CN111040295A - Polypropylene composite material for low-shrinkage low-emission primer-free automobile parts and preparation method and application thereof - Google Patents
Polypropylene composite material for low-shrinkage low-emission primer-free automobile parts and preparation method and application thereof Download PDFInfo
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- CN111040295A CN111040295A CN201911316049.7A CN201911316049A CN111040295A CN 111040295 A CN111040295 A CN 111040295A CN 201911316049 A CN201911316049 A CN 201911316049A CN 111040295 A CN111040295 A CN 111040295A
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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
- C08L23/12—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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- 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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- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention belongs to the technical field of automobile materials, and particularly relates to a low-shrinkage low-emission primer-free polypropylene composite material for automobile parts, and a preparation method and application thereof. The polypropylene composite material specifically comprises the following components in percentage by mass: 60-80% of polypropylene resin, 1-20% of elastomer, 1-10% of porous filler, 1-20% of talcum powder, 0.1-1% of antioxidant, 0.1-1% of lubricant and 0.1-1% of light stabilizer. According to the invention, the molecular sieve and the porous ceramic filler are added at the specific position of the screw, and the filler can form uniformly distributed micropores on the surface of the base material to form physical adsorption points, wherein the molecular sieve adsorbs paint components with molecules with smaller volume, and the porous ceramic mainly adsorbs paint components with molecules with larger volume, so that the adhesive force of the polypropylene base material and the paint is greatly increased. And also reduces the odor and VOC levels of the polypropylene composite.
Description
Technical Field
The invention belongs to the technical field of automobile materials, and particularly relates to a low-shrinkage low-emission primer-free polypropylene composite material for automobile parts, and a preparation method and application thereof.
Background
The method has the advantages of low carbon, environmental protection, energy conservation and emission reduction, and is one of the important issues of the twelve-five planning. For automobile manufacturers, green and environment-friendly materials are considered from the design and development stage, so that the requirements of enterprise product upgrading and technical innovation are met, and the social responsibility of enterprises is reflected. Aiming at the trend of automobile materials towards light weight and environmental protection, material manufacturers actively push new solutions, and the sprayable material with plastic for replacing steel, low emission and no primer is just one of the representative materials for light weight and environmental protection.
The polypropylene composite material is widely applied to automobile parts because of the characteristics of low density, low price and the like. The exterior parts of automobiles usually need to be painted on the surface of the products to meet the requirements of beauty and high-grade weather resistance. At present, the mainstream polypropylene material spraying process is a three-spraying two-baking process, and primer spraying treatment is carried out before spraying of the finish paint and the varnish so as to increase the adhesive force of the finish paint and the polypropylene base material. The process has the problems of multiple links, complexity and long time consumption, not only causes serious factory environment pollution, but also causes high paint spraying price, and the paint adhesion is easy to reduce due to the imprecise treatment, and the product is unqualified in spraying. On the other hand, the size of the parts such as the fender and the tail gate in the automobile outer decoration needs to be matched with a plurality of peripheral parts, and the requirement on the size stability of the product is strict, so the parts are mainly made of metal materials at present, the weight of the product is large, and the design freedom degree is low. The requirements of automotive interiors for odor and Volatile Organic Compounds (VOC) are also increasing, so that the emission of interior materials must be well controlled.
Chinese patent publication CN103627262A discloses a primer-free bumper composite material capable of being directly sprayed and a preparation method thereof. Compared with the common talcum powder filling material, the supported nickel ion talcum powder can increase the adhesive force of a paint film, can be directly sprayed with finish paint, and simplifies the process of spraying the primer.
Chinese patent publication CN109181118A discloses a primer-free spray-coating automobile exterior material and a preparation method thereof, the invention mainly improves the adhesive force of a PP (polypropylene) base material and a paint film by adding a high-activity synergist and an interface promoter, can directly spray paint or finish paint, and has the characteristics of environmental protection, no pollution and low VOC.
However, the current researches mainly have the following defects that the process of ① loading metal ions on an inorganic filler is complex, the stability is poor, and ② high-activity substances have high activity and poor controllability of the production process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a polypropylene composite material for low-shrinkage low-emission primer-free automobile parts.
The invention also aims to provide a method for preparing the polypropylene composite material for the low-shrinkage low-emission primer-free automobile part.
The invention further aims to provide application of the polypropylene composite material for the low-shrinkage low-emission primer-free automobile parts in the field of automobiles.
The purpose of the invention is realized by the following scheme:
the polypropylene composite material for the low-shrinkage low-emission primer-free automobile part specifically comprises the following components in percentage by mass:
the polypropylene resin (PP) is at least one of homopolymerized polypropylene and ethylene-propylene block copolymerization polypropylene.
The elastomer is at least one of ethylene propylene rubber, ethylene-octene copolymer (POE), ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) and ethylene-vinyl acetate (EVA).
The porous filler is at least one of a molecular sieve, porous ceramic and glass beads; preferably a mixture of molecular sieves and porous ceramics.
The average grain diameter of the talcum powder is 1-20 μm.
The lubricant is one or the combination of two of stearate and silicone master batch.
The antioxidant is at least one of hindered phenol antioxidant, thioester antioxidant, phosphite antioxidant and ester antioxidant.
The light stabilizer is at least one of hindered amine light stabilizer, light shielding agent, ultraviolet absorbent and quenching agent.
The preparation method of the polypropylene composite material for the low-shrinkage low-emission primer-free automobile part specifically comprises the following preparation steps:
(1) weighing the raw materials according to the proportion;
(2) uniformly mixing polypropylene resin, elastomer and talcum powder, adding antioxidant, lubricant and light stabilizer, and continuously and uniformly mixing to obtain premix;
(3) adding the premix from the main feeding port of the double-screw extruder, adding the porous filler from the side feeding port of the double-screw extruder, and performing melt extrusion granulation to obtain the polypropylene composite material.
The first mixing uniformity and the second mixing uniformity in the step (2) are respectively and independently mixed for 5-10 minutes at 800-1500 rpm; preferably, the mixing is carried out at 55 to 65 ℃.
When the porous filler in the step (3) is a mixture, the mixing is preferably performed at 200-500 rpm for 5-10 minutes, and more preferably at 45-55 ℃.
The temperature of each section of the feeding section of the twin-screw extruder in the step (3) is set to be 190-205 ℃, 205-215 ℃, 215-225 ℃, 205-215 ℃, the head temperature is 215-225 ℃, and the screw rotation speed is 300-600 revolutions per minute. Preferably, the temperatures of the sections of the twin-screw extruder in the step (3) are set to 200 ℃, 210 ℃, 220 ℃, 210 ℃ and 220 ℃ of the head temperature.
And (3) arranging the side feeding port on a fifth section of a cylinder body of the double-screw extruder, wherein the side feeding frequency is 2-10 Hz.
The polypropylene composite material for the low-shrinkage low-emission primer-free automobile parts is applied to the field of automobiles.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the molecular sieve and the porous ceramic filler are added at the specific position of the screw, and the filler can form uniformly distributed micropores on the surface of the base material to form physical adsorption points, wherein the molecular sieve adsorbs paint components with molecules with smaller volume, and the porous ceramic mainly adsorbs paint components with molecules with larger volume, so that the adhesive force of the polypropylene base material and the paint is greatly increased.
(2) The porous ceramic filler has a porous structure inside, and plays a role similar to a steel bar skeleton in the polypropylene base material, so that the crystallization of the polypropylene material is hindered, the shrinkage rate and the linear expansion coefficient of the polypropylene composite material are greatly reduced, and the dimensional stability of the material is improved.
(3) The porous filler has a porous structure inside, so that micromolecular substances generated by thermal decomposition of the polypropylene composite material in the extrusion process can be adsorbed, and the odor and VOC level of the polypropylene composite material are reduced.
(4) The toughening system adopted by the invention is a compound system of three toughening agents, namely ethylene-octene copolymer, ethylene-octene copolymer grafted maleic anhydride and vinyl acetate, wherein the vinyl acetate has higher polarity, so that the adhesive force of the polypropylene composite material and polar paint is increased, and the ethylene-octene copolymer grafted maleic anhydride has amphipathy and exists as a compatilizer of the ethylene-octene copolymer toughening agent and the vinyl acetate toughening agent, so that the compatibility of each component of the polypropylene composite material is improved, and the performance of the material is more uniform and stable.
(5) According to the invention, the porous filler is added at the specific position of the screw, so that the damage degree of the screw shearing to the porous structure of the porous filler is reduced, and the number of physical adsorption points is increased.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The reagents used in the examples are commercially available without specific reference.
The polypropylene resin is Zhonghai Shell PP 548R; POE is Dow POE 8200; POE-g-MAH is 493D of DuPont; EVA is 250 of DuPont, and the molecular sieve is Dalianhaixin, Y-type molecular sieve; the porous ceramic is alumina porous ceramic which is a research institute of Jiaao ceramic in Yixing city.
The polypropylene composite material in the examples is prepared by the following steps:
1. weighing the raw materials according to the proportion in the table 1;
2. mixing polypropylene resin, elastomer and talcum powder at high speed for 5-10 minutes at 1500 rpm of 800-;
3. mixing the porous filler at low speed of 200-500 rpm for 5-10 min, and controlling the temperature of the mixer at 45-55 ℃ to obtain 2# premix;
4. adding the 1# premix from the main feeding port of the double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each section of the extruder is set to be 200 ℃, 210 ℃, 220 ℃, 210 ℃, the head temperature is 220 ℃, and the screw rotating speed is 300-600 revolutions per minute.
5. Adding the 2# premix from a side feeding port of the double-screw extruder, wherein the side feeding port is arranged in a fifth section of a cylinder body of the extruder, and the side feeding frequency is 2-10 HZ.
TABLE 1 amounts of raw material components and properties of the resulting products in examples 1 to 8 and comparative example 1
Shrinkage was measured according to the GB 17037 standard. The linear expansion coefficient was measured according to ASTM D696 standard. The adhesion of the paint film is tested according to the ISO-2409 standard. Surface tension was tested using a dyne pen. The odor is tested by the method of the experimental specification of the odor of the nonmetallic materials in the Changan automobile VS-01.00-T-14004-A6-2017. The TVOC is tested according to the VS-01.00-T-14012-A3-2017 interior trim parts/materials and VOC sampling test specification of Changan automobiles.
As can be seen from the above table, the composite obtained in comparative example 1 has no porous filler and polar toughening agent, high adhesion level, large number of lattice drops, low surface tension, and relatively high odor and TVOC. After a part of toughening agent with certain polarity is added (examples 1 and 2), the paint film adhesion and surface tension are improved to a certain extent, the shrinkage rate and linear expansion coefficient which characterize dimensional stability, and the odor and TVOC which characterize emission are not changed greatly, which shows that the polar toughening agent has a positive effect on the adhesion of a polypropylene base material and a paint surface, but has no positive effect on the dimensional stability and the emission.
In examples 3-5 in which the molecular sieve and the porous ceramic were filled in the main feeding manner, the paint film adhesion, dimensional stability and dispersibility of the obtained product were greatly improved, indicating that the porous filler had significant positive effects on the above properties. And when the molecular sieve and the porous ceramic are used simultaneously, the performance of the material is improved greatly.
Examples 6-8, in which the porous filler was added in a side feeding manner, further improved the paint film adhesion, dimensional stability and dispersibility of the obtained product compared to example 5 in a main feeding manner, and the better the effect with the increase of the addition ratio. The side feeding mode is more beneficial to the porous filler to play an active role.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The polypropylene composite material for the low-shrinkage low-emission primer-free automobile part is characterized by comprising the following components in percentage by mass:
2. the polypropylene composite for low shrinkage, low emission and primer-free automobile parts as claimed in claim 1, wherein:
the polypropylene resin is at least one of homopolymerized polypropylene and ethylene propylene block copolymerization polypropylene;
the elastomer is at least one of ethylene-propylene rubber, ethylene-octene copolymer grafted maleic anhydride and ethylene-vinyl acetate.
3. The polypropylene composite for low shrinkage, low emission and primer-free automobile parts as claimed in claim 1, wherein: the porous filler is at least one of a molecular sieve, porous ceramic and glass beads.
4. The polypropylene composite for low shrinkage, low emission and primer-free automobile parts as claimed in claim 1, wherein: the porous filler is a mixture of a molecular sieve and porous ceramic.
5. The polypropylene composite for low shrinkage, low emission and primer-free automobile parts as claimed in claim 1, wherein:
the lubricant is one or the combination of two of stearate and silicone master batch;
the antioxidant is at least one of hindered phenol antioxidant, thioester antioxidant, phosphite antioxidant and ester antioxidant;
the light stabilizer is at least one of hindered amine light stabilizer, light shielding agent, ultraviolet absorbent and quenching agent.
6. A method for preparing the polypropylene composite material for the low-shrinkage low-emission primer-free automobile part as claimed in any one of claims 1 to 5, which is characterized by comprising the following preparation steps:
(1) weighing the raw materials according to the proportion;
(2) uniformly mixing polypropylene resin, elastomer and talcum powder, adding antioxidant, lubricant and light stabilizer, and continuously and uniformly mixing to obtain premix;
(3) adding the premix from the main feeding port of the double-screw extruder, adding the porous filler from the side feeding port of the double-screw extruder, and performing melt extrusion granulation to obtain the polypropylene composite material.
7. The method of claim 6, wherein:
the first mixing uniformity and the second mixing uniformity in the step (2) are respectively and independently mixed for 5-10 minutes at 800-1500 rpm;
when the porous filler in the step (3) is a mixture, the mixture is mixed for 5 to 10 minutes at 200 revolutions per minute and 500 revolutions per minute.
8. The method of claim 6, wherein:
the temperature of each section of the feeding section of the twin-screw extruder in the step (3) is set to be 190-205 ℃, 205-215 ℃, 215-225 ℃, 205-215 ℃, the head temperature is 215-225 ℃, and the screw rotation speed is 300-600 revolutions per minute.
9. The method of claim 6, wherein: and (3) arranging the side feeding port on a fifth section of a cylinder body of the double-screw extruder, wherein the side feeding frequency is 2-10 Hz.
10. The use of the polypropylene composite material for low-shrinkage low-emission primer-free automobile parts according to any one of claims 1 to 5 in the automobile field.
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| CN201911316049.7A CN111040295B (en) | 2019-12-19 | 2019-12-19 | Polypropylene composite material for low-shrinkage low-emission primer-free automobile parts and preparation method and application thereof |
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| CN201911316049.7A CN111040295B (en) | 2019-12-19 | 2019-12-19 | Polypropylene composite material for low-shrinkage low-emission primer-free automobile parts and preparation method and application thereof |
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| CN111040295B CN111040295B (en) | 2022-05-24 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789012A (en) * | 2021-09-29 | 2021-12-14 | 重庆会通科技有限公司 | Polypropylene composite material with high paint adhesion and preparation method thereof |
| CN114957856A (en) * | 2022-06-17 | 2022-08-30 | 会通新材料股份有限公司 | Regenerated polypropylene composite material and preparation method thereof |
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| CN106832574A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | Low smell low-density lower shrinkage talc powder filled polypropylene material and preparation method thereof |
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| CN110551340A (en) * | 2019-09-03 | 2019-12-10 | 会通新材料股份有限公司 | modified polypropylene composite material for spraying and preparation method thereof |
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Patent Citations (5)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113789012A (en) * | 2021-09-29 | 2021-12-14 | 重庆会通科技有限公司 | Polypropylene composite material with high paint adhesion and preparation method thereof |
| CN114957856A (en) * | 2022-06-17 | 2022-08-30 | 会通新材料股份有限公司 | Regenerated polypropylene composite material and preparation method thereof |
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