阅读说明：本技术 一种抗氧化仿金属塑料母料及其制备方法 (Antioxidant metal-like plastic master batch and preparation method thereof ) 是由 陈庆 白涛 陈涛 司文彬 于 2020-06-24 设计创作，主要内容包括：本发明涉及塑料母料的领域,公开了一种抗氧化仿金属塑料母料及其制备方法。制备过程包括：(1)利用清洗剂溶液对金属颜料粉末进行超声清洗,得到清洗后的金属颜料粉末；(2)将氟锆酸钛、γ-氨基丙基三乙氧基硅烷、缓冲剂、成膜助剂和防锈剂加入水中,得到包覆溶液；(3)将包覆溶液喷淋在清洗后的金属颜料粉末表面,静置、末水洗、过滤、干燥,得到抗氧化金属颜料；(4)将载体树脂、分散剂、偶联剂、抗氧化金属颜料混合挤出造粒,即可得到抗氧化仿金属塑料母料。本发明通过将金属颜料粉末表面清洗后包覆复合陶瓷膜,制得的仿金属塑料母料具有优异的抗氧化性和耐腐蚀性,能够在长时间储存和使用中保持仿金属塑料良好的金属光泽与质感。(The invention relates to the field of plastic master batches and discloses an antioxidant metal-like plastic master batch and a preparation method thereof. The preparation process comprises the following steps: (1) carrying out ultrasonic cleaning on the metal pigment powder by using a cleaning agent solution to obtain cleaned metal pigment powder; (2) adding titanium fluozirconate, gamma-aminopropyl triethoxysilane, a buffering agent, a film forming aid and an antirust agent into water to obtain a coating solution; (3) spraying the coating solution on the surface of the cleaned metal pigment powder, standing, washing with water, filtering and drying to obtain the antioxidant metal pigment; (4) and mixing, extruding and granulating the carrier resin, the dispersing agent, the coupling agent and the antioxidant metal pigment to obtain the antioxidant metal-like plastic master batch. According to the invention, the surface of the metal pigment powder is cleaned and then coated with the composite ceramic membrane, so that the prepared metal-like plastic master batch has excellent oxidation resistance and corrosion resistance, and can keep good metal luster and texture of metal-like plastic during long-time storage and use.)

1. the preparation method of the antioxidant metal-like plastic master batch is characterized by comprising the following specific steps:

(1) firstly, mixing metal pigment powder and a cleaning agent solution, adding the mixture into an ultrasonic dispersion machine, then carrying out ultrasonic cleaning, removing foreign matters and grease on the surface of the metal powder, and then washing with water to prepare cleaned metal pigment powder; the raw material mixture ratio is, by weight, 0.5-1.5 parts of metal pigment powder and 3-4 parts of cleaning agent solution;

(2) firstly, adding water into a normal-temperature reaction tank, then sequentially adding titanium fluozirconate, gamma-aminopropyl triethoxysilane, a buffering agent, a film-forming assistant and an antirust agent, and uniformly stirring to obtain a coating solution; the raw materials comprise, by weight, 1000 parts of water, 25-36 parts of titanium fluorozirconate, 1-8 parts of gamma-aminopropyltriethoxysilane, 5-18 parts of a buffering agent, 0.1-5 parts of a film-forming assistant and 0.1-6 parts of an antirust agent;

(3) putting the cleaned metal pigment powder prepared in the step (1) into a stirrer, then uniformly spraying the coating solution prepared in the step (2) on the surface of the metal pigment, standing, washing the metal pigment powder with water after water is volatilized, filtering and drying to obtain the antioxidant metal pigment;

(4) uniformly mixing carrier resin, a dispersing agent and a coupling agent, adding the antioxidant metal pigment obtained in the step (3) for mixing and melting, and extruding and granulating by using a screw extruder to obtain antioxidant metal-like plastic master batch; the raw materials comprise, by weight, 25-30 parts of carrier resin, 10-15 parts of dispersing agent, 1-3 parts of coupling agent and 52-64 parts of antioxidant metal pigment.

2. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: the metal pigment powder in the step (1) is one of flaky aluminum powder, silver powder, copper powder, zinc powder and stainless steel powder with the fineness of 1-10 mu m; the cleaning agent solution is a solution prepared by adding water into HT-A5C (produced by Sichuan Hengxingda science and technology Co., Ltd.) degreasing agent to form a solution with the mass concentration of 3-5%, and the main components are inorganic acid salt and surfactant.

3. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: the ultrasonic disperser in the step (1) is an HDG20-3000 type ultrasonic disperser, the rated power is 3kW, and the maximum frequency is 20 kHz; the frequency of ultrasonic cleaning is 10-15 KHz, and the time is 5-10 min.

4. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: the buffer in the step (2) is one of ethylenediamine and diisopropylamine; the film-forming additive is at least one of ammonium molybdate and sodium molybdate; the antirust agent is one of sodium borate and ammonium borate.

5. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: and (3) stirring in the step (2) at a rotating speed of 200-300 r/min for 5-10 min.

6. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: and (3) the rotating speed of the stirrer during spraying is 50-100 r/min, the spraying time is 5-15 min, and the standing time is 1-2 h.

7. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: and (4) filtering in the step (3) by one of sedimentation, suction filtration and filter pressing.

8. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: the carrier resin in the step (4) is at least one of atactic polypropylene (APP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), Chlorinated Polyethylene (CPE), ethylene-vinyl acetate copolymer (EVA) and polyvinyl chloride (PVC); the dispersing agent is one of polyethylene wax and stearic acid; the coupling agent is one of silane coupling agent and aluminate coupling agent.

9. The preparation method of the antioxidant metal-like plastic master batch as claimed in claim 1, which is characterized in that: and (4) the screw extruder in the step (4) is a 38-type co-rotating double-screw extruder.

10. The antioxidant metal-like plastic master batch prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to the field of plastic master batches and discloses an antioxidant metal-like plastic master batch and a preparation method thereof.

Background

Plastics are important organic synthetic polymer materials, and with the development of industrial technology and social life, plastics are receiving attention because of their plasticity, recyclability, and strength adjustability. The plastic integrates the hardness of metal, the portability of wood, the transparency of glass, the corrosion resistance of ceramic and the elasticity and toughness of rubber, so that the plastic is widely applied to various industries such as aerospace, medical appliances, petrochemical industry, mechanical manufacturing, national defense, building and the like besides daily necessities.

With the increasing decoration and functionality of plastics, many functional plastics are continuously available. In the product design and production process of the industries of automobiles, household appliances, toys and the like, plastic parts are often required to have metal texture, the traditional method mainly comprises the secondary treatment method after plastic molding such as paint spraying, finishing, film coating, electroplating and the like, and the method has the defects of long process route, high production cost and environmental protection. Therefore, research into new technologies of metal-like plastics is increasing.

In recent years, with the development of material technology, a preparation process of metal-like master batch appears, and the metal-like master batch is mainly prepared by adding metal powder, a dispersing agent, a coupling agent and the like into carrier plastic and mixing and extruding the mixture, can be directly used in the production of metal-like plastic, reduces the cost of obtaining metal texture of plastic products, and improves the production efficiency and environmental protection of metal-like plastic products. The metal powder added in the metal-like plastic master batch is usually aluminum powder, iron powder, copper powder, zinc powder and the like, and is widely applied to the industries of metal coatings, printing ink and plastic processing, but the metal powder is active in property and is easy to corrode or oxidize in water, acidic or alkaline media to generate hydrogen, the surface of a commercially available metal pigment is usually provided with an organic protective layer, but the coating is not high-temperature resistant and can be damaged in the process of mixing and extruding the metal pigment and carrier resin, so that the oxidation resistance and the corrosion resistance of the metal pigment are influenced, and the appearance and the metal texture of a metal-like plastic product are gradually lowered along with the service time. Therefore, much attention has been paid to the research for improving the oxidation resistance and corrosion resistance of the metal-like plastic products.

The Chinese patent application No. 201710469638.3 discloses a high weather-resistant spraying-free imitation metal ABS composite material, which comprises the following raw materials in parts by weight: 80-95 parts of ABS, 5-20 parts of modified ABS, 1-10 parts of spraying-free metal-like master batch, 0.5-2 parts of silane coupling agent, 1-5 parts of auxiliary crosslinking agent, 0.5-2 parts of dispersing agent and 1-5 parts of toughening agent; wherein the modified ABS is a copolymer of ABS and 4- [2- (3, 5-dihydroxyphenyl) vinyl ] -1, 2-benzenediol and diallyl acetal pentaerythritol; the spraying-free imitation metal master batch is the modified ABS-coated pearlescent metal pigment.

Chinese patent application No. 201710628484.8 discloses a PP material with metal-like texture and a preparation method thereof. The metal-like PP material comprises the following raw materials in parts by weight: 40-70 parts of PP resin, 5-10 parts of toughening agent, 2-8 parts of compatilizer, 5-50 parts of reinforcing powder, 1-5 parts of flash powder, 0.5-2 parts of pigment, 0.2-0.4 part of antioxidant, 0.5-2 parts of lubricant and 0.1-0.3 part of silane coupling agent; the preparation method comprises powder treatment and extrusion granulation.

According to the technical method for producing the metal-like plastic by using the metal-like master batch in the prior scheme, because the metal pigment in the metal-like master batch is easy to corrode or oxidize in water, acidic or alkaline media, and when the traditional organic protective layer is used, the coating is not high-temperature resistant and is easy to damage, the appearance and the metal texture of a metal-like product are poorer and poorer, and the application of the metal-like plastic is influenced.

Disclosure of Invention

At present, the metal pigment in the widely applied metal-like plastic master batch has the problem of poor corrosion resistance and oxidation resistance, so that the appearance and the metal texture of the metal-like plastic are worse and worse along with the use time, and the development and the application of the metal-like plastic are restricted.

The invention achieves the above purpose by the following technical scheme:

a preparation method of an antioxidant metal-like plastic master batch comprises the following specific steps:

(1) firstly, mixing metal pigment powder and a cleaning agent solution, adding the mixture into an ultrasonic dispersion machine, then carrying out ultrasonic cleaning, removing foreign matters and grease on the surface of the metal powder, and then washing with water to prepare cleaned metal pigment powder; the raw material mixture ratio is, by weight, 0.5-1.5 parts of metal pigment powder and 3-4 parts of cleaning agent solution;

(2) firstly, adding water into a normal-temperature reaction tank, then sequentially adding titanium fluozirconate, gamma-aminopropyl triethoxysilane, a buffering agent, a film-forming assistant and an antirust agent, and uniformly stirring to obtain a coating solution; the raw materials comprise, by weight, 1000 parts of water, 25-36 parts of titanium fluorozirconate, 1-8 parts of gamma-aminopropyltriethoxysilane, 5-18 parts of a buffering agent, 0.1-5 parts of a film-forming assistant and 0.1-6 parts of an antirust agent;

(3) putting the cleaned metal pigment powder prepared in the step (1) into a stirrer, then uniformly spraying the coating solution prepared in the step (2) on the surface of the metal pigment, standing, washing the metal pigment powder with water after water is volatilized, filtering and drying to obtain the antioxidant metal pigment;

(4) uniformly mixing carrier resin, a dispersing agent and a coupling agent, adding the antioxidant metal pigment obtained in the step (3) for mixing and melting, and extruding and granulating by using a screw extruder to obtain antioxidant metal-like plastic master batch; the raw materials comprise, by weight, 25-30 parts of carrier resin, 10-15 parts of dispersing agent, 1-3 parts of coupling agent and 52-64 parts of antioxidant metal pigment.

The metal pigment is common flaky metal pigment powder, the flaky metal pigment is small flaky metal powder with a large diameter-thickness ratio, and the flaky metal pigment can be arranged in multiple layers and mutually covered to form a layer-by-layer barrier when being added into a plastic substrate, so that the metal-like texture can be well exerted, the permeation of external harmful gas or liquid can be prevented to a certain extent, and the metal pigment has certain oxidation resistance and corrosion resistance. Preferably, the metal pigment powder in the step (1) is one of flaky aluminum powder, silver powder, copper powder, zinc powder and stainless steel powder with the fineness of 1-10 microns; in a further preferred embodiment of the present invention, the metallic pigment powder is selected from aluminum flakes, which have a silvery white metallic luster, a low water vapor permeability and a good rust resistance.

The metal powder is cleaned by using the cleaning agent solution, so that impurities, grease and other dirt on the surface of the metal can be effectively removed, the surface activity is improved, the metal pigment powder is more convenient to carry out surface ceramic treatment, the obtained ceramic coating layer is more tightly combined with the surface of the metal powder, the metal powder is not easy to damage, the oxidation resistance and the corrosion resistance are higher, the metal powder can be used under the conditions of high temperature, acidity or alkalinity, and the metal luster and the texture of the metal-like plastic can be kept in the long-time storage and use processes. Preferably, the cleaning agent solution is a solution prepared by adding water into a degreasing agent of HT-A5C type (produced by Sichuan Hengxingda technologies, Inc.) to prepare the solution with the mass concentration of 3-5%, and the main components are inorganic acid salt and surfactant.

The invention utilizes the ultrasonic cleaning process, mainly utilizes the direct and indirect actions of the cavitation action, the acceleration action and the direct current action of the ultrasonic waves in the liquid on the impurities, the grease and other dirt on the surface of the metal powder, so that the dirt layers of the impurities, the grease and the like are dispersed, emulsified and stripped to achieve the cleaning purpose, and the invention has the advantages of good cleaning effect, high cleaning speed, no damage to the surface of the powder and the like. Preferably, the ultrasonic disperser in the step (1) is an HDG20-3000 type ultrasonic disperser, the rated power is 3kW, and the maximum frequency is 20 kHz; the frequency of ultrasonic cleaning is 10-15 KHz, and the time is 5-10 min.

The invention prepares titanium fluozirconate, gamma-aminopropyl triethoxysilane, a buffering agent, a film forming auxiliary agent and an antirust agent into a coating solution. The gamma-aminopropyl triethoxy silane is amino silane which can be used for coupling organic high polymer and inorganic filler, and can raise its cohesiveness and mechanical, water-resistant and ageing-resistant properties. When the coating solution is uniformly sprayed on the surface of the cleaned metal pigment, aminosilane (gamma-aminopropyltriethoxysilane) and titanium fluorozirconate can deposit on the surface of clean metal powder to form a layer of composite ceramic film under a certain pH value in a solution state, and the ceramic film has the characteristics of good oxidation resistance, corrosion resistance, high temperature resistance, wear resistance and the like, so that the oxidation resistance and the corrosion resistance of the metal pigment are greatly improved, and the good oxidation resistance and corrosion resistance effects can be still kept in the long-time storage and use process.

Preferably, the buffer in step (2) is a weakly basic amine buffer; as a further preferred aspect of the present invention, the buffer is one of ethylenediamine and diisopropylamine.

Preferably, the film-forming aid in the step (2) is molybdate; in a further preferred embodiment of the present invention, the film-forming aid is at least one of ammonium molybdate and sodium molybdate.

Preferably, the rust inhibitor in the step (2) is a borate rust inhibitor; in a further preferred embodiment of the present invention, the rust inhibitor is one of sodium borate and ammonium borate.

Preferably, the rotation speed of the stirring in the step (2) is 200-300 r/min, and the time is 5-10 min.

Preferably, the rotating speed of the stirrer in the spraying in the step (3) is 50-100 r/min, the spraying time is 5-15 min, and the standing time is 1-2 h.

Preferably, the filtration mode in the step (3) is one of sedimentation, suction filtration and filter pressing; in a further preferred embodiment of the present invention, the filtration is suction filtration.

Finally, the metal pigment with the surface coated with the composite ceramic membrane, the carrier resin, the dispersing agent and the coupling agent are blended and then extruded and granulated by a double-screw extruder, so that the obtained antioxidant metal-like plastic master batch has excellent antioxidant and corrosion resistance, and can be stored and used for a long time to keep good metal luster and texture.

Preferably, the carrier resin in step (4) is at least one of atactic polypropylene (APP), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Chlorinated Polyethylene (CPE), ethylene-vinyl acetate copolymer (EVA) and polyvinyl chloride (PVC); as a further preference of the present invention, the carrier resin is Low Density Polyethylene (LDPE).

Preferably, the dispersant in step (4) is one of polyethylene wax and stearic acid; as a further preferred aspect of the present invention, the dispersant is polyethylene wax.

In the present invention, the coupling agent in step (4) is preferably one of a silane coupling agent and an aluminate coupling agent.

As a preferable mode of the present invention, the screw extruder in the step (4) is a 38-type co-rotating twin-screw extruder.

The antioxidant metal-like plastic master batch prepared by the method has excellent antioxidant and corrosion resistance. Through the test, the prepared metal-like plastic master batch has no corrosion points on the surface and has good metal luster after the corrosion resistance test.

The invention provides an antioxidant metal-like plastic master batch and a preparation method thereof, wherein metal pigment powder and a cleaning agent solution are mixed and added into an ultrasonic dispersion machine, and after foreign matters and grease on the surface of the metal powder are removed by ultrasonic cleaning, the metal pigment powder after cleaning is obtained by water; adding water into a normal-temperature reaction tank, sequentially adding titanium fluozirconate, gamma-aminopropyl triethoxysilane, a buffering agent, a film-forming auxiliary agent and an antirust agent, and stirring to obtain a coating solution; putting the cleaned metal pigment powder into a stirrer, uniformly spraying the coating solution on the surface of the metal pigment, standing after spraying, washing, filtering and drying the metal pigment powder after water is volatilized to obtain the antioxidant metal pigment; and (3) uniformly mixing the carrier resin with the dispersing agent and the coupling agent, adding the obtained antioxidant metal pigment for mixing and melting, and finally extruding and granulating by using a double-screw extruder.

The invention provides an antioxidant metal-like plastic master batch and a preparation method thereof, and compared with the prior art, the antioxidant metal-like plastic master batch has the outstanding characteristics and excellent effects that:

1. provides a method for preparing the antioxidant metal-like plastic master batch by coating metal pigment with a composite ceramic membrane.

2. The composite ceramic membrane is coated on the surface of the metal pigment powder after the surface of the metal pigment powder is cleaned, so that the oxidation resistance and the corrosion resistance of the metal pigment powder are obviously improved, and the further prepared metal-like plastic master batch and the metal-like plastic can be used under the conditions of high temperature, acidity or alkalinity, and the good metal luster and texture of the metal-like plastic can be kept in the long-time storage and use process.

3. The preparation method is simple in preparation process, convenient to operate and has excellent application and popularization prospects.

Drawings

FIG. 1 shows the results of corrosion resistance tests on the metal-like plastic master batch obtained in example 6 of the present invention.

FIG. 2 shows the effect of the metal-like plastic master batch obtained in comparative example 1 after corrosion resistance test.

FIG. 3 shows the effect of the corrosion resistance test of the metal-like plastic master batch obtained in comparative example 2.

FIG. 4 shows the effect of the metal-like plastic master batch obtained in comparative example 3 after corrosion resistance test.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.