CN111764154A - Method for improving flame retardant property of modified ramie fabric - Google Patents
Method for improving flame retardant property of modified ramie fabric Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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Abstract
The invention discloses a method for improving the flame retardant property of a modified ramie fabric, which comprises the following steps: (1) cleaning the ramie fabric in deionized water for 5-10 minutes, and then drying; (2) soaking the ramie fabric treated in the step (1) in an aldehyde functional reagent solution for 6-10 h, taking out and drying; (3) dipping the ramie fabric treated in the step (2) in a chitosan solution, and then baking; according to the method, periodic acid or sodium periodate is used for treating surface aldehyde groups for functionalization, the chemical method of Schiff base reaction between the aldehyde groups and amino groups is used for pretreating the surface of the ramie fabric in advance, Polyethyleneimine (PEI) is used as positive charge, ammonium polyphosphate (APP) is used as negative charge, the ramie fabric is prepared by a layer-by-layer self-assembly method, the process operation is simple and flexible, the stability is good, and the flame retardant property of the ramie fabric can be effectively improved.
Description
Technical Field
The invention relates to the technical field of ramie fiber treatment, in particular to a method for improving the flame retardant property of modified ramie fabric.
Background
As a natural cellulose fiber, ramie has many advantages, such as low cost, light weight, environmental friendliness, and the like. The tensile strength of the ramie fiber is 850-900N/mm2, which is much higher than other natural fibers such as flax, jute and the like, and is almost equivalent to glass fiber. As a composite material reinforcement, ramie fibers are widely researched and used in systems such as polylactic acid, polypropylene, epoxy resin, phenolic resin, benzoxazine resin and the like. However, the thermal stability of plant fibers is poor and the fibers are easily burned, and these deficiencies limit their practical applications. Therefore, the research on the flame retardant modification of ramie fibers or fabrics and the research on the reinforced composite materials thereof have received attention.
Layer-by-layer (lbl) assembly is a technique for forming multilayer films on solid surfaces by alternate deposition based on the physical adsorption of oppositely charged polyelectrolytes. The method is simple, flexible and good in stability, is not only suitable for a polyelectrolyte system, but also suitable for any charged substance, and therefore receives more and more attention. The wide adaptability of LBL technology makes it potentially useful in many areas. However, to date, this method requires assembly of 15-20 bilayers, even 30 bilayers, in order to obtain satisfactory flame-retardant modification, thereby limiting its widespread use in industry.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: the method comprises the steps of treating surface aldehyde groups with periodic acid or sodium periodate for functionalization, pretreating the surface of the ramie fabric by using a chemical method of Schiff base reaction between the aldehyde groups and amino groups, using Polyethyleneimine (PEI) as positive charge and ammonium polyphosphate (APP) as negative charge, and preparing the ramie fabric by a layer-by-layer self-assembly method, wherein the method is simple and flexible in process operation and good in stability, and can effectively improve the flame retardant property of the ramie fabric.
The technical solution of the invention is as follows: a method for improving the flame retardant property of modified ramie fabric comprises the following steps:
(1) cleaning the ramie fabric in deionized water for 5-10 minutes, and then drying;
(2) soaking the ramie fabric treated in the step (1) in an aldehyde functional reagent solution for 6-10 h, taking out and drying;
(3) dipping the ramie fabric treated in the step (2) in a chitosan solution, and then baking;
(4) soaking the ramie fabric treated in the step (3) in an APP solution for 2-5 min, then washing for 1-3 times in deionized water, and drying;
(5) soaking the ramie fabric treated in the step (4) in a PEI solution for 2-5 min, then washing for 1-3 times in deionized water, and drying;
(6) the processes of step (4) and step (5) describe an assembly cycle comprising a complete bilayer of PEI and APP, and the processes of step (4) and step (5) are repeated until the desired number of layers is reached;
(7) and (4) drying the ramie fabric obtained in the step (6) to obtain the flame-retardant modified ramie fabric.
The aldehyde group functional reagent in the step (2) is one of periodic acid and sodium periodate.
The concentration of the aldehyde functional reagent solution in the step (2) is 3-5 wt%.
The pH value of the aldehyde functional reagent solution in the step (2) is 5-6 wt%.
The concentration of the chitosan solution in the step (3) is 1-2 wt%.
The dipping treatment conditions in the step (3) are as follows: and (4) carrying out secondary soaking and secondary rolling, wherein the rolling residual rate is controlled to be 70-90%.
The baking conditions in the step (3) are as follows: baking for 5-10min in a baking machine at the temperature of 90-100 ℃.
The concentration of the APP solution in the step (4) is 1.0-2.0 wt%, and the concentration of the PEI solution in the step (5) is 1.0-2.0 wt%.
The drying in the steps (1) and (2) specifically refers to: drying in a blast drier at 70-90 ℃ for 5-10 min; the drying in the steps (3) and (4) specifically refers to: placing the ramie fabric in the application N2Blow-dried quartz plate, and then placing onAnd drying in a forced air drying oven at 70-90 ℃ for 5-10 min.
The drying in the step (7) specifically comprises the following steps: the ramie fabric is placed in a vacuum drying oven at 50-60 ℃ for drying for 15-30min, and then is placed in a drying dish for drying for 10-12 h.
The invention has the beneficial effects that: compared with the prior art, the invention has the following remarkable advantages and beneficial effects:
(1) the chemical method is used for pretreating the ramie fabric, so that the number of positive charges on the surface of the ramie fabric can be increased, the adsorption quantity of the flame retardant for one time of layer-by-layer self-assembly is greatly increased, and the number of assembled layers of layer-by-layer self-assembly can be reduced.
(2) Compared with the process without pretreatment, the ramie fabric assembled by the method has obviously improved flame retardant adsorption capacity and flame retardant effect, can realize self-healing under the condition of only assembling 10 double layers, shortens the assembly treatment time to a certain extent, further improves the flexibility and stability of the method and reduces the cost;
(3) the ramie fabric prepared by the method has excellent heat resistance, carbon residue rate, heat release rate peak value (PHRR), total heat release amount (THR), CO and CO2The average release amount is obviously reduced; the Limiting Oxygen Index (LOI) is improved from 18.0 percent to 30.6 percent; after vertical combustion, a continuous and compact protective carbon layer structure is formed, the original orthogonal plain weave structure of the fabric is completely reserved, and the flame retardant effect with excellent self-extinguishing property is achieved;
(4) the ramie fabric prepared by the method is suitable for manufacturing high-performance high-temperature-resistant flame-retardant green composite materials.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the flame retardant modified ramie fabric of the present invention;
FIG. 2 shows scanning electron micrographs of ramie fabric before and after the assembly of the flame-retardant modified ramie fabric layer of the present invention;
FIG. 3 is a photograph showing the flame retardant modified ramie fabric of the present invention after 5 seconds of ignition in a vertical burning test;
FIG. 4 is a photograph showing carbon residue after a vertical burning test of the flame retardant modified ramie fabric of the present invention;
FIG. 5 is a scanning electron microscope image of carbon residue after a vertical combustion experiment of the flame-retardant modified ramie fabric of the present invention;
Detailed Description
The present invention will be described in further detail with reference to examples. It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1:
cleaning the ramie fabric in deionized water, taking out, and drying in a 90 ℃ forced air dryer for 5 min. Soaking the cleaned ramie fabric in an aldehyde functional reagent solution with the concentration of 3 wt% for 10h, taking out, and drying in a 90 ℃ forced air dryer for 5 min. And (3) padding the ramie fabric subjected to the aldehyde group treatment in a chitosan solution with the concentration of 1 wt%, wherein the padding rate is 90%, and baking for 10min at the temperature of 90 ℃. And then sequentially soaking the treated ramie fabric in an APP solution with the concentration of 1.0 wt% and a PEI solution with the concentration of 1.0 wt% for 5min, cleaning and drying to obtain the double-layer ramie fabric with flame retardant finish. This procedure was repeated until 5 double flame retardant coatings were assembled on the ramie fabric surface, the preparation of which is shown in fig. 1. And drying the ramie fabric. The content of the flame-retardant coating was calculated to be 18.12% by weighing the ramie fabric before and after the treatment. The result of the analysis of the sample by the thermogravimetric analyzer shows that the residual carbon at 600 ℃ under the nitrogen condition is 36.9%. The sample is subjected to limit oxygen index measurement by an oxygen index tester, and the LOI reaches 26.7%.
Example 2:
cleaning the ramie fabric in deionized water, taking out, and drying in a 90 ℃ forced air dryer for 5 min. Soaking the cleaned ramie fabric in 5wt% aldehyde functional reagent solution for 6h, taking out, and drying in a 90 deg.C forced air dryer for 5 min. Padding the ramie fabric subjected to the aldehyde group treatment in a chitosan solution with the concentration of 2wt%, wherein the padding rate is 70%, and baking for 5min at the temperature of 100 ℃. And then sequentially soaking the treated ramie fabric in 2.0 wt% of APP solution and 2.0 wt% of PEI solution for 2min, cleaning and drying to obtain the flame-retardant finished double-layer ramie fabric. This procedure was repeated until 10 double-layer flame retardant coatings were assembled on the ramie fabric surface, and the preparation procedure is shown in fig. 1. And drying the ramie fabric. The content of the flame-retardant coating was calculated to be 26.03% by weighing the ramie fabric before and after the treatment. The result of the analysis of the sample by the thermogravimetric analyzer shows that the residual carbon at 600 ℃ is 39.3% under the condition of nitrogen. The sample is subjected to limit oxygen index measurement by an oxygen index tester, and the LOI reaches 30.6%.
Comparative example
Cleaning the ramie fabric in deionized water, taking out, and drying in a 90 ℃ forced air dryer for 5 min. And sequentially soaking the cleaned ramie fabric in an APP solution with the concentration of 2.0 wt% and a PEI solution with the concentration of 2.0 wt% for 2min, cleaning and drying to obtain the double-layer ramie fabric with flame retardant finish. This procedure was repeated until 10 double flame retardant coatings were assembled on the ramie fabric surface. Mixing the obtained ramie fabric ((PEI/APP)10) Drying is carried out. The content of the flame-retardant coating was 8.29% by weighing the ramie fabric before and after the treatment. The results of the analysis of this sample by the thermogravimetric analyzer showed that the residual carbon amounts at 600 ℃ under the nitrogen condition were 28.7% respectively. The sample is subjected to limit oxygen index measurement by an oxygen index tester, and the LOI reaches 23.6%.
Untreated ramie fabric sample: the result of analyzing this sample by a thermogravimetric analyzer showed that the carbon residue of the Pristineramie ramie fabric was 10.5%. The sample is subjected to limit oxygen index measurement by an oxygen index tester, and the LOI reaches 18.0.
The test results are shown in tables 1 and 2. The invention takes the original ramie fabrics which are not treated in the examples 1 and 2 and the comparative examples 1-3 as detection objects.
TABLE 1 thermal Property data of Ramie fabrics before and after modification in Nitrogen atmosphere
TABLE 2 Ramie Fabric Cone calorimetry test results before and after treatment
Note: t is tign: a time of ignition; t is tduration: a duration of combustion; PHRR: a peak rate of heat release; THR: total amount of heat release; y isCO：；YCO2: (ii) a Char: carbon residue;
FIG. 2 is a scanning electron microscope image of the ramie fabric before and after the flame-retardant modified ramie fabric layer is assembled. Compared with the original ramie fabric, the gaps between the treated ramie fabrics are gradually filled, and the flame retardant attached to the surfaces of the fabrics is obviously increased along with the increase of the number of the assembly layers. This indicates that the fabric surface has been successfully constructed with a PEI/APP bi-component intumescent coating structure. Compared with the comparative example result, the preparation method can obtain a thick and compact PEI/APP bi-component intumescent flame retardant coating when 10 layers are assembled, and the preparation method is favorable for improving the adsorption quantity of the flame retardant and further reducing the number of layers of layer-by-layer self-assembly.
FIGS. 3 and 4 show photographs of the carbon residue of the flame retardant modified ramie fabric of the present invention after 5 seconds of ignition in the vertical burn test and after the vertical burn test. After the original ramie fabric is ignited, the flame quickly spreads from the bottom of the fabric to the top of the fabric and almost burns out. The flame propagation rate of a contrast sample is obviously slowed down, the combustion process is mild, and finally, the carbon residue of the contrast sample well keeps the original woven structure of the fabric, but the carbon residue is also obviously broken. For examples 1 and 2, the ramie fabric, after chemical pretreatment, exhibited a more excellent self-extinguishing property only when 10 PEI/APP bilayers were assembled.
FIG. 5 is a scanning electron microscope image of carbon residue after a vertical combustion experiment of the flame-retardant modified ramie fabric of the present invention. The carbon residue of the original ramie fabric keeps a plain weave structure, but the fiber is seriously shrunk in the burning process, and the fiber surface is smooth and clean. Compared with the ramie fabric, the fiber shrinkage and the gaps after combustion are obviously reduced, the integrity of the carbon residue is also obviously improved, and a plurality of expansion type carbon particles exist in the gaps among the fibers. For examples 1 and 2, after chemical pretreatment, only 10 PEI/APP bilayers were assembled on the ramie fabric, and a thick and compact intumescent flame retardant carbon layer was formed on the burned surface of the ramie fabric. The carbon layer plays a strong flame shielding role for the ramie fabric substrate at the bottom layer, so that the flame-retardant modified ramie fabric disclosed by the invention has a better flame-retardant effect.
Table 1 shows the thermal performance data of the ramie fabric before and after the flame retardant modified ramie fabric of the present invention is modified in nitrogen atmosphere. Compared with the original ramie fabric, the temperature (T) of all the assembled ramie fabrics at the thermal weight loss of 5wt% is increased along with the increase of the concentration of the flame retardant and the increase of the number of the assembled layers5％) Both decrease gradually, mainly due to the earlier thermal degradation of the flame retardants PEI and APP. However, the carbon residue of the treated ramie at 600 ℃ is obviously higher than that of the original ramie fabric. For the ramie fabrics of examples 1 and 2 of the present invention, after chemical pretreatment, only 10 PEI/APP bilayers were assembled to increase the carbon residue of the ramie fabric from 10.5% to 39.3% at 600 ℃. Compared with the comparative example, the decomposition rate is obviously slowed down, and the carbon residue at 600 ℃ is also obviously improved. Therefore, the PEI/APP flame retardant promotes the ramie fabric to have excellent char forming performance, and further endows the ramie fabric with excellent flame retardant performance.
Table 2 shows the results of the cone calorimetry test of the flame-retardant modified ramie fabric of the present invention. For the original ramie fabric, the ignition time is shortest, the combustion duration is longest, the heat release rate and the total heat release are also the greatest, and the carbon residue is the lowest. Ramie Fabric of comparative example, construction (PEI/APP)10The flame-retardant coating can effectively prolong the ignition time, shorten the combustion duration, reduce the heat release rate and the total heat release amount, and improve the carbon residue. While the ramie fabrics of examples 1 and 2 of the present invention, after chemical pretreatment, were minimized (PEI/APP)nThe flame retardant coating layer has the longest ignition time, the shortest combustion duration, the lowest heat release rate and total heat release under the condition of the number of the flame retardant coating layers, and further has the highest carbon residue.
The above results all show that: after the ramie fabric is subjected to chemical surface pretreatment, the layer-by-layer self-assembly single-time adsorption effect can be effectively improved, the number of assembly layers is obviously reduced, the adsorption quantity of the flame-retardant coating is improved, and the ramie fabric has an excellent flame-retardant effect.
The limit oxygen index test of the invention is based on the test standard GB/T5454-1997, the vertical burning test is based on the test standard GB/T5455-1997, and the cone calorimetry test is based on the test standard ISO 5660-1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and these modifications and decorations shall also fall within the protection scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (10)
1. A method for improving the flame retardant property of modified ramie fabric is characterized by comprising the following steps:
(1) cleaning the ramie fabric in deionized water for 5-10 minutes, and then drying;
(2) soaking the ramie fabric treated in the step (1) in an aldehyde functional reagent solution for 6-10 h, taking out and drying;
(3) dipping the ramie fabric treated in the step (2) in a chitosan solution, and then baking;
(4) soaking the ramie fabric treated in the step (3) in an APP solution for 2-5 min, then washing for 1-3 times in deionized water, and drying;
(5) soaking the ramie fabric treated in the step (4) in a PEI solution for 2-5 min, then washing for 1-3 times in deionized water, and drying;
(6) the processes of step (4) and step (5) describe an assembly cycle comprising a complete bilayer of PEI and APP, and the processes of step (4) and step (5) are repeated until the desired number of layers is reached;
(7) and (4) drying the ramie fabric obtained in the step (6) to obtain the flame-retardant modified ramie fabric.
2. The method for improving the flame retardant property of the modified ramie fabric according to claim 1, wherein the aldehyde-based functionalizing agent in the step (2) is one of periodic acid and sodium periodate.
3. The method for improving the flame retardant property of the modified ramie fabric according to claim 2, wherein the concentration of the aldehyde-based functionalization reagent solution in the step (2) is 3-5 wt%.
4. The method for improving the flame retardant property of the modified ramie fabric according to claim 1, wherein the pH of the aldehyde-based functionalization reagent solution in the step (2) is 5-6 wt%.
5. The method for improving the flame retardant property of the modified ramie fabric according to claim 1, wherein the concentration of the chitosan solution in step (3) is 1-2 wt%.
6. The method for improving the flame retardant property of the modified ramie fabric according to claim 1, wherein the dipping treatment in the step (3) is carried out under the following conditions: and (4) carrying out secondary soaking and secondary rolling, wherein the rolling residual rate is controlled to be 70-90%.
7. The method for improving the flame retardant property of the modified ramie fabric according to claim 1, wherein the baking conditions in step (3) are as follows: the temperature is 90-100 DEG CoAnd C, baking for 5-10min in a baking machine.
8. The method for improving the flame retardant property of the modified ramie fabric according to claim 1, wherein the concentration of the APP solution in the step (4) is 1.0-2.0 wt%, and the concentration of the PEI solution in the step (5) is 1.0-2.0 wt%.
9. The method of improving the flame retardant properties of a modified ramie fabric according to claim 1, wherein the flame retardant is a mixture of a first and a second component,the drying in the steps (1) and (2) specifically refers to: in the range of 70 to 90oC, drying in a blast drier for 5-10 min; the drying in the steps (3) and (4) specifically refers to: placing the ramie fabric in the application N2Drying the quartz plate, and placing the quartz plate on a 70-90 DEG air-dried quartz plateoAnd C, drying in a forced air drying oven for 5-10 min.
10. The method for improving the flame retardant property of the modified ramie fabric according to claim 1, wherein the drying in step (7) is specifically: placing the ramie fabric in 50-60% of the total weightoAnd C, drying in a vacuum drying oven for 15-30min, and then drying in a drying dish for 10-12 h.
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Application publication date: 20201013 |