CN112210629B - Biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent and preparation method thereof - Google Patents
Biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent and preparation method thereof Download PDFInfo
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- C14—SKINS; HIDES; PELTS; LEATHER
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- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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Abstract
The invention relates to a biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent and a preparation method thereof, which overcome the defect thatThe pollution problem caused by the traditional flame-retardant leather fatting agent in the prior art is solved. The invention is prepared from the following raw materials in parts by mass: sulfonated beta-cyclodextrin 3-10, mixed solution of methanol and water 40-80ml, ferrocene 4-10, Zn (NO)3)2·6H2O4‑10，Al(NO3)3·9H2O2-5, deionized water 20-50, a proper amount of NaOH, 30-100 parts of pepper seed oil, 98% concentrated sulfuric acid with the mass of 2% of the pepper seed oil, 1.13-3.7 parts of glycerol, 1.13-3.7 parts of methanol, 10.62-35.40 parts of maleic anhydride, 0.6-2.0 parts of p-toluenesulfonic acid and 10.32-34.40 parts of sodium metabisulfite solution.
Description
The technical field is as follows:
the invention belongs to the field of preparation of leather greasing agents, and relates to a biological cyclodextrin modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather greasing agent and a preparation method thereof.
Background art:
in recent years, the amount of leather products used has been rapidly increasing with the increase in living standard, but at the same time, the problem of fire caused by the use of leather products has been increasing. How to solve the flame retardant problem of leather to meet the market demand for high-performance leather is one of the key directions for the development of functional leather. In the leather processing process, fatliquoring is an indispensable process, but because the raw materials used for synthesizing the fatliquoring agent are all combustible grease, part of grease can migrate to the surface of the leather due to unstable combination after fatliquoring and directly become fuel, thereby causing the leather to be flammable. Therefore, in order to solve the problem of flammability of leather after fatliquoring, a flame retardant needs to be added to the fatliquoring agent. The traditional flame retardant is mainly an organic compound and a halogen-containing compound, and generates a large amount of smoke and harmful gases during combustion to pollute the environment and endanger life. Meanwhile, in recent years, the development of flame retardant products pays more attention to green and environmental protection, and the bio-based environment-friendly flame retardant becomes a hotspot in the field of current flame retardant research.
Hydrotalcite-like compounds are layered double hydroxides (referred to as LDHs). The LDHs has the characteristics of anion exchange performance and laminate cation regulation and control, and is environment-friendly, and the LDHs becomes a research hotspot due to the excellent performances. Hydrotalcite-like compounds have received much attention from researchers as clean flame retardants, mainly because of the large amount of metal elements with excellent flame retardant properties present in the sheet layers thereof, and the layered structure thereof facilitates the formation of a carbon-layer-protecting substrate; at the same time, the substrate is protected from further loss due to its barrier effect of the layered structure during combustion. (Xu, Sheng, et al, "The effect of ammonium polyphosphate on The mechanism of phosphoric-containing hydrotalcite synthesis of flame reaction of polypropylene" Applied Clay Science 185(2020): 105348.). However, since hydrotalcite-like compounds have high surface energy and are not easily dispersed in a polymer matrix, it has been studied to improve the dispersibility of hydrotalcite-like compounds by modifying hydrotalcite-like compounds with a surfactant or the like; however, the excessive use of the organic modifier limits further improvement of flame retardancy and also causes environmental pollution. In order to eliminate the negative effects of organic modifiers, some green and environmentally friendly biomass materials can be selected as the modifier.
The biomass polymer material is a novel material manufactured by means of biology, physics or chemistry and the like by utilizing renewable biomass, and is widely concerned by the flame retardant field due to the characteristics of green, environment-friendly, renewable, biodegradable and the like. Cyclodextrin is a general name of natural cyclic oligosaccharide, has a slightly conical hollow cyclic structure, can play a role of a coke forming agent in a combustion process due to a large number of hydroxyl functional groups in molecules, and is widely applied to various flame retardant systems. (Li, Zhi, et al, "Bio-based layered double hydroxide nanovehicle heated fire-registered epoxy resin with improved knowledge and improved knowledge" Chemical Engineering Journal 378(2019): 122046.).
At present, no report exists that green and environment-friendly hydrotalcite-like compound and cyclodextrin with a bio-based source are combined to prepare a composite material, and the composite material is introduced into pepper seed oil to prepare the environment-friendly flame-retardant leather fatting agent.
The invention content is as follows:
the invention aims to provide a biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor and a preparation method thereof, which overcome the pollution problem caused by the traditional flame-retardant leather fatliquor in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent is characterized in that: the feed is prepared from the following raw materials in parts by mass: 3-10 parts of sulfonated beta-cyclodextrin, 40-80ml of mixed solution of methanol and water, 4-10 parts of ferrocene and Zn (NO)3)2·6H2O4-10 parts, Al (NO)3)3·9H2The detergent comprises, by mass, O2-5 parts, 20-50 parts of deionized water, a proper amount of NaOH, 30-100 parts of pepper seed oil, 98% concentrated sulfuric acid with 2% of the mass of the pepper seed oil, 1.13-3.7 parts of glycerol, 1.13-3.7 parts of methanol, 10.62-35.40 parts of maleic anhydride, 0.6-2.0 parts of p-toluenesulfonic acid and 10.32-34.40 parts of a sodium metabisulfite solution with the mass fraction of 40%.
A preparation method of a biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor is characterized by comprising the following steps: the method comprises the following steps: the raw materials are all in parts by mass
The method comprises the following steps: dissolving 3-10 parts of sulfonated beta-cyclodextrin in 40-80ml of mixed solution of methanol and water, adding 4-10 parts of ferrocene under the stirring action, carrying out adsorption reaction for 24 hours, and filtering to obtain filtrate A;
step two: weighing 4-10 parts of Zn (NO)3)2·6H2O, 2-5 parts of Al (NO)3)3·9H2Dissolving O in 20-50 parts of deionized water to prepare a metal salt solution, dripping the metal salt solution into A under the stirring action at 80 ℃ under the protection of nitrogen, regulating the pH of the system to be 10 by using NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing and centrifuging by using the deionized water until the supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modification productA hydrotalcite composite material;
step three: the specific synthesis method comprises the following steps: taking 30-100 parts of pricklyash peel seed oil, heating to 70 ℃, adding the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material obtained in the second step, wherein the amount of the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material is 0-12% of the mass of the pricklyash peel seed oil, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding concentrated sulfuric acid with the mass being 2% of that of the pricklyash seed oil and 1.13-3.7 parts of glycerol, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 1.13-3.7 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 10.62-35.40 parts of maleic anhydride and 0.6-2.0 parts of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 10.32-34.40 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; and cooling to 60 ℃, adjusting the pH to 7.0, adjusting the solid content of the reaction system by using deionized water, and reacting for 40-60 min to obtain the environment-friendly flame-retardant leather fatting agent prepared by the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil.
In the first step, the volume ratio of the mixed solution of methanol and water is 3: 2.
In the second step, Zn is contained in the metal salt solution2+、Al3+The molar ratio is 3: 1, the concentration of the metal salt solution is 1 mol/L.
In the third step, the solid content of the reaction system is 45%.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention provides a preparation method of a biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor, which adopts green and environment-friendly hydrotalcite-like compound and biological base material cyclodextrin as raw materials, has low cost and meets the environment-friendly requirement.
2. The invention utilizes the intercalation of the biological cyclodextrin inclusion ferrocene to improve the dispersibility of the hydrotalcite-like compound and simultaneously improve the compatibility between the hydrotalcite-like compound and a polymer matrix.
3. According to the invention, the flame retardant property of the fatliquored leather is further improved through the synergistic effect of the hydrotalcite-like compound and the cyclodextrin; meanwhile, the ferrocene can endow leather with excellent smoke suppression performance.
Description of the drawings:
FIG. 1 is a diagram of cone calorimetry test results of crust leather after application of cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame retardant leather fatliquor with different introduction amounts.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to specific embodiments. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The implementation conditions used in the examples can be further adjusted according to the specific experimental environment, and the implementation conditions not mentioned are generally the conditions in routine experiments.
The invention relates to a biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent, which is prepared by introducing biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound with a synergistic flame-retardant effect into a fatting agent system on the basis of a patent of succinic acid ester sulfonated pepper seed oil/nano hydrotalcite composite flame-retardant fatting agent and a preparation method thereof (patent number: 201711075935.6), modifying the hydrotalcite-like compound by using cyclodextrin derived from a biological base and ferrocene with excellent smoke suppression performance, further improving the dispersibility of the hydrotalcite-like compound and simultaneously preparing the environment-friendly flame-retardant leather fatting agent based on the forward synergistic flame-retardant effect of the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound.
The invention is prepared from the following raw materials in parts by mass: 3-10 parts of sulfonated beta-cyclodextrin, 40-80ml of mixed solution of methanol and water, 4-10 parts of ferrocene and Zn (NO)3)2·6H2O4-10 parts, Al (NO)3)3·9H2The detergent comprises, by mass, O2-5 parts, 20-50 parts of deionized water, a proper amount of NaOH, 30-100 parts of pepper seed oil, 98% concentrated sulfuric acid with 2% of the mass of the pepper seed oil, 1.13-3.7 parts of glycerol, 1.13-3.7 parts of methanol, 10.62-35.40 parts of maleic anhydride, 0.6-2.0 parts of p-toluenesulfonic acid and 10.32-34.40 parts of a sodium metabisulfite solution with the mass fraction of 40%.
The preparation method comprises the following steps: (the raw materials are in parts by mass)
The method comprises the following steps: dissolving 3-10 parts of sulfonated beta-cyclodextrin in 40-80ml of mixed solution of methanol and water, wherein the volume ratio of the mixed solution of methanol and water is 3: 2. Adding 4-10 parts of ferrocene under the stirring action, carrying out adsorption reaction for 24 hours, and filtering to obtain filtrate A;
step two: weighing 4-10 parts of Zn (NO)3)2·6H2O, 2-5 parts of Al (NO)3)3·9H2Dissolving O in 20-50 portions of deionized water to prepare metal salt solution, and dissolving Zn in the metal salt solution2+、Al3+The molar ratio is 3: 1, the concentration of the metal salt solution is 1 mol/L. Dripping a metal salt solution into the A under the stirring action at the temperature of 80 ℃ under the protection of nitrogen, regulating the pH of a system to be constant at 10 by using a NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing by using deionized water, centrifuging until supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material;
step three: the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound with the synergistic flame retardant effect is introduced into a fatliquor system, and the specific synthetic method comprises the following steps: taking 30-100 parts of pricklyash peel seed oil, heating to 70 ℃, adding the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material obtained in the second step, wherein the amount of the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material is 0-12% of the mass of the pricklyash peel seed oil, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding concentrated sulfuric acid with the mass being 2% of that of the pricklyash seed oil and 1.13-3.7 parts of glycerol, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 1.13-3.7 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 10.62-35.40 parts of maleic anhydride and 0.6-2.0 parts of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 10.32-34.40 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; cooling to 60 ℃, adjusting the pH value to 7.0, and adjusting the solid content of the reaction system by using deionized water, wherein the solid content of the reaction system is 45%. Reacting for 40-60 min to obtain the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent.
Example 1
The method comprises the following steps: dissolving 4 parts of sulfonated beta-cyclodextrin in 40ml of mixed solution of methanol and water, adding 4.9 parts of ferrocene under the stirring action, carrying out adsorption reaction for 24 hours, and filtering to obtain filtrate A.
Step two: 4.6 parts of Zn (NO) are weighed out3)2·6H2O, 2.3 parts of Al (NO)3)3·9H2Dissolving O in 24 parts of deionized water to prepare a metal salt solution, dripping the metal salt solution into the A under the stirring action at the temperature of 80 ℃ under the protection of nitrogen, regulating the pH of the system to be constant at 10 by using NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing and centrifuging by using the deionized water until the supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material.
Step three: the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound with the synergistic flame retardant effect is introduced into a fatliquor system, and the specific synthetic method comprises the following steps: taking 30 parts of pricklyash peel seed oil, heating to 70 ℃, adding 2% of the mass of the pricklyash peel seed oil to the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound material obtained in the step two, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding 98% concentrated sulfuric acid and 1.13 parts of glycerol which are 2% of the pepper seed oil in mass, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 1.13 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 10.62 parts of maleic anhydride and 0.6 part of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 10.32 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; and cooling to 60 ℃, adjusting the pH to 7.0, adjusting the solid content of the reaction system by using deionized water, and reacting for 40-60 min to obtain the environment-friendly flame-retardant leather fatting agent prepared by the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil.
Example 2
The method comprises the following steps: dissolving 5 parts of sulfonated beta-cyclodextrin in 50ml of mixed solution of methanol and water, adding 6.1 parts of ferrocene under the stirring action, carrying out adsorption reaction for 24 hours, and filtering to obtain filtrate A.
Step two: weighing 5.6 parts of Zn (NO)3)2·6H2O, 2.6 parts of Al (NO)3)3·9H2Dissolving O in 28 parts of deionized water to prepare a metal salt solution, and dissolving the metal salt at 80 ℃ under the protection of nitrogenAnd dripping the solution into the A under the stirring action, regulating the pH value of the system to be constant at 10 by using a NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing and centrifuging by using deionized water until the supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material.
Step three: the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound with the synergistic flame retardant effect is introduced into a fatliquor system, and the specific synthetic method comprises the following steps: taking 40 parts of pepper seed oil, heating to 70 ℃, adding 4% of the mass of the pepper seed oil to the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound material obtained in the step two, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding 98% concentrated sulfuric acid and 1.50 parts of glycerol which are 2% of the pepper seed oil in mass, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 1.50 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 14.16 parts of maleic anhydride and 0.8 part of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 13.73 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; and cooling to 60 ℃, adjusting the pH to 7.0, adjusting the solid content of the reaction system by using deionized water, and reacting for 40-60 min to obtain the environment-friendly flame-retardant leather fatting agent prepared by the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil.
Example 3
The method comprises the following steps: 6 parts of sulfonated beta-cyclodextrin is dissolved in 60ml of mixed solution of methanol and water, 7.4 parts of ferrocene is added under the stirring action, the adsorption reaction is carried out for 24 hours, and the filtrate A is obtained by filtration.
Step two: weighing 5.6 parts of Zn (NO)3)2·6H2O, 2.6 parts of Al (NO)3)3·9H2Dissolving O in 28 parts of deionized water to prepare a metal salt solution, dripping the metal salt solution into the A under the stirring action at the temperature of 80 ℃ under the protection of nitrogen, regulating the pH of the system to be constant at 10 by using NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing and centrifuging by using the deionized water until the supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material.
Step three: the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound with the synergistic flame retardant effect is introduced into a fatliquor system, and the specific synthetic method comprises the following steps: taking 50 parts of pepper seed oil, heating to 70 ℃, adding 6% of the mass of the pepper seed oil to the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound material obtained in the step two, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding 98% concentrated sulfuric acid and 1.88 parts of glycerol which are 2% of the pepper seed oil in mass, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 1.88 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 17.70 parts of maleic anhydride and 1.0 part of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 17.20 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; and cooling to 60 ℃, adjusting the pH to 7.0, adjusting the solid content of the reaction system by using deionized water, and reacting for 40-60 min to obtain the environment-friendly flame-retardant leather fatting agent prepared by the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil.
Example 4
The method comprises the following steps: dissolving 7 parts of sulfonated beta-cyclodextrin in 70ml of mixed solution of methanol and water, adding 8.6 parts of ferrocene under the stirring action, carrying out adsorption reaction for 24 hours, and filtering to obtain filtrate A.
Step two: weighing 7.7 parts of Zn (NO)3)2·6H2O, 3.8 parts of Al (NO)3)3·9H2Dissolving O in 42 parts of deionized water to prepare a metal salt solution, dripping the metal salt solution into the A under the stirring action at the temperature of 80 ℃ under the protection of inert gas, regulating the pH of the system to be constant at 10 by using NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing and centrifuging by using the deionized water until the supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modified hydrotalcite-like flame-retardant composite material.
Step three: the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound with the synergistic flame retardant effect is introduced into a fatliquor system, and the specific synthetic method comprises the following steps: taking 80 parts of pepper seed oil, heating to 70 ℃, adding the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material obtained in the step two, wherein the mass of the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material is 8% of that of the pepper seed oil, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding 98% concentrated sulfuric acid and 3.01 parts of glycerol which are 2% of the pepper seed oil in mass, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 3.01 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 28.32 parts of maleic anhydride and 1.6 parts of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 27.52 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; and cooling to 60 ℃, adjusting the pH to 7.0, adjusting the solid content of the reaction system by using deionized water, and reacting for 40-60 min to obtain the environment-friendly flame-retardant leather fatting agent prepared by the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil.
Example 5
The method comprises the following steps: dissolving 8 parts of sulfonated beta-cyclodextrin in 80ml of mixed solution of methanol and water, adding 9.8 parts of ferrocene under the stirring action, carrying out adsorption reaction for 24 hours, and filtering to obtain filtrate A.
Step two: 9.6 parts of Zn (NO) are weighed out3)2·6H2O, 4.7 parts of Al (NO)3)3·9H2Dissolving O in 50 parts of deionized water to prepare a metal salt solution, dripping the metal salt solution into the A under the stirring action at the temperature of 80 ℃ under the protection of inert gas, regulating the pH of the system to be constant at 10 by using NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing and centrifuging by using the deionized water until the supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modified hydrotalcite-like flame-retardant composite material.
Step three: the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound with the synergistic flame retardant effect is introduced into a fatliquor system, and the specific synthetic method comprises the following steps: heating 100 parts of pricklyash peel seed oil to 70 ℃, adding 10% of the mass of the pricklyash peel seed oil to the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound composite material obtained in the step two, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding 98% concentrated sulfuric acid and 3.76 parts of glycerol which are 2% of the pepper seed oil in mass, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 3.76 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 35.40 parts of maleic anhydride and 2.0 parts of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 34.40 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; and cooling to 60 ℃, adjusting the pH to 7.0, adjusting the solid content of the reaction system by using deionized water, and reacting for 40-60 min to obtain the environment-friendly flame-retardant leather fatting agent prepared by the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil.
Experimental example:
in order to verify the technical effect of the prepared biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor, the flame-retardant performance of the fatliquor prepared in the embodiment 1 is tested on the fatliquor of the fatliquor. The results of the vertical combustion test are shown in table 1, the flaming combustion time and the damage length of crust leather after the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor is fatliquored are both reduced, when the introduction amount is 8%, the damage length of the crust leather is 11.2mm, meanwhile, the flaming combustion time is reduced to 26.6s, and the oxygen index reaches 27.8.
TABLE 1 flame retardancy of fatliquored crust leather
FIG. 1 shows the cone calorimetric detection results of crust leather after the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor with different introduction amounts is applied. Graphs (a) to (d) show the heat release rate, total heat release, smoke generation rate and CO respectively2The ratio of (a) to (b). When the introduced amount is 8%, the heat release rate and the total heat release of the crust leather are respectively reduced by 42.5% and 45.1%, and the smoke release amount of the crust leather is remarkably inhibited as can be seen in the graph (c), and when the introduced amount is 8%, the smoke generation rate is reduced by 62.5%, which is attributed to the good smoke inhibition of the modifier, and the chain reaction in the combustion process can be terminated, and the smoke inhibition of the crust leather can be improved. From the graph (d), it can be observed that the amount of CO released during combustion is significantly reduced. Therefore, the cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil is environment-friendlyThe flame-retardant leather greasing agent obviously improves the flame-retardant and smoke-suppressing performance of crust leather after being applied.
The above embodiments are merely illustrative of the principles and effects of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and the scope of the present invention is defined by the appended claims.
Claims (4)
1. A preparation method of a biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor is characterized by comprising the following steps: the method comprises the following steps: the raw materials are all in parts by mass
The method comprises the following steps: dissolving 3-10 parts of sulfonated beta-cyclodextrin in 40-80ml of mixed solution of methanol and water, adding 4-10 parts of ferrocene under the stirring action, carrying out adsorption reaction for 24 hours, and filtering to obtain filtrate A;
step two: weighing 4-10 parts of Zn (NO)3)2·6H2O, 2-5 parts of Al (NO)3)3·9H2Dissolving O in 20-50 parts of deionized water to prepare a metal salt solution, dripping the metal salt solution into the filtrate A under the stirring action at 80 ℃ under the protection of nitrogen, adjusting the pH of the system to be 10 by using a NaOH solution, stirring at constant temperature for two hours after dripping is finished, crystallizing at room temperature for 8 hours, washing and centrifuging by using deionized water until the supernatant is neutral, and freeze-drying a filter cake to obtain the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material;
step three: taking 30-100 parts of pricklyash peel seed oil, heating to 70 ℃, adding the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material obtained in the second step, wherein the amount of the cyclodextrin inclusion ferrocene modified hydrotalcite-like composite material is 0-12% of the mass of the pricklyash peel seed oil, and carrying out heat preservation reaction for 25-30 min; then, heating to 130 ℃, adding concentrated sulfuric acid with the mass being 2% of that of the pricklyash seed oil and 1.13-3.7 parts of glycerol, and reacting for 3-4 hours in a heat preservation manner; reducing the temperature of the system to 70 ℃, adding 1.13-3.7 parts of methanol, and reacting for 3-4 h; then, heating to 111 ℃, adding 10.62-35.40 parts of maleic anhydride and 0.6-2.0 parts of p-toluenesulfonic acid, and reacting for 3-4 hours in a heat preservation manner; cooling to 60 ℃, and adjusting the pH value of the system to 6.0; heating to 80 ℃, adding 10.32-34.40 parts of sodium metabisulfite solution with the mass fraction of 40%, and reacting for 2-2.5 h; and cooling to 60 ℃, adjusting the pH to 7.0, adjusting the solid content of the reaction system by using deionized water, and reacting for 40-60 min to obtain the environment-friendly flame-retardant leather fatting agent prepared by the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil.
2. The preparation method of the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor according to claim 1, which is characterized in that: in the first step, the volume ratio of the mixed solution of methanol and water is 3: 2.
3. The preparation method of the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor according to claim 2, which is characterized in that: in the second step, Zn is contained in the metal salt solution2+、Al3+The molar ratio is 3: 1, the concentration of the metal salt solution is 1 mol/L.
4. The preparation method of the biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatliquor according to claim 3, which is characterized in that: in the third step, the solid content of the reaction system is 45%.
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