阅读说明：本技术 一种易清洁免喷涂聚丙烯材料及其制备方法 (Easy-to-clean spray-free polypropylene material and preparation method thereof ) 是由 蔡雄 韩春春 李白羽 于 2019-12-06 设计创作，主要内容包括：本发明提供了一种易清洁免喷涂聚丙烯材料及其制备方法,所述易清洁免喷涂聚丙烯材料由包括以下重量份的原料制备而成：低粘度聚丙烯树脂70-90份；高粘度聚丙烯树脂10-30份；所述低粘度聚丙烯树脂与所述高粘度聚丙烯树脂的重量份总和为100份；抗氧剂0.5-1份；润滑剂0.5-1份；易清洁-金属色粉母粒1-5份。将低粘度聚丙烯树脂、高粘度聚丙烯树脂、抗氧剂、润滑剂使用高速搅拌机混合,通过主喂料加入双螺杆挤出机；易清洁-金属色粉母粒通过侧喂料加入双螺杆挤出机,然后熔融挤出造粒,即得。上述易清洁免喷涂聚丙烯材料具有优异的力学性能、加工性能和易清洁能力,可应用于汽车外饰、空调装饰条、小家电外部装饰结构等汽车与家电领域。(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.)

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.

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.