Uvioresistant flame-retardant antistatic composite functional emulsion

Abstract

The application discloses an anti-ultraviolet flame-retardant antistatic composite functional emulsion which is prepared by polymerization of silica sol, acrylate monomer, styrene, vinyl triethoxysilane, SiPQAS monomer, SiPBPQAS monomer and initiators, emulsifiers and water; the preparation method comprises the following steps: adding part of acrylate monomer, acrylic acid, styrene, emulsifiers and water into a reactor, emulsifying, adding appropriate initiators, setting the temperature to 80 DEG C, and reacting for 0.5 h to obtain a seed emulsion; taking the rest of the acrylate monomer, emulsifiers, initiators and water, and emulsifying all of the silica sol, vinyl triethoxysilane, SiPQAS monomer and SiPBPQAS monomer for 15 min, then dropping the pre-emulsion into the reactor, dropping for 2 h, and reacting for a period of time at 85 DEG C after the dropping is completed; after the reaction is completed, the emulsion is cooled to room temperature, the pH is adjusted to neutral, and a cationic anti-ultraviolet flame-retardant antistatic composite functional emulsion is obtained.

Description

Technical Field

[0001] This invention relates to an anti-ultraviolet, flame-retardant, and antistatic composite functional emulsion, belonging to the field of functional finishing agents for textiles. Background Technology

[0002] Polyester, nylon, and other synthetic fibers have poor moisture absorption and are flammable. During friction and contact, positive and negative charges are generated on the fiber surface, but these static charges cannot be directly eliminated and instead accumulate on the material surface. Since polyester and other fibers are non-conductive, the static charges generated during use will accumulate on the fabric surface for a long time and cannot dissipate, causing serious static electricity buildup. This results in poor human comfort, and more seriously, in certain special environments, static electricity buildup can easily cause safety hazards. Therefore, it is essential to eliminate static electricity and improve the antistatic and flame-retardant properties of fabrics through dyeing and finishing processes.

[0003] The properties of fabrics, such as antistatic, UV resistance, waterproofing, flame retardancy, and antibacterial properties, are mostly achieved through finishing processes, that is, by using finishing agents to give the fabric the corresponding functions. If a fabric needs to achieve multiple functions, multiple finishing processes are required, which is cumbersome. Therefore, there is a need to develop composite functional finishing agents that integrate multiple functions. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the purpose of this invention is to provide a composite functional emulsion with anti-ultraviolet, flame-retardant and antistatic properties, which has good anti-ultraviolet, flame-retardant and antistatic properties.

[0005] To achieve the above objectives, the present invention adopts the following technical solution.

[0006] An anti-ultraviolet flame retardant and antistatic composite functional emulsion is made by polymerization of silica sol, acrylate monomers, glycidyl methacrylate, vinyltriethoxysilane, SiPQAS monomers, SiPBPQAS monomers, initiators, emulsifiers, and water.

[0007] By weight, the amounts of each component are as follows: 10-14 parts silica sol, 60-70 parts acrylate monomer, 6-9 parts glycidyl methacrylate, 3-5 parts vinyltriethoxysilane, 14-18 parts SiPQAS monomer, 10-15 parts SiPBPQAS monomer, 1-1.5 parts initiator, 12-16 parts emulsifier, and 420-460 parts water.

[0008] A method for preparing an anti-ultraviolet, flame-retardant, and antistatic composite functional emulsion includes the following steps:

[0009] Glycidyl methacrylate, some acrylate monomers, emulsifiers, and water were added to a reactor, stirred, emulsified, and an appropriate amount of initiator was added. The reaction was carried out at 80°C with continuous stirring for 0.5 hours to obtain a bluish seed emulsion.

[0010] The remaining acrylate monomers, emulsifiers, initiators, water, and all the silica sol, vinyltriethoxysilane, SiPQAS monomers, and SiPBPQAS monomers were pre-emulsified using a high-speed shear dispersion emulsifier. After emulsification for 15 minutes, the pre-emulsified liquid was added dropwise to the reactor over a period of 2 hours. After the addition was complete, the mixture was reacted at 85°C for a period of time.

[0011] After the reaction was completed, the emulsion was cooled to room temperature and adjusted to neutral with a pH adjuster to obtain a cationic anti-UV flame retardant and antistatic composite functional emulsion.

[0012] The acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:7.

[0013] The initiator is one of azobisisobutyronitrile (AIBN) and azobisisobutyramidine hydrochloride (AIBA).

[0014] The emulsifier is composed of cationic emulsifier and nonionic emulsifier.

[0015] The cationic emulsifiers are dodecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride.

[0016] The nonionic emulsifier is one or more of fatty alcohol polyoxyethylene ether (O-10), octadecylamine polyoxyethylene (12) ether, and isomeric tridecyl alcohol polyoxyethylene ether (E1309).

[0017] The cationic emulsifier and the nonionic emulsifier are in a mass ratio of 2:1.

[0018] Acrylic ester emulsions dry easily to form films, exhibiting excellent weather and oil resistance, as well as high mechanical stability, making them widely used in the textile industry. Polyacrylates tend to become brittle at low temperatures and sticky at high temperatures, while silica sol, containing a large number of Si-O bonds, can enhance the heat and weather resistance of polyacrylates. The polymer prepared by combining silica sol with polyacrylate compounds possesses the excellent properties of both materials; its good film-forming and adhesive properties further enhance its wash resistance.

[0019] Nano-SiO2 molecules have a three-dimensional network structure and are characterized by good chemical stability, low thermal conductivity, and good high-temperature performance. Adding nano-SiO2 to emulsions can achieve good flame retardant effects and has a good synergistic flame retardant effect with phosphorus compounds.

[0020] Nanoparticles possess a large surface area and high surface energy, ensuring better affinity and improving the durability of functional finishing on fabrics. Silica nanoparticles can reflect and scatter ultraviolet light, exhibiting UV shielding properties. Benzophenone-based UV absorbers enhance the UV resistance of nano-silica, thereby strengthening the UV protection performance of fabrics.

[0021] The UV-resistant, flame-retardant, and antistatic composite functional emulsion of the present invention has good compatibility and coordination among its components, and can impart excellent flame-retardant, antistatic, and UV-resistant properties to textile fabrics. Detailed Implementation

[0022] The unit "parts" of the substances involved in this invention refers to "parts by mass".

[0023] This invention discloses an anti-ultraviolet flame-retardant and antistatic composite functional emulsion, which is made by polymerization of silica sol, acrylate monomer, glycidyl methacrylate, vinyltriethoxysilane, SiPQAS monomer, SiPBPQAS monomer, initiator, emulsifier, and water.

[0024] By weight, the amounts of each component are as follows: 10-14 parts silica sol, 60-70 parts acrylate monomer, 6-9 parts glycidyl methacrylate, 3-5 parts vinyltriethoxysilane, 14-18 parts SiPQAS monomer, 10-15 parts SiPBPQAS monomer, 1-1.5 parts initiator, 12-16 parts emulsifier, and 420-460 parts water.

[0025] A method for preparing an anti-ultraviolet, flame-retardant, and antistatic composite functional emulsion includes the following steps:

[0026] Glycidyl methacrylate, some acrylate monomers, emulsifiers, and water were added to a reactor, stirred, emulsified, and an appropriate amount of initiator was added. The reaction was carried out at 80°C with continuous stirring for 0.5 hours to obtain a bluish seed emulsion.

[0027] The remaining acrylate monomers, emulsifiers, initiators, water, and all the silica sol, vinyltriethoxysilane, SiPQAS monomers, and SiPBPQAS monomers were pre-emulsified using a high-speed shear dispersion emulsifier. After emulsification for 15 minutes, the pre-emulsified liquid was added dropwise to the reactor over a period of 2 hours. After the addition was complete, the mixture was reacted at 85°C for a period of time.

[0028] After the reaction was completed, the emulsion was cooled to room temperature and adjusted to neutral with a pH adjuster to obtain a cationic anti-ultraviolet flame retardant and antistatic composite functional emulsion with blue light.

[0029] The acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:7.

[0030] The initiator is one of azobisisobutyronitrile (AIBN) and azobisisobutyramidine hydrochloride (AIBA).

[0031] The emulsifier is composed of cationic emulsifier and nonionic emulsifier.

[0032] The cationic emulsifiers are dodecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride.

[0033] The nonionic emulsifier is one or more of fatty alcohol polyoxyethylene ether (O-10), octadecylamine polyoxyethylene (12) ether, and isomeric tridecyl alcohol polyoxyethylene ether (E1309).

[0034] The cationic emulsifier and the nonionic emulsifier are in a mass ratio of 2:1.

[0035] The silica sol is prepared by the following method:

[0036] First, add 15 parts of tetraethyl orthosilicate, 8 parts of phosphorus-containing siloxane, 5 parts of vinyltriethoxysilane, and 24 parts of ethanol to 300 parts of distilled water, and adjust the pH value to 5 with hydrochloric acid; keep warm at 30°C for 20 hours and then cool to obtain silica sol.

[0037] The preparation method of the phosphorus-containing siloxane is as follows:

[0038] 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.

[0039] 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 γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560) 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 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 reaction formulas 1 and 2.

[0040]

[0041] The SiPQAS monomer is prepared by the following method:

[0042] Add 0.1 mol of diethyl chlorophosphonate and 50 mL of tetrahydrofuran to a clean three-necked flask. Under nitrogen protection in an ice bath, add 0.1 mol of N,N-dimethylethanolamine and 0.1 mol of triethylamine. Stir the mixture in an ice bath for 4 hours. After the reaction is complete, if there is a precipitate, filter it and remove the tetrahydrofuran by vacuum distillation. Add 0.1 mol of γ-(2,3-epoxypropoxy)propyltrimethoxysilane and 100 mL of isopropanol to the product. Stir until homogeneous and reflux at 70°C for 10 hours. After the reaction is complete, remove the isopropanol by rotary evaporation to obtain the final product. The reaction process is shown in reaction formula 3.

[0043]

[0044] The SiPBPQAS monomer is prepared by the following method:

[0045] A measured amount of 4-hydroxybenzophenone and IPDI (isophorone diisocyanate) were loaded into a reactor under nitrogen protection. A small amount of butyltin 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 SiPQAS monomer was then added, and the reaction continued until the isocyanate content reached the new theoretical level, yielding the product SiPBPQAS monomer. The molar ratio of SiPQAS monomer, IPDI, and 4-hydroxybenzophenone was 1:1:1. The reaction process is shown in reaction formula 4.

[0046]

[0047] Vinyltriethoxysilane is attached to the polyacrylate molecular chain via C=C bonds. The alkoxy groups in SiPQAS monomer and SiPBPQAS monomer condense with the alkoxy groups in vinyltriethoxysilane and are grafted onto the side of the acrylate polymer backbone.

[0048] Example 1:

[0049] An anti-ultraviolet flame retardant and antistatic composite functional emulsion is made by polymerization of silica sol, acrylate monomers, glycidyl methacrylate, vinyltriethoxysilane, SiPQAS monomers, SiPBPQAS monomers, initiators, emulsifiers, and water.

[0050] By weight, the amounts of each component are as follows: 10 parts silica sol, 60 parts acrylate monomer, 6 parts glycidyl methacrylate, 3 parts vinyltriethoxysilane, 14 parts SiPQAS monomer, 10 parts SiPBPQAS monomer, 1 part initiator, 12 parts emulsifier, and 420 parts water.

[0051] A method for preparing an anti-ultraviolet, flame-retardant, and antistatic composite functional emulsion includes the following steps:

[0052] 20 parts of acrylate monomer, 6 parts of glycidyl methacrylate, 4 parts of emulsifier, and 180 parts of water were added to a reactor, stirred, emulsified, and 0.4 parts of azobisisobutyronitrile initiator were added. The reaction was carried out at 80℃ with continuous stirring for 0.5 h to obtain a bluish seed emulsion.

[0053] 40 parts of acrylate monomer, 8 parts of emulsifier, 0.6 parts of initiator azobisisobutyronitrile, 10 parts of 240 water and silica sol, 3 parts of vinyltriethoxysilane, 14 parts of SiPQAS monomer, and 10 parts of SiPBPQAS monomer were pre-emulsified using a high-speed shear dispersion emulsifier. After emulsification for 15 minutes, the pre-emulsified liquid was added dropwise to the reactor over a period of 2 hours. After the addition was complete, the mixture was reacted at 85°C for a period of time.

[0054] After the reaction was completed, the emulsion was cooled to room temperature and adjusted to neutral with a pH adjuster to obtain a cationic anti-UV flame retardant and antistatic composite functional emulsion.

[0055] Among them: the acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:7;

[0056] The emulsifier is composed of dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, fatty alcohol polyoxyethylene ether (O-10), and isomeric tridecyl alcohol polyoxyethylene ether (E1309), with a cationic emulsifier to nonionic emulsifier mass ratio of 2:1.

[0057] Example 2:

[0058] An anti-ultraviolet flame retardant and antistatic composite functional emulsion is made by polymerization of silica sol, acrylate monomers, glycidyl methacrylate, vinyltriethoxysilane, SiPQAS monomers, SiPBPQAS monomers, initiators, emulsifiers, and water.

[0059] By weight, the amounts of each component are as follows: 14 parts silica sol, 70 parts acrylate monomer, 9 parts glycidyl methacrylate, 5 parts vinyltriethoxysilane, 18 parts SiPQAS monomer, 15 parts SiPBPQAS monomer, 1.5 parts initiator, 16 parts emulsifier, and 460 parts water.

[0060] A method for preparing an anti-ultraviolet, flame-retardant, and antistatic composite functional emulsion includes the following steps:

[0061] 30 parts of acrylate monomer, 9 parts of glycidyl methacrylate, 6 parts of emulsifier, and 220 parts of water were added to a reactor, stirred, emulsified, and 0.5 parts of initiator were added. The reaction was carried out at 80°C with continuous stirring for 0.5 hours to obtain a bluish seed emulsion.

[0062] 40 parts of acrylate monomer, 10 parts of emulsifier, 1 part of initiator, 240 parts of water, and all of the silica sol, vinyltriethoxysilane, SiPQAS monomer, and SiPBPQAS monomer were pre-emulsified using a high-speed shear dispersion emulsifier. After emulsification for 15 minutes, the pre-emulsified liquid was added dropwise to the reactor over a period of 2 hours. After the addition was complete, the mixture was reacted at 85°C for a period of time.

[0063] After the reaction was completed, the emulsion was cooled to room temperature and adjusted to neutral with a pH adjuster to obtain a cationic anti-UV flame retardant and antistatic composite functional emulsion.

[0064] Among them: the acrylate monomer is composed of methyl methacrylate, ethyl acrylate and butyl acrylate in a mass ratio of 2:1:7;

[0065] The emulsifier is composed of dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, fatty alcohol polyoxyethylene ether (O-10), and octadecylamine polyoxyethylene (12) ether, with a cationic emulsifier to nonionic emulsifier mass ratio of 2:1. The initiator is azobisisobutyramidine hydrochloride.

[0066] The emulsion is milky white and does not separate into layers upon centrifugation. The emulsion particle size is approximately 160 nm.

[0067] The UV-resistant, flame-retardant, and antistatic composite functional emulsions prepared by the methods described in Examples 1 and 2 were used to treat polyester fabrics, and the relevant properties of the treated fabrics were then tested.

[0068] Fabric: 100% polyester, 100D x 100D, weight 170g / m² 2 Surface resistivity: >1×10 12 Ω.

[0069] Finishing solution formulation: A finishing solution with a concentration of 120g / L is prepared by mixing an anti-UV, flame-retardant, and anti-static composite functional emulsion with water.

[0070] Process flow: Impregnation (10 min, liquor ratio 1:20) → two dips and two rolls (90% roll-off, room temperature) → pre-drying (80℃×3 min) → baking (160℃×3 min).

[0071] Example 1: Surface resistivity: 7.2 × 10⁻⁶ 8 Ω; UPF value > 50, T(UV) A The flame retardancy was 3.82%; afterflame time was 0s, smoldering time was 0s, and the damage length was 9.6cm.

[0072] Example 2: Surface resistivity: 6.5 × 10⁻⁶ 8 Ω; UPF value > 50, T(UV) AThe percentage of flame retardancy was 3.61%; flame retardant performance: afterflame time 0s, smoldering time 0s, and damage length 9.2cm.

[0073] Flame retardant properties were tested according to GB / T5455—2014 "Vertical Method for Testing the Burning Performance of Textiles".

[0074] UV protection performance: UV protection factor tester, which tests the fabric's UV protection factor UPF and UVA (320-420nm) transmittance T(UVA).

[0075] Antistatic performance test: Surface resistivity is measured using a surface resistivity meter.

Claims

1. An anti-ultraviolet flame retardant and antistatic composite functional emulsion, which is made by polymerization of silica sol, acrylate monomer, glycidyl methacrylate, vinyltriethoxysilane, SiPQAS monomer, SiPBPQAS monomer, initiator, emulsifier and water. By weight, the amounts of each component are as follows: 10-14 parts silica sol, 60-70 parts acrylate monomer, 6-9 parts glycidyl methacrylate, 3-5 parts vinyltriethoxysilane, 14-18 parts SiPQAS monomer, 10-15 parts SiPBPQAS monomer, 1-1.5 parts initiator, 12-16 parts emulsifier, and 420-460 parts water.

2. The UV-resistant, flame-retardant, and antistatic composite functional 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:

7.

3. The UV-resistant, flame-retardant, and antistatic composite functional emulsion as described in claim 1, characterized in that: The initiator is one of azobisisobutyronitrile (AIBN) and azobisisobutyramidine hydrochloride.

4. The UV-resistant, flame-retardant, and antistatic composite functional emulsion as described in claim 1, characterized in that: The emulsifier is composed of cationic emulsifier and nonionic emulsifier.

5. The UV-resistant, flame-retardant, and antistatic composite functional emulsion as described in claim 4, characterized in that: The cationic emulsifiers are dodecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride.

6. The UV-resistant, flame-retardant, and antistatic composite functional emulsion as described in claim 4, characterized in that: The nonionic emulsifier is one or more of fatty alcohol polyoxyethylene ether (O-10), octadecylamine polyoxyethylene (12) ether, and isomeric tridecyl alcohol polyoxyethylene ether (E1309).

7. The UV-resistant, flame-retardant, and antistatic composite functional emulsion as described in claim 4, characterized in that: The cationic emulsifier and the nonionic emulsifier are in a mass ratio of 2:

1.

8. The preparation method of the UV-resistant, flame-retardant, and antistatic composite functional emulsion as described in claim 1, comprising the following steps: Glycidyl methacrylate, some acrylate monomers, emulsifiers, and water were added to a reactor, stirred, emulsified, and an appropriate amount of initiator was added. The reaction was carried out at 80°C with continuous stirring for 0.5 hours to obtain a bluish seed emulsion. The remaining acrylate monomers, emulsifiers, initiators, water, and all the silica sol, vinyltriethoxysilane, SiPQAS monomers, and SiPBPQAS monomers were pre-emulsified using a high-speed shear dispersion emulsifier. After emulsification for 15 minutes, the pre-emulsified liquid was added dropwise to the reactor over a period of 2 hours. After the addition was complete, the mixture was reacted at 85°C for a period of time. After the reaction was completed, the emulsion was cooled to room temperature and adjusted to neutral with a pH adjuster to obtain a cationic anti-UV flame retardant and antistatic composite functional emulsion.

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