POSS material flame retardant using silicon dioxide as dispersant and preparation method and application thereof

Abstract

The invention belongs to the technical field of flame retardants, and in particular to a POSS material flame retardant with silicon dioxide as a dispersant, which is made of the following raw materials in parts by weight: 3-7 parts of silicon dioxide, 8-12 parts of methyltrichlorosilane, 0.5-1.5 parts of KH-550, 80-100 parts of deionized water, and 8-12 parts of anhydrous ethanol. The present invention also provides a preparation method and application of the POSS material flame retardant. The POSS material flame retardant raw material of the present invention is green and environmentally friendly, and has good flame retardancy, stability, and dispersibility, and the preparation method is simple, no pollutants are generated, and it can be applied in coatings to improve the flame retardancy of coatings.

Description

Technical Field

[0001] The invention belongs to the technical field of flame retardants, and in particular relates to a POSS material flame retardant using silicon dioxide as a dispersant, and a preparation method and application thereof. Background Art

[0002] POSS stands for polyhedral oligomeric silsesquioxane. The cage-type POSS is a nanomaterial with an organic-inorganic hybrid core-shell structure. Its internal inorganic framework is a hexahedral cage structure composed of Si-O-Si or Si-O bonds as the core. Each corner has a -Si bond, and each face is composed of Si-O-Si octahedral rings, which has a strong structural symmetry. Due to the stable structure of Si-O-Si, POSS will form a dense silicon oxide film at high temperature, which can effectively prevent the escape of small molecules and the dripping of molten droplets after the cracking of the polymer, and block the transfer of oxygen and heat to the inside of the polymer, thereby improving the flame retardant properties of the polymer material.

[0003] At present, the materials for preparing flame retardants after composite modification of POSS at home and abroad mainly include alkali metal oxides and organic polymers. The Chinese invention patent with application number 201510422170.3 discloses a method for preparing a composite flame retardant material of POSS and alkali metal oxides. The invention gives full play to the synergistic effect of alkali metal oxides and POSS, and the flame retardant performance is greatly improved. However, the solvent of the preparation method is acetone, which is not environmentally friendly and is a controlled drug. The Chinese invention patent with application number 201910452119.5 discloses a phosphorus-containing POSS and its preparation method and application in flame retardants. The invention overcomes the defects of high reaction temperature, high energy consumption, and low phosphorus content in the preparation of phosphorus-containing POSS materials in the prior art, resulting in poor phosphorus-silicon synergistic flame retardant effect. However, the invention has a cumbersome production process, expensive drugs, and is difficult to industrialize.

[0004] Therefore, it is very necessary to research and develop a POSS material flame retardant with a simple preparation method and green and environmentally friendly raw materials. Summary of the invention

[0005] The present invention aims to solve the above technical problems and provide a POSS material flame retardant using silicon dioxide as a dispersant, the raw materials of which are green and environmentally friendly and have good flame retardancy, stability and dispersibility.

[0006] The technical solution of the present invention is:

[0007] The POSS material flame retardant with silicon dioxide as a dispersant is made of the following raw materials in parts by weight: 3-7 parts of silicon dioxide, 8-12 parts of methyltrichlorosilane, 0.5-1.5 parts of KH-550, 80-100 parts of deionized water, and 8-12 parts of anhydrous ethanol. Preferably, it is made of the following raw materials in parts by weight: 5 parts of silicon dioxide, 10 parts of methyltrichlorosilane, 1 part of KH-550, 90 parts of deionized water, and 10 parts of anhydrous ethanol.

[0008] Preferably, the silicon dioxide described in the present invention is fumed nano-silicon dioxide.

[0009] Preferably, the present invention also provides a method for preparing the POSS material flame retardant using silicon dioxide as a dispersant, comprising the following steps:

[0010] S1. Take the raw material components by weight;

[0011] S2. Deionized water and anhydrous ethanol were placed in a reaction vessel A, and KH-550 was added dropwise to obtain a mixed solution A;

[0012] S3. Take nano-silica and place it in a reactor B with a reflux device, then add methyltrichlorosilane and stir to obtain a mixed solution B;

[0013] S4. The mixed solution A is slowly added dropwise to the mixed solution B obtained in S3, and condensed and refluxed to obtain a product;

[0014] S5. After cooling to room temperature, wash the product and filter it, then wash it with distilled water until it is neutral, dry it and disperse it to obtain the POSS material flame retardant.

[0015] The fully condensed POSS obtained in step S3 of the present invention is a hexahedral cage structure with missing corners. The subsequent reaction in S4 is a closed cage reaction, and KH-550 is the vertex. In order to dilute KH-550, slow down the reaction in step S4, and prevent methyltrichlorosilane from being hydrolyzed into hydrogen chloride, it is necessary to control the reaction temperature and time. If the reaction temperature is too low, the raw materials cannot be hydrolyzed and condensed, and too high a temperature is not conducive to controlling the reaction; if the reaction time is too long, the product is over-crosslinked, and the target product cannot be obtained in the subsequent steps; if the reaction time is too short, the reaction is incomplete, and the purity of the subsequent product is poor. Therefore, preferably, in the method of the present invention, in step S2, the reaction temperature is 45-60°C, and the time is 0.8-1.2h

[0016] Preferably, in the method of the present invention, in step S4, the reaction mixture is condensed and refluxed at 55-65° C. for 20-26 hours.

[0017] Preferably, in the method of the present invention, in S5, the product is washed with a mixture of hydrochloric acid solution and ice water in a volume ratio of 1:1.

[0018] Preferably, in the method of the present invention, the concentration of the hydrochloric acid solution is 1.18 g / ml.

[0019] The present invention also provides the use of the POSS material flame retardant with silicon dioxide as a dispersant in coatings. More preferably, the amount of the POSS material flame retardant is 3-6% of the mass of the coating.

[0020] Due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0021] 1. The raw material of the POSS material flame retardant of the present invention is green and environmentally friendly, and has no environmental pollution. The gas-phase nano-silicon dioxide is used as a dispersion medium, which can reduce the reaction speed of methyltrichlorosilane and prevent methyltrichlorosilane from being hydrolyzed into hydrogen chloride; the gas-phase nano-silicon dioxide can be used as a raw material for the flame retardant, and does not need to be separated, so that the flame retardant effect of the flame retardant can be improved. The prepared POSS material flame retardant has good flame retardancy, stability and dispersibility.

[0022] 2. The preparation method of the POSS material flame retardant of the present invention has a simple preparation process, no waste discharge, and can realize industrial production.

[0023] 3. The POSS material flame retardant of the present invention is applied in coatings to improve the flame retardant effect of fuels and solve the problem of flammability of organic coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the SEM image of nano-silicon dioxide of Comparative Example 2 of the present invention;

[0025] Figure 2 The SEM image of the POSS flame retardant prepared in Example 1 of the present invention;

[0026] Figure 3 This is the SEM image of the POSS flame retardant prepared in Comparative Example 3 of the present invention. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] Example 1

[0029] The POSS flame retardant with silicon dioxide as a dispersion medium contains the following raw materials in parts by weight: 90 parts of deionized water, 10 parts of anhydrous ethanol, 1 part of KH-550, 5 parts of gas-phase nano-silica, and 10 parts of methyltrichlorosilane.

[0030] The preparation method of a POSS flame retardant using silicon dioxide as a dispersant comprises the following steps:

[0031] S1. Take the raw material components by weight;

[0032] S2. Deionized water and anhydrous ethanol were placed in a reaction vessel A, and then KH-550 was slowly added dropwise, the reaction temperature was set to 50°C, the reaction time was 1h, and a mixed solution A was obtained;

[0033] S3. Take the gas phase nano-silica and place it in a reactor B with a reflux device, then add methyltrichlorosilane and stir until evenly dispersed to obtain a mixed solution B;

[0034] S4. Slowly add the mixed solution A dropwise to the mixed solution B obtained in S3, and condense and reflux at 60° C. for 24 h to obtain the product;

[0035] S5. After cooling to room temperature, 50 ml of 1.18 g / ml hydrochloric acid solution and 50 ml of ice water were mixed to wash the product and filtered, then washed with distilled water until neutral, dried and dispersed to obtain POSS flame retardant, the SEM image of which is as follows Figure 2 As shown, from Figure 2 It can be seen that the POSS flame retardant prepared in this embodiment using silicon dioxide as a dispersion medium has a hexahedral structure, which is similar to the target structure and has good dispersibility.

[0036] Example 2

[0037] The POSS material flame retardant using silicon dioxide as a dispersant contains the following raw materials in parts by weight: 80 parts of deionized water, 8 parts of anhydrous ethanol, 0.5 parts of KH-550, 3 parts of fumed silicon dioxide, and 8 parts of methyltrichlorosilane.

[0038] The preparation method of a POSS material flame retardant using silicon dioxide as a dispersant comprises the following steps:

[0039] S1. Take the raw material components by weight;

[0040] S2. Deionized water and anhydrous ethanol were placed in a reactor A, and then KH-550 was slowly added dropwise, the reaction temperature was set to 45°C, the reaction time was 1.2h, and a mixed solution A was obtained;

[0041] S3. Take the gas phase nano-silica and place it in a reactor B with a reflux device, then add methyltrichlorosilane and stir until evenly dispersed to obtain a mixed solution B;

[0042] S4. The mixed solution A was slowly added dropwise to the mixed solution B obtained in S3, and condensed and refluxed for 24 hours, and condensed and refluxed at 55° C. for 26 hours to obtain the product;

[0043] S5. After cooling to room temperature, the product was washed with 50 ml of 1.18 g / ml hydrochloric acid solution and 50 ml of ice water, and then filtered, and then washed with distilled water until neutral, dried and dispersed to obtain a silica composite POSS material flame retardant.

[0044] Example 3

[0045] The POSS material flame retardant using silicon dioxide as a dispersant contains the following raw materials in parts by weight: 100 parts of deionized water, 12 parts of anhydrous ethanol, 1.5 parts of KH-550, 7 parts of fumed silicon dioxide, and 12 parts of methyltrichlorosilane.

[0046] The preparation method of a POSS material flame retardant using silicon dioxide as a dispersant comprises the following steps:

[0047] S1. Take the raw material components by weight;

[0048] S2. Deionized water and anhydrous ethanol were placed in a reactor A, and then KH-550 was slowly added dropwise, the reaction temperature was set to 60°C, the reaction time was 0.8h, and a mixed solution A was obtained;

[0049] S3. Take the gas phase nano-silica and place it in a reactor B with a reflux device, then add methyltrichlorosilane and stir until evenly dispersed to obtain a mixed solution B;

[0050] S4. The mixed solution A was slowly added dropwise to the mixed solution B obtained in S3, and condensed and refluxed for 24 hours, and condensed and refluxed at 65° C. for 20 hours to obtain the product;

[0051] S5. After cooling to room temperature, the product was washed with 50 ml of 1.18 g / ml hydrochloric acid solution and 50 ml of ice water, and then filtered, and then washed with distilled water until neutral, dried and dispersed to obtain a silica composite POSS material flame retardant.

[0052] In order to illustrate the technical effect of the present invention, the present invention sets the following comparative example:

[0053] Comparative Example 1: The only difference from Example 1 is that the fumed nano-silicon dioxide is removed, and the rest is the same as Example 1;

[0054] Comparative Example 2: The only difference from Example 1 is that methyltrichlorosilane is removed, and the rest is the same as Example 1; the final product is nano-silicon dioxide, and its SEM image is shown in Figure 1 .

[0055] Comparative Example 3: The only difference from Example 1 is that the fumed nano-silicon dioxide is replaced with acetone, and the rest is the same as Example 1. The SEM image is shown in Figure 3 .

[0056] Example 4: Application of POSS flame retardant in coatings

[0057] A latex paint containing a POSS material flame retardant of the present invention, comprising the following raw materials in parts by weight:

[0058] 38 parts of water, 0.4 parts of cellulose, 0.5 parts of sodium salt dispersant, 0.2 parts of multifunctional additives, 0.2 parts of wetting agents, 0.4 parts of defoaming agents, 4 parts of POSS material flame retardant prepared in Example 1 of the present invention, 8 parts of titanium dioxide, 10 parts of calcined kaolin, 5.5 parts of talc, 16 parts of heavy calcium, 0.8 parts of ethylene glycol, 0.5 parts of film-forming aids, 0.2 parts of preservatives and bactericides, 0.2 parts of leveling agents, 0.4 parts of thickeners, and 11 parts of styrene-acrylic emulsions.

[0059] The cellulose is hydroxyethyl cellulose with a brand name of HS3000YP2; the sodium salt dispersant is sodium polycarboxylate; the multifunctional auxiliary agent is 2-amino-2-methyl-1-propanol containing 5wt% of water with a brand name of Amp-95; the wetting agent is octylphenol polyoxyethylene ether with a brand name of CX-407; the film-forming auxiliary agent is alcohol ester twelve; the defoaming agent is a composite of organic polyether ester and mineral oil with a brand name of NXZ; the preservative and bactericidal agent is a mixture of formaldehyde releaser and Kathon with a brand name of CHS5; the leveling agent is polyether modified dimethyl siloxane with a brand name of H003; the thickener is an acrylic acid hydrophobically modified alkali swelling associative type with a brand name of TT-935; and the emulsion is a styrene acrylic emulsion with a brand name of 5939.

[0060] The titanium dioxide is rutile type, and the particle size is 1000 mesh; the particle size of kaolin is 2000 mesh; the particle sizes of talc and heavy calcium are both 1250 mesh.

[0061] A preparation method of a latex paint containing a POSS material flame retardant of the present invention is:

[0062] S1. Weigh the raw materials according to the above weight parts;

[0063] S2. First, water and cellulose were placed in the reactor in sequence, the speed was adjusted to 700-800 rpm, and stirred for 10 minutes;

[0064] S3. Reduce the speed to 500-600 rpm, add the multifunctional additive, dispersant, wetting agent and 1 / 2 defoamer in turn, and stir and disperse for 10 minutes;

[0065] S4. Then titanium dioxide, kaolin, wollastonite, barium sulfate and heavy calcium were added in turn, the speed was adjusted to 1500 rpm, and the mixture was dispersed for 40 min;

[0066] S5. The speed was adjusted to 700 rpm, the POSS material flame retardant prepared in Example 1 of the present invention was added, and stirred for 10 min;

[0067] S6. Then slowly add ethylene glycol and film-forming aid in sequence, stirring and dispersing for 5 minutes;

[0068] S7. Add styrene acrylic emulsion and remaining defoamer, stir and disperse for 5 minutes, then add leveling agent and thickener in sequence, and then stir for 10 minutes, filter with a 120-mesh sieve to obtain a latex paint containing the flame retardant of the POSS material of the present invention.

[0069] Comparative Example A

[0070] A latex paint containing the POSS material flame retardant of the present invention is different from Example 4 only in that the flame retardant added in Example 4 is the flame retardant prepared in Comparative Example 1.

[0071] Comparative Example B

[0072] A latex paint containing the POSS material flame retardant of the present invention is different from Example 4 only in that the flame retardant added in Example 4 is the flame retardant prepared in Comparative Example 2.

[0073] Comparative Example C

[0074] A latex paint containing the POSS material flame retardant of the present invention is different from Example 4 only in that the flame retardant added in Example 4 is the flame retardant prepared in Comparative Example 3.

[0075] According to the national standard GB12441-2005 "Fire retardant coating for surfaces", the latex paints of Example 4 and Comparative Examples A, B and C were tested for flame retardancy, and the obtained data are shown in Table 1.

[0076] Table 1 Flame retardant test results of different latex paints

[0077] Example 4 Comparative Example A Comparative Example B Comparative Example C Flame retardant time / min 20 13 8 21 Flame spread ratio 17 26 30 19 Mass loss / g 0.8 6.3 7.2 1.0 <![CDATA[Carbonized volume / cm 3 > 17.8 25 31.1 17

[0078] The longer the flame retardant time, the smaller the flame propagation ratio, the less mass loss, and the smaller the carbonization volume, the better the flame retardancy of the material. It can be seen from the data obtained in Table 1 that the POSS flame retardant with silicon dioxide as a dispersion medium can improve the flame retardant effect of the latex paint when applied in the latex paint; in Comparative Example 1, no gas-phase nano-silicon dioxide dispersion medium is added, and the synthesis rate of the POSS material is low, so the flame retardant effect of the latex paint containing the flame retardant is general; Comparative Example 2 does not contain methyltrichlorosilane, and POSS is not synthesized. The flame retardant contains only silicon dioxide, and the flame retardant effect is poor; in Comparative Example 3, acetone is used as a dispersion medium, and the flame retardant effect of the synthesized POSS material is not much different from the latex paint of Example 4, but the overall flame retardant effect is still slightly worse than that of Example 4.

[0079] From the above, it can be known that, in the present invention, in cooperation with methyltrichlorosilane, the gas-phase nano-silica can be used as a dispersion medium to replace acetone in the synthesis of POSS materials, and the synthesis process is pollution-free. The obtained POSS material flame retardant, when used in latex paint, makes the latex paint have a good flame retardant effect.

[0080] The above description is a detailed description of the preferred feasible embodiments of the present invention, but the embodiments are not intended to limit the scope of the patent application of the present invention. All equivalent changes or modified changes completed under the technical spirit suggested by the present invention should fall within the patent scope covered by the present invention.

Claims

1. A POSS material flame retardant using silicon dioxide as a dispersant, characterized in that: It is made of the following raw materials in parts by weight: 3-7 parts of silicon dioxide, 8-12 parts of methyltrichlorosilane, 0.5-1.5 parts of KH-550, 80-100 parts of deionized water, and 8-12 parts of anhydrous ethanol; the silicon dioxide is gas-phase nano-silicon dioxide; The preparation method of the POSS material flame retardant using silicon dioxide as a dispersant comprises the following steps: S1. Take the raw material components according to their weight; S2. Deionized water and anhydrous ethanol were placed in a reaction vessel A, and KH-550 was added dropwise to obtain a mixed solution A; S3. Take nano-silica and place it in a reactor B with a reflux device, then add methyltrichlorosilane and stir to obtain a mixed solution B; S4. The mixed solution A is added dropwise to the mixed solution B obtained in S3, and condensed and refluxed to obtain a product; S5. After cooling to room temperature, wash the product and filter it, then wash it with distilled water until it is neutral, dry it and disperse it to obtain the POSS material flame retardant.

2. as claimed in claim 1, the POSS material fire retardant taking silicon dioxide as a dispersant, is characterized in that: The invention is prepared from the following raw materials in parts by weight: 5 parts of silicon dioxide, 10 parts of methyltrichlorosilane, 1 part of KH-550, 90 parts of deionized water and 10 parts of anhydrous ethanol.

3. as claimed in claim 1, the POSS material fire retardant taking silicon dioxide as a dispersant, is characterized in that: In step S2, the reaction temperature is 45-60° C. and the reaction time is 0.8-1.2 h.

4. The POSS material fire retardant with silicon dioxide as a dispersant as claimed in claim 1, characterized in that: In the step S4, the mixture is condensed and refluxed at 55-65° C. for 20-26 hours.

5. The POSS material flame retardant with silicon dioxide as a dispersant as claimed in claim 1, characterized in that: In S5, the product is washed with a mixture of hydrochloric acid solution and ice water in a volume ratio of 1:

1.

6. A POSS material flame retardant with silicon dioxide as a dispersant as claimed in claim 5, characterized in that: The concentration of the hydrochloric acid solution is 1.18 g / ml.

7. as claimed in claim 1 or 2, the application of POSS material fire retardant in coating with silicon dioxide as dispersion agent.

8. The use according to claim 7, characterized in that: The amount of the POSS material flame retardant is 3-6% of the coating mass.

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