CN110819008A - Easy-to-clean spray-free polypropylene material and preparation method thereof - Google Patents
Easy-to-clean spray-free polypropylene material and preparation method thereof Download PDFInfo
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- 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
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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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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- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/0812—Aluminium
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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
- C08K3/02—Elements
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- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
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- 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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- 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 provides an easy-to-clean spray-free polypropylene material and a preparation method thereof, wherein the easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight: 70-90 parts of low-viscosity polypropylene resin; 10-30 parts of high-viscosity polypropylene resin; the sum of the parts by weight of the low-viscosity polypropylene resin and the parts by weight of the high-viscosity polypropylene resin is 100 parts; 0.5-1 part of antioxidant; 0.5-1 part of lubricant; easy cleaning-1-5 parts of metal toner master batch. Mixing low-viscosity polypropylene resin, high-viscosity polypropylene resin, an antioxidant and a lubricant by using a high-speed mixer, and adding the mixture into a double-screw extruder through a main feed; and (3) adding the easy-to-clean metal toner master batch into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the metal toner master batch. The easy-to-clean spraying-free polypropylene material has excellent mechanical property, processability and easy-to-clean capability, and can be applied to the fields of automobiles and household appliances, such as automobile exterior decorations, air conditioner decorative strips, small household appliance exterior decorative structures and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to an easy-to-clean spray-free polypropylene material and a preparation method thereof.
Background
The polypropylene (PP) has the advantages of no toxicity, low odor, low cost, chemical corrosion resistance, good mechanical property and the like, and is widely applied to the fields of household appliances, bathrooms, electronics and the like. In recent years, with the development of spray-free materials, more and more parts are starting to adopt spray-free technology. The spraying-free paint not only can save the process steps and reduce the cost, but also is environment-friendly.
However, in practical use, the spraying-free polypropylene material also has many challenges, for example, the spraying-free polypropylene material used in the housing of an electric cooker and an electric pressure cooker cannot avoid water or oil sticking on the surface of the material due to being in a kitchen environment for a long time, and the long-time placement of the spraying-free polypropylene material can adsorb more dust, so that the stain on the surface of the material is serious, and the use experience of consumers is greatly reduced. Therefore, the easy cleaning performance of the spraying-free polypropylene material is improved, and the spraying-free polypropylene material has important practical significance in the field of household appliances.
At present, most of reports on polymers easy to clean are based on modification of organic siloxane or fluorine-containing auxiliaries, and Chinese patent CN 201510437696.9 reports a high-hydrophobicity modified PP material prepared by using hydrophobic auxiliaries, a preparation method thereof and a dish-washing machine. Wherein the hydrophobic auxiliary agent is organic siloxane or modified organic siloxane; chinese patents CN201611217108.1 and CN 201710433892.8 report polypropylene with hydrophobic surface, wherein the former uses at least one of perfluoroalkane or fluorine-containing silicone, and the latter uses polytetrafluoroethylene micropowder as a fluorine-containing adjuvant. The above patent shows a certain degree of increase in the contact angle of water after the addition of the low surface active energy substance. However, the fluorine-containing additives in the above reports all adopt a direct addition method, and do not adopt a method of preparing master batches and then adding the master batches. By the method of adding the master batch, the dispersion of the auxiliary agent can be effectively improved, and the effect of the auxiliary agent can be better exerted.
In the field of spraying-free, silane coupling agents are used relatively more, and the silane coupling agents are used in spraying-free patents such as Chinese patent CN201710469638.3, Chinese patent CN201611079305.1, Chinese patent CN201510205663.1 and the like. In the above patent, the silane coupling agent is usually mixed directly with other resins and additives to feed the main material and the metallic toner side material to complete the preparation of the spray-free sample. In the process of preparing the spraying-free metal-imitating color master batch and in the process of processing the color master batch, the Chinese patent CN201410447111.7 also adds a silane coupling agent. However, the silane coupling agents in the above patents have improved compatibility during processing, and the improvement is relatively limited. If the silane coupling agent can be used for preferentially treating the metal toner, the compatibility of the metal toner and resin can be greatly improved, and the using amount of the metal toner is reduced.
In the field of spray-free materials, there is less disclosure of easily cleanable patents. Chinese patents CN201610268533.7 and CN201810814340.6, namely, by introducing an antistatic agent into the formula, the adsorption of the material to dust is effectively avoided, and the cleanliness of the material is further improved, and meanwhile, the addition of the antistatic agent is also beneficial to the cleaning of the dust on the surface of the material. However, the scene is suitable for dry and non-polluted environments, and the applicability of the scene to kitchen environments is poor. Chinese patent 201611217108.1 discloses an easy-to-clean material obtained by directly adding hydrophobic modifier polytetrafluoroethylene micropowder into the formula to improve the hydrophobic angle. However, the polytetrafluoroethylene micropowder has a high melting point, so that the polytetrafluoroethylene micropowder cannot be melted in the processing process, and the problem of pockmarks on the appearance is easily caused. Chinese patent CN201710865581.9 discloses a self-cleaning spray-free injection molding material and a preparation method thereof, wherein a doped visible light photocatalytic self-cleaning layer containing bismuth vanadate can be formed on the surface of the self-cleaning material, and the self-cleaning effect can be obtained through photocatalysis.
Disclosure of Invention
Based on the above, the invention provides an easy-to-clean spray-free polypropylene material and a preparation method thereof. The easy-to-clean spraying-free polypropylene material has excellent mechanical property, processability and easy-to-clean capability, and can be applied to the fields of automobiles and household appliances, such as automobile exterior decorations, air conditioner decorative strips, small household appliance exterior decorative structures and the like.
The specific technical scheme is as follows:
an easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
70-90 parts of low-viscosity polypropylene resin;
10-30 parts of high-viscosity polypropylene resin;
the sum of the parts by weight of the low-viscosity polypropylene resin and the parts by weight of the high-viscosity polypropylene resin is 100 parts;
0.5-1 part of antioxidant;
0.5-1 part of lubricant;
easy-to-clean-1-5 parts of metal toner master batch;
the low-viscosity polypropylene resin has a melt index of 30-50g/10min under the condition of 230 ℃/2.16 KG;
the melt index of the high-viscosity polypropylene resin is 2-10g/10min under the condition of 230 ℃/2.16 KG;
the preparation method of the easy-cleaning metal toner master batch comprises the following steps: firstly, pretreating the metal toner by using a fluorine-containing silane coupling agent, then mixing the pretreated system with polypropylene powder, and processing and granulating by using a double-screw extruder to obtain the easy-to-clean metal toner master batch.
In one embodiment, the easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
in some of these embodiments, the low viscosity polypropylene resin has a melt index of 35 to 45g/10min measured at 230 ℃/2.16 KG.
In one embodiment, the low viscosity polypropylene resin has a melt index of 40g/10min measured at 230 ℃/2.16 KG.
In some of the examples, the high viscosity polypropylene resin has a melt index of 4-8g/10min measured at 230 ℃/2.16 KG.
In one embodiment, the high viscosity polypropylene resin has a melt index of 6g/10min measured at 230 ℃/2.16 KG.
In some embodiments, the easy-to-clean-metal toner masterbatch is prepared by the following method:
1) mixing the metal toner and the fluorine-containing silane coupling agent in a mixer according to the mass ratio of 1:1-1:10, wherein the rotation speed of the mixer is 100-300r/min, and the mixing time is 1-3 min;
2) adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1-1:4, and continuing mixing by using a stirrer, wherein the rotating speed of the stirrer is 100-;
3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch; the technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone is 150-170 ℃, the temperature of the second zone is 190-210 ℃, the temperature of the third zone is 190-210 ℃, the temperature of the fourth zone is 200-220 ℃, the temperature of the fifth zone is 200-220 ℃, the temperature of the sixth zone is 190-210 ℃, the temperature of the seventh zone is 190-210 ℃, the temperature of the eighth zone is 200-220 ℃, the temperature of the die head is 200-220 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa; the ratio L/D of the length L and the diameter D of the screw of the double-screw extruder is 35-50; the screw is provided with more than 1-2 meshing block areas and more than 1-2 reverse thread areas.
In some embodiments, the mass ratio of the fluorine-containing silane coupling agent to the metal toner to the polypropylene powder is (0.1-1): 0.1: 1.
in some embodiments, the mass ratio of the fluorine-containing silane coupling agent to the metal toner to the polypropylene powder is (0.3-0.8): 0.1: 1.
in one embodiment, the mass ratio of the fluorine-containing silane coupling agent to the metal toner to the polypropylene powder is 0.5: 0.1: 1.
in some embodiments, the polypropylene powder has a melt index of 10-30g/10min under the condition of 230 ℃/2.16KG, and the particle size of the powder is 0.01-5 mm.
In some of the embodiments, the metal toner is selected from one or more of aluminum powder, copper powder, gold powder, silver powder, zinc powder, tin powder, iron powder, and nickel powder.
In some of these embodiments, the fluorochemical silane coupling agent is one or more of trifluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, per (heptadecafluorodecyltrimethoxysilane, per (heptadecafluorodecyltriethoxysilane), per (tridecafluorooctyltrimethoxysilane, per (tridecafluorooctyltriethoxysilane).
In some of these embodiments, the antioxidant is selected from one or more of β N-octadecyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite.
In some of these embodiments, the lubricant is selected from one or more of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate, ethylene bisstearamide.
The invention also provides a preparation method of the easy-to-clean spray-free polypropylene material.
The specific technical scheme is as follows:
a preparation method of an easy-to-clean spray-free polypropylene material comprises the following steps:
weighing low-viscosity polypropylene resin, high-viscosity polypropylene resin, an antioxidant and a lubricant according to the weight fraction, mixing by using a high-speed mixer, and adding into a double-screw extruder through a main feed; and adding the easy-to-clean metal toner master batch into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-to-clean spray-free polypropylene material.
In some embodiments, the mixing speed of the high-speed mixer is 500-1200 rpm.
In some of the examples, the process parameters of the twin-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone is 150-170 ℃, the temperature of the second zone is 190-210 ℃, the temperature of the third zone is 190-210 ℃, the temperature of the fourth zone is 200-220 ℃, the temperature of the fifth zone is 200-220 ℃, the temperature of the sixth zone is 190-210 ℃, the temperature of the seventh zone is 190-210 ℃, the temperature of the eighth zone is 200-220 ℃, the temperature of the die head is 200-220 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa.
In some of these embodiments, the ratio L/D of the screw length L to the diameter D of the twin-screw extruder is 35 to 50; the screw is provided with more than 1-2 meshing block areas and more than 1-2 reverse thread areas.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention solves the problems that the surface dirt is not easy to remove and the metallic toner is not easy to disperse in the existing spray-free polypropylene material, so that the spray-free polypropylene material easy to clean has excellent mechanical property, processability and easy-to-clean capability.
2. The preparation method and the process of the easy-to-clean spraying-free polypropylene material are simple, easy to control and low in equipment requirement, the used equipment is general processing equipment, and the easy-to-clean spraying-free polypropylene material can be applied to the kitchen electric field such as an electric cooker shell and an electric pressure cooker shell, and can also be expanded to be applied to the fields such as automobile exterior decorations, air conditioner decorative strips and other small household appliances, and the application prospect is wide.
The possible principle is as follows:
aiming at the problems that surface dirt is not easy to remove and metal toner is not easy to disperse in the existing spraying-free polypropylene material, the invention prepares the easy-to-clean metal toner master batch by pretreating the metal toner with a fluorine-containing silane coupling agent and then mixing the metal toner with polypropylene powder. On one hand, the introduction of fluorine and silicon elements can obviously improve the water contact angle of the polypropylene surface, so that the dirt on the surface can be removed more easily. Meanwhile, the pretreatment of the fluorine-containing silane coupling agent on the metal toner can also obviously improve the compatibility of the metal toner and the matrix resin polypropylene, and simultaneously, the polypropylene resin with high viscosity and low viscosity is compounded to ensure the mechanical property and the processing property of the polypropylene. By compounding the antioxidant and the lubricant, the processing performance of the easy-to-clean spray-free polypropylene material can be obviously improved.
The master batch is prepared by preparing the easy-cleaning metal toner master batch, wherein the metal toner is pretreated by a fluorine-containing silane coupling agent preferentially, then polypropylene powder is added and mixed, and then the master batch is obtained by extrusion granulation. Then the easy-to-clean metal toner master batch is matched with two polypropylene resins with different viscosities to be mixed in a proper proportion, and the antioxidant and the lubricant with proper proportion are compounded and used. The master batch improves the compatibility of the metallic toner and the polypropylene resin on the premise of not influencing the metallic texture and the luster, thereby greatly improving the dispersibility of the metallic toner in the polypropylene material and enabling the material to have strong metallic texture by only using a small amount of the metallic toner. On the other hand, the master batch can also greatly improve the hydrophobic capacity of the polypropylene resin, and the water contact angle is also obviously improved. The increase of the water contact angle can enable impurities and dirt on the surface of the polypropylene to be removed more easily, and the polypropylene matrix resin is endowed with better easy cleaning capability.
The antioxidant improves the processing stability of matrix resin in the processing process of polyacrylamide, and avoids the problems of material degradation and the like caused by a high-temperature processing process, thereby improving the overall performance of the material.
The lubricant has good thermal stability and is not easy to decompose in the processing process of polypropylene. Meanwhile, in order to improve the processability of the material and reduce the comprehensive energy consumption by considering the high-viscosity polypropylene in the formula composition, a lubricant is introduced, and the two are matched with each other in a proper ratio so as to obviously reduce the torque of the material in the processing process.
Drawings
FIG. 1 is a flow chart of a preparation process of the easy-to-clean spray-free polypropylene material of the present invention.
FIG. 2 is a diagram of an actual product of example 7 of the present invention.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. It is to be understood that the experimental procedures in the following examples, where specific conditions are not noted, are generally in accordance with conventional conditions, or with conditions recommended by the manufacturer. The various reagents used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
High viscosity polypropylene resin (melt index 40), high viscosity polypropylene resin (melt index 35), purchased from the well known division of petrochemical company, ltd, china;
low viscosity polypropylene resin (melt index 6), low viscosity polypropylene resin (melt index 8), purchased from Guangzhou division, petrochemical, Inc., China;
the antioxidants are β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester and tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, which are purchased from Beijing extremely easy chemical industry Co., Ltd;
antioxidant: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite, purchased from beijing Tiangang adjuncts, llc;
lubricant silicone powder, purchased from Chuanhua chemical industry technologies, Inc., Guangzhou;
lubricant pentaerythritol stearate, purchased from Guangzhou Reynaud technologies, Inc.;
lubricant calcium stearate, lubricant zinc stearate, purchased from zichuan ruifeng plastics auxiliaries factory;
ethylene bis stearamide, a lubricant, was purchased from one chemical technology ltd, guangzhou;
metallic toner, purchased from new color plastics industries, llc, of the shude district, mountain, fo;
per (heptadecafluorodecyltrimethoxysilane, purchased from sigma aldrich trade ltd;
polypropylene powder (melt index 20) was purchased from the registered petrochemical company, ltd.
Example 1
The easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner aluminum powder and the trifluoropropyltriethoxysilane in a mixer according to the mass ratio of 1:10, wherein the rotation speed of the mixer is 100r/min, and the mixing time is 1 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 100r/min, and the mixing time is 1 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer of 500 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone is 150 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 190 ℃, the temperature of the seventh zone is 190 ℃, the temperature of the eighth zone is 200 ℃, the temperature of the die head is 200 ℃, the rotating speed of the screw is 200rpm, and the vacuum degree is-0.05 MPa.
The ratio L/D of the length L of the screw to the diameter D is 35; and the screw is provided with 1 meshing block area and 1 reverse thread area.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Example 2
The easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner silver powder and the trifluoropropyltrimethoxysilane in a stirrer according to the mass ratio of 1:5, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Example 3
An easy-to-clean spray-free polypropylene material comprises the following components in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metallic toner copper powder and the per (heptadecafluorodecyltrimethoxysilane in a mixer according to the mass ratio of 1:1, wherein the rotating speed of the mixer is 300r/min, and the mixing time is 3 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 300r/min, and the mixing time is 3 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 170 ℃, the temperature of the second zone was 210 ℃, the temperature of the third zone was 210 ℃, the temperature of the fourth zone was 220 ℃, the temperature of the fifth zone was 220 ℃, the temperature of the sixth zone was 210 ℃, the temperature of the seventh zone was 210 ℃, the temperature of the eighth zone was 220 ℃, the temperature of the die head was 220 ℃, the rotation speed of the screw was 500rpm, and the vacuum was-0.08 MPa. The ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Example 4
The easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner silver powder and the per (heptadecafluorodecyl) triethoxysilane in a mixer according to the mass ratio of 1:5, wherein the rotation speed of the mixer is 200r/min, and the mixing time is 2 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Example 5
The easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner silver powder and the per (heptadecafluorodecyl) triethoxysilane in a mixer according to the mass ratio of 1:5, wherein the rotation speed of the mixer is 200r/min, and the mixing time is 2 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Example 6
The easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner silver powder and the per (heptadecafluorodecyl) triethoxysilane in a mixer according to the mass ratio of 1:5, wherein the rotation speed of the mixer is 200r/min, and the mixing time is 2 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Example 7
The easy-to-clean spray-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner silver powder and the per (heptadecafluorodecyl) triethoxysilane in a mixer according to the mass ratio of 1:5, wherein the rotation speed of the mixer is 200r/min, and the mixing time is 2 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Comparative example 1
The easy-to-clean spraying-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner silver powder and the per (heptadecafluorodecyl) triethoxysilane in a mixer according to the mass ratio of 1:5, wherein the rotation speed of the mixer is 200r/min, and the mixing time is 2 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Comparative example 2
The easy-to-clean spraying-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean metal toner master batch comprises the following steps: 1) mixing the metal toner silver powder and the per (heptadecafluorodecyl) triethoxysilane in a mixer according to the mass ratio of 1:5, wherein the rotation speed of the mixer is 200r/min, and the mixing time is 2 min; 2) continuously adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1, and then continuously mixing by using a stirrer, wherein the rotating speed of the stirrer is 200r/min, and the mixing time is 2 min; 3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch. The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding easy-to-clean metal toner master batches into the parallel double-screw extruder (total eight zones) in the lateral direction for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Comparative example 3
The easy-to-clean spraying-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant, the lubricant and the fluorine-containing silane coupling agent according to the weight percentage, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Comparative example 4
The easy-to-clean spraying-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant and the lubricant according to the weight fraction, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metallic toner in the lateral direction of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
Comparative example 5
The easy-to-clean spraying-free polypropylene material is prepared from the following raw materials in parts by weight:
the preparation method of the easy-to-clean spray-free polypropylene material comprises the following steps:
1) weighing the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant, the lubricant and the fluorine-containing silane coupling agent according to the weight percentage, and mixing by using a high-speed mixer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding a metal toner line in the lateral direction of the parallel double-screw extruder (total eight zones), melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone was 160 ℃, the temperature of the second zone was 200 ℃, the temperature of the third zone was 200 ℃, the temperature of the fourth zone was 210 ℃, the temperature of the fifth zone was 210 ℃, the temperature of the sixth zone was 200 ℃, the temperature of the seventh zone was 200 ℃, the temperature of the eighth zone was 210 ℃, the temperature of the die head was 210 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.06 MPa. The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) under the process conditions, performing melt extrusion and granulation by using a double-screw extruder to obtain the granular easy-to-clean spray-free polypropylene material.
The following is a summary of examples and comparative examples:
TABLE 1 summary of the composition parts by weight of the raw materials of the examples and comparative examples
The easy-to-clean spray-free polypropylene materials prepared in the above examples and comparative examples were subjected to the following performance tests, and the results are shown in table 2:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: according to the test of GB/T1843-2008 standard, the thickness of the sample strip is 4 mm;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 230 ℃, and the load is 2.16 kg;
gloss: testing according to GB/T8807-1988 standard, and selecting an angle of 60 degrees;
water contact angle: testing according to GB/T30693-2014 standard.
The higher the glossiness of the material is, the stronger the texture of the material is, and the better the spraying-free effect is; the larger the water contact angle of the material is, the stronger the easy cleaning capability of the material is, and when dirt is adhered to the surface of the material, the dirt can be better taken away by water.
TABLE 2 Properties of the Polypropylene materials of the examples and comparative examples
In examples 1 to 7, the proportions of the low-viscosity polypropylene resin, the high-viscosity polypropylene resin, the antioxidant, the lubricant and the easy-cleaning metal toner masterbatch are adjusted, and as can be seen from table 2, the tensile strength and the melt index of the low-viscosity polypropylene resin tend to increase and the notch impact strength tends to decrease with the increase of the proportion of the low-viscosity polypropylene resin. The change in antioxidants and lubricants has little effect on the mechanical properties. The easy-to-clean metal toner master batch has the advantages that the surface glossiness is remarkably improved along with the increase of the addition amount, and meanwhile, the contact angle of a resin matrix also tends to increase. By comparison, the polypropylene material of example 7 has the best overall properties.
Comparative example 1 compared with example 7, comparative example 1 uses more high viscosity polypropylene resin, the impact strength of the material is obviously reduced, the tensile strength is obviously increased, and the material is not suitable for being used in actual products in a whole view; comparative example 2 compared with example 7, comparative example 2 uses more low viscosity polypropylene resin, the tensile strength of the material is reduced remarkably, the impact strength is increased obviously, and the material is not suitable for being used in actual products in a whole view. Comparative example 3 compared with example 7, comparative example 3 directly used a fluorine-containing silane coupling agent in an amount slightly larger than the content in the mother particle of example 7. In comparative example 3, since no metallic toner is present, the decrease in gloss is significant, and the contact angle is lower than that in example 7, which shows that the master batch is prepared and used again, which is beneficial to the dispersion of the auxiliary agent and the improvement of the efficiency of the auxiliary agent. Comparative example 4 compared with example 7, comparative example 4 directly used a metallic toner in an amount slightly larger than the content in the mother particle of example 7. In comparative example 4, since no fluorine-containing silane coupling agent is present, the contact angle is reduced significantly, and the gloss is lower than that in example 7, which shows that the treatment of the fluorine-containing silane coupling agent and the preparation of the master batch are helpful for improving the interface between the metal toner and the matrix resin, the metal toner is dispersed better, and the gloss is improved more. Comparative example 5 compared with example 7, comparative example 5 directly used a fluorine-containing silane coupling agent and a metal toner, and was not as good as example 7 in terms of both gloss and contact angle.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The easy-to-clean spraying-free polypropylene material is characterized by being prepared from the following raw materials in parts by weight:
the low-viscosity polypropylene resin has a melt index of 30-50g/10min under the condition of 230 ℃/2.16 KG;
the melt index of the high-viscosity polypropylene resin is 2-10g/10min under the condition of 230 ℃/2.16 KG;
the preparation method of the easy-cleaning metal toner master batch comprises the following steps: firstly, pretreating the metal toner by using a fluorine-containing silane coupling agent, then mixing the pretreated system with polypropylene powder, and processing and granulating by using a double-screw extruder to obtain the easy-to-clean metal toner master batch.
2. The easy-to-clean spray-free polypropylene material as claimed in claim 1, which is prepared from the following raw materials in parts by weight:
3. the easy-to-clean spray-free polypropylene material according to any one of claims 1 to 2, wherein the low viscosity polypropylene resin has a test melt index of 35 to 45g/10min at 230 ℃/2.16 KG; the melt index of the high-viscosity polypropylene resin is 4-8g/10min under the condition of 230 ℃/2.16 KG.
4. The easy-to-clean spray-free polypropylene material according to any one of claims 1 to 2, wherein the preparation method of the easy-to-clean metal toner masterbatch is as follows:
1) mixing the metal toner and the fluorine-containing silane coupling agent in a mixer according to the mass ratio of 1:1-1:10, wherein the rotation speed of the mixer is 100-300r/min, and the mixing time is 1-3 min;
2) adding the polypropylene powder into the high-speed mixer according to the mass ratio of the total mass of the materials to the polypropylene powder in the step 1) of 1:1-1:4, and continuing mixing by using a stirrer, wherein the rotating speed of the stirrer is 100-;
3) adding the mixed material obtained in the step 2) into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-cleaning metal toner master batch; the technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone is 150-170 ℃, the temperature of the second zone is 190-210 ℃, the temperature of the third zone is 190-210 ℃, the temperature of the fourth zone is 200-220 ℃, the temperature of the fifth zone is 200-220 ℃, the temperature of the sixth zone is 190-210 ℃, the temperature of the seventh zone is 190-210 ℃, the temperature of the eighth zone is 200-220 ℃, the temperature of the die head is 200-220 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa; the ratio L/D of the length L and the diameter D of the screw of the double-screw extruder is 35-50; the screw is provided with more than 1-2 meshing block areas and more than 1-2 reverse thread areas.
5. The easy-to-clean spray-free polypropylene material as claimed in claim 4, wherein the mass ratio of the fluorine-containing silane coupling agent to the metallic toner to the polypropylene powder is (0.1-1): 0.1: 1; the melt index of the polypropylene powder is 10-30g/10min under the condition of 230 ℃/2.16KG, and the particle size of the powder is 0.01-5 mm.
6. The easy-to-clean spray-free polypropylene material as claimed in claim 5, wherein the mass ratio of the fluorine-containing silane coupling agent to the metallic toner to the polypropylene powder is (0.3-0.8): 0.1: 1.
7. the easy-to-clean spray-free polypropylene material according to claim 4, wherein the metallic toner is selected from one or more of aluminum powder, copper powder, gold powder, silver powder, zinc powder, tin powder, iron powder and nickel powder; the fluorine-containing silane coupling agent is one or more of trifluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, per (heptadecyl) fluorodecyltrimethoxysilane, per (heptadecyl) fluorodecyltriethoxysilane, per (tridecyl) fluorooctyltrimethoxysilane and per (tridecyl) fluorooctyltriethoxysilane.
8. The easy-to-clean spray-free polypropylene material according to any one of claims 1 to 7, wherein the antioxidant is selected from one or more of β N-octadecyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and N, N' -bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite, and the lubricant is selected from one or more of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate and ethylene bis stearamide.
9. The preparation method of the easy-to-clean spray-free polypropylene material according to any one of claims 1 to 8, comprising the following steps:
weighing low-viscosity polypropylene resin, high-viscosity polypropylene resin, an antioxidant and a lubricant according to the weight fraction, mixing by using a high-speed mixer, and adding into a double-screw extruder through a main feed; and adding the easy-to-clean metal toner master batch into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the easy-to-clean spray-free polypropylene material.
10. The method for preparing easy-to-clean spray-free polypropylene material as claimed in claim 9, wherein the mixing speed of the high speed mixer is 500-1200 rpm; the technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone is 150-170 ℃, the temperature of the second zone is 190-210 ℃, the temperature of the third zone is 190-210 ℃, the temperature of the fourth zone is 200-220 ℃, the temperature of the fifth zone is 200-220 ℃, the temperature of the sixth zone is 190-210 ℃, the temperature of the seventh zone is 190-210 ℃, the temperature of the eighth zone is 200-220 ℃, the temperature of the die head is 200-220 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa; the ratio L/D of the length L and the diameter D of the screw of the double-screw extruder is 35-50; the screw is provided with more than 1-2 meshing block areas and more than 1-2 reverse thread areas.
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