CN110835443A - Lightweight modified polypropylene material, preparation method thereof and application thereof in automobile stand column guard plate - Google Patents
Lightweight modified polypropylene material, preparation method thereof and application thereof in automobile stand column guard plate 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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Abstract
The invention discloses a lightweight modified polypropylene material, a preparation method thereof and application thereof in an automobile upright post guard plate, and belongs to the technical field of chemical materials. The composite material comprises the following raw material components in percentage by mass: 70-85% of polypropylene; 1.0-4.5% of inorganic filler; 11-26% of a toughening agent; 0.2-0.8% of antioxidant; 0-0.2% of a lubricant; 1.0-3.0% of an odor adsorbent; the polypropylene is high-crystallinity high-fluidity co-polypropylene, and the high-crystallinity high-fluidity co-polypropylene meets the technical indexes that the crystallinity is more than 60%, the bending modulus is 1500-1800 MPa, and the melt index is 50-100 g/min. The inorganic filler with relatively low content is adopted, and the excellent performance of the high-crystallization high-fluidity co-polypropylene is combined, so that the sufficient rigidity and toughness of the modified polypropylene material under the premise of relatively low material density are ensured.
Description
Technical Field
The invention relates to a modified polypropylene material, belongs to the technical field of chemical materials, and particularly relates to a lightweight modified polypropylene material, a preparation method thereof and application thereof in an automobile upright guard plate.
Background
The polypropylene material has the characteristics of good chemical resistance, high cost performance, convenience in recycling and the like, and is widely applied to automobile interior protection plates such as instrument plates, door protection plates, upright post protection plates and the like. Due to different regulatory performance requirements, different interior trim panels have different performance requirements on polypropylene materials, which requires modification such as reinforcement and toughening of the polypropylene materials. The current modification method comprises compounding an elastomer and an inorganic filler to obtain a PP composite material. The inorganic filler comprises calcium carbonate, talcum powder, kaolin and the like, and the addition of the inorganic filler can effectively improve the rigidity of the PP material and reduce the shrinkage rate and the corrosion resistance of the PP material. The elastomer mainly comprises ethylene propylene diene monomer, ethylene-octene copolymer and the like, and the addition of the elastomer can effectively improve the toughness and low-temperature impact property of the PP material.
For example, the Chinese patent application (application publication No. CN104744812A, application publication date 2015-07-01) discloses an ultra-low temperature high toughness modified polypropylene and a preparation method thereof, wherein 5-30 parts by mass of inorganic rigid particles as the rigidity of a reinforcing material and 5-30 parts by mass of amorphous poly-a-olefin are added into polypropylene to improve the low temperature toughness of the material, and the density of the obtained modified material is 1.031g/cm3、1.035g/cm3、1.033g/cm3、1.029g/cm3、1.036g/cm3、0.94g/cm3(ii) a The notched impact strength at room temperature was 15.47kJ/m3、29.04kJ/m3、39.65kJ/m3、29.51kJ/m2、30.33kJ/m2、31.53kJ/m2(ii) a A notched impact strength of 7.72kJ/m at-50 DEG C2、11.43kJ/m2、14.86kJ/m2、12.17kJ/m2、12.94kJ/m2、10.22kJ/m2(ii) a The bending strength is 40.56MPa, 30.23MPa, 24.74MPa, 29.67MPa, 28.75MPa and 18.74 MPa; flexural modulus 2113.18MPa, 1794.59MPa, 1471.43MPa, 1752.8MPa, 1678.89MPa, 1226.16 MPa;
the Chinese invention patent application (application publication No. CN103665570A, application publication date: 2014-03-26) discloses an ultralow temperature toughness polypropylene composition and a preparation method thereof, wherein 5-30% of filling reinforcing agent is added into polypropylene to serve as rigidity of a reinforcing material and 15-30% of toughening agent to improve low temperature toughness of the material, wherein the filling reinforcing agent is talcum powder master batch taking POE as a carrier; the modified materials obtained have a density of 0.857g/cm3、0.864g/cm3、0.87g/cm3、0.862g/cm3、0.86g/cm3(ii) a The notch impact strength at room temperature is 57.1kJ/m2、58.7kJ/m2、55.3kJ/m2、56.8kJ/m2、60kJ/m2(ii) a A notched impact strength of 16.4kJ/m at-40 DEG C2、19.4kJ/m2、17.4kJ/m2、18.7kJ/m2、17.8kJ/m2(ii) a The flexural modulus was 1062MPa, 1488MPa, 1841MPa, 1583MPa, 1925 MPa.
Researches show that although the addition of the filling reinforcing agent can improve the rigidity of the material, the addition of the filling reinforcing agent can bring about the increase of the density of the material along with the increase of the content of the filling reinforcing agent, which is not beneficial to the light weight of the whole automobile, and in order to reduce the weight of the automobile body, Chinese patent application (application publication No. 106188845A, application publication No. 2016-12-07) discloses a light weight automobile upright guard plate and a preparation method thereof, wherein the upright guard plate is mainly made of two parts, one part is a main composite material, and the other part is a fabric wrapped on the surface of the main composite material, wherein the main composite material comprises polypropylene, mineral powder, branched polypropylene, a nucleating agent, an antioxidant, a lubricant and a scratch-resistant auxiliary agent, the crystallinity of which is more than or equal to 70 percent and the melt index of which isAnd the fabric is made of any one of glass fiber, carbon fiber, fibrilia and synthetic fiber. This application combines together interior decoration technique and polymer micropore foaming technique, can utilize the fabric reinforcement effect even under the weight reduction exceeds 18% circumstances at the car stand backplate, can also keep material high mechanical strength, realizes that low density, high strength performance are balanced with the application to finally realize car stand backplate lightweight. Meanwhile, the functional master batch realizes the pre-dispersion of the foaming agent and the foaming auxiliary agent in the resin, thereby being beneficial to improving the uniformity of foam holes in the upright post guard plate, reducing the dust of a factory, improving the production efficiency and reducing the production and manufacturing cost. The density of the resulting product is exemplified in the examples as 0.926g/cm3、0.910g/cm3、0.915g/cm3、0.938g/cm3(ii) a Tensile strength of 38.6MPa, 63.2MPa, 34.7MPa, 65.3MPa, flexural modulus of 3350MPa, 4720MPa, 2710MPa, 3950MPa, and notched Izod impact strength of 24.6kJ/m at room temperature2、16.3kJ/m2、17.7kJ/m2、26.8kJ/m2(ii) a The heat distortion temperature is 113 ℃, 125 ℃, 110 ℃ and 120 ℃.
The upright post guard plate needs to meet the requirement of low temperature, such as the requirement of gas curtain blasting at the extreme temperature of-35 ℃, so the upright post guard plate needs to have excellent low-temperature toughness in advance under the condition of ensuring the sufficient rigidity of parts, the rigidity and the low-temperature toughness are represented by two technical indexes which are usually opposite in product performance, and how to ensure that the modified polypropylene material has excellent low-temperature toughness on the basis of better preparing sufficient rigidity is the technical problem which needs to be solved at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lightweight modified polypropylene material, a preparation method thereof and application thereof in an automobile upright guard plate. Meanwhile, the modified polypropylene material has excellent low-temperature performance, and the unnotched impact strength at-30 ℃ is more than or equal to 80kJ/m2(ii) a Notched impact strength at-50 DEG CThe degree is more than or equal to 20kJ/m2(ii) a The column guard board made of the material can be blasted by an air curtain in a low-temperature box at-35 ℃, and the column guard board is intact and has no splash after the air curtain blasting.
In order to achieve the aim, the invention discloses a light-weight modified polypropylene material which comprises the following raw material components in percentage by mass:
1.0-3.0% of an odor adsorbent; the polypropylene is high-crystallinity high-fluidity co-polypropylene, and the high-crystallinity high-fluidity co-polypropylene meets the technical indexes that the crystallinity is more than 60%, the bending modulus is 1500-1800 MPa, and the melt index is 50-100 g/min.
Preferably, the high-crystallinity and high-fluidity polypropylene meets the technical indexes of 72-88% of crystallinity, 1550-1800 MPa of bending modulus and 55-90 g/min of melt index.
The high-crystallinity and high-fluidity co-polypropylene disclosed by the invention has excellent processing performance, and can ensure the rigidity and high-temperature deformation resistance of the material.
Further, the particle size of the inorganic filler is greater than 3000 mesh. Although the inorganic filler is filled in the gaps of the polypropylene and synergistically plays a role in improving the rigidity of the product together with the polypropylene, the increase of the content of the inorganic filler inevitably brings about an increase in the density or quality of the product, which is not favorable for the light weight requirement of the product. According to the invention, the inorganic filler with high mesh number and relatively low content is used for uniformly filling the high-crystallization high-fluidity polypropylene, so that the product has relatively high rigidity and low density, and the adverse effect of adding a large amount of the toughening agent on the rigidity of the product is compensated.
Further, the inorganic filler comprises at least one of talcum powder, crystal whisker, wollastonite, mica powder, calcium carbonate or kaolin, and the granularity of the talcum powder is 3000-5000 meshes.
Further, the toughening agent is more than one of ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-propylene-diene monomer or styrene-butadiene-styrene triblock copolymer.
Preferably, the toughening agent is at least one of an ethylene-octene copolymer or a styrene-butadiene-styrene triblock copolymer.
Preferably, the ethylene-octene copolymer has an octene content of 25% by mass and a melt index of 5g/10 min.
Preferably, the styrene-butadiene-styrene triblock copolymer has a styrene content of 30-35%.
Further, the antioxidant is any one or a mixture of more of phenols, amines, phosphites, semi-hindered phenols, complexes of acryloyl functional groups and thioesters, or calixarene.
Preferably, the antioxidant is sonox 1010, sonox 168, THANOX DSTDP, antioxidant-412S, antioxidant Y-001 or antioxidant Y-002, etc
Further, the lubricant is one or a mixture of more of fatty acid esters, fatty acid amides or fatty acid alcohols.
Preferably, the lubricant is ethylene bis stearamide.
Further, the odor adsorbent is one or a mixture of activated carbon, silica gel, attapulgite, molecular sieve and diatomite.
Meanwhile, the invention also discloses a preparation method of the lightweight modified polypropylene material, which comprises the steps of uniformly mixing 70-85% of polypropylene, 1.0-4.5% of inorganic filler, 11-26% of toughening agent, 0.2-0.8% of antioxidant, 0-0.2% of lubricant and 1.0-3.0% of odor adsorbent by mass percent, and obtaining the composite material particles through melt extrusion, bracing, water cooling and granulation.
Further, the melt extrusion process is completed in a double-screw extruder, the vacuum degree is controlled to be less than or equal to-0.08 bar, and the extrusion temperature is 190-220 ℃. The extrusion temperature is 120 ℃ in the first zone, 190 ℃ in the second zone, 200 ℃ in the third zone, 220 ℃ in the fourth zone, 230 ℃ in the fifth zone, 230 ℃ in the sixth zone, 230 ℃ in the seventh zone and 210 ℃ in the eighth zone.
Further, the screw combination in the double-screw extruder is a high-shear screw combination and comprises a disc thread with a hole. Dense pores are arranged between the discs, so that the convection blending shearing effect is realized, and the full dispersion of the inorganic filler in the resin matrix is enhanced.
Further, the rotation speed of the screw is 300-800 rpm, and the total feeding amount is 100-800 kg/h.
Further, the polypropylene is high-crystallinity high-fluidity co-polypropylene, and the high-crystallinity high-fluidity co-polypropylene meets the technical indexes that the crystallinity is more than 60%, the bending modulus is 1500-1800 MPa, and the melt index is 50-100 g/min.
In order to better realize the technical purpose of the invention, the invention also discloses application of the lightweight modified polypropylene material in preparing an automobile upright guard plate. The method comprises the steps of detecting the blasting of a side air curtain of the whole vehicle upright post guard plate at-35 ℃, wherein the test result shows that the air curtain is completely unfolded, the appearance is good and the air curtain is not damaged; the upright post guard plates are all intact and have no damage.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the invention discloses a modified polypropylene material, which can realize the light weight of a whole vehicle upright post guard plate and is beneficial to reducing the vehicle manufacturing cost;
2. the modified polypropylene material disclosed by the invention can better ensure the rigidity and toughness of the whole vehicle upright post guard plate, wherein the unnotched impact strength at-30 ℃ is more than or equal to 80kJ/m2(ii) a The unnotched impact strength at minus 50 ℃ is more than or equal to 20kJ/m2(ii) a And the air curtain can be completely unfolded when the side air curtain is exploded at the low temperature of 35 ℃ below zero, the appearance is good and is not damaged, and the safety of a driver and passengers can be better protected.
Detailed Description
The invention discloses a preparation method of a lightweight modified polypropylene material, which comprises the steps of uniformly mixing 70-85% of polypropylene, 1.0-4.5% of inorganic filler, 11-26% of toughening agent, 0.2-0.8% of antioxidant, 0-0.2% of lubricant and 1.0-3.0% of odor adsorbent by mass percent, and performing melt extrusion, bracing, water cooling and granulation to obtain composite particles. The melt extrusion process is completed in a double-screw extruder, the vacuum degree is controlled to be less than or equal to-0.08 bar, the extrusion temperature is 190-220 ℃, the screw rotating speed is 300-800 rpm, and the total feeding amount is 100-800 kg/h.
The polypropylene is high-crystallinity high-fluidity co-polypropylene, and the high-crystallinity high-fluidity co-polypropylene meets the technical indexes that the crystallinity is more than 60%, the bending modulus is 1500-1800 MPa, and the melt index is 50-100 g/min.
The properties of the modified polypropylene material are researched by controlling different contents of the raw material components, and the properties are as follows:
TABLE 1 composition of the raw materials in different proportions
Wherein, in the above Table 1, the crystallinity of the general copolymerized polypropylene is 56%, the flexural modulus is 1350MPa, and the melt index is 50 g/min. The high-crystallinity and high-fluidity copolymerized polypropylene meets the requirements of 75 percent of crystallinity, 1700MPa of flexural modulus and 55g/min of melt index
The toughening agent is an ethylene-octene copolymer, the content of octene is 25%, and the melt index is 5g/10 min; the inorganic filler 1 is 5000 meshes of talcum powder, and the inorganic filler 2 is 2500 meshes of talcum powder; the antioxidant is any mixture ratio of sonox 1010 and sonox 168, the lubricant is ethylene bis stearamide, and the odor adsorbent is diatomite.
And (3) detecting the material performance: the lightweight modified polypropylene material suitable for the automobile interior upright guard plate prepared in the embodiments 1-3 and the polypropylene material prepared in the comparative examples are dried in an oven at the temperature of 80-90 ℃ for 2 hours, and then the dried particle material is injected on an injection molding machine to form a standard test sample strip. The density is detected according to the GB/T1033.1 standard; the bending strength and the bending modulus are measured according to the GB/T9341 standard, and the bending speed is 2 mm/min. The impact strength of the cantilever beam is detected according to the GB/T1843 standard, the size of a sample strip is 80mm multiplied by 10mm multiplied by 4mm, the depth of an A-type notch is 2 mm; the shrinkage was measured according to GB/T15585. Specific test results are shown in table 2;
TABLE 2 list of properties of examples and comparative examples
The lightweight modified polypropylene material suitable for the automobile interior upright post protection plate prepared in the embodiments 1-4 and the comparative examples 1-3 and the polypropylene material prepared in the comparative examples are dried in an oven at 80-90 ℃ for 2 hours, and then the dried particle material is injected on an injection molding machine to form the automobile left front upright post upper protection plate.
And (3) low-temperature side gas curtain blasting detection: keeping the temperature in an environment cabin at the temperature of minus 35 ℃ for 5 hours, and then carrying out air bag blasting.
Specific test results are shown in table 3;
table 3 stand bar panel air bag burst test results of examples and comparative examples
As can be seen from the above embodiments, the invention selects the high-crystallization high-fluidity polypropylene copolymer component polypropylene to be matched with a small amount of inorganic filler and relatively more toughening agent, and the density of the prepared modified material is 0.90-0.96 g/cm3Compared with PP + EPDM-TD15 and PP + EPDM-TD20 which are commonly used for upright guard plates, the density is relatively reduced by 5-10%. The unnotched impact strength at minus 30 ℃ is more than or equal to 80kJ/m2(ii) a The unnotched impact strength at minus 50 ℃ is more than or equal to 20kJ/m2(ii) a The column guard board made of the material can be blasted by an air curtain in a low-temperature box at-35 ℃, and the column guard board is intact and has no splash after the air curtain blasting.
In addition, the invention also researches the influence of polypropylene with related technical indexes on the performance of the modified material, and as a result, the comprehensive performance of the modified material is the best when the high-crystallinity and high-fluidity polypropylene meets the technical indexes of 72-88% of crystallinity, 1550-1800 MPa of flexural modulus and 55-90 g/min of melt index.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (10)
1. A light-weight modified polypropylene material comprises the following raw material components in percentage by mass:
the polypropylene is high-crystallinity high-fluidity co-polypropylene, and the high-crystallinity high-fluidity co-polypropylene meets the technical indexes that the crystallinity is more than 60%, the bending modulus is 1500-1800 MPa, and the melt index is 50-100 g/min.
2. The light-weight modified polypropylene material according to claim 1, wherein: the high-crystallinity and high-fluidity co-polypropylene meets the technical indexes that the crystallinity is 72-88%, the bending modulus is 1550-1800 MPa, and the melt index is 55-90 g/min.
3. The light-weight modified polypropylene material according to claim 1, wherein: the particle size of the inorganic filler is larger than 3000 meshes.
4. The light-weight modified polypropylene material according to claim 3, wherein: the inorganic filler comprises at least one of talcum powder, crystal whiskers, wollastonite, mica powder, calcium carbonate or kaolin, and the granularity of the talcum powder is 3000-5000 meshes.
5. The light-weight modified polypropylene material according to any one of claims 1 to 4, wherein: the toughening agent is more than one of ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-propylene-diene monomer or styrene-butadiene-styrene triblock copolymer.
6. The light-weight modified polypropylene material according to any one of claims 1 to 4, wherein: the modified polypropylene material comprises the following raw material components in percentage by mass:
7. a preparation method of a lightweight modified polypropylene material comprises the steps of uniformly mixing 70-85% by mass of polypropylene, 1.0-4.5% by mass of inorganic filler, 11-26% by mass of toughening agent, 0.2-0.8% by mass of antioxidant, 0-0.2% by mass of lubricant and 1.0-3.0% by mass of odor adsorbent, and carrying out melt extrusion, bracing, water cooling and granulation to obtain composite particles.
8. The method for preparing a lightweight modified polypropylene material according to claim 7, wherein: the melt extrusion process is completed in a double-screw extruder, the vacuum degree is controlled to be less than or equal to-0.08 bar, the extrusion temperature is 190-220 ℃, and the specific extrusion temperature is 120 ℃ in a first zone, 190 ℃ in a second zone, 200 ℃ in a third zone, 220 ℃ in a fourth zone, 230 ℃ in a fifth zone, 230 ℃ in a sixth zone, 230 ℃ in a seventh zone and 210 ℃ in an eighth zone.
9. The method for preparing a lightweight modified polypropylene material according to claim 8, wherein: the screw combination in the double-screw extruder is a high-shear screw combination and comprises a disc thread with a hole.
10. Use of the lightweight modified polypropylene material of claim 1 in the preparation of an automotive pillar panel.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114408023A (en) * | 2022-01-15 | 2022-04-29 | 重庆长安汽车股份有限公司 | A post backplate and with ceiling cooperation structure thereof |
| CN114989528A (en) * | 2022-06-27 | 2022-09-02 | 重庆长安汽车股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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| CN108219277A (en) * | 2018-01-18 | 2018-06-29 | 金发科技股份有限公司 | A kind of fascia interior trim PP composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114408023A (en) * | 2022-01-15 | 2022-04-29 | 重庆长安汽车股份有限公司 | A post backplate and with ceiling cooperation structure thereof |
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