Silica sol modified acrylate ester flame-retardant waterproof emulsion

Abstract

The application discloses a kind of silicasol modified acrylate ester flame-retardant waterproof emulsion, by silicasol, acrylate monomer, KH-570 (gamma-methacryloxy propyl), long-chain siloxane and initiator, emulsifier, water is made by polymerization;The component dosage is silicasol 8-12 parts, acrylate monomer 60-75 parts, KH-570 2.5-3 parts, long-chain siloxane 12-15 parts and initiator 0.5-0.7 parts, emulsifier 8-10 parts, water 450-480 parts.Organic silicon hydrophobic side chain in emulsion will migrate to film surface, make fabric fiber surface micro-nano rough structure and low surface energy organic silicon coexist, present similar microstructure with lotus leaf surface, so that it reaches hydrophobic effect.Silicasol, long-chain siloxane contain phosphorus flame-retardant group, by polymerization reaction access polyacrylate molecular chain, so that polymer has flame-retardant and waterproof performance, can be finished in one bath, so that fabric realizes flame-retardant, waterproof function simultaneously.

Description

Technical Field

[0001] This invention relates to a silica sol-modified acrylate flame-retardant and waterproof emulsion, belonging to the field of functional acrylate emulsions. Background Technology

[0002] The public's enthusiasm for outdoor activities has driven the development and sales of functional fabrics such as waterproof and breathable materials. Functional finishing can endow fabrics with multiple composite functions, such as waterproofing, flame retardancy, and antibacterial properties. Waterproofing and flame retardancy are standard fabric functions, typically achieved through a two-bath finishing process. This is because commonly used flame retardants are hydrophilic, while waterproofing agents are hydrophobic, resulting in a mutual incompatibility between flame retardant and waterproofing finishing. If flame retardants and waterproofing agents are mixed and finished using a one-bath method, the agents may not mix evenly; if a two-bath method is used, the washing resistance of the finishing agent is poor. Therefore, developing a fabric treatment agent that combines flame retardant and waterproofing functions is essential. Summary of the Invention

[0003] To overcome the shortcomings of the prior art, the purpose of this invention is to provide a silica sol-modified acrylate flame-retardant and waterproof emulsion with good flame-retardant and waterproof properties.

[0004] To achieve the above objectives, the present invention adopts the following technical solution.

[0005] The silica sol-modified acrylate flame-retardant and waterproof emulsion is made by polymerization of silica sol, acrylate monomers, KH-570 (γ-methacryloyloxypropyl), long-chain siloxanes, initiators, emulsifiers, and water.

[0006] By weight, the amounts of each component are as follows: 8-12 parts silica sol, 60-75 parts acrylate monomer, 2.5-3 parts KH-570, 12-15 parts long-chain siloxane, 0.5-0.7 parts initiator, 8-10 parts emulsifier, and 450-480 parts water.

[0007] The preparation method of the silica sol-modified acrylate flame-retardant and waterproof emulsion is as follows:

[0008] Add a certain amount of water and emulsifier to a container, stir well, then add acrylate monomer, silica sol, and KH-570 (γ-methacryloyloxypropyl) dropwise, stir for 30 minutes to obtain a pre-emulsion; dissolve the initiator in an appropriate amount of water to form an initiator aqueous solution for later use.

[0009] Transfer 1 / 3 of the pre-emulsion to a reactor, purge with nitrogen for protection, and heat under stirring. Add long-chain siloxane to the remaining 2 / 3 of the pre-emulsion and shear for 15 minutes on a high-speed shear press.

[0010] After the temperature in the reactor is raised to 75°C, 1 / 3 volume of initiator aqueous solution is added to initiate the polymerization reaction, and the reaction is kept at this temperature for 0.5 h. The remaining pre-emulsion and initiator aqueous solution are added dropwise over 2-3 h, and the reaction is kept at a constant temperature for 4 h to obtain a milky white silica sol modified acrylate flame retardant and waterproof emulsion.

[0011] The acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:5.

[0012] The initiator is one of sodium persulfate, potassium persulfate, or ammonium persulfate.

[0013] The emulsifier is composed of anionic emulsifier and nonionic emulsifier.

[0014] The anionic emulsifiers mentioned are sodium dodecyl sulfate and sodium dodecylbenzene sulfonate.

[0015] The nonionic emulsifiers mentioned are fatty alcohol polyoxyethylene ethers AEO-3 and AEO-9.

[0016] The anionic emulsifier and the nonionic emulsifier are in a mass ratio of 2:1.

[0017] Polyacrylates possess good film-forming properties, weather resistance, and flexibility, exhibiting excellent adhesion to fabric surfaces. However, polyacrylates tend to become brittle at low temperatures and sticky at high temperatures. Silica sol, containing numerous Si-O bonds, can enhance the heat and weather resistance of polyacrylates. The polymer prepared by combining silica sol with polyacrylate compounds possesses the superior properties of both materials; its excellent film-forming and adhesive properties further enhance its washability.

[0018] When silica sol-modified acrylic flame-retardant and waterproof emulsion is impregnated and adhered to the fabric surface, and then baked at high temperature, it gradually solidifies on the fabric surface to form a film. Due to the difference in surface energy, the hydrophobic side chains of the organosilicon in the silica sol-modified acrylic flame-retardant and waterproof emulsion migrate to the film surface and are more effectively concentrated on the surface of the film rather than buried inside. This allows the micro-nano rough structure of the fabric fiber surface and the low surface energy organosilicon to coexist, presenting a microstructure similar to the surface of a lotus leaf, thus giving it a hydrophobic effect.

[0019] Phosphorus-containing groups in silica sol and long-chain siloxanes have good flame retardant properties. By adding them to the polyacrylate molecular chain through polymerization, the polymer can have both flame retardant and waterproof properties. It can be finished in one bath to make the fabric achieve good flame retardant and waterproof functions at the same time. Attached Figure Description

[0020] Figure 1 This is a static contact angle diagram of the polyester fabric after emulsion finishing in Example 3. Detailed Implementation

[0021] The unit "parts" of the substances involved in this invention refers to "parts by mass".

[0022] The silica sol-modified acrylate flame-retardant and waterproof emulsion is made by polymerization of silica sol, acrylate monomers, KH-570 (γ-methacryloyloxypropyl), long-chain siloxanes, initiators, emulsifiers, and water.

[0023] By weight, the amounts of each component are as follows: 8-12 parts silica sol, 60-75 parts acrylate monomer, 2.5-3 parts KH-570, 12-15 parts long-chain siloxane, 0.5-0.7 parts initiator, 8-10 parts emulsifier, and 450-480 parts water.

[0024] The silica sol is prepared from tetraethyl orthosilicate, phosphorus-containing siloxane, vinyltriethoxysilane, ammonia, water, and emulsifier. First, 15 parts of tetraethyl orthosilicate, 5 parts of phosphorus-containing siloxane, 3 parts of vinyltriethoxysilane, 0.3 parts of AEO-3, 0.4 parts of AEO-9, and 0.5 g of sodium dodecyl sulfate are added to 120 parts of distilled water and emulsified and homogenized by high-speed shearing for 30 min. The mixture is then poured into a reaction vessel, heated to 60°C in a water bath, and ammonia is slowly added dropwise to adjust the pH to 8-9. After maintaining the temperature for 6 hours, the mixture is cooled to obtain the silica sol.

[0025] The preparation method of the phosphorus-containing siloxane is as follows:

[0026] 0.15 mol of diethyl chlorophosphonate and 50 mL of tetrahydrofuran were added to a clean three-necked flask. The mixture was then protected with nitrogen under ice bath conditions. 0.15 mol of N-methylethanolamine and 0.15 mol of triethylamine were added, and the mixture was stirred for 4 h under ice bath conditions. After filtration, tetrahydrofuran was removed by vacuum distillation to obtain the intermediate.

[0027] In a four-necked flask equipped with a stirrer, thermometer, and condenser, 0.1 mol of the intermediate and 150 ml of DMF (N,N-dimethylformamide) were added. The mixture was heated to 90 °C with stirring and activated for 30 min. Under nitrogen protection, 0.1 mol of KH560 (γ-(2,3-epoxypropoxy)propyltrimethoxysilane) was added, and the mixture was heated to 80 °C and maintained at this temperature for 24 hours. The mixture was filtered, and the DMF in the filtrate was removed by rotary evaporation. The filtrate was dissolved in ethyl acetate and then washed three times each with dilute hydrochloric acid, 10% NaOH solution, and saturated NaCl solution. Finally, the solvent was removed by rotary evaporation to obtain the product, i.e., the phosphorus-containing siloxane. The reaction process is shown in reactions 1 and 2.

[0028]

[0029] The long-chain siloxane is prepared by the following method:

[0030] A measured amount of phosphorus-containing siloxane and IPDI (isophorone diisocyanate) were loaded into a reactor under nitrogen protection. A small amount of dibutyltin dilaurate was added to catalyze the reaction, and the temperature was slowly raised to 70°C. The reaction was carried out for about 2 hours until the isocyanate content reached the theoretical level. A measured amount of monohydroxy-terminated dimethicone oil (Mn = 1000) was added, and the reaction continued until the isocyanate content reached the new theoretical level, yielding the long-chain siloxane product. The molar ratio of phosphorus-containing siloxane, IPDI, and monohydroxy-terminated dimethicone oil was 1:1:1. The reaction process is shown in reaction formula 3.

[0031]

[0032] The acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:5.

[0033] The initiator is one of sodium persulfate, potassium persulfate, or ammonium persulfate.

[0034] The emulsifier is composed of anionic emulsifier and nonionic emulsifier.

[0035] The anionic emulsifiers mentioned are sodium dodecyl sulfate and sodium dodecylbenzene sulfonate.

[0036] The nonionic emulsifiers mentioned are fatty alcohol polyoxyethylene ethers AEO-3 and AEO-9.

[0037] The anionic emulsifier and the nonionic emulsifier are in a mass ratio of 2:1.

[0038] A method for preparing a silica sol-modified acrylate flame-retardant and waterproof emulsion includes the following steps:

[0039] Add a certain amount of water and emulsifier to the container, stir well, add acrylate monomer, silica sol and KH-570 dropwise, stir for 30 minutes to obtain a pre-emulsion; dissolve the initiator in an appropriate amount of water to form an initiator aqueous solution for later use.

[0040] Transfer 1 / 3 of the pre-emulsion to a reactor, purge with nitrogen for protection, and heat under mechanical stirring; add long-chain siloxane to the remaining 2 / 3 of the pre-emulsion and shear for 15 minutes on a high-speed shear press.

[0041] After the temperature in the reactor is raised to 75°C, 1 / 3 volume of initiator aqueous solution is added to initiate the polymerization reaction. The reaction is kept at this temperature for 0.5 hours. Then, the remaining pre-emulsion and initiator aqueous solution are added dropwise over 2-3 hours. The reaction is kept at this temperature for 4 hours to obtain a milky white silica sol modified acrylate flame retardant and waterproof emulsion.

[0042] KH-570 is attached to the polyacrylate molecular chain via C=C bonds. The alkoxy groups in the long-chain siloxane condense with the alkoxy groups in KH-570 and are grafted onto the acrylate polymer backbone to form comb-shaped side chains. The relatively long silicone side chains have high mobility and the silicone has low surface tension, allowing the silicone to migrate to the air interface during film formation, forming a hydrophobic protective layer on the film surface.

[0043] Example 1:

[0044] The silica sol modified acrylate flame-retardant and waterproof emulsion is made by polymerization of silica sol, acrylate monomers, KH-570, long-chain siloxanes, initiators, emulsifiers, and water.

[0045] By weight, the amounts of each component are as follows: 8 parts silica sol, 75 parts acrylate monomer, 2.5 parts KH-570, 12 parts long-chain siloxane, 0.7 parts initiator, 10 parts emulsifier, and 480 parts water.

[0046] The preparation method of silica sol modified acrylate flame-retardant and waterproof emulsion is as follows:

[0047] Add 450 parts water and 10 parts emulsifier to a container, stir well, add 75 parts acrylate monomer, 8 parts silica sol and 2.5 parts KH-570 dropwise, stir for 30 minutes to obtain a pre-emulsion; dissolve 0.7 parts initiator in 30 parts water to form an initiator aqueous solution for later use.

[0048] Transfer 1 / 3 of the pre-emulsion to a reactor, purge with nitrogen for protection, and heat under mechanical stirring; add 12 parts of long-chain siloxane to the remaining 2 / 3 of the pre-emulsion and shear for 15 minutes on a high-speed shear press.

[0049] After the temperature in the reactor is raised to 75°C, 1 / 3 volume of initiator aqueous solution is added to initiate the polymerization reaction. The reaction is kept at this temperature for 0.5 hours. Then, the remaining pre-emulsion and initiator aqueous solution are added dropwise over 2-3 hours. The reaction is kept at this temperature for 4 hours to obtain a milky white silica sol modified acrylate flame retardant and waterproof emulsion.

[0050] Among them: the acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:5;

[0051] The emulsifier is composed of sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-3, and AEO-9, and consists of anionic and nonionic emulsifiers in a mass ratio of 2:1.

[0052] The initiator is potassium persulfate.

[0053] Example 2:

[0054] The silica sol modified acrylate flame-retardant and waterproof emulsion is made by polymerization of silica sol, acrylate monomers, KH-570, long-chain siloxanes, initiators, emulsifiers, and water.

[0055] By weight, the amounts of each component are as follows: 10 parts silica sol, 65 parts acrylate monomer, 3 parts KH-570, 15 parts long-chain siloxane, 0.6 parts initiator, 9 parts emulsifier, and 480 parts water.

[0056] The preparation method of silica sol modified acrylate flame-retardant and waterproof emulsion is as follows:

[0057] Add 450 parts water and 10 parts emulsifier to a container, stir well, then add 65 parts acrylate monomer, 10 parts silica sol, and 3 parts KH-570 dropwise, and stir for 30 minutes to obtain a pre-emulsion; dissolve 0.6 parts initiator in 30 parts water to form an initiator aqueous solution for later use.

[0058] Transfer 1 / 3 of the pre-emulsion to a reactor, purge with nitrogen for protection, and heat under mechanical stirring. Add 15 parts of long-chain siloxane to the remaining 2 / 3 of the pre-emulsion and shear for 15 minutes on a high-speed shear press.

[0059] After the temperature in the reactor is raised to 75°C, 1 / 3 volume of initiator aqueous solution is added to initiate the polymerization reaction. The reaction is kept at this temperature for 0.5 hours. Then, the remaining pre-emulsion and initiator aqueous solution are added dropwise over 2-3 hours. The reaction is kept at this temperature for 4 hours to obtain a milky white silica sol modified acrylate flame retardant and waterproof emulsion.

[0060] Among them: the acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:5;

[0061] The emulsifier is composed of sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-3, and AEO-9, and consists of anionic and nonionic emulsifiers in a mass ratio of 2:1.

[0062] The initiator is sodium persulfate.

[0063] Example 3:

[0064] The silica sol modified acrylate flame-retardant and waterproof emulsion is made by polymerization of silica sol, acrylate monomers, KH-570, long-chain siloxanes, initiators, emulsifiers, and water.

[0065] By weight, the amounts of each component are as follows: 12 parts silica sol, 60 parts acrylate monomer, 3 parts KH-570, 15 parts long-chain siloxane, 0.5 parts initiator, 8 parts emulsifier, and 450 parts water.

[0066] The preparation method of silica sol modified acrylate flame-retardant and waterproof emulsion is as follows:

[0067] Add 420 parts water and 8 parts emulsifier to a container, stir well, then add 60 parts acrylate monomer, 12 parts silica sol, and 3 parts KH-570 dropwise, and stir for 30 minutes to obtain a pre-emulsion; dissolve 0.5 parts initiator in 30 parts water to form an initiator aqueous solution for later use.

[0068] Transfer 1 / 3 of the pre-emulsion to a reactor, purge with nitrogen for protection, and heat under mechanical stirring. Add 15 parts of long-chain siloxane to the remaining 2 / 3 of the pre-emulsion and shear for 15 minutes on a high-speed shear press.

[0069] After the temperature in the reactor is raised to 75°C, 1 / 3 volume of initiator aqueous solution is added to initiate the polymerization reaction. The reaction is kept at this temperature for 0.5 hours. Then, the remaining pre-emulsion and initiator aqueous solution are added dropwise over 2-3 hours. The reaction is kept at this temperature for 4 hours to obtain a milky white silica sol modified acrylate flame retardant and waterproof emulsion.

[0070] Among them: the acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:5;

[0071] The emulsifier is composed of sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether AEO-3, and AEO-9, and consists of anionic and nonionic emulsifiers in a mass ratio of 2:1.

[0072] The initiator is ammonium persulfate.

[0073] The silica sol-modified acrylate flame-retardant and waterproof emulsion of Example 3 was used to finish the polyester fabric.

[0074] Fabric: 100% polyester, weight 180g / m² 2 .

[0075] The silica sol-modified acrylate flame-retardant and waterproof emulsion was mixed with water to form a finishing solution with a concentration of 120 g / L. The solution was then subjected to two dips and two nips with a nip-to-liquid ratio of 80-90%. The solution was pre-dried at 80℃ for 2 min and then baked at 160-170℃ for 60-90 s.

[0076] Water-repellent performance: 100 points.

[0077] Flame retardant performance: afterflame time 0s, smoldering time 0s, damage length 9.6cm.

[0078] Static contact angle: 137°.

[0079] Water repellency performance is tested according to AATCC-22.

[0080] Flame retardant properties were tested according to GB / T 5455—2014 "Vertical Method for Testing the Burning Performance of Textiles".

[0081] The static contact angle of the fabric was measured using a contact angle measuring instrument.

Claims

1. Silica sol modified acrylate flame retardant and waterproof emulsion, which is made by polymerization of silica sol, acrylate monomer, KH-570, long-chain siloxane, initiator, emulsifier and water; By weight, the amounts of each component are as follows: 8-12 parts silica sol, 60-75 parts acrylate monomer, 2.5-3 parts KH-570, 12-15 parts long-chain siloxane, 0.5-0.7 parts initiator, 8-10 parts emulsifier, and 450-480 parts water. The preparation method of the silica sol-modified acrylate flame-retardant and waterproof emulsion is as follows: Add a certain amount of water and emulsifier to the container, stir well, add acrylate monomer, silica sol and KH-570 dropwise, stir for 30 minutes to obtain a pre-emulsion; dissolve the initiator in an appropriate amount of water to form an initiator aqueous solution for later use. Transfer 1 / 3 of the pre-emulsion to a reactor, purge with nitrogen for protection, and heat under mechanical stirring; add long-chain siloxane to the remaining 2 / 3 of the pre-emulsion and shear for 15 minutes on a high-speed shear press. After the temperature in the reactor is raised to 75°C, 1 / 3 volume of initiator aqueous solution is added to initiate the polymerization reaction, and the reaction is kept at this temperature for 0.5 h. Then the remaining pre-emulsion and initiator aqueous solution are added dropwise over 2-3 h. The reaction is kept at a constant temperature for 4 h to obtain a milky white silica sol modified acrylate flame retardant and waterproof emulsion.

2. The silica sol-modified acrylate flame-retardant and waterproof emulsion as described in claim 1, characterized in that: The acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:

5.

3. The silica sol-modified acrylate flame-retardant and waterproof emulsion as described in claim 1, characterized in that: The initiator is one of sodium persulfate, potassium persulfate, or ammonium persulfate.

4. The silica sol-modified acrylate flame-retardant and waterproof emulsion as described in claim 1, characterized in that: The emulsifier is composed of anionic emulsifier and nonionic emulsifier.

5. The silica sol-modified acrylate flame-retardant and waterproof emulsion as described in claim 4, characterized in that: The anionic emulsifier is sodium dodecyl sulfate.

6. The silica sol-modified acrylate flame-retardant and waterproof emulsion as described in claim 4, characterized in that: The nonionic emulsifiers mentioned are fatty alcohol polyoxyethylene ethers AEO-3 and AEO-9.

7. The silica sol-modified acrylate flame-retardant and waterproof emulsion as described in claim 4, characterized in that: The anionic emulsifier and the nonionic emulsifier are in a mass ratio of 2:1.

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