Preparation method of flame-retardant waterproof and ultraviolet resistant finishing emulsion for textiles

Abstract

The application discloses a preparation method of a flame-retardant waterproof ultraviolet-resistant finishing emulsion for textiles, which comprises the following steps: placing isophorone diisocyanate into a reactor, stirring, and adding polyethylene glycol, with the temperature controlled at 75 DEG C, and then reacting for 3 hours; adding dimethylol propionic acid, and then reacting for 2 hours; adding 1,4-butanediol, and then carrying out chain extension reaction for 2 hours; adding bis-hydroxyl siloxane, and then reacting for 1 hour; adding P-PDMS monomer and Si-P-BP monomer, and then adding water dropwisely under stirring at 70 DEG C, and then reacting for 4 hours; adding appropriate hydrochloric acid, slowly heating the system to 130 DEG C under reduced pressure, and then carrying out condensation reaction for 3 hours under reduced pressure; adding triethylamine, and then neutralizing for 30 minutes, so as to obtain a modified polyurethane prepolymer; adding water and a composite emulsifier into an emulsifier, stirring and dissolving, adding the modified polyurethane prepolymer and silica sol, and then carrying out strong mechanical stirring for 30 minutes by using a high-shear emulsifier. The emulsion is used for functional finishing and processing of textiles, so that the fabric has good functions of flame retardation, waterproofness and ultraviolet resistance.

Description

Technical Field

[0001] This invention relates to a method for preparing a flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles, belonging to the field of functional polyurethane emulsions for textiles. Background Technology

[0002] While moderate sun exposure is beneficial to health, excessive sun exposure can accelerate skin aging and pose certain health risks. Therefore, the UV resistance of textiles is becoming increasingly important. Most textiles possess a degree of flammability and combustibility, posing varying degrees of fire hazard, making flame-retardant treatment essential. With the continuous advancement of the textile industry, various textile products are emerging and widely used in daily life, industry, agriculture, transportation, and national defense. Textiles are developing towards multi-functional properties such as flame retardancy, waterproofing, moisture permeability, breathability, antibacterial properties, antistatic properties, and UV resistance. The research and development of multi-functional textile fabrics is receiving increasing attention. The functionality of textiles is generally achieved by applying finishing agents with specific functions during the finishing process. Typically, one finishing agent corresponds to one function. To achieve multiple functions in a textile, multiple finishing agents are required through multiple treatments. Therefore, developing finishing agents with multiple functions for textiles is highly necessary. Summary of the Invention

[0003] To overcome the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing a flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles. The prepared emulsion is used for functional finishing of textiles, enabling the fabric to have good flame-retardant, waterproof, and UV-resistant properties.

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

[0005] The preparation method of flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles includes the following specific steps:

[0006] 90 parts of isophorone diisocyanate were placed in a reactor, stirred and 300 parts of polyethylene glycol (PEG, molecular weight 1000) were added. The temperature was controlled at 75°C, and 2 parts of dibutyltin dilaurate were added dropwise. The reaction was carried out for 3 hours.

[0007] Add 7 parts of dimethylolpropionic acid and react for 2 hours;

[0008] Add 2 parts of 1,4-butanediol and allow the chain extension reaction to proceed for 2 hours.

[0009] Add 40 parts of dihydroxysiloxane and react for 1 hour;

[0010] Add 25 parts of P-PDMS monomer and 12 parts of Si-P-BP monomer, keep the temperature at 70℃, add 2 parts of water dropwise while stirring, and react for 4 hours; then first distill at 80℃ under normal pressure to distill off most of the solvent, then add an appropriate amount of hydrochloric acid, and slowly raise the temperature of the system to 130℃ under reduced pressure, and decompression synthesis reaction for 3 hours; then cool to room temperature, add 6 parts of triethylamine to the reactor, neutralize for 30 minutes, and obtain modified polyurethane prepolymer;

[0011] Add 2400 parts water and 30 parts composite emulsifier to an emulsifier and stir to dissolve. Then add modified polyurethane prepolymer and 300 parts silica sol. Stir vigorously with a high-shear emulsifier for 30 minutes to obtain a flame-retardant, waterproof and UV-resistant finishing emulsion for textiles.

[0012] The composite emulsifier is a compound of sodium dodecyl sulfate (SDS) and AEO-9.

[0013] The mass ratio of sodium dodecyl sulfate (SDS) to AEO-9 is 1:4.

[0014] The silica sol is made from tetraethyl orthosilicate (TEOS), phosphorus-containing siloxane, and water. First, 15 parts of tetraethyl orthosilicate, 10 parts of phosphorus-containing siloxane, and 20 parts of ethanol are added to 300 parts of distilled water, and the pH value is adjusted to 5 with hydrochloric acid. After keeping it at 30°C for 20 hours, it is cooled to obtain the silica sol.

[0015] Waterborne polyurethane possesses excellent weather resistance, flexibility, abrasion resistance, and mechanical properties, making it widely used in the textile industry. However, waterborne polyurethane films suffer from drawbacks such as poor water resistance and flammability. Polysiloxanes, on the other hand, offer advantages such as low surface tension, low-temperature flexibility, thermal stability, and water resistance. During emulsion film formation, the side chains of organosiloxanes migrate to the film surface, and modification with polysiloxanes can impart excellent water resistance to polyurethane. Furthermore, modifying the rough surface structure of silica nanoparticles with low-surface-energy organosilicon compounds achieves superior hydrophobic properties in the film.

[0016] 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 polyurethane can achieve a good flame retardant effect and has a good synergistic flame retardant effect with phosphorus compounds.

[0017] 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 improving the UV protection performance of textiles.

[0018] The flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles prepared by the method of this invention has good compatibility and coordination among its components, and can impart excellent flame-retardant, waterproof, and UV-resistant properties to textile fabrics. Attached Figure Description

[0019] Figure 1 This is a static contact angle diagram of the polyester fabric treated with the emulsion in Example 1. Detailed Implementation

[0020] The unit "parts" of the substances involved in this invention refers to "parts by mass".

[0021] This invention discloses a method for preparing a flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles, the specific steps of which are as follows:

[0022] 90 parts of isophorone diisocyanate were placed in a reactor, stirred and 300 parts of polyethylene glycol (PEG, molecular weight 1000) were added. The temperature was controlled at 75°C, and 2 parts of dibutyltin dilaurate were added dropwise. The reaction was carried out for 3 hours.

[0023] Add 7 parts of dimethylolpropionic acid and react for 2 hours;

[0024] Add 2 parts of 1,4-butanediol and allow the chain extension reaction to proceed for 2 hours.

[0025] Add 40 parts of dihydroxysiloxane and react for 1 hour;

[0026] Add 25 parts of P-PDMS monomer and 12 parts of Si-P-BP monomer, keep the temperature at 70℃, add 2 parts of water dropwise while stirring, and react for 4 hours; then first distill at 80℃ under normal pressure to distill off most of the solvent, then add an appropriate amount of hydrochloric acid, and slowly raise the temperature of the system to 130℃ under reduced pressure, and decompression synthesis reaction for 3 hours; then cool to room temperature, add 6 parts of triethylamine to the reactor, neutralize for 30 minutes, and obtain modified polyurethane prepolymer;

[0027] Add 2400 parts water and 30 parts composite emulsifier to an emulsifier and stir to dissolve. Then add modified polyurethane prepolymer and 300 parts silica sol. Stir vigorously with a high-shear emulsifier for 30 minutes to obtain a flame-retardant, waterproof and UV-resistant finishing emulsion for textiles.

[0028] The composite emulsifier is a compound of sodium dodecyl sulfate (SDS) and AEO-9.

[0029] The mass ratio of sodium dodecyl sulfate (SDS) to AEO-9 is 1:4.

[0030] The silica sol is made from tetraethyl orthosilicate, phosphorus-containing siloxane, and water. First, 15 parts of tetraethyl orthosilicate, 10 parts of phosphorus-containing siloxane, and 20 parts of ethanol are added to 300 parts of distilled water, and the pH value is adjusted to 5 with hydrochloric acid. After keeping it at 30°C for 20 hours, it is cooled to obtain the silica sol.

[0031] The preparation method of the phosphorus-containing siloxane is as follows:

[0032] 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.

[0033] 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 reaction formulas 1 and 2.

[0034]

[0035] The dihydroxysiloxane is prepared by the following method:

[0036] A di-terminated epoxy polysiloxane (molecular weight 1050) and isopropanol solvent were added to a reactor. After stirring for 30 min, N-(γ,-dimethylaminopropyl)-γ-aminopropylmethyldimethoxysilane (HD-121) was slowly added dropwise. The system was heated to 50 °C and kept at that temperature for 4 h. The solvent was then removed to obtain dihydroxysiloxane.

[0037] The molar ratio of the di-epoxy polysiloxane to HD-121 is 1:2. The reaction process is shown in the following formula.

[0038]

[0039] The P-PDMS monomer is prepared by the following method:

[0040] 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 value reached the theoretical content. A measured amount of monohydroxy-terminated dimethicone (Mn = 1000) was added, and the reaction continued until the isocyanate value reached the new theoretical content, yielding the product phosphorus-containing PDMS. The molar ratio of phosphorus-containing siloxane, IPDI, and monohydroxy-terminated dimethicone was 1:1:1. The reaction process is shown in reaction formula 4.

[0041]

[0042] The Si-P-BP monomer is prepared by the following method:

[0043] 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 phosphorus-containing siloxane was then added, and the reaction continued until the isocyanate content reached the new theoretical level, yielding the product Si-P-BP monomer. The molar ratio of phosphorus-containing siloxane, IPDI, and 4-hydroxybenzophenone was 1:1:1. The reaction process is shown in reaction formula 5.

[0044]

[0045] Example 1:

[0046] A method for preparing a flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles, comprising the following steps:

[0047] 90 parts of isophorone diisocyanate were placed in a reactor, stirred and 300 parts of polyethylene glycol (PEG, molecular weight 1000) were added. The temperature was controlled at 75°C, and 2 parts of dibutyltin dilaurate were added dropwise. The reaction was carried out for 3 hours.

[0048] Add 7 parts of dimethylolpropionic acid and react for 2 hours;

[0049] Add 2 parts of 1,4-butanediol and allow the chain extension reaction to proceed for 2 hours.

[0050] Add 40 parts of dihydroxysiloxane and react for 1 hour;

[0051] Add 25 parts of P-PDMS monomer and 12 parts of Si-P-BP monomer, keep the temperature at 70℃, add 2 parts of water dropwise while stirring, and react for 4 hours; then first distill at 80℃ under normal pressure to distill off most of the solvent, then add an appropriate amount of hydrochloric acid, and slowly raise the temperature of the system to 130℃ under reduced pressure, and decompression synthesis reaction for 3 hours; then cool to room temperature, add 6 parts of triethylamine to the reactor, neutralize for 30 minutes, and obtain modified polyurethane prepolymer;

[0052] Add 2400 parts water and 30 parts composite emulsifier to an emulsifier and stir to dissolve. Then add modified polyurethane prepolymer and 300 parts silica sol, and stir vigorously with a high-shear emulsifier for 30 minutes to obtain a flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles. The composite emulsifier includes 6 parts sodium dodecyl sulfate and 24 parts AEO-9.

[0053] The emulsion is milky white and does not separate into layers upon centrifugation.

[0054] The silica sol is made from tetraethyl orthosilicate, phosphorus-containing siloxane, and water. First, 15 parts of tetraethyl orthosilicate, 10 parts of phosphorus-containing siloxane, and 20 parts of ethanol are added to 300 parts of distilled water, and the pH value is adjusted to 5 with hydrochloric acid. After keeping it at 30°C for 20 hours, it is cooled to obtain the silica sol.

[0055] The flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles prepared by the method described in Example 1 was used to finish polyester fabric, and then the relevant properties of the finished fabric were tested.

[0056] Fabric: 100% polyester, weight 180g / m² 2 .

[0057] Finishing solution formulation: Prepare a 100g / L finishing solution by mixing organosilicon waterborne polyurethane emulsion with water.

[0058] Process flow: Impregnation (10 min, liquor ratio 1:20) → two dips and two rolls (100% roll-off, room temperature) → pre-drying (80℃×2 min) → baking (160℃×2 min).

[0059] UPF value > 50, T(UV) A The percentage was 3.75%.

[0060] Water-repellent performance: 100 points.

[0061] Static contact angle: 134°.

[0062] Flame retardant performance: afterflame time 0s, smoldering time 0s, damage length 10.8cm.

[0063] Water repellency performance is tested according to AATCC-22.

[0064] Flame retardant properties were tested according to GB / T 5455—2014 "Vertical Method for Testing the Burning Performance of Textiles".

[0065] The static contact angle of the fabric was measured using a contact angle measuring instrument.

[0066] UV protection performance: UV protection factor tester, which tests the fabric's UV protection factor UPF and UVA (320-420nm) transmittance T(UVA).

Claims

1. A method for preparing a flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles, comprising the following specific steps: 90 parts of isophorone diisocyanate were placed in a reactor, stirred and 300 parts of polyethylene glycol were added. The temperature was controlled at 75°C, and 2 parts of dibutyltin dilaurate were added dropwise. The reaction was carried out for 3 hours. Add 7 parts of dimethylolpropionic acid and react for 2 hours; Add 2 parts of 1,4-butanediol and allow the chain extension reaction to proceed for 2 hours. Add 40 parts of dihydroxysiloxane and react for 1 hour; Add 25 parts of P-PDMS monomer and 12 parts of Si-P-BP monomer, keep the temperature at 70℃, add 2 parts of water dropwise while stirring, and react for 4 hours; then first distill at 80℃ under normal pressure to distill off most of the solvent, then add an appropriate amount of hydrochloric acid, and slowly raise the temperature of the system to 130℃ under reduced pressure, and decompression synthesis reaction for 3 hours; then cool to room temperature, add 6 parts of triethylamine to the reactor, neutralize for 30 minutes, and obtain modified polyurethane prepolymer; Add 2400 parts water and 30 parts composite emulsifier to an emulsifier and stir to dissolve. Then add modified polyurethane prepolymer and 300 parts silica sol. Stir vigorously with a high-shear emulsifier for 30 minutes to obtain a flame-retardant, waterproof and UV-resistant finishing emulsion for textiles.

2. The method for preparing the flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles as described in claim 1, characterized in that, The silica sol is made from tetraethyl orthosilicate, phosphorus-containing siloxane, and water. First, 15 parts of tetraethyl orthosilicate, 10 parts of phosphorus-containing siloxane, and 20 parts of ethanol are added to 300 parts of distilled water, and the pH value is adjusted to 5 with hydrochloric acid. After keeping it at 30°C for 20 hours, it is cooled to obtain the silica sol.

3. The method for preparing the flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles as described in claim 1, characterized in that: The composite emulsifier is a compound of sodium dodecyl sulfate (SDS) and AEO-9.

4. The method for preparing the flame-retardant, waterproof, and UV-resistant finishing emulsion for textiles as described in claim 3, characterized in that: The mass ratio of sodium dodecyl sulfate (SDS) to AEO-9 is 1:4.

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