CN110408120B - Antistatic spraying-free polypropylene composite material with low linear thermal expansion coefficient and preparation method thereof - Google Patents
Antistatic spraying-free polypropylene composite material with low linear thermal expansion coefficient and preparation method thereof Download PDFInfo
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- CN110408120B CN110408120B CN201810396548.0A CN201810396548A CN110408120B CN 110408120 B CN110408120 B CN 110408120B CN 201810396548 A CN201810396548 A CN 201810396548A CN 110408120 B CN110408120 B CN 110408120B
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses an antistatic spraying-free polypropylene composite material with low linear thermal expansion coefficient and a preparation method thereof. The functional auxiliary agent is prepared by mixing wollastonite whiskers and glycerol monostearyl ester according to the mass ratio of 1: 1-4: 1 is prepared by compounding. The polypropylene and mineral filling and toughening agent are compounded, so that the strength, rigidity and toughness of the composite material are ensured, the crystallization speed and crystallinity of the material are improved by adding the functional auxiliary agent, the post-shrinkage of the product is reduced, the product forming period is shortened, and meanwhile, a conductive network is formed in the material, so that the material has certain conductivity, the surface antistatic property of the material is improved, and the modified polypropylene composite material can be widely used for spraying-free products.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to an antistatic spray-free polypropylene composite material with a low linear thermal expansion coefficient and a preparation method thereof.
Background
The polypropylene has the advantages of light weight, high cost performance, easy processing, oil resistance, acid and alkali resistance and the like, so that the polypropylene can be widely applied to various industries. Under the promotion of the lightweight process, the process is optimized, the cost is reduced, and the production efficiency is improved in each production stage.
The spraying-free polypropylene composite material is a material which can achieve the spraying effect by direct injection molding without spraying. The special color effect is achieved by filling special effect pigments such as metal pigments, pearlescent pigments and the like into the resin base material, so that a spraying process is omitted, the production efficiency is improved, and the comprehensive cost of a workpiece is reduced; in addition, the finished piece can be directly recycled without special treatment, and is an environment-friendly new material. Therefore, the spraying-free polypropylene composite material has huge market prospect and wide application prospect in the fields of automotive interior, exterior, household appliances and the like.
The spray-free technique, while giving the polypropylene composite a colorful appearance, also exhibits and magnifies some of the deficiencies of its articles. Because the polypropylene material belongs to a semi-crystalline material, the spraying technology can further ensure the dimensional stability of the polypropylene composite material, and the polypropylene is free from high surface glossiness and bright color of the sprayed polypropylene, and can inevitably generate static electricity in the production, transportation and use processes, thereby adsorbing dust, seriously influencing the attractiveness of the material and causing unqualified product appearance. These disadvantages severely limit the application of spray-free polypropylene composites.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an antistatic spray-free polypropylene composite material suitable for industrial batch production and used for low linear thermal expansion coefficient and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
an antistatic spraying-free polypropylene composite material with a low linear thermal expansion coefficient and a preparation method thereof are prepared from the following components in parts by weight: 50-94 parts of polypropylene, 5-20 parts of mineral filler, 0-20 parts of toughening agent, 0.2-1 part of effect pigment, 1-5 parts of functional assistant, 0.1-0.5 part of coupling agent, 0.1-0.5 part of antioxidant, 0.1-0.5 part of lubricant and 0.1-0.5 part of light stabilizer;
the functional auxiliary agent is prepared by mixing wollastonite whiskers and glycerol monostearyl ester according to the mass ratio of 1: 1-1: 4 are compounded.
Further, the melt index of the polypropylene is more than 20g/10min under the condition of 230 ℃/2.16Kg, and the tensile strength is more than 19MPa under the condition of 50mm/min of tensile speed.
The mineral filler is talc powder and calcium carbonate with particle size larger than 1500 meshes.
The toughening agent is ethylene propylene diene monomer, ethylene octene copolymer or butadiene rubber.
The effect pigment is a metal pigment or a metal pigment with a coating layer coated on the surface, wherein the metal pigment is one or more of aluminum powder, stainless steel powder, copper powder, gold powder, silver powder, tin powder and iron powder, the metal pigment is spherical or silver strip or corn flake, the particle size of the metal pigment is 1-300 mu m, and the particle size is preferably 15-100 mu m; the coating layer is selected from one or a combination of several of polyethylene wax, acrylate, dioctyl adipate or mineral oil.
The wollastonite whiskers are needle-shaped wollastonite, and the length-diameter ratio of the wollastonite whiskers is 10-30; the glycerol monostearyl ester is a hydrophilic internal antistatic agent.
The coupling agent is at least one of silane coupling agent and titanate coupling agent.
The antioxidant is one or a mixture of more than two of antioxidant 1010, antioxidant DSTDP and antioxidant 168.
The lubricant is at least one of ethylene bis stearamide, silicone, zinc stearate, lead stearate, barium stearate, calcium stearate or pentaerythritol stearate; the light stabilizer is a hindered amine compound light stabilizer.
The invention also aims to provide a preparation method of the antistatic spray-free polypropylene composite material with the low linear thermal expansion coefficient, which comprises the steps of adding the polypropylene, the mineral filler, the flexibilizer, the metal pigment, the functional assistant, the coupling agent, the antioxidant, the lubricant and the light stabilizer into a high-speed mixer together according to parts by weight, uniformly mixing, melting and extruding the uniformly mixed mixture through an extruder, and granulating to prepare the antistatic spray-free polypropylene composite material with the low linear thermal expansion coefficient; the temperature of the extruder from the feed opening to the die opening is respectively 180 ℃, 190 ℃, 195 ℃, 200 ℃ and 205 ℃, the rotating speed of the extruder is 180-400 rpm, and the vacuum degree is-0.07-0.03 MPa.
The invention has the following beneficial effects:
1. the polypropylene, the mineral filling agent and the toughening agent are compounded, so that the strength, the rigidity and the toughness of the composite material are ensured, the crystallization speed and the crystallinity of the material are improved by adding the functional auxiliary agent, the post-shrinkage of the product is reduced, the product forming period is shortened, a conductive network is formed in the material, the specific conductivity of the material is ensured, and the surface antistatic property of the material is improved.
2. The invention utilizes the low linear thermal expansion coefficient and nucleation of wollastonite whiskers in the functional additive to improve the crystallinity of the composite material and effectively reduce the linear thermal expansion coefficient of the polypropylene composite material.
3. The invention utilizes the antistatic and lubricating properties of glycerol monostearate in the functional auxiliary agent, and protects wollastonite whiskers from keeping enough length-diameter ratio in the screw extrusion process in the premixing process with wollastonite, thereby better playing the role of low linear thermal expansion coefficient; in addition, the glycerol monostearyl ester antistatic agent and the metal pigment have synergistic effect, a conductive path is formed inside a manufactured part, the surface resistivity of the material is reduced, and the antistatic performance is improved; and thirdly, due to the hydrophilicity and the mobility of the glycerol monostearate, the glycerol monostearate can migrate to the surface of a workpiece to a certain degree, covers the surface of the polymer to absorb moisture in the air, and forms a conductive layer on the surface of the spraying-free material, so that the charges on the surface of the material can be effectively dissipated, and the anti-static effect is achieved.
Detailed Description
The following examples are given to illustrate the present invention and it should be noted that the following examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that the modification and modification of the present invention by those of ordinary skill in the art are not essential to the present invention.
The types of the components in the invention are as follows:
wherein the polypropylene is PP-K9026, PP-K7926, PP-BX3800, PP-BX3900 and PP-BX 3920;
the mineral fillers are talc powder AH51210 and calcium carbonate LD-1000C;
the toughening agents are POE8200, POE8842, EPDM and BR;
the functional auxiliary agent is a mixture of wollastonite whiskers (Jiangxi Otetril) and ATMER 129 (Ciba), and the mixing mass ratio is 1: 1-1: 4, and compounding the components.
The metal pigment is Shanghai jin aluminum strip;
the coupling agent is KH 550;
the antioxidant is 1010, antioxidant 168 and antioxidant DSTDP;
the lubricant is ethylene bis stearamide EBS/P-130, calcium stearate, zinc stearate, lead stearate, barium stearate and pentaerythritol stearate;
the light stabilizer used is V703.
The present invention will be further described with reference to the following examples.
Example 1
Respectively weighing 50 parts of dried polypropylene PP-K7926, 20 parts of talcum powder AH51210, 20 parts of toughener POE8200, 0.2 part of metal pigment, 5 parts of functional additive (wollastonite whisker: ATMER 129: 4: 1), 0.1 part of antioxidant 1010, 0.1 part of antioxidant DSTDP, 0.2 part of lubricant EBS, 0.3 part of coupling agent KH550 and 0.1 part of light stabilizer V703 according to the weight ratio, adding the uniformly mixed materials into a high-speed mixer, uniformly mixing, adding the uniformly mixed materials into an extruder, cooling by water and then granulating. Wherein the processing temperature of the extruder is sequentially 180 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, the rotating speed of a main machine is 180rpm and the vacuum degree is-0.03 MPa from the feed opening to the die opening.
Example 2
70 parts of dry polypropylene PP-K9026, 10 parts of talcum powder AH51210, 15 parts of toughening agent EPDM, 0.4 part of metallic pigment, 1 part of functional additive (wollastonite whisker: ATMER 129 ═ 2: 1), 0.1 part of antioxidant DSTDP, 0.2 part of antioxidant 168, 0.2 part of lubricant calcium stearate, 0.3 part of coupling agent KH550 and 0.3 part of light stabilizer V703 are weighed according to the weight ratio, powder and granules in the materials are added into a high-speed mixer to be uniformly mixed, and are granulated after water cooling. Wherein the processing temperature of the extruder is 180 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, the rotating speed of the main machine is 200rpm and the vacuum degree is-0.05 MPa from the feed opening to the die opening in sequence.
Example 3
60 parts of dried polypropylene PP-K9026, 34 parts of PP-BX3800, 5 parts of talcum powder AH51210, 9 parts of toughener POE8200, 1 part of metal pigment, 4 parts of functional additive (wollastonite whisker: ATMER 129: 1), 0.1 part of antioxidant 1010, 0.1 part of antioxidant DSTDP, 0.2 part of antioxidant 168, 0.2 part of lubricant EBS, 0.3 part of coupling agent KH550 and 0.3 part of light stabilizer V703 are weighed according to the weight ratio respectively, the materials are added into a high-speed mixer to be uniformly mixed, then the uniformly mixed mixture is added into an extruder, and the mixture is cooled by water and then cut into granules. Wherein the processing temperature of the extruder is 180 ℃, 190 ℃, 195 ℃, 200 ℃ and 205 ℃ from the feed opening to the die orifice in sequence, the rotating speed of the main machine is 350rpm, and the vacuum degree is-0.05 MPa.
Example 4
Respectively weighing 50 parts of dried polypropylene PP-BX3920, 20 parts of calcium carbonate LD-1000C, 20 parts of toughener POE8842, 1 part of metal pigment, 5 parts of functional additive (wollastonite whisker: ATMER 129: 3: 1), 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168, 0.2 part of lubricant EBS, 0.2 part of coupling agent KH550 and 0.4 part of light stabilizer V703 according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding the uniformly mixed mixture into an extruder, cooling by water and then granulating. Wherein the processing temperature of the extruder is 180 ℃, 190 ℃, 195 ℃, 200 ℃ and 205 ℃ in sequence from the feed opening to the die orifice, the rotating speed of the main machine is 400rpm, and the vacuum degree is-0.06 MPa.
Example 5
Respectively weighing 45 parts of dried polypropylene PP-K9026, 30 parts of PP-BX3900, 20 parts of talcum powder AH51210, 0.6 part of metallic pigment, 3 parts of functional additives (wollastonite whisker: ATMER 129: 4: 1), 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168, 0.2 part of lubricant EBS, 0.2 part of coupling agent KH550 and 0.4 part of light stabilizer V703 according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding the uniformly mixed mixture into an extruder, cooling by water, and granulating. Wherein the processing temperature of the extruder is 180 ℃, 190 ℃, 195 ℃, 200 ℃ and 205 ℃ in sequence from the feed opening to the die orifice, the rotating speed of the main machine is 400rpm, and the vacuum degree is-0.06 MPa.
Comparative example
Respectively weighing 48 parts by weight of dried polypropylene PP-K9026, 30 parts by weight of PP-BX3900, 20 parts by weight of talcum powder AH51210, 0.6 part by weight of metallic pigment, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, 0.2 part by weight of lubricant EBS, 0.2 part by weight of coupling agent KH550 and 0.4 part by weight of light stabilizer V703, adding the materials into a high-speed mixer, uniformly mixing, adding the uniformly mixed mixture into an extruder, cooling by water and then granulating. Wherein the processing temperature of the extruder is 180 ℃, 190 ℃, 195 ℃, 200 ℃ and 205 ℃ in sequence from the feed opening to the die orifice, the rotating speed of the main machine is 400rpm, and the vacuum degree is-0.06 MPa.
The test data for the composites prepared in examples 1-5 and comparative examples are shown in the following table:
remarking: surface resistivity in the upper surface was measured according to ASTM D257; coefficient of linear thermal expansion was tested according to ASTM E831.
As the functional additive is added to the polypropylene composite materials prepared in the embodiments 1-5, the linear thermal expansion coefficient and the surface resistivity of the prepared composite materials are obviously reduced compared with those of a comparative example without the functional additive, the product size is more stable, the antistatic property is good, and surface dust is avoided. Therefore, the polypropylene composite material prepared by the invention can be applied to more spray-free products according to the needs of customers.
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 to these embodiments may be made, and the generic principles described 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 improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. The utility model provides a low linear thermal expansion coefficient's antistatic spraying polypropylene composite material of exempting from which characterized in that: the composition is prepared from the following components in parts by weight: 50-94 parts of polypropylene, 5-20 parts of mineral filler, 0-20 parts of toughening agent, 0.2-1 part of effect pigment, 1-5 parts of functional assistant, 0.1-0.5 part of coupling agent, 0.1-0.5 part of antioxidant, 0.1-0.5 part of lubricant and 0.1-0.5 part of light stabilizer;
the functional auxiliary agent is prepared from wollastonite whiskers and glycerol monostearyl ester according to the mass ratio of 1: 1-4: 1 is compounded; the wollastonite whiskers are needle-shaped wollastonite, and the length-diameter ratio of the wollastonite whiskers is 10-30; the glycerol monostearyl ester is a hydrophilic internal antistatic agent;
the effect pigment is a metal pigment or a metal pigment with a coating layer coated on the surface; the coating layer is selected from one or a combination of several of polyethylene wax, acrylate, dioctyl adipate or mineral oil.
2. The antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to claim 1, wherein: the melt index of the polypropylene is more than 20g/10min under the condition of 230 ℃/2.16Kg, and the tensile strength is more than 19MPa under the condition that the drawing speed is 50 mm/min.
3. The antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to claim 1, wherein: the mineral filling is talcum powder or calcium carbonate with the grain size larger than 1500 meshes.
4. The antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to claim 1, wherein: the metal pigment is one or more of aluminum powder, stainless steel powder, copper powder, gold powder, silver powder, tin powder and iron powder, the metal pigment is in one of a spherical shape, a silver strip shape or a corn flake shape, and the particle size of the metal pigment is 1-300 mu m.
5. The antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to claim 1, wherein: the coupling agent is at least one of silane coupling agent and titanate coupling agent.
6. The antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to claim 1, wherein: the toughening agent is ethylene propylene diene monomer, ethylene octene copolymer or butadiene rubber.
7. The antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to claim 1, wherein: the antioxidant is one or a mixture of more than two of antioxidant 1010, antioxidant DSTDP and antioxidant 168.
8. The antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to claim 1, wherein: the lubricant is at least one of ethylene bis stearamide, silicone, zinc stearate, lead stearate, barium stearate, calcium stearate or pentaerythritol stearate; the light stabilizer is a hindered amine compound light stabilizer.
9. A process for preparing the antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient according to any one of claims 1 to 8, characterized in that: adding polypropylene, mineral filler, toughening agent, effect pigment, functional assistant, antioxidant, coupling agent, lubricant and light stabilizer into a high-speed mixer according to the parts by weight, and uniformly mixing; then, melting and extruding the uniformly mixed mixture by an extruder, and granulating to prepare the antistatic spray-free polypropylene composite material with low linear thermal expansion coefficient; the temperature of the extruder from the feed opening to the die opening is respectively 180 ℃, 190 ℃, 195 ℃, 200 ℃ and 205 ℃, the rotating speed of the extruder is 180-400 rpm, and the vacuum degree is-0.07-0.03 MPa.
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| CN111454515A (en) * | 2020-04-20 | 2020-07-28 | 盘锦海兴科技股份有限公司 | Rigidity-enhancing and toughening antistatic polypropylene master batch and preparation method thereof |
| CN111423665B (en) * | 2020-05-18 | 2022-06-07 | 红壹佰照明有限公司 | Polypropylene-based composite material for coating metal and preparation method and application thereof |
| CN112225995A (en) * | 2020-09-23 | 2021-01-15 | 重庆会通科技有限公司 | Spraying-free polypropylene composite material and preparation method thereof |
| CN113831641B (en) * | 2021-09-26 | 2023-06-06 | 上海日之升科技有限公司 | Polypropylene material composite material with low linear expansion coefficient and high surface hardness and preparation method thereof |
| CN115610063B (en) * | 2022-12-20 | 2023-04-07 | 温州鑫泰新材料股份有限公司 | Low-crimping high-temperature-resistant flame-retardant insulating packaging film and preparation method thereof |
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