CN114196116A - High-weather-resistance heat-resistant polypropylene material and preparation method thereof - Google Patents
High-weather-resistance heat-resistant polypropylene material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a high-weather-resistance heat-resistant polypropylene material and a preparation method thereof, belonging to the technical field of polypropylene materials. The high-weather-resistance heat-resistant polypropylene material disclosed by the invention is high in color vividness and stability, high in weather resistance, heat resistance and heat-resistance retention property, and capable of meeting the use requirements of color system plastic parts of most outdoor vehicles (such as electric vehicles, bicycles and the like) due to the mechanical properties. The invention also discloses a preparation method of the high weather-resistant heat-resistant polypropylene material and application of the high weather-resistant heat-resistant polypropylene material in preparation of color system plastic parts of outdoor vehicles.
Description
Technical Field
The invention relates to the technical field of polypropylene materials, in particular to a high-weather-resistance polypropylene material and a preparation method thereof.
Background
The polypropylene is used as one of general plastics, has the advantages of wide source, low price and the like, has huge use amount in modern industry, is a semi-crystalline thermoplastic plastic, and has higher impact resistance, resistance to various organic solvents and acid-base corrosion and high stability. In recent years, with the development of fire heat of products such as electric vehicles and the like, high-chroma polypropylene materials are hot-dipped, but as outdoor products, whether the materials have good weather resistance is the most critical. In addition, the temperature of the polypropylene material during processing can reach 240 ℃, so the heat resistance of the material also has higher requirement; the single polypropylene material part of the product of the electric vehicle has larger size, and in order to ensure the stability of the part and longer pressure holding time, the prepared polypropylene material also needs to have better heat-resistant retention performance, otherwise, the product has insufficient weather resistance or heat resistance in the processing or application process, and the appearance color is easy to be unstable or changed after the product is processed or used for a period of time.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a high-weather-resistance and heat-resistance polypropylene material which has high color vividness and stability, high weather resistance, heat resistance and heat retention resistance, and mechanical properties capable of meeting the use requirements of color-series plastic parts of most outdoor vehicles (such as electric vehicles, bicycles and the like).
In order to achieve the purpose, the invention adopts the technical scheme that:
a high weather-resistant heat-resistant polypropylene material comprises the following components in parts by weight:
61-75 parts of polypropylene resin, 20-30 parts of talcum powder, 5-7 parts of thermoplastic elastomer POE, 0.25-0.5 part of toner and 0.2-0.7 part of processing aid;
the toner is a mixture of DPP red (bis (p-chlorophenyl) -1, 4-diketopyrrolopyrrole) and cerium sulfide; the weight portion of the DPP red is 0.05-0.12 part, and the weight portion of the cerium sulfide is 0.2-0.4 part.
In the existing polypropylene materials, in order to achieve high weather resistance or high heat resistance of products, various weather-resistant agents or heat-resistant auxiliaries are often required to be added into the products, but the performance improvement effects of the auxiliaries are often single and not high in improvement degree, if various obvious resistance improvement effects are to be achieved, the types and the contents of the added auxiliaries are inevitably large, and the cost and the environmental protection performance of the products (the added auxiliaries are mostly organic substances) need to be measured again; on the other hand, since a toner needs to be added to the product for coloring, if an auxiliary agent is added excessively, the compatibility or uniformity of the toner of the product may be degraded, and it is difficult to maintain a stable color system.
Based on the consideration, the inventor carries out a plurality of experimental research and screening on the premise of ensuring the basic mechanical application performance of the product, and uses DPP red and cerium sulfide as toner, wherein the DPP red serving as an organic toner not only has certain temperature resistance essentially, but also can effectively adjust the integral crystallinity of a polypropylene material, so that the product does not have obvious transmittance change in the processing and using processes; on the other hand, the inorganic dye cerium sulfide is adopted as a matched toner to be uniformly dispersed in the polypropylene resin, the intrinsic color is bright, the integral vividness (color system) of the material can be effectively adjusted, and under the condition of only adding a small amount of the inorganic dye cerium sulfide, the obtained red polypropylene material product can realize ideal weather resistance, heat resistance and heat-resistant retention performance without adding an extra resistant reagent; the obtained product has high color vividness.
Preferably, the average particle size of the DPP red is 0.8-1.5 μm, and the average particle size of the cerium sulfide is 1.5-2.5 μm.
Due to the mutual synergy of the two toners, the particle size of the two toners also has a great influence on the comprehensive performance of the product. Experiments show that the product has the best weather-resistant, heat-resistant and heat-resistant retention performance only when the average particle size of the DPP red is 0.8-1.5 mu m and the average particle size of the cerium sulfide is 1.5-2.5 mu m.
Preferably, in the toner, the weight parts of the DPP red and the cerium sulfide are respectively 0.1-0.12 and 0.25-0.35.
DPP red in the toner of the high-weather-resistant heat-resistant polypropylene material is used as an auxiliary color pigment, excellent polypropylene resin crystallinity adjustment can be realized by only adding a small amount of DPP red, and the influence of more DPP red on the performance and color vividness of the product is small; if the addition content of cerium sulfide as a main coloring material is too small, the vividness of the product may be insufficient; with the increase of the addition content, the heat resistance, weather resistance and heat retention resistance of the product are improved, and after the addition reaches a certain content, the comprehensive properties of the product tend to be stable, and the cost of raw materials can only be increased by continuously adding the product.
Preferably, the polypropylene resin is at least one of homo-polypropylene and co-polypropylene;
preferably, the polypropylene resin has a melt index of 15-25 g/10min at 230 ℃ under 2.16kg according to ASTM D1238-2010;
preferably, the mesh number of the talcum powder is 1000-1500 meshes;
preferably, the thermoplastic elastomer POE is at least one of ethylene-butene copolymer and ethylene-octene copolymer.
Preferably, the processing aid is at least one of an antioxidant and a light stabilizer;
more preferably, the antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant;
more preferably, the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is (0.8-1.2): (0.8 to 1.2).
More preferably, the light stabilizer is a hindered amine light stabilizer.
The invention also aims to provide a preparation method of the high weather-resistant and heat-resistant polypropylene material, which comprises the following steps:
uniformly mixing polypropylene resin, talcum powder, thermoplastic elastomer POE, processing aid and toner according to a ratio, adding the mixture into a double-screw extruder for melt blending, extruding and granulating to obtain the high-weather-resistant heat-resistant polypropylene material.
The preparation method of the high weather-resistant heat-resistant polypropylene material has simple operation steps and can realize industrial large-scale production.
Preferably, the temperature during melt blending is 190-220 ℃.
Preferably, the rotating speed of the main machine of the double-screw extruder is 200-300 rpm, the diameter of the screw is 30-40 mm, and the length-diameter ratio of the screw is (45-50): 1.
The invention further aims to provide application of the high weather-resistant and heat-resistant polypropylene material in preparing color system plastic parts of outdoor vehicles.
Compared with the existing product, the high-weather-resistance heat-resistant polypropylene material has better weather-resistance, heat-resistance and heat-resistance retention performances, and is more environment-friendly because no additional resistance reagent is added; the obtained product has bright red color and high stability, and is particularly suitable for being applied to preparing color system plastic parts of outdoor vehicles, which have outdoor application environments, high processing and using temperatures and higher requirements on color system colors.
The invention has the beneficial effects that the high-weather-resistance heat-resistant polypropylene material provided by the invention has high color brilliance and stability, and simultaneously has higher weather resistance, heat resistance and heat-resistance retention, and the mechanical property of the polypropylene material can meet the use requirements of color system plastic parts of most outdoor vehicles (such as electric vehicles, bicycles and the like); the invention also provides a preparation method of the high weather-resistant heat-resistant polypropylene material and application of the high weather-resistant heat-resistant polypropylene material in preparation of color system plastic parts of outdoor vehicles.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments involved in the practice of the present invention are, unless otherwise specified, common reagents and instruments.
Examples 1 to 17
An embodiment of the high weather-resistant and heat-resistant polypropylene material and the preparation method thereof according to the present invention comprises the following components shown in tables 1 and 2.
The preparation method of the high weather-resistant heat-resistant polypropylene material comprises the following steps:
uniformly mixing polypropylene resin, talcum powder, thermoplastic elastomer POE, processing aid and toner according to a ratio, adding the mixture into a main machine cylinder in a double-screw extruder, and carrying out melt blending, extrusion and granulation to obtain the high-weather-resistant heat-resistant polypropylene material.
The temperature conditions of the main barrel of the double-screw extruder during melt extrusion are as follows: the temperature of a first area is 190 ℃, the temperature of a second area is 195 ℃, the temperature of a third area is 210 ℃, the temperature of a fourth area is 215 ℃, and the temperature of a fifth area is 215 ℃;
the rotating speed of the main machine of the double-screw extruder is 240rpm, the diameter of the screw is 35mm, and the length-diameter ratio of the screw is 48: 1.
The polypropylene resin 1 is homopolymerized polypropylene resin, a PP Z30S model product produced by Dalian petrochemical company Limited company has a melt index of 20g/10min at 230 ℃ under the load of 2.16 kg;
the polypropylene resin 2 is copolymerized polypropylene resin, and the melt index of a PPEP548R product produced by China petrochemical company Limited is 20g/10min at 230 ℃ under the load of 2.16 kg;
the polypropylene resin 3 is homopolymerized polypropylene resin, namely a PP HP500N product produced by Daqing petrochemical industry, and the melt index is 15g/10min at 230 ℃ under the load of 2.16 kg;
the polypropylene resin 4 was a homopolypropylene resin, a product of PP HP552R manufactured by Dahlian, Korea, having a melt index of 25g/10min at 230 ℃ under a load of 2.16 kg;
the polypropylene resin 5 is homopolymerized polypropylene resin, a PP 1100N product produced by Sauter APC, and the melt index is 12g/10min at 230 ℃ under the load of 2.16 kg;
the polypropylene resin 6 is homopolymerized polypropylene resin, named as a PP N-Z30S product produced by petrochemical production, and has a melt index of 28g/10min at 230 ℃ under the load of 2.16 kg;
the thermoplastic elastomer POE1 is a copolymer of butylene and ethylene, POEENGAGE7467 product produced by Dow company;
the thermoplastic elastomer POE2 is a copolymer of butene and octene, product 8480 produced by Dow company;
the talcum powder is 1250-mesh talcum powder sold in the market; the antioxidant is a mixture obtained by mixing a commercially available hindered phenol antioxidant and a commercially available phosphite ester antioxidant according to a mass ratio of 1: 1;
the light stabilizer is a commercially available hindered amine light stabilizer;
DPP red 1 is commercially available DPP red, and the average particle size of the DPP red after raw material particle screening is 1 mu m;
DPP red 2 is commercially available DPP red, and the average particle size of the DPP red after raw material particle screening is 0.5 mu m;
DPP red 3 is commercially available DPP red, and the average particle size of the DPP red after raw material particle screening is 2 microns;
the cerium sulfide 1 is commercially available cerium sulfide, and the average particle size of the screened raw material particles is 2 microns;
the cerium sulfide 2 is commercially available cerium sulfide, and the average particle size of the screened raw material particles is 1 mu m;
the cerium sulfide 3 is commercially available cerium sulfide, and the average particle size after the raw material particles are screened is 3 μm.
Comparative examples 1 to 3
The composition of the flame retardant polypropylene material of this comparative example is shown in table 2. The preparation of the comparative products is carried out in the same manner as in the examples.
The raw materials used in each proportion and the raw materials used in each example are, except for the specific description, the same commercial or reprocessed brands of products.
Comparative example 4
The comparative example differs from example 8 only in that cerium sulfide 1 was replaced with iron red model R206 manufactured by seiko technologies ltd.
Comparative example 5
This comparative example differs from example 8 only in that DPP red 1 was replaced with a commercially available azo red.
TABLE 1
TABLE 2
Effect example 1
The products obtained in the examples and comparative examples were subjected to basic mechanical properties (tensile strength, notched izod impact strength), heat resistance, heat retention resistance, weather resistance and color vividness tests:
(1) and (3) testing tensile strength: measuring by adopting GB/T228-2002 standard, wherein the stretching speed is 50 mm/min;
(2) testing the notch impact strength of the cantilever beam: the impact strength of a cantilever notch of the material is tested by adopting ISO180-2000, and the impact pendulum capacity of an A-type notch is 5.5J;
(3) heat resistance, heat retention resistance test: after drying each product in a forced air oven at 80 ℃ for 4h, smooth plaques with a surface free of skin marks were injection molded with an injection molding machine under the following four injection molding conditions to a size of 83MM 54MM 2 MM.
Injection molding conditions 1: staying at 260 ℃ for 30s for injection molding;
injection molding conditions 2: staying at 200 ℃ for 100s for injection molding;
injection molding conditions 3: injection molding at 240 ℃ for 26 s;
injection molding conditions 4: staying at 240 ℃ for 100s for injection molding;
after the experiment is finished, measuring test data of the color plate D65 under different temperatures by using an X-rite7000A color difference instrument, wherein the color difference is expressed by delta E, and the larger the delta E is, the larger the color difference is;
(4) and (3) weather resistance test: after drying the products in a blast oven at 120 ℃ for 4h, injection molding is carried out by an injection molding machine to obtain smooth color plates with 83MM 54MM 2MM size and no skin marks on the surfaces, the injection molding conditions are 240 ℃, and the injection molding period is 5 s. The test was carried out in a UVA-340 test box as specified in GB/T16422.3-2014 cycle 1: drying for 8h and condensing for 4h are 1 cycle, and 6 cycles are carried out for total 72 h. Measuring data of the color plate under a D65 light source by using an X-rite7000A color difference meter before and after the color plate is placed in a test box, comparing the color difference before and after the color plate is compared, and expressing the color difference by using delta E, wherein the larger the delta E is, the color difference is expressed;
(5) testing the vividness: after drying the products in a forced air oven at 80 ℃ for 4h, smooth plaques without skin striae were injection molded (dwell 30s) at 200 ℃ with an injection molding machine to a size of 83MM 54MM 2 MM. The value of A under a light source of D65 is measured by an X-rite7000A color difference meter, and the larger value of A represents the better vividness of the material.
The test results are shown in tables 3 and 4.
TABLE 3
TABLE 4
As can be seen from the table, the products obtained in the embodiments of the present invention have excellent heat resistance (Delta E < 1.5), heat retention resistance (Delta E < 2) and weather resistance (Delta E < 1), high brilliance and adjustable and maintained mechanical properties at a high level according to the addition ratio of the toughening agent and the talc powder. From examples 5 to 9, it is obvious that the toner proportioning in the high weather-resistant and heat-resistant polypropylene material has little influence on the overall mechanical properties of the product, and the influence of the addition amount change on the addition amounts of other components can be almost ignored due to the small addition amount of the toner; according to the embodiment, when the weight parts of the DPP red and the cerium sulfide are 0.1-0.12 and 0.25-0.35, the product has the best heat resistance, heat retention resistance and weather resistance improving effects, and when the contents of the two components are continuously added, the performance of the product cannot be further improved; from comparative examples 1 to 3, it is known that, if one of the two toners is absent or the added content is small, the obtained product is difficult to achieve the heat-resistant and weather-resistant performances described in the examples, and the vividness of the product is also affected; it is also difficult to achieve the desired effect by replacing the two kinds of toners according to the products of comparative examples 4 and 5. From examples 10 to 13, it is known that the particle sizes of DPP red and cerium sulfide also affect the improvement of heat resistance, heat retention resistance and weather resistance of the product, and when the particle size of DPP red or cerium sulfide is increased or decreased, the heat resistance and weather resistance of the obtained product may be decreased due to the reduction of toner dispersibility, the reduction of color stability adjustment capability and other factors.
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 (9)
1. The high weather-resistant heat-resistant polypropylene material is characterized by comprising the following components in parts by weight:
61-75 parts of polypropylene resin, 20-30 parts of talcum powder, 5-7 parts of thermoplastic elastomer POE, 0.25-0.5 part of toner and 0.2-0.7 part of processing aid;
the toner is a mixture of DPP red and cerium sulfide; the weight portion of the DPP red is 0.05-0.12 part, and the weight portion of the cerium sulfide is 0.2-0.4 part.
2. The highly weather-resistant and heat-resistant polypropylene material according to claim 1, wherein the DPP red has an average particle size of 0.8 to 1.5 μm, and the cerium sulfide has an average particle size of 1.5 to 2.5 μm.
3. The high weather-resistant and heat-resistant polypropylene material as claimed in claim 1, wherein the toner comprises DPP red 0.1-0.12 part by weight and cerium sulfide 0.25-0.35 part by weight.
4. The highly weather-resistant and heat-resistant polypropylene material according to claim 1, comprising at least one of the following (a) to (d):
(a) the polypropylene resin is at least one of homopolymerized polypropylene and copolymerized polypropylene;
(b) the mesh number of the talcum powder is 1000-1500 meshes;
(c) the melt index of the polypropylene resin is 15-25 g/10min at 230 ℃ under a load of 2.16kg according to ASTM D1238-2010;
(d) the thermoplastic elastomer POE is at least one of ethylene-butene copolymer and ethylene-octene copolymer.
5. The high weatherability and heat resistance polypropylene material according to claim 1, wherein the processing aid is at least one of an antioxidant and a light stabilizer.
6. The highly weather-resistant and heat-resistant polypropylene material according to claim 5, wherein the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; the light stabilizer is a hindered amine light stabilizer.
7. The method for preparing the high weather-resistant and heat-resistant polypropylene material as claimed in any one of claims 1 to 6, comprising the steps of:
uniformly mixing polypropylene resin, talcum powder, thermoplastic elastomer POE, processing aid and toner according to a ratio, adding the mixture into a double-screw extruder for melt blending, extruding and granulating to obtain the high-weather-resistant heat-resistant polypropylene material.
8. The preparation method of the high weather-resistant heat-resistant polypropylene material as claimed in claim 7, wherein the temperature during melt blending is 190-220 ℃, the rotation speed of a main machine of the twin-screw extruder is 200-300 rpm, the diameter of the screw is 30-40 mm, and the length-diameter ratio of the screw is (45-50): 1.
9. Use of the highly weather-resistant and heat-resistant polypropylene material as claimed in any one of claims 1 to 6 for preparing color-based plastic parts for outdoor vehicles.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024125252A1 (en) * | 2022-12-15 | 2024-06-20 | 金发科技股份有限公司 | High-performance color masterbatch and polypropylene composition prepared therefrom |
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| CN101717554A (en) * | 2009-12-16 | 2010-06-02 | 广东盛恒昌化学工业有限公司 | Plastic profiled bar decorative layer combination material with metal-like natural texture, preparation method and application thereof |
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