CN109852739B - Silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent with controllable particle size and preparation method thereof - Google Patents
Silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent with controllable particle size and preparation method thereof Download PDFInfo
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Abstract
Grain diameter controllable ZnO @ SiO2The composite nano particle/plant tannin compound tanning agent and the preparation method thereof can effectively regulate and control ZnO @ SiO by changing the proportion of the added raw materials2The particle size and the size of the composite nanometer particles are found to be unfavorable for the penetration and the absorption of the composite nanometer particles on the white and wet skin of the sheep by means of mechanical force of a rotary drum. The particle size range of the composite nano particles is optimized, the tanning performance of the prepared novel composite tanning agent is greatly improved, and an ideal tanning effect is obtained. The chrome tanning agent is applied to tanning white and wet sheep skins, the shrinkage temperature of tanned skins reaches over 80 ℃, only 0.1wt% of chromium powder needs to be compounded, the shrinkage temperature of tanned leathers can reach over 90 ℃, the tanned leathers are obviously thickened, the finished leathers have better aging resistance, air permeability, flame retardance and the like, and the chrome tanning agent is a novel green environment-friendly tanning agent capable of replacing chrome tanning.
Description
Technical Field
The invention belongs to the field of inorganic-polymer composite materials, and particularly relates to ZnO @ SiO with controllable particle size2Composite nanometer particle/plant tannin composite tanning agent and its preparation method are provided.
Background
The chrome tanning agent which occupies an important position in the traditional tanning process has high toxicity, the problem of environmental pollution caused by chrome tanning waste liquid seriously restricts the development of the tanning industry all the time, the chrome tanning is thoroughly abandoned as a fundamental method for solving the chrome pollution, and the chrome-free or less-chrome tanning is one of the hot spots of the research of global tanners. The chrome-free tanning agent developed by the traditional method is difficult to completely meet the requirement of good service performance of finished leather, and the key point for realizing chrome-free tanning is that the stability of a cross-linking structure of the tanning agent and leather collagen is fully improved and the finished leather is endowed with a certain filling effect. ZnO @ SiO with controllable particle size2Composite nano particles, plant tannin as polymer carrier to synthesize nano composite tanning agent, polyalcohol surface modified ZnO@SiO2The composite nano particles show good dispersibility in water phase and tannin matrix, the prepared composite tanning agent has stable performance, and the multi-component system of the composite tanning agent simultaneously plays a synergistic tanning effect in the leather tanning process, thereby greatly improving the damp-heat stability of the leather. Addition of ZnO @ SiO in the case of chrome-free tanning2The composite nanometer particles not only obviously enhance the physical and mechanical properties of leather, but also endow finished leather with certain aging resistance, air permeability, flame retardance and other excellent properties.
Disclosure of Invention
The invention utilizes a new nano technology and a new nano material to improve the traditional leather making technology and aims to provide silicon dioxide coated zinc oxide (hereinafter referred to as ZnO @ SiO) with controllable particle size2And @ represents coating) composite nano particle/plant tannin composite tanning agent and preparation method thereof, each component in the composite can exert synergistic tanning effect, the wet heat resistance stability and mechanical property of tanned leather are obviously improved, and simultaneously finished leather is obviously thickened and shows excellent characteristics such as good weather resistance, air permeability and flame retardance. The invention provides a new technology and a new method for solving the problem of chromium pollution in the leather-making industry at present.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent with controllable particle size comprises the following steps:
ZnO @ SiO with the grain diameter of 300-1800 nm (preferably 307-1780 nm, more preferably 425-731 nm)2Adding the composite nanoparticles into the vegetable tannin, performing ultrasonic dispersion to form uniform dispersion liquid, generally performing ultrasonic treatment for 15-30 min, and stirring at room temperature for 2-4 h (nanoparticle filling method) to obtain ZnO @ SiO with different particle sizes2Composite nanoparticle/vegetable tannin complex tanning agent, ZnO @ SiO2The composite nanometer particles account for 0.25 wt% -6 wt% of the effective substance content of the plant tannin matrix.
Further, ZnO @ SiO with different particle sizes2The preparation process of the composite nanometer particle is as follows:
(1) adding 0.01-0.03 g of nano ZnO and polyethylene glycol with the molecular weight of 400-20000 into a mixed solvent of absolute ethyl alcohol and deionized water with the volume ratio of 8-12: 1 (preferably 10: 1), wherein the volume of the mixed solvent is 100-120 mL, and performing ultrasonic dispersion uniformly to obtain a solution I, wherein the mass ratio of the nano ZnO to the polyethylene glycol is (0.01-0.03): 0.8-1.0; the molecular weight of the polyethylene glycol is preferably 8000, the molecular weight is 8000, and the polyethylene glycol is analytically pure and purchased from chemical reagents of Mi Europe, Inc. of Tianjin;
(2) dropwise adding 0.01-5 mL of ammonia water into the solution I, and uniformly dispersing by ultrasonic to obtain a solution II;
(3) dissolving 0.02-0.2 mL of ethyl orthosilicate into 20-30 mL of ethanol to obtain a solution (c); the mass ratio of the nano ZnO to the tetraethoxysilane is 1: 0.9-10, and the volume ratio of the ammonia water to the tetraethoxysilane is 0.01-5: 0.02-0.2;
(4) adding the solution III into the solution II, performing ultrasonic reaction for 2-3 h, performing centrifugal separation on the obtained sample, collecting solids, washing and drying to obtain ZnO @ SiO with different particle sizes of 300-1800 nm2And (3) compounding the nanoparticles.
Further, the preparation process of the nano ZnO is as follows: adding zinc acetate dihydrate and absolute ethyl alcohol into a stainless steel high-pressure reaction kettle (with the volume of 40 mL) according to the proportion of 1 g: 10mL, sealing, and placing into an oven to react for 20-30 hours at 160-180 ℃. And after the reaction is finished, cooling the autoclave to room temperature, centrifugally separating the obtained sample, collecting the solid, repeatedly washing the solid with absolute ethyl alcohol, and drying to obtain the catalyst.
Preferably, ZnO @ SiO2The amount of the composite nanoparticles is 0.03-1.0 g.
Preferably, the stirring speed cannot be lower than 1000r/min during the stirring at room temperature.
When the dosage of the nano ZnO is 0.02g and the dosage of the tetraethoxysilane is 0.02mL, and the dosage of the ammonia water is from 0.01 to 5mL, the ZnO @ SiO is2The particle size of the composite nano particles is increased from 307nm to 1098 nm.
When the dosage of the nano ZnO is 0.02g and the dosage of the ammonia water is 0.5mL, the dosage of the tetraethyl silicate is 0.02-0.2 mL, and the dosage of the ZnO @ SiO is 0.02-0.2 mL2The particle size of the composite nano particles is increased from 343nm to 1780 nm.
Preferably, the vegetable tannin is condensed tannin, the content of effective substances of the condensed tannin is 30-35 wt%, and the condensed tannin is purchased from Strobitan chemical Co., Ltd.
The silicon dioxide coated zinc oxide composite nano particles/vegetable tannin composite tanning agent prepared by the preparation method.
The application of the silicon dioxide coated zinc oxide composite nano particles/vegetable tannin composite tanning agent in leather tanning accounts for 4-6 wt% of the weight of the leather.
The nano compound tanning agent is used for tanning sheep white wet leather, the thickening rate reaches 291%, and the utilization rate of the leather is greatly improved. The tanning shrinkage temperature can reach more than 80 ℃ (the temperature meeting the damp-heat stability requirement of leather in use), the tanning shrinkage temperature can reach more than 90 ℃ only by compounding 0.1wt% (based on the weight of the leather) of chromium powder, and the finished leather has good weather resistance, air permeability, flame retardance and the like. In which the ZnO @ SiO prepared in example 22Composite nanometer particles (the average particle size is 601 nm)/white and wet sheep leather tanned by the plant tannin composite (the using amount of the tanning agent is 4wt% of the weight of the leather), and the shrinkage temperature of the leather after tanning reaches 86 ℃.
Drawings
FIG. 1 shows nano zinc oxide (ZnO) and nano silicon dioxide (SiO)2）、ZnO@SiO2Composite nanoparticles (figure 1 a) and vegetable Tannin (Tannin), ZnO @ SiO2Comparative fourier spectra of composite nanoparticle/vegetable tannin complexes (from example 2) (fig. 1 b);
FIG. 2 shows nano ZnO and nano SiO2，ZnO@SiO2XRD spectrum of composite nanoparticles (prepared in example 2);
FIG. 3 shows the nano ZnO, ZnO @ SiO observed under a scanning electron microscope and a transmission electron microscope respectively2Morphology of the composite nanoparticles (prepared in example 2);
FIG. 4 shows nano ZnO and nano SiO2And ZnO @ SiO2The UV absorption spectrum of the composite nanoparticles (prepared in example 2);
FIG. 5 is ZnO @ SiO2Plant Tannin (Tannin) complexes (prepared in example 2) and pure plantsUltraviolet absorption spectrum of Tannin (Tannin);
FIG. 6 shows that the amount of ammonia water is changed (the amount of other raw materials is not changed) to control the content of ZnO @ SiO2The particle size and particle size distribution of the composite nanoparticles;
FIG. 7 shows that the amount of tetraethoxysilane (other raw materials are not changed) is changed to regulate and control ZnO @ SiO2The particle size and particle size distribution of the composite nanoparticles.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited thereto.
1. Preparation of nano ZnO
2.5g of zinc acetate dihydrate and 25mL of absolute ethanol were charged into a stainless steel autoclave (40 mL in volume), sealed, and placed in an oven at 170 ℃ for 24 hours. And naturally cooling the autoclave to room temperature after the reaction is finished, centrifugally separating the obtained sample at the rotating speed of 9000r/min, collecting the solid, repeatedly washing the solid with absolute ethyl alcohol, and drying the solid in vacuum at the temperature of 60 ℃ for later use. The infrared spectrum is shown in figure 1, the XRD spectrum is shown in figure 2, and the scanning electron microscope picture is shown in figure 3. The particle size of the prepared nano zinc oxide is 100-150 nm.
2. Preparation of nano ZnO/Tannin compound tanning agent
0.24g of nano ZnO is dispersed into 10mL of mixed solvent of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 1:1), 40mL of plant Tannin (30-35% of active substance content, purchased from Strand chemical Co., Ltd. of Foshan, Guangdong) is added, ultrasonic treatment (power of 80W) is carried out for 20 min-1 h at 25 ℃, and then strong mechanical stirring is carried out for 2-4 h at the rotating speed of 1000rpm, so as to obtain the nano ZnO/plant Tannin composite tanning agent (marked as ZnO/Tannin).
3. Nano SiO2Preparation of
5mL of ethyl orthosilicate is firstly dissolved in 20mL of absolute ethyl alcohol to form a uniform solution, the solution and 10mL of ammonia water are simultaneously and slowly dripped into 100mL of absolute ethyl alcohol, the mixture is stirred and reacted for 24 hours in thermostatic waterbath at 50 ℃, the obtained sample is centrifugally separated, the solid is collected and washed by the absolute ethyl alcohol for three times, and the mixture is dried in vacuum at 60 ℃ for standby.
Example 1
Dispersing 0.02g of nano ZnO and 0.9g of polyethylene glycol (molecular weight is 8000, analytically pure, purchased from Mi Europe chemical reagent Co., Ltd., Tianjin City) in 100mL of absolute ethyl alcohol, adding 10mL of deionized water, carrying out ultrasonic (80W) treatment for 30min, then dropwise adding 0.5mL of ammonia water (the mass percentage concentration is 25-28%, the same below), and carrying out ultrasonic (80W) treatment for 10min to obtain a solution I; dissolving 0.02mL of ethyl orthosilicate into 25mL of absolute ethyl alcohol to obtain a solution II, dropwise adding the solution II into the solution I, continuing to perform ultrasonic wave (800W, XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer purchased from Beijing Xiangkun scientific and technological development Limited) to react for 2 hours, centrifugally separating, washing the solid for three times by absolute ethyl alcohol, and performing vacuum drying at 60 ℃ to obtain ZnO @ SiO2The composite nano particles are ready for use. Accurately weigh 0.06g ZnO @ SiO2Adding the composite nano particles into 40mL of plant Tannin (Tannin, 30-35% of effective substance content, purchased from Strongshan Steron chemical Co., Ltd.) to perform ultrasonic treatment (80W) at 25 ℃ for 20min, and then strongly and mechanically stirring at the rotating speed of 1000r/min for 2h to obtain ZnO @ SiO2Plant tannin compound tanning agent (marked as ZnO @ SiO)2/Tannin). Wherein ZnO @ SiO2The composite nanometer particles account for 0.5 wt% of the effective matter content of the plant tannin.
Example 2
Dispersing 0.02g of nano ZnO and 0.9g of polyethylene glycol (molecular weight is 8000, analytically pure, purchased from Mi Europe chemical reagent Co., Ltd. of Tianjin) in 100mL of absolute ethyl alcohol, adding 10mL of deionized water, carrying out ultrasonic (80W) treatment for 30min, then dropwise adding 1mL of ammonia water into the mixture, and carrying out ultrasonic (80W) treatment for 15min to obtain a solution I; dissolving 0.02mL of ethyl orthosilicate into 25mL of absolute ethyl alcohol to obtain a solution II, dropwise adding the solution II into the solution I, continuing to perform ultrasonic wave (800W, XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer, purchased from Beijing Xiangkun scientific and technological development Limited) to react for 2.5h, performing centrifugal separation, repeatedly washing the solid with absolute ethyl alcohol, and performing vacuum drying at 60 ℃ to obtain ZnO @ SiO2The composite nano particles are ready for use. Nano ZnO, nano SiO2，ZnO@SiO2The XRD pattern of the composite nanoparticles is detailed in FIG. 2, and it can be seen from FIG. 2 that: nano ZnO characterThe crystal purity is higher in combination with a typical hexagonal wurtzite structure; nano SiO2The surface coating of the nano ZnO does not influence the crystal form of the nano ZnO, and on the other hand, the successful preparation of the target product is also proved. Nano ZnO, ZnO @ SiO2The morphology of the composite nanoparticles is shown in FIG. 3, and can be seen in FIG. 3: the nano zinc oxide is in a sheet structure, ZnO @ SiO2The composite nano particles present a typical core-shell coating structure; nano ZnO, nano SiO2And ZnO @ SiO2The ultraviolet absorption spectrum of the composite nanoparticles is shown in fig. 4, and can be seen from fig. 4: ZnO @ SiO2The composite nano particles respectively show obvious ultraviolet absorption at the wavelengths of 202nm and 376nm, and can effectively improve the weather resistance of leather.
Accurately weigh 0.12g ZnO @ SiO2Adding the composite nano particles into 40mL of plant tannin (Tannins, 30-35% of effective substance, purchased from Strongylon chemical Co., Ltd.) to perform ultrasonic treatment (80W) at 25 ℃ for 25min, and then strongly and mechanically stirring at the rotating speed of 1000r/min for 2.5h to obtain ZnO @ SiO2Plant tannin compound tanning agent (marked as ZnO @ SiO)2/Tannin). Wherein ZnO @ SiO2The composite nanometer particles account for 1wt% of the effective matter content of the plant tannin. FIG. 1 shows nano zinc oxide (ZnO) and nano silicon dioxide (SiO)2）、ZnO@SiO2Composite nanoparticles (figure 1 a) and vegetable Tannin (Tannin), ZnO @ SiO2Comparative fourier spectra (fig. 1 b) of composite nanoparticle/plant tannin complexes (from example 2) and fig. 1 provides the molecular structure of the prepared samples, demonstrating the successful preparation of the target product. ZnO @ SiO2The UV absorption spectra of the/plant Tannin (Tannin) complex and pure plant Tannin (Tannin) are shown in FIG. 5, and can be seen from FIG. 5: ZnO @ SiO2The addition of the composite nano particles obviously improves the ultraviolet absorption of the plant tannin matrix.
ZnO @ SiO prepared in example 22Crust leather obtained by tanning sheep white wet leather with vegetable tannin complex tanning agent (the amount of tanning agent is 4wt% of the leather weight) the thickening rate is tested according to the following method: and selecting three positions along the direction vertical to the leather ridge line for thickness measurement, and taking the average value to obtain the thickness of the measured leather. Each place is againAnd respectively taking three points at different positions for thickness measurement, and then taking the average value of the three points as the thickness of the position of the skin. The thickness of the leather was measured using a model TX-3130-A3 digital thickness meter (available from Tianxiang measuring instruments, Inc., Dongguan). The thickening ratio was calculated as follows: Δ δ = [ (δ)2-δ1) /δ1] x 100%。
In the formula: delta is the thickening ratio (%) of the skin; delta1 Is the thickness of the white wet skin before tanning; delta2 Is the thickness of tanned leather
The thickening rate of the leather obtained by testing is 291%, and the utilization rate of the raw leather is greatly improved.
ZnO @ SiO prepared in example 22Leather shrinkage temperature was measured by the following method for crust leather obtained by tanning sheep white wet leather with vegetable tannin complex tanning agent (tanning agent used in 4wt% of leather weight): measuring the shrinkage temperature of leather by using a TX-3055 leather shrinkage temperature tester ((available from Tianxiang testing instruments Co., Ltd., Dongguan), cutting 3-5 10 mm x 60 mm sample strips from the edge of a crust leather sample to be measured, inserting the sample strips into a water bath, and keeping the sample length to be 2 mmoThe temperature rise rate of C/min is used for heating the bath liquid, the initial temperature when the leather sample strip is obviously shrunk is the shrinkage temperature of the leather, the shrinkage temperature of the leather obtained by testing is 86 ℃, and the requirement of the humidity and heat resistance stability of the leather in actual use can be met.
Example 3
Dispersing 0.02g of nano ZnO and 0.9g of polyethylene glycol (molecular weight is 8000, analytically pure, purchased from Mi Europe chemical reagent Co., Ltd. of Tianjin) in 100mL of absolute ethyl alcohol, adding 10mL of deionized water, carrying out ultrasonic (80W) treatment for 30min, then dropwise adding 5mL of ammonia water into the mixture, and carrying out ultrasonic (80W) treatment for 20min to obtain a solution I; dissolving 0.02mL of ethyl orthosilicate into 25mL of absolute ethyl alcohol to obtain a solution II, dropwise adding the solution II into the solution I, continuing to perform ultrasonic wave (800W, XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer purchased from Beijing Xiangkun scientific and technological development Limited) to react for 3 hours, centrifugally separating, repeatedly washing the solid with absolute ethyl alcohol, and performing vacuum drying at 60 ℃ to obtain ZnO @ SiO2The composite nano particles are ready for use. Accurately weighing 0.24g of composite nanoparticles, and adding the composite nanoparticles into 40mL of plant Tannin (Tannin, content of effective substances is 30-35%Purchased from Shitlang chemical Co., Ltd.) at 25 deg.C, ultrasonically treating at 80W for 30min, and strongly mechanically stirring at 1000r/min for 3h to obtain ZnO @ SiO2Plant tannin compound tanning agent (marked as ZnO @ SiO)2/Tannin). Wherein ZnO @ SiO2The composite nanometer particles account for 2wt% of the effective matter content of the plant tannin.
Example 4
Dispersing 0.02g of nano ZnO and 0.9g of polyethylene glycol (molecular weight is 8000, analytically pure, purchased from Tianjin, Kemiou chemical reagent Co., Ltd.) in 100mL of absolute ethyl alcohol, adding 10mL of deionized water, carrying out ultrasonic (80W) treatment for 30min, then dropwise adding 0.5mL of ammonia water, carrying out ultrasonic (80W) treatment for 10min to obtain a solution I, dissolving 0.04mL of ethyl orthosilicate in 25mL of ethyl alcohol to obtain a solution II, dropwise adding the solution II to the solution, continuing to carry out ultrasonic wave (800W, XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer, purchased from Beijing auspicious science and technology Co., Ltd.) to react for 2h, carrying out centrifugal separation, repeatedly washing the solid with absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain ZnO @ SiO2The composite nano particles are ready for use. Accurately weighing 0.48g of nano composite particles, adding the nano composite particles into 40mL of plant tannin (Tannins, available from Shanghai Shitzerlang chemical Co., Ltd., effective substance content of 30-35%), carrying out ultrasonic treatment (80W) at 25 ℃ for 35min, and then carrying out strong mechanical stirring at the rotating speed of 1000r/min for 3h to obtain ZnO @ SiO2Nano-particle/tannin composite tanning agent (marked as ZnO @ SiO)2/Tannin). Wherein ZnO @ SiO2The composite nanometer particles account for 4wt% of the effective matter content of the plant tannin.
Example 5
Dispersing 0.02g nanometer ZnO and 0.9g polyethylene glycol (molecular weight 8000, analytically pure, available from Tianjin, Kemiou chemical reagent Co., Ltd.) in 100mL absolute ethyl alcohol, adding 10mL deionized water, treating with ultrasound (80W) for 30min, adding 0.5mL ammonia water dropwise, treating with ultrasound (80W) for 10min to obtain solution I, dissolving 0.06mL ethyl orthosilicate in 25mL ethanol to obtain solution II, adding solution II, continuing to perform ultrasonic wave (800W, XH-300UL computer microwave ultrasonic ultraviolet light combined catalysis synthesizer available from Beijing auspicious science and technology Co., Ltd.) to react for 2h, centrifuging, and using absolute ethyl alcohol to obtain solidRepeatedly washing, and drying in vacuum at 60 ℃ to obtain ZnO @ SiO2The composite nano particles are ready for use. Accurately weighing 0.36g of nano composite particles, adding the nano composite particles into 40mL of plant Tannin (Tannin, 30-35% of effective substance content, purchased from Guangdong Fushan Steron chemical Co., Ltd.), carrying out ultrasonic treatment (80W) for 35min at 25 ℃, and then strongly and mechanically stirring for 3h at the rotating speed of 1000r/min to obtain ZnO @ SiO2Nano-particle/tannin composite tanning agent (marked as ZnO @ SiO)2/Tannin). Wherein ZnO @ SiO2The composite nanometer particles account for 3wt% of the effective matter content of the plant tannin.
Example 6
Dispersing 0.02g nanometer ZnO and 0.9g polyethylene glycol (molecular weight 8000, analytically pure, available from Tianjin, Kemiou chemical reagent Co., Ltd.) in 100mL absolute ethyl alcohol, adding 10mL deionized water, treating with ultrasound (80W) for 30min, adding 0.5mL ammonia water dropwise, treating with ultrasound (80W) for 10min to obtain solution I, dissolving 0.1mL ethyl orthosilicate in 25mL ethanol to obtain solution II, adding solution II, continuing to perform ultrasonic wave (800W, XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer available from Beijing auspicious science and technology Co., Ltd.) to react for 2.5h, centrifugally separating, repeatedly washing the solid with absolute ethyl alcohol, and vacuum drying at 60 ℃ to obtain ZnO @ SiO2The composite nano particles are ready for use. Accurately weighing 0.6g of nano composite particles, adding the nano composite particles into 40mL of plant Tannin (Tannin, 30-35% of effective substance, purchased from Guangdong Fushan Steron chemical Co., Ltd.), carrying out ultrasonic treatment (80W) for 40min at 25 ℃, and then strongly and mechanically stirring for 3.5h at the rotating speed of 1000r/min to obtain ZnO @ SiO2Nano-particle/tannin composite tanning agent (marked as ZnO @ SiO)2/Tannin). Wherein ZnO @ SiO2The composite nanometer particles account for 5wt% of the effective matter content of the plant tannin.
Example 7
Dispersing 0.02g of nano ZnO and 0.9g of polyethylene glycol (molecular weight is 8000, analytically pure, purchased from Miou chemical reagent Co., Ltd., Tianjin, City) in 100mL of ethanol, adding 10mL of deionized water, carrying out ultrasonic (80W) treatment for 30min, then dropwise adding 0.5mL of ammonia water, carrying out ultrasonic (80W) treatment for 10min to obtain a solution I, dissolving 0.2mL of ethyl orthosilicate in 25mL of ethanol to obtain a solution II, and dropwise adding the solution II to the solution IContinuously performing ultrasonic wave (800W, XH-300UL computer microwave ultrasonic ultraviolet light combined catalytic synthesizer, available from Beijing-Iukun scientific and technological development Co., Ltd.) for 3h, centrifuging, repeatedly washing the solid with anhydrous ethanol, and vacuum drying at 60 deg.C to obtain ZnO @ SiO2The composite nano particles are ready for use. Accurately weighing 0.72g of nano composite particles, adding the nano composite particles into 40mL of plant Tannin (Tannin, 30-35% of effective substance content, purchased from Guangdong Fushan Steron chemical Co., Ltd.), carrying out ultrasonic treatment (80W) for 1h at 25 ℃, and then strongly and mechanically stirring for 4h at the rotating speed of 1000r/min to obtain ZnO @ SiO2Nano-particle/tannin composite tanning agent (marked as ZnO @ SiO)2/Tannin). Wherein ZnO @ SiO2The composite nanometer particles account for 6wt% of the effective matter content of the plant tannin.
ZnO @ SiO obtained in example 1, example 4, example 5, example 6 and example 72The average particle diameters of the composite nanoparticles are shown in FIG. 7, and it is understood from FIG. 7 that the amounts of tetraethoxysilane are 0.02mL (example 1), 0.06mL (example 5), 0.1mL (example 6) and 0.2mL (example 7) of ZnO @ SiO2The average particle diameters of the composite nanoparticles were 343, 731nm, 990nm, and 1780nm, respectively.
Example 8
Except that the amount of ammonia added was changed to 0.2mL as compared with example 1.
Example 8, example 1, example 2 and example 3 ZnO @ SiO2The average particle diameters of the composite nanoparticles are shown in FIG. 6, and it is understood from FIG. 6 that the amounts of aqueous ammonia used in examples 8, 1, 2 and 3 were 0.2mL, 0.5mL, 1mL and 5mL, respectively, to obtain ZnO @ SiO2The average particle diameters of the composite nanoparticles were 307nm (prepared in example 8), 425nm (prepared in example 1), 601nm (prepared in example 2) and 1098nm (prepared in example 3), respectively.
TABLE 1 comparison of the white and wet skins of sheep tanned with different tanning agents (tanning agent amounts are 4wt% of the skin weight)
Table 1 shows the raw materials sheep white and wet leather, pure vegetable Tannin tanned leather (Tannin/L, the same below), ZnO/Tannin tanned leather (ZnO/Tannin/L, the same below) and ZnO @ SiO2the/Tannin composite (from example 2, prepared as ZnO @ SiO)2and/Tannin/L, the same below) were compared in series of properties, and the test instruments were a TC3000 thermal conductivity meter (available from west ann xiaxi electronics science and technology limited), a JF-3 oxygen index tester (available from jiangning district analytical instrument factory, south kyo), and a TX-3107 leather softness tester (available from tianxiang test instruments limited, east guan). It can be seen that: ZnO @ SiO2The air permeability (the higher the heat conductivity coefficient of the leather is, the better the air permeability of the leather) and the softness and the flame retardant property (the higher the limited oxygen index of the leather is, the better the flame retardant property of the leather) of the/Tannin compound tanned leather are obviously improved.
TABLE 2 comparison of the physical and mechanical properties of white and wet sheep skins tanned with different tanning agents (the tanning agent amounts are 4wt% of the leather weight, according to the requirements of Chinese and ISO standards for clothing leather, QB/T2710-
Table 2 shows pure vegetable Tannin tanned leather, ZnO/Tannin and ZnO @ SiO2Comparison of the physical and mechanical properties of tanned leather/Tannin composite (from example 2) with a WDM-20E electronic universal tester (available from Lissangsi instruments Ltd., Jinan). It can be seen that: ZnO @ SiO2The maximum load, tensile strength, breaking strength and breaking elongation of the/Tannin compound tanned leather are all obviously improved.
TABLE 3 ZnO @ SiO of different particle diameters2ZnO @ SiO prepared from composite nano particles2Comparison of physical and mechanical properties of white and wet sheep leather tanned by Tannin composite tanning agent (the amount of the tanning agent is 4wt% of the leather weight, according to the requirements of Chinese standard and ISO standard of clothing leather, QB/T2710-
Table 3 shows ZnO @ SiO particles of different particle diameters2ZnO @ SiO prepared from composite nano particles2The physical and mechanical properties of the/Tannin compound tanning agent are compared, and a testing instrument is a WDM-20E electronic universal testing machine (purchased from Jinan Hengsi Shengda instruments Co., Ltd.) and a TX-5227 leather cracking testing machine (purchased from Tianxiang testing instruments Co., Ltd., Dongguan). It can be seen that: ZnO @ SiO with particle size of 425-731 nm2The maximum load, the tensile strength, the breaking elongation, the cracking strength and the cracking height of the composite nano-particle tanned leather are obviously superior to those of ZnO @ SiO in other particle size ranges2Physical properties of the composite nanoparticle tanned leather.
TABLE 4 different particle sizes ZnO @ SiO2ZnO @ SiO prepared from composite nano particles2Comparison of tanning Performance with Tannin Complex tanning agent (the tanning agent amounts are 4wt% of the tare weight, in reference to the requirements of Chinese Standard and ISO Standard for clothing leather, QB/T2710-
Table 4 shows ZnO @ SiO films having different particle diameters2ZnO @ SiO prepared from composite nano particles2The performance comparison of the Tannin compound tanning agent is that a TC3000 thermal conductivity coefficient instrument (purchased from Xian Xixi electronic technology Co., Ltd.), a TX-3107 leather softness tester (purchased from Tianxiang tester Co., Ltd. of Dongguan) and a JF-3 oxygen index tester (purchased from Jiangning district analytical instrument factory of Nanjing) are respectively used as the testing instruments. It can be seen that: ZnO @ SiO with particle size of 425-731 nm2The air permeability (the higher the heat conductivity coefficient of the leather is, the better the air permeability of the leather) and the softness and the flame retardant property (the higher the limited oxygen index of the leather is, the better the flame retardant property of the leather) of the/Tannin compound tanned leather are all superior to ZnO @ SiO in other particle size ranges2Tanning performance of composite nano particles.
Claims (9)
1. A preparation method of a silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent with controllable particle size is characterized by comprising the following steps:
ZnO @ SiO with the particle size of 300-1800 nm2Adding the composite nano particles into the plant tannin, performing ultrasonic dispersion to form uniform dispersion liquid, and mechanically stirring at room temperature for 2-4 hours to obtain ZnO @ SiO with different particle sizes2Composite nanoparticle/vegetable tannin complex tanning agent, ZnO @ SiO2The composite nanometer particles account for 0.25 to 6 weight percent of the content of the effective substances of the plant tannin matrix, and ZnO @ SiO with different particle diameters2The preparation process of the composite nanometer particle is as follows:
(1) adding nano ZnO and polyethylene glycol into a mixed solvent of absolute ethyl alcohol and deionized water, and performing ultrasonic dispersion and uniform mixing to obtain a solution I, wherein the mass ratio of the nano ZnO to the polyethylene glycol is (0.01-0.03): 0.8-1.0;
(2) dropwise adding ammonia water into the solution I, and uniformly mixing to obtain a solution II;
(3) dissolving ethyl orthosilicate into ethanol to obtain solution (c); the mass ratio of the nano ZnO to the tetraethoxysilane is 1: 0.9-10; the volume ratio of the ammonia water to the ethyl orthosilicate is (0.01-5): 0.02-0.2;
(4) adding the solution III into the solution II, carrying out ultrasonic reaction for 2-3 h, carrying out centrifugal separation on the obtained sample, collecting solids, washing and drying to obtain ZnO @ SiO with the particle size of 300-1800 nm2And (3) compounding the nanoparticles.
2. The preparation method of the particle size controllable silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent as claimed in claim 1, wherein when the amount of nano ZnO is 0.02g and the amount of tetraethoxysilane is 0.02mL, the amount of ZnO @ SiO @ in the process of using ammonia water in the amount of 0.01 to 5mL2The particle size of the composite nano particles is increased from 307nm to 1098 nm.
3. The method for preparing the silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent with controllable particle size as claimed in claim 1, wherein when the amount of nano ZnO is 0.02g and the amount of ammonia water is 0.02g, the tanning agent is preparedWhen the volume is 0.5mL, the dosage of the tetraethyl silicate is 0.02-0.2 mL, ZnO @ SiO2The particle size of the composite nano particles is increased from 343nm to 1780 nm.
4. The method for preparing the silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent with controllable particle size according to claim 1, wherein the molecular weight of the polyethylene glycol is 400-20000.
5. The method for preparing the particle size-controllable tanning agent of silica-coated zinc oxide composite nanoparticles/vegetable tannin compound according to claim 1, wherein ZnO @ SiO2The range of the composite nanometer particles is 400 nm-750 nm.
6. The method for preparing the particle size-controllable tanning agent of silica-coated zinc oxide composite nanoparticles/vegetable tannin compound according to claim 1, wherein ZnO @ SiO2The amount of the composite nanoparticles is 0.03-1.0 g.
7. The method for preparing the particle size-controllable silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent according to claim 1, wherein the vegetable tannin is condensed tannin, and the content of active ingredients is 30-35 wt%.
8. A silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent prepared by the preparation method as set forth in any one of claims 1 to 7.
9. The application of the silica-coated zinc oxide composite nano particle/vegetable tannin composite tanning agent in leather tanning as claimed in claim 8, wherein the usage amount of the tanning agent is 4-6 wt% of the weight of leather.
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| DE2822075A1 (en) * | 1978-05-20 | 1979-11-22 | Henkel Kgaa | Water-insoluble aluminium silicate used in leather mfr. - contain alkali-, di:- and tri:valent ions and have coarser particle size |
| CN102127604A (en) * | 2011-02-18 | 2011-07-20 | 四川大学 | Tannin-laponite chromium-free combined tanning method for manufacturing leather |
| CN106609308A (en) * | 2016-12-25 | 2017-05-03 | 常州市鼎日环保科技有限公司 | Preparation method of environment-friendly chromium-free tanning agent |
| CN107201413A (en) * | 2017-06-28 | 2017-09-26 | 常州美帛纺织品有限公司 | A kind of chrome-free tanning agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2822075A1 (en) * | 1978-05-20 | 1979-11-22 | Henkel Kgaa | Water-insoluble aluminium silicate used in leather mfr. - contain alkali-, di:- and tri:valent ions and have coarser particle size |
| CN102127604A (en) * | 2011-02-18 | 2011-07-20 | 四川大学 | Tannin-laponite chromium-free combined tanning method for manufacturing leather |
| CN106609308A (en) * | 2016-12-25 | 2017-05-03 | 常州市鼎日环保科技有限公司 | Preparation method of environment-friendly chromium-free tanning agent |
| CN107201413A (en) * | 2017-06-28 | 2017-09-26 | 常州美帛纺织品有限公司 | A kind of chrome-free tanning agent and preparation method thereof |
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