CN111718539B - Self-repairing polypropylene material and preparation method thereof - Google Patents
Self-repairing polypropylene material and preparation method thereof Download PDFInfo
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- CN111718539B CN111718539B CN202010454807.8A CN202010454807A CN111718539B CN 111718539 B CN111718539 B CN 111718539B CN 202010454807 A CN202010454807 A CN 202010454807A CN 111718539 B CN111718539 B CN 111718539B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
Abstract
The invention relates to a self-repairing polypropylene material and a preparation method thereof, wherein the self-repairing polypropylene material comprises the following components in parts by weight: 94-99 parts of polypropylene, 0.1-2.0 parts of scratch repairing agent, 0.5-2.0 parts of dispersing agent, 0.2-2.0 parts of heat stabilizer and 0.2-2.0 parts of processing aid. According to the invention, through the molecular structure design, hydrogen bonds are generated between the scratch repairing agent and the dispersing agent, when the material is damaged by scratches, the scratch self-repairing agent can be placed for 10-30min at the room temperature of 23+/-2 ℃ to realize the scratch self-repairing through the hydrogen bonds, and the scratch self-repairing agent is applicable to automobile plastic part products.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and particularly relates to a self-repairing polypropylene material and a preparation method thereof.
Background
With the development of the automobile industry, new materials, particularly high polymer materials, meet good development opportunities. The polymer material has the advantages of low density, easy processing, good insulativity, low price and the like, and is widely applied to the vehicle materials. However, with the improvement of the living standard of people, consumers have put higher demands on the aesthetic appearance of automotive materials, especially on scratch of automotive parts. The polypropylene (PP) material has the advantages of low density, excellent mechanical property, high cost performance, environment friendliness, recyclability and the like, and is widely applied to the field of automobiles. In order to avoid a great deal of scratches generated in the use process of the vehicle parts, a certain amount of scratch-resistant auxiliary agents are often added into the polypropylene materials, so that the lubricating effect is realized when the parts are scratched, but the mechanical scratches are usually irreversible, and the scratches generated by the parts cannot be repaired. In recent years, the self-repairing technology has received extensive attention, along with the improvement of the living standard of people and the improvement of the requirements on the quality of automobiles, automobile materials are also required to have good scratch resistance and good automatic scratch repairing property at the same time, wherein the higher scratch resistance can enable a vehicle to directly avoid lighter scratches, the good automatic scratch repairing property can carry out self-repairing on the generated scratches, and the two aspects of the self-repairing technology can solve the problems that the scratches are easy to generate in common plastic products and the vehicle needs to be subjected to secondary paint spraying or other repairing operations after the scratches are generated.
However, the existing materials are difficult to achieve high scratch resistance and good automatic repair performance at the same time. While more and more automobile manufacturers have made demands on scratch properties of materials, the poor scratch resistance of materials themselves has limited their widespread use. In order to widen the application field of the polymer material and solve the problem of poor scratch resistance, a great deal of researches are carried out on the scratch resistance of the polymer material by material engineers, and a great deal of researches on the scratch resistance of the material are reported. In the prior art, the scratch resistance of materials is improved by adding polysiloxane lubricants to polymers; the surface friction coefficient of the material is reduced by adding the aliphatic primary amide lubricant into the polypropylene, the scratch resistance of the polypropylene material is improved, the scratch resistance of the material can be improved to a certain extent by adding the lubricant, but the lubricant is easy to separate out in the long-term use process of the material, so that the appearance and the use performance of the material are seriously affected, and meanwhile, the usage amount is generally larger when the amide substances are used, the cost is higher, and the scratch resistance effect is poor; the surface hardness of the material is improved by adding polymethyl methacrylate into the material, so that the scratch resistance of the material is improved; in addition, the scratch-resistant talcum powder-filled polypropylene with high rigidity and high toughness is prepared by a method of adding the organosilicon elastomer, so that the scratch resistance of the material is improved. However, the above methods have limited improvement in scratch resistance of materials, and have large limitations in use, and in addition, scratch sites are not repairable.
Disclosure of Invention
The invention aims to solve the technical problem of providing a self-repairing polypropylene material and a preparation method thereof, wherein the material has good scratch resistance and good self-repairing performance.
The invention provides a self-repairing polypropylene material which comprises the following components in parts by weight: 94-99 parts of polypropylene, 0.1-2.0 parts of scratch repairing agent, 0.5-2.0 parts of dispersing agent, 0.2-2.0 parts of heat stabilizer and 0.2-2.0 parts of processing aid; wherein, hydrogen bonds exist between the scratch repair agent and the dispersing agent.
The melt flow rate of the polypropylene is 1-100g/10min under the condition of 230 ℃/2.16 kg.
The scratch repairing agent is polyethyleneimine, and the polymerization degree is 10-100.
The dispersing agent is polyacrylic acid, and the polymerization degree is 10-100.
The heat stabilizer is at least one of a phenolic heat stabilizer, an amine heat stabilizer, a phosphite ester heat stabilizer, a semi-hindered phenolic heat stabilizer, a compound heat stabilizer formed by an acryl functional group and a thioester and a calixarene heat stabilizer.
The processing aid is at least one of low molecular esters, metal soaps, stearic acid composite esters and amides, and the main function of the processing aid is lubrication.
The invention provides a preparation method of a self-repairing polypropylene material, which comprises the following steps:
mixing polypropylene, scratch repair agent, dispersant, heat stabilizer and processing aid according to the proportion to obtain a premix; adding the premix into a double screw extruder for melt mixing, dispersing, extruding and granulating to obtain granules, and drying the granules (below 80 ℃) to obtain the self-repairing scratch-resistant polypropylene composite material based on hydrogen bonding.
The mixing speed is 400-600r/min, and the mixing time is 5-10min.
The technological parameters of the double-screw extruder are as follows: the processing temperature of each section is as follows: 170-190 ℃ in the first region, 190-230 ℃ in the second region, 230-240 ℃ in the third region, 230-240 ℃ in the fourth region, 230-240 ℃ in the fifth region, 230-240 ℃ in the sixth region, 230-240 ℃ in the seventh region, 240-250 ℃ in the eighth region, and 230-240 ℃ in the ninth region; the rotating speed of the screw is 300-800r/min.
Advantageous effects
According to the invention, through the molecular structure design, hydrogen bonds are generated between the scratch repairing agent and the dispersing agent, when the material is damaged by scratches, the scratch self-repairing agent can be placed for 10-30min at the room temperature of 23+/-2 ℃ to realize the scratch self-repairing through the hydrogen bonds, and the scratch self-repairing agent is applicable to automobile plastic part products.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The types and types of polypropylene, scratch-resistant dispersant, heat stabilizer and processing aid selected in the following specific examples and comparative examples are as follows:
polypropylene: EP548R.
Polyethyleneimine: the polymerization degree n=15, n=50 provided by the company aa Ding Shiji.
Polyacrylic acid: the polymerization degree n=10, n=70 provided by the company aa Ding Shiji.
Firstly, the scratch-resistant effect of the polyethyleneimine ensures that the polypropylene composite material has higher scratch resistance; second, NH and NH on the molecular chain of polyethyleneimine 2 With polypropyleneThe c=o and O-H groups on the acid have hydrogen bonding.
Heat stabilizer: beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Processing aid: zinc stearate.
Organosilicon scratch agent: HG-600.
The twin screw extruder selected in the following specific examples and comparative examples was a 75A type twin screw extruder manufactured by Ruiya corporation, and the aspect ratio of the twin screw extruder was 40:1.
The polypropylene materials of the specific examples and the comparative examples are prepared by the above selected components, and the preparation method comprises the following steps:
(1) Respectively weighing polypropylene, polyethyleneimine, polyacrylic acid, a heat stabilizer and a processing aid according to the dosage of each formula in Table 1;
(2) Placing the weighed polypropylene, polyethyleneimine, polyacrylic acid, heat stabilizer and processing aid into a high-speed mixer, and mixing for 5min at the speed of 400r/min to obtain a premix;
(3) Adding the premix into a double-screw extruder for melt mixing, dispersing, extruding and granulating to obtain granules, and drying the granules below 80 ℃ to obtain the polypropylene nano material; wherein the processing temperature of each section of the double-screw extruder is as follows: first zone 170 ℃, second zone 190 ℃, third zone 230 ℃, fourth zone 232 ℃, fifth zone 234 ℃, sixth zone 236 ℃, seventh zone 240 ℃, eighth zone 240 ℃, ninth zone 230 ℃; and the screw rotating speed of the double-screw extruder is 800r/min.
TABLE 1 amounts of the components (unit: parts by weight) of the examples and comparative examples
The polypropylene materials prepared in the specific examples and the comparative examples are subjected to scratch resistance and scratch automatic repair performance tests and other basic physical properties. Wherein the scratch resistance test is tested by the PV3952 mass scratch resistance test, the scratch resistance being characterized by dL (immediate test); the scratch self-repairing performance is that the prepared polypropylene material is subjected to scratch test after being injection molded into a dermatoglyph sample plate, and the scratch force used in the test is 10N. The automatic repair temperature is 23+/-2 ℃ for 30min, and the test delta L is compared when the test is placed for 15 min. The scratch resistance is represented by DeltaL, L represents whiteness, deltaL represents whiteness after scratch minus whiteness before scratch, and DeltaL becomes smaller after automatic repair, indicating that automatic repair occurs. The tensile property test is carried out according to ISO 527-2, the size of the sample is 150 multiplied by 10 multiplied by 4mm, and the tensile speed is 10mm/min; bending performance test was conducted according to ISO 178, the sample size was 80X 10X 4mm, the bending speed was 2mm/min, and the span was 64mm; the notched impact strength test of the simply supported beams was carried out according to ISO 179-1/1eA, with sample dimensions of 80X 8X 4mm. The smaller values of Dl and Δl indicate better scratch resistance of the material. The test results are described in table 2.
Table 2 results of performance testing of specific examples and comparative examples
As can be seen from the test results of the specific examples and the comparative examples, the scratch-resistant repairing agent and the scratch-resistant dispersing agent are used together, so that the scratch resistance and the automatic repairing performance of the polypropylene composite material can be greatly improved when the polypropylene composite material is placed for 30min at the room temperature of 23+/-2 ℃, but the scratch resistance and the automatic repairing performance of the polypropylene composite material when the scratch-resistant repairing agent is only used or the scratch-resistant dispersing agent is only used can not reach the technical effects of the invention when the polypropylene composite material is placed for 30min at the room temperature of 23+/-2 ℃. And the rigidity of the material is improved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and it should be noted that it is possible for those skilled in the art to make several improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.
Claims (7)
1. The self-repairing polypropylene material is characterized in that: the coating comprises the following components in parts by weight: 94-99 parts of polypropylene, 0.1-2.0 parts of scratch repairing agent, 0.5-2.0 parts of dispersing agent, 0.2-2.0 parts of heat stabilizer and 0.2-2.0 parts of processing aid; wherein, hydrogen bonds exist between the scratch repairing agent and the dispersing agent; the scratch repairing agent is polyethyleneimine, and the polymerization degree is 10-100; the dispersing agent is polyacrylic acid, and the polymerization degree is 10-100.
2. A material according to claim 1, characterized in that: the melt flow rate of the polypropylene is 1-100g/10min under the condition of 230 ℃/2.16 kg.
3. A material according to claim 1, characterized in that: the heat stabilizer is at least one of a phenolic heat stabilizer, an amine heat stabilizer, a phosphite ester heat stabilizer, a semi-hindered phenolic heat stabilizer, a compound heat stabilizer formed by an acryl functional group and a thioester and a calixarene heat stabilizer.
4. A material according to claim 1, characterized in that: the processing aid is at least one of low molecular esters, metal soaps, stearic acid composite esters and amines.
5. A method of preparing the self-healing polypropylene material of claim 1, comprising:
mixing polypropylene, scratch repair agent, dispersant, heat stabilizer and processing aid according to the proportion to obtain a premix; adding the premix into a double-screw extruder for melt mixing, dispersing, extruding and granulating to obtain granules, and drying the granules to obtain the self-repairing scratch-resistant polypropylene composite material for the vehicle based on the hydrogen bond effect.
6. The method of manufacturing according to claim 5, wherein: the mixing speed is 400-600r/min, and the mixing time is 5-10min.
7. The method of manufacturing according to claim 5, wherein: the technological parameters of the double-screw extruder are as follows: the processing temperature of each section is as follows: 170-190 ℃ in the first region, 190-230 ℃ in the second region, 230-240 ℃ in the third region, 230-240 ℃ in the fourth region, 230-240 ℃ in the fifth region, 230-240 ℃ in the sixth region, 230-240 ℃ in the seventh region, 240-250 ℃ in the eighth region, and 230-240 ℃ in the ninth region; the rotating speed of the screw is 300-800r/min.
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| CN112409700B (en) * | 2020-11-19 | 2022-12-02 | 江苏金发科技新材料有限公司 | High-performance polypropylene composite material for vehicles and preparation method thereof |
| CN114621522B (en) * | 2022-03-25 | 2024-01-02 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method and application thereof |
| CN114634673B (en) * | 2022-03-28 | 2023-10-31 | 上海金发科技发展有限公司 | Reinforced polypropylene material and preparation method thereof |
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| CN103113663B (en) * | 2011-11-17 | 2016-06-15 | 上海金发科技发展有限公司 | A kind of damage resistant polypropylene composite with self-regeneration function and preparation method thereof |
| WO2014099070A1 (en) * | 2012-12-19 | 2014-06-26 | Empire Technology Development Llc | Self-healing coatings from recycled polymer blends |
| CN105802021B (en) * | 2016-05-13 | 2019-06-14 | 上海金发科技发展有限公司 | A kind of damage resistant flame-proof polypropelene composition and preparation method thereof |
| CN108659340A (en) * | 2018-05-23 | 2018-10-16 | 江苏金发科技新材料有限公司 | Damage resistant polymer composite containing graphene and preparation method thereof |
| CN109762258A (en) * | 2018-12-17 | 2019-05-17 | 会通新材料股份有限公司 | A kind of high scratch-proof polypropylene material and preparation method thereof |
| CN111499965B (en) * | 2019-01-30 | 2022-12-02 | 江苏金发科技新材料有限公司 | Self-repairing scratch-resistant polypropylene nano material for automobile clothes and preparation method thereof |
| CN110396245A (en) * | 2019-08-05 | 2019-11-01 | 中国建筑股份有限公司 | Selfreparing polypropylene epidermis and preparation and application for building template surface |
| CN110724282B (en) * | 2019-11-28 | 2021-02-19 | 山东大学 | Super-long stretching self-repairing hydrogel bonding material and preparation method thereof |
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