CN111057338B - Thickening agent for suspension - Google Patents

Abstract

The present invention is a thickener for suspension, which adopts methacrylic acid, allyl (meth)acrylate, pentaerythritol diallyl ether, hydrogen peroxide, phenol, concentrated sulfuric acid, formaldehyde, epichlorohydrin and The catalyst is prepared as a raw material. In the process of use, each insulation material is dispersed and kept in a uniform suspension state, which solves the problem that the density difference between different materials is too large and difficult to mix uniformly during the mixing and preparation process of the insulation material.

Description

A suspension thickener

technical field

The invention belongs to the technical field of thickeners, in particular to a thickener for suspension.

Background technique

In the preparation of thermal insulation interlayer composite materials, metal particles and ceramic materials are often added to increase its service life, improve fire resistance and thermal insulation performance. When mixing various materials, due to the different densities of each raw material, it is extremely Delamination and uneven mixing occur, so it is necessary to add a thickener to make the upper fibrous material and the lower denser material form a uniform suspension state.

SUMMARY OF THE INVENTION

The present invention provides a kind of thickener which makes the raw materials dispersed in the thermal insulation composite material to form a suspended state and prevents the coagulation and precipitation of the raw materials. In order to achieve the above purpose, the present invention provides the following technical solutions:

A thickener for suspension, the raw materials of the thickener are proportioned by weight: 170-225 parts of dispersion liquid, 260-330 parts of methacrylic acid, and 300-360 parts of allyl (meth)acrylate , 4-8 parts of pentaerythritol diallyl ether and 0.4-0.6 part of hydrogen peroxide; the raw materials of the dispersion liquid are proportioned by weight: 60-80 parts of phenol, 60-90 parts of concentrated sulfuric acid, 30-70 parts of formaldehyde parts, 100-130 parts of epichlorohydrin and 0.3-0.4 parts of catalyst.

Further, the catalyst includes one or more of tetramethylammonium chloride, tetrabutylammonium chloride and tetraethylammonium chloride.

Specifically, the preparation method of the thickener is:

(1) Put methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing evenly, add hydrogen peroxide, and react at 70-90° C. for 1.5-3 hours to obtain mixture;

(2) The obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(3) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Further, the solvent in step (1) includes one or more of n-hexane, cyclohexane and ethyl acetate.

Specifically, the preparation method of the dispersion is as follows:

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 90-110°C for 2-3 hours, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C and continue the reaction for 2h to obtain dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with alkaline solution, then add catalyst and epichlorohydrin in sequence at 75°C and adjust the pH to 13-14, then react at 105-120°C for 2.5-3.5h, A colloidal dispersion was obtained after distillation under reduced pressure.

Further, the alkali solution described in step (2) is one of sodium hydroxide solution and potassium hydroxide solution.

Further, the raw materials of the thickener are proportioned by weight: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid, 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

Compared with the prior art, the present invention has the following advantages:

1. The present invention combines the dispersant with the thickener. During the use process, the fine raw materials in the stirring process are dispersed first to prevent the sedimentation and aggregation of the particles, and then the viscosity is increased to make the materials of various densities uniform. suspended in the mixture.

2. During the use of the thickener of the present invention, one end of the effective molecules of the dispersion liquid can be quickly adsorbed and combined with the surface of each raw material, and the other end can be combined with water to make each raw material more hydrophilic, more dispersed in water, and reduce cohesion. It is convenient to mix the materials evenly.

3. The polymerization of the thickener methacrylic acid and allyl (meth)acrylate of the present invention can be compatible with the dispersion liquid using epoxy sulfonated phenolic resin as the main raw material in the present invention, so as to increase the viscosity and improve the viscosity. Suspension and stabilization of different materials.

4. The present invention has good dispersibility and high thickening efficiency. During the use process, the agglomeration of each raw material is reduced, the overall compatibility is improved, and the materials are mixed more uniformly.

Detailed ways

The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

The proportion of raw materials by weight percentage is: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid , 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 105°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 115°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 80° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 2

The proportion of raw materials by weight percentage is: 260 parts of methacrylic acid, 300 parts of allyl (meth)acrylate, 4 parts of pentaerythritol diallyl ether and 0.4 parts of hydrogen peroxide, 80 parts of phenol, 90 parts of concentrated sulfuric acid , 70 parts of formaldehyde, 130 parts of epichlorohydrin and 0.4 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 105°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 115°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 80° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 3

The proportion of raw materials by weight percentage is: 330 parts of methacrylic acid, 360 parts of allyl (meth)acrylate, 8 parts of pentaerythritol diallyl ether and 0.6 parts of hydrogen peroxide, 60 parts of phenol, 60 parts of concentrated sulfuric acid , 30 parts of formaldehyde, 100 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 105°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 115°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 80° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 4

The proportion of raw materials by weight percentage is: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid , 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 90°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 115°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 80° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 5

The proportion of raw materials by weight percentage is: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid , 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 110°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h, to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 115°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 80° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 6

The proportion of raw materials by weight percentage is: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid , 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 105°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 105°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 80° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 7

The proportion of raw materials by weight percentage is: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid , 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 105°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) The pH of the dispersion mother liquor is adjusted to neutrality with sodium hydroxide solution, then tetrabutylammonium chloride and epichlorohydrin are added successively at 75°C and the pH is adjusted to 13-14, and the reaction is carried out at 120°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 80° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 8

The proportion of raw materials by weight percentage is: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid , 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 105°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 115°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 70° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Example 9

The proportion of raw materials by weight percentage is: 290 parts of methacrylic acid, 330 parts of allyl (meth)acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 parts of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid , 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 parts of tetrabutylammonium chloride.

(1) Add concentrated sulfuric acid to the liquid phenol, stir evenly, react at 105°C for 3h, then cool down to 65°C, slowly add formaldehyde and stir, then heat up to 90°C, continue the reaction for 2h to obtain a dispersion mother liquor;

(2) Adjust the pH of the dispersing mother liquor to neutrality with sodium hydroxide solution, then add tetrabutylammonium chloride and epichlorohydrin successively at 75°C and adjust the pH to 13-14, then react at 115°C After 3.5h, a colloidal dispersion was obtained after vacuum distillation.

(3) placing methacrylic acid, allyl (meth)acrylate and pentaerythritol diallyl ether in a solvent, after mixing uniformly, adding hydrogen peroxide, and reacting at 90° C. for 2 hours to obtain a mixed solution;

(4) the obtained mixed solution of step (1) is filtered to obtain a solid mixture, which is cleaned and removed from impurities and then placed in a vacuum oven for vacuum drying to obtain a powder;

(5) The powder obtained in step (2) is placed in the dispersion liquid and mixed evenly, and the finished product is obtained after homogenization.

Preparation of thermal insulation material: Pour water, composite resin, metal tailings or ceramics and other fireproof materials and functional additives into a mixing container in a mass ratio of 1:4:1.25:0.5 and stir evenly, and add the present invention during the stirring process. Finished product, vested.

The performance comparison of the finished products of each embodiment in the preparation of thermal insulation materials is as follows:

In the table, in the preparation process of the composite thermal insulation material, 0.3 wt% was added to the finished products of each embodiment respectively.

Table 1

Test items Viscosity (MPa·s) bottom sediment Example 1 227 No precipitation Example 2 153 a small amount of precipitation Example 3 342 a small amount of agglomeration Example 4 257 microagglomeration Example 5 176 microagglomeration Example 6 234 microagglomeration Example 7 212 microagglomeration Example 8 166 microprecipitation Example 9 286 microprecipitation

As shown in Table 1, the viscosity of the mixed liquid in the mixing process of the materials added with the same content of the finished products of each embodiment is all above 150MPa·s. The reduction of acrylic acid and allyl (meth)acrylate, the viscosity of the mixture will decrease correspondingly, and a small amount of precipitation will occur in the bottom layer, and on the contrary, the decrease of the content of the dispersion will correspond to the decrease of methacrylic acid and allyl (meth)acrylate. The increase of base) acrylate will increase the viscosity of the mixed solution, the bottom layer will not produce precipitation but a small amount of agglomeration will occur anywhere in the mixed solution; in Examples 4 to 7, as the preparation temperature of the dispersion decreases, the dispersion of the dispersion will be reduced. The amount of production is slightly reduced, thereby reducing the overall dispersibility, increasing the viscosity of the mixture, and there will be a small amount of agglomeration in the mixture. Correspondingly, as the preparation temperature of the dispersion increases, the amount of the dispersion will increase slightly. , reducing the viscosity and leaving a part of the sediment at the bottom of the mixture.

In addition to the test results in the above table, after adding 0.5 wt% of the finished products of each example in the preparation process of each thermal insulation material, the bottom layer of the mixture did not precipitate, and the entire mixture did not agglomerate.

For those skilled in the art, various other corresponding changes and deformations can be made according to the technical solutions and concepts described above, and all these changes and deformations should fall within the protection scope of the claims of the present invention.

Claims (5)

1. The thickening agent for suspension is characterized by being prepared from the following raw materials in parts by weight: 170-225 parts of dispersion liquid, 260-330 parts of methacrylic acid, 300-360 parts of allyl (methyl) acrylate, 4-8 parts of pentaerythritol diallyl ether and 0.4-0.6 part of hydrogen peroxide; the dispersion liquid is prepared from the following raw materials in parts by weight: 60-80 parts of phenol, 60-90 parts of concentrated sulfuric acid, 30-70 parts of formaldehyde, 100-130 parts of epoxy chloropropane and 0.3-0.4 part of catalyst; the catalyst comprises one or two of tetrabutylammonium chloride and tetraethylammonium chloride;

the preparation method of the thickening agent comprises the following steps:

(1) placing methacrylic acid, allyl (methyl) acrylate and pentaerythritol diallyl ether in a solvent, uniformly mixing, adding hydrogen peroxide, and reacting at 70-90 ℃ for 1.5-3 h to obtain a mixed solution;

(2) filtering the mixed solution obtained in the step (1) to obtain a solid mixture, cleaning the solid mixture to remove impurities, and placing the solid mixture in a vacuum box for vacuum drying to obtain powder;

(3) and (3) placing the powder obtained in the step (2) into a dispersion liquid, uniformly mixing, and homogenizing to obtain a finished product.

2. The thickener for suspension as claimed in claim 1, wherein the solvent of step (1) is one or more of n-hexane, cyclohexane or ethyl acetate.

3. The thickener for suspension as claimed in claim 1, wherein the dispersion is prepared by a method comprising:

(1) adding concentrated sulfuric acid into liquid phenol, stirring uniformly, reacting at 90-110 ℃ for 2-3 h, cooling to 65 ℃, slowly adding formaldehyde, stirring, heating to 90 ℃, and continuing to react for 2h to obtain dispersed mother liquor;

(2) adjusting the dispersion mother liquor to be neutral, sequentially adding a catalyst and epoxy chloropropane at 75 ℃, adjusting the pH to 13-14, reacting for 2.5-3.5 h at 105-120 ℃, and carrying out reduced pressure distillation to obtain colloidal dispersion liquid.

4. The thickener for suspension as claimed in claim 3, wherein the pH adjustment in the step (2) is carried out by using an alkali solution of sodium hydroxide solution or potassium hydroxide solution.

5. The thickening agent for suspension as claimed in claim 1, wherein the thickening agent is prepared from the following raw materials in parts by weight: 290 parts of methacrylic acid, 330 parts of allyl (methyl) acrylate, 5 parts of pentaerythritol diallyl ether, 0.5 part of hydrogen peroxide, 70 parts of phenol, 75 parts of concentrated sulfuric acid, 50 parts of formaldehyde, 120 parts of epichlorohydrin and 0.3 part of tetrabutylammonium chloride.