Water-based wear-resistant polyurethane resin for pultrusion of basalt fiber as well as preparation method and application of water-based wear-resistant polyurethane resin

Abstract

The invention discloses water-based wear-resistant polyurethane resin for basalt fiber pultrusion and a preparation method and application thereof.The water-based wear-resistant polyurethane resin is prepared from, by mass, 16-25 parts of isocyanate, 45-60 parts of polyether polyol, 1-4 parts of fluorosilicone acrylic acid modifier, 10-25 parts of modified nanometer aluminum oxide and 2-4 parts of 2, 3-butanediol. 2-4 parts of an antioxidant, 1-3 parts of a catalyst, 1-3 parts of a chain extender, 1-5 parts of a neutralizer and 40-100 parts of water. Through the synergistic effect of the fluorosilicone acrylic acid modifier and the modified nano aluminum oxide, the mechanical properties, especially wear resistance, of the waterborne polyurethane are improved, and meanwhile, the waterborne polyurethane has excellent oxidation resistance and stain resistance and has wide application prospects in the field of pultrusion profiles.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a water-based wear-resistant polyurethane resin for basalt fiber pultrusion molding, and a preparation method and application thereof. Background Art

[0002] Basalt fiber is a new type of inorganic environmentally friendly green high-performance fiber material. It not only has high strength, but also has excellent wear resistance, which is mainly due to its stable chemical properties and high hardness. At the same time, it also has many excellent properties such as electrical insulation, corrosion resistance, and high temperature resistance. Due to its many excellent properties, basalt fiber has been widely used in pultruded profiles, but the matrix materials used in basalt fiber reinforced composite materials are usually thermosetting epoxy resins, polyester unsaturated resins, vinyl resins, etc. Polyester unsaturated resins and vinyl resins contain a large amount of organic solvents. Epoxy resins themselves do not contain solvents, but solvents are added in the pultrusion process due to process requirements. Organic solvents are very dangerous during the production process. They are easy to volatilize into flammable gases, and are prone to deflagration, explosion, and fire. In addition, organic solvents are irritating to human skin and mucous membranes to varying degrees, and are carcinogenic and teratogenic. In addition, once thermosetting resins are fixed, they cannot change their shape, are difficult to recycle, and are poorly environmentally friendly.

[0003] In view of this, the present invention is proposed. Summary of the invention

[0004] In view of the defects of the prior art, the purpose of the present invention is to provide a water-based wear-resistant polyurethane resin for basalt fiber pultrusion molding and a preparation method and application thereof, so as to at least solve the problem of organic solvents in the basalt fiber pultrusion molding matrix material.

[0005] To solve the above problems, the present invention adopts the following technical solutions:

[0006] In a first aspect, a water-based wear-resistant polyurethane resin for basalt fiber pultrusion molding comprises the following raw materials in parts by weight: 16-25 parts of isocyanate, 45-60 parts of polyether polyol, 1-4 parts of fluorosilicone acrylic modifier, 10-25 parts of modified nano-alumina, 2-4 parts of 2,3-butanediol, 2-4 parts of antioxidant, 1-3 parts of catalyst, 1-3 parts of chain extender, 1-5 parts of neutralizer, and 40-100 parts of water.

[0007] Furthermore, the raw materials for preparing the fluorosilicone acrylic modifier are as follows: by mass, 10-30 parts of hexafluoroisobutyl acrylate, 10-20 parts of hexadecyltrimethoxysilane, 0.5-2 parts of azobisisobutyronitrile, 10-20 parts of ethanol and 40-60 parts of water.

[0008] Furthermore, the preparation method of the fluorosilicone acrylic modifier is: after mixing the raw materials for preparing the fluorosilicone acrylic modifier, reacting at 50-70° C. for 2-5 hours to obtain the fluorosilicone acrylic modifier.

[0009] Furthermore, the modified nano-alumina is nano-alumina whose surface is modified by a high concentration of silane coupling agent.

[0010] Furthermore, the preparation method of the modified nano-alumina is as follows:

[0011] S1: prepare a silane coupling agent ethanol solution with a mass concentration of 30-50%;

[0012] S2: Add nano-alumina and silane coupling agent ethanol solution in a weight ratio of 100:0.1-2 into a ball mill and grind for 30-60 minutes. Dry the ground powder in a vacuum dryer at 60-100°C for 2-3 hours to obtain modified nano-alumina.

[0013] Further, the isocyanate is at least one of diphenylmethane diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, and 2,4-toluene diisocyanate;

[0014] And / or, the polyether polyol is at least one of polyethanol ether, polypropylene glycol, polyethylene glycol, and polyglycerol ether;

[0015] And / or, the antioxidant is antioxidant 1010;

[0016] And / or, the catalyst is at least one of bismuth neodecanoate, dibutyltin dilaurate, and stannous octoate;

[0017] And / or, the chain extender is at least one of sodium ethylenediamineethanesulfonate, sodium N,N-(2-hydroxyethyl)-2-aminoethanesulfonate, and sodium 1,4-butanediol-2-sulfonate;

[0018] And / or, the neutralizing agent is triethylamine.

[0019] In a second aspect, a method for preparing the water-based wear-resistant polyurethane resin as described in the first aspect comprises the following steps:

[0020] Step (1): adding polyether polyol into a reaction container, vacuuming and dehydrating, cooling for the first time, adding fluorosilicone acrylic modifier and isocyanate, heating for the first time, and performing polymerization reaction;

[0021] Step (2): cooling for a second time, adding 2,3-butanediol, an antioxidant, a catalyst and a chain extender, and heating for a second time;

[0022] Step (3): Cool down three times, add neutralizer, deionized water and modified nano-alumina, stir and disperse evenly to obtain water-based wear-resistant polyurethane resin.

[0023] Furthermore, in the step (1), vacuum dehydration is performed at 60-80°C for 0.5h; and / or, the temperature is first lowered to 60°C; and / or, the temperature is first raised to 80-90°C; and / or, the polymerization reaction time is 1-3h.

[0024] Furthermore, in the step (2), the second temperature reduction is to 60-70°C; and / or the second temperature increase is to 70-90°C and the reaction is carried out for 1-4h.

[0025] Furthermore, in the step (3), the temperature is lowered to 50-55° C. for three times; and / or the stirring time is 10-30 min.

[0026] In a third aspect, a use of the water-based wear-resistant polyurethane resin as described in the first aspect or the water-based wear-resistant polyurethane resin prepared by the preparation method as described in the second aspect as a basalt fiber pultrusion molding matrix material.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. The water-based wear-resistant polyurethane resin of the present invention, as a new resin system, uses water instead of organic solvent as a dispersion medium, is environmentally friendly, reduces fire risks, is highly efficient and energy-saving, and helps to reduce energy consumption and production costs.

[0029] 2. The water-based wear-resistant polyurethane resin of the present invention increases the mechanical properties and weather resistance of the water-based polyurethane through the synergistic effect of the fluorosilicone acrylic modifier and the modified nano-alumina, so that the water-based wear-resistant polyurethane resin is not only high-strength, high-hardness and high-toughness, but also has excellent wear resistance, oxidation resistance and anti-fouling properties, can resist ultraviolet rays and yellowing, and has broad application prospects in the field of pultruded profiles. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. The process parameters of the following embodiments that do not specify specific conditions are usually based on conventional conditions.

[0031] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0032] According to a first aspect of the present invention, a water-based wear-resistant polyurethane resin for basalt fiber pultrusion molding comprises the following raw materials in parts by weight: 16-25 parts of isocyanate, 45-60 parts of polyether polyol, 1-4 parts of fluorosilicone acrylic modifier, 10-25 parts of modified nano alumina, 2-4 parts of 2,3-butanediol, 2-4 parts of antioxidant, 1-3 parts of catalyst, 1-3 parts of chain extender, 1-5 parts of neutralizer, and 40-100 parts of water.

[0033] The water-based wear-resistant polyurethane of the present invention uses water instead of organic solvent as a dispersion medium, so that it is water-based, does not contain organic solvents, is not easy to burn, can significantly reduce the emission of harmful substances in the process of basalt fiber pultrusion, avoids the volatilization of organic solvents into a large amount of flammable gas and different degrees of stimulation to the skin and mucous membranes of operators, ensures environmental protection, safety and personal health, and has significant advantages of environmental protection, low fire risk, high efficiency and energy saving. In addition, it does not need to carry out complicated organic solvent recovery and treatment during use, simplifies the production process, improves production efficiency, and helps to reduce energy consumption and production costs.

[0034] The water-based wear-resistant polyurethane of the present invention increases the wear resistance, anti-fouling and anti-oxidation properties of the water-based polyurethane through the synergistic effect of the fluorosilicone acrylic modifier and the modified nano-alumina. Specifically, the fluorosilicone acrylic modifier is applied to the preparation of the water-based polyurethane, which can not only improve the anti-fouling performance of the water-based polyurethane, but also improve the anti-oxidation performance of the water-based polyurethane, make it resistant to ultraviolet and yellowing, and increase its weather resistance and service life. It can also increase the dispersion and compatibility of the modified nano-alumina in the polyurethane, thereby increasing the wear resistance of the water-based polyurethane. The modified nano-alumina used in the present invention not only has the high wear resistance brought by the high hardness and stable crystal structure of alumina, but also has the general characteristics of nano materials such as high hardness, high strength and high toughness mechanical properties and high surface activity chemical reaction performance; in particular, it is surface-modified and has a large number of active groups. When applied to the preparation of the water-based polyurethane, it can be finely and evenly dispersed in the water-based polyurethane, enhancing the mechanical properties such as hardness, strength and toughness of the water-based polyurethane, and especially improving the wear resistance of the water-based polyurethane.

[0035] As an optional embodiment of the water-based wear-resistant polyurethane resin of the present invention, the raw materials for preparing the fluorosilicone acrylic modifier are as follows: 10-30 parts by mass of hexafluoroisobutyl acrylate, 10-20 parts by mass of hexadecyltrimethoxysilane, 0.5-2 parts by mass of azobisisobutyronitrile, 10-20 parts by mass of ethanol and 40-60 parts by mass of water; further, the preparation method of the fluorosilicone acrylic modifier is as follows: after mixing the raw materials for preparing the fluorosilicone acrylic modifier, reacting at 50-70°C for 2-5 hours to obtain the fluorosilicone acrylic modifier.

[0036] The fluorosilicone acrylic modifier of the present invention is formed by copolymerization of fluorine-containing acrylic ester monomers and long-chain silanes under the action of an initiator. The long-chain siloxane group is introduced into the fluorine-containing acrylic resin molecule, which has excellent compatibility and stronger anti-fouling and anti-oxidation properties. First, the fluorine-containing group itself has good hydrophobicity and strong anti-fouling performance; second, the fluorine-containing group and the relatively long siloxane group introduced can spontaneously enrich upward, thereby reducing the surface energy and further enhancing the anti-fouling performance; third, the acrylic resin molecule contains a large number of polar groups, such as carboxyl, hydroxyl, etc., which can physically or chemically react with the surface of other materials, thereby being well compatible with other materials and forming a strong adhesion layer; fourth, the fluorine-containing group has good anti-oxidation due to the extremely strong electronegativity and small atomic radius of the fluorine atom, and other groups such as siloxane, carboxyl, hydroxyl, etc. also have certain anti-oxidation properties. Therefore, the application of the fluorosilicone acrylic modifier in the preparation of waterborne polyurethane can not only improve the anti-fouling performance of the waterborne polyurethane, but also improve the antioxidant performance of the waterborne polyurethane, making it resistant to UV and yellowing, and increase its weather resistance and service life. It can also increase the dispersion and compatibility of modified nano-alumina in polyurethane, thereby increasing the wear resistance of the waterborne polyurethane.

[0037] As an optional implementation of the water-based wear-resistant polyurethane resin of the present invention, the modified nano-alumina is nano-alumina whose surface is modified by a high-concentration silane coupling agent.

[0038] As an optional embodiment of the water-based wear-resistant polyurethane resin of the present invention, the preparation method of the modified nano-alumina is as follows:

[0039] S1: prepare a silane coupling agent ethanol solution with a mass concentration of 30-50%;

[0040] S2: Add nano-alumina and silane coupling agent ethanol solution in a weight ratio of 100:0.1-2 into a ball mill and grind for 30-60 minutes. Dry the ground powder in a vacuum dryer at 60-100°C for 2-3 hours to obtain modified nano-alumina.

[0041] The modified nano aluminum oxide of the present invention not only has the high wear resistance brought by the high hardness and stable crystal structure of aluminum oxide, but also has the general characteristics of nano materials such as high hardness, high strength and high toughness mechanical properties and high surface activity chemical reaction performance. In particular, it also has a large number of amphiphilic groups brought by surface modification with a high concentration of silane coupling agent, one end of the group can react with the silanol group on the surface of the nano aluminum oxide to generate a covalent bond, and the other end can react with an organic polymer. Therefore, the modified nano aluminum oxide is applied to the preparation of waterborne polyurethane, can be finely and evenly dispersed in the waterborne polyurethane, enhance the mechanical properties such as hardness, strength and toughness of the waterborne polyurethane, and especially improve the wear resistance of the waterborne polyurethane.

[0042] As an optional embodiment of the water-based wear-resistant polyurethane resin of the present invention, the isocyanate is at least one of diphenylmethane diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, and 2,4-toluene diisocyanate;

[0043] And / or, the polyether polyol is at least one of polyethanol ether, polypropylene glycol, polyethylene glycol, and polyglycerol ether;

[0044] And / or, the antioxidant is antioxidant 1010;

[0045] And / or, the catalyst is at least one of bismuth neodecanoate, dibutyltin dilaurate, and stannous octoate;

[0046] And / or, the chain extender is at least one of sodium ethylenediamineethanesulfonate, sodium N,N-(2-hydroxyethyl)-2-aminoethanesulfonate, and sodium 1,4-butanediol-2-sulfonate;

[0047] And / or, the neutralizing agent is triethylamine.

[0048] In the present invention, the above-mentioned isocyanate, polyether polyol, antioxidant, catalyst, chain extender and neutralizer may also be other common substances in the art, which are not listed here one by one.

[0049] According to a second aspect of the present invention, a method for preparing the water-based wear-resistant polyurethane resin according to the first aspect comprises the following steps:

[0050] Step (1): adding polyether polyol into a reaction container, vacuuming and dehydrating, cooling for the first time, adding fluorosilicone acrylic modifier and isocyanate, heating for the first time, and performing polymerization reaction;

[0051] Step (2): cooling for a second time, adding 2,3-butanediol, an antioxidant, a catalyst and a chain extender, and heating for a second time;

[0052] Step (3): Cool down three times, add neutralizer, deionized water and modified nano-alumina, stir and disperse evenly to obtain water-based wear-resistant polyurethane resin.

[0053] The reaction vessel of the present invention is not particularly limited, and can be equipped with a stirrer, a condensing device and a temperature measuring device as required, such as a reaction kettle equipped with a stirrer, a condensing device and a temperature measuring device. The preparation method of the present invention is simple and feasible, stable and reliable, and can be produced under existing production processes and equipment conditions, thereby achieving industrial large-scale production, and has broad application prospects in the field of pultruded profiles.

[0054] As an optional embodiment of the preparation method of the present invention, in the step (1), vacuum dehydration is carried out at 60-80°C for 0.5h; and / or, the first temperature is lowered to 60°C; and / or, the first temperature is raised to 80-90°C; and / or, the polymerization reaction time is 1-3h.

[0055] As an optional implementation of the preparation method of the present invention, in the step (2), the second temperature reduction is to 60-70° C.; and / or the second temperature increase is to 70-90° C. and the reaction is carried out for 1-4 hours.

[0056] As an optional implementation of the preparation method of the present invention, in the step (3), the temperature is lowered to 50-55° C. three times; and / or the stirring time is 10-30 min.

[0057] According to a third aspect of the present invention, an aqueous wear-resistant polyurethane resin as described in the first aspect or an aqueous wear-resistant polyurethane resin prepared by the preparation method as described in the second aspect is used as a basalt fiber pultrusion molding matrix material.

[0058] The water-based wear-resistant polyurethane resin of the present invention has good compatibility and can be used to form a uniform and compact wear-resistant layer (pultruded profile) in the basalt fiber pultrusion molding process. The basalt fiber and the water-based wear-resistant polyurethane resin play a synergistic role to maximize the wear resistance purpose.

[0059] The present invention will be further described in detail below with reference to specific embodiments and comparative examples.

[0060] Examples 1-5

[0061] A water-based wear-resistant polyurethane resin for basalt fiber pultrusion and a preparation method thereof, comprising the following raw materials in parts by weight: 16-25 parts of isocyanate, 45-60 parts of polyether polyol, 1-4 parts of fluorosilicone acrylic modifier, 10-25 parts of modified nano alumina, 2-4 parts of 2,3-butanediol, 2-4 parts of antioxidant, 1-3 parts of catalyst, 1-3 parts of chain extender, 1-5 parts of neutralizer and 40-100 parts of water.

[0062] The preparation method of the fluorosilicone acrylic modifier is as follows: by mass, 22 parts of hexafluoroisobutyl acrylate, 13 parts of hexadecyltrimethoxysilane, 1.3 parts of azobisisobutyronitrile, 15 parts of ethanol and 55 parts of water are mixed, and reacted at 50-70° C. for 2-5 hours to obtain the fluorosilicone acrylic modifier.

[0063] The preparation method of modified nano-alumina is as follows:

[0064] S1: Prepare 40% DL602 ethanol solution;

[0065] S2: Add nano-alumina and silane coupling agent ethanol solution in a weight ratio of 100:1.2 into a ball mill and grind for 30-60 minutes. Dry the ground powder in a vacuum dryer at 60-100°C for 2-3 hours to obtain modified nano-alumina.

[0066] The preparation of water-based wear-resistant polyurethane resin comprises the following steps:

[0067] B1: Add polyether polyol to a reaction kettle equipped with a stirrer, condenser and temperature measuring device, vacuum dehydrate at 60-80℃ for 0.5h, cool to 60℃, add fluorosilicone acrylic modifier and isocyanate, heat to 80-90℃, and polymerize for 1-3h;

[0068] B2: Cool down to 60-70℃, add 2,3-butanediol, antioxidant, catalyst, chain extender, heat up to 70-90℃, and react for 1-4h;

[0069] B3: Cool down to 50-55℃, add neutralizer, deionized water, modified nano-alumina, stir for 10-30min, disperse evenly, and obtain water-based wear-resistant polyurethane resin.

[0070] According to the above preparation process, the water-based wear-resistant polyurethane resins of Examples 1-5 were obtained according to the same preparation parameters, and the raw materials for the preparations are shown in Table 1 below:

[0071] Table 1 Components of water-based wear-resistant polyurethane resins in Examples 1-5

[0072] project Example 1 Example 2 Example 3 Example 4 Example 5 2,4-Toluene diisocyanate / g 16 18 20 22 25 Polyethanol ether / g 45 49 53 57 60 Fluorosilicone acrylic modifier / g 1 2 3 4 4 Modified nano-alumina / g 10 14 18 22 25 2,3-Butanediol / g 2 2 3 4 4 Antioxidant 1010 / g 2 2 3 4 4 Bismuth neodecanoate / g 1 1 2 3 3 1,4-Butanediol-2-sulfonate sodium / g 1 1 2 3 3 Triethylamine / g 1 2 3 4 5 Water / g 100 100 100 100 100

[0073] Embodiment 6-8

[0074] The only difference from Example 3 is that the amount of hexafluoroisobutyl acrylate and hexadecyltrimethoxysilane added during the preparation of the fluorosilicone acrylic modifier is different, and the rest of the settings are the same as Example 3. See Table 2 for details:

[0075] Table 2 Components of Fluorosilicone Acrylic Modifiers for Examples 6-8

[0076] project Hexafluoroisobutyl acrylate / g Hexadecyltrimethoxysilane / g Example 6 10 20 Example 7 17 17 Example 3 22 13 Example 8 30 10

[0077] Example 9

[0078] The only difference from Example 3 is that, when preparing the modified nano-alumina, the mass concentration of the DL602 ethanol solution is 33%, and the other settings are the same as those in Example 3.

[0079] Example 10

[0080] The only difference from Example 3 is that, when preparing the modified nano-alumina, the mass concentration of the DL602 ethanol solution is 47%, and the other settings are the same as those in Example 3.

[0081] Comparative Example 1

[0082] The only difference from the water-based wear-resistant polyurethane resin in Example 3 is that it does not contain the fluorosilicone acrylic modifier component, and the rest of the settings are the same as in Example 3.

[0083] Comparative Example 2

[0084] The only difference from the water-based wear-resistant polyurethane resin in Example 3 is that it does not contain modified nano-aluminum oxide, and the rest of the configurations are the same as those in Example 3.

[0085] Comparative Example 3

[0086] The only difference from Example 3 is that when preparing the water-based wear-resistant polyurethane resin, the order of adding the fluorosilicone acrylic modifier and the modified nano alumina is replaced, that is, the fluorosilicone acrylic modifier is not added in step B1 but added in step B3, and the modified nano alumina is not added in step B3 but added in step B1. The rest of the settings are the same as Example 3.

[0087] Comparative Example 4

[0088] The only difference from Example 3 is that, when preparing the water-based wear-resistant polyurethane resin, the fluorosilicone acrylic modifier and the modified nano-alumina are added together in step B1, and the rest of the settings are the same as those in Example 3.

[0089] Comparative Example 5

[0090] The only difference from Example 3 is that, when preparing the water-based wear-resistant polyurethane resin, the fluorosilicone acrylic modifier and the modified nano-alumina are added together in step B3, and the rest of the settings are the same as those in Example 3.

[0091] Application and testing

[0092] The water-based wear-resistant polyurethane resin obtained in Examples 1-10 and Comparative Examples 1-5 was used as a basalt fiber matrix material for pultrusion molding to obtain a 5mm thick basalt fiber reinforced water-based wear-resistant polyurethane composite material layer, wherein the diameter of the basalt fiber is 8-13 microns, the length is 2-7 mm, and the total mass accounts for 10%. The obtained composite material layers were randomly grouped and subjected to the following tests, including a yellowing test. After being placed outdoors for a long time, their appearance was observed. The composite material layers obtained in all examples did not turn yellow after 90 days. The longitudinal tensile strength and transverse tensile strength of the composite material layer were tested before and after ultraviolet irradiation with reference to GB / T 31539-2015. The ultraviolet irradiation time was 240h, and the total irradiation amount was 100kwh / m 2 The ratio of longitudinal / transverse tensile strength after UV irradiation to that before irradiation is used as the longitudinal / transverse strength retention rate to characterize its weather resistance. The larger the ratio, the stronger the weather resistance and the higher the antioxidant and UV resistance. The Shore hardness tester is used to test the hardness of the composite material layer. The water contact angle test of the composite material layer is carried out in accordance with GB / T 30693-2014. The larger the water contact angle, the better the anti-fouling performance. The wear resistance of the composite material layer is tested using an abrasion tester with a test load of 800g and a test time of 2h. The wear resistance is characterized by the mass retention rate of the composite material layer before and after abrasion. The higher the mass ratio, the better the wear resistance. The specific test results are shown in Table 3:

[0093] Table 3 Performance test results of water-based wear-resistant polyurethane resin in basalt fiber pultrusion molding application

[0094]

[0095]

[0096] As can be seen from Table 3, the water-based wear-resistant polyurethane of the present invention increases the wear resistance, stain resistance and oxidation resistance of the water-based polyurethane through the synergistic effect of the fluorosilicone acrylic modifier and the modified nano-alumina. In particular, during preparation, the fluorosilicone acrylic modifier is first added before the chain extender is added, and the modified nano-alumina is added when the neutralizer is added after the polymerization reaction is complete. The fluorosilicone acrylic modifier is added first to improve the anti-staining performance of the water-based polyurethane, and to improve the antioxidant performance of the water-based polyurethane, so that it is resistant to ultraviolet and yellowing, and the weather resistance and service life are increased, and the dispersion and compatibility of the modified nano-alumina in the polyurethane are increased, thereby increasing the wear resistance of the water-based polyurethane.

[0097] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions claimed to be protected by the present invention.

Claims

1. A water-based wear-resistant polyurethane resin for basalt fiber pultrusion molding, characterized in that: The preparation method comprises the following raw materials in parts by weight: 16-25 parts of isocyanate, 45-60 parts of polyether polyol, 1-4 parts of fluorosilicone acrylic modifier, 10-25 parts of modified nano alumina, 2-4 parts of 2,3-butanediol, 2-4 parts of antioxidant, 1-3 parts of catalyst, 1-3 parts of chain extender, 1-5 parts of neutralizer and 40-100 parts of water.

2. The water-based wear-resistant polyurethane resin according to claim 1, characterized in that: The raw materials for preparing the fluorosilicone acrylic modifier are as follows: by mass, 10-30 parts of hexafluoroisobutyl acrylate, 10-20 parts of hexadecyltrimethoxysilane, 0.5-2 parts of azobisisobutyronitrile, 10-20 parts of ethanol and 40-60 parts of water; further, the preparation method of the fluorosilicone acrylic modifier is: after mixing the raw materials for preparing the fluorosilicone acrylic modifier, react at 50-70°C for 2-5 hours to obtain the fluorosilicone acrylic modifier.

3. The water-based wear-resistant polyurethane resin according to claim 1, characterized in that: The modified nano-alumina is nano-alumina whose surface is modified by a high-concentration silane coupling agent.

4. The water-based wear-resistant polyurethane resin according to claim 1, characterized in that: The preparation method of the modified nano-alumina is as follows: S1: prepare a silane coupling agent ethanol solution with a mass concentration of 30-50%; S2: Add nano-alumina and silane coupling agent ethanol solution in a weight ratio of 100:0.1-2 into a ball mill and grind for 30-60 minutes. Dry the ground powder in a vacuum dryer at 60-100°C for 2-3 hours to obtain modified nano-alumina.

5. The water-based wear-resistant polyurethane resin according to claim 1, characterized in that: The isocyanate is at least one of diphenylmethane diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, and 2,4-toluene diisocyanate; And / or, the polyether polyol is at least one of polyethanol ether, polypropylene glycol, polyethylene glycol, and polyglycerol ether; And / or, the antioxidant is antioxidant 1010; And / or, the catalyst is at least one of bismuth neodecanoate, dibutyltin dilaurate, and stannous octoate; And / or, the chain extender is at least one of sodium ethylenediamineethanesulfonate, sodium N,N-(2-hydroxyethyl)-2-aminoethanesulfonate, and sodium 1,4-butanediol-2-sulfonate; And / or, the neutralizing agent is triethylamine.

6. A method for preparing the water-based wear-resistant polyurethane resin according to any one of claims 1 to 5, characterized in that: The steps include: Step (1): adding polyether polyol into a reaction container, vacuuming and dehydrating, cooling for the first time, adding fluorosilicone acrylic modifier and isocyanate, heating for the first time, and performing polymerization reaction; Step (2): cooling for a second time, adding 2,3-butanediol, an antioxidant, a catalyst and a chain extender, and heating for a second reaction; Step (3): Cool down three times, add neutralizer, deionized water and modified nano-alumina, stir and disperse evenly to obtain water-based wear-resistant polyurethane resin.

7. The preparation method according to claim 6, characterized in that: In the step (1), vacuum dehydration is performed at 60-80°C for 0.5h; and / or, the temperature is first lowered to 60°C; and / or, the temperature is first raised to 80-90°C; and / or, the polymerization reaction time is 1-3h.

8. The preparation method according to claim 6, characterized in that: In the step (2), the second temperature is lowered to 60-70°C; and / or the second temperature is raised to 70-90°C and the reaction is carried out for 1-4 hours.

9. The preparation method according to claim 6, characterized in that: In the step (3), the temperature is lowered three times to 50-55° C.; and / or the stirring time is 10-30 min.

10. Use of the water-based wear-resistant polyurethane resin as claimed in any one of claims 1 to 5 or the water-based wear-resistant polyurethane resin prepared by the preparation method as claimed in any one of claims 6 to 9 as a base material for basalt fiber pultrusion molding.

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