A kind of anti-aging polyurethane high-strength composite material and its preparation method and application

Abstract

The present invention relates to the technical field of polymer material modification, and discloses an anti-aging polyurethane high-strength composite material and its preparation method and application. The anti-aging polyurethane high-strength composite material is prepared by polyurethane raw material A component, polyurethane raw material B component and TiO2-SiO2 carrier. The present invention starts with the raw material and preparation method of polyurethane modified material. First, pure rutile nano titanium dioxide particles with extremely strong photocatalytic activity prepared by a low-temperature method are fused with silicon dioxide by a sol-gel method to form a TiO2-SiO2 carrier, which is then mixed with the polyurethane raw material B component, and finally subjected to a polymerization foaming reaction with the A component to prepare an anti-aging polyurethane high-strength composite material for grouting repair of road bridges, plugging of mine coal holes, solidified roadbed, and dam protection. The present invention enhances the strength of the polyurethane material, reduces the aging of the polyurethane material due to ultraviolet rays, and improves the durability and fire resistance of the polyurethane material.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material modification, in particular to an anti-aging high-strength polyurethane composite material and a preparation method and application thereof. Background Art

[0002] As a polymer material, polyurethane (PU) boasts excellent comprehensive properties, including excellent sound insulation, heat insulation, water blocking, and caulking. It is widely used in a variety of fields, including construction, transportation, medical devices, and the textile industry. However, polyurethane materials can age during actual use due to the effects of light, heat, oxygen, and other elements, leading to reduced performance and durability. Furthermore, polyurethane materials are significantly affected by changes in ambient temperature.

[0003] Ultraviolet rays are a significant factor in accelerating the aging of polyurethane. Titanium dioxide is a common light-shielding agent. Adding it to polyurethane materials can improve their resistance to UV aging and effectively reduce the polymer's photoaging. Furthermore, titanium dioxide can significantly improve the thermal, mechanical, and antibacterial properties of the polymer.

[0004] In the current research and development of modified polyurethane materials, titanium dioxide is commonly used as an additive raw material for polyurethane, and then dispersed in the polyurethane material using nanopowder technology. However, due to the large specific surface energy and surface activity of these dispersed nanoparticles, they tend to self-aggregate with each other, forming aggregates and agglomerates, which affect the molding and foaming reaction of the polymer and reduce its mechanical properties. To solve this problem, it is necessary to improve existing polyurethane material modification technology and develop a high-strength polyurethane composite material that is resistant to aging. Summary of the Invention

[0005] The present invention provides an anti-aging high-strength polyurethane composite material, which solves the problem in the prior art that dispersed nano-titanium dioxide particles in polyurethane materials easily form aggregates and agglomerates, affecting the molding and foaming reaction of the polymer and reducing its mechanical properties.

[0006] The present invention discloses an anti-aging high-strength polyurethane composite material, which is prepared from a polyurethane raw material component A, a polyurethane raw material component B and a TiO2-SiO2 carrier;

[0007] The raw materials in the polyurethane raw material component A are reacted according to the following mass ratios:

[0008]

[0009] The sum of the percentages of the above substances is 100%;

[0010] The polyurethane raw material component B is polymethylene polyphenyl polyisocyanate.

[0011] Preferably, the method for preparing the TiO2-SiO2 carrier is as follows:

[0012] (1) adding titanium chloride solution to deionized water in an ice bath, heating, cooling after the reaction is completed, separating, and drying the precipitate to obtain pure rutile nano-titanium dioxide particles;

[0013] (2) dispersing the nano-titanium dioxide particles obtained in (1) into deionized water, adding tetraethyl silicate and dispersing, adjusting the pH value, and stirring until it becomes an orange sol solution; adding ammonia water dropwise until the solution gels, aging, and drying to obtain a TiO2-SiO2 carrier;

[0014] Preferably, in the TiO2-SiO2 carrier preparation method (1), the concentration of the titanium chloride solution is 0.5-1 mol / L.

[0015] Preferably, in the TiO2-SiO2 carrier preparation method (1), the reaction conditions are stirring in an ice bath for 20-30 minutes, and then heating and stirring at 80-85°C for 6-7 hours.

[0016] Preferably, in (1) of the TiO2-SiO2 carrier preparation method, the separation method is centrifugal separation, and the centrifugal conditions are 30-40 min, 3000-3500 rpm.

[0017] Preferably, in step (2) of the TiO2-SiO2 carrier preparation method, nano-titanium dioxide particles are dispersed at 30-40°C.

[0018] Preferably, in (2) of the TiO2-SiO2 carrier preparation method, the concentration of the ammonia water is 2 mol / L, and hydrochloric acid is used to adjust the pH value, and the concentration of the hydrochloric acid is 0.2 mol / L.

[0019] Preferably, the method for preparing the anti-aging high-strength polyurethane composite material specifically comprises the following steps:

[0020] (1) Prepare the raw materials according to the formula;

[0021] (2) mixing the first four raw materials in the polyurethane raw material component A according to the mass ratio and stirring, and adding bismuth isooctanoate and triester phosphate dropwise until the solution becomes a light yellow transparent solution to obtain the polyurethane raw material component A;

[0022] (3) Component B of the polyurethane raw material is polymethylene polyphenyl polyisocyanate;

[0023] (4) The prepared TiO2-SiO2 carrier is mixed with the polyurethane raw material component B in (3), dibutyltin dilaurate is added for reaction, and then mixed with the polyurethane raw material component A obtained in (2) for reaction, to obtain an anti-aging polyurethane high-strength composite material; wherein the usage ratio of the TiO2-SiO2 carrier, component A, component B and dibutyltin dilaurate is 0.1:1:1:0.005.

[0024] The second purpose of the present invention is to apply the anti-aging polyurethane high-strength composite material to grouting repair, plugging of mine coal holes, solidified roadbed, and dam protection.

[0025] The third object of the present invention is to apply the anti-aging high-strength polyurethane composite material to solve the problems of poor interlayer adhesion, hollowing of the bottom of the plate, and loose base layer in road bridges.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. The present invention provides an anti-aging high-strength polyurethane composite material and its preparation method. Starting from the raw materials and preparation method of polyurethane modified materials, before the polymerization reaction of polyurethane raw material component A (diethylene glycol, polyether polyol, phthalic anhydride, trimethylolpropane, bismuth isooctanoate, phosphate triester) and component B (polymethylene polyphenyl polyisocyanate), pure rutile nano-titanium dioxide particles prepared by a low-temperature method are fused with silicon dioxide through a sol-gel method to form a TiO2-SiO2 carrier, which is then mixed with the polyurethane raw material component B, and finally subjected to a polymerization foaming reaction with component A. The key innovation of the present invention is to use rutile nano-titanium dioxide with extremely strong photocatalytic activity and silicon dioxide to prepare a prepolymer modifier, thereby enhancing the strength of the polyurethane material, reducing the aging of the polyurethane material due to ultraviolet rays, and improving the durability and fire resistance of the polyurethane material.

[0028] 2. The nanoparticles prepared by the method for preparing pure rutile nano-titanium dioxide particles of the present invention have a size of 6-20 nm, and the specific surface area of ​​the powder is increased, so that the rutile nano-titanium dioxide has extremely high photocatalytic performance.

[0029] 3. The dibutyltin dilaurate used in the present invention is an organic tin additive with good light stability and no sulfurization pollution. It can catalyze the cross-linking reaction of components A and B in the preparation of anti-aging high-strength polyurethane composite materials. DETAILED DESCRIPTION

[0030] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0031] The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified. The materials and reagents used are all commercially available unless otherwise specified.

[0032] Example 1

[0033] A method for preparing an anti-aging high-strength polyurethane composite material, wherein the raw material dosage conditions are as follows:

[0034] (1) Preparation of pure rutile nano-titanium dioxide particles: 2 g of 0.5 mol / L titanium chloride solution was added dropwise to 100 ml of deionized water in an ice bath at -2°C, and then placed in a magnetic stirrer and stirred for 20 min. The stirring speed is not limited here, and the stirring is only to accelerate the dissolution; a 0.5 mol / L titanium oxychloride solution was prepared; the titanium oxychloride solution was heated in an oil bath at 80°C for 6 h. After the solution reaction was completed and cooled, the precipitate was separated by centrifugation at 3000 rpm for 20 min. The precipitate was washed twice with distilled water and anhydrous ethanol, and dried in a vacuum drying oven at 80°C to obtain pure rutile nano-titanium dioxide particles.

[0035] (2) Preparation of TiO2-SiO2 carrier for anti-aging polyurethane material modification: 6 g of pure rutile nano-titanium dioxide particles obtained in (1) were dispersed in 40 ml of deionized water at 30°C, 10 g of tetraethyl silicate was added and ultrasonic dispersion was performed for 30 min, then 0.2 mol / L hydrochloric acid was slowly added dropwise under magnetic stirring, the pH value of the solution was adjusted to 2 for acid hydrolysis, and stirring was continued until the solution turned into an orange-yellow sol solution; then 2 mol / L ammonia water was added dropwise until the solution gelled, and after aging at room temperature for 3 days, the TiO2-SiO2 carrier was obtained by drying in a vacuum drying oven at 80°C.

[0036] (3) Preparation of polyurethane raw material component A: 24 g of phthalic anhydride was ground into powder, mixed with 1.5 g of trimethylolpropane, 43 g of anhydrous ethanol, and 30 g of polyether polyol, and placed in a magnetic stirrer for stirring at a stirring speed of 1000 rpm. During the stirring process, 0.003 g of bismuth isooctanoate and 1.5 g of triester phosphate were added dropwise until the solution became a light yellow transparent solution to obtain polyurethane raw material component A.

[0037] (4) Component B of the polyurethane raw material is polymethylene polyphenyl polyisocyanate.

[0038] (5) Preparation of anti-aging high-strength polyurethane composite materials: 1 g of the TiO2-SiO2 carrier obtained in (2) was mixed with 10 g of the polyurethane raw material component B, 0.05 g of dibutyltin dilaurate was added, and ultrasonic reaction was carried out at 70°C for 2 h. Then, it was mixed and stirred with 10 g of the polyurethane raw material component A, and polymerization and foaming reaction was carried out for 0.5 h at a stirring speed of 1000 rpm to generate an anti-aging high-strength polyurethane composite material.

[0039] Table 1 Strength of the anti-aging high-strength polyurethane composite material prepared in Example 1

[0040] index unit Test results Testing standards tensile strength MPa 9.8 GB / T 1040 Compressive strength MPa 17.5 GB / T 8813 Shear strength MPa 10.2 GB / T 7124 Bending strength MPa 9.5 GB / T 8812

[0041] Example 2

[0042] A method for preparing an anti-aging high-strength polyurethane composite material, wherein the raw material dosage conditions are as follows:

[0043] (1) Preparation of pure rutile nano-titanium dioxide particles: 3 g of 0.5 mol / L titanium chloride solution was added dropwise to 100 ml of deionized water in an ice bath at 0°C, and then the mixture was placed in a magnetic stirrer and stirred for 25 min. The stirring speed was not limited here, and the stirring was only to accelerate the dissolution; a 0.8 mol / L titanium oxychloride solution was prepared; the titanium oxychloride solution was heated in an oil bath at 83°C for 6.5 h. After the solution was cooled after the reaction, the precipitate was separated by centrifugation at 3000 rpm for 25 min. The precipitate was washed with distilled water and anhydrous ethanol 3 times each, and dried in a vacuum drying oven at 83°C to obtain pure rutile nano-titanium dioxide particles.

[0044] (2) Preparation of TiO2-SiO2 carrier of anti-aging polyurethane material modification material: 12 g of pure rutile nano-titanium dioxide particles obtained in (1) were dispersed in 80 ml of deionized water at 35°C, 20 g of tetraethyl silicate was added and ultrasonic dispersion was performed for 35 min, then 0.2 mol / L hydrochloric acid was slowly added dropwise under magnetic stirring, the pH value of the solution was adjusted to 2.5 for acid hydrolysis, and stirring was continued until the solution turned into an orange sol solution; then 2 mol / L ammonia water was added dropwise until the solution gelled, and after aging at room temperature for 4 days, the TiO2-SiO2 carrier was obtained by drying in a vacuum drying oven at 83°C.

[0045] (3) Preparation of polyurethane raw material component A: 25 g of phthalic anhydride was ground into powder, mixed with 1 g of trimethylolpropane, 45 g of anhydrous ethanol, and 27 g of polyether polyol, and placed in a magnetic stirrer for stirring at a stirring speed of 1000 rpm. During the stirring process, 0.004 g of bismuth isooctanoate and 2 g of triester phosphate were added dropwise until the solution became a light yellow transparent solution to obtain polyurethane raw material component A.

[0046] (4) Component B of the polyurethane raw material is polymethylene polyphenyl polyisocyanate.

[0047] (5) Preparation of anti-aging high-strength polyurethane composite materials: 2 g of the TiO2-SiO2 carrier obtained in (2) was mixed with 20 g of the polyurethane raw material component B, 0.1 g of dibutyltin dilaurate was added, and ultrasonic reaction was carried out at 72°C for 2.5 h. Then, it was mixed and stirred with 20 g of the polyurethane raw material component A, and polymerization and foaming reaction was carried out for 1 h at a stirring speed of 1000 rpm to generate an anti-aging high-strength polyurethane composite material.

[0048] Table 2 Strength of the anti-aging high-strength polyurethane composite material prepared in Example 2

[0049] index unit Test results Testing standards tensile strength MPa 9.3 GB / T 1040 Compressive strength MPa 16.9 GB / T 8813 Shear strength MPa 9.8 GB / T 7124 Bending strength MPa 8.8 GB / T 8812

[0050] Example 3

[0051] A method for preparing an anti-aging high-strength polyurethane composite material, wherein the raw material dosage conditions are as follows:

[0052] (1) Preparation of pure rutile nano-titanium dioxide particles: 4 g of 0.5 mol / L titanium chloride solution was added dropwise to 100 ml of deionized water in an ice bath at 0°C, and then the mixture was placed in a magnetic stirrer and stirred for 30 min. The stirring speed was not limited here, and the stirring was only to accelerate the dissolution; a 1 mol / L titanium oxychloride solution was prepared; the titanium oxychloride solution was heated in an oil bath at 85°C for 7 h. After the solution was cooled after the reaction, the precipitate was separated by centrifugation at 3000 rpm for 30 min. The precipitate was washed 3 times with distilled water and 3 times with anhydrous ethanol, and then dried in a vacuum drying oven at 85°C to obtain pure rutile nano-titanium dioxide particles.

[0053] (2) Preparation of TiO2-SiO2 carrier for anti-aging polyurethane material modification: 18 g of pure rutile nano-titanium dioxide particles obtained in (1) were dispersed in 120 ml of deionized water at 40°C, 30 g of tetraethyl silicate was added and ultrasonic dispersion was performed for 35 min, then 0.2 mol / L hydrochloric acid was slowly added dropwise under magnetic stirring, the pH value of the solution was adjusted to 2.5 for acid hydrolysis, and stirring was continued until the solution turned into an orange sol solution; then 2 mol / L ammonia water was added dropwise until the solution gelled, and after aging at room temperature for 5 days, the TiO2-SiO2 carrier was obtained by drying in a vacuum drying oven at 85°C.

[0054] (3) Preparation of polyurethane raw material component A: 26 g of phthalic anhydride was ground into powder, mixed with 0.5 g of trimethylolpropane, 44 g of anhydrous ethanol, and 28 g of polyether polyol, and placed in a magnetic stirrer for stirring at a stirring speed of 1000 rpm. During the stirring process, 0.005 g of bismuth isooctanoate and 1.5 g of triester phosphate were added dropwise until the solution became a light yellow transparent solution to obtain polyurethane raw material component A.

[0055] (4) Component B of the polyurethane raw material is polymethylene polyphenyl polyisocyanate.

[0056] (5) Preparation of anti-aging high-strength polyurethane composite materials: 3 g of the TiO2-SiO2 carrier obtained in (2) was mixed with 30 g of the polyurethane raw material component B, 0.15 g of dibutyltin dilaurate was added, and ultrasonic reaction was carried out at 75°C for 2.5 h. Then, it was mixed and stirred with 30 g of the polyurethane raw material component A, and polymerization and foaming reaction was carried out for 1 h at a stirring speed of 1000 rpm to generate an anti-aging high-strength polyurethane composite material.

[0057] Table 3 Strength of the anti-aging high-strength polyurethane composite material prepared in Example 3

[0058] index unit Test results Testing standards tensile strength MPa 9.5 GB / T 1040 Compressive strength MPa 17.2 GB / T 8813 Shear strength MPa 10.3 GB / T 7124 Bending strength MPa 9.1 GB / T 8812

[0059] Comparative Example 1:

[0060] The preparation method of common anti-aging polyurethane composite material, the dosage conditions of raw materials are as follows:

[0061] (1) Preparation of polyurethane raw material component A: 26 g of phthalic anhydride was ground into powder, mixed with 0.5 g of trimethylolpropane, 44 g of anhydrous ethanol, and 28 g of polyether polyol, and placed in a magnetic stirrer for stirring at a stirring speed of 1000 rpm. During the stirring process, 0.005 g of bismuth isooctanoate and 1.5 g of triester phosphate were added dropwise until the solution became a light yellow transparent solution to obtain polyurethane raw material component A.

[0062] (4) Component B of the polyurethane raw material is polymethylene polyphenyl polyisocyanate.

[0063] (5) Preparation of ordinary anti-aging polyurethane composite materials: Take 30g of polyurethane raw material component B and 3g of titanium dioxide, add 0.15g of dibutyltin dilaurate, and then mix and stir with 30g of polyurethane raw material component A. React for 1h at a stirring speed of 1000rpm to generate ordinary anti-aging polyurethane composite materials.

[0064] Table 4 Strength of the common anti-aging polyurethane composite material prepared in Comparative Example 1

[0065] index unit Test results Testing standards tensile strength MPa 7.1 GB / T 1040 Compressive strength MPa 13.5 GB / T 8813 Shear strength MPa 8.9 GB / T 7124 Bending strength MPa 8.4 GB / T 8812

[0066] As can be seen from Tables 1-4, the tensile strength, compressive strength, shear strength, and flexural strength of Tables 1-3 are all superior to those of Table 4. Tables 1-3 present the data measured for the design schemes of Examples 1-3, while Table 4 presents the data measured for the design scheme of Comparative Example 1. Comparative Example 1 directly reacts polyurethane raw material component A and polyurethane raw material component B with titanium dioxide to produce an anti-aging polyurethane composite material. Therefore, it can be concluded that the technical solution of the present invention achieves unexpected results.

[0067] Although the preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0068] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. An anti-aging high-strength polyurethane composite material, characterized in that: The anti-aging high-strength polyurethane composite material is prepared from polyurethane raw material component A, polyurethane raw material component B and TiO2-SiO2 carrier; The raw materials in the polyurethane raw material component A are reacted according to the following mass ratios: The sum of the percentages of the above substances is 100%; The polyurethane raw material component B is polymethylene polyphenyl polyisocyanate; The anti-aging high-strength polyurethane composite material is prepared by the following steps: (1) Prepare the raw materials according to the formula; (2) mixing the first four raw materials in the polyurethane raw material component A according to the mass ratio and stirring, and adding bismuth isooctanoate and triester phosphate dropwise until the solution becomes a light yellow transparent solution to obtain the polyurethane raw material component A; (3) Component B of the polyurethane raw material is polymethylene polyphenyl polyisocyanate; (4) mixing the prepared TiO2-SiO2 carrier with the polyurethane raw material component B in (3), adding dibutyltin dilaurate to react, and then mixing and stirring with the polyurethane raw material component A obtained in (2) to obtain an anti-aging polyurethane high-strength composite material; wherein the amount ratio of the TiO2-SiO2 carrier, component A, component B and dibutyltin dilaurate is 0.1:1:1:0.005; The method for preparing the TiO2-SiO2 carrier is as follows: (1) adding titanium chloride solution to deionized water in an ice bath, heating, cooling after the reaction is completed, separating, and drying the precipitate to obtain pure rutile nano-titanium dioxide particles; (2) The nano-titanium dioxide particles obtained in (1) are dispersed in deionized water, tetraethyl silicate is added and dispersed, the pH value is adjusted, and the solution is stirred until it becomes an orange sol solution; ammonia water is added dropwise until the solution gels, and after aging, the TiO2-SiO2 carrier is dried.

2. The anti-aging high-strength polyurethane composite material according to claim 1, characterized in that: In the TiO2-SiO2 carrier preparation method (1), the concentration of the titanium chloride solution is 0.5-1 mol / L.

3. The anti-aging high-strength polyurethane composite material according to claim 1, characterized in that: In the TiO2-SiO2 carrier preparation method (1), the reaction conditions are stirring in an ice bath for 20-30 minutes, and then heating and stirring at 80-85°C for 6-7 hours.

4. The anti-aging high-strength polyurethane composite material according to claim 1, characterized in that: In (1) of the TiO2-SiO2 carrier preparation method, the separation method is centrifugal separation, and the centrifugal conditions are 30-40 minutes and 3000-3500 rpm.

5. The anti-aging high-strength polyurethane composite material according to claim 1, characterized in that: In the TiO2-SiO2 carrier preparation method (2), nano-titanium dioxide particles are dispersed at 30-40°C.

6. The anti-aging high-strength polyurethane composite material according to claim 1, characterized in that: In (2) of the TiO2-SiO2 carrier preparation method, the concentration of the ammonia water is 2 mol / L, and hydrochloric acid is used to adjust the pH value, and the concentration of the hydrochloric acid is 0.2 mol / L.

7. The method for preparing an anti-aging high-strength polyurethane composite material according to claim 1, characterized in that: The specific steps include: (1) Prepare the raw materials according to the formula; (2) mixing the first four raw materials in the polyurethane raw material component A according to the mass ratio and stirring, and adding bismuth isooctanoate and triester phosphate dropwise until the solution becomes a light yellow transparent solution to obtain the polyurethane raw material component A; (3) Component B of the polyurethane raw material is polymethylene polyphenyl polyisocyanate; (4) The prepared TiO2-SiO2 carrier is mixed with the polyurethane raw material component B in (3), dibutyltin dilaurate is added for reaction, and then mixed with the polyurethane raw material component A obtained in (2) for reaction, to obtain an anti-aging polyurethane high-strength composite material; wherein the usage ratio of the TiO2-SiO2 carrier, component A, component B and dibutyltin dilaurate is 0.1:1:1:0.

005.

8. The use of the anti-aging high-strength polyurethane composite material according to claim 1, characterized in that: The obtained anti-aging high-strength polyurethane composite material is used in grouting repair, plugging of mine coal holes, solidifying roadbed, and dam protection.

9. The use of the anti-aging high-strength polyurethane composite material according to claim 8, characterized in that: The anti-aging high-strength polyurethane composite material is used to solve the problems of poor interlayer bonding, hollowing of the bottom of the slab, and loose base layer in pavement bridges.

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