CN118048786A - A flame retardant with ultra-high heat expansion resistance, a preparation method thereof, and application of flame-retardant nylon fabric - Google Patents
A flame retardant with ultra-high heat expansion resistance, a preparation method thereof, and application of flame-retardant nylon fabric Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
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Abstract
The invention relates to an ultra-high heat-resistant expansion flame retardant, a preparation method thereof and an application of flame-retardant nylon fabric, wherein the preparation method comprises the following steps: dispersing microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 1-1.5 hours at 60-80 ℃, cooling to room temperature after the reaction is finished, washing and drying to obtain cellulose nanocrystalline; dispersing cellulose nanocrystals in water, adding 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid, adjusting the pH to 7.5-8.5, adding tannic acid, reacting at room temperature for 12-24h, finally adding phytic acid aqueous solution, reacting at room temperature for 1-2h, cooling to room temperature after the reaction is finished, washing, and drying to obtain the ultra-high heat resistance expansion flame retardant. According to the invention, cellulose nanocrystalline and tannic acid are used as charring agents, and phytic acid is used as an acid source and an air source, so that the flame retardant property of the intumescent flame retardant is effectively improved, the flame retardant can be used as modified flame retardant for fibers such as nylon 66, and the economic value of functional fibers is improved.
Description
Technical Field
The invention belongs to the technical field of flame retardant materials, and particularly relates to an ultra-high thermal expansion resistant flame retardant, a preparation method thereof and an application of flame retardant nylon fabric.
Background
Flame Retardants (FRs) are effective strategies to prevent fires in order to reduce the risk of fire. The main types of flame retardants can be classified into halogen flame retardants and halogen-free flame retardants. Halogen flame retardants are considered to be harmful to the environment and the human body because they generate a large amount of smoke and toxic corrosive gases during combustion. In contrast, halogen-free flame retardants are receiving great attention because of their environmental friendliness, good compatibility and high flame retardant properties.
The Intumescent Flame Retardant (IFRs) in the halogen-free flame retardant has the advantages of low smoke, low toxicity, environmental protection, high efficiency and the like, so that the halogen-free flame retardant becomes one of research hotspots in the fields at home and abroad at present. IFRs can form a porous foam char layer that acts as a physical barrier protecting the underlying material from flame, heat, and oxygen. Thus, the flame retardant effect of IFRs is largely dependent on the formation of an intumescent char layer, which is a multiphase system comprising solid, liquid and gaseous products.
In the combustion process of the polymer, a carbon layer is formed on the surface of the polymer, and the carbon layer has the functions of heat insulation, oxygen insulation, smoke suppression and molten drop prevention in a condensed phase, is low in smoke, low in toxicity and free of corrosive gas generation, and has high-efficiency flame retardant performance. Cellulose is one of the most abundant biodegradable polymers in the world, and has unique characteristics of no toxicity, low price, renewable resources, temperature resistance, stability of pH value change and the like. Cellulose has a rich molecular structure of polyhydroxy groups, and can form a crosslinked carbon layer during combustion, and thus is considered to be a crosslinked carbon layer. However, the flammability of cellulose limits its further use as a flame retardant. The bio-based intumescent flame retardant is formed by taking renewable cellulose nanocrystalline, tannic acid and phytic acid as materials in a green and synergistic efficient mode. Therefore, a simple and economical method is developed to prepare the flame retardant with high thermal stability and expansibility, and the scheme provides a new thought for a preparation method for preparing the flame retardant with ultrahigh thermal expansion resistance.
Disclosure of Invention
Based on the above-mentioned drawbacks and deficiencies of the prior art, it is an object of the present invention to at least solve one or more of the above-mentioned problems of the prior art, in other words, to provide an ultra-high thermal expansion resistant flame retardant satisfying one or more of the above-mentioned needs, a method for preparing the same and flame retardant nylon fabric applications.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
The preparation method of the ultra-high heat-resistant expansion flame retardant comprises the following steps:
(1) Dispersing microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 1-1.5 hours at 60-80 ℃, cooling to room temperature after the reaction is finished, washing and drying to obtain cellulose nanocrystalline;
(2) Dispersing cellulose nanocrystals in water, adding 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid, adjusting the pH to 7.5-8.5, adding tannic acid, reacting at room temperature for 12-24h, finally adding phytic acid aqueous solution, reacting at room temperature for 1-2h, cooling to room temperature after the reaction is finished, washing, and drying to obtain the ultra-high heat resistance expansion flame retardant.
In the step (2), the mass ratio of the cellulose nanocrystals to the tannic acid to the phytic acid aqueous solution is 1: (0.025-0.1): (0.5-2).
Preferably, in the step (2), the mass fraction of the aqueous solution of phytic acid is 60-70%.
In the preferred scheme, in the step (2), the mass parts of the cellulose nanocrystalline and the 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid are prepared as 1: (0.1-0.2).
The invention also provides the ultra-high thermal expansion resistant flame retardant prepared by the preparation method according to any scheme.
The invention also provides a preparation method of the high flame retardant nylon 66 fabric, which comprises the following steps:
(a) Pretreating nylon 66 fabric with alkali solution;
Preparing Na 2CO3 solution, heating to boiling, putting the solution into nylon 66 fabric, continuously boiling and washing, and dehydrating and drying for later use;
(b) Sequentially carrying out dipping flame retardant finishing, dehydration and drying on the nylon 66 fabric dried in the step (a);
Wherein, the impregnating solution adopted for impregnating the flame retardant is aqueous dispersion of the ultra-high heat-resistant expansion flame retardant according to the scheme;
(c) Sequentially performing coating flame-retardant spraying finishing and drying on the nylon 66 fabric dried in the step (b); wherein, the flame-retardant coating liquid adopted by the flame-retardant spraying finishing of the coating comprises 30-50wt% of aqueous polyurethane with the solid content of 40%, 15-45wt% of the ultra-high thermal expansion-resistant flame retardant according to the scheme, and the balance of water.
Preferably, in the step (a), the concentration of the Na 2CO3 solution is 1-3g/L, and the washing time is 10-20min.
Preferably, in the step (b), the impregnation bath ratio of the impregnation flame retardant finishing is 1: (10-20), wherein the dipping temperature is 30-50 ℃ and the dipping time is 1-2h;
the concentration of the aqueous dispersion of the ultra-high thermal expansion resistant flame retardant is 100-200g/L.
Preferably, in the step (c), the flame-retardant coating solution sprayed on the unit area of the nylon 66 fabric is 200-220g/m 2.
The invention also provides the high flame retardant nylon 66 fabric prepared by the preparation method according to any one of the schemes.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, cellulose nanocrystalline and tannic acid are used as charring agents, and phytic acid is used as an acid source and an air source, so that the phytic acid can promote dehydration and charring of the cellulose nanocrystalline and tannic acid to form a denser carbon layer in the combustion process, hydrogen is generated, on one hand, oxygen in air is diluted, and on the other hand, water is generated by combining the hydrogen and the oxygen, so that the surface temperature of a substrate is reduced; tannic acid has carbonization capability of a plurality of aromatic rings, so that a condensed phase flame-retardant mechanism is caused, and meanwhile, in the heating process, ortho-phenolic hydroxyl contained in tannic acid is an excellent hydrogen donor, has obvious scavenging effect on oxygen free radicals such as superoxide anion free radicals and hydroxyl free radicals, and interrupts a burning reaction chain;
(2) The invention adopts cellulose nanocrystalline, tannic acid and phytic acid as materials, and all come from renewable green materials, so that the damage to the environment can be reduced, and non-renewable resources are saved;
(3) The preparation method of the ultra-high heat-resistant expansion flame retardant has high heat stability, excellent expansion performance, simple preparation process, environment friendliness and low cost, and has wide application prospects in the fields of nano-composite and reinforced materials, biomedicine, textiles and the like;
(4) The limiting oxygen index of the high flame retardant nylon 66 fabric is improved from 22% to 29%, the residual quantity of hot heavy carbon is improved by 241%, the number of molten drops is reduced during combustion, and the fabric has good char formation.
Drawings
FIG. 1 is a scanning electron microscope image of an ultra-high thermal expansion resistant flame retardant according to example a of the present invention;
FIG. 2 is an infrared spectrum of the ultra-high thermal expansion resistant flame retardant of the Cellulose Nanocrystals (CNC) of the present invention and example a;
FIG. 3 is a thermogravimetric plot of the inventive Cellulose Nanocrystals (CNC), the ultra high thermal expansion resistant flame retardant of example a, and the flame retardants of comparative examples a-d;
FIG. 4 is a graph showing the expansion effects of the ultra-high thermal expansion flame retardant of example a (CNC-TA-PA) of the present invention and the flame retardant of comparative example a (CNC-PA-TA);
FIG. 5 is an infrared spectrum of the high flame retardant nylon 66 fabrics of examples 1-3 of the present invention and the modified nylon 66 fabric of comparative example 1;
FIG. 6 is a thermogravimetric plot of the high flame retardant nylon 66 fabrics of examples 1-3 of the present invention and the modified nylon 66 fabric of comparative example 1;
FIG. 7 is a graph of ultraviolet absorbance of the highly flame retardant nylon 66 fabrics of examples 1-3 of the present invention and the modified nylon 66 fabric of comparative example 1;
FIG. 8 is a graph of limiting oxygen index for nylon 66 fabric and the high flame retardant nylon 66 fabric of example 3 of the present invention;
fig. 9 is a picture of anti-drip qualitative analysis of nylon 66 fabric and the high flame retardant nylon 66 fabric of example 3 of the present invention.
Detailed Description
The following further illustrates an ultra-high thermal expansion resistant flame retardant, a preparation method thereof and an application of the flame retardant nylon fabric by specific examples.
Example a:
The preparation method of the ultra-high thermal expansion resistant flame retardant comprises the following steps:
(1) Dispersing 2 parts of microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 90min at 60 ℃, cooling to room temperature after the reaction is finished, washing, and drying to obtain cellulose nanocrystalline.
(2) Dispersing 1 part of cellulose nanocrystalline in deionized water, adding 0.119 part of 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid (HEPES) buffer, magnetically stirring at room temperature for 10min, gradually dropwise adding NaOH1M solution until pH=8, then adding 1/20 part of tannic acid, reacting at room temperature for 24h, then adding 1 part of phytic acid aqueous solution (70 wt%) and reacting at room temperature for 2h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain the CNC-TA-PA flame retardant with ultrahigh heat resistance.
As shown in FIG. 1, the cellulose nanocrystals modified by tannic acid and phytic acid show a spherical shape, which shows that tannic acid is well coated on the outer side of the cellulose nanocrystals, and phenolic hydroxyl groups of the tannic acid can be electrostatically adsorbed with more phytic acid. As shown in fig. 2, carbon-oxygen double bonds (c=o) appear in cellulose nanocrystals at 1500-2000cm -1, and because tannic acid coats cellulose nanocrystals, characteristic peaks of the carbon-oxygen double bonds (c=o) incline rightward, and at the same time, about 1470cm -1 and 1380cm -1 respectively represent c=c framework vibration and C-O stretching vibration on benzene rings, which indicates that tannic acid is successfully coated on cellulose nanocrystals, and about 794cm -1、956cm-1 and 1200cm -1 respectively represent P-O-C, O-P-O and p=o, which indicates that PA grafting modification is successful.
Comparative example a:
The preparation method of the flame retardant of the comparative example comprises the following steps:
(1) Dispersing 2 parts of microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 90min at 60 ℃, cooling to room temperature after the reaction is finished, washing, and drying to obtain cellulose nanocrystalline.
(2) Dispersing 1 part of cellulose nanocrystalline in deionized water, adding 1 part of phytic acid aqueous solution (70 wt%) for reaction at room temperature for 2 hours, then adding 0.119 part of 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid (HEPES) buffer, magnetically stirring at room temperature for 10 minutes, then gradually dropwise adding NaOH1M solution until pH=8, then adding 1/20 part of tannic acid, reacting at room temperature for 24 hours, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain the flame retardant CNC-PA-TA.
Comparative example b:
The preparation method of the flame retardant of the comparative example comprises the following steps:
(1) Dispersing 2 parts of microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 90min at 60 ℃, cooling to room temperature after the reaction is finished, washing, and drying to obtain cellulose nanocrystalline.
(2) Dispersing 1 part of cellulose nanocrystalline in deionized water, adding 1/20 part of tannic acid, 1 part of phytic acid aqueous solution (70 wt%) and 0.119 part of 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid (HEPES) buffer, magnetically stirring at room temperature for 10min, gradually dropwise adding NaOH1M solution until pH=8, reacting at room temperature for 24h, cooling to room temperature after the reaction is finished, centrifugally separating, washing and drying to obtain the flame retardant CNC/TA/PA.
Comparative example c:
The preparation method of the flame retardant of the comparative example comprises the following steps:
(1) Dispersing 2 parts of microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 90min at 60 ℃, cooling to room temperature after the reaction is finished, washing, and drying to obtain cellulose nanocrystalline.
(2) Dispersing 1 part of cellulose nanocrystalline in deionized water, then adding 1 part of phytic acid aqueous solution (70 wt%) for reaction at room temperature for 2 hours, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain the flame retardant CNC-PA.
Comparative example d:
The preparation method of the flame retardant of the comparative example comprises the following steps:
(1) Dispersing 2 parts of microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 90min at 60 ℃, cooling to room temperature after the reaction is finished, washing, and drying to obtain cellulose nanocrystalline.
(2) Dispersing 1 part of cellulose nanocrystalline in deionized water, adding 0.119 part of 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid (HEPES) buffer, magnetically stirring at room temperature for 10min, gradually dropwise adding NaOH1M solution until pH=8, then adding 1/20 part of tannic acid, reacting at room temperature for 24h, cooling to room temperature after the reaction is finished, centrifuging, washing, and drying to obtain the flame retardant CNC-TA.
The thermal stability performance of the product was evaluated using a thermogravimetric analyzer (TG 209F 1, netzsch) and the thermal weights of the Cellulose Nanocrystals (CNC), example a, and comparative examples a-d are shown in fig. 3. Example a compared to CNC, T max was increased from 213.9 ℃ to 324.9 ℃ and the char residue at 600 ℃ was increased from 29.3% to 59.3%. Compared with comparative examples b and c, example a has more excellent thermal stability, which shows that the coacervation phase and the gas phase of tannic acid and phytic acid have synergistic effect, the maximum mass loss rate of CNC-TA-PA is reduced, and the thermal resistance of CNC-TA-PA is greatly improved and the further degradation of the matrix is prevented due to the heat insulation and oxygen insulation of the compact carbon layer. Through the comparison of the embodiment a with the comparison of the embodiment a and the comparison of the embodiment b, although the materials are the same, the sequences of adding tannic acid and phytic acid are different, but the thermal weight and the expansion effect of the embodiment a are better than those of the comparison of the embodiment a, because the tannic acid is added firstly, on one hand, the tannic acid can better coat the cellulose nanocrystalline to protect the matrix, on the other hand, more phenolic hydroxyl groups on the tannic acid and phytic acid are subjected to electrostatic adsorption, the adsorption capacity of the phytic acid is improved, more substances such as phosphoric acid and the like can be released by the phytic acid in the heating process, the carbonization of the tannic acid and the cellulose nanocrystalline is promoted, a denser carbon layer is formed, and the condensed phase flame retardant mechanism is achieved. Comparative example b, since tannic acid and phytic acid were added simultaneously, there were cases of CNC and TA reactions, CNC and PA reactions, CNC and TA, and PA simultaneous reactions during the reaction, as can be seen from FIG. 3, the thermal stability performance of example a was best because CNC and TA reactions reached the condensation wanted flame retardant mechanism, CNC and PA reactions reached the gas phase flame retardant mechanism, and it was found by example a that the condensation phase and gas phase synergized effect was best. Qualitative analysis was performed on the flame retardants prepared in example 1 and comparative example a, and as can be obtained in fig. 4, the expansion effect of the CNC-TA-PA flame retardant is relatively good, and the tannic acid and cellulose nanocrystals are accelerated to dehydrate and carbonize mainly due to substances such as phosphoric acid generated by heating phytic acid, so that a compact carbon layer is formed. The CNC-PA-TA flame retardant is lower in height than CNC-TA-PA, and the phytic acid is possibly present in a small amount, so that substances such as phosphoric acid generated by heating are relatively small, and the formed carbon layer is not expanded enough. Meanwhile, the thermogravimetric graph 3 also proves that the carbon residue of the comparative example b is better than that of the comparative example c, which shows that phytic acid has a slightly larger effect on cellulose nanocrystals than tannic acid, and the sequence of tannic acid and phytic acid can influence the thermal stability and the expansion performance of the cellulose nanocrystals.
The high flame retardant nylon 66 fabric and the preparation method thereof according to the present invention are further explained by specific examples.
Example 1:
the preparation method of the high-flame-retardance nylon 66 fabric comprises the following steps:
(1) Pretreatment of nylon 66 fabric with alkali solution: preparing 1g/L Na 2CO3 alkali solution, heating, putting into fabric after the solution is boiled, continuously boiling and washing for 20min, dehydrating the washed nylon 66 fabric for 3min, drying at 60 ℃ for 30min in a drying box, and standing at room temperature for 6h.
(2) Dipping the dried nylon 66 fabric in the step (1) into the dipping liquid modified by the CNC-TA-PA flame retardant solution in the embodiment a, wherein the bath ratio (the dipping liquid of the nylon 66 fabric) is 1:10, the dipping temperature is 35 ℃, and the dipping time is 1h; then, dehydration treatment is carried out for 4min, and the mixture is baked for 30min at 60 ℃ in an oven, and then is placed at room temperature for 6h; wherein the impregnating solution is an aqueous dispersion of CNC-TA-PA flame retardant, and the concentration is 150g/L.
(3) And (3) sequentially coating, flame-retardant finishing and drying the nylon 66 fabric baked in the step (2), wherein the flame-retardant coating liquid sprayed on the nylon 66 fabric in unit time area is 200g/m 2, drying the nylon 66 fabric, wherein the drying temperature is 60 ℃ for 30min, and then standing at room temperature for 6h to obtain the high flame-retardant nylon 66 fabric.
Wherein the flame-retardant coating liquid comprises 45wt% of aqueous polyurethane with the solid content of 40%, 15wt% of CNC-TA-PA flame retardant and the balance of water.
Example 2:
the preparation method of the high-flame-retardance nylon 66 fabric comprises the following steps:
(1) Pretreatment of nylon 66 fabric with alkali solution: preparing 1g/L Na 2CO3 alkali solution, heating, putting into fabric after the solution is boiled, continuously boiling and washing for 20min, dehydrating the washed nylon 66 fabric for 3min, drying at 60 ℃ for 30min in a drying box, and standing at room temperature for 6h.
(2) Dipping the dried nylon 66 fabric in the step (1) into the dipping liquid modified by the CNC-TA-PA flame retardant solution in the embodiment a, wherein the bath ratio (the dipping liquid of the nylon 66 fabric) is 1:10, the dipping temperature is 35 ℃, and the dipping time is 1h; then, dehydration treatment is carried out for 4min, and the mixture is baked for 30min at 60 ℃ in an oven, and then is placed at room temperature for 6h; wherein the impregnating solution is an aqueous dispersion of CNC-TA-PA flame retardant, and the concentration is 150g/L.
(3) And (3) sequentially coating, flame-retardant finishing and drying the nylon 66 fabric baked in the step (2), wherein the flame-retardant coating liquid sprayed on the nylon 66 fabric in unit time area is 200g/m 2, drying the nylon 66 fabric, wherein the drying temperature is 60 ℃ for 30min, and then standing the nylon 66 fabric at room temperature for 6h to obtain the nylon 66 fabric with high flame retardance.
Wherein the flame-retardant coating liquid comprises 45wt% of aqueous polyurethane with the solid content of 40% and 30wt% of CNC-TA-PA flame retardant, and the balance of water.
Example 3:
the preparation method of the high-flame-retardance nylon 66 fabric comprises the following steps:
(1) Pretreatment of nylon 66 fabric with alkali solution: preparing 1g/L Na 2CO3 alkali solution, heating, putting into fabric after the solution is boiled, continuously boiling and washing for 20min, dehydrating the washed nylon 66 fabric for 3min, drying at 60 ℃ for 30min in a drying box, and standing at room temperature for 6h.
(2) Dipping the dried nylon 66 fabric in the step (1) into the dipping liquid modified by the CNC-TA-PA flame retardant solution in the embodiment a, wherein the bath ratio (the dipping liquid of the nylon 66 fabric) is 1:10, the dipping temperature is 35 ℃, and the dipping time is 1h; then, dehydration treatment is carried out for 4min, and the mixture is baked for 30min at 60 ℃ in an oven, and then is placed at room temperature for 6h; wherein the impregnating solution is an aqueous dispersion of CNC-TA-PA flame retardant, and the concentration is 150g/L.
(3) And (3) sequentially coating, flame-retardant finishing and drying the nylon 66 fabric baked in the step (2), wherein the flame-retardant coating liquid sprayed on the nylon 66 fabric in unit time area is 200g/m 2, drying the nylon 66 fabric, wherein the drying temperature is 60 ℃ for 30min, and then standing the nylon 66 fabric at room temperature for 6h to obtain the nylon 66 fabric with high flame retardance.
Wherein the flame-retardant coating liquid comprises 45wt% of aqueous polyurethane with the solid content of 40%, 45wt% of CNC-TA-PA flame retardant and the balance of water.
Comparative example 1:
the preparation method of the modified nylon 66 fabric of the comparative example comprises the following steps:
(1) Pretreatment of nylon 66 fabric with alkali solution: preparing 1g/L Na 2CO3 alkali solution, heating, putting into fabric after the solution is boiled, continuously boiling and washing for 20min, dehydrating the washed nylon 66 fabric for 3min, drying at 60 ℃ for 30min in a drying box, and standing at room temperature for 6h.
(2) Dipping the dried nylon 66 fabric in the step (1) into the dipping liquid modified by the CNC-TA-PA flame retardant solution in the embodiment a, wherein the bath ratio (the dipping liquid of the nylon 66 fabric) is 1:10, the dipping temperature is 35 ℃, and the dipping time is 1h; and then carrying out dehydration treatment for 4min, drying for 30min at 60 ℃ in an oven, and then standing for 6h at room temperature to obtain the modified nylon 66 fabric.
Wherein the impregnating solution is an aqueous dispersion of CNC-TA-PA flame retardant, and the concentration is 150g/L.
This example analyzed the successful modification, thermal stability, and uv resistance properties of the samples of examples 1-3 and comparative example 1 using fourier transform infrared (Nicolet IS 50), thermogravimetric analyzer (TG 209F 1, netzsch) and uv-vis spectrophotometer (UH 4150, hitachi, japan).
Analysis of the samples of PA66, examples 1-3 and comparative example 1 using a fourier infrared spectrometer (Nicolet IS 50) as shown in fig. 5, shows that after finishing of the CNC-TA-PA flame retardant, the c=o peaks of examples 1-3 and comparative example 1 shift left, indicating influence of c=o groups in CNC and TA, representing c= C, C-O-C, P-O-C, respectively, around 1467cm -1、1148cm-1、1039cm-1, indicating successful grafting modification.
The thermal stability of the samples of PA66, examples 1-3 and comparative example 1 was analyzed using a thermogravimetric analyzer (TG 209F 1, netzsch) as shown in fig. 6, which shows that the char residue of example 3 works best, increasing from 4.1% to 14% compared to PA66, indicating that after finishing with flame retardant, CNC-TA-PA can produce polyphosphoric acid or phosphoric acid during pyrolysis, catalyzing and promoting dehydration and carbonization of CNC and PA66, protecting part of the PA66 matrix from burning, forming more residual char.
The samples of PA66, examples 1-3 and comparative example 1 were analyzed for uv resistance using a uv-vis spectrophotometer (UH 4150, hitachi, japan), as shown in fig. 7, since TA has an aromatic structure, it absorbs uv light, T UVA、TUVB, UFP of PA66 are 22.69%, 11.67% and 7.47%, respectively, and the uv resistance of example 3 is best, T UVA、TUVB, UFP are 11.64%, 3.65% and 16.35%, respectively, after finishing treatment.
The PA66 and example 3 were analyzed using limiting oxygen index, which increased from 22% to 29% as shown in fig. 8.
Meanwhile, qualitative analysis is carried out on the PA66 and the embodiment 3, as shown in fig. 9, the burning of the alcohol lamp can find that the PA66 has a molten drop phenomenon in the burning process, the embodiment 3 has a self-extinguishing phenomenon after leaving the alcohol lamp, and no molten drop is caused, mainly because after finishing treatment of the flame retardant, a compact carbon layer is formed by burning, and the molten drop phenomenon is not generated, which indicates that the flame propagation of the PA66 fabric is greatly inhibited.
In view of the numerous embodiments of the present invention, each raw material, usage amount and process parameters can be adjusted within the corresponding range according to the actual application requirements, and experimental data of each embodiment is huge and numerous, which is not suitable for one-by-one enumeration and description herein, but the content of verification required by each embodiment and the obtained final conclusion are close. The verification contents of the respective embodiments are not explained one by one here.
The foregoing is only illustrative of the preferred embodiments and principles of the present invention, and changes in specific embodiments will occur to those skilled in the art upon consideration of the teachings provided herein, and such changes are intended to be included within the scope of the invention as defined by the claims.
Claims (10)
1. An ultra-high heat-resistant expansion flame retardant, a preparation method thereof and an application of flame-retardant nylon fabric are characterized by comprising the following steps:
(1) Dispersing microcrystalline cellulose in a sodium periodate aqueous solution, then reacting for 1-1.5 hours at 60-80 ℃, cooling to room temperature after the reaction is finished, washing and drying to obtain cellulose nanocrystalline;
(2) Dispersing cellulose nanocrystals in water, adding 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid, adjusting the pH to 7.5-8.5, adding tannic acid, reacting at room temperature for 12-24h, finally adding phytic acid aqueous solution, reacting at room temperature for 1-2h, cooling to room temperature after the reaction is finished, washing, and drying to obtain the ultra-high heat resistance expansion flame retardant.
2. The method according to claim 1, wherein in the step (2), the mass ratio of the cellulose nanocrystals to the aqueous solution of tannic acid to the aqueous solution of phytic acid is 1: (0.025-0.1): (0.5-2).
3. The method according to claim 2, wherein in the step (2), the mass fraction of the aqueous solution of phytic acid is 60 to 70%.
4. The preparation method according to claim 1, wherein in the step (2), the mass parts of the cellulose nanocrystals and the 4- (2-hydroxyethyl) -1-piperazine ethane sulfonic acid are prepared as 1: (0.1-0.2).
5. The ultra-high thermal expansion resistant flame retardant produced by the production process according to any one of claims 1 to 4.
6. The preparation method of the high-flame-retardance nylon 66 fabric is characterized by comprising the following steps of:
(a) Pretreating nylon 66 fabric with alkali solution;
Preparing Na 2CO3 solution, heating to boiling, putting the solution into nylon 66 fabric, continuously boiling and washing, and dehydrating and drying for later use;
(b) Sequentially carrying out dipping flame retardant finishing, dehydration and drying on the nylon 66 fabric dried in the step (a);
Wherein the impregnating solution adopted for impregnating the flame retardant is an aqueous dispersion of the ultra-high heat-resistant expansion flame retardant according to claim 5;
(c) Sequentially coating, flame-retardant coating, finishing and drying the nylon 66 fabric dried in the step (b);
wherein, the flame-retardant coating solution used for the flame-retardant coating finishing of the coating comprises 30-50wt% of aqueous polyurethane with the solid content of 40% and 15-45wt% of the ultra-high heat-resistant expansion flame retardant as defined in claim 5, and the balance of water.
7. The method according to claim 6, wherein in the step (a), the Na 2CO3 solution has a concentration of 1 to 3g/L and the washing time is 10 to 20 minutes.
8. The method of claim 6, wherein in step (b), the impregnating bath ratio of the impregnating flame retardant finish is 1: (10-20), wherein the dipping temperature is 30-50 ℃ and the dipping time is 1-2h; the concentration of the aqueous dispersion of the ultra-high thermal expansion resistant flame retardant is 100-200g/L.
9. The method of claim 6, wherein in the step (c), the nylon 66 fabric is coated with a flame retardant coating solution having a specific area of 200-220g/m 2.
10. A highly flame retardant nylon 66 fabric made by the method of any one of claims 6-9.
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| CN202311720969.1A CN118048786A (en) | 2023-12-14 | 2023-12-14 | A flame retardant with ultra-high heat expansion resistance, a preparation method thereof, and application of flame-retardant nylon fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118910886A (en) * | 2024-08-08 | 2024-11-08 | 浙江理工大学 | Antibacterial flame-retardant nylon 66 fiber based on interfacial adhesion and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118910886A (en) * | 2024-08-08 | 2024-11-08 | 浙江理工大学 | Antibacterial flame-retardant nylon 66 fiber based on interfacial adhesion and preparation method thereof |
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