Titanium hybrid silicon resin as well as preparation method and application thereof

Abstract

The invention discloses titanium hybrid silicon resin as well as a preparation method and application thereof, and belongs to the technical field of polymer functional composite materials. The specific scheme is as follows: (1) preparing low-resistivity titanium hybrid silicon resin; (2) preparing intelligent fire alarm coating slurry; and (3) preparing the intelligent fire alarm coating. The intelligent fire alarm coating slurry mainly comprises titanium atom hybrid silicon resin, a conductive filler, a heat-sensitive filler, a coupling agent and a curing agent. The coating prepared by the invention not only has good flame retardant property, but also has better response speed to flame, can be repeatedly used, and is a good high-temperature-resistant coating with a fire alarm function.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer functional composite materials, and specifically relates to a titanium hybrid silicone resin and a preparation method and application thereof. Background Art

[0002] With the continuous advancement of technology, polymer materials are increasingly used in daily life. Most polymer materials are flammable materials. Once a fire occurs, it will spread rapidly. A serious fire accident will cause very serious casualties and economic losses. Therefore, it is urgent to develop a functional material with flame retardancy and fire alarm. The high-temperature resistant early warning coating can play a dual role in protecting internal combustible materials and responding to fire warnings. The high-temperature resistant coating can protect the internal combustible materials in the event of a fire. The coating is modified at the molecular level and the corresponding molecules or groups are introduced. The coating can monitor the ambient temperature and respond when the ambient temperature changes, thereby achieving the purpose of fire warning. Compared with traditional fire detection alarms, functional coatings can improve the early warning efficiency while protecting the internal combustible substrate. Therefore, it has received widespread attention in the field of fire warning. Summary of the invention

[0003] In order to develop a material that can protect internal combustible substrates and realize fire warning function, the present invention provides a titanium hybrid silicone resin and a preparation method and application thereof.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A titanium hybrid silicone resin, which is a titanium atom hybrid silicone resin, wherein the molar ratio of titanium atoms to silicon atoms in the titanium atom hybrid silicone resin is 5-40:100, the ratio of organic groups to silicon atoms in the titanium atom hybrid silicone resin is 1.4-1.8:1, and the content of phenyl groups in the titanium atom hybrid silicone resin is 10%-45%.

[0006] A method for preparing the titanium hybrid silicone resin comprises the following steps:

[0007] Step 1: uniformly mix the organic titanium, stabilizer and n-butanol in a molar ratio of 1:0.8-1.2:4-8, and heat at 40°C-60°C for 4-8h to obtain solution A;

[0008] Step 2, adding alkoxysilane to solution A, heating at 40°C and stirring evenly, then slowly dropping 0.5-5L 0.5-2mol / L dilute hydrochloric acid solution, heating at 70°C for 6-12 hours after the dropping is completed, and cooling to room temperature to obtain solution B; wherein the molar ratio of alkoxysilane to organic titanium is 2.5-20:1;

[0009] Step 3, add 1-5 mol / L sodium bicarbonate solution to solution B until the solution pH=7, then add 5-20 mol ultrapure water, let stand and take out the oily substance to obtain a low resistivity titanium hybrid silicone resin prepolymer;

[0010] Step 4: distill the low-resistivity titanium hybrid silicone resin prepolymer under reduced pressure to obtain the low-resistivity titanium hybrid silicone resin.

[0011] In step 1, the organic titanium is one or a combination of tetraisopropyl titanate and tetrabutyl titanate, and the stabilizer is one or more of acetylacetone, 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, and pyrophosphoric acid.

[0012] In step 2, the alkoxysilane is a composition of dimethyldiethoxysilane and phenyltrimethoxysilane, and the molar ratio thereof is 1 to 6:1.

[0013] An application of the titanium hybrid silicone resin, wherein the titanium hybrid silicone resin is used to prepare an intelligent fire alarm coating.

[0014] Furthermore, the intelligent fire alarm coating slurry includes the following components:

[0015]

[0016] Furthermore, the conductive filler is potassium titanate whisker, and the particle size of the potassium titanate whisker is 5 to 20 μm; the thermosensitive filler is titanium dioxide powder and tin oxide, the particle size of titanium dioxide is ≤60 microns, the particle size of tin oxide is ≤45 microns, and the mass ratio of the two is 1:1 to 5; the coupling agent is a combination of one or more of bis[3-(triethylsilane)propyl]amine, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; the curing agent is a combination of dibutyltin diacetate and dibutyltin dilaurate, with a mass ratio of 2:1 to 5; the solvent is one or a combination of two of anhydrous ethanol and isopropanol.

[0017] Furthermore, the preparation method of the intelligent fire alarm coating slurry includes the following steps: uniformly mixing the titanium hybrid silicone resin and the solvent to obtain a solution C, weighing the conductive filler and the heat-sensitive filler in proportion, and adding them to the solution C in sequence, stirring at a stirring rate of 1000 to 2000 rpm for 20 to 30 minutes after each powder is added, and after the powder is added, adding the coupling agent and the curing agent in proportion, and continuing to stir for 10 to 20 minutes to obtain the intelligent fire alarm coating slurry.

[0018] Furthermore, the preparation method of the intelligent fire alarm coating includes the following steps: spraying or scraping the intelligent fire alarm coating slurry on the surface of the flammable material, curing at room temperature for 2 to 5 days or heating and curing to obtain the titanium hybrid silicone resin flame retardant intelligent fire alarm coating.

[0019] Furthermore, the intelligent fire alarm coating is connected in series with the alarm and the power supply.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The present invention introduces titanium atoms into the silicone resin skeleton structure through covalent bonds, which has better conductivity than traditional silicone resins. The introduction of titanium atoms also gives the coating better bonding properties.

[0022] (2) The present invention mainly uses potassium titanate whiskers and titanium dioxide powder as conductive fillers and thermosensitive fillers respectively. Compared with carbon conductive fillers, they have better resistance to high-temperature oxidation, and the prepared alarm function can be reused. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a curve diagram of resistivity variation with temperature after high temperature sintering of silicone resin prepared in Comparative Example 1 and Example 1;

[0024] Figure 2 is a graph showing the change in resistivity of the coating prepared in Example 2 as a function of temperature;

[0025] Figure 3 Schematic diagram of the alarm of the titanium hybrid silicone resin flame retardant intelligent alarm coating prepared in Example 3 when it comes into contact with flame, wherein (a) is a schematic diagram of the scene before the alarm coating comes into contact with flame, (b) is a schematic diagram of the alarm scene when it comes into contact with flame, and (c) is a schematic diagram of the scene after the coating leaves the flame. DETAILED DESCRIPTION

[0026] The technical solutions in the present invention will be clearly and completely described below through examples and drawings. Obviously, the described examples are only part of the examples of the invention, rather than all of them. Based on the examples in the present invention, all other examples obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0027] Comparative Example 1

[0028] (1) Preparation of hybrid silicone resin

[0029] Step I: add 2 mol of dimethyldiethoxysilane and 0.5 mol of phenyltrimethoxysilane to 2 mol of n-butanol, heat at 40°C and stir evenly, then slowly drop 0.7 L of 2 mol / L dilute hydrochloric acid solution, heat at 70°C for 8 hours after the dropwise addition, and cool to room temperature to obtain solution B;

[0030] Step II: Add 1 mol / L sodium bicarbonate solution dropwise to the solution B obtained in step I until the pH of the solution is 7, then add 10 mol ultrapure water, let stand for 6 hours, remove the lower layer of oil, and obtain a silicone resin prepolymer;

[0031] Step III: distill the silicone resin prepolymer obtained in step II under reduced pressure at 125° C. to completely remove the solvent, thereby obtaining silicone resin.

[0032] (2) Preparation of coating slurry

[0033] Take 25 parts of the synthesized silicone resin, 20 parts of anhydrous ethanol and 20 parts of isopropanol and mix them evenly, then add 25 parts of potassium titanate whiskers with a particle size of 15 μm, 10 parts of titanium dioxide with a particle size of 30 μm, and 15 parts of tin oxide with a particle size of 25 μm in sequence, and stir each time adding a powder material at a stirring rate of 1500 rpm for 20 minutes, then stir 2 parts of bis[3-(triethylsilane)propyl]amine, 0.4 parts of dibutyltin diacetate and 0.2 parts of dibutyltin dilaurate at a stirring rate of 1500 rpm for 15 minutes to obtain a coating slurry.

[0034] (3) Coating preparation

[0035] The coating slurry prepared as above was sprayed on the surface of the flammable material, the coating thickness was controlled to be 50 nm by the number of flat coatings, and it was cured at room temperature for 3 days. Then, electrodes and a 15V power supply were connected to obtain a silicone resin flame retardant coating.

[0036] Example 1

[0037] (1) Preparation of low resistivity titanium hybrid silicone resin

[0038] Step I: 0.5 mol of tetraisopropyl titanate, 0.6 mol of acetylacetone and 2 mol of n-butanol were mixed and heated at 40° C. for 4 h to obtain solution A;

[0039] Step II: Add 2 mol of dimethyldiethoxysilane and 0.5 mol of phenyltrimethoxysilane to the solution A obtained in step I, heat at 40°C and stir evenly, then slowly drop 0.7 L of 2 mol / L dilute hydrochloric acid solution, heat at 70°C for 8 hours after the dropwise addition, and cool to room temperature to obtain solution B;

[0040] Step III: Add 1 mol / L sodium bicarbonate solution dropwise to the solution B obtained in step II until the pH of the solution is 7, then add 10 mol ultrapure water, let it stand for 6 hours, remove the oily substance, and obtain a low resistivity titanium hybrid silicone resin prepolymer;

[0041] Step IV: The low-resistivity titanium hybrid silicone resin prepolymer obtained in step III is subjected to reduced pressure distillation at 125° C. to completely remove the solvent, thereby obtaining a low-resistivity titanium hybrid silicone resin.

[0042] (2) Preparation of intelligent fire alarm coating slurry

[0043] Take 25 parts of the synthesized titanium hybrid silicone resin, 20 parts of anhydrous ethanol and 20 parts of isopropanol and mix them evenly, then add 25 parts of potassium titanate whiskers with a particle size of 15 μm, 15 parts of titanium dioxide with a particle size of 30 μm, and 15 parts of tin oxide with a particle size of 25 μm in sequence, and stir each time adding a powder material at a stirring rate of 1500 rpm for 20 minutes, then stir 2 parts of bis[3-(triethylsilane)propyl]amine, 0.4 parts of dibutyltin diacetate and 0.2 parts of dibutyltin dilaurate at a stirring rate of 1500 rpm for 15 minutes to obtain an intelligent fire alarm coating slurry.

[0044] (3) Preparation of intelligent fire alarm coating

[0045] The prepared intelligent fire alarm coating slurry is sprayed on the surface of the flammable material, and the coating thickness is controlled to be 50nm by the number of flat coatings. The coating is cured at room temperature for 3 days to obtain a titanium hybrid silicone resin flame retardant intelligent fire alarm coating. The titanium hybrid silicone resin flame retardant intelligent fire alarm coating is connected to an electrode and connected in series with a 15V power supply and an alarm. When the coating is exposed to high temperature, it acts as an alarm.

[0046] The resistivity of the silicone resin prepared in Comparative Example 1 and Example 1 varies with temperature from room temperature to 700°C as shown in the attached figure. Figure 1 shown.

[0047] Example 2

[0048] (1) Preparation of low resistivity titanium hybrid silicone resin

[0049] Step I: 1 mol of butyl titanate, 0.7 mol of 2-ethylhexyl phosphate, 0.5 mol of pyrophosphoric acid and 6 mol of n-butanol were mixed, and heated at 40° C. for 8 h to obtain solution A;

[0050] Step II: Add 5 mol of dimethyldiethoxysilane and 2 mol of phenyltrimethoxysilane to the solution A obtained in step I, heat at 40°C and stir evenly, then slowly drop 1.2 L of 2 mol / L dilute hydrochloric acid solution, heat at 70°C for 12 hours, and cool to room temperature to obtain solution B;

[0051] Step III: Add 1 mol / L sodium bicarbonate solution dropwise to the solution B obtained in step II until the pH of the solution is 7, then add 15 mol ultrapure water, let it stand for 6 hours, remove the oily substance, and obtain a low resistivity titanium hybrid silicone resin prepolymer;

[0052] Step IV: The low-resistivity titanium hybrid silicone resin prepolymer obtained in step III is subjected to reduced pressure distillation at 125° C. to completely remove the solvent, thereby obtaining a low-resistivity titanium hybrid silicone resin.

[0053] (2) Preparation of intelligent fire alarm coating slurry

[0054] Take 30 parts of the titanium hybrid silicone resin synthesized above and 30 parts of anhydrous ethanol and mix them evenly, then add 25 parts of potassium titanate whiskers with a particle size of 15 μm, 15 parts of titanium dioxide with a particle size of 25 μm, and 25 parts of tin oxide with a particle size of 45 μm in sequence, each time a powder material is added, stir at a stirring rate of 1800 rpm for 20 minutes, then stir 3 parts of bis[3-(triethylsilane)propyl]amine at a stirring rate of 2000 rpm for 20 minutes to obtain an intelligent fire alarm coating slurry.

[0055] (3) Preparation of intelligent fire alarm coating

[0056] The prepared intelligent fire alarm coating slurry is sprayed on the surface of the flammable material, and the coating thickness is controlled to be 500 nanometers by the number of flat coatings, and then heated at 80°C for 1 hour, 120°C for 1 hour, 150°C for 1 hour, 200°C for 1 hour, and 250°C for 4 hours for curing to obtain a hybrid silicone resin flame retardant intelligent fire alarm coating. The titanium hybrid silicone resin flame retardant intelligent fire alarm coating is connected to an electrode, and connected in series with a 15V power supply and an alarm. When the coating is exposed to high temperature, it acts as an alarm.

[0057] The resistivity of the alarm coating prepared in Example 2 varies with temperature from room temperature to 700°C as shown in the attached figure. Figure 2 shown.

[0058] Example 3

[0059] (1) Preparation of low resistivity titanium hybrid silicone resin

[0060] Step I: 0.5 mol of tetraisopropyl titanate, 0.5 mol of tetrabutyl titanate, 0.8 mol of di(2-ethylhexyl) phosphate and 5 mol of n-butanol were mixed, and heated at 40° C. for 4 h to obtain solution A;

[0061] Step II: Add 4 mol of dimethyldiethoxysilane and 1.5 mol of phenyltrimethoxysilane to the solution A obtained in step I, heat at 40°C and stir evenly, then slowly drop 1.5 L of 2 mol / L dilute hydrochloric acid solution, heat at 70°C for 8 hours, and cool to room temperature to obtain solution B;

[0062] Step III: Add 1 mol / L sodium bicarbonate solution dropwise to the solution B obtained in step II until the pH of the solution is 7, then add 18 mol ultrapure water, let it stand for 6 hours, remove the oily substance, and obtain a low resistivity titanium hybrid silicone resin prepolymer;

[0063] Step IV: The low-resistivity titanium hybrid silicone resin prepolymer obtained in step III is subjected to reduced pressure distillation at 125° C. to completely remove the solvent, thereby obtaining a low-resistivity titanium hybrid silicone resin.

[0064] (2) Preparation of intelligent fire alarm coating slurry

[0065] Take 20 parts of the titanium hybrid silicone resin synthesized above and 35 parts of anhydrous ethanol and mix them evenly, then add 20 parts of potassium titanate whiskers with a particle size of 15 μm, 15 parts of titanium dioxide with a particle size of 25 μm, and 20 parts of tin oxide with a particle size of 40 μm in sequence, and stir each time adding a powder material at a stirring rate of 1500 rpm for 20 minutes, then stir 2 parts of bis[3-(triethylsilane)propyl]amine, 0.5 parts of dibutyltin diacetate and 0.4 dibutyltin dilaurate at a stirring rate of 2000 rpm for 20 minutes to obtain an intelligent fire alarm coating slurry.

[0066] (3) Preparation of intelligent fire alarm coating

[0067] The prepared intelligent fire alarm coating slurry is sprayed on the surface of the flammable material, and the coating thickness is controlled to 400nm by the number of flat coatings. The coating is cured at room temperature for 3 days to obtain the hybrid silicone resin flame retardant intelligent fire alarm coating. The titanium hybrid silicone resin flame retardant intelligent fire alarm coating is connected to a 17V power supply and then connected in series with the alarm. When the alarm coating contacts the flame, the corresponding alarm is shown in the attached schematic diagram. Figure 3 shown.

[0068] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A titanium hybrid silicone resin, characterized in that: The titanium hybrid silicone resin is a titanium atom hybrid silicone resin, the molar ratio of titanium atoms to silicon atoms in the titanium atom hybrid silicone resin is 5-40:100, the ratio of organic groups to silicon atoms in the titanium atom hybrid silicone resin is 1.4-1.8:1, and the content of phenyl groups in the titanium atom hybrid silicone resin is 10%-45%.

2. A method for preparing the titanium hybrid silicone resin according to claim 1, characterized in that: The following steps are involved: Step 1: uniformly mix the organic titanium, stabilizer and n-butanol in a molar ratio of 1:0.8-1.2:4-8, and heat at 40°C-60°C for 4-8h to obtain solution A; Step 2, adding alkoxysilane to solution A, heating at 40°C and stirring evenly, then slowly dropping 0.5-5L 0.5-2mol / L dilute hydrochloric acid solution, heating at 70°C for 6-12 hours after the dropping is completed, and cooling to room temperature to obtain solution B; wherein the molar ratio of alkoxysilane to organic titanium is 2.5-20:1; Step 3, add 1-5 mol / L sodium bicarbonate solution to solution B until the pH value of the solution is 7, then add ultrapure water, let stand and take out the oily substance to obtain a low resistivity titanium hybrid silicone resin prepolymer; Step 4: distill the low-resistivity titanium hybrid silicone resin prepolymer under reduced pressure to obtain the low-resistivity titanium hybrid silicone resin.

3. The preparation method according to claim 2, characterized in that: In step 1, the organic titanium is one or a combination of tetraisopropyl titanate and tetrabutyl titanate, and the stabilizer is one or more of acetylacetone, 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, and pyrophosphoric acid.

4. The preparation method according to claim 2, characterized in that: In step 2, the alkoxysilane is a composition of dimethyldiethoxysilane and phenyltrimethoxysilane, and the molar ratio thereof is 1 to 6:

1.

5. An application of the titanium hybrid silicone resin according to claim 1, characterized in that: The titanium hybrid silicone resin is used for preparing an intelligent fire alarm coating.

6. The use according to claim 5, characterized in that: Smart fire alarm coating slurry includes the following components:

7. The use according to claim 6, characterized in that: The conductive filler is potassium titanate whisker, and the particle size of the potassium titanate whisker is 5 to 20 μm; the heat-sensitive filler is titanium dioxide powder and tin oxide, the particle size of titanium dioxide is ≤60 microns, the particle size of tin oxide is ≤45 microns, and the mass ratio of the two is 1:1 to 5; the coupling agent is a combination of one or more of bis[3-(triethylsilane)propyl]amine, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; the curing agent is a combination of dibutyltin diacetate and dibutyltin dilaurate, and the mass ratio is 2:1 to 5; The solvent is one of anhydrous ethanol and isopropanol or a combination of the two.

8. The use according to claim 6, characterized in that: The preparation method of intelligent fire alarm coating slurry comprises the following steps: uniformly mixing titanium hybrid silicone resin and solvent to obtain solution C, weighing conductive filler and heat-sensitive filler respectively in proportion, and adding them to solution C in sequence, stirring at a stirring rate of 1000 to 2000 rpm for 20 to 30 minutes after each powder is added, and adding coupling agent and curing agent in proportion after the powder is added, and continuing stirring for 10 to 20 minutes to obtain intelligent fire alarm coating slurry.

9. The use according to claim 6, characterized in that: The preparation method of the intelligent fire alarm coating comprises the following steps: spraying or scraping the intelligent fire alarm coating slurry on the surface of the flammable material, curing at room temperature for 2 to 5 days or heating and curing to obtain the titanium hybrid silicone resin flame retardant intelligent fire alarm coating.

10. The use according to claim 5, characterized in that: Connect the intelligent fire alarm coating in series with the alarm and power supply.

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