Preparation process and application of flame retardant and water repellent finishing liquid for fabrics

Abstract

The invention discloses a preparation process and application of a flame retardant and water repellent finishing liquid applied to fabrics. The invention utilizes acryl triphenyl silicon piperazine monomer and 2,2'-diallyl hexafluorobis DOPO phenyl ester monomer as functional monomers, and copolymerizes with acrylate monomers to obtain a flame retardant and water repellent finishing liquid containing acrylate polymer. And cotton fabric is finished, the acrylate polymer in the finishing liquid contains DOPO, piperazine and triphenyl silicon structure, forming nitrogen phosphorus silicon flame retardant, which can promote the formation of silicon carbon composite layer on the surface of cotton fabric during combustion, reduces the continuous burning time, smoldering time and damage length of cotton fabric, and improves the limiting oxygen index and flame retardant performance. And the acrylate polymer molecular chain contains a bis trifluoromethyl hydrophobic group and a triphenyl silicon hydrophobic structure, which improves the water contact angle of cotton fabric, so that cotton and other fabrics have better practical applications in the field of flame retardant and waterproof textiles.

Description

Technical Field

[0001] The invention relates to the technical field of finishing agents, in particular to a preparation process and application of a flame retardant and water repellent finishing liquid for fabrics. Background Art

[0002] Cotton fabric has good hydrophilicity, moisture absorption, breathability and wearing comfort, and is one of the most widely used textile fabrics. With the rapid development of science and technology, people's demand for functional textiles is also increasing, and higher requirements are also put forward for the flame retardancy, waterproofness, softness and other properties of textiles. Finishing the fabric with finishing agents can give the textiles some unique properties.

[0003] Polyacrylate finishing agents have the advantages of adjustable polymerization monomers, simple preparation methods, and diverse functionality, and are widely used in the finishing of cotton fabrics and other textiles. For example, adding fluorine-containing hydrophobic monomers to polyacrylate finishing agents can give the finishing agents excellent hydrophobic properties. Adding flame retardant monomers can make the finishing agents exhibit good flame retardant properties. The present invention obtains a finishing liquid with flame retardant and water repellent effects by regulating the polymerization monomers, thereby improving the flame retardant and water repellent properties of cotton and other fabrics. Summary of the invention

[0004] The invention solves the problem that fabrics such as cotton do not have flame retardant properties and water repellent properties.

[0005] The technical solution of the present invention is a preparation process of a flame retardant and water repellent finishing liquid, comprising the following steps:

[0006] Step (1), adding acrylate monomer, propylene triphenylsilyl piperazine monomer, 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer and emulsifier to distilled water, stirring and mixing to obtain a prepolymer solution; adding an initiator to the distilled water, stirring and dissolving to obtain an initiator solution.

[0007] The structural formula of the propenyl triphenylsilyl piperazine monomer is formula (I):

[0008] Formula (I).

[0009] The structural formula of 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer is formula (II):

[0010] Formula (II).

[0011] Step (2), taking 30-40% volume of the prepolymer solution, heating to 70-80° C., adding 25-35% volume of the initiator solution dropwise, controlling the adding time to be 60-90 min, then adding the remaining 60-70% volume of the prepolymer solution and 65-75% volume of the initiator solution, reacting for 3-5 h, and cooling to obtain a flame retardant and water repellent finishing liquid.

[0012] The mass ratio of the acrylic acid ester monomer, the acryl triphenylsilyl piperazine monomer and the 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer is 100:(12-30):(25-65).

[0013] Among them, the acrylate monomers include methyl acrylate, methyl methacrylate, butyl acrylate, and butyl methacrylate.

[0014] Among them, the emulsifiers include OP-10, fatty alcohol polyoxyethylene ether AEO-15, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.

[0015] Wherein, the initiator is potassium persulfate or ammonium persulfate.

[0016] Among them, the preparation process of propenyl triphenylsilane piperazine monomer is as follows: in a nitrogen atmosphere, at -5 to 0°C, triphenylchlorosilane, 1-allylpiperazine, and triethylamine in a molar ratio of 1: (1-1.1): (1-1.1) are added to tetrahydrofuran, reacting for 1-2 hours, and then reacting at room temperature for 4-6 hours, concentrating the solution, washing with distilled water and methanol in turn, and recrystallizing the product with ethyl acetate to obtain propenyl triphenylsilane piperazine monomer.

[0017] The preparation process of 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer is as follows: at -5 to 0°C, 2,2'-diallyl hexafluorobisphenol A, chloro-DOPO and triethylamine in a molar ratio of 1:(2-2.4):(2-2.4) are added to toluene, mixed and reacted at room temperature for 12-18 hours, the solution is concentrated and washed with methanol, and the product is recrystallized in chloroform to obtain 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer.

[0018] Among them, the application of flame retardant and water repellent finishing liquid in fabrics.

[0019] The technical effect of the present invention is that the present invention utilizes acryltriphenylsilylpiperazine monomer and 2,2'-diallylhexafluorobisDOPOphenyl ester monomer as functional monomers, and copolymerizes with acrylate monomers to obtain a flame retardant and water repellent finishing liquid containing acrylate polymer.

[0020] The present invention uses a flame retardant and water-repellent finishing liquid to finish cotton fabrics. The acrylate polymer in the finishing liquid contains DOPO, piperazine and triphenylsilicon structures to form a nitrogen-phosphorus-silicon flame retardant, which can promote the formation of a silicon-carbon composite layer on the surface of the cotton fabric during combustion, and has a condensed phase flame retardant effect, reducing the afterburning time, smoldering time and damage length of the cotton fabric, and significantly improving the limiting oxygen index and flame retardant performance. In addition, the acrylate polymer molecular chain contains a bistrifluoromethyl hydrophobic group and a triphenylsilicon hydrophobic structure, which significantly improves the water contact angle of the cotton fabric and exhibits excellent water repellent performance. Cotton and other fabrics have better practical applications in the field of flame retardant and waterproof textiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the reaction formula for preparing acryltriphenylsilylpiperazine monomer.

[0022] Figure 2 This is the reaction formula for preparing 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer. DETAILED DESCRIPTION

[0023] In order to more clearly illustrate the present invention and have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention. Example 1

[0024] In a nitrogen atmosphere, at -5°C, 10 mmol of triphenylsilyl chloride (structural formula: , CAS registration number is 76-86-8), 10 mmol 1-allylpiperazine (structural formula is , CAS registration number is 13961-36-9), 10 mmol triethylamine, react for 1 hour, then react for 6 hours at room temperature, concentrate the solution, wash with distilled water and methanol in turn, and recrystallize the product with ethyl acetate to obtain propenyl triphenylsilyl piperazine monomer. The yield is 2.23g. The structural formula is .

[0025] At 0°C, 4 mmol of 2,2'-diallyl hexafluorobisphenol A (structural formula: , CAS registration number is 128481-73-2. ), 8.4mmol chloro-DOPO (structural formula is , CAS registration number is 32186-92-8), 8.4mmol triethylamine, mixed and reacted at room temperature for 18h, the solution was concentrated, washed with methanol, and the product was recrystallized in chloroform to obtain 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer. The yield is 2.53g. The structural formula is .

[0026] To 20 mL of distilled water, 3.7 g of methyl acrylate, 6.3 g of butyl methacrylate, 1.2 g of propylene triphenylsilyl piperazine monomer, 2.5 g of 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer, 0.08 g of OP-10, and 0.15 g of sodium dodecyl sulfate were added, and the mixture was stirred to obtain a prepolymer solution. To the distilled water, 0.12 g of initiator ammonium persulfate was added, and the mixture was stirred to dissolve to obtain an initiator solution.

[0027] Take 30% volume of the prepolymer solution, heat it to 75°C, add 25% volume of the initiator solution, control the dropping time to 60 minutes, then add the remaining 70% volume of the prepolymer solution and 75% volume of the initiator solution, react for 3 hours, cool, and obtain a flame retardant and water-repellent finishing liquid. Example 2

[0028] In a nitrogen atmosphere, at -5°C, 10 mmol of triphenylsilyl chloride, 10 mmol of 1-allylpiperazine, and 10 mmol of triethylamine were added to 10 mL of tetrahydrofuran, and the mixture was reacted for 2 h, and then at room temperature for 4 h. The solution was concentrated, washed with distilled water and methanol in turn, and the product was recrystallized with ethyl acetate to obtain allyl triphenylsilylpiperazine monomer. The yield was 2.05 g.

[0029] At 0°C, 4 mmol of 2,2'-diallyl hexafluorobisphenol A, 8 mmol of chloro-DOPO, and 8 mmol of triethylamine were added to 20 mL of toluene, mixed and reacted at room temperature for 12 hours, the solution was concentrated, washed with methanol, and the product was recrystallized in chloroform to obtain 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer. The yield was 2.41 g.

[0030] To 25 mL of distilled water, 3.7 g of methyl methacrylate, 6.3 g of butyl acrylate, 2 g of propylene triphenylsilyl piperazine monomer, 4.5 g of 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer, 0.1 g of fatty alcohol polyoxyethylene ether AEO-15, and 0.22 g of sodium dodecylbenzene sulfonate were added, and the mixture was stirred to obtain a prepolymerization solution; 0.13 g of initiator ammonium persulfate was added to the distilled water, and the mixture was stirred to dissolve to obtain an initiator solution.

[0031] Take 40% volume of the prepolymer solution, heat it to 70°C, add 30% volume of the initiator solution, control the dropping time to 90 minutes, then add the remaining 60% volume of the prepolymer solution and 70% volume of the initiator solution, react for 5 hours, cool, and obtain a flame retardant and water-repellent finishing liquid. Example 3

[0032] In a nitrogen atmosphere, at 0°C, 10 mmol of triphenylsilyl chloride, 11 mmol of 1-allylpiperazine, and 11 mmol of triethylamine were added to 15 mL of tetrahydrofuran, and the mixture was reacted for 2 h, and then at room temperature for 5 h. The solution was concentrated, washed with distilled water and methanol in turn, and the product was recrystallized with ethyl acetate to obtain allyl triphenylsilyl piperazine monomer. The yield was 2.12 g.

[0033] At 0°C, 4 mmol of 2,2'-diallyl hexafluorobisphenol A, 9.6 mmol of chloro-DOPO, and 9.6 mmol of triethylamine were added to 30 mL of toluene, mixed and reacted at room temperature for 12 hours, the solution was concentrated, washed with methanol, and the product was recrystallized in chloroform to obtain 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer. The yield was 2.72 g.

[0034] To 35 mL of distilled water, 3.7 g of methyl methacrylate, 6.3 g of butyl methacrylate, 3 g of propylene triphenylsilyl piperazine monomer, 6.5 g of 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer, 0.18 g of OP-10, and 0.4 g of sodium dodecyl sulfate were added, and the mixture was stirred to obtain a prepolymer solution. To the distilled water, 0.15 g of potassium persulfate as an initiator was added, and the mixture was stirred to dissolve to obtain an initiator solution.

[0035] Take 40% volume of the prepolymer solution, heat it to 80°C, add 35% volume of the initiator solution, control the dropping time to 90 minutes, then add the remaining 60% volume of the prepolymer solution and 65% volume of the initiator solution, react for 3 hours, cool, and obtain a flame retardant and water-repellent finishing liquid.

[0036] Comparative Example 1

[0037] Add 3.7 g of methyl acrylate, 6.3 g of butyl methacrylate, 0.08 g of OP-10, and 0.15 g of sodium dodecyl sulfate to 20 mL of distilled water, stir and mix to obtain a prepolymer solution; add 0.12 g of initiator ammonium persulfate to the distilled water, stir and dissolve to obtain an initiator solution.

[0038] Take 30% volume of the prepolymer solution, heat it to 75°C, add 25% volume of the initiator solution, control the dropping time to 60 min, then add the remaining 70% volume of the prepolymer solution and 75% volume of the initiator solution, react for 3 hours, cool, and obtain the finishing solution.

[0039] Comparative Example 2

[0040] According to the process of Example 1, prepare propenyl triphenylsilyl piperazine monomer.

[0041] Add 3.7 g of methyl acrylate, 6.3 g of butyl methacrylate, 1.2 g of propylene triphenylsilyl piperazine monomer, 0.08 g of OP-10, and 0.15 g of sodium dodecyl sulfate to 20 mL of distilled water, stir and mix to obtain a prepolymer solution; add 0.12 g of initiator ammonium persulfate to the distilled water, stir and dissolve to obtain an initiator solution.

[0042] Take 30% volume of the prepolymer solution, heat it to 75°C, add 25% volume of the initiator solution, control the dropping time to 60 min, then add the remaining 70% volume of the prepolymer solution and 75% volume of the initiator solution, react for 3 hours, cool, and obtain the finishing solution.

[0043] Comparative Example 3

[0044] According to the process of Example 1, 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer was prepared.

[0045] To 20 mL of distilled water, 3.7 g of methyl acrylate, 6.3 g of butyl methacrylate, 2.5 g of 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer, 0.08 g of OP-10, and 0.15 g of sodium dodecyl sulfate were added, and the mixture was stirred to obtain a prepolymer solution. To the distilled water, 0.12 g of initiator ammonium persulfate was added, and the mixture was stirred to dissolve to obtain an initiator solution.

[0046] Take 30% volume of the prepolymer solution, heat it to 75°C, add 25% volume of the initiator solution, control the dropping time to 60 min, then add the remaining 70% volume of the prepolymer solution and 75% volume of the initiator solution, react for 3 hours, cool, and obtain the finishing solution.

[0047] The finishing liquid was dried to remove water, weighed, and then distilled water was added and stirred to prepare a finishing liquid with a mass concentration of 40 g / L.

[0048] Add cotton fabric to the finishing liquid, control the bath ratio to 1:50, immerse for 30 minutes, perform double immersion and double rolling, control the rolling ratio to 80%. Then take out the cotton fabric, pre-bake at 100℃ for 5 minutes, and bake at 170℃ for 3 minutes to obtain the finished cotton fabric.

[0049] Use a contact angle meter to test the water contact angle of cotton fabric according to the method of GB / T 42694-2023. Each sample is measured 5 times and the average value is taken. The larger the water contact angle, the better the water repellency.

[0050] Table 1 Water contact angle test of cotton fabric

[0051] Water contact angle (°) Example 1 138.4 Example 2 144.9 Example 3 148.3 Comparative Example 1 88.5 Comparative Example 2 112.3 Comparative Example 3 123.5 Comparative Example 4 -

[0052] The combustion performance of cotton fabrics was tested using a vertical combustion tester according to the GB / T 5455-2014 method.

[0053] The limiting oxygen index of cotton fabric was tested using an oxygen index tester according to the GB / T 5454-1997 method.

[0054] Table 2 Flame retardant properties test of cotton fabric

[0055] Afterburning time (s) Smoldering time (s) Damaged length (mm) Limiting oxygen index (%) Example 1 4.9 0.4 47 28.0 Example 2 0.9 0 39 30.3 Example 3 0.7 0 36 30.6 Comparative Example 1 20.1 2.1 125 21.2 Comparative Example 2 18.3 1.8 123 22.3 Comparative Example 3 8.8 0.9 74 26.5 Comparative Example 4 32.6 2.3 130 20.7

[0056] Comparative Example 4 is a cotton fabric that has not been treated with a finishing liquid.

[0057] After testing, the cotton fabric in Comparative Example 4, which was not treated with the finishing liquid, had good hydrophilicity. Water droplets immediately wetted the cotton fabric after contacting it, so the water contact angle was not measured, and no water repellent effect was shown. In addition, the afterflaming time and smoldering time were long, the damage length was large, the limiting oxygen index was low, and the flame retardant performance was very poor.

[0058] Each embodiment uses a flame retardant and water repellent finishing liquid to finish cotton fabrics. The acrylic polymer in the finishing liquid is the main component of the finishing agent, which contains DOPO, piperazine and triphenylsilicon structures to form a nitrogen-phosphorus-silicon flame retardant. When burned, it can promote the formation of a silicon-carbon composite layer on the surface of the cotton fabric, play a condensed phase flame retardant effect, reduce the afterburning time, smoldering time and damage length of the cotton fabric, and significantly improve the limiting oxygen index and flame retardant performance. In addition, the acrylic polymer molecular chain contains a bistrifluoromethyl hydrophobic group and a triphenylsilicon hydrophobic structure, which significantly improves the water contact angle of the cotton fabric and exhibits excellent water repellent performance.

[0059] Compared with Example 1, in Comparative Example 1, when preparing the finishing liquid containing acrylic ester polymer, no propylene triphenylsilyl piperazine monomer and 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer were added, and the cotton fabric after finishing had very poor flame retardancy, low water contact angle, and poor water repellency.

[0060] Comparative Example 2 does not add 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer, the acrylic polymer molecular chain does not contain bis-trifluoromethyl hydrophobic groups, and the flame-retardant DOPO structure, and the cotton fabric has poor flame retardancy and water repellency.

[0061] In Comparative Example 3, no propylene triphenylsilyl piperazine monomer was added, the acrylate polymer molecular chain did not contain a triphenylsilicon hydrophobic structure, the water contact angle was lower than that of Example 1, and no piperazine structure and silicon element were contained, and no nitrogen-phosphorus-silicon flame retardant was formed, and the cotton fabric had poor flame retardancy.

[0062] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A process for preparing a flame retardant and water repellent finishing liquid, characterized in that: The preparation process comprises the following steps: step (1), adding acrylate monomer, propylene triphenylsilyl piperazine monomer, 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer and emulsifier into distilled water, stirring and mixing to obtain a prepolymer solution; adding an initiator into the distilled water, stirring and dissolving to obtain an initiator solution; The structural formula of the acryltriphenylsilylpiperazine monomer is formula (I): Formula (I); The structural formula of the 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer is formula (II): Formula (II); Step (2), taking 30-40% volume of the prepolymer solution, heating to 70-80° C., adding 25-35% volume of the initiator solution dropwise, controlling the adding time to be 60-90 min, then adding the remaining 60-70% volume of the prepolymer solution and 65-75% volume of the initiator solution, reacting for 3-5 h, and cooling to obtain a flame retardant and water repellent finishing liquid.

2. The process for preparing the flame retardant and water repellent finishing liquid according to claim 1, characterized in that: The mass ratio of the acrylic acid ester monomer, the acryl triphenyl silicon piperazine monomer and the 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer is 100:(12-30):(25-65).

3. The process for preparing the flame retardant and water repellent finishing liquid according to claim 2, characterized in that: The acrylic acid ester monomers include methyl acrylate, methyl methacrylate, butyl acrylate and butyl methacrylate.

4. The process for preparing the flame retardant and water repellent finishing liquid according to claim 1, characterized in that: The emulsifiers include OP-10, fatty alcohol polyoxyethylene ether AEO-15, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.

5. The process for preparing the flame retardant and water repellent finishing liquid according to claim 1, characterized in that: The initiator is potassium persulfate or ammonium persulfate.

6. The process for preparing the flame retardant and water repellent finishing liquid according to claim 2, characterized in that: The preparation process of the acryltriphenylsilane piperazine monomer is as follows: in a nitrogen atmosphere, at -5 to 0° C., triphenylchlorosilane, 1-allylpiperazine and triethylamine are added to tetrahydrofuran, reacting for 1-2 hours, and then reacting at room temperature for 4-6 hours, concentrating the solution, washing with distilled water and methanol in turn, and recrystallizing the product with ethyl acetate to obtain the acryltriphenylsilane piperazine monomer.

7. The process for preparing the flame retardant and water repellent finishing liquid according to claim 6, characterized in that: The molar ratio of triphenylchlorosilane, 1-allylpiperazine and triethylamine is 1:(1-1.1):(1-1.1).

8. The process for preparing the flame retardant and water repellent finishing liquid according to claim 2, characterized in that: The preparation process of the 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer is as follows: 2,2'-diallyl hexafluorobisphenol A and a structural formula of Chloro-DOPO and triethylamine are mixed and reacted at room temperature for 12-18 hours. The solution is concentrated and washed with methanol. The product is recrystallized in chloroform to obtain 2,2'-diallyl hexafluorobis-DOPO phenyl ester monomer.

9. The process for preparing the flame retardant and water repellent finishing liquid according to claim 8, characterized in that: The molar ratio of the 2,2'-diallyl hexafluorobisphenol A, chloro-DOPO and triethylamine is 1:(2-2.4):(2-2.4).

10. Use of the flame retardant and water repellent finishing liquid obtained by the preparation process according to any one of claims 1 to 9 in fabrics.

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