CN110951156B - Polypropylene composite material with high surface tension and excellent comprehensive performance and preparation method thereof - Google Patents
Polypropylene composite material with high surface tension and excellent comprehensive performance and preparation method thereof Download PDFInfo
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- CN110951156B CN110951156B CN201811146523.1A CN201811146523A CN110951156B CN 110951156 B CN110951156 B CN 110951156B CN 201811146523 A CN201811146523 A CN 201811146523A CN 110951156 B CN110951156 B CN 110951156B
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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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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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Abstract
The invention discloses a polypropylene composite material with high surface tension and excellent comprehensive performance and a preparation method thereof, wherein the polypropylene composite material is prepared by mixing, extruding and granulating 51-76 parts of polypropylene, 6-12 parts of toughening agent, 15-32 parts of inorganic filler, 3-5 parts of polar additive, 0.2-1.0 part of antioxidant and 0-0.5 part of other auxiliary agent. The polar additive is used for modifying the surface tension of the polypropylene composite material, so that the adhesive force of paint is enhanced, and the coating property of polypropylene is improved.
Description
Technical Field
The invention relates to the technical field of modified materials, in particular to a polypropylene composite material with high surface tension and excellent comprehensive performance and a preparation method thereof.
Background
Polypropylene (PP for short) has the advantages of excellent mechanical property, lower density, good heat resistance, excellent bending fatigue resistance, chemical stability, electrical property and the like, and is one of general plastics with the largest using amount.
Among various plastic varieties for automobiles, the development and application of modified polypropylene (PP) in automobiles are always the focus of attention in the automobile industry and the plastic industry. The polypropylene is used as the bumper material, and the polypropylene bumper sprayed with the paint has good appearance and can generate good visual effect. This requires polypropylene materials that not only have good impact properties and processability, but also have excellent paint adhesion properties. Because the PP material is a non-polar material, the surface energy of the PP material is low, so that the PP material has poor compatibility with most polymers, is difficult to infiltrate, adhere and print, has poor coating performance and low bonding strength with paint. In order to improve the paint adhesion of polypropylene, the polypropylene is usually subjected to surface treatment before coating, generally, dust and oil stains adsorbed on the surface of the polypropylene are removed by a solvent, and then surface oxidation treatment is performed by flame, corona discharge or gas plasma and the like to increase polar groups on the surface and enhance the coating adhesion, but the method has a complex process and potential safety hazard.
Disclosure of Invention
The invention aims to provide a polypropylene composite material with high surface tension and excellent comprehensive performance and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the polypropylene composite material with high surface tension and excellent comprehensive performance is prepared from the following components in parts by weight:
the polypropylene is at least one of homopolymerized polypropylene and copolymerized polypropylene.
The toughening agent is at least one of ethylene-octene copolymer and ethylene-propylene copolymer.
The inorganic filler is at least one of calcium carbonate, calcium carbonate whiskers, wollastonite, talcum powder, kaolin, montmorillonite, barite, mica, titanium dioxide and fly ash.
The polar additive is epoxy silane oligomer powder.
The epoxy silane oligomer powder is formed by dispersing epoxy silane in fumed silica, wherein the number average molecular weight of the epoxy silane is 1000-8000; the particle size of the epoxy silane oligomer powder is 50-100 mu m, wherein the mass percent of the epoxy silane is not less than 50%.
The antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl thiodipropionate.
The other auxiliary agents comprise a coupling agent, a lubricating agent and a dispersing agent.
The invention also aims to provide a preparation method of the polypropylene composite material with high surface tension and excellent comprehensive performance, which comprises the following steps:
(1) weighing 51-76 parts of polypropylene, 15-32 parts of inorganic filler, 6-12 parts of toughening agent, 3-5 parts of polar additive, 0.2-1.0 part of antioxidant and 0-0.5 part of other auxiliary agent, adding into a high-speed mixer, and mixing for 5-15 min;
(2) adding the uniformly mixed materials into a double-screw extruder, mixing and extruding to obtain the high-surface-tension polypropylene composite material; wherein the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
The invention has the beneficial effects that:
according to the invention, the epoxy silane oligomer is used as a polar additive, and is easier to migrate to the surface of a workpiece after being compounded with polypropylene due to relatively small molecular weight, so that the surface tension of the polypropylene composite material is modified, the coating property of the polypropylene is improved, and the adhesive force of paint coated on the surface of the polypropylene composite material is enhanced; the workpiece made of the composite material prepared by the invention can realize surface treatment without flame, corona discharge or gas plasma and the like in the coating process, can be directly coated and sprayed with paint, is an environment-friendly and efficient method, and can reduce the cost of the coating process.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The epoxy silane oligomer powder described in the following examples is prepared by dispersing epoxy silane in fumed silica, wherein the number average molecular weight of epoxy silane is 8000-; the particle size of the epoxy silane oligomer powder is 50-100 mu m, wherein the mass percent of the epoxy silane is not less than 50%. Such as SIC 6654S manufactured by Guangzhou Si-C New Material Co
Example 1
(1) 76 parts of homo-polypropylene, 6 parts of ethylene-octene copolymer, 15 parts of talcum powder, 3 parts of epoxy silane oligomer powder, 1.0 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1.0 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 0.1 part of coupling agent and 0.2 part of lubricating agent are weighed.
(2) Mixing for 5min in a high-speed mixer, uniformly mixing the raw materials, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperatures of all regions of the extruder are 150 ℃, 170 ℃, 175 ℃, 180 ℃ and 185 ℃ in sequence from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 350 r/min.
Example 2
(1) 70 parts of polypropylene copolymer, 7 parts of ethylene-propylene copolymer, 10 parts of calcium carbonate whisker, 3 parts of epoxy silane oligomer powder, 0.2 part of dioctadecyl thiodipropionate, 0.1 part of coupling agent, 0.1 part of lubricant and 0.1 part of dispersant are weighed.
(2) Mixing for 10min in a high-speed mixer, uniformly mixing the raw materials, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperature of each zone of the extruder is 170 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, the length-diameter ratio of an extrusion screw is 36, and the rotating speed of the extrusion screw is 350 r/min from the feeding section to the head.
Example 3
(1) Weighing 18 parts of homo-polypropylene, 50 parts of co-polypropylene, 8 parts of ethylene-octene copolymer, 20 parts of fly ash, 4 parts of epoxy silane oligomer powder, 0.4 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 0.1 part of coupling agent, 0.1 part of lubricant and 0.2 part of dispersant.
(2) Mixing for 15min in a high-speed mixer, uniformly mixing the raw materials, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperatures of all regions of the extruder are 150 ℃, 170 ℃, 175 ℃, 180 ℃ and 195 ℃ in sequence from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 350 r/min.
Example 4
(1) 63 parts of homo-polypropylene, 8 parts of ethylene-propylene copolymer, 10 parts of titanium dioxide, 15 parts of fly ash, 4 parts of epoxy silane oligomer powder, 0.5 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1 part of coupling agent, 0.1 part of lubricant and 0.3 part of dispersant are weighed.
(2) Mixing for 15min in a high-speed mixer, uniformly mixing the raw materials, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperatures of all zones of the extruder are 160 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ and 195 ℃ in sequence from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 44, and the rotating speed of the extrusion screw is 300 revolutions per minute.
Example 5
(1) 55 parts of polypropylene copolymer, 5 parts of ethylene-octene copolymer, 5 parts of ethylene-propylene copolymer, 10 parts of talcum powder, 10 parts of kaolin, 10 parts of montmorillonite, 5 parts of epoxy silane oligomer powder, 0.3 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.3 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are weighed.
(2) Mixing for 15min in a high-speed mixer, uniformly mixing the raw materials, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperatures of all regions of the extruder are 160 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 36, and the rotating speed of the extrusion screw is 400 r/min.
Example 6
(1) 51 parts of polypropylene copolymer, 12 parts of ethylene-octene copolymer, 32 parts of talcum powder, 5 parts of epoxy silane oligomer powder, 0.8 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.2 part of coupling agent and 0.2 part of lubricating agent are weighed.
(2) Mixing for 15min in a high-speed mixer, uniformly mixing the raw materials, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperatures of all zones of the extruder are 160 ℃, 170 ℃, 175 ℃, 185 ℃, 190 ℃ from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 400 r/min.
The polypropylene composites prepared in examples 1 to 6 were prepared into plaques according to the standard and were subjected to the respective performance tests, the results of which are shown in Table 1.
TABLE 1
Wherein the surface tension test: a series of ethanol solutions were prepared according to FLMT BO 116-03 standard, and the ethanol solutions were dipped with a cotton swab and tested on the surface of an uncoated sample plate, and the liquid film was held for 5 seconds.
As can be seen from the data in Table 1, the polypropylene composite material prepared by the invention has excellent comprehensive performance and can meet the performance requirements of products such as automobile bumpers, door panels and the like.
Comparative example 1
Weighing the following raw materials in parts by weight: 79 parts of polypropylene, 6 parts of POE, 15 parts of talcum powder, 1 part of antioxidant, 0.2 part of lubricant and 0.1 part of coupling agent, and the polypropylene composite material of the comparative example 1 is produced according to the process conditions of the example 1.
Comparative example 2
Weighing the following raw materials in parts by weight: 56 parts of polypropylene copolymer, 12 parts of POE, 32 parts of talcum powder, 0.8 part of antioxidant, 0.3 part of lubricant and 0.2 part of coupling agent are produced according to the process conditions of the embodiment 6 to obtain the polypropylene composite material of the comparative example 2.
The polypropylene composites prepared in examples 1 and 6 and comparative examples 1 to 2 were subjected to surface tension test, and the test results are shown in Table 2.
TABLE 2
| Test item/Unit | Unit of | Example 1 | Comparative example 1 | Example 6 | Comparative example 2 |
| Surface tension | N/m | 0.049 | 0.029 | 0.067 | 0.034 |
As can be seen from the data in table 2, the polypropylene composite prepared according to the present invention has a higher surface tension, which is about 2 times that of the comparative example composite.
The high surface tension polypropylene composites prepared in examples 1 to 6 were prepared into samples, wiped with isopropyl alcohol, and then purged with high pressure air to spray primer, color paint, and clear coat, respectively (the primer and color paint were sprayed and then baked at 80 ℃ for 5min, and the clear coat was sprayed and then baked at 80 ℃ for 50 min). The sprayed parts were subjected to the Baige test and the peel strength test, the results are shown in Table 3, wherein the Baige test was performed according to GB/T9286-1998, and the peel strength was performed according to GB/T2790-1995.
TABLE 3
| Test items | Test standard | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Baige test | GB/T9286 | Level 0 | Level 0 | Level 0 | Level 0 | Level 0 | Level 0 |
| Peel strength N/m | GB/T2790 | 854 | 896 | 922 | 929 | 987 | 998 |
As can be seen from the data in Table 3, the polypropylene composite material prepared by the invention can be directly sprayed without flame, corona discharge or gas plasma or the like in the coating process, and the paint surface strength meets the requirement.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications can be made to the embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (7)
1. A polypropylene composite material with high surface tension and excellent comprehensive performance is characterized in that: the composition is prepared from the following components in parts by weight:
51-76 Parts of Polypropylene (PP),
6-12 parts of a toughening agent,
15-32 parts of an inorganic filler,
3-5 parts of a polar additive,
0.2 to 1.0 portion of antioxidant,
0-0.5 part of other auxiliary agents;
the polar additive is epoxy silane oligomer powder; the epoxy silane oligomer powder is formed by dispersing epoxy silane in fumed silica, wherein the number average molecular weight of the epoxy silane is 1000-8000; the particle size of the epoxy silane oligomer powder is 50-100 mu m, wherein the mass percent of the epoxy silane is not less than 50%.
2. The polypropylene composite according to claim 1, wherein: the polypropylene is at least one of homopolymerized polypropylene and copolymerized polypropylene.
3. The polypropylene composite according to claim 1, wherein: the toughening agent is at least one of ethylene-octene copolymer and ethylene-propylene copolymer.
4. The polypropylene composite according to claim 1, wherein: the inorganic filler is at least one of calcium carbonate, calcium carbonate whiskers, wollastonite, talcum powder, kaolin, montmorillonite, barite, mica, titanium dioxide and fly ash.
5. The polypropylene composite according to claim 1, wherein: the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl thiodipropionate.
6. The polypropylene composite according to claim 1, wherein: the other auxiliary agents comprise a coupling agent, a lubricating agent and a dispersing agent.
7. A method for preparing the polypropylene composite material according to claim 1, wherein: the method comprises the following steps:
(1) weighing 51-76 parts of polypropylene, 15-32 parts of inorganic filler, 6-12 parts of toughening agent, 3-5 parts of polar additive, 0.2-1.0 part of antioxidant and 0-0.5 part of other auxiliary agent, adding into a high-speed mixer, and mixing for 5-15 min;
(2) adding the uniformly mixed materials into a double-screw extruder, and mixing and extruding to obtain a polypropylene composite material; wherein the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
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| CN112625344B (en) * | 2020-12-09 | 2023-10-31 | 浙江普利特新材料有限公司 | Vehicle polypropylene composite material modified based on organosilicon-based amphiphilic polymer and preparation method thereof |
| CN112679861A (en) * | 2020-12-15 | 2021-04-20 | 江苏金发科技新材料有限公司 | Flame-treatment-free polypropylene composition for automobile bumpers and preparation method thereof |
| CN115368675B (en) * | 2022-09-19 | 2024-03-29 | 会通新材料股份有限公司 | Polypropylene composition easy to treat by plasma, and preparation method and application thereof |
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