Self-cleaning coated co-extruded functional materials, methods for their preparation and coated co-extruded shaped bodies

Abstract

The present application provides a kind of self-cleaning coated co-extrusion functional material, its preparation method and coated co-extrusion molding body.Self-cleaning coated co-extrusion functional material includes polyolefin and surface modified polyorganosiloxane spherulitic microparticle, surface modified polyorganosiloxane spherulitic microparticle has hydrophobic and oleophobic performance, so that coated co-extrusion functional material can effectively resist hydrophilic or lipophilic substance and dust, ice and snow and other pollution, and has high heat resistance, wear resistance, scratch resistance and other properties.The self-cleaning coated co-extrusion functional material is coated with the coated material and is integrally formed by co-extrusion, and a self-cleaning protective layer is constructed on the surface of the coated material.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coated co-extrusion materials, and particularly relates to a self-cleaning coated co-extrusion functional material, a preparation method thereof and a coated co-extrusion molded body. BACKGROUND

[0002] Coated co-extrusion integrated molding is a commonly used material forming process, which can directly form a coated protective layer on the surface of the coated material. Exploring a coated co-extrusion functional material with self-cleaning, high heat resistance, wear resistance, scratch resistance and other properties to effectively protect the coated material has always been a research hotspot for researchers in the field.

[0003] For example, wood-plastic profiles combine the renewable biomass resources and the processable forming characteristics of polymer materials, can make full use of waste biomass while reducing the use of non-degradable petroleum-based plastics, are a low-carbon, green and recyclable material with excellent mechanical properties, environmental adaptability, surface properties, rapid assembly and other characteristics, and have been widely used in building, furniture, vehicles, packaging, transportation and other fields. However, the traditional wood-plastic profiles have common problems such as easy water absorption deformation, easy aging and discoloration, easy pollution and mildew, poor wear and scratch resistance, and cannot meet the new requirements. At present, high molecular materials and wood-plastic profiles are usually used for coated co-extrusion integrated molding to build a coated functional protective layer on the surface of the wood-plastic profile, which can improve its moisture resistance, wear resistance and aging resistance. However, the existing coating layer is still susceptible to pollution by sewage, oil stains, dust and mold, and is prone to wear, scratching and peeling at high temperatures, which greatly limits the application range of wood-plastic profiles in some special engineering fields. SUMMARY

[0004] In view of the above technical status, the present application aims to provide a self-cleaning coated co-extrusion functional material with self-cleaning, high heat resistance, wear resistance and other properties.

[0005] The technical solution adopted by the present application to achieve the above technical purpose is as follows: a self-cleaning coated co-extrusion functional material, comprising polyolefin and surface-modified polyorganosiloxane spherulitic microparticles, wherein the polyolefin accounts for 30% to 75% and the surface-modified polyorganosiloxane spherulitic microparticles account for 5% to 35% according to the mass percentage.

[0006] The preparation method of the surface-modified polyorganosiloxane spherulitic microparticles comprises the following steps:

[0007] (1) adding polyorganosilsesquioxane spherical microparticles, deionized water and a catalyst into a container and stirring under heating to hydrolyze the polyorganosilsesquioxane molecular chains on the surface of the polyorganosilsesquioxane spherical microparticles and simultaneously convert part of the silicon-oxygen bonds on the surface of the polyorganosilsesquioxane spherical microparticles into silicon hydroxyl groups, and then cooling to room temperature; the catalyst is a binary catalytic system of a ruthenium complex with a tertiary phosphorus ligand and a basic compound;

[0008] (2) adding a perfluoroalkylsilazane solution into the container and stirring under heating to make the perfluoroalkylsilazane react with the silicon hydroxyl groups and graft fluorine-containing alkyl siloxane onto the surface of the polyorganosilsesquioxane particles, and then removing the solvent by heating under nitrogen.

[0009] The polyorganosilsesquioxane spherical microparticles can be unmodified polyorganosilsesquioxane spherical microparticles such as polymethylsilsesquioxane spherical microparticles, etc., or modified polyorganosilsesquioxane spherical microparticles such as polyorganosilsesquioxane spherical microparticles containing vinyl groups, epoxy groups, methacryloxy groups, aminoalkyl groups, phenyl groups, etc.

[0010] Preferably, in step (1), the average particle size of the polyorganosilsesquioxane spherical microparticles is 0.1-30 μm.

[0011] Preferably, in step (1), the mass of the deionized water is 0.1%-5% of the mass of the polyorganosilsesquioxane spherical microparticles, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, etc., preferably 0.1%-1%.

[0012] Preferably, in step (1), the mass of the catalyst is 0.01%-0.1% of the mass of the polyorganosilsesquioxane spherical microparticles, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, etc., preferably 0.01%-0.05%.

[0013] Preferably, in step (1), the hydrolysis reaction temperature is 40-90°C, further preferably 50-70°C.

[0014] Preferably, in step (1), the hydrolysis reaction time is 2h-16h, further preferably 8h-12h.

[0015] Preferably, in step (1), the stirring speed is 120-600 rpm, further preferably 240-480 rpm.

[0016] The catalyst is a mixed catalyst of a tertiary phosphine ligand ruthenium complex and a basic compound. As a preference, the ruthenium complex contains a tertiary phosphine ligand, including but not limited to one or several of tricarbonylbis(triphenylphosphine) ruthenium, dichlorotris(triphenylphosphine) ruthenium, hydridochlorotris(triphenylphosphine) ruthenium, dihydrotetrakis(triphenylphosphine) ruthenium, ethylenetris(triphenylphosphine) ruthenium.

[0017] As a preference, the basic compound includes but is not limited to one or several of alkali metal hydroxides, aqueous ammonia, urea, pyridine, alkyl amines.

[0018] In the step (2), the perfluoroalkylsilazane solution is a solution of perfluoroalkylsilazane mixed with a solvent, where the solvent plays a dilution role and no chemical reaction occurs between the two. The solvent includes but is not limited to hexafluorobenzene.

[0019] As a preference, in the step (2), the mass percentage concentration of the perfluoroalkylsilazane solution is 1% to 5%.

[0020] As a preference, in the step (2), the number of carbon atoms of the perfluoroalkylsilazane is 3 to 15.

[0021] As a preference, in the step (2), the mass of the perfluoroalkylsilazane is 0.1% to 5% of the mass of the polyorganosilsesquioxane spherical microparticles, such as 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, and the like, and further preferably 0.5% to 3%.

[0022] As a preference, in the step (2), the reaction time is 12 h to 48 h, and further preferably 16 h to 30 h.

[0023] As a preference, in the step (2), the stirring speed is 120 to 600 rpm, and further preferably 240 to 480 rpm.

[0024] As a preference, in the step (2), when the solvent is hexafluorobenzene, the heating temperature is 60 to 200 °C, and further preferably 80 to 120 °C.

[0025] In the step (2), the perfluoroalkylsilazane reacts with the silicon hydroxyl group to generate small molecule ammonia, and in the process of purging nitrogen and removing the solvent by heating, as a preference, the reaction byproduct ammonia is also removed.

[0026] In the step (2), if there is residual perfluoroalkylsilazane after the reaction, as a preference, the following step (3) is further included:

[0027] (3) adding deionized water into the container and stirring under seal, the deionized water reacts with the residual perfluoroalkylsilazane to form fluorosiloxane and ammonia, and the surface modification of the polyorganosilsesquioxane is terminated; after the reaction is completed, cooling to room temperature.

[0028] As a preference, in the step (3), the reaction temperature is 30-90°C, and further preferably 50-70°C.

[0029] As a preference, in the step (3), the reaction time is 2h-18h, and further preferably 8h-14h.

[0030] As a preference, in the step (3), the stirring speed is 120-600rpm, and further preferably 240-480rpm.

[0031] As a preference, in the step (3), the mass of the deionized water added is 0.2%-2% of the mass of the polyorganosilsesquioxane.

[0032] In the step (3), if residual moisture remains after the reaction is completed, as a preference, the following step (4) is further included:

[0033] (4) adding methyl disilazane into the container and stirring under seal at room temperature, the methyl disilazane reacts with the unreacted water in the system to further remove the residual moisture in the reaction system; after the reaction is completed, nitrogen is introduced and the methyl disilazane is removed by heating.

[0034] As a preference, in the step (4), during the process of introducing nitrogen and removing the methyl disilazane by heating, the reaction byproduct ammonia is also removed.

[0035] As a preference, in the step (4), the heating temperature is 60-200°C.

[0036] As a preference, in the step (4), the reaction time is 12h-36h.

[0037] As a preference, in the step (4), the stirring speed is 240-480rpm.

[0038] As a preference, in the step (4), the methyl disilazane includes but is not limited to one or more of dimethyl disilazane, tetramethyl disilazane, and hexamethyl disilazane.

[0039] As a preference, in the step (4), the mass of the methyl disilazane is 0.2%-2% of the mass of the polyorganosilsesquioxane.

[0040] The polyolefin includes, but is not limited to, polyethylene, polypropylene, ethylene-propylene copolymer, polybutylene, polystyrene, styrene-butadiene copolymer, chlorinated polyethylene, or a mixed material of two or more of them.

[0041] The polyorganosilsesquioxane spherical microparticle surface is smooth and has no reactivity, the present application makes the polyorganosilsesquioxane spherical microparticle surface polyorganosilsesquioxane molecular chain partially hydrolyze by using a specific catalyst, constructs a rough micro-nano structure similar to chemical etching on the surface, and significantly improves the roughness of the polyorganosilsesquioxane spherical microparticle; at the same time, the process also converts part of the silicon-oxygen bond on the surface of the polyorganosilsesquioxane spherical microparticle into silicon hydroxyl, and the silicon hydroxyl reacts with perfluoroalkylsilazane to graft fluorine-containing alkyl siloxane to the surface of the polyorganosilsesquioxane particle, realizing the surface modification of the polyorganosilsesquioxane spherical microparticle, and making the surface have hydrophobic, oleophobic fluorine-containing groups, so that the modified polyorganosilsesquioxane spherical microparticle has super-hydrophobic and super-oleophobic properties, anti-icing properties, and the sheet material formed by hot pressing has a water contact angle and an oil contact angle of more than 150°, that is, the micro-nano rough structure surface has self-cleaning properties for hydrophilic and oleophilic pollutants, and can effectively resist hydrophilic or oleophilic substances and dust, ice and snow pollution. And because the fluorine-containing group has low surface energy, it will not have obvious interaction with polar and non-polar solvents or solutions such as water, alcohol, ketone, ester and alkane, and there will be no obvious interaction between microparticles, so the modified polyorganosilsesquioxane spherical microparticle will not agglomerate in polar and non-polar solvents or solutions such as water, alcohol, ketone, ester and alkane, and will float on the liquid surface without sinking, having good dispersibility and compatibility, and can be widely used in the fields of resins and coatings. In addition, after the surface of the polyorganosilsesquioxane spherical microparticle is modified, the surface is grafted with fluorine-containing siloxane components, the presence of the fluorine-containing components can increase the high-temperature resistance and organic solvent resistance of the microparticle, and the introduction of fluorine also helps to improve the thermal stability of the microparticle, that is, the heat resistance is increased. Therefore, the hydrophobic and oleophobic polyorganosilsesquioxane spherical microparticle also has excellent high-temperature resistance, lubricity, organic solvent resistance and other properties, and it does not melt at a high temperature of 900℃, can be converted into ceramic microparticles, and has high flame retardance and fire resistance, and can be applied to various extreme harsh application fields. Considering the preparation process, the preparation process of the hydrophobic and oleophobic polyorganosilsesquioxane spherical microparticle is mild, simple and easy to implement, and can realize large-scale and efficient preparation.

[0042] Therefore, the present application includes polyolefin and the surface modified polyorganosilsesquioxane spherical microparticle in the coated co-extrusion functional material, and has the following beneficial effects:

[0043] (1) The surface-modified polyorganosilsesquioxane spherical microparticles endow the coated co-extrusion functional material with self-cleaning, anti-pollution, and anti-icing properties, which can effectively resist hydrophilic or oleophilic substances and dust, ice, and snow pollution, and the coated co-extrusion functional material has a contact angle with water and oil higher than 150°; without adding an antifungal agent, the growth and reproduction of microorganisms can also be inhibited, and the coated co-extrusion functional material has high antifungal and antibacterial properties.

[0044] (2) The surface-modified polyorganosilsesquioxane spherical microparticles have high lubricity and reinforcing properties, which can significantly improve the resistance of the coated co-extrusion functional material to external forces such as wear, scratching, and impact, and greatly extend the service life of the coated material.

[0045] As a preference, the self-cleaning coated co-extrusion functional material further comprises an ultraviolet absorber for improving the ultraviolet aging resistance of the self-cleaning coated co-extrusion functional material. As a preference, the ultraviolet absorber accounts for 0.5% to 10%. The ultraviolet absorber includes, but is not limited to, one or more than two mixed materials of salicylate, benzophenone, benzotriazole, etc.

[0046] As a preference, the self-cleaning coated co-extrusion functional material further comprises an inorganic filler for increasing the mechanical rigidity and bending strength of the self-cleaning coated co-extrusion functional material. As a preference, the inorganic filler accounts for 1% to 10%. The inorganic filler includes, but is not limited to, one or more than two mixed materials of calcium carbonate, talc, white carbon black, clay, montmorillonite, mica, etc.

[0047] As a preference, the self-cleaning coated co-extrusion functional material further comprises toner for endowing the self-cleaning coated co-extrusion functional material with a specific color. As a preference, the toner accounts for 0.2% to 1.5%. The toner includes, but is not limited to, one or more than two mixed materials of iron oxide toner, magnetite toner, titanium oxide toner, carbon black toner, zinc oxide toner, lithopone toner, etc.

[0048] (3) The self-cleaning coated co-extrusion functional material of the present application can be coated and co-extruded integrally with the coated material to form a protective layer on the surface of the coated material (the coated material as the core layer and the self-cleaning coated co-extrusion functional material as the coating layer). For example, the coated material can be a wood-plastic profile, i.e., the wood-plastic profile is coated and co-extruded integrally to form a molded body, and a protective layer is formed on the surface of the wood-plastic profile, the wood-plastic profile as the core layer and the self-cleaning coated co-extrusion functional material as the coating layer. At this time, as a preferred embodiment, the self-cleaning coated co-extrusion functional material further comprises an epoxy-based organosiloxane, the epoxy group on the epoxy-based organosiloxane can react with the hydroxyl group on the plant fibers such as wood powder in the wood-plastic profile, thereby enhancing the interfacial bonding force between the core layer and the coating layer of the wood-plastic profile and eliminating the adverse phenomena such as peeling, cracking and bubbling of the coating layer at high temperatures. As a preferred embodiment, the epoxy-based organosiloxane accounts for 0.5% to 7%.

[0049] The epoxy-based organosiloxane includes but is not limited to one or more than two kinds of mixed materials selected from the group consisting of (3-epoxypropoxy)trimethoxysilane, (3-epoxypropoxy)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane. As a preferred embodiment, the self-cleaning coated co-extrusion functional material further comprises an activator for increasing the reactivity of the epoxy-based organosiloxane. As a preferred embodiment, the activator accounts for 0.1% to 1.4%.

[0050] The present application further provides a preparation method of the self-cleaning coated co-extrusion functional material, comprising the following steps:

[0051] The polyolefin and the surface-modified polyorganosilsesquioxane spherical microparticles are added to a high-speed mixer, mixed uniformly, cooled to room temperature to obtain a premix; the premix is added to an extruder for mixing, extrusion, granulation and cooling to obtain the self-cleaning coated co-extrusion functional material.

[0052] When the self-cleaning coated co-extrusion functional material further comprises an epoxy-based organosiloxane, an activator, and one or more of an ultraviolet absorber, an inorganic filler and a toner, as a preferred embodiment, the following steps are included:

[0053] (1) The surface-modified polyorganosilsesquioxane spherical microparticles, the epoxy-based organosiloxane and the activator are added to a mixer, mixed uniformly, and cooled to room temperature;

[0054] As a preferred embodiment, in step (1), the mixing temperature is 80 to 200°C and the mixing time is 5 to 30 min.

[0055] (2) adding one or more of polyolefin, ultraviolet absorber, inorganic filler, and color powder into the high-speed mixer of step (1), mixing uniformly, cooling to room temperature, vacuuming, and obtaining a premix;

[0056] As preferred, in step (2), the mixing temperature is 60-120℃, and the mixing time is 5-30 min.

[0057] (3) adding the premix into an extruder for mixing, extruding, granulating, cooling, and obtaining a self-cleaning coated co-extrusion functional material for wood-plastic profiles.

[0058] As preferred, the extruder is a parallel double-screw extruder, and the screw is preferably a combined double screw, and the length-diameter ratio is preferably 16-30.

[0059] As preferred, the barrel temperature of the parallel double-screw extruder is 165-185℃, and the screw rotation speed is 80-180 r / min.

[0060] As preferred, the extrusion die diameter of the parallel double-screw extruder is 1-4 mm. BRIEF DESCRIPTION OF DRAWINGS

[0061] Figure 1 is a scanning electron microscope morphology diagram of the surface-modified polymethylsilsesquioxane spherical microparticles prepared in Example 1 of the present application.

[0062] Figure 2 is a result diagram when a sheet sample of the surface-modified polymethylsilsesquioxane spherical microparticles prepared in Example 1 of the present application is subjected to water and oil contact angle tests.

[0063] Figure 3 is an atomic force microscope photo of the self-cleaning coated co-extrusion functional sheet material in Example 1 of the present application.

[0064] Figure 4 is a result diagram when the self-cleaning coated co-extrusion functional sheet material in Example 1 of the present application is subjected to water and oil contact angle tests.

[0065] Figure 5 is a scanning electron microscope morphology diagram of the surface-modified polymethylsilsesquioxane spherical microparticles prepared in Example 2 of the present application.

[0066] Figure 6 is a result diagram when a sheet sample of the surface-modified polymethylsilsesquioxane spherical microparticles prepared in Example 2 of the present application is subjected to water and oil contact angle tests.

[0067] Figure 7 is an atomic force microscope photo of the self-cleaning coated co-extrusion functional sheet material in Example 2 of the present application.

[0068] Figure 8 is the result graph when the self-cleaning coated co-extrusion functional sheet in embodiment 2 is tested for water, oil contact angle. DETAILED DESCRIPTION

[0069] The application will be further described in conjunction with the following examples. It should be noted that the following examples are intended to facilitate the understanding of the application and do not limit the application in any way.

[0070] Example 1:

[0071] The self-cleaning coated co-extrusion functional material consists of the following components by mass percentage:

[0072] High-density polyethylene 45%

[0073] Homopolypropylene 25%

[0074] Surface-modified polyorganosilsesquioxane spherical microparticles 20%

[0075] (3-glycidoxypropyl)trimethoxysilane 2.4%

[0076] Zirconium acetylacetonate 0.8%

[0077] Nano calcium carbonate 3.2%

[0078] Benzophenone ultraviolet absorber 2.8%

[0079] Iron oxide color powder 0.8%.

[0080] The preparation method of the surface-modified polyorganosilsesquioxane spherical microparticles is as follows:

[0081] (1) 300 g of polymethylsilsesquioxane spherical microparticles with an average diameter of 0.27 μm, 1.5 g of deionized water, 0.110 g of tricarbonylbis(triphenyl) ruthenium, and 0.093 g of pyridine were added to a planetary stirrer with a volume of 3 L, and stirred at a stirring speed of 400 rpm and a heating temperature of 60°C for 10 h in a closed state. After the reaction was completed, it was cooled to room temperature.

[0082] (2) 100 g of a hexafluoroxylene solution of perfluorooctylsilazane was added to the star-shaped stirrer, and the mass fraction of perfluorooctylsilazane in the hexafluoroxylene solution was 3%. The solution was stirred at room temperature for 24 h in a closed state, and then nitrogen was introduced and heated to 120°C to remove hexafluoroxylene and the reaction byproduct ammonia.

[0083] (3) 1.5 g of deionized water was added to the star-shaped stirrer, and stirred at 60°C for 10 h in a closed state, and then cooled to room temperature.

[0084] (4) Add 3 g of hexamethyldisilazane into the star-shaped stirrer, stir for 24 h at room temperature in a closed state, then remove the methyl disilazane and reaction by-product ammonia by passing nitrogen and heating to 120°C to obtain the surface-modified polymethylsilsesquioxane spherical microparticle powder.

[0085] The morphology of the surface-modified polymethylsilsesquioxane spherical microparticles prepared above under a scanning electron microscope is shown in Figure 1

[0086] The surface-modified polymethylsilsesquioxane spherical microparticles prepared above do not agglomerate in polar and non-polar solvents or solutions such as water, alcohols, ketones, esters, and alkanes, and can float on the liquid surface without sinking. For example, by dispersibility analysis by a carbon black dispersing instrument, the dispersibility of the polymethylsilsesquioxane spherical microparticles in step (1) above is grade 3-4, while the dispersibility of the surface-modified polymethylsilsesquioxane spherical microparticles prepared in step (4) in polyolefin reaches grade 10, indicating that the surface-modified polymethylsilsesquioxane spherical microparticles have excellent dispersibility.

[0087] The surface-modified polymethylsilsesquioxane spherical microparticles prepared above are subjected to high-temperature hot pressing to prepare a sheet-shaped sample, and then subjected to water, oil contact angle and rolling angle tests, and the results are shown in Figure 2 The water contact angle of the sheet-shaped sample is 156.2°, the water rolling angle is 4.2°, the water hysteresis angle is 3.8°, the oil contact angle is 153.4°, the oil rolling angle is 4.9°, and the oil hysteresis angle is 4.1°, showing excellent superhydrophobic and superoleophobic properties.

[0088] The preparation method of the self-cleaning coated co-extrusion functional material includes the following steps:

[0089] (1) Add the surface-modified polyorganosilsesquioxane spherical microparticles, (3- glycidoxypropyl) trimethoxysilane, and zirconium acetylacetonate according to the mass percentages of the components above into a high-speed mixer, mix at 175°C for 20 min, and cool to room temperature.

[0090] (2) Add high-density polyethylene, nano calcium carbonate, benzophenone ultraviolet absorber, and iron oxide color powder according to the mass percentages of the components above into the high-speed mixer in step (1), mix at 105°C for 20 min, cool to room temperature, and vacuum exhaust to obtain a premix.

[0091] (3) Add the uniformly mixed premix into a parallel twin-screw extruder with a length-diameter ratio of 25:1 and a die diameter of 1.5 mm, set the extruder processing temperature to 175°C and the screw rotation speed to 90 r / min, and mix, extrude, pelletize, and cool to obtain the self-cleaning coated co-extrusion functional material.

[0092] ​The self-cleaning coated co-extrusion functional material prepared above was melt-extruded to prepare a sheet with a thickness of 2 mm, and various performance tests were performed on the sheet, and the specific results are as follows:

[0093]

[0094]

[0095] The surface atomic force microscope of the sheet showed a coarse and rough micro-nano structure, and the surface roughness thereof was measured to be 18.1 μm, as shown in Figure 3 The water and oil contact angle and rolling angle tests were performed on the sheet, and the results are shown in Figure 4 The water contact angle was 152.3°, the water rolling angle was 6.4°, the oil contact angle was 151.1°, and the water rolling angle was 7.7°, indicating that the surface of the material exhibited super-hydrophobic and super-oleophobic properties, and could have excellent resistance to pollution by sewage, oil stains, dust, mold, and the like.

[0096] The self-cleaning coated co-extrusion functional material prepared above was used as a protective coating layer for a wood-plastic profile. That is, the wood-plastic profile was used as a core layer, and the self-cleaning coated co-extrusion functional material was used as a coating layer, and the core layer and the coating layer were integrally formed by co-extrusion, so that a coating layer was formed around the core layer. The coating layer had excellent resistance to pollution by sewage, oil stains, dust, mold, and the like, and had high heat resistance, wear resistance, scratch resistance, and the like. The wood-plastic profile with the self-cleaning coated co-extrusion functional material as the coating layer was subjected to a 96-hour boiling water cooking test, and no peeling or peeling phenomenon occurred; a freeze-thaw test was performed in accordance with ASTM D7032, and no peeling or peeling phenomenon occurred after 60 cycles, that is, the coating layer and the core layer had good bonding force.

[0097] Example 2:

[0098] The self-cleaning coated co-extrusion functional material consisted of the following components by mass percentage:

[0099] Co-polypropylene 55%

[0100] High-density polyethylene 10%

[0101] Surface-modified polyorganosilsesquioxane spherical microparticles 25.5%

[0102] 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane 2%

[0103] Citric acid 0.2%

[0104] White carbon black 5%

[0105] Salicylate ultraviolet absorber 1.5%

[0106] Titanium oxide color powder 0.8%.

[0107] The preparation method of the surface-modified polyorganosilsesquioxane spherical microparticles is as follows:

[0108] (1) 200 g of polyphenylsilsesquioxane spherical microparticles with an average diameter of 0.25 μm, 1 g of deionized water, 0.084 g of hydrogen chloro tris (triphenyl phosphorus) ruthenium, and 0.037 g of potassium hydroxide were added to a planetary stirrer with a volume of 1 L, and stirred at a stirring speed of 200 rpm and a heating temperature of 70 °C for 10 h in a closed state. After the reaction was completed, the temperature was cooled to room temperature.

[0109] (2) 70 g of a hexafluoroxylene solution of perfluorooctylsilazane was added to the planetary stirrer, and the mass fraction of perfluorooctylsilazane in the hexafluoroxylene solution was 2.6%. The solution was stirred at room temperature in a closed state for 19 h, and then nitrogen was introduced and heated to 130 °C to remove hexafluoroxylene and its reaction byproduct ammonia.

[0110] (3) 1 g of deionized water was added to the planetary stirrer, and stirred at 50 °C in a closed state for 12 h, and then cooled to room temperature.

[0111] (4) 2 g of hexamethyldisilazane was added to the planetary stirrer, and stirred at room temperature in a closed state for 20 h, and then nitrogen was introduced and heated to 130 °C to remove hexamethyldisilazane and its reaction byproduct ammonia, thereby obtaining a surface-modified polyphenylsilsesquioxane spherical microparticle powder.

[0112] The appearance of the surface-modified polymethylsilsesquioxane spherical microparticles prepared above under a scanning electron microscope is shown in FIG. 1. Figure 5

[0113] The surface-modified polyphenylsilsesquioxane spherical microparticles prepared above do not agglomerate in polar and non-polar solvents or solutions such as water, alcohols, ketones, esters, and alkanes, and can float on the liquid surface without sinking. For example, dispersibility analysis was performed by a carbon black dispersing instrument, and the dispersibility of the polymethylsilsesquioxane spherical microparticles in step (1) above was 3-4 levels, and the dispersibility of the surface-modified polymethylsilsesquioxane spherical microparticles prepared in step (4) in polyolefin reached 10 levels, indicating that the surface-modified polymethylsilsesquioxane spherical microparticles have excellent dispersibility.

[0114] The surface-modified polyphenylsilsesquioxane spherical microparticles prepared above were subjected to high-temperature hot pressing to prepare a sheet-shaped sample, and then water, oil contact angle, and rolling angle tests were performed, and the results are shown in FIG. 2. The water contact angle of the sheet-shaped sample was 155.3°, the water rolling angle was 4.1°, the water hysteresis angle was 3.9°, the oil contact angle was 153.8°, the oil rolling angle was 4.5°, and the oil hysteresis angle was 3.9°, showing excellent superhydrophobic and superoleophobic properties. Figure 6

[0115] The preparation method of the self-cleaning coated co-extrusion functional material includes the following steps:​​

[0116] (1) Add the surface-modified polysiloxane spherical microparticles, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and citric acid to a high-speed mixer according to the above-mentioned mass percentages of each component, mix at 155°C for 25 min, and cool to room temperature.

[0117] (2) Add copolymer polypropylene, high-density polyethylene, silica, salicylate UV absorber and titanium dioxide pigment to the high-speed mixer in step (1) according to the above component mass percentages, mix at 105°C for 25 min, cool to room temperature, and vacuum exhaust to obtain the premix.

[0118] (3) The uniformly mixed premix was added to a parallel twin-screw extruder with a length-to-diameter ratio of 30:1 and a die diameter of 1.2 mm. The extruder processing temperature was set to 185℃ and the screw speed to 80 r / min. The mixture was then compounded, extruded, granulated, and cooled to obtain a self-cleaning co-extruded functional material for polypropylene wood-plastic profiles.

[0119] The self-cleaning coated co-extruded functional material prepared above was melt-extruded to obtain a sheet with a thickness of 1.5 mm. Various performance tests were conducted on the sheet, and the specific results are as follows:

[0120]

[0121] The surface atomic force microscope of this self-cleaning co-extruded functional sheet is as follows: Figure 7 As shown, the sheet exhibits a rough micro / nano structure, with a measured surface roughness of 19.2 μm. Water and oil contact angles and roll-off angles were tested on the sheet, and the results are as follows... Figure 8 As shown, the water contact angle is 153.3° and the water roll-off angle is 5.3°, while the oil contact angle is 150.9° and the oil roll-off angle is 6.3°. This indicates that the material surface exhibits superhydrophobic and superoleophobic properties and has excellent resistance to contamination from sewage, oil, dust, mold, and other pollutants.

[0122] The self-cleaning co-extruded functional material prepared above is used as a protective coating layer for wood-plastic composite profiles. Specifically, the wood-plastic composite profile serves as the core layer, and the self-cleaning co-extruded functional material serves as the coating layer. Through co-extrusion molding, a coating layer is formed around the core layer. This coating layer exhibits excellent resistance to contamination from sewage, oil, dust, and mold, as well as high heat resistance, wear resistance, and scratch resistance. Furthermore, there is good adhesion between the coating layer and the core layer. Wood-plastic composite profiles with this self-cleaning co-extruded functional material as the coating layer underwent a 96-hour boiling water test, showing no peeling or flaking. A freeze-thaw test according to ASTM D7032 was conducted, and no peeling or flaking was observed after 60 cycles, indicating good adhesion between the coating layer and the core layer.

[0123] Example 3:

[0124] The present embodiment is basically the same as Embodiment 1, except that in the step (1) of the preparation method of the surface-modified polyorganosilsesquioxane spherical microparticles, dichlorotris(triphenylphosphine) ruthenium is used instead of tricarbonylbis(triphenyl) ruthenium, and alkylamine is used instead of pyridine, and the amount of deionized water added is 3 g.

[0125] The surface-modified polymethylsilsesquioxane spherical microparticles prepared in the present embodiment do not agglomerate in polar and non-polar solvents or solutions such as water, alcohols, ketones, esters, and alkanes, and can float on the liquid surface without sinking. The surface-modified polymethylsilsesquioxane spherical microparticles prepared are subjected to high-temperature hot pressing to prepare a sheet-shaped sample, and then water and oil contact angle and rolling angle tests are performed, and the water and oil contact angles are both higher than 150°.

[0126] The self-cleaning coated co-extrusion functional material prepared in the present embodiment has a sheet prepared by melt extrusion, and the water and oil contact angles are both higher than 150°.

[0127] Embodiment 4:

[0128] The present embodiment is basically the same as Embodiment 2, except that in the step (1) of the preparation method of the surface-modified polyorganosilsesquioxane spherical microparticles, dihydrogen tetrakis(triphenylphosphine) ruthenium is used instead of dichlorotris(triphenylphosphine) ruthenium, and ammonia is used instead of potassium hydroxide.

[0129] The surface-modified polymethylsilsesquioxane spherical microparticles prepared in the present embodiment do not agglomerate in polar and non-polar solvents or solutions such as water, alcohols, ketones, esters, and alkanes, and can float on the liquid surface without sinking. The surface-modified polymethylsilsesquioxane spherical microparticles prepared are subjected to high-temperature hot pressing to prepare a sheet-shaped sample, and then water and oil contact angle and rolling angle tests are performed, and the water and oil contact angles are both higher than 150°.

[0130] The self-cleaning coated co-extrusion functional material prepared in the present embodiment has a sheet prepared by melt extrusion, and the water and oil contact angles are both higher than 150°.

[0131] Embodiment 5:

[0132] The present embodiment is basically the same as Embodiment 1, except that in the step (1) of the preparation method of the surface-modified polyorganosilsesquioxane spherical microparticles, ethylene tris(triphenylphosphine) ruthenium is used instead of tricarbonylbis(triphenyl) ruthenium, and urea is used instead of pyridine.

[0133] The surface-modified polymethylsilsesquioxane spherical microparticles prepared by the embodiment do not agglomerate in polar and non-polar solvents or solutions such as water, alcohols, ketones, esters, and alkanes, and can float on the liquid surface without sinking. The surface-modified polymethylsilsesquioxane spherical microparticles prepared are subjected to high-temperature hot pressing to prepare a sheet-shaped sample, and then subjected to water / oil contact angle and rolling angle tests, and the water / oil contact angles are both higher than 150°.

[0134] The self-cleaning coated co-extrusion functional material prepared by the embodiment has a sheet prepared by melt extrusion, and the water / oil contact angles are both higher than 150°.

[0135] The above embodiments are used to describe the technical solutions of the present application in detail, and it should be understood that the above description is only a specific embodiment of the present application and is not used to limit the present application. Any modification, supplement or similar replacement within the principle range of the present application should be included in the protection range of the present application.

Claims

1. A self-cleaning coated co-extruded functional material, characterized in that: It includes polyolefin and surface-modified polysiloxane spherical microparticles, wherein, by mass percentage, polyolefin accounts for 30% to 75% and surface-modified polysiloxane spherical microparticles account for 5% to 35%; The preparation method of the surface-modified polyorganosilicon silsesquioxane spherical microparticles includes the following steps: (1) Polyorganosilicon silsesquioxane spherical particles, deionized water and catalyst are added to a container and heated and stirred in a sealed manner to hydrolyze the polyorganosilicon silsesquioxane molecular chains on the surface of the polyorganosilicon silsesquioxane spherical particles, while some of the silicon-oxygen bonds on the surface of the polyorganosilicon silsesquioxane spherical particles are converted into silanol groups; then cooled to room temperature; the catalyst is a binary catalytic system of ruthenium complex with tertiary phosphorus coordination group and basic compound; (2) Add the perfluoroalkyl silazane solution to the container and stir in a closed manner at room temperature. The perfluoroalkyl silazane reacts with the silanol group to graft the fluoroalkyl siloxane onto the surface of the polyorganosilicon silsesquioxane particles. Then, nitrogen gas is introduced and heated to remove hexafluoroxylene. The sheet material formed by hot pressing the obtained polyorganosilicon silsesquioxane spherical microparticles has a contact angle of more than 150° with water and a contact angle of more than 150° with oil.

2. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: The polyolefins include one or more of polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, polystyrene, styrene-butadiene copolymer, and chlorinated polyethylene.

3. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: The polyorganosilicon silsesquioxane spherical particles are either unmodified polyorganosilicon silsesquioxane spherical particles or modified polyorganosilicon silsesquioxane spherical particles.

4. The self-cleaning co-extruded functional material as described in claim 3, characterized in that: Unmodified polyorganosilicon silsesquioxane spherical microparticles include polymethylsilsesquioxane spherical microparticles.

5. The self-cleaning co-extruded functional material as described in claim 3, characterized in that: The modified polyorganosilicon silsesquioxane spherical particles include polyorganosilicon silsesquioxane spherical particles containing one or more of vinyl, epoxy, methacryloxy, aminoalkyl, and phenyl groups.

6. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: The ruthenium complexes of the tertiary phosphorus ligands include one or more of tricarbonylbis(triphenyl)ruthenium, dichlorotri(triphenylphosphine)ruthenium, hydrochlorotri(triphenylphosphine)ruthenium, dihydrotetra(triphenylphosphine)ruthenium, and ethylenetri(triphenylphosphine)ruthenium.

7. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: Alkaline compounds include one or more of alkali metal hydroxides, ammonia, urea, pyridine, and alkylamines.

8. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: In step (1), the mass of deionized water is 0.1% to 5% of the mass of polyorganosilicon sesquioxane spherical particles.

9. The self-cleaning co-extruded functional material as described in claim 8, characterized in that: In step (1), the mass of deionized water is 0.1% to 1% of the mass of polyorganosilicon sesquioxane spherical particles.

10. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: In step (1), the mass of the catalyst is 0.01% to 0.1% of the mass of the polyorganosilicon silsesquioxane spherical particles.

11. The self-cleaning coated co-extruded functional material as described in claim 10, characterized in that: In step (1), the mass of the catalyst is 0.01% to 0.05% of the mass of the polyorganosilicon silsesquioxane spherical particles.

12. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: In step (1), the hydrolysis reaction temperature is 40~90℃.

13. The self-cleaning coated co-extruded functional material as described in claim 12, characterized in that: In step (1), the hydrolysis reaction temperature is 50~70℃.

14. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: In step (1), the hydrolysis reaction time is 2h~16h.

15. The self-cleaning coated co-extruded functional material as described in claim 14, characterized in that: In step (1), the hydrolysis reaction time is 8h~12h.

16. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: In step (1), the stirring speed is 120~600 rpm.

17. The self-cleaning coated co-extruded functional material as described in claim 16, characterized in that: In step (1), the stirring speed is 240~480 rpm.

18. The self-cleaning coated co-extruded functional material as described in claim 10, characterized in that: In step (1), the average particle size of the polyorganosilicon sesquioxane spherical microparticles is 0.1~30μm.

19. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: In step (2), the mass percentage concentration of the perfluorocarbon-based silazane solution is 1% to 5%.

20. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: In step (2), the solvent in the perfluorocarbon-based silazane solution is hexafluoroxylene.

21. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: In step (2), the number of carbon atoms in the perfluoroalkylsilazane is 3 to 15.

22. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: In step (2), the mass of the perfluorocarbon-based silazane is 0.1% to 5% of the mass of the polyorganosilicon spherical particles.

23. The self-cleaning coated co-extruded functional material as described in claim 22, characterized in that: In step (2), the mass of the perfluorocarbon silazane is 0.5% to 3% of the mass of the polyorganosilicon spherical particles.

24. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: In step (2), the reaction time is 12h~48h.

25. The self-cleaning coated co-extruded functional material as described in claim 24, characterized in that: In step (2), the reaction time is 16h~30h.

26. The self-cleaning co-extruded functional material as described in claim 1, characterized in that: In step (2), the stirring speed is 120~600 rpm.

27. The self-cleaning coated co-extruded functional material as described in claim 26, characterized in that: In step (2), the stirring speed is 240~480 rpm.

28. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: In step (2), when the solvent is hexafluoroxylene, the heating temperature is 60~200℃.

29. The self-cleaning coated co-extruded functional material as described in claim 28, characterized in that: The heating temperature is 80~120℃.

30. The self-cleaning coated co-extruded functional material as described in claim 1, characterized in that: If there is residual perfluoroalkylsilazane after the reaction in step (2), the following step (3) is also included: (3) Add deionized water to the container and stir in a closed container. The deionized water reacts with the remaining perfluoroalkyl silazane to form fluorosiloxane and ammonia, thereby terminating the surface modification of polyorganosilicon silsesquioxane. After the reaction is completed, cool to room temperature.

31. The self-cleaning coated co-extruded functional material as described in claim 30, characterized in that: In step (3), the reaction temperature is 30~90℃.

32. The self-cleaning coated co-extruded functional material as described in claim 31, characterized in that: In step (3), the reaction temperature is 50~70℃.

33. The self-cleaning coated co-extruded functional material as described in claim 30, characterized in that: In step (3), the reaction time is 2h to 18h.

34. The self-cleaning co-extruded functional material as described in claim 33, characterized in that: In step (3), the reaction time is 8h~14h.

35. The self-cleaning coated co-extruded functional material as described in claim 30, characterized in that: In step (3), the stirring speed is 120~600 rpm.

36. The self-cleaning coated co-extruded functional material as described in claim 35, characterized in that: In step (3), the stirring speed is 240~480 rpm.

37. The self-cleaning coated co-extruded functional material as described in claim 30, characterized in that: The mass of deionized water added in step (3) is 0.2% to 2% of the mass of polyorganosilicon sesquioxane.

38. The self-cleaning coated co-extruded functional material as described in claim 30, characterized in that: If residual water remains after the reaction in step (3), the following step (4) is also included: (4) Add methyldisilazane to a container and stir in a closed container at room temperature. Methyldisilazane reacts with unreacted water in the system to remove residual water in the reaction system. After the reaction is complete, nitrogen gas is introduced and heated to remove methyldisilazane.

39. The self-cleaning coated co-extruded functional material as described in claim 38, characterized in that: In step (4), the heating temperature is 60~200℃.

40. The self-cleaning coated co-extruded functional material as described in claim 38, characterized in that: In step (4), the reaction time is 12~36h.

41. The self-cleaning coated co-extruded functional material as described in claim 38, characterized in that: In step (4), the stirring speed is 240~480 rpm.

42. The self-cleaning coated co-extruded functional material as described in claim 38, characterized in that: In step (4), methyldisilazane includes one or more of dimethyldisilazane, tetramethyldisilazane, and hexamethyldisilazane.

43. The self-cleaning coated co-extruded functional material as described in claim 38, characterized in that: In step (4), during the process of introducing nitrogen gas and heating to remove methyldisilazane, the reaction byproduct ammonia is also removed.

44. The self-cleaning coated co-extruded functional material as described in claim 38, characterized in that: In step (4), the mass of methyldisilazane is 0.2% to 2% of the mass of polyorganosilicon sesquioxane.

45. The self-cleaning coated co-extruded functional material according to any one of claims 1 to 44, characterized in that: The self-cleaning co-extruded functional material also includes an ultraviolet absorber.

46. ​​The self-cleaning coated co-extruded functional material as described in claim 45, characterized in that: Ultraviolet absorbers account for 0.5% to 10%.

47. The self-cleaning coated co-extruded functional material as described in claim 45, characterized in that: Ultraviolet absorbers include one or more of salicylates, benzophenones, benzotriazoles, etc.

48. The self-cleaning coated co-extruded functional material according to any one of claims 1 to 44, characterized in that: The self-cleaning coated co-extruded functional material also includes inorganic fillers.

49. The self-cleaning coated co-extruded functional material as described in claim 48, characterized in that: The inorganic filler accounts for 1% to 10%.

50. The self-cleaning coated co-extruded functional material as described in claim 48, characterized in that: The inorganic filler includes one or more of the following: calcium carbonate, talc, silica, clay, montmorillonite, and mica.

51. The self-cleaning coated co-extruded functional material according to any one of claims 1 to 44, characterized in that: The self-cleaning co-extruded functional material also includes color powder.

52. The self-cleaning coated co-extruded functional material as described in claim 51, characterized in that: Pigment content is 0.2% to 1.5%.

53. The self-cleaning coated co-extruded functional material as described in claim 51, characterized in that: The color powder includes one or more of the following: iron oxide color powder, ferric oxide color powder, titanium dioxide color powder, carbon black powder, zinc oxide color powder, and zinc barium white powder.

54. The method for preparing the self-cleaning coated co-extruded functional material according to any one of claims 1 to 44, characterized in that: Polyolefin and surface-modified polysiloxane spherical particles are added to a high-speed mixer, mixed evenly, and cooled to room temperature to obtain a premix. The premix is ​​then added to an extruder for kneading, extrusion, granulation, and cooling to obtain a self-cleaning coated co-extruded functional material.

55. The preparation method according to claim 54, characterized in that: When the self-cleaning co-extruded functional material further includes epoxy-based organosiloxanes, activators, and one or more of ultraviolet absorbers, inorganic fillers, and colorants, the following steps are included: (1) Add the surface-modified polysilicon silsesquioxane spherical particles, epoxy organosiloxane, and activator to a mixer, mix evenly, and cool to room temperature; (2) Add one or more of the following to the high-speed mixer in step (1): polyolefin, ultraviolet absorber, inorganic filler, and color powder, mix evenly, cool to room temperature, and exhaust under vacuum to obtain a premix; (3) The premix is ​​added to the extruder for mixing, extrusion, granulation and cooling to obtain a self-cleaning co-extruded functional material for wood-plastic profiles.

56. The preparation method according to claim 55, characterized in that: In step (1), the mixing temperature is 80-200℃ and the mixing time is 5-30 min.

57. The preparation method according to claim 55, characterized in that: In step (2), the mixing temperature is 60-120℃ and the mixing time is 5-30 min.

58. The preparation method according to claim 55, characterized in that: The extruder is a parallel twin-screw extruder.

59. The preparation method according to claim 58, characterized in that: The screw of the parallel twin-screw extruder is a combined twin-screw.

60. The preparation method according to claim 59, characterized in that: The aspect ratio is 16 to 30.

61. The preparation method according to claim 58, characterized in that: The barrel temperature of the parallel twin-screw extruder is 165–185℃, and the screw speed is 80–180 r / min.

62. The preparation method according to claim 58, characterized in that: The diameter of the extrusion die of the parallel twin-screw extruder is 1-4 mm.

63. A co-extruded composite, formed by co-extruded a self-cleaning co-extruded functional material as described in any one of claims 1 to 44 and a coated material in one piece.

64. The co-extruded material as described in claim 63, characterized in that: The covering material is wood-plastic composite.

65. The co-extruded material as described in claim 63, characterized in that: The self-cleaning co-extruded functional material also includes epoxy-based organosiloxanes.

66. The co-extruded material as described in claim 65, characterized in that: In the self-cleaning coated co-extruded functional material, epoxy-based organosiloxanes account for 0.5% to 7%.

67. The co-extruded material as described in claim 65, characterized in that: The epoxy organosiloxane includes one or a mixture of two or more of the following: (3-epoxypropoxy)trimethoxysilane, (3-epoxypropoxy)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrihexyloxysilane.

68. The co-extruded material as described in claim 63, characterized in that: The self-cleaning co-extruded functional material also includes an activator.

69. The co-extruded material as described in claim 68, characterized in that: In the self-cleaning coated co-extruded functional material, the activator accounts for 0.1% to 1.4%.

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