CN118600733B - Multifunctional wool fabric and preparation method thereof - Google Patents
Multifunctional wool fabric and preparation method thereof Download PDFInfo
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- CN118600733B CN118600733B CN202411075048.9A CN202411075048A CN118600733B CN 118600733 B CN118600733 B CN 118600733B CN 202411075048 A CN202411075048 A CN 202411075048A CN 118600733 B CN118600733 B CN 118600733B
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- vanillin
- phytic acid
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- finishing agent
- acid ester
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- 239000004744 fabric Substances 0.000 title claims abstract description 111
- 210000002268 wool Anatomy 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 113
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229940068041 phytic acid Drugs 0.000 claims abstract description 109
- 239000000467 phytic acid Substances 0.000 claims abstract description 109
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 106
- 235000012141 vanillin Nutrition 0.000 claims abstract description 106
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- -1 vanillin phytic acid ester Chemical class 0.000 claims abstract description 76
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 51
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002250 absorbent Substances 0.000 claims abstract description 16
- 230000002745 absorbent Effects 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 31
- 239000003063 flame retardant Substances 0.000 abstract description 31
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 abstract description 7
- 239000010452 phosphate Substances 0.000 abstract description 7
- 239000004753 textile Substances 0.000 abstract description 7
- 239000002262 Schiff base Substances 0.000 abstract description 4
- 150000004753 Schiff bases Chemical class 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 3
- 125000003172 aldehyde group Chemical group 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 25
- 238000005406 washing Methods 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 16
- 230000000844 anti-bacterial effect Effects 0.000 description 15
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000006750 UV protection Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000010025 steaming Methods 0.000 description 7
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a multifunctional wool fabric and a preparation method thereof, and belongs to the technical field of textiles. The preparation method of the invention comprises the following steps: s1, under the action of a catalyst and a water absorbent, carrying out esterification reaction on phytic acid and vanillin in an organic solvent to obtain a vanillin phytic acid ester finishing agent; s2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution for finishing, and then adding phosphite ester compounds for finishing continuously to obtain the multifunctional wool fabric. On one hand, the aldehyde group of the vanillin phytic acid ester finishing agent, the P-H bond of the phosphite ester compound and the amino group of the wool fabric can generate Schiff base reaction and Pudovik addition reaction, and the vanillin phytic acid ester finishing agent is grafted on the wool fabric through covalent bonds, so that the durability is improved; on the other hand, the phosphate radical of the phytic acid and the phosphate radical of the phosphite ester compound have higher catalytic carbonizing performance, and the aromatic structure of the vanillin can be used as a carbonizing agent to generate an expanded carbon layer, so that the three can generate a synergistic flame-retardant effect.
Description
Technical Field
The invention belongs to the technical field of textiles, and particularly relates to a multifunctional wool fabric and a preparation method thereof.
Background
The wool fabric is a high-grade fiber and is widely applied to the fields of aircraft carpets, indoor decorative wall cloths and the like, however, the fields have higher requirements on flame retardance, antibacterial performance and ultraviolet resistance of the wool fabric, and the development of the environment-friendly durable multifunctional wool fabric is significant.
The phytic acid is mainly present in plants and grains, the phosphorus content is up to 28.0%, and the flame retardant efficiency is high. However, the phosphate structure of phytic acid is mainly combined with wool fabrics by electrostatic attraction, and phytic acid is easily dissolved in water, resulting in poor durability of the modified wool fabrics.
The preparation of polyethylene imine/phytic acid layer-by-layer self-assembled flame-retardant polyester/cotton blended fabric and performance [ J ]. Textile theory, 2021,42 (11): 103-109.) adopts polyethylene imine and phytic acid to construct a flame-retardant coating on the surface of the polyester/cotton blended fabric by adopting a layer-by-layer self-assembly method, however, the layer-by-layer self-assembly technology needs to deposit enough flame retardant on the surface of the fabric by repeated dipping, the process flow is complicated, and the physical properties of the fabric such as hand feeling and the like are seriously influenced.
Chinese patent No. 115323771A discloses a preparation method of modified wool fabric with flame retardant property, firstly, aramid fiber with flame retardant property is doped in wool, then 1,2,3, 4-butane tetracarboxylic acid is adopted as a cross-linking agent to graft phytic acid/silicon hybrid sol on the wool fabric, however, the active groups of the phytic acid/silicon hybrid sol are fewer, the grafting efficiency is poor, the reaction efficiency of the 1,2,3, 4-butane tetracarboxylic acid is low, and the reaction is required to be baked at 155-165 ℃ to promote the cross-linking reaction, so that the wool fiber is damaged.
Reference （Cheng X W, Wang Z Y, Jin W J, et al. Covalent flame-retardant functionalization of wool fabric using ammonium phytate with improved washing durability[J]. Industrial Crops and Products, 2022, 187: 115332.） uses phytic acid and urea to synthesize phytic acid ammonium salt, however, the reaction efficiency is low, the flame retardant is required to be grafted on the wool fabric through a baking treatment at 160 ℃, however, the wool fiber is easy to be damaged under the high-temperature treatment condition, and the washing resistance is still required to be further improved.
Therefore, how to develop a novel phytic acid-based flame retardant and prepare wool fabric with durable flame-retardant, antibacterial, anti-ultraviolet and other functions under mild conditions is significant, and great challenges still exist.
Disclosure of Invention
In order to solve the technical problems, the invention provides a multifunctional wool fabric and a preparation method thereof, firstly, biomass phytic acid and vanillin are adopted to synthesize vanillin phytic acid ester finishing agent, and then modifying the wool fabric by using vanillin phytic acid ester finishing agent and phosphite ester to prepare the durable flame-retardant antibacterial ultraviolet-resistant multifunctional wool fabric.
The first object of the invention is to provide a method for preparing a multifunctional wool fabric, comprising the following steps:
s1, under the action of a catalyst and a water absorbent, carrying out esterification reaction on phytic acid and vanillin in an organic solvent to obtain a vanillin phytic acid ester finishing agent;
S2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution for first-stage finishing, and then adding phosphite ester compounds into the vanillin phytic acid ester finishing agent solution for second-stage finishing to obtain the multifunctional wool fabric; the vanillin phytic acid ester finishing agent solution comprises the vanillin phytic acid ester finishing agent and a solvent as described in S1.
In one embodiment of the invention, in S1, the molar ratio of the phytic acid to the vanillin is 1 (4-4.5), and the vanillin is used in a small excess amount, so as to facilitate the grafting reaction of the vanillin on the phytic acid; the mole ratio of the water absorbing agent to the vanillin is 1 (1.2-2); the dosage ratio of the vanillin to the organic solvent is 1g (20-30 mL).
In one embodiment of the invention, in S1, the concentration of catalyst during the esterification reaction is 3g/L to 5g/L.
In one embodiment of the invention, in S1, the catalyst is 4-dimethylaminopyridine; the water absorbent is dicyclohexylcarbodiimide, and can absorb water molecules generated by esterification reaction of phytic acid and vanillin, so that the reaction is promoted; the organic solvent is selected from N, N-dimethylformamide and/or N, N-dimethylacetamide.
In one embodiment of the present invention, in S1, the esterification reaction is performed at a temperature of 120 ℃ to 130 ℃ for 3h to 4h, and the phosphate of the phytic acid and the phenolic hydroxyl of the vanillin are subjected to the esterification reaction, so that the vanillin phytic acid ester finishing agent is synthesized.
In one embodiment of the present invention, in S1, the method further comprises the steps of filtering, spin-steaming, water-washing, and drying the crude vanillin phytic acid ester finishing agent to remove impurities and organic solvent.
In one embodiment of the invention, in S2, the concentration of the vanillin phytic acid ester finishing agent solution is 50g/L-80g/L, the pH is 4-5, and the higher the dosage of the vanillin phytic acid ester finishing agent is, the higher the flame retardant property, the antibacterial property and the ultraviolet resistance of the modified wool fabric is, but the higher the dosage is, the waste is caused; the mol ratio of the vanillin phytic acid ester finishing agent to the phosphite ester compound is 1 (3-4).
In one embodiment of the invention, the pH adjusting agent is selected from sodium hydroxide and/or sodium carbonate.
In one embodiment of the present invention, in S2, the solvent includes ethanol and water; the volume ratio of the ethanol is 5-10%.
In one embodiment of the present invention, in S2, the phosphite compound is selected from diethyl phosphite and/or dimethyl phosphite.
In one embodiment of the present invention, in S2, the temperature of the first stage finishing is 85 ℃ to 90 ℃ for 30min to 50min; the finishing time of the second stage is 30min-40min; the aldehyde group of the vanillin phytic acid ester finishing agent, the P-H bond of the phosphite ester compound and the amino group of the wool fabric can undergo Schiff base reaction and Pudovik addition reaction, so that the vanillin phytic acid ester finishing agent is grafted on the wool fabric through covalent bonds.
A second object of the present invention is to provide a multifunctional wool fabric prepared by the method.
In one embodiment of the invention, the damage length of the multifunctional wool fabric is lower than 8.3cm, the flame retardance B 1 is achieved, and the limiting oxygen index is higher than 30.5%; the antibacterial rate to escherichia coli and staphylococcus aureus is higher than 91%, and UPF is 50+, so that the multifunctional wool fabric has excellent flame retardant property, antibacterial property and ultraviolet resistance; the damage length of the multifunctional wool fabric after 30 times of washing is still lower than 14.7cm, and the flame retardant grade B 1 is achieved; the antibacterial rate to escherichia coli and staphylococcus aureus is higher than 83%, and UPF is 50+, so that the multifunctional wool fabric has good washing resistance.
Compared with the prior art, the technical scheme of the invention has the following advantages:
In the preparation method, the phytic acid and the vanillin are combined through covalent bonds to synthesize the vanillin phytic acid ester finishing agent, and then the vanillin phytic acid ester finishing agent and the phosphite ester are adopted to modify the wool fabric to prepare the multifunctional wool fabric. On the one hand, the aldehyde group of the vanillin phytic acid ester finishing agent, the P-H bond of the phosphite ester compound and the amino group of the wool fabric can undergo Schiff base reaction and Pudovik addition reaction, and the vanillin phytic acid ester finishing agent and the phosphite ester compound are grafted on the wool fabric through covalent bonds, so that lasting functionality is provided; on the other hand, the phosphate radical of the phytic acid and the phosphate radical of the phosphite ester compound have higher catalytic carbonizing performance, the aromatic structure of the vanillin can be used as a carbonizing agent to form charcoal under the catalysis of phosphate radical, and an expanded charcoal layer is generated, which is favorable for protecting the wool fabric below, so that the synergistic flame retardant effect can be generated among the phytic acid, the phosphite ester compound and the vanillin, and the flame retardant efficiency is high.
The vanillin adopted by the preparation method has stronger antibacterial property and ultraviolet resistance, and is beneficial to improving the antibacterial property and ultraviolet resistance of the wool fabric. The combination of the vanillin phytic acid ester finishing agent prepared by the method and Schiff base generated by the combination of the wool fabric also helps to further improve the antibacterial performance of the wool fabric.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a schematic diagram of the chemical bonding of vanillin phytate finish, diethyl phosphite and wool fabric of example 1 of the invention;
fig. 2 is a vertical burning test chart of the multifunctional wool fabric of example 1 of the present invention.
Detailed Description
The present invention will be further described in conjunction with the drawings and the detailed embodiments so that those skilled in the art may better understand and practice the invention and it is evident that the described embodiments are only some, but not all, of the embodiments of the invention. It should be understood that the detailed description is intended to illustrate the invention, but is not intended to limit the invention to the particular embodiments disclosed.
In the present invention, unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In the present invention, the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, unless otherwise indicated.
In the present invention, unless otherwise indicated, all the experimental methods used in the examples of the present invention are conventional methods, and materials, reagents and the like used, unless otherwise indicated, are commercially available.
Example 1
The invention relates to a multifunctional wool fabric and a preparation method thereof, which specifically comprise the following steps:
S1, under the action of 4-dimethylaminopyridine serving as a catalyst and dicyclohexylcarbodiimide serving as a water absorbent, carrying out esterification reaction on phytic acid and vanillin in N, N-dimethylformamide serving as an organic solvent at 125 ℃ for 3.5 hours, and then filtering, rotary steaming, washing and drying to remove impurities and the organic solvent to obtain a vanillin phytic acid ester finishing agent; wherein, the mol ratio of the phytic acid to the vanillin is 1:4.3; the molar ratio of the water absorbent to the vanillin is 1:1.6; the dosage ratio of vanillin to organic solvent is 1g to 25mL; the concentration of the catalyst is 4g/L;
S2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution, finishing for 40min at 88 ℃, then adding diethyl phosphite into the vanillin phytic acid ester finishing agent solution according to the volume ratio, continuously finishing for 35min, and finally taking out the wool fabric, and naturally airing to obtain a multifunctional wool fabric (figure 1); wherein the vanillin phytic acid ester finishing agent solution comprises vanillin phytic acid ester finishing agent and mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 8%), the concentration is 65g/L, and the pH is adjusted to 4.5 by adopting sodium hydroxide; the molar ratio of vanillin phytic acid ester finishing agent to diethyl phosphite is 1:3.5.
Example 2
The invention relates to a multifunctional wool fabric and a preparation method thereof, which specifically comprise the following steps:
S1, under the action of a catalyst 4-dimethylaminopyridine and a water absorbent dicyclohexylcarbodiimide, carrying out esterification reaction on phytic acid and vanillin in an organic solvent N, N-dimethylformamide at 120 ℃ for 4 hours, and then filtering, rotary steaming, washing and drying to remove impurities and the organic solvent to obtain a vanillin phytic acid ester finishing agent; wherein, the mol ratio of the phytic acid to the vanillin is 1:4.1; the molar ratio of the water absorbent to the vanillin is 1:1.2; the dosage ratio of vanillin to organic solvent is 1g to 20mL; the concentration of the catalyst is 3g/L;
S2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution, finishing for 50min at the temperature of 85 ℃, then adding dimethyl phosphite into the vanillin phytic acid ester finishing agent solution according to the volume ratio, continuously finishing for 40min, finally taking out the wool fabric, and naturally airing to obtain the multifunctional wool fabric; wherein the vanillin phytic acid ester finishing agent solution comprises vanillin phytic acid ester finishing agent and mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 5%), the concentration is 50g/L, and the pH is adjusted to 4 by adopting sodium hydroxide; the molar ratio of vanillin phytic acid ester finishing agent to dimethyl phosphite is 1:3.
Example 3
The invention relates to a multifunctional wool fabric and a preparation method thereof, which specifically comprise the following steps:
S1, under the action of 4-dimethylaminopyridine serving as a catalyst and dicyclohexylcarbodiimide serving as a water absorbent, carrying out esterification reaction on phytic acid and vanillin in N, N-dimethylformamide serving as an organic solvent at 130 ℃ for 3 hours, and then filtering, rotary steaming, washing and drying to remove impurities and the organic solvent to obtain a vanillin phytic acid ester finishing agent; wherein, the mol ratio of the phytic acid to the vanillin is 1:4.5; the molar ratio of the water absorbent to the vanillin is 1:2; the dosage ratio of vanillin to organic solvent is 1g to 30mL; the concentration of the catalyst is 5g/L;
s2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution, finishing for 30min at 90 ℃, then adding diethyl phosphite into the vanillin phytic acid ester finishing agent solution according to the volume ratio, continuously finishing for 30min, and finally taking out the wool fabric, and naturally airing to obtain the multifunctional wool fabric; wherein the vanillin phytic acid ester finishing agent solution comprises vanillin phytic acid ester finishing agent and mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 10%), the concentration is 80g/L, and the pH is adjusted to 5 by adopting sodium hydroxide; the molar ratio of vanillin phytic acid ester finishing agent to diethyl phosphite is 1:4.
Comparative example 1
Substantially the same as in example 1, the difference is that: directly adopts phytic acid as a finishing agent, and specifically comprises the following steps:
S1, soaking a wool fabric in a phytic acid finishing agent solution, finishing for 40min at 88 ℃, then adding diethyl phosphite into the phytic acid finishing agent solution according to the volume ratio, continuously finishing for 35min, and finally taking out the wool fabric and naturally airing to obtain the multifunctional wool fabric; the phytic acid finishing agent solution comprises a phytic acid finishing agent and a mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 8%), the concentration is 65g/L, and the pH is adjusted to 4.5 by adopting sodium hydroxide; the mole ratio of the phytic acid finishing agent to the diethyl phosphite is 1:3.5.
Comparative example 2
Substantially the same as in example 1, the difference is that: directly adopts vanillin as a finishing agent, and specifically comprises the following steps:
S1, soaking a wool fabric in a vanillin finishing agent solution, finishing for 40min at 88 ℃, then adding diethyl phosphite into the vanillin finishing agent solution according to the volume ratio, continuously finishing for 35min, and finally taking out the wool fabric and naturally airing to obtain a multifunctional wool fabric; wherein the vanillin finishing agent solution comprises vanillin finishing agent and mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 8%), the concentration is 65g/L, and the pH is adjusted to 4.5 by adopting sodium hydroxide; the molar ratio of vanillin finishing agent to diethyl phosphite is 1:3.5.
Comparative example 3
Substantially the same as in example 1, the difference is that: the method for replacing vanillin with parahydroxybenzoic acid specifically comprises the following steps:
s1, under the action of 4-dimethylaminopyridine serving as a catalyst and dicyclohexylcarbodiimide serving as a water absorbent, carrying out esterification reaction on phytic acid and p-hydroxybenzoic acid in N, N-dimethylformamide serving as an organic solvent at 125 ℃ for 3.5 hours, and then filtering, rotary steaming, washing with water and drying to remove impurities and the organic solvent to obtain a p-hydroxybenzoic acid phytic acid ester finishing agent; wherein, the mol ratio of the phytic acid to the p-hydroxybenzoic acid is 1:4.3; the molar ratio of the water absorbent to the parahydroxybenzoic acid is 1:1.6; the dosage ratio of the parahydroxybenzoic acid to the organic solvent is 1g to 25mL; the concentration of the catalyst is 4g/L;
s2, soaking the wool fabric in a parahydroxybenzoic acid phytic acid finishing agent solution, finishing for 40min at 88 ℃, then adding diethyl phosphite into the parahydroxybenzoic acid phytic acid finishing agent solution according to the volume ratio, continuously finishing for 35min, finally taking out the wool fabric, and naturally airing to obtain the multifunctional wool fabric; wherein, the parahydroxybenzoic acid phytic acid ester finishing agent solution comprises parahydroxybenzoic acid phytic acid ester finishing agent and mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 8%), the concentration is 65g/L, and the pH is adjusted to 4.5 by adopting sodium hydroxide; the molar ratio of the parahydroxybenzoic acid phytic acid finishing agent to the diethyl phosphite is 1:3.5.
Comparative example 4
Substantially the same as in example 1, the difference is that: the method does not adopt diethyl phosphite for finishing, and specifically comprises the following steps:
S1, under the action of 4-dimethylaminopyridine serving as a catalyst and dicyclohexylcarbodiimide serving as a water absorbent, carrying out esterification reaction on phytic acid and vanillin in N, N-dimethylformamide serving as an organic solvent at 125 ℃ for 3.5 hours, and then filtering, rotary steaming, washing and drying to remove impurities and the organic solvent to obtain a vanillin phytic acid ester finishing agent; wherein, the mol ratio of the phytic acid to the vanillin is 1:4.3; the molar ratio of the water absorbent to the vanillin is 1:1.6; the dosage ratio of vanillin to organic solvent is 1g to 25mL; the concentration of the catalyst is 4g/L;
S2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution, finishing for 40min at 88 ℃, taking out the wool fabric, and naturally airing to obtain a multifunctional wool fabric; the vanillin phytic acid ester finishing agent solution comprises vanillin phytic acid ester finishing agent and mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 8%), the concentration is 65g/L, and the pH is adjusted to 4.5 by adopting sodium hydroxide.
Comparative example 5
Substantially the same as in example 1, the difference is that: the method for replacing diethyl phosphite with triethyl phosphate specifically comprises the following steps:
S1, under the action of 4-dimethylaminopyridine serving as a catalyst and dicyclohexylcarbodiimide serving as a water absorbent, carrying out esterification reaction on phytic acid and vanillin in N, N-dimethylformamide serving as an organic solvent at 125 ℃ for 3.5 hours, and then filtering, rotary steaming, washing and drying to remove impurities and the organic solvent to obtain a vanillin phytic acid ester finishing agent; wherein, the mol ratio of the phytic acid to the vanillin is 1:4.3; the molar ratio of the water absorbent to the vanillin is 1:1.6; the dosage ratio of vanillin to organic solvent is 1g to 25mL; the concentration of the catalyst is 4g/L;
S2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution, finishing for 40min at 88 ℃, then adding triethyl phosphate into the vanillin phytic acid ester finishing agent solution according to the volume ratio, continuously finishing for 35min, and finally taking out the wool fabric, and naturally airing to obtain the multifunctional wool fabric; wherein the vanillin phytic acid ester finishing agent solution comprises vanillin phytic acid ester finishing agent and mixed solution (the mixed solution consists of ethanol and water, the volume fraction of the ethanol is 8%), the concentration is 65g/L, and the pH is adjusted to 4.5 by adopting sodium hydroxide; the molar ratio of vanillin phytic acid ester finishing agent to triethyl phosphate is 1:3.5.
Comparative example 6
Substantially the same as in example 1, the difference is that: the method adopts diethyl phosphite for finishing, and specifically comprises the following steps:
S1, soaking a wool fabric in a diethyl phosphite solution, finishing for 75 minutes at 88 ℃, taking out the wool fabric, and naturally airing to obtain a multifunctional wool fabric; wherein the diethyl phosphite solution comprises diethyl phosphite and ethanol, and the concentration is 65g/L.
Test case
The untreated wool fabric (as it is), the multifunctional wool fabrics prepared in examples 1 to 3 and comparative examples 1 to 6 were tested for flame retardant properties and the like:
damage length of fabric: according to GB/T5455-2014 standard of determination of smoldering and continuous burning time of damage length in vertical direction of burning property of textiles;
burning properties of the fabric: according to GB/T17591-2006 flame retardant fabrics;
limiting oxygen index of fabric: according to GB/T5454-1997 standard of oxygen index method for experimental combustion Performance of textiles;
Antibacterial rate of the fabric: according to GB/T20944.3-2008, evaluation of antibacterial Properties of textiles, section 3, vibration method;
Uv-blocking factor (UPF) of fabric: according to GB/T18830-2009 'evaluation of ultraviolet resistance of textiles';
the water wash method was as per AATCC 61-2006 accelerated test of washing fastness for domestic and commercial applications.
FIG. 2 is a vertical burning pattern of the multifunctional wool fabric of example 1;
table 1 shows the relevant properties of the final measured multifunctional wool fabric:
TABLE 1
As can be seen from table 1 and fig. 2, the modified wool fabric of the example has excellent flame retardant property, antibacterial property, uv resistance and water washing resistance.
As can be seen from the comparison between the example 1 and the comparative example 1, the wool fabric modified by the phytic acid alone has good flame retardant property, because the phytic acid contains 6 phosphate groups in the molecule, the flame retardant effect can be achieved by catalyzing the carbonization of the wool fabric, and the flame retardant efficiency is high; however, the water washing resistance is poor, and the practical application performance is poor, because phosphate radical in phytic acid can only be combined with wool fabric through ionic bond, and covalent bond combination cannot be generated.
As can be seen from the comparison of example 1 and comparative example 2, the wool fabric modified with vanillin alone has good antibacterial and uv-resistant properties, but poor flame retardant and water washing resistant properties.
As can be seen from comparative examples 1 and 3, the modified wool fabric has good flame retardant properties by synthesizing parahydroxybenzoic acid phytate using parahydroxybenzoic acid and phytic acid, but has poor washing resistance because parahydroxybenzoic acid phytate cannot be covalently bonded to the wool fabric.
As can be seen from the comparison of example 1 and comparative example 4, the flame retardant property of the modified wool fabric is lowered without using diethyl phosphite for the second stage, and the flame retardant property is lost after 30 times of washing, and the washing resistance is poor because diethyl phosphite can be combined with the wool fabric through covalent bonds, and the durability of the wool fabric.
As can be seen from the comparison of example 1 and comparative example 5, the flame retardant property of the modified wool fabric was not significantly changed by using triethyl phosphate in the second stage, but the flame retardant property was lost after 30 times of washing, and the washing resistance was poor because the triethyl phosphate could not be covalently bonded to the wool fabric.
As can be seen from comparative examples 1 and 6, the flame retardant property of the modified wool fabric is good, but the antibacterial property and the uv resistance are poor, and the flame retardant and wash resistance are poor, because the diethyl phosphite cannot be covalently bonded with wool.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the multifunctional wool fabric is characterized by comprising the following steps of:
S1, under the action of a catalyst and a water absorbent, carrying out esterification reaction on phytic acid and vanillin in an organic solvent to obtain a vanillin phytic acid ester finishing agent; the organic solvent is selected from N, N-dimethylformamide and/or N, N-dimethylacetamide;
S2, soaking the wool fabric in a vanillin phytic acid ester finishing agent solution for first-stage finishing, and then adding phosphite ester compounds into the vanillin phytic acid ester finishing agent solution for second-stage finishing to obtain the multifunctional wool fabric; the vanillin phytic acid ester finishing agent solution comprises the vanillin phytic acid ester finishing agent of S1 and a solvent; the solvent includes ethanol and water.
2. The method for preparing a multifunctional wool fabric according to claim 1, wherein in S1, the mole ratio of the phytic acid to the vanillin is 1 (4-4.5); the mole ratio of the water absorbing agent to the vanillin is 1 (1.2-2); the dosage ratio of the vanillin to the organic solvent is 1g (20-30 mL).
3. The method for preparing a multifunctional wool fabric according to claim 1, wherein the concentration of the catalyst during the esterification reaction in S1 is 3g/L to 5g/L.
4. The method for preparing a multifunctional wool fabric according to claim 1, wherein in S1, the catalyst is 4-dimethylaminopyridine; the water absorbing agent is dicyclohexylcarbodiimide.
5. The method for preparing a multifunctional wool fabric according to claim 1, wherein in S1, the esterification reaction is performed at a temperature of 120 ℃ to 130 ℃ for 3 hours to 4 hours.
6. The method for preparing a multifunctional wool fabric according to claim 1, wherein in S2, the concentration of the vanillin phytic acid ester finishing agent solution is 50g/L to 80g/L and the pH is 4 to 5; the mol ratio of the vanillin phytic acid ester finishing agent to the phosphite ester compound is 1 (3-4).
7. The method for preparing a multifunctional wool fabric according to claim 1, wherein in S2, the volume ratio of the ethanol is 5% -10%.
8. The method for producing a multifunctional wool fabric according to claim 1, wherein in S2, the phosphite ester compound is selected from diethyl phosphite and/or dimethyl phosphite.
9. The method for preparing a multifunctional wool fabric according to claim 1, wherein in S2, the first-stage finishing temperature is 85 ℃ to 90 ℃ for 30min to 50min; the finishing time of the second stage is 30min-40min.
10. A multifunctional wool fabric produced by the method of any one of claims 1-9.
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