阅读说明：本技术 一种苯并恶嗪型超疏水喷剂的制备方法及其应用 (Preparation method and application of benzoxazine type super-hydrophobic spray ) 是由 胡强 吴春春 李群业 王基成 包泳先 于 2021-10-29 设计创作，主要内容包括：本发明提供一种苯并恶嗪型超疏水喷剂的制备方法及其应用,涉及防水材料加工技术领域。所述苯并恶嗪型超疏水喷剂的制备方法主要包括：甲醛水溶液的制备、氨丙基三乙氧基硅烷甲苯溶液的制备、苯并恶嗪硅烷产物的制备、正硅酸四乙酯乙醇溶液的制备和最终原料的混合等步骤。本发明克服了现有技术的不足,将疏水基团正硅酸四乙酯水解的二氧化硅引入到苯并噁嗪分子内,进一步改善苯并噁嗪的疏水性能,同时本申请的制备工艺有效提升疏水产品的稳定性,满足其在防水领域的应用。(The invention provides a preparation method and application of a benzoxazine type super-hydrophobic spray, and relates to the technical field of waterproof material processing. The preparation method of the benzoxazine type super-hydrophobic spray mainly comprises the following steps: the method comprises the steps of preparation of formaldehyde aqueous solution, preparation of aminopropyl triethoxysilane toluene solution, preparation of benzoxazine silane product, preparation of tetraethyl orthosilicate ethanol solution, mixing of final raw materials and the like. The invention overcomes the defects of the prior art, introduces silicon dioxide hydrolyzed by tetraethyl orthosilicate serving as a hydrophobic group into benzoxazine molecules, further improves the hydrophobic property of benzoxazine, and effectively improves the stability of hydrophobic products by the preparation process, thereby meeting the application of the hydrophobic products in the waterproof field.)

1. A preparation method of a benzoxazine type super-hydrophobic spray is characterized by comprising the following steps:

(1) adding paraformaldehyde into distilled water, adjusting pH to 8.0-9.5, stirring to completely dissolve paraformaldehyde to obtain formaldehyde aqueous solution;

(2) dissolving aminopropyl triethoxysilane in toluene, stirring to fully dissolve, and obtaining aminopropyl triethoxysilane toluene solution for later use;

(3) slowly dropwise adding the aminopropyl triethoxysilane toluene solution into the formaldehyde water solution obtained in the step (1) in a water bath environment, then dropwise adding a cardanol/toluene solution into the solution, fully stirring for reaction after dropwise adding is completed, adjusting the pH value to be neutral, standing in anhydrous sodium sulfate for 12 hours, and filtering and separating through a drying solvent to obtain a benzoxazine silane product for later use;

(4) adding tetraethyl orthosilicate into an ethanol solution, fully stirring and dispersing, and then dropwise adding ammonia water to prepare a tetraethyl orthosilicate ethanol solution for later use;

(5) and (4) adding the benzoxazine silane product obtained in the step (3) into the tetraethyl orthosilicate ethanol solution obtained in the step (4), and fully stirring for 30min to obtain the benzoxazine-type super-hydrophobic spray.

2. The process for producing a benzoxazine-type superhydrophobic substance according to claim 1, wherein: the benzoxazine type super-hydrophobic spray is prepared from the following raw materials in parts by mass: 2 parts of paraformaldehyde, 50 parts of distilled water, 5 parts of aminopropyltriethoxysilane, 10 parts of toluene, 4-6 parts of cardanol/toluene solution, 2-4 parts of tetraethyl orthosilicate, 20 parts of ethanol and 4-8 parts of ammonia water.

3. The process for producing a benzoxazine-type superhydrophobic substance according to claim 1, wherein: the structural formula of the benzoxazine silicon source in the benzoxazine type super-hydrophobic spray is as follows:

。

4. the process for producing a benzoxazine-type superhydrophobic substance according to claim 1, wherein: and (3) adjusting the pH value by adopting a NaOH aqueous solution in the step (1) and the step (3).

5. The process for producing a benzoxazine-type superhydrophobic substance according to claim 1, wherein: the rotating speed of stirring in the steps (1), (4) and (5) is 800r/min, and the rotating speed of stirring in the step (2) is 500 r/min.

6. The process for producing a benzoxazine-type superhydrophobic substance according to claim 1, wherein: the temperature of the water bath environment in the step (3) is 65-80 ℃.

7. The process for producing a benzoxazine-type superhydrophobic substance according to claim 1, wherein: the rotating speed of the fully stirring reaction in the step (3) is 1000r/min, and the reaction time is 5 h.

8. Use of a benzoxazine superhydrophobic spray according to any one of claims 1-6 in water proofing of concrete surfaces.

Technical Field

The invention relates to the technical field of waterproof material processing, in particular to a preparation method and application of a benzoxazine type super-hydrophobic spray.

Background

In recent years, the degree of attention paid to superhydrophobic materials having a surface contact angle with water of more than 150 ° in various fields is becoming stronger, and with the progress of current scientific technology, it has become possible to make high value-added products by making rational use of its excellent hydrophobicity. Hydrophobicity is one of the important characteristics of a material surface, which is determined by both the chemical composition and the micro-geometry of the material surface. Generally, the preparation of the super-hydrophobic surface material needs to meet two conditions, namely, the surface of the material has very low solid surface energy, and a micron and nanometer combined hierarchical structure with certain roughness is constructed on the surface of the material.

Benzoxazine is a novel phenolic resin material, is developed on the basis of the traditional phenolic resin, effectively overcomes the defect of poor condensation polymerization curing controllability of the traditional phenolic resin due to the special structure and the ring-opening polymerization mechanism of the benzoxazine, has the characteristics of excellent mechanical property, flexible molecular design, stable size in the curing process and the like on the basis of keeping the excellent thermal property, flame retardance and electric insulation property of the traditional phenolic resin, and is expected to replace the traditional phenolic resin material in many fields. With the improvement of the requirements on the hydrophobic material, the existing preparation methods have certain limitations and disadvantages, and have certain influence on the hydrophobicity and the stability of the final material.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a preparation method and application of a benzoxazine-type super-hydrophobic spray, wherein silicon dioxide hydrolyzed by tetraethyl orthosilicate serving as a hydrophobic group is introduced into benzoxazine molecules, so that the hydrophobic property of benzoxazine is further improved, and meanwhile, the preparation process effectively improves the stability of a hydrophobic product and meets the application requirement of the hydrophobic product in the waterproof field.

In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:

a preparation method of a benzoxazine type super-hydrophobic spray comprises the following steps:

(1) adding paraformaldehyde into distilled water, adjusting pH to 8.0-9.5 with NaOH aqueous solution, stirring at 800r/min to completely dissolve paraformaldehyde to obtain formaldehyde aqueous solution;

(2) dissolving aminopropyltriethoxysilane in toluene, and stirring at a rotation speed of 500r/min until the aminopropyltriethoxysilane is fully dissolved to obtain an aminopropyltriethoxysilane toluene solution for later use;

(3) slowly dropwise adding the aminopropyl triethoxysilane toluene solution into the formaldehyde aqueous solution obtained in the step (1) in a water bath environment at 65-80 ℃, then dropwise adding a cardanol/toluene solution into the solution, fully stirring and reacting for 5 hours at the rotating speed of 1000r/min after dropwise adding is finished, adjusting the pH to be neutral by adopting a NaOH aqueous solution, standing for 12 hours in anhydrous sodium sulfate, and filtering and separating by using a drying solvent to obtain a benzoxazine silane product for later use;

(4) adding tetraethyl orthosilicate into an ethanol solution, fully stirring and dispersing at the rotating speed of 800r/min, and then dropwise adding ammonia water to prepare the tetraethyl orthosilicate ethanol solution for later use;

(5) and (4) adding the benzoxazine silane product obtained in the step (3) into tetraethyl orthosilicate ethanol solution obtained in the step (4), and fully stirring at the rotating speed of 800r/min for 30min to obtain the benzoxazine-type super-hydrophobic spray.

Preferably, the benzoxazine type super-hydrophobic spray is prepared from the following raw materials in parts by mass: 2 parts of paraformaldehyde, 50 parts of distilled water, 5 parts of aminopropyltriethoxysilane, 10 parts of toluene, 4-6 parts of cardanol/toluene solution, 2-4 parts of tetraethyl orthosilicate, 20 parts of ethanol and 4-8 parts of ammonia water.

The structural formula of the benzoxazine silicon source in the benzoxazine type super-hydrophobic spray is as follows:

the invention provides the application of the benzoxazine super-hydrophobic spray in the concrete surface water prevention.

The invention provides a preparation method and application of a benzoxazine type super-hydrophobic spray, and compared with the prior art, the benzoxazine type super-hydrophobic spray has the advantages that:

(1) according to the invention, silicon dioxide generated by hydrolysis of a benzoxazine silicon source and tetraethyl orthosilicate in an ammonia water environment is bonded together in a chemical bonding manner, so that the surface of the prepared super-hydrophobic spray is not easy to damage after use, and the waterproof performance is stable.

(2) The super-hydrophobic spray prepared by the invention has a simple synthesis preparation method, is synthesized at low temperature, is easy to control the reaction, saves energy, and effectively ensures the economic benefit of the spray.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the preparation method of the benzoxazine type super-hydrophobic spray comprises the following steps:

(1) the raw materials are proportioned according to the following weight portions: 2 parts of paraformaldehyde, 50 parts of distilled water, 5 parts of aminopropyltriethoxysilane, 10 parts of toluene, 4 parts of cardanol/toluene solution, 2 parts of tetraethyl orthosilicate, 20 parts of ethanol and 8 parts of ammonia water;

(2) adding paraformaldehyde into distilled water, adjusting pH to 8.0-9.5 with NaOH aqueous solution, stirring at 800r/min to completely dissolve paraformaldehyde to obtain formaldehyde aqueous solution;

(3) dissolving aminopropyltriethoxysilane in toluene, and stirring at a rotation speed of 500r/min until the aminopropyltriethoxysilane is fully dissolved to obtain an aminopropyltriethoxysilane toluene solution for later use;

(4) slowly dropwise adding the aminopropyl triethoxysilane toluene solution into the formaldehyde aqueous solution obtained in the step (2) in a water bath environment at 65 ℃, then dropwise adding a cardanol/toluene solution into the solution, fully stirring and reacting for 5 hours at the rotating speed of 1000r/min after dropwise adding is finished, adjusting the pH to be neutral by adopting a NaOH aqueous solution, standing for 12 hours in anhydrous sodium sulfate, and filtering and separating by using a drying solvent to obtain a benzoxazine silane product for later use;

(5) adding tetraethyl orthosilicate into an ethanol solution, fully stirring and dispersing at the rotating speed of 800r/min, and then dropwise adding ammonia water to prepare the tetraethyl orthosilicate ethanol solution for later use;

(6) and (3) adding the benzoxazine silane product obtained in the step (4) into tetraethyl orthosilicate ethanol solution obtained in the step (5), and fully stirring at the rotating speed of 800r/min for 30min to obtain the benzoxazine-type super-hydrophobic spray.

Example 2:

the preparation method of the benzoxazine type super-hydrophobic spray comprises the following steps:

(1) the raw materials are proportioned according to the following weight portions: 2 parts of paraformaldehyde, 50 parts of distilled water, 5 parts of aminopropyltriethoxysilane, 10 parts of toluene, 5 parts of cardanol/toluene solution, 3 parts of tetraethyl orthosilicate, 20 parts of ethanol and 6 parts of ammonia water;

(2) adding paraformaldehyde into distilled water, adjusting pH to 8.0-9.5 with NaOH aqueous solution, stirring at 800r/min to completely dissolve paraformaldehyde to obtain formaldehyde aqueous solution;

(3) dissolving aminopropyltriethoxysilane in toluene, and stirring at a rotation speed of 500r/min until the aminopropyltriethoxysilane is fully dissolved to obtain an aminopropyltriethoxysilane toluene solution for later use;

(4) slowly dropwise adding the aminopropyl triethoxysilane toluene solution into the formaldehyde aqueous solution obtained in the step (2) in a water bath environment at 70 ℃, then dropwise adding a cardanol/toluene solution into the solution, fully stirring and reacting for 5 hours at the rotating speed of 1000r/min after dropwise adding is finished, adjusting the pH to be neutral by adopting a NaOH aqueous solution, standing for 12 hours in anhydrous sodium sulfate, and filtering and separating by using a drying solvent to obtain a benzoxazine silane product for later use;

(5) adding tetraethyl orthosilicate into an ethanol solution, fully stirring and dispersing at the rotating speed of 800r/min, and then dropwise adding ammonia water to prepare the tetraethyl orthosilicate ethanol solution for later use;

(6) and (3) adding the benzoxazine silane product obtained in the step (4) into tetraethyl orthosilicate ethanol solution obtained in the step (5), and fully stirring at the rotating speed of 800r/min for 30min to obtain the benzoxazine-type super-hydrophobic spray.

Example 3:

the preparation method of the benzoxazine type super-hydrophobic spray comprises the following steps:

(1) the raw materials are proportioned according to the following weight portions: 2 parts of paraformaldehyde, 50 parts of distilled water, 5 parts of aminopropyltriethoxysilane, 10 parts of toluene, 6 parts of cardanol/toluene solution, 4 parts of tetraethyl orthosilicate, 20 parts of ethanol and 4 parts of ammonia water;

(2) adding paraformaldehyde into distilled water, adjusting pH to 8.0-9.5 with NaOH aqueous solution, stirring at 800r/min to completely dissolve paraformaldehyde to obtain formaldehyde aqueous solution;

(3) dissolving aminopropyltriethoxysilane in toluene, and stirring at a rotation speed of 500r/min until the aminopropyltriethoxysilane is fully dissolved to obtain an aminopropyltriethoxysilane toluene solution for later use;

(4) slowly dropwise adding the aminopropyl triethoxysilane toluene solution into the formaldehyde aqueous solution obtained in the step (2) in a water bath environment at the temperature of 80 ℃, then dropwise adding a cardanol/toluene solution into the solution, fully stirring and reacting for 5 hours at the rotating speed of 1000r/min after dropwise adding is finished, adjusting the pH to be neutral by adopting a NaOH aqueous solution, standing for 12 hours in anhydrous sodium sulfate, and filtering and separating by using a drying solvent to obtain a benzoxazine silane product for later use;

(5) adding tetraethyl orthosilicate into an ethanol solution, fully stirring and dispersing at the rotating speed of 800r/min, and then dropwise adding ammonia water to prepare the tetraethyl orthosilicate ethanol solution for later use;

(6) and (3) adding the benzoxazine silane product obtained in the step (4) into tetraethyl orthosilicate ethanol solution obtained in the step (5), and fully stirring at the rotating speed of 800r/min for 30min to obtain the benzoxazine-type super-hydrophobic spray.

And (3) detection:

the benzoxazine super-hydrophobic spray prepared in the example 1-3 is mixed according to the ratio of 300g/m²The amount of the water-soluble organic silicon dioxide is uniformly sprayed on the surface of concrete, dried for 3 days at room temperature (about 20 ℃), the contact angle of the surface of the concrete is tested, and the contact angle is tested and detected by using a contact angle measuring instrumentThe performance of the benzoxazine superhydrophobic spray in terms of water resistance was measured and the results are shown in the following table:

numbering	Storage stability (45 ℃ C.)	Contact angle (°)	Sliding angle (°)
				Example 1	>14d	152	10
Example 2	>14d	158	7
				Example 3	>14d	162	5

The above table shows that the benzoxazine super-hydrophobic spray prepared by the invention has high stability and good waterproof performance when sprayed on the surface of concrete.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.