阅读说明：本技术 一种有机硅单体改性的纳米无机硅树脂的制备方法 (Preparation method of organic silicon monomer modified nano inorganic silicon resin ) 是由 纪庆绪 沙千辰 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种有机硅单体改性的纳米无机硅树脂的制备方法,包括以下步骤：将PH值为8-11的硅溶胶溶液放置在反应釜当中,升温至50-80℃,持续进行搅拌；滴加硅溶胶溶液质量的1.5％-3％的亲水性有机硅单体后,保持S1中的温度不变,反应3-4h完成共聚；降低温度至50-60℃,滴加1-3％的疏水性有机硅单体,反应5-6h,再次完成共聚。通过上述设置,通过该方法制备的纳米无机硅树脂具有良好的成膜性、展色性、疏水性、兼容性,即可用来制作纯无机建筑涂料,也可与常用的乳液复配生产符合行业标准规定的无机建筑涂料。(The invention discloses a preparation method of organic silicon monomer modified nano inorganic silicon resin, which comprises the following steps: placing the silica sol solution with the pH value of 8-11 in a reaction kettle, heating to 50-80 ℃, and continuously stirring; after hydrophilic organic silicon monomer accounting for 1.5-3% of the mass of the silica sol solution is dripped, the temperature in S1 is kept unchanged, and the copolymerization is completed after the reaction is carried out for 3-4 h; reducing the temperature to 50-60 ℃, dropwise adding 1-3% of hydrophobic organic silicon monomer, reacting for 5-6h, and finishing copolymerization again. Through the arrangement, the nano inorganic silicon resin prepared by the method has good film forming property, color development property, hydrophobicity and compatibility, can be used for preparing a pure inorganic building coating, and can also be compounded with a common emulsion to produce an inorganic building coating meeting the industrial standard.)

1. A preparation method of organic silicon monomer modified nano inorganic silicone resin is characterized by comprising the following steps: the method comprises the following steps:

s1, placing the silica sol solution with the pH value of 8-11 in a reaction kettle, and heating to 50-80 ℃;

continuously stirring at the rotating speed of 60-80 revolutions;

s2, dripping hydrophilic organic silicon monomers accounting for 1.5-3% of the mass of the silica sol solution;

keeping the temperature in the S1 constant, and reacting for 3-4h to complete copolymerization;

s3, reducing the temperature to 50-60 ℃, and dropwise adding 1-3% of hydrophobic organic silicon monomer;

the rotating speed is increased to 80-120 turns, the reaction lasts for 5-6h, and the copolymerization is completed again.

2. The preparation method of the organosilicon monomer modified nano inorganic silicone resin as claimed in claim 1, wherein: the hydrophilic organosilicon monomer is gamma-glycidoxypropyltrimethoxysilane and/or gamma-methacryloyloxytrimethoxysilane.

3. The preparation method of the organosilicon monomer modified nano inorganic silicone resin as claimed in claim 2, wherein: the hydrophobic organic silicon monomer is methyl trioxysilane and/or isobutyl trioxysilane.

4. The preparation method of the organosilicon monomer modified nano inorganic silicone resin as claimed in claim 3, wherein: the silica sol solution is selected from LS-30 type silica sol solution and SiO of Zhejiang Uuda chemical company Limited₂The content is 30 percent.

5. An organosilicon monomer modified nano inorganic silicone resin prepared by any one of claims 1 to 4.

6. The organosilicon monomer-modified nano inorganic silicone resin according to claim 5, wherein: the application as a matrix material in the preparation and production process of inorganic coatings.

Technical Field

The invention relates to the field of inorganic coatings, in particular to a preparation method of organic silicon monomer modified nano inorganic silicon resin.

Background

The inorganic coating is an inorganic polymer coating which is composed of inorganic polymer, metal subjected to dispersion activation, metal oxide nano material and rare earth ultrafine powder, can quickly react with iron atoms on the surface of a steel structure to generate an inorganic polymer anticorrosive coating which has physical and chemical double protection effects and is firmly combined with a matrix through a chemical bond, has no pollution to the environment, long service life and anticorrosive performance reaching the international advanced level, and is a high-tech upgrading product meeting the requirement of environmental protection.

Potassium silicate inorganic exterior wall coatings and silica sol inorganic exterior wall coatings have been developed in recent years in China. Inorganic coatings have also begun to be used in China in a large amount as exterior wall decoration and protection, and the excellent weather resistance and color retention and air permeability of the inorganic coatings are accepted by people.

However, after long-term use and testing, the two inorganic exterior wall coatings respectively have the following disadvantages: the potassium silicate inorganic paint has poor compatibility, needs special emulsion, auxiliary agent, color paste and powder, has poor storage stability, slow film forming, early water resistance, poor scrubbing resistance and long curing time, and is accompanied with salting-out phenomenon to cause blooming. The silica sol inorganic paint has fast filming, violent shrinkage in drying process, too strong rigidity, water resistance, compatibility and color development property slightly superior to potassium silicate, but has difference from actual requirements.

In order to solve the problems, the application provides a preparation method of nano inorganic silicon resin.

Disclosure of Invention

The invention aims to provide a preparation method of organic silicon monomer modified nano inorganic silicone resin, and the nano inorganic silicone resin prepared by the method has good film forming property, color development property, hydrophobicity and compatibility, can be used for preparing pure inorganic building coating, and can also be compounded with common emulsion to produce inorganic building coating meeting the industrial standard regulation.

In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of organic silicon monomer modified nano inorganic silicone resin comprises the following steps:

s1, placing the silica sol solution with the pH value of 8-11 in a reaction kettle, heating to 50-80 ℃, and continuously stirring at the rotating speed of 60-80 revolutions;

s2, dropwise adding a hydrophilic organic silicon monomer accounting for 1.5-3% of the mass of the silica sol solution, keeping the temperature in the S1 unchanged, and reacting for 3-4 hours to complete copolymerization;

s3, reducing the temperature to 50-60 ℃, dropwise adding 1-3% of hydrophobic organic silicon monomer, increasing the rotation speed to 80-120 r, reacting for 5-6h, and finishing copolymerization again.

By adopting the technical scheme, the compatibility of the pure hydrophilic inorganic silicone resin and the hydrophobic organic silicon monomer is improved by copolymerizing the pure hydrophilic inorganic silicone resin and the relatively hydrophilic organic silicon monomer; the film forming property, color development property, hydrophobicity and compatibility of the inorganic silicon resin are greatly improved through two times of polymerization; can be used for preparing pure inorganic building coatings, and can also be compounded with common emulsion to produce inorganic building coatings meeting the industrial standard.

Preferably, the hydrophilic organosilicon monomer is gamma-glycidoxypropyltrimethoxysilane and/or gamma-methacryloxytrimethoxysilane.

Through the technical scheme, flexible selection can be performed according to the cost.

Preferably, the hydrophobic organosilicon monomer is methyl trioxysilane and/or isobutyl trioxysilane.

Through the technical scheme, flexible selection can be performed according to the cost.

Preferably, the silica sol solution is selected from LS-30 type silica sol solution of Zhejiang Uuda chemical company Limited, SiO₂The content is 30 percent.

Through the technical scheme, the requirement of batch production can be met.

Preferably, the nano inorganic silicone resin modified by organosilicon monomer.

Through the technical scheme, the inorganic silicon resin has good film forming property, color development property, hydrophobicity and compatibility.

Preferably, the organic silicon monomer modified nano inorganic silicon resin is applied as a base material in the preparation process of the inorganic coating.

By the technical scheme, the inorganic silicon resin can be used as a base material to be added with other corresponding materials to prepare the inorganic coating meeting the national standard.

Compared with the prior art, the invention has the beneficial effects that:

(1) the compatibility of the pure hydrophilic inorganic silicone resin and the hydrophobic organic silicon monomer is improved by copolymerization with the relatively hydrophilic organic silicon monomer;

(2) the film forming property, the hydrophobicity and the color development property of the inorganic silicon resin are greatly improved through two times of polymerization;

(3) the inorganic silicone resin can be used as a base material to be added with other corresponding materials to prepare inorganic paint meeting national standards.

Drawings

FIG. 1 is a graph showing the results of comparison between examples 3 to 6 of the present invention and comparative example 1.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

Referring to fig. 1, the following is an embodiment of the present invention:

example 1: a preparation method of organic silicon monomer modified nano inorganic silicone resin comprises the following steps:

s1, placing the silica sol solution with the pH value of 8-11 in a reaction kettle, and heating to 50-80 ℃; the silica sol solution is selected from LS-30 type silica sol solution of Zhejiang Uuda chemical Co., Ltd, SiO₂The content is 30 percent; continuously stirring at the rotating speed of 60-80 revolutions;

s2, dripping hydrophilic organic silicon monomers accounting for 1.5-3% of the mass of the silica sol solution; the hydrophilic organic silicon monomer is gamma-glycidoxypropyltrimethoxysilane and/or gamma-methacryloyloxytrimethoxysilane; keeping the temperature in the S1 constant, and reacting for 3-4h to complete copolymerization;

s3, reducing the temperature to 50-60 ℃, and dropwise adding 1-3% of hydrophobic organic silicon monomer; the hydrophobic organic silicon monomer is methyl trioxysilane and/or isobutyl trioxysilane; the rotating speed is increased to 80-120 turns, the reaction lasts for 5-6h, and the copolymerization is completed again.

Example 2: an application of organosilicon monomer modified nano inorganic silicone resin as a matrix material in the preparation and production processes of inorganic coatings. The nano inorganic silicone resin material is prepared by the method of the first embodiment.

Example 3: an organic silicon monomer modified nano inorganic silicone resin is prepared by the following method:

s1, placing the silica sol solution with the pH value of 8-11 in a reaction kettle, and heating to 50-80 ℃; the silica sol solution is selected from LS-30 type silica sol solution of Zhejiang Uuda chemical Co., Ltd, SiO₂The content is 30 percent; continuously stirring at the rotating speed of 60-80 revolutions;

s2, dropwise adding a hydrophilic organic silicon monomer accounting for 1.5% of the mass of the silica sol solution; the hydrophilic organic silicon monomer is gamma-glycidol ether oxygen propyl trimethoxy silane; keeping the temperature in the S1 constant, and reacting for 3-4h to complete copolymerization;

s3, reducing the temperature to 50-60 ℃, and dropwise adding 1-3% of hydrophobic organic silicon monomer; the hydrophobic organic silicon monomer is methyl trioxysilane; the rotating speed is increased to 80-120 turns, the reaction lasts for 5-6h, and the copolymerization is completed again.

Example 4: an organic silicon monomer modified nano inorganic silicone resin is prepared by the following method:

s1, placing the silica sol solution with the pH value of 8-11 in a reaction kettle, and heating to 50-80 ℃; the silica sol solution is selected from LS-30 type silica sol solution of Zhejiang Uuda chemical Co., Ltd, SiO₂The content is 30 percent; continuously stirring at the rotating speed of 60-80 revolutions;

s2, dropwise adding a hydrophilic organic silicon monomer accounting for 1.5% of the mass of the silica sol solution; the hydrophilic organic silicon monomer is gamma-methacryloxy trimethoxy silane; keeping the temperature in the S1 constant, and reacting for 3-4h to complete copolymerization;

s3, reducing the temperature to 50-60 ℃, and dropwise adding 1-3% of hydrophobic organic silicon monomer; the hydrophobic organic silicon monomer is isobutyl trioxysilane; the rotating speed is increased to 80-120 turns, the reaction lasts for 5-6h, and the copolymerization is completed again.

Example 5: an organic silicon monomer modified nano inorganic silicone resin is prepared by the following method:

s1, placing the silica sol solution with the pH value of 8-11 in a reaction kettle, and heating to 50-80 ℃; the silica sol solution is selected from LS-30 type silica sol solution of Zhejiang Uuda chemical Co., Ltd, SiO₂The content is 30 percent; continuously stirring at the rotating speed of 60-80 revolutions;

s2, dropwise adding hydrophilic organic silicon monomers accounting for 3% of the mass of the silica sol solution; the hydrophilic organic silicon monomer is gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloyloxytrimethoxysilane, and the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the gamma-methacryloyloxytrimethoxysilane is 1: 1; keeping the temperature in the S1 constant, and reacting for 3-4h to complete copolymerization;

s3, reducing the temperature to 50-60 ℃, and dropwise adding 3% of hydrophobic organic silicon monomer; the hydrophobic organic silicon monomer is methyl trioxysilane and isobutyl trioxysilane, and the mass ratio of the methyl trioxysilane to the isobutyl trioxysilane is 1: 1; the rotating speed is increased to 80-120 turns, the reaction lasts for 5-6h, and the copolymerization is completed again.

Example 6: an organic silicon monomer modified nano inorganic silicone resin is prepared by the following method:

s1, placing the silica sol solution with the pH value of 8-11 in a reaction kettle, and heating to 50-80 ℃; the silica sol solution is selected from LS-30 type silica sol solution of Zhejiang Uuda chemical Co., Ltd, SiO₂The content is 30 percent; continuously stirring at the rotating speed of 60-80 revolutions;

s2, dropwise adding hydrophilic organic silicon monomers accounting for 2% of the mass of the silica sol solution; the hydrophilic organic silicon monomer is gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloyloxytrimethoxysilane, and the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the gamma-methacryloyloxytrimethoxysilane is 1: 1; keeping the temperature in the S1 constant, and reacting for 3-4h to complete copolymerization;

s3, reducing the temperature to 50-60 ℃, and dropwise adding 2% of hydrophobic organic silicon monomer; the hydrophobic organic silicon monomer is methyl trioxysilane and isobutyl trioxysilane, and the mass ratio of the methyl trioxysilane to the isobutyl trioxysilane is 1: 1; the rotating speed is increased to 80-120 turns, the reaction lasts for 5-6h, and the copolymerization is completed again.

Comparative example 1: conventional inorganic silicone resins commercially available in the art were used as comparative examples.

Adding powdery inorganic mineral powder which accounts for 100 to 150 percent of the mass of the silica sol solution into the inorganic silicon resins prepared in the examples 3 to 6 and the inorganic silicon resin in the comparative example 1, increasing the rotating speed to 500-1000 r/min, continuously reacting for 1 to 2h, wherein the main materials of the inorganic mineral powder are calcium carbonate, kaolin, titanium dioxide and the like, diluting the inorganic mineral powder so that the content of the solid after dilution is the same as that of the solid in the comparative example 1, and comparing the performances of the inorganic mineral powder with the comparative result shown in figure 1. As can be seen from figure 1, the inorganic coating prepared by using the inorganic silicone resin prepared by the method as a base material has greatly improved film forming property, application property, adhesive force, stain resistance and water resistance.

In conclusion, the beneficial effects of the invention are as follows: (1) the compatibility of the pure hydrophilic inorganic silicone resin and the hydrophobic organic silicon monomer is improved by copolymerization with the relatively hydrophilic organic silicon monomer; (2) the film forming property, the hydrophobicity and the color development property of the inorganic silicon resin are greatly improved through two times of polymerization; (3) the inorganic silicone resin can be used as a base material to be added with other corresponding materials to prepare inorganic paint meeting national standards; (4) the inorganic coating prepared by using the inorganic silicone resin prepared by the method as the base material has greatly improved film forming property, construction property, adhesive force, stain resistance and water resistance.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.