silicone scratch-resistant agent is 1.5-2.5:1.5-2.5: 1.
Further, the mass ratio of the high-density polyethylene to the linear low-density polyethylene to the silicone-based scratch resistant agent is 2:2: 1.
The scratch resistant agent is prepared from raw materials including high-density polyethylene, linear low-density polyethylene and silicone scratch resistant agent through extrusion granulation, wherein the extrusion granulation process specifically comprises the following steps: adopting a double-screw extruder, wherein the temperature of the double-screw extruder is 175-: 1.
the preparation method of the polypropylene composite material comprises the following steps:
according to the weight percentage, the polypropylene, the toughening elastomer, the talcum powder, the scratch-resistant agent, the black seed, the antioxidant and the weather-resistant agent are added into a mixer to be uniformly mixed, and then extrusion, cooling and granulation are carried out to obtain the polypropylene composite material.
The uniform mixing specifically comprises the following steps: adding into a mixer to mix evenly, the temperature of the high-speed mixer is 60-70 ℃, and the rotating speed of the mixer is 120-140 r/min.
The specific extrusion process parameters are as follows: adopting a double-screw extruder, wherein the temperature of the double-screw extruder is 175-: 1.
the invention provides an application of the polypropylene composite material, such as other large-area decorative parts of automobiles, household appliances, door panels and the like.
Advantageous effects
(1) According to the scratch-resistant polypropylene composite material prepared by the invention, the scratch-resistant agent is added, so that the good scratch resistance of the polypropylene composite material under normal temperature storage can be realized;
(2) according to the scratch-resistant polypropylene composite material prepared by the invention, the scratch-resistant agent is added, and the polypropylene composite material can realize good scratch resistance when the polypropylene composite material is put out for the first time under high-temperature storage;
(3) the scratch-resistant polypropylene composite material prepared by the invention has simple preparation process, and can be widely used for other large-area decorative parts such as automobiles, household appliances and the like;
(4) according to the invention, the high-density polyethylene, the linear low-density polyethylene and the silicone scratch-resistant agent are compounded and combined with extrusion granulation to obtain the scratch-resistant agent, and the scratch-resistant agent is added into the system disclosed by the invention to finally obtain the high-temperature scratch-resistant polypropylene composite material, so that the high-temperature scratch-resistant polypropylene composite material can still maintain good scratch resistance after being stored for 500 hours at the normal temperature and at the temperature of up to 150 ℃, and in addition, the composite material disclosed by the invention also has good comprehensive performance.
Note: the scratch resistant agent is obtained by taking high-density polyethylene, linear low-density polyethylene and silicone type scratch resistant agent as raw materials and performing extrusion granulation, wherein the silicone type scratch resistant agent is silicone grafted polypropylene type scratch resistant agent, and the mass grafting rate of silicone is 30-70%.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
(1) The raw material sources are as follows:
copolymerized polypropylene: the melt mass flow rate of the polypropylene BX3900 is 60g/10min, the test conditions are 230 ℃, 2.16kg and the manufacturer is exxon;
elastomer: POE ENGAGE 7467, manufacturer: (ii) the chemistry of the dow;
talc powder: 777A adding raw materials (3000 mesh talcum powder);
carbon black: PLASBLAK PE2772 KF carbopol;
an antioxidant A: antioxidant 1010 basf;
and (3) antioxidant B: antioxidant 168 basf;
weather resisting agent: UV-3808PP5 Cyanid;
amide-based scratch resistance agents (NR001-2) are commercially available;
silicone-based scratch resistance agent A (HMB-0221) is commercially available;
silicone-based scratch resistance agent B (MB50-001) commercially available;
scratch resistance agent a: mixing commercially available high-density polyethylene, linear low-density polyethylene and silicone scratch-resistant agent A according to a mass ratio of 2:2:1, and extruding and granulating by using a double-screw extruder, wherein the temperature of the double-screw extruder is 180 ℃, 195 ℃, 190 ℃, 185 ℃ and 185 ℃ from a feeding section to a machine head in sequence, the screw rotation speed is 180 revolutions per minute, and the screw length-diameter ratio is 40: 1. wherein the silicone scratch resistant agent A is silicone grafted polypropylene scratch resistant agent, the mass grafting rate of silicone is 50%, the high density polyethylene is HDPE DMDA8008, and the manufacturer is Lanzhou petrochemical; the low density polyethylene is LDPE 2426H, and the manufacturer is Zhonghai Shell brand.
Scratch resistance agent B: mixing commercially available high-density polyethylene, linear low-density polyethylene and silicone scratch-resistant agent A according to a mass ratio of 5:5:1, and extruding and granulating by a double-screw extruder, wherein the temperature of the double-screw extruder is 180 ℃, 195 ℃, 190 ℃, 185 ℃ and 185 ℃ from a feeding section to a machine head in sequence, the screw rotation speed is 180 revolutions per minute, and the screw length-diameter ratio is 40: 1. wherein the silicone scratch resistant agent A is silicone grafted polypropylene scratch resistant agent, the mass grafting rate of silicone is 50%, the high density polyethylene is HDPE DMDA8008, and the manufacturer is Lanzhou petrochemical; the low density polyethylene is LDPE 2426H, and the manufacturer is Zhonghai Shell brand.
Scratch resistance agent C: mixing commercially available high-density polyethylene, linear low-density polyethylene and silicone scratch-resistant agent B according to the mass ratio of 2:2:1, and extruding and granulating by using a double-screw extruder, wherein the temperature of the double-screw extruder is 180 ℃, 195 ℃, 190 ℃, 185 ℃ and 185 ℃ from a feeding section to a machine head in sequence, the screw rotation speed is 180 revolutions per minute, and the screw length-diameter ratio is 40: 1. wherein the silicone scratch resistant agent B has no grafting rate, and the high-density polyethylene is HDPE DMDA8008, a manufacturer Lanzhou petrochemical; the low density polyethylene is LDPE 2426H, and the manufacturer is Zhonghai Shell brand.
(2) Test standards and methods:
tensile strength test method ISO 527 tensile speed 50 mm/min;
flexural modulus test method ISO 178 flexural speed 2 mm/min;
notched impact test method ISO 179 plate hammer energy is 1J;
the scratch resistance test method PV3952 has the load of 10N, the scratch speed of 1000mm/min and the diameter of a scribing head of 10 mm.
Example 1
73.4 parts of polypropylene copolymer, 10 parts of elastomer, 5 parts of scratch resistant agent A, 10 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
example 2
61.4 parts of polypropylene copolymer, 10 parts of elastomer, 7 parts of scratch resistant agent A, 20 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
example 3
Adding 48.4 parts by weight of polypropylene copolymer, 10 parts by weight of elastomer, 10 parts by weight of scratch resistant agent A, 30 parts by weight of talcum powder, 1 part by weight of carbon black, 0.2 part by weight of antioxidant A, 0.2 part by weight of antioxidant B and 0.2 part by weight of weather resistant agent into a mixer, and uniformly mixing. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 1
77.4 parts of polypropylene copolymer, 10 parts of elastomer, 1 part of amide scratch resistant agent (NR001-2), 10 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 2
67 parts of co-polypropylene, 10 parts of elastomer, 1.4 parts of amide scratch resistant agent (NR001-2), 20 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 3
56.4 parts of polypropylene copolymer, 10 parts of elastomer, 2 parts of amide scratch-resistant agent (NR001-2), 30 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather-resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 4
77.4 parts of polypropylene copolymer, 10 parts of elastomer, 1 part of silicone scratch-resistant agent A, 10 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather-resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 5
67 parts of polypropylene copolymer, 10 parts of elastomer, 1.4 parts of silicone scratch-resistant agent A, 20 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather-resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 6
56.4 parts of polypropylene copolymer, 10 parts of elastomer, 2 parts of silicone scratch-resistant agent A, 30 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather-resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 7
73.4 parts of polypropylene copolymer, 10 parts of elastomer, 2 parts of high-density polyethylene, 2 parts of linear low-density polyethylene, 1 part of silicone scratch-resistant agent A, 10 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather-resistant agent are added into a mixer and evenly mixed. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 8
73.4 parts of polypropylene copolymer, 10 parts of elastomer, 5 parts of scratch resistant agent B, 10 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 9
77.4 parts of polypropylene copolymer, 10 parts of elastomer, 1 part of silicone scratch-resistant agent B, 10 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather-resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 10
73.4 parts of polypropylene copolymer, 10 parts of elastomer, 5 parts of scratch resistant agent C, 10 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 11
61.4 parts of polypropylene copolymer, 10 parts of elastomer, 7 parts of scratch resistant agent C, 20 parts of talcum powder, 1 part of carbon black, 0.2 part of antioxidant A, 0.2 part of antioxidant B and 0.2 part of weather resistant agent are added into a mixer and mixed uniformly. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
comparative example 12
Adding 48.4 parts by weight of polypropylene copolymer, 10 parts by weight of elastomer, 10 parts by weight of scratch-resistant agent C, 30 parts by weight of talcum powder, 1 part by weight of carbon black, 0.2 part by weight of antioxidant A, 0.2 part by weight of antioxidant B and 0.2 part by weight of weather-resistant agent into a mixer, and uniformly mixing. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 180 ℃, 195 ℃, 190 ℃, 185 ℃ in sequence, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
examples 1-4 and comparative examples 1-12 were subjected to basic performance tests and the scratch resistance of the materials was tested according to the popular PV3952 test, the results are shown in the table, wherein Table 1 shows the results of the performance tests of examples 1-4 and comparative examples 1-4, and Table 2 shows the results of the performance tests of comparative examples 5-12.
TABLE 1 results of Performance test of examples 1 to 4 and comparative examples 1 to 4
TABLE 2 results of the Performance test of comparative examples 5 to 12
From the above example 1, comparative example 1 and comparative example 4, it is evident that the scratch resistance effect of the scratch resistance agent a of the present invention is significantly better than that of the conventional amide and silicone type scratch resistance agents after being stored for 24 hours at room temperature by adding the scratch resistance agent a to a low-content talc powder filling system, and the scratch resistance performance of the material is substantially not lost in terms of the retention rate of the scratch resistance performance after being stored for 500 hours at room temperature, 100 ℃ and 150 ℃, while the attenuation of the scratch resistance performance of the conventional amide and silicone type scratch resistance agents is very significant after being stored at room temperature or high temperature, and the normal requirements of automobile decorative parts cannot be satisfied. And the addition of the scratch resistant agent A has no influence on other comprehensive properties of the material.
From the above example 2, comparative example 2 and comparative example 5, it is evident that the scratch resistance effect of the scratch resistance agent a of the present invention is significantly better than that of the conventional amide and silicone type scratch resistance agents after being stored for 24 hours at room temperature by adding the scratch resistance agent a to a medium-content talc powder filling system, and the scratch resistance performance of the material is substantially not lost in terms of the retention rate of the scratch resistance performance after being stored for 500 hours at room temperature, 100 ℃ and 150 ℃, while the attenuation of the scratch resistance performance of the conventional amide and silicone type scratch resistance agents is very significant after being stored at room temperature or high temperature, and the normal requirements of automobile decorative parts cannot be satisfied. And the addition of the scratch resistant agent A has no influence on other comprehensive properties of the material.
From the above examples 3, comparative examples 3 and 6, it is evident that the scratch resistance effect of the scratch resistance agent a of the present invention is significantly better than that of the conventional amide and silicone based scratch resistance agents after being stored for 24 hours at room temperature by adding the scratch resistance agent a to a high-content talc powder filled system, and the scratch resistance performance of the material is substantially not lost in terms of the retention rate of the scratch resistance performance after being stored for 500 hours at room temperature, 100 ℃ and 150 ℃, while the deterioration of the scratch resistance performance of the conventional amide and silicone based scratch resistance agents is very significant after being stored at room temperature or high temperature, and the normal requirements of automobile trim parts cannot be satisfied. And the addition of the scratch resistant agent has no influence on other comprehensive properties of the material.
From the above example 1 and comparative example 7, it is apparent that the addition of the scratch resistant agent a of the present invention, and the separate addition of each component of the scratch resistant agent a, the effect of the scratch resistant agent a on the scratch resistance after storage at room temperature for 24 hours is significantly superior to the effect of the separate addition of each component of the scratch resistant agent a, the addition of the scratch resistant agent a results in substantially no loss of the scratch resistance of the material in terms of the retention of the scratch resistance after storage at room temperature, 100 ℃, 150 ℃ for 500 hours, while the addition of each component of the scratch resistant agent a results in a significant deterioration in the scratch resistance after storage at room temperature or at high temperature, and the deterioration of the scratch resistance is not satisfactory as required for normal automobile trims. And the addition of the scratch resistant agent A has no influence on other comprehensive properties of the material.
From the above example 1 and comparative example 8, it is apparent that the scratch resistance effect of the scratch resistance agent a of the present invention after being added and the proportion of the scratch resistance agent B adjusted is significantly better than that of the scratch resistance agent B after being adjusted after being stored for 24 hours at normal temperature, and the addition of the scratch resistance agent a makes the scratch resistance of the material substantially lossless in terms of the retention rate of the scratch resistance after being stored for 500 hours at normal temperature, 100 ℃ and 150 ℃, while the attenuation of the scratch resistance agent B is very significant after being stored at normal temperature and high temperature, and the normal requirements of automobile decorative parts cannot be satisfied. And the addition of the scratch resistant agent A has no influence on other comprehensive properties of the material.
From the above example 1 and comparative example 9, it is apparent that the scratch resistance effect of the scratch resistance agent a of the present invention, after being stored at room temperature for 24 hours, is significantly superior to that of the silicone type scratch resistance agent B without grafting, and that the scratch resistance property of the material is not substantially lost by the addition of the scratch resistance agent a in terms of the retention of the scratch resistance property after being stored at room temperature, 100 ℃, 150 ℃ for 500 hours, whereas the scratch resistance property is significantly attenuated by the use of the silicone type scratch resistance agent B without grafting, and the normal automobile trim requirements cannot be satisfied. And the addition of the scratch resistant agent A has no influence on other comprehensive properties of the material.
From the above example 1 and comparative example 10, comparative example 11 and comparative example 12, it is apparent that the addition of the scratch resistant agent a of the present invention and the scratch resistant agent C prepared using the silicone type scratch resistant agent B having no graft ratio and the high density polyethylene and the linear low density polyethylene has a significantly better scratch resistant effect than the scratch resistant agent C after being stored at normal temperature for 24 hours, and the addition of the scratch resistant agent a makes the scratch resistant property of the material substantially lossless in terms of the retention of the scratch resistant property after being stored at normal temperature, 100 ℃, 150 ℃ for 500 hours, whereas the use of the scratch resistant agent C has a significantly reduced scratch resistant property after being stored at normal temperature or high temperature, and fails to satisfy the normal automobile decorative part requirements. And the addition of the scratch resistant agent A has no influence on other comprehensive properties of the material.
Example 4
The only difference from example 1 is that the scratch-resistant agents used were: the high-density polyethylene, the linear low-density polyethylene and the silicone scratch-resistant agent A are mixed according to the mass ratio of 1.5:2.5:1, and are extruded and granulated by a double-screw extruder, and the extrusion and granulation process is the same as that of example 1.
Comparative example 13
Compared with the existing CN109749249A, the polypropylene composite material has the scratch resistance equivalent to or even better than that of CN109749249A under the condition that the scratch resistance synergist fatty acid ester is omitted, and has better scratch resistance under the high-temperature condition.
Claims (7)
1. The polypropylene composite material is characterized by comprising the following raw material components in percentage by weight:
40% -75% of polypropylene;
5% -10% of toughened elastomer;
10-30% of talcum powder;
5 to 10 percent of scratch resistant agent;
1% -1.5% of black seeds;
0.2 to 0.4 percent of antioxidant;
0.2 to 0.4 percent of weather resistant agent;
the scratch resistant agent is prepared by taking high-density polyethylene, linear low-density polyethylene and silicone scratch resistant agent as raw materials and extruding and granulating; wherein the silicone scratch resistant agent is silicone grafted polypropylene scratch resistant agent, wherein the mass grafting rate of silicone is 30-70%; the mass ratio of the high-density polyethylene to the linear low-density polyethylene to the silicone scratch-resistant agent is 1.5-2.5:1.5-2.5: 1.
2. The composite material of claim 1, wherein the polypropylene is a co-polypropylene; the toughening elastomer is one or more of polybutadiene rubber, ethylene-butylene copolymer, ethylene-octene copolymer and ethylene-propylene-diene rubber; the particle size of the talcum powder is 1-50 mu m, and the weight percentage content of the silicon dioxide is 60-90%; the black seeds are carbon black with the particle size of 10-1000 nm.
3. The composite material according to claim 1, wherein the antioxidant is one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the weather resisting agent is one or more of hindered amine, benzotriazole, benzophenone and triazine benzylidene malonate light stabilizers.
4. The composite material of claim 1, wherein the mass ratio of the high density polyethylene to the linear low density polyethylene to the silicone based scratch resistant agent is 2:2: 1.
5. A method of making a polypropylene composite comprising:
the polypropylene composite material is prepared by the following steps of adding the polypropylene, the toughened elastomer, the talcum powder, the scratch resistant agent, the black seed, the antioxidant and the weather resistant agent into a mixer according to the weight percentage of the polypropylene, uniformly mixing, extruding, cooling and granulating.
6. The preparation method according to claim 5, wherein the extrusion specific process parameters are as follows: adopting a double-screw extruder, wherein the temperature of the double-screw extruder is 175-: 1.
7. use of the polypropylene composite according to claim 1.
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