CN118562442B - A porcelain fireproof decorative beauty glue - Google Patents

Abstract

The utility model provides a porcelain fire prevention formula of formula for decoration uses cosmetic glue, belongs to adhesive technical field, porcelain fire prevention formula for decoration uses cosmetic glue specifically for decoration does, by weight: 95-130 parts of alpha, omega-dihydroxy polydimethylsiloxane, 13-28 parts of simethicone, 1-3 parts of fumed silica, 5-15 parts of organic polysilazane, 4-8 parts of composite fluxing agent, 25-50 parts of modified whisker mixture, 0.1-1 part of catalyst and 6-11 parts of cross-linking agent; the ceramic fireproof type cosmetic glue for decoration is 9-13 min in surface drying time, 1.75-1.92 MPa in bonding strength, 1.85-2.21 MPa in tensile strength, 90-99% in elastic recovery rate, 57-61 in Shore hardness, 5.7-6.4 h in flame retardant grade V0 and fireproof integrity.

Description

A porcelain fireproof decorative beauty glue

Technical Field

The invention relates to a porcelain fireproof decorative beauty glue, belonging to the technical field of adhesives.

Background Art

Decorative beauty glue, with silicone material as the base material, is also called silicone glue or silicone sealant. Its formula is 107 glue (hydroxyl-terminated polydimethylsiloxane), silicone oil or white oil, plus cross-linking agent and coupling agent, and color powder. The curing principle is moisture curing. Its mechanical properties such as tensile strength, elongation, modulus, etc. can meet the requirements of structural adhesives. The formula of the beauty glue does not contain organic solvents. The organic small molecules released during the sizing and curing process are extremely low in toxicity and the release amount is very small. It is a relatively environmentally friendly adhesive material. After long-term practical application, decorative beauty glue has been recognized by the domestic and foreign construction industry as a reliable high-performance chemical building material for elastic structures, bonding, sealing and caulking. However, conventional decorative beauty glue is not flame retardant and will continue to burn after contact with flames. With the improvement of building fire protection level requirements and the construction industry's emphasis on curtain wall fire resistance, the flame retardant and fireproof properties of decorative beauty glue have become one of its inevitable development directions.

An effective way to flame retardant and fireproof the decorative glue is to add flame retardant fillers and fillers that can undergo ceramic transformation at high temperature into the formula to achieve high-efficiency flame retardant and fireproof performance. However, in actual applications, the sealant layer is prone to flow, powder or crack at high temperature, and the ceramic body formed at high temperature has low mechanical properties and is bonded with integrity damage, which directly leads to the loss of the blocking and isolation efficiency of the decorative glue against high-temperature fireworks, or even failure, and cannot meet the actual use requirements of the application scenario.

Chinese patent CN110003844A discloses a method for preparing a ceramic fireproof silicone sealant, the sealant comprising: 80-100 parts of α,ω-dihydroxy polydimethylsiloxane, 1-50 parts of polydimethylsiloxane, 50-100 parts of functional filler, 2-24 parts of silane coupling agent, 2-15 parts of plasticizer, 0.5-3 parts of catalyst, 5-20 parts of water glass; the method introduces reactive functional groups by surface modification of solid fillers such as ceramic powder and flame retardant, so that it can react with the base glue to form a cross-linked network structure, further improving its bonding strength. The fireproof integrity of the colloid obtained in this patent is relatively poor, only 3 hours, which shows that the ceramic effect of the colloid itself is poor, and it is difficult to block the flame for a long time.

Chinese patent CN116376509A discloses a flame retardant silicone fireproof sealant and a preparation method thereof. The flame retardant silicone fireproof sealant comprises the following components by weight: 95-105 parts of base material, 80-260 parts of flame retardant, 1-10 parts of filler, 0.5-2 parts of catalyst and 0.5-5 parts of coupling agent; the base material is composed of α,ω-dihydroxy polydimethylsiloxane, trimethoxy-terminated polydimethylsiloxane, 1-butyl-3-methylimidazolium salt ionic liquid compound and paraffin oil in a weight ratio of 100:(30-45):(10-15):(5-10). The flame retardant silicone fireproof sealant provided by the present invention effectively solves the problem of poor system compatibility of existing silicone fireproof sealants, thereby further improving the mechanical properties of silicone fireproof sealants such as tensile strength. The performance of the sealant obtained by this patent is good, but the patent does not disclose relevant data on its fire prevention and fire blocking performance. However, judging from the formula composition disclosed in the patent, no effective ceramic filler is added, so this patent does not solve the fire prevention problem of the sealant.

From the above, we can see that the porcelain fireproof decorative beauty glue still has the disadvantages of being difficult to form an effective flame-blocking ceramic body under high-temperature flame erosion of the glue layer, or the formed ceramic body has low mechanical properties, poor bonding integrity, and short fire-retardant time. Therefore, it is of great practical significance to develop a porcelain fireproof decorative beauty glue that can form a high mechanical strength ceramic body and a long fire-retardant time under high-temperature flames.

Summary of the invention

In view of the deficiencies in the above-mentioned prior art, the present invention provides a ceramic fireproof decorative beauty glue to achieve the following invention objectives: to prepare a ceramic fireproof decorative beauty glue that is easy to form a high mechanical strength ceramic body under high-temperature flame ablation and has a long fire-retardant time.

In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

A porcelain fireproof decorative beauty glue, the specific formula of the porcelain fireproof decorative beauty glue is, in parts by weight:

100-140 parts of α,ω-dihydroxy polydimethylsiloxane,

Dimethyl silicone oil 15~30 parts,

Fumed silica 0.5~2 parts,

Modified zirconium phosphate 10~35 parts,

Modified flux 5~11 parts,

Modified calcium sulfate whisker 15~28 parts,

Catalyst 0.3~1.3 parts,

Cross-linking agent 2~5 parts,

Cross-linking agent 6-11 parts;

The particle size of the fumed silica is 10-100 nm;

The catalyst is dibutyltin dilaurate;

The auxiliary cross-linking agent is a mixture of tris(trimethylsilyl)silane and triethyl borate;

The mass ratio of tris(trimethylsilyl)silane to triethyl borate is 1-8:20;

The cross-linking agent is one of methyltrimethoxysilane and methyltriethoxysilane;

The following are further improvements to the above technical solution:

Step 1: Preparation of modified zirconium phosphate

The zirconium phosphate powder is dried at 110-140° C. for 4-7 hours, cooled to room temperature, added to a high-speed dispersion kettle, and then methyl ethyl ketone is added. After strong dispersion at a speed of 8000-12000 rpm for 2-4 hours, the dispersion rate is reduced to 1000-4000 rpm, the temperature is increased and kept constant at 65-85° C., and then 3-isocyanate propyl trimethoxy silane is added. The reaction is carried out at a constant temperature under condensation reflux for 4-7 hours. Then, ethylene bis stearamide is added, and the reaction is continued at a constant temperature under condensation reflux for 3-6 hours, and then the reaction is cooled to room temperature. The material is centrifuged, and the solid obtained by centrifugation is washed with anhydrous ethanol for 2-4 times, and vacuum dried at 40-70° C. for 6-11 hours to obtain modified zirconium phosphate.

The particle size of the zirconium phosphate powder is 50-5000 nm;

The mass ratio of the zirconium phosphate powder, methyl ethyl ketone, 3-isocyanate propyl trimethoxy silane and ethylene bisstearamide is 15-30:120-180:1-6:3-10.

Step 2: Preparation of modified flux

The flux and heptane are mixed in a mass ratio of 6-14:18, and then put into a ball mill to be ball-milled into a slurry. After the solid particles in the slurry are ball-milled to a particle size of 0.1-3 μm, the slurry is obtained by discharging the material, and then the slurry is added into a reactor, and then heptane of 1-2.3 times the mass of the slurry is added, and after stirring and dispersing for 2-5 hours at a speed of 1500-3500 rpm, octadecyltrichlorosilane is added, and then the stirring rate is reduced to 900-1300 rpm, and the temperature is increased and kept constant to 55-75° C., and the reaction is carried out under condensation reflux for 3-7 hours, and then the temperature is reduced to room temperature, and the material is discharged and filtered, and the filtered solid is washed with anhydrous ethanol for 3-5 times, and then vacuum dried at 40-60° C. for 2-5 hours to obtain a modified flux;

The flux is one of sodium pyrophosphate, sodium hexametaphosphate, calcium phosphate, aluminum phosphate, zinc phosphate, magnesium phosphate, iron phosphate, calcium pyrophosphate, and boron phosphate;

The added mass of the octadecyltrichlorosilane is 3-10% of the mass of the slurry added to the reactor.

Step 3: Preparation of modified calcium sulfate whiskers

After drying the calcium sulfate whisker at 120-150° C. for 3-6 hours, cooling to room temperature, adding the calcium sulfate whisker to a reaction kettle, adding toluene, controlling the stirring rate at 1000-2000 rpm, raising the temperature and maintaining the temperature at 45-60° C., stirring and dispersing for 4-9 hours under condensation reflux, reducing the stirring rate to 600-950 rpm, then adding butyl phosphate, monooctadecyl phosphate, and triisobutyl aluminum, continuing to stir and react for 5-11 hours under condensation reflux, filtering, washing the filtered solid with anhydrous ethanol for 2-4 times, and drying at 75-95° C. for 3-8 hours to obtain modified calcium sulfate whiskers;

The mass ratio of the calcium sulfate whisker, toluene, butyl phosphate, monooctadecyl phosphate, and triisobutylaluminum is 15-40:150-300:2-7:1-5:0.1-0.5;

The diameter of the calcium sulfate whisker is 1-5 μm, and the aspect ratio is 10-240.

Step 4: Preparation of porcelain fireproof decorative glue

According to the specific formula of the porcelain fireproof decorative beauty glue in parts by weight, α, ω-dihydroxy polydimethylsiloxane, dimethyl silicone oil, a cross-linking agent, a catalyst and a cross-linking agent are put into a double planetary mixer. Under the conditions of a stirring rate of 80-110 rpm and a dispersion rate of 5000-8000 rpm, the stirring rate is increased to 120-140 rpm and the dispersion rate is increased to 8500-10000 rpm. Then, fumed silica is added, and the stirring and dispersion is continued for 3-6 hours. Then, modified zirconium phosphate, modified flux and modified calcium sulfate whisker are added, and the stirring and dispersion is continued for 9-14 hours to obtain a glue solution. After vacuum degassing, the glue solution is filled into a plastic finished product bottle, and sealed with nitrogen to obtain a finished porcelain fireproof decorative beauty glue product.

Compared with the prior art, the present invention achieves the following beneficial effects:

1. The present invention utilizes a high-speed dispersion process to uniformly disperse zirconium phosphate powder in a methyl ethyl ketone solvent, and then adds 3-isocyanate propyltrimethoxysilane to modify the surface of the zirconium phosphate powder. Isocyanate functional groups and methoxysilane functional groups remain on the surface of the modified zirconium phosphate powder particles. These two functional groups react with the added ethylene bisstearamide, so that the surface of the zirconium phosphate powder is tightly coated with a layer of ethylene bisstearamide. The molecular structure of ethylene bisstearamide has a non-polar and strongly hydrophobic property, and is very compatible with α, ω-dihydroxy polydimethylsiloxane in the beauty glue formula, which greatly promotes the uniformity of the dispersion of the zirconium phosphate powder in the beauty glue formula, thereby ensuring that the zirconium phosphate powder can improve the mechanical properties, flame retardant properties and fire resistance of the colloid after curing;

2. The phosphorus-containing fluxing agents added in the present invention, such as sodium pyrophosphate, sodium hexametaphosphate, calcium phosphate, aluminum phosphate, zinc phosphate, magnesium phosphate, iron phosphate, calcium pyrophosphate, and boron phosphate, have relatively low melting points. When the colloid obtained after the beauty glue is cured is burned by a high-temperature flame, these fluxing agents begin to melt into a viscous melt at a relatively low temperature. The melt will bond together the high-temperature resistant fillers such as zirconium phosphate powder, calcium sulfate whiskers, and fumed silica in the colloid. At the same time, the fluxing agent and the above-mentioned high-temperature resistant fillers and the organic polysiloxane cross-linked network in the cured colloid undergo a high-temperature porcelainization reaction to form a dense and ablation-resistant colloid. The above-mentioned phosphorus-containing flux is surface-modified by octadecyltrichlorosilane, and non-polar long-chain alkane groups containing carbon-silicon bonds are grafted on the surface. This surface structure has very good compatibility with α,ω-dihydroxypolydimethylsiloxane, so the surface-modified phosphorus-containing flux can be well dispersed in the beauty glue matrix, thereby reducing the negative effects of the phosphorus-containing flux on the beauty glue due to uneven dispersion, and also promoting the improvement of the flame retardant and fire resistance of the beauty glue by the phosphorus-containing flux.

3. The present invention adds calcium sulfate whiskers with excellent high temperature resistance to the beauty glue formula. In order to improve the dispersion uniformity of the calcium sulfate whiskers, triisobutyl aluminum is used as a catalyst, and butyl phosphate and monooctadecyl phosphate are used to modify the surface of the calcium sulfate whiskers. The modified calcium sulfate whiskers can be evenly dispersed in the colloid formula mainly composed of α, ω-dihydroxypolydimethylsiloxane during the high-speed dispersion, stirring and mixing process of a double planetary mixer, thereby obtaining a cured glue layer with particularly excellent high-temperature ablation performance;

4. The present invention uses a mixture of tri(trimethylsilyl)silane and triethyl borate as a co-crosslinking agent, and cooperates with methyltrimethoxysilane or methyltriethoxysilane to form a highly reactive crosslinking curing system. Tri(trimethylsilyl)silane and triethyl borate are active substances that are very easy to hydrolyze. After the glue is applied, the trace amount of moisture adsorbed on the surface of the glue layer can quickly catalyze the hydrolysis reaction of tri(trimethylsilyl)silane and triethyl borate, promote the rapid curing of the glue layer, and also promote the crosslinking reaction speed and the density of the crosslinking network inside the glue layer, thereby improving the mechanical properties, flame retardant properties and flame ablation resistance of the glue layer;

5. The porcelain fireproof decorative beauty glue obtained by the present invention has a surface drying time of 9 to 13 minutes, a bonding strength of 1.75 to 1.92 MPa, a tensile strength of 1.85 to 2.21 MPa, an elastic recovery rate of 90 to 99%, a Shore hardness of 57 to 61, a flame retardant grade of V0, and a fire resistance integrity of 5.7 to 6.4 hours.

DETAILED DESCRIPTION

The preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

Example 1: A porcelain fireproof decorative beauty glue

Step 1: Preparation of modified zirconium phosphate

The zirconium phosphate powder is dried at 120° C. for 5 hours, cooled to room temperature and added to a high-speed dispersion kettle, and then methyl ethyl ketone is added. After intensive dispersion at a speed of 9000 rpm for 3 hours, the dispersion rate is reduced to 3000 rpm, the temperature is increased and kept constant at 80° C., and then 3-isocyanate propyl trimethoxy silane is added. The reaction is carried out at a constant temperature for 5 hours under condensation reflux. Then, ethylene bis stearamide is added. The reaction is continued at a constant temperature for 5 hours under condensation reflux and then cooled to room temperature. The material is centrifuged, and the solid obtained by centrifugation is washed 3 times with anhydrous ethanol and vacuum dried at 60° C. for 7 hours to obtain modified zirconium phosphate.

The particle size of the zirconium phosphate powder is 2000 nm;

The mass ratio of the zirconium phosphate powder, methyl ethyl ketone, 3-isocyanate propyltrimethoxysilane and ethylene bisstearamide is 19:150:4:7.

Step 2: Preparation of modified flux

The flux and heptane were mixed in a mass ratio of 7:18, and then put into a ball mill to be ball-milled into a slurry. After the solid particles in the slurry were ball-milled to a particle size of 2 μm, the slurry was obtained by discharging the material. Then, the slurry was added into a reactor, and then heptane with a mass of 1.3 times that of the slurry was added. After stirring and dispersing at a speed of 1900 rpm for 4 hours, octadecyltrichlorosilane was added, and then the stirring rate was reduced to 1200 rpm, and the temperature was raised and kept constant at 70° C., and the reaction was carried out under condensation reflux for 4 hours, and then the temperature was reduced to room temperature, and the material was discharged and filtered. The filtered solid was washed with anhydrous ethanol for 4 times, and then vacuum dried at 55° C. for 3 hours to obtain a modified flux.

The flux is sodium pyrophosphate;

The mass of the added octadecyltrichlorosilane is 5% of the mass of the slurry added to the reactor.

Step 3: Preparation of modified calcium sulfate whiskers

After drying the calcium sulfate whisker at 140° C. for 4 hours, cooling to room temperature, adding the calcium sulfate whisker to a reaction kettle, adding toluene, controlling the stirring rate at 1600 rpm, raising the temperature and maintaining the temperature at 55° C., stirring and dispersing for 8 hours under condensation reflux, reducing the stirring rate to 850 rpm, then adding butyl phosphate, monooctadecyl phosphate, and triisobutylaluminum, continuing to stir and react for 7 hours under condensation reflux, filtering, washing the filtered solid with anhydrous ethanol for 3 times, and drying at 90° C. for 7 hours to obtain modified calcium sulfate whisker;

The mass ratio of the calcium sulfate whisker, toluene, butyl phosphate, monooctadecyl phosphate, and triisobutylaluminum is 30:190:5:2:0.4;

The diameter of the calcium sulfate whisker is 4 μm, and the aspect ratio is 200.

Step 4: Preparation of porcelain fireproof decorative glue

The specific formula of the porcelain fireproof decorative beauty glue is as follows, in parts by weight:

α,ω-dihydroxy polydimethylsiloxane 130 parts,

Dimethyl silicone oil 19 parts,

1 part of fumed silica,

Modified zirconium phosphate 20 parts,

Modified flux 9 parts,

Modified calcium sulfate whisker 22 parts,

Catalyst 1 part,

3 parts of cross-linking agent,

Cross-linking agent 7 parts;

The particle size of the fumed silica is 40 nm;

The catalyst is dibutyltin dilaurate;

The auxiliary cross-linking agent is a mixture of tris(trimethylsilyl)silane and triethyl borate;

The mass ratio of tris(trimethylsilyl)silane to triethyl borate is 5:20;

The cross-linking agent is methyltrimethoxysilane;

According to the specific formula of porcelain fireproof decorative beauty glue in parts by weight, α, ω-dihydroxy polydimethylsiloxane, dimethyl silicone oil, co-crosslinking agent, catalyst and crosslinking agent are put into a double planetary mixer. Under the conditions of stirring rate of 100 rpm and dispersion rate of 7000 rpm, stirring and dispersing for 80 minutes, the stirring rate is increased to 135 rpm and the dispersion rate is increased to 9500 rpm, and then fumed silica is added. After continuous stirring and dispersing for 4 hours, modified zirconium phosphate, modified flux and modified calcium sulfate whisker are added. After continuous stirring and dispersing for 11 hours, a glue solution is obtained. After vacuum degassing, it is filled into plastic finished product bottles. After sealing with nitrogen, a finished product of porcelain fireproof decorative beauty glue is obtained.

Example 2: A porcelain fireproof decorative beauty glue

Step 1: Preparation of modified zirconium phosphate

The zirconium phosphate powder is dried at 110° C. for 4 hours, cooled to room temperature and added to a high-speed dispersion kettle, and then methyl ethyl ketone is added. After intensive dispersion at a speed of 8000 rpm for 2 hours, the dispersion rate is reduced to 1000 rpm, the temperature is increased and kept constant at 65° C., and then 3-isocyanate propyl trimethoxysilane is added. The reaction is carried out at a constant temperature for 4 hours under condensation reflux. Then, ethylene bisstearamide is added. The reaction is continued at a constant temperature for 3 hours under condensation reflux and then cooled to room temperature. The material is centrifuged, and the solid obtained by centrifugation is washed twice with anhydrous ethanol and vacuum dried at 40° C. for 6 hours to obtain modified zirconium phosphate.

The particle size of the zirconium phosphate powder is 50 nm;

The mass ratio of the zirconium phosphate powder, methyl ethyl ketone, 3-isocyanate propyltrimethoxysilane and ethylene bisstearamide is 15:120:1:3.

Step 2: Preparation of modified flux

The flux and heptane were mixed in a mass ratio of 6:18, and then put into a ball mill to be ball-milled into a slurry. After the solid particles in the slurry were ball-milled to a particle size of 0.1 μm, the slurry was obtained by discharging the material. Then, the slurry was added into a reactor, and then heptane with a mass of 1 times that of the slurry was added. After stirring and dispersing for 2 hours at a speed of 1500 rpm, octadecyltrichlorosilane was added, and then the stirring rate was reduced to 900 rpm, and the temperature was raised and kept constant at 55° C., and the reaction was carried out under condensation reflux for 3 hours, and then the temperature was reduced to room temperature, and the material was discharged and filtered. After the filtered solid was washed with anhydrous ethanol for 3 times, it was vacuum dried at 40° C. for 2 hours to obtain a modified flux.

The flux is sodium hexametaphosphate;

The added mass of the octadecyltrichlorosilane is 3% of the mass of the slurry added to the reactor.

Step 3: Preparation of modified calcium sulfate whiskers

After drying the calcium sulfate whisker at 120° C. for 3 hours, cooling to room temperature, adding the calcium sulfate whisker to a reaction kettle, adding toluene, controlling the stirring rate at 1000 rpm, raising the temperature and maintaining the temperature at 45° C., stirring and dispersing for 4 hours under condensation reflux, reducing the stirring rate to 600 rpm, then adding butyl phosphate, monooctadecyl phosphate, and triisobutylaluminum, continuing to stir and react under condensation reflux for 5 hours, filtering, washing the filtered solid with anhydrous ethanol twice, and drying at 75° C. for 3 hours to obtain modified calcium sulfate whisker;

The mass ratio of the calcium sulfate whisker, toluene, butyl phosphate, monooctadecyl phosphate, and triisobutylaluminum is 15:150:2:1:0.1;

The diameter of the calcium sulfate whisker is 1 μm, and the aspect ratio is 10.

Step 4: Preparation of porcelain fireproof decorative glue

The specific formula of the porcelain fireproof decorative beauty glue is as follows, in parts by weight:

100 parts of α,ω-dihydroxypolydimethylsiloxane,

15 parts of dimethyl silicone oil,

0.5 parts of fumed silica,

Modified zirconium phosphate 10 parts,

Modified flux 5 parts,

Modified calcium sulfate whisker 15 parts,

Catalyst 0.3 parts,

2 parts of cross-linking agent,

Cross-linking agent 6 parts;

The particle size of the fumed silica is 10 nm;

The catalyst is dibutyltin dilaurate;

The auxiliary cross-linking agent is a mixture of tris(trimethylsilyl)silane and triethyl borate;

The mass ratio of tris(trimethylsilyl)silane to triethyl borate is 1:20;

The cross-linking agent is methyltriethoxysilane;

According to the specific formula of porcelain fireproof decorative beauty glue in parts by weight, α, ω-dihydroxy polydimethylsiloxane, dimethyl silicone oil, co-crosslinking agent, catalyst and crosslinking agent are put into a double planetary mixer. Under the conditions of stirring rate of 80 rpm and dispersion rate of 5000 rpm, stirring and dispersing for 40 minutes, the stirring rate is increased to 120 rpm and the dispersion rate is increased to 8500 rpm, and then fumed silica is added. After continuous stirring and dispersing for 3 hours, modified zirconium phosphate, modified flux and modified calcium sulfate whisker are added. After continuous stirring and dispersing for 9 hours, a glue solution is obtained. After vacuum degassing, it is filled into plastic finished product bottles. After sealing with nitrogen, a finished product of porcelain fireproof decorative beauty glue is obtained.

Example 3: A porcelain fireproof decorative beauty glue

Step 1: Preparation of modified zirconium phosphate

The zirconium phosphate powder is dried at 140° C. for 7 hours, cooled to room temperature and added to a high-speed dispersion kettle, and then methyl ethyl ketone is added. After intensive dispersion at a speed of 12,000 rpm for 4 hours, the dispersion rate is reduced to 4,000 rpm, the temperature is increased and kept constant at 85° C., and then 3-isocyanate propyltrimethoxysilane is added. The reaction is carried out at a constant temperature for 7 hours under condensation reflux. Then, ethylene bisstearamide is added, and the reaction is continued at a constant temperature for 6 hours under condensation reflux. The reaction is cooled to room temperature, the material is centrifuged, and the solid obtained by centrifugation is washed 4 times with anhydrous ethanol, and vacuum dried at 70° C. for 11 hours to obtain modified zirconium phosphate.

The particle size of the zirconium phosphate powder is 5000 nm;

The mass ratio of the zirconium phosphate powder, methyl ethyl ketone, 3-isocyanate propyltrimethoxysilane and ethylene bisstearamide is 30:180:6:10.

Step 2: Preparation of modified flux

The flux and heptane were mixed in a mass ratio of 14:18, and then put into a ball mill to be ball-milled into a slurry. After the solid particles in the slurry were ball-milled to a particle size of 3 μm, the slurry was obtained by discharging the material. Then, the slurry was added into a reactor, and then heptane with a mass of 2.3 times that of the slurry was added. After stirring and dispersing at a speed of 3500 rpm for 5 hours, octadecyltrichlorosilane was added, and then the stirring rate was reduced to 1300 rpm, and the temperature was raised and kept constant at 75° C., and the reaction was carried out under condensation reflux for 7 hours, and then the temperature was reduced to room temperature, and the material was discharged and filtered. After the filtered solid was washed with anhydrous ethanol for 5 times, it was vacuum dried at 60° C. for 5 hours to obtain a modified flux.

The flux is calcium phosphate;

The added mass of the octadecyltrichlorosilane is 10% of the mass of the slurry added to the reactor.

Step 3: Preparation of modified calcium sulfate whiskers

After drying the calcium sulfate whisker at 150° C. for 6 hours, cooling to room temperature, adding the calcium sulfate whisker to a reaction kettle, adding toluene, controlling the stirring rate at 2000 rpm, raising the temperature and maintaining the temperature at 60° C., stirring and dispersing for 9 hours under condensation reflux, reducing the stirring rate to 950 rpm, then adding butyl phosphate, monooctadecyl phosphate, and triisobutylaluminum, continuing to stir and react for 11 hours under condensation reflux, filtering, washing the filtered solid with anhydrous ethanol for 4 times, and drying at 95° C. for 8 hours to obtain modified calcium sulfate whisker;

The mass ratio of the calcium sulfate whisker, toluene, butyl phosphate, monooctadecyl phosphate, and triisobutylaluminum is 40:300:7:5:0.5;

The diameter of the calcium sulfate whisker is 5 μm, and the aspect ratio is 240.

Step 4: Preparation of porcelain fireproof decorative glue

The specific formula of the porcelain fireproof decorative beauty glue is as follows, in parts by weight:

140 parts of α,ω-dihydroxy polydimethylsiloxane,

30 parts of dimethyl silicone oil,

2 parts of fumed silica,

Modified zirconium phosphate 35 parts,

Modified flux 11 parts,

Modified calcium sulfate whisker 28 parts,

Catalyst 1.3 parts,

5 parts of cross-linking agent,

Cross-linking agent 11 parts;

The particle size of the fumed silica is 100 nm;

The catalyst is dibutyltin dilaurate;

The auxiliary cross-linking agent is a mixture of tris(trimethylsilyl)silane and triethyl borate;

The mass ratio of tris(trimethylsilyl)silane to triethyl borate is 8:20;

The cross-linking agent is methyltriethoxysilane;

According to the specific formula of porcelain fireproof decorative beauty glue in parts by weight, α, ω-dihydroxy polydimethylsiloxane, dimethyl silicone oil, co-crosslinking agent, catalyst and crosslinking agent are put into a double planetary mixer. Under the conditions of stirring rate of 110 rpm and dispersion rate of 8000 rpm, stirring and dispersing for 90 minutes, the stirring rate is increased to 140 rpm and the dispersion rate is increased to 10000 rpm, and then fumed silica is added. After continuous stirring and dispersing for 6 hours, modified zirconium phosphate, modified flux and modified calcium sulfate whisker are added. After continuous stirring and dispersing for 14 hours, a glue solution is obtained. After vacuum degassing, it is filled into plastic finished product bottles. After sealing with nitrogen, a finished product of porcelain fireproof decorative beauty glue is obtained.

Example 4: A porcelain fireproof decorative beauty glue

The operation of step 1 is the same as that of embodiment 1;

Step 2: Preparation of modified flux

The flux is aluminum phosphate, and the other operations are the same as in Example 1;

The operations of steps 3 and 4 are the same as those of Example 1.

Example 5: A porcelain fireproof decorative beauty glue

The operation of step 1 is the same as that of embodiment 1;

Step 2: Preparation of modified flux

The flux is zinc phosphate, and the other operations are the same as in Example 1;

The operations of steps 3 and 4 are the same as those of Example 1.

Example 6: A porcelain fireproof decorative beauty glue

The operation of step 1 is the same as that of embodiment 1;

Step 2: Preparation of modified flux

The flux is magnesium phosphate, and the other operations are the same as in Example 1;

The operations of steps 3 and 4 are the same as those of Example 1.

Example 7: A porcelain fireproof decorative beauty glue

The operation of step 1 is the same as that of embodiment 1;

Step 2: Preparation of modified flux

The flux is ferric phosphate, and the other operations are the same as in Example 1;

The operations of steps 3 and 4 are the same as those of Example 1.

Example 8: A porcelain fireproof decorative beauty glue

The operation of step 1 is the same as that of embodiment 1;

Step 2: Preparation of modified flux

The flux is calcium pyrophosphate, and the other operations are the same as in Example 1;

The operations of steps 3 and 4 are the same as those of Example 1.

Example 9: A porcelain fireproof decorative beauty glue

The operation of step 1 is the same as that of embodiment 1;

The flux is boron phosphate, and the other operations are the same as in Example 1;

The operations of steps 3 and 4 are the same as those of Example 1.

Comparative Example 1: Based on Example 1, step 1, preparation of modified zirconium phosphate, is not performed, and in step 4, 20 parts of modified zirconium phosphate are replaced by 20 parts of α, ω-dihydroxypolydimethylsiloxane. The specific operation is as follows:

Step 1, preparation of modified zirconium phosphate is not performed;

The operations of steps 2 and 3 are the same as those of Example 1;

Step 4: Preparation of porcelain fireproof decorative glue

The 20 parts of modified zirconium phosphate were replaced by 20 parts of α,ω-dihydroxypolydimethylsiloxane, and the other operations were the same as in Example 1.

Comparative Example 2: Based on Example 1, step 1, preparation of modified zirconium phosphate, is not performed, and in step 4, 20 parts of modified zirconium phosphate are replaced by 20 parts of zirconium phosphate powder. The specific operation is as follows:

Step 1, preparation of modified zirconium phosphate is not performed;

The operations of steps 2 and 3 are the same as those of Example 1;

Step 4: Preparation of porcelain fireproof decorative glue

Replace 20 parts of modified zirconium phosphate with 20 parts of zirconium phosphate;

The particle size of the zirconium phosphate powder is 2000 nm and it is dried at 120° C. for 5 hours. Other operations are the same as in Example 1.

Comparative Example 3: Based on Example 1, step 2, preparation of modified flux, is not performed, and in step 4, 9 parts of modified flux are replaced by 9 parts of α,ω-dihydroxypolydimethylsiloxane in equal amounts. The specific operation is as follows:

The operation of step 1 is the same as that of embodiment 1;

Step 2, preparation of modified flux is not performed;

The operation of step 3 is the same as that of embodiment 1;

Step 4: Preparation of porcelain fireproof decorative glue

9 parts of modified flux were replaced by 9 parts of α,ω-dihydroxypolydimethylsiloxane, and other operations were the same as in Example 1.

Comparative Example 4: Based on Example 1, step 2, preparation of modified flux, is not performed, and 9 parts of modified flux are replaced by 9 parts of flux in step 4. The specific operation is as follows:

The operation of step 1 is the same as that of embodiment 1;

Step 2, preparation of modified flux is not performed;

The operation of step 3 is the same as that of embodiment 1;

Step 4: Preparation of porcelain fireproof decorative glue

Replace 9 parts of modified flux with 9 parts of α,ω-dihydroxypolydimethylsiloxane;

The flux is sodium pyrophosphate with a particle size of 2 μm;

The other operations are the same as those in Example 1.

Comparative Example 5: Based on Example 1, step 3, preparation of modified calcium sulfate whiskers, is not performed, and in step 4, 22 parts of modified calcium sulfate whiskers are replaced by 22 parts of calcium sulfate whiskers in equal amounts. The specific operation is as follows:

The operations of steps 1 and 2 are the same as those of Example 1;

Step 3, preparation of modified calcium sulfate whiskers is not performed;

Step 4: Preparation of porcelain fireproof decorative glue

The 22 parts of modified calcium sulfate whiskers were replaced by 22 parts of calcium sulfate whiskers, and the other operations were the same as in Example 1;

The calcium sulfate whisker has a diameter of 4 μm and an aspect ratio of 200, and is dried at 140° C. for 4 hours.

Comparative Example 6: Based on Example 1, in step 4, in the preparation of porcelainized fireproof decorative beauty glue, no auxiliary cross-linking agent is added, and 3 parts of the auxiliary cross-linking agent are replaced by 3 parts of α, ω-dihydroxy polydimethylsiloxane in equal amounts. The specific operation is as follows:

The operations of steps 1, 2, and 3 are the same as those of Example 1;

Step 4: Preparation of porcelain fireproof decorative glue

The 3 parts of auxiliary cross-linking agent were replaced by 3 parts of α,ω-dihydroxypolydimethylsiloxane, and the other operations were the same as in Example 1.

Performance Test:

The following performance tests were conducted on the porcelain fireproof decorative beauty glue obtained in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and Comparative Examples 1, 2, 3, 4, 5, 6:

1. Surface drying time: Tested in accordance with GB/T13477.3-2017;

2. Adhesion performance: Tested in accordance with GB/T 11211-2009;

3. Tensile strength: Tested in accordance with GB/T528-2009;

4. Elastic recovery rate: Tested in accordance with GB/T13477.17-2002;

5. Shore hardness: Tested in accordance with GB/T531.1-2008;

6. Flame retardant performance and fire resistance integrity: Tested in accordance with GB/T24267-2009 and GB23864-2009 respectively;

The specific test results are shown in Table 1:

Table 1

From the data in Table 1, it can be seen that the surface drying time of Comparative Example 1 without modified zirconium phosphate is slightly shorter than that of Example 1, and the bonding strength is similar to that of Example 1, which shows that the addition of modified zirconium phosphate will slightly affect the surface drying time and bonding strength, but the tensile strength, elastic recovery rate and Shore hardness of Comparative Example 1 are significantly lower than those of Example 1, which shows that the modified zirconium phosphate has a very significant improvement effect on the mechanical properties of the colloid after curing. The flame retardant performance and fire resistant integrity of Comparative Example 1 are far worse than those of Example 1, which shows that the modified zirconium phosphate plays a very key role in improving the flame retardant performance and flame ablation resistance of the colloid after curing; the zirconium phosphate added to Comparative Example 2 is not modified, and the surface drying time, bonding strength and bonding strength are slightly lower than those of Example 1, which shows that the modified zirconium phosphate has a very significant improvement effect on the mechanical properties of the colloid after curing. The flame retardant performance and fire resistant integrity of Comparative Example 1 are far worse than those of Example 1, which shows that the modified zirconium phosphate plays a very key role in improving the flame retardant performance and flame ablation resistance of the colloid after curing. The strength, tensile strength, elastic recovery rate and Shore hardness all dropped significantly, which shows that zirconium phosphate is difficult to be evenly dispersed in the colloid without modification, which leads to a serious decline in the curing rate and various mechanical properties of the colloid. It is also because of the poor dispersion that the flame erosion resistance of Comparative Example 2 is significantly deteriorated; the surface drying time, bonding strength, tensile strength, elastic recovery rate and Shore hardness of Comparative Example 3 without modified flux are very close to those of Example 1, which shows that the addition of modified flux does not affect the curing rate and mechanical properties of the colloid, but the flame retardant performance and fire resistant integrity of Comparative Example 3 are far worse than those of Example 1, which shows that the modified flux plays a very important role in the flame retardancy and flame erosion resistance of the colloid. The flux added in Example 4 is not modified. Similar to Example 2, the surface drying time and various mechanical properties are greatly reduced, which shows that the unmodified flux is difficult to be effectively and evenly dispersed inside the colloid, which will seriously affect the curing rate of the colloid and the mechanical properties after curing. The flame retardant and fire resistant integrity of Example 4 are much worse than those of Example 1, which shows that the unmodified flux is difficult to be evenly dispersed, which will also affect the improvement of the flame retardant and fire resistant properties of the colloid by the flux; in Example 5, the modified calcium sulfate whiskers are replaced with calcium sulfate whiskers in equal amounts, and the surface drying time, bonding strength and all mechanical properties of the colloid after curing, as well as the flame retardant and fire resistant integrity, are reduced to all Examples. The comparison example 6 has no auxiliary cross-linking agent, and the surface drying time is significantly longer than that of Example 1. The bonding strength, tensile strength, elastic recovery rate and Shore hardness are significantly lower than those of Example 1, which shows that the auxiliary cross-linking agent plays an important role in improving the curing rate and curing cross-linking density of the colloid. The flame retardant performance of the comparison example 6 is the same as that of Example 1, but the fire resistance integrity is significantly worse than that of Example 1, which shows that the auxiliary cross-linking agent can improve the flame erosion resistance of the colloid after curing by increasing the cross-linking density.

The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims (5)

1. A porcelain fireproof cosmetic glue for decoration and fitment is characterized in that:

the specific formula of the ceramic fireproof type cosmetic glue for decoration comprises the following components in parts by weight:

100-140 parts of alpha, omega-dihydroxy polydimethylsiloxane,

15-30 Parts of dimethyl silicone oil,

0.5-2 Parts of fumed silica,

10-35 Parts of modified zirconium phosphate,

5-11 Parts of modified fluxing agent,

15-28 Parts of modified calcium sulfate whisker,

0.3 To 1.3 parts of catalyst,

2-5 Parts of auxiliary cross-linking agent,

6-11 Parts of a cross-linking agent;

the particle size of the fumed silica is 10-100 nm;

the catalyst is dibutyl tin dilaurate;

The auxiliary cross-linking agent is a mixture of tri (trimethylsilyl) silane and triethyl borate;

the mass ratio of the tri (trimethylsilyl) silane to the triethyl borate is 1-8:20;

The cross-linking agent is one of methyltrimethoxysilane and methyltriethoxysilane;

The preparation method of the modified zirconium phosphate comprises the following steps: drying zirconium phosphate powder for 4-7 hours at 110-140 ℃, cooling to room temperature, adding into a high-speed dispersion kettle, adding methyl ethyl ketone, strongly dispersing for 2-4 hours at 8000-12000 rpm, reducing the dispersion rate to 1000-4000 rpm, heating and keeping the temperature to 65-85 ℃, adding 3-isocyanatopropyl trimethoxysilane, reacting for 4-7 hours at a constant temperature in a condensation reflux state, adding ethylene bis stearamide, continuously reacting for 3-6 hours at a constant temperature in a condensation reflux state, cooling to room temperature, discharging, centrifuging, washing the solid obtained by centrifuging with absolute ethyl alcohol for 2-4 times, and vacuum drying for 6-11 hours at 40-70 ℃ to obtain modified zirconium phosphate;

The charging mass ratio of the zirconium phosphate powder to the methyl ethyl ketone to the 3-isocyanatopropyl trimethoxysilane to the ethylene bis stearamide is 15-30:120-180:1-6:3-10;

The preparation method of the modified fluxing agent comprises the following steps: mixing a fluxing agent and heptane according to a mass ratio of 6-14:18, putting the mixture into a ball mill for ball milling to obtain slurry, discharging the slurry after ball milling until the particle size of solid particles in the slurry is 0.1-3 mu m, adding the slurry into a reaction kettle, adding heptane with the mass 1-2.3 times that of the slurry, stirring and dispersing for 2-5 hours at a rotating speed of 1500-3500 rpm, adding octadecyl trichlorosilane, reducing the stirring speed to 900-1300 rpm, heating and keeping the temperature to 55-75 ℃, reacting for 3-7 hours in a condensing and refluxing state, then reducing the temperature to room temperature, discharging and filtering, washing the filtered solid for 3-5 times by absolute ethyl alcohol, and vacuum drying for 2-5 hours at 40-60 ℃ to obtain a modified fluxing agent;

The fluxing agent is one of sodium pyrophosphate, sodium hexametaphosphate, calcium phosphate, aluminum phosphate, zinc phosphate, magnesium phosphate, ferric phosphate, calcium pyrophosphate and boron phosphate;

The preparation method of the modified calcium sulfate whisker comprises the following steps: drying the calcium sulfate whisker at 120-150 ℃ for 3-6 hours, cooling to room temperature, adding the calcium sulfate whisker into a reaction kettle, adding toluene, controlling the stirring speed to be 1000-2000 r/min, heating and keeping the temperature to be 45-60 ℃, stirring and dispersing for 4-9 hours in a condensing reflux state, reducing the stirring speed to 600-950 r/min, adding butyl phosphate, mono-octadecyl phosphate and triisobutyl aluminum, continuing to stir and react for 5-11 hours in the condensing reflux state, filtering, washing the filtered solid with absolute ethyl alcohol for 2-4 times, and drying for 3-8 hours at 75-95 ℃ to obtain the modified calcium sulfate whisker;

the feeding mass ratio of the calcium sulfate whisker to the toluene to the butyl phosphate to the mono-octadecyl phosphate to the triisobutyl aluminum is 15-40:150-300:2-7:1-5:0.1-0.5.

2. The cosmetic glue for porcelain fireproof decoration as set forth in claim 1, wherein:

The particle size of the zirconium phosphate powder is 50-5000 nm.

3. The cosmetic glue for porcelain fireproof decoration as set forth in claim 1, wherein:

the added mass of the octadecyl trichlorosilane is 3-10% of the mass of the slurry added into the reaction kettle.

4. The cosmetic glue for porcelain fireproof decoration as set forth in claim 1, wherein:

The diameter of the calcium sulfate whisker is 1-5 mu m, and the length-diameter ratio is 10-240.

5. The cosmetic glue for porcelain fireproof decoration as set forth in claim 1, wherein:

The preparation method of the cosmetic glue for porcelain fireproof type decoration comprises the following steps: according to the specific formula of the ceramic fireproof decorative finishing beautifying adhesive in parts by weight, putting alpha, omega-dihydroxypolydimethylsiloxane, dimethyl silicone oil, a crosslinking aid, a catalyst and a crosslinking agent into a double planetary stirrer, stirring and dispersing for 40-90 minutes under the conditions of stirring speed of 80-110 r/min and dispersing speed of 5000-8000 r/min, then lifting the stirring speed to 120-140 r/min and dispersing speed to 8500-10000 r/min, then adding fumed silica, continuously stirring and dispersing for 3-6 hours, then adding modified zirconium phosphate, modified fluxing agent and modified calcium sulfate whisker, continuously stirring and dispersing for 9-14 hours to obtain a glue solution, filling into a plastic finished product bottle after vacuum defoamation, and sealing by nitrogen filling to obtain the ceramic fireproof decorative finishing beautifying adhesive finished product.