CN112127171A - Preparation method of durable flame-retardant coating of water-based phosphorus-containing polymer nanocomposite fabric - Google Patents
Preparation method of durable flame-retardant coating of water-based phosphorus-containing polymer nanocomposite fabric Download PDFInfo
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- CN112127171A CN112127171A CN202010935686.9A CN202010935686A CN112127171A CN 112127171 A CN112127171 A CN 112127171A CN 202010935686 A CN202010935686 A CN 202010935686A CN 112127171 A CN112127171 A CN 112127171A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a durable flame-retardant coating of a water-based phosphorus-containing polymer nano composite fabric. The invention takes water as a solvent, takes a water-based phosphorus-containing flame retardant monomer and an acrylate monomer as comonomers, and utilizes strong ionic bonds between phosphate groups and metal oxide nano particles to prepare the water-based core-shell phosphorus-containing polymer nano composite fabric flame retardant through water-phase free radical polymerization; then the nano composite flame-retardant coating is covalently bonded on the surface of the fabric through a cross-linking agent; and then the efficient durable flame-retardant fabric can be obtained through padding, pre-drying and baking treatment processes. The flame-retardant finishing agent prepared by the invention solves the problem of poor flame-retardant durability of the fabric, maintains the original toughness and hand feeling of the fabric, is halogen-free and environment-friendly, has simple synthesis process, cheap and easily-obtained raw materials, has high-efficiency flame-retardant effect on cotton, terylene and blended fabric, and has good market popularization value.
Description
Technical Field
The invention relates to the field of flame-retardant finishing methods for textiles, in particular to a preparation method of a durable flame-retardant coating for a water-based phosphorus-containing polymer nano composite fabric.
Background
With the rapid development of modern construction, the living standard of people is continuously improved, the requirements of textile fabrics for decoration and clothing are increasingly increased, and the problem of disaster caused by ignition of the textile fabrics is more and more serious. The burning of textile fabrics can generate harmful gases such as carbon monoxide, carbon dioxide, cyanide, nitrogen oxide and the like to cause great damage to human bodies, so that the flame retardant requirement of people on the textile fabrics is higher and higher. The flame retardant is an application of flame retardant technology in actual life, and is a special chemical auxiliary agent for improving the combustion performance of combustible and combustible materials. Most of the existing textile flame-retardant finishing agents are halogen-containing flame-retardant finishing agents, and although the flame-retardant finishing agents have good flame-retardant effect and small addition amount and have small influence on the performance of materials, the smoke generation amount is large, the released hydrogen halide gas is corrosive, and toxic carcinogenic substances dioxin or dibenzofuran can be generated to influence the normal metabolism of human bodies. Therefore, the method has very urgent significance for carrying out green, environment-friendly and efficient flame-retardant finishing on the textile.
Among the various fabric flame retardants, the phosphorus-containing flame retardant is the most typical condensed phase flame retardant finishing agent and is suitable for fabrics such as cotton, terylene, polyester cotton and the like. The phosphorus flame retardant can generate phosphoric acid when being heated and decomposed, the phosphoric acid can further generate difficultly volatile viscous polyphosphoric acid and polymetaphosphoric acid at high temperature, and the polyphosphoric acid and the polymetaphosphoric acid can promote dehydration and carbonization at high temperature to form a compact carbon layer to prevent heat and oxygen from entering the inside of the matrix. The flame-retardant finishing agent for the phosphorus-based fabrics on the market at present has a not ideal effect, and the durability and the environmental protection performance of the finished fabrics cannot be considered at the same time. For example, in chinese patent publication No. CN103790006A, a flame retardant finishing agent for fabric is prepared from phosphorus-containing substances, diammonium hydrogen phosphate and tricresyl phosphate, and the fabric finished by the flame retardant finishing agent for fabric has good flame retardancy and hidden flame retardancy, can prevent dripping, and is resistant to washing and dry cleaning. However, the simultaneous addition of the crosslinking agent tris (hydroxymethyl) triamide causes problems with free formaldehyde emission. In Chinese patent publication No. CN102162188A, MDPPA containing phosphorus and nitrogen compounds is used as a flame retardant, and dichloropropane is used as a cross-linking agent, so that the release amount of formaldehyde is reduced, and the whiteness, hand feeling, mechanical property and other properties of the flame-retardant finished fabric are improved. But the durability of the finished fabric does not achieve the ideal effect.
Therefore, research and development of a novel flame-retardant system which is environment-friendly, halogen-free, smokeless and low-toxicity and has excellent durability and vigorous development of ultralow-formaldehyde and even formaldehyde-free flame-retardant finishing technologies are important and development trends of the flame-retardant finishing and flame-retardant technology of fabrics in China to realize green flame-retardant finishing of textiles.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a durable flame-retardant coating of a water-based phosphorus-containing polymer nano composite fabric. The water-based phosphorus-containing polymer nano composite fabric flame-retardant coating solves the problem of poor flame-retardant durability of the fabric, maintains the original toughness and hand feeling of the fabric, and is halogen-free and environment-friendly. The flame-retardant finishing agent has the advantages of simple synthesis process, cheap and easily-obtained raw materials, high-efficiency flame-retardant effect on cotton, terylene and polyester cotton, and good market popularization value.
According to the invention, the water-based phosphorus-containing polymer nano composite fabric durable flame-retardant coating is prepared, the water-based phosphorus-containing flame-retardant monomer is introduced into the system, a compact and stable carbon layer structure can be formed on the surface of the fabric in the flame-retardant process, external heat and oxygen are prevented from entering the inside of the matrix, and meanwhile, the volatilization of combustible gas generated in the matrix to the outside is also inhibited, so that the flame-retardant property of the fabric is improved. In view of the high synergistic effect of the nano-particles and the phosphorus-containing flame retardant, the water-based phosphorus-containing polymer and acrylate copolymer is prepared, and the water-based phosphorus-containing polymer nano composite fabric durable flame-retardant coating is prepared by utilizing the strong ionic bond effect between the phosphate group and the nano-particles. The prepared flame-retardant coating has a stable core-shell type multistage nano structure, and the structure endows the carbon layer structure with integrity and compactness. Meanwhile, the halogen-free efficient durable flame retardant of the cotton fabric is realized by utilizing the reactive functional group in the acrylate molecule and adopting a proper cross-linking agent to covalently bond the nano composite durable flame retardant coating on the surface of the cotton fabric and then carrying out the processes of padding, pre-baking and baking.
After the flame-retardant finishing agent is used for finishing the fabric, the LOI value of the fabric can reach 39.8 percent at most, and the flame retardant property of the fabric is obviously improved. Preparing soap solution with concentration of 4g/L according to GB/T12490-. After being washed by different times of standard water, the LOI value of the fabric is only slightly reduced, and the fabric meets the national durable flame-retardant standard. Therefore, the treated fabric can be used as a durable fabric while realizing efficient halogen-free flame retardance, and the treated fabric keeps the original hand feeling and toughness.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a durable flame-retardant coating of a water-based phosphorus-containing polymer nano composite fabric comprises the following steps:
(1) sequentially adding a water-based phosphorus-containing flame-retardant monomer and an acrylate monomer into deionized water, adding an initiator, and then dissolving, heating and carrying out a first stirring reaction; then adding metal oxide nano particles, continuously heating and continuously stirring for the second time for reaction; finally obtaining the durable flame-retardant finishing agent of the water-based phosphorus-containing polymer nano composite fabric;
(2) preparing the durable flame-retardant finishing agent, the cross-linking agent and the water of the aqueous phosphorus-containing polymer nano composite fabric prepared in the step (1) into coating finishing liquid, soaking the fabric into the coating finishing liquid, and then carrying out padding, pre-drying and baking treatment to obtain the fabric containing the durable flame-retardant coating of the aqueous phosphorus-containing polymer nano composite fabric, thus obtaining the high-efficiency durable flame-retardant fabric.
In the invention, a water-based phosphorus-containing flame-retardant monomer and an acrylate monomer are sequentially added into deionized water, and an initiator is added for dissolving, heating and stirring reaction; then adding metal oxide nano particles, continuously heating and continuously stirring for reaction; finally obtaining the durable flame-retardant finishing agent of the water-based phosphorus-containing polymer nano composite fabric.
The flame-retardant finishing agent has a core-shell type multilevel nanostructure in view of strong ionic bonding between the phosphate group and the nanoparticles; the core of the core-shell structure is a metal oxide nanoparticle, and the shell of the core-shell structure is a water-based flame-retardant polymer; the durable flame-retardant coating of the composite fabric formed by the core-shell type multilevel nano structure has excellent flame retardance and durability.
Preferably, in the step (1), the durable flame-retardant finishing agent of the water-based phosphorus-containing polymer nanocomposite fabric adopts the following raw materials in percentage by mass based on 100 percent of the total mass:
further preferably, in the step (1), the durable flame-retardant finishing agent for the water-based phosphorus-containing polymer nanocomposite fabric comprises the following components in percentage by mass of 100 percent:
the water-based flame-retardant polymer is formed by copolymerizing a water-based phosphorus-containing flame-retardant monomer and an acrylate monomer. The water-based phosphorus-containing flame-retardant monomer is one or more of vinyl phosphonic acid, dimethyl vinyl phosphate and dimethyl allyl phosphate, and the mass ratio is 1: 0-0.5: 0 to 0.25, most preferably, the aqueous phosphorus-containing flame retardant monomer comprises: the mass ratio of the vinyl phosphonic acid to the dimethyl vinyl phosphate to the dimethyl allyl phosphate is 1: 0.5: 0.25. the acrylate monomer is one or more of Acrylic Acid (AA), methacrylic acid (MAA) or ethylene glycol methacrylate (EDMA), namely one or more than two (including two).
The initiator is one or more of water-soluble initiator azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride or ammonium persulfate, namely one or more than two (including two).
The metal oxide nanoparticles are one or more of titanium dioxide, cerium dioxide, zinc oxide and nickel oxide, namely one or more than two (including two), and the particle size of the nanoparticles is 50-200 nm.
The reaction parameters after the initiator is added are as follows: the reaction temperature is 60-70 ℃, the stirring time is 6-8 h, namely the condition of the first stirring reaction is 60-70 ℃, and the stirring reaction is 6-8 h.
The reaction parameters after adding the metal oxide nanoparticles are as follows: the reaction temperature is 70-80 ℃, and the stirring time is 2-3 h. Namely, the second stirring reaction is carried out for 2-3 h at the temperature of 70-80 ℃.
In the step (2), the invention also discloses an application of the durable flame-retardant finishing agent for the water-based phosphorus-containing polymer nano composite fabric in the flame-retardant finishing of the fabric, which comprises the following steps: preparing a coating finishing liquid from the finishing agent and the cross-linking agent, soaking the fabric in the impregnating liquid according to a certain bath ratio, and then carrying out padding, pre-drying and baking treatment to obtain the high-efficiency durable flame-retardant fabric.
The cross-linking agent is a polymer which has a reactive functional group and can react with hydroxyl on the fabric, so that the nano-composite flame-retardant coating is covalently bonded on the surface of the fabric, and the aim of high-efficiency durable flame retardance is fulfilled.
Preferably, the cross-linking agent is one or more, namely one or more (including two) of citric acid, pentaerythritol-tris (3-aziridinyl) propionate, hypophosphorous acid or silane coupling agent KH-792, and the dosage of the cross-linking agent is 1-5% of the mass of the durable flame-retardant finishing agent for the waterborne phosphorus-containing polymer nanocomposite fabric.
The bath ratio of the fabric to the coating finishing liquid (namely the weight ratio of the fabric to the coating finishing liquid) is 1: 15-25 ℃, the padding time is 0.5-1.5 h, the padding vehicle pressure is 0.3-0.5 MPa, and the pre-drying condition is as follows: pre-baking for 5-15 min at 100-120 ℃ in an oven, most preferably pre-baking for 8min at 110 ℃ in the oven, wherein the baking condition is baking for 3-5 min at 140-160 ℃ in the oven, and most preferably baking for 4min at 150 ℃ in the oven.
The Limit Oxygen Index (LOI) and the disposal burning grade (UL-94) of the finished fabric are respectively tested by adopting a limit oxygen index tester and a vertical burning instrument, and the result shows that the limit oxygen index of the phosphorus-containing waterborne polymer nano composite flame-retardant fabric prepared by the invention can be improved to 39.8 percent from 17 percent to the maximum, the flame retardant property is obviously improved, and the vertical burning test (UL-94) can reach V-0 grade.
Preparing soap solution with concentration of 4g/L according to GB/T12490-. After being washed by different times of standard water, the LOI value of the fabric is only slightly reduced, and the fabric meets the national durable flame-retardant standard. Therefore, the treated fabric can be used as a durable fabric while realizing efficient halogen-free flame retardance, and the treated fabric keeps the original hand feeling and toughness.
Compared with the prior art, the invention has the following beneficial effects:
(1) the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric prepared by the invention has the advantages of cheap and easily-obtained raw materials, no organic pollution, safety, no halogen and capability of realizing a green flame-retardant target.
(2) The invention utilizes the synergistic effect between the green water-based flame-retardant monomer and the nano particles to design the integrity and compactness of the carbon layer formed by catalysis, thereby achieving the aim of high-efficiency flame retardance.
(3) The invention finds out a proper covalent crosslinking system to improve the binding force between the flame-retardant coating and the cotton fabric, and then utilizes a padding-pre-baking post-treatment method to achieve the purpose of durable flame retardance.
Drawings
FIG. 1 shows the reaction scheme for the synthesis of p (VPA-co-EDMA) copolymer in this example 1, wherein VPA is vinylphosphonic acid, EDMA is ethylene glycol methacrylate, p (VPA-co-EDMA) is a copolymer of vinylphosphonic acid and ethylene glycol methacrylate, and AIBA is initiator azobisisobutylamidine hydrochloride.
FIG. 2 shows p (VPA-co-EDMA) @ TiO in example 12Process for finishing NPs nano composite durable flame-retardant finishing agent on fabric, TiO in figure 22NPs are titanium dioxide nanoparticles, citric acid is citric acid, p (VPA-co-EDMA) @ TiO2NPs are titanium dioxide nano-particle composite vinylphosphonic acid and ethylene glycol methacrylate copolymer flame retardant.
FIG. 3 is a vertical burning photo of the fabric with the durable flame-retardant nano-composite coating in comparative example 2 and examples 1 to 8.
FIG. 4 shows p (VPA-co-EDMA) @ TiO in example 12The simple flame-retardant mechanism diagram of the NPs nano composite durable flame retardant is shown in figure 4, wherein solid phase is shown in figure 4, Heat is shown in figure 4 as released Heat, Char layer is shown in figure 4, and phosphor-rich cross-links is shown in figure 4 as a Phosphorus-rich cross-linked network structure.
Detailed Description
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1:
sequentially adding 20.3g of vinylphosphoric acid and 20.3g of ethylene glycol methacrylate into a three-neck flask, and dissolving by using 100ml of deionized water as a solvent; adding 1.45g of initiator azobisisobutylamidine hydrochloride, stirring and heating at 60 ℃ for reacting for 6 hours; then adding 5.2g titanium dioxide nano particles, heating to 70 ℃, continuously stirring and reacting for 2h to obtain p (VPA-co-EDMA) @ TiO2NPs nano composite flame-retardant finishing agent.
Dissolving the finishing agent in deionized water according to the mass ratio of 1g:50mL to prepare a steeping liquor, and adding 10mL of cross-linking agent citric acid; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.5h, and the padding pressure is 0.3 MPa; then pre-baking in an oven at 100 ℃ for 5min and baking at 140 ℃ for 3 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
The reaction scheme for the synthesis of p (VPA-co-EDMA) copolymer in this example is shown in FIG. 1.
In this example, p (VPA-co-EDMA) @ TiO2The process of finishing the NPs nanocomposite durable flame retardant finish on fabric is shown in figure 2.
In this example, p (VPA-co-EDMA) @ TiO2The simple flame-retardant mechanism diagram of the NPs nano composite durable flame retardant is shown in figure 4.
Example 2:
31.2g of vinyl phosphoric acid and 15.6g of ethylene glycol methacrylate are sequentially added into a three-neck flask, and 100ml of deionized water is used as a solvent for dissolving; adding 2.18g of initiator azobisisobutylamidine hydrochloride, and stirring and heating at 65 ℃ for reaction for 7 hours; then adding 7.2g titanium dioxide nano particles, heating to 75 ℃, and continuously stirring for reaction for 2.5h to obtain p (VPA-co-EDMA) @ TiO2NPs nano composite flame-retardant finishing agent.
Dissolving the finishing agent in deionized water according to the mass ratio of 1g:50mL to prepare a steeping liquor, and adding 12mL of cross-linking agent citric acid; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.75h, and the padding pressure is 0.4 MPa; then pre-baking in a baking oven at 110 ℃ for 8min and baking at 150 ℃ for 4 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
Example 3:
adding 34.5g of vinylphosphoric acid and 11.5g of ethylene glycol methacrylate into a three-neck flask in sequence, and dissolving by using 100ml of deionized water as a solvent; adding 2.38g of initiator azobisisobutylamidine hydrochloride, and stirring and heating at 70 ℃ for reacting for 8 hours; then 8.3g of titanium dioxide nano-particles are added, the temperature is raised to 80 ℃, and the reaction is continuously stirred for 3 hours to obtain p (VPA-co)-EDMA)@TiO2NPs nano composite flame-retardant finishing agent.
Dissolving the finishing agent in deionized water according to the mass ratio of 1g:50mL to prepare a steeping liquor, and adding 15mL of cross-linking agent citric acid; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.5h, and the padding pressure is 0.5 MPa; then pre-baking in a baking oven at 120 ℃ for 10min and baking at 160 ℃ for 5 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
Example 4:
31.2g of vinyl phosphoric acid and 15.6g of ethylene glycol methacrylate are sequentially added into a three-neck flask, and 100ml of deionized water is used as a solvent for dissolving; adding 2.18g of initiator azobisisobutylimidazoline hydrochloride, stirring and heating at 65 ℃ for reaction for 7 hours; then adding 6.8g of cerium dioxide nano-particles, heating to 75 ℃, and continuously stirring for reaction for 2.5h to obtain p (VPA-co-EDMA) @ CeO2NPs nano composite flame-retardant finishing agent.
Dissolving a finishing agent in deionized water according to the mass ratio of 1g to 100mL to prepare a steeping liquor, and adding 11mL of cross-linking agent hypophosphorous acid; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.75h, and the padding pressure is 0.4 MPa; then pre-baking in a baking oven at 110 ℃ for 8min and baking at 150 ℃ for 4 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
Example 5:
31.2g of vinyl phosphoric acid and 15.6g of ethylene glycol methacrylate are sequentially added into a three-neck flask, and 100ml of deionized water is used as a solvent for dissolving; adding 2.18g of initiator azobisisobutylimidazoline hydrochloride, stirring and heating at 65 ℃ for reaction for 7 hours; then adding 8.93g of zinc oxide nano particles, heating to 75 ℃, and continuously stirring for reaction for 2.5h to obtain the p (VPA-co-EDMA) @ ZnO NPs nano composite flame-retardant finishing agent.
Dissolving a finishing agent in deionized water according to the mass ratio of 1g:100mL to prepare a dipping solution, and adding 16mL of a cross-linking agent pentaerythritol-tri (3-aziridinyl) propionate; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.75h, and the padding pressure is 0.4 MPa; then pre-baking in a baking oven at 110 ℃ for 8min and baking at 150 ℃ for 4 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
Example 6:
31.2g of vinyl phosphoric acid and 15.6g of ethylene glycol methacrylate are sequentially added into a three-neck flask, and 100ml of deionized water is used as a solvent for dissolving; adding 2.18g of initiator azobisisobutylamidine hydrochloride, and stirring and heating at 65 ℃ for reaction for 7 hours; then adding 5.63g of nickel oxide nano-particles, heating to 75 ℃, and continuously stirring for reacting for 2.5h to obtain the p (VPA-co-EDMA) @ NiO NPs nano-composite flame-retardant finishing agent.
Dissolving a finishing agent in deionized water according to the mass ratio of 1g to 100mL to prepare a steeping liquor, and adding 15mL of a cross-linking agent silane coupling agent KH-792; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.75h, and the padding pressure is 0.4 MPa; then pre-baking in a baking oven at 110 ℃ for 8min and baking at 150 ℃ for 4 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
Example 7:
31.2g of vinylphosphoric acid, 15.6g of dimethyl vinylphosphate and 15.6g of methacrylic acid were successively charged into a three-necked flask and dissolved in 100ml of deionized water as a solvent. Adding 1.6g of initiator azobisisobutylamidine hydrochloride, and stirring and heating at 65 ℃ for reaction for 7 hours; then adding 7g of titanium dioxide nano particles, heating to 75 ℃, and continuously stirring for reacting for 2.5h to obtain p (VPA-TMA-co-MAA) @ TiO2NPs nano composite flame-retardant finishing agent.
Dissolving the finishing agent in deionized water according to the mass ratio of 1g:50mL to prepare a steeping liquor, and adding 13mL of cross-linking agent citric acid; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.75h, and the padding pressure is 0.4 MPa; then pre-baking in a baking oven at 110 ℃ for 8min and baking at 150 ℃ for 4 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
Example 8:
adding 34.5g of vinyl phosphoric acid, 17.2g of dimethyl vinyl phosphate, 8.6g of dimethyl allyl phosphate and 11.5g of acrylic acid into a three-neck flask in sequence, and dissolving by using 100ml of deionized water as a solvent; adding 2.23g of initiator azobisisobutylamidine hydrochloride, and stirring and heating at 70 ℃ for reacting for 8 hours; then adding 8.6g of titanium dioxide nano-particles, heating to 80 ℃, and continuously stirring for reacting for 3 hours to obtain p (VPA-TMA-DAP-co-AA) @ TiO2NPs nano composite flame-retardant finishing agent.
Dissolving the finishing agent in deionized water according to the mass ratio of 1g:50mL to prepare a steeping liquor, and adding 15mL of cross-linking agent citric acid; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.5h, and the padding pressure is 0.5 MPa; then pre-baking in a baking oven at 120 ℃ for 10min and baking at 160 ℃ for 5 min; taking out and cooling to obtain the high-efficiency durable flame-retardant cotton fabric, namely the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
Comparative example 1:
the method comprises the steps of washing and bleaching cotton fabrics of the same type purchased in the market for 2-3 times, and then pre-drying the cotton fabrics in an oven at 110 ℃ for 8min and baking the cotton fabrics at 150 ℃ for 4 min. Taking out and cooling to obtain the comparative example 1.
Comparative example 2:
31.2g of vinyl phosphoric acid and 15.6g of ethylene glycol methacrylate are sequentially added into a three-neck flask, and 100ml of deionized water is used as a solvent for dissolving; 2.18g of initiator azobisisobutylamidine hydrochloride is added, and then the mixture is stirred and heated at 65 ℃ for reaction for 7 hours to obtain the p (VPA-co-EDMA) composite flame-retardant finishing agent.
Dissolving the finishing agent in deionized water according to the mass ratio of 1g:50mL to prepare a steeping liquor, and adding 12mL of cross-linking agent citric acid; then, the pure cotton fabric is put into the dipping solution for soaking for 0.5h at a bath ratio of 1: 20. Padding the fabric by using an MU504A type bench padder, wherein the padding time is 0.75h, and the padding pressure is 0.4 MPa; then pre-baking in a baking oven at 110 ℃ for 8min and baking at 150 ℃ for 4 min; taking out and cooling to obtain the comparative example 2.
The flame retardant performance test results of the high-efficiency durable flame retardant coated fabrics prepared in comparative examples 1-2 and examples 1-8 are shown in table 1.
TABLE 1
The flame-retardant finishing agent for the water-based phosphorus-containing polymer nano composite fabric prepared by the invention can be obtained from comparative example 1 and examples 1-8 in the table 1, the flame-retardant capability of the cotton fabric is effectively improved, and the vertical burning test (UL-94) can reach V-0 level. After being washed by different times of standard water, the LOI value is slightly reduced, but the flame retardant fabric still has excellent flame retardant capability and can reach the standard of durable flame retardant fabrics.
From comparative example 2 and examples 2 and 4-6 in table 1, the addition of the metal oxide nanoparticles can effectively enhance the flame retardant capability of the p (VPA-co-EDMA) composite flame retardant finishing agent. Containing TiO therein2The coating effect of the NPs is optimal, and the flame retardant capability is optimal.
The vertical burning photo of the high-efficiency durable flame-retardant coated fabric prepared in the comparative example 2 and the examples 1 to 8 is shown in FIG. 3. From the vertical burning coal length of each sample in the figure can be seen: the carbon length of comparative example 2, to which no metal oxide nanoparticles were added, was 3.0cm, and the carbon lengths of examples 1 to 8 were 2.4cm, 1.0cm, 1.1cm, 1.3cm, 0.99cm, and 0.98cm, respectively. The carbon length comparison of comparative example 2, examples 2 and 4-6 still can obtain that the addition of the metal oxide nanoparticles can effectively enhance the flame retardant capability of the p (VPA-co-EDMA) composite flame retardant finishing agent. Containing TiO therein2The coating effect of the NPs is optimal, and the flame retardant capability is optimal. From a comparison of the carbon lengths of examples 3, 7 and 8: multiple aqueous phosphorus-containing flame retardant monomers in the systemThe synergistic effect of the nano composite flame retardant finishing agent can enhance the flame retardant capability of the nano composite flame retardant finishing agent.
Claims (10)
1. The preparation method of the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric is characterized by comprising the following steps of:
(1) sequentially adding a water-based phosphorus-containing flame-retardant monomer and an acrylate monomer into deionized water, adding an initiator, and then dissolving, heating and carrying out a first stirring reaction; then adding metal oxide nano particles, continuously heating and continuously stirring for the second time for reaction; finally obtaining the durable flame-retardant finishing agent of the water-based phosphorus-containing polymer nano composite fabric;
(2) preparing the durable flame-retardant finishing agent, the cross-linking agent and the water of the water-based phosphorus-containing polymer nano composite fabric prepared in the step (1) into coating finishing liquid, soaking the fabric into the coating finishing liquid, and then carrying out padding, pre-drying and baking treatment to obtain the fabric containing the durable flame-retardant coating of the water-based phosphorus-containing polymer nano composite fabric.
2. The preparation method of claim 1, wherein in the step (1), the aqueous phosphorus-containing polymer nanocomposite fabric durable flame-retardant finishing agent is prepared from the following raw materials in percentage by mass, based on 100% of the total mass fraction:
3. the method according to claim 1, wherein in step (1), the aqueous phosphorus-containing flame retardant monomer is one or more of vinyl phosphonic acid, dimethyl vinyl phosphate and dimethyl allyl phosphate.
4. The method according to claim 1, wherein in step (1), the acrylate monomer is one or more of acrylic acid, methacrylic acid or ethylene glycol methacrylate.
5. The preparation method of claim 1, wherein in the step (1), the initiator is one or more of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride or ammonium persulfate.
6. The method according to claim 1, wherein in step (1), the metal oxide nanoparticles are one or more of titanium dioxide, cerium dioxide, zinc oxide and nickel oxide.
7. The preparation method according to claim 1, wherein in the step (1), the first stirring reaction is carried out at 60-70 ℃ for 6-8 h.
8. The preparation method according to claim 1, wherein in the step (1), the second stirring reaction is carried out at 70-80 ℃ for 2-3 h.
9. The method according to claim 1, wherein in step (2), the crosslinking agent is one or more of citric acid, pentaerythritol-tris (3-aziridinyl) propionate, hypophosphorous acid, or silane coupling agent KH-792.
10. The method according to claim 1, wherein in the step (2), the bath ratio of the textile to the coating finishing liquid is 1: 15-25;
the padding time is 0.5-1.5 h, and the padding vehicle pressure is 0.3-0.5 MPa;
the pre-drying conditions are as follows: pre-drying for 5-15 min at 100-120 ℃ in an oven;
the baking condition is baking for 3-5 min in an oven at 140-160 ℃.
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