WO2018086247A1

WO2018086247A1 - Nano-composite fatliquor based on synergistic anti-mould of alkyl glycoside and nano-silver and preparation method therefor

Info

Publication number: WO2018086247A1
Application number: PCT/CN2017/071040
Authority: WO
Inventors: 马建中; 高建静; 吕斌
Original assignee: 陕西科技大学; 马建中; 高建静; 吕斌
Priority date: 2016-11-11
Filing date: 2017-01-13
Publication date: 2018-05-17
Also published as: DE112017005674T5; CN106755636B; DE112017005674B4; CN106755636A

Abstract

Disclosed are a nano-composite fatliquor based on synergistic anti-mould of an alkyl glycoside and a nano-silver, and a preparation method therefor. The method comprises the following steps: adding alkyl glycoside and a sodium borohydride solution into a silver nitrate solution in an ice bath for a reaction to obtain a nano-silver-alkyl glycoside solution; adding 1-allyloxy-2,3-epoxypropane into soybean phospholipid, then adding formic acid and concentrated sulfuric acid, and adding hydrogen peroxide dropwise; after adjusting the pH, adding a sodium bisulfite solution dropwise to obtain a polyhydric soybean phospholipid fatliquor, and adding the nano-silver-alkyl glycoside solution to prepare the anti-mould nano-composite fatliquor.

Description

Nano composite fatliquor based on synergistic mildew resistance of alkyl glycoside and nano silver and preparation method thereof

Technical field

The invention relates to a nano-composite fatliquor, in particular to a nano-composite fatliquor based on synergistic mildew prevention of alkyl glycosides and nano-silver and a preparation method thereof.

Background technique

The tanning industry is one of the traditional industries in China and has a long history. However, the use of leather products in the process of use, transportation and storage will be mildew, affecting the appearance and performance of the leather. There are two main reasons for the mildew of leather: on the one hand, because the main component of the animal skin used for tanning is collagen, it is easy to contaminate the animal skin during the preservation process (Sharma P., Sharma KD. Utilization of fatliquors by fungi[J].Defence Science Journal,1980,30(2):93-94;Deng Yunxia,Du Wei,Zhu Xiaowei, et al.Study on the antifungal effect of leather materials and their products[J].China Leather , 2010, 39 (11): 22-24), the modified skin collagen has been denatured into a cross-linking protein that is not susceptible to mold. On the other hand, due to the chemicals added during the processing of leather, especially the fat added in the fatliquoring process, it will be used by microorganisms to provide a nutrient matrix for the growth of microorganisms (Alois O.. Microbial biodeterioration of leather and its control: a Review [J]. International Biodeterioration & Biodegradation, 2004, 53(3): 157-163). The proliferation of microorganisms, especially molds, has seriously affected the quality, appearance and performance of leather products. Therefore, the mildew of leather, especially the anti-mildew of fatliquors, is a tannery. A problem that cannot be ignored.

At present, the main solution for tanners is to directly add anti-fungal agents to the fatliquor, or to add anti-mold agents in the fatliquoring process. These two methods generally have poor combination, long-term effect, and serious environmental pollution. Other disadvantages (Farhana M., Elisabeth G., Rais A., et al. Environmental deterioration and human health: natural and anthropogenic determinants [M]. London/New York: Springer Dordrecht Heidelberg; Peng Huijuan, Sang Jun, Yu Lingyun, etc. . Leather anti-corrosion and anti-mold chemicals and their environmental risk analysis [J]. China Leather, 2014, 43 (15): 48-50). In addition to the traditional anti-mold materials, there are two kinds of environmentally-friendly anti-mold materials that are currently studied. One is to use the special nano-size of nano-materials to adsorb microorganisms, thereby achieving the effect of inhibiting and killing mold. The other is to use some natural materials or derivatives thereof to prevent mildew, such as chitosan, alkyl glycosides, chitin, mugwort, comfrey, etc., wherein alkyl glycosides are a kind of green environmental protection. Non-ionic natural surfactant with strong detergency, good compatibility, mild, non-toxic, biodegradable and broad-spectrum antibacterial properties (Liu YM, Tao JL, Jiao S., et al. Removing) Polysaccharides-and saccharides-related coloring impurities in alkyl polyglycosides by bleaching with the H ₂ O ₂ /TAED/NaHCO ₃ system[J].Carbohydrate Polymers,2014,112(4):416-421;Karlheinz H.,Wolfgang VR, Gerhard S.. Alkyl Polyglycosides: Technology, Properties and Applications [M]. Germany: Wiley-VCH (Wiley-VCH Verlag GmbH & Co. KGaA), 1997: 1-2). Therefore, combined with the emerging green anti-mold material, the preparation of a compound fatliquor with good anti-mildew effect provides an effective way to solve the problem that the leather product is prone to mildew.

Summary of the invention

The object of the present invention is to provide a nano-composite fatliquor based on synergistic mildew resistance between alkyl glycoside and nano-silver and a preparation method thereof, which overcome the disadvantages of fat-promoting and fat-removing leather products.

The technical solution adopted by the invention is:

A method for preparing a nano-composite fatliquor based on synergistic mildew resistance between an alkyl glycoside and nano-silver, characterized in that:

Includes the following steps:

Step 1: Preparation of nano silver-alkyl glycoside solution:

Take 10 parts by volume and a molar volume fraction of 0.01 mol·L ^-1 silver nitrate solution in a beaker. Add 10 to 20 parts by volume and a molar volume fraction of 0.01 mol·L ^-1 under magnetic stirring. After the alkyl glycoside is fully mixed, slowly add 25-25 parts by volume, a molar volume fraction of 0.02 mol·L ^-1 sodium borohydride solution, and react in an ice bath for 30-60 min to obtain a stable nano-silver-alkane. Glycoside solution;

Step 2: Preparation of polyhydroxy soybean phospholipid fatliquor:

The mass fraction is 45-50 parts of soybean phospholipid in a three-necked flask, and then 1 to 1.5 parts by mass of 1-allyloxy-2,3-epoxypropane is added, and the temperature is raised to 50 ° C, and the temperature is reacted for 3 hours. Then, a mass fraction of 1.7-2.2 parts of formic acid, 0.48 parts of concentrated sulfuric acid is added, and 23 to 26 parts by mass of hydrogen peroxide is slowly added dropwise to the three-necked flask, and the temperature is raised to 60 ° C for 4 hours; For the pH adjuster, adjust the pH to 7.5, add 23-25 parts by volume, 40% by volume of sodium bisulfite solution, and raise the temperature to 80 ° C for 2 h; use a volume fraction of 40%. Sodium hydroxide adjusts the pH of the system to 6-7, stirring After 30 minutes, a polyhydroxy soybean phospholipid fatliquor is obtained;

Step 3: Obtain a mold-proof nanocomposite fatliquor:

Take 50 parts of polyhydroxy soybean phospholipid fatliquor in a three-necked flask, add 20-30 parts of nano-silver-alkyl glycoside solution at a constant temperature of 50 ° C, stir for 30 min, and prepare antifungal nanocomposite. Fatliquor.

A nanocomposite fatliquor prepared by the method for preparing a nanocomposite fatliquor based on synergistic mildew resistance of an alkyl glycoside and nanosilver.

The invention has the following advantages:

In the present invention, by multi-modification of soybean phospholipids, the number of unsaturated bonds on the oil-based substrate is reduced, and the growth and reproduction of the mold are structurally suppressed. Secondly, the present invention combines inorganic anti-mold materials and organic anti-mold materials. Anti-mildew property, the obtained alkyl glucoside and nano-silver in the composite fatliquor exhibit good synergistic anti-mildew effect, further enhance the anti-fungal property of the nano-composite fatliquor, and is an excellent and green leather. Fatliquor, cheap raw materials, and good market applicability.

DRAWINGS

Figure 1 shows the results of the mold resistance test of leather on Aspergillus flavus (ATCC 10836) after fatliquoring.

Figure 2 shows the results of the mold resistance test of the leather after the fatliquoring against Trichoderma viride (IFO 31137).

Among them, Figures 1 and 2 are observation photos of different mold strains growing for four days and seven days respectively. The A test sample is a polyhydroxy soy lecithin fatliquor after fatliquoring and crust leather; the B test sample is based on alkyl glycoside and nano silver. The leather of the nano-composite fatliquor after fatliquoring.

detailed description

The invention will now be described in detail in connection with the specific embodiments.

The invention adopts the natural material derivative alkyl glycoside and the inorganic material nano silver as raw materials, combines the anti-mildew property of the inorganic anti-mold material and the organic anti-mold material, and introduces the soybean to the soybean with less unsaturated bond by the blending method. In the phospholipid fatliquor, a nanocomposite fatliquor having good mold resistance is prepared. The anti-fungal nano-composite fatliquor prepared by the method has good placement stability and emulsion stability, and the particle size is small and easy to penetrate into the leather fiber; the leather has good mechanical properties after fatliquoring, and has excellent mold resistance. .

The invention relates to a method for preparing a nano-composite fatliquor based on synergistic mildew resistance between an alkyl glycoside and nano-silver, comprising the following steps:

Step 1: Preparation of nano silver-alkyl glycoside solution:

Step 2: Preparation of polyhydroxy soybean phospholipid fatliquor:

The mass fraction is 45-50 parts of soybean phospholipid in a three-necked flask, and then 1 to 1.5 parts by mass of 1-allyloxy-2,3-epoxypropane is added, and the temperature is raised to 50 ° C, and the temperature is reacted for 3 hours. Then, a mass fraction of 1.7-2.2 parts of formic acid, 0.48 parts of concentrated sulfuric acid is added, and 23 to 26 parts by mass of hydrogen peroxide is slowly added dropwise to the three-necked flask, and the temperature is raised to 60 ° C for 4 hours; For the pH adjuster, adjust the pH to 7.5, and add the mass fraction as 23～25 parts, 40% volume of sodium bisulfite solution, the system is heated to 80 ° C, the reaction is 2h; adjust the pH of the system to 6~7 with sodium hydroxide with a volume fraction of 40%, and obtain more after stirring for 30min. Hydroxy soybean phospholipid fatliquor;

Step 3: Obtain a mold-proof nanocomposite fatliquor:

Example 1:

Take 10 parts by volume of 0.01 mol·L ^-1 silver nitrate solution in a beaker, add 10 parts by volume of 0.01 mol·L ^-1 alkyl glycoside under magnetic stirring, mix well and then slowly A volume fraction of 27 parts of 0.02 mol·L ^-1 sodium borohydride solution was added, and the reaction was carried out for 30 min in an ice bath to obtain a stable nanosilver-alkyl glycoside solution.

The mass fraction was 46 parts of soybean phospholipid in a three-necked flask, and then 1.2 parts by mass of 1-allyloxy-2,3-epoxypropane was added thereto, and the temperature was raised to 50 ° C, and the reaction was carried out at a constant temperature for 3 hours; The parts are 1.8 parts of formic acid, 0.48 parts of concentrated sulfuric acid, and 25 parts by mass of hydrogen peroxide is slowly added dropwise to a three-necked flask, and the temperature is raised to 60 ° C for 4 hours; the pH is adjusted with ammonia water as a pH adjuster. 7.5, adding 24 parts by weight of 40% sodium hydrogen sulfite solution, heating the system to 80 ° C, reaction for 2 h; adjusting the pH of the system to 6.5 with 40% sodium hydroxide, stirring for 30 min to obtain polyhydroxy soy phospholipid Fatliquor.

Take 50 parts by mass of polyhydroxy soybean phospholipid fatliquor in a three-necked flask, add 20 parts by mass of nano silver-alkyl glycoside solution, and keep at 50 ° C for 30 min to prepare mold-proof nanocomposite fatliquoring. Agent.

Example 2:

Take 10 parts by volume of 0.01 mol·L ^-1 silver nitrate solution in a beaker, add 20 parts by volume of 0.01 mol·L ^-1 alkyl glycoside under magnetic stirring, mix well and then slowly A volume fraction of 35 parts of 0.02 mol·L ^-1 sodium borohydride solution was added, and the reaction was carried out for 60 min in an ice bath to obtain a stable nanosilver-alkyl glycoside solution.

Take 50 parts by mass of soybean phospholipid in a three-necked flask, add 1.5 parts by mass of 1-allyloxy-2,3-epoxypropane, heat to 50 ° C, and react at constant temperature for 3 h; then add mass. The parts are 2.2 parts of formic acid, 0.48 parts of concentrated sulfuric acid, and 26 parts by mass of hydrogen peroxide is slowly added dropwise to a three-necked flask, and the temperature is raised to 60 ° C for 4 hours; the pH is adjusted with ammonia water as a pH adjuster. 7.5, add 25 parts by weight of 40% sodium hydrogen sulfite solution, heat the system to 80 ° C, and react for 2 h; adjust the pH of the system to 7 with 40% sodium hydroxide, and obtain polyhydroxy soy phospholipid after stirring for 30 min. Fatliquor.

Take 50 parts of polyhydroxy soybean phospholipid fatliquor in a three-necked flask, add 29 parts by mass of nano-silver-alkyl glycoside solution, keep at 50 ° C, stir for 30 min, and prepare anti-mold nano-composite fatliquoring Agent.

Example 3:

Take 10 parts by volume of 0.01 mol·L ^-1 silver nitrate solution in a beaker, add 16 parts by volume of 0.01 mol·L ^-1 alkyl glycoside under magnetic stirring, mix well and then slowly A volume fraction of 26 parts of 0.02 mol·L ^-1 sodium borohydride solution was added, and the reaction was carried out for 50 min in an ice bath to obtain a stable nanosilver-alkyl glycoside solution.

The mass fraction was 47 parts of soybean phospholipid in a three-necked flask, and then 1.4 parts by mass of 1-allyloxy-2,3-epoxypropane was added thereto, and the temperature was raised to 50 ° C, and the reaction was carried out at a constant temperature for 3 hours; Adding 1.9 parts by mass of formic acid and 0.48 parts of concentrated sulfuric acid, and adding 25 parts by mass of hydrogen peroxide to the three-necked flask slowly, and heating to 60 ° C for 4 hours; adjusting with ammonia as a pH adjuster pH to 7.5, 24 parts by mass of 40% sodium hydrogen sulfite solution was added dropwise, the system was heated to 80 ° C, and reacted for 2 h; the pH of the system was adjusted to 6 with 40% sodium hydroxide, and the polyhydroxyl group was obtained after stirring for 30 min. Soybean phospholipid fatliquor.

Take 50 parts of polyhydroxy soybean phospholipid fatliquor in a three-necked flask, add 23 parts by mass of nano-silver-alkyl glycoside solution, and keep at 50 ° C for 30 min to prepare mold-proof nanocomposite fatliquoring. Agent.

Example 4:

Take 10 parts by volume of 0.01 mol·L ^-1 silver nitrate solution in a beaker, and add 12 parts by volume of 0.01 mol·L ^-1 alkyl glycoside under magnetic stirring, mix well and then slowly. A volume fraction of 25 parts of 0.02 mol·L ^-1 sodium borohydride solution was added, and the reaction was carried out for 40 min in an ice bath to obtain a stable nanosilver-alkyl glycoside solution.

Take 45 parts by mass of soybean phospholipid in a three-necked flask, add 1.3 parts by mass of 1-allyloxy-2,3-epoxypropane, heat to 50 ° C, and react at constant temperature for 3 h; then add mass. The parts are 2.0 parts of formic acid, 0.48 parts of concentrated sulfuric acid, 23 parts by mass of hydrogen peroxide is slowly added dropwise to a three-necked flask, and the temperature is raised to 60 ° C for 4 hours; the pH is adjusted with ammonia water as a pH adjuster. 7.5, add 24 parts by mass of 40% sodium hydrogen sulfite solution, heat the system to 80 ° C, react for 2 h; adjust the pH of the system to 7 with 40% sodium hydroxide, and obtain polyhydroxy soy phospholipid after stirring for 30 min. Fatliquor.

Take 50 parts of polyhydroxy soybean phospholipid fatliquor in a three-necked flask, add 30 parts by mass of nano-silver-alkyl glycoside solution, keep at 50 ° C, stir for 30 min. A mold-resistant nanocomposite fatliquor is prepared.

The anti-fungal nanocomposite fatliquor based on alkyl glycoside and nanosilver prepared according to the preparation method of the invention has good placement stability and emulsion stability, and the emulsion has a small particle size and is easy to penetrate into the interior of the leather fiber; It has good mechanical properties and excellent mildew resistance. It is an excellent and environmentally-friendly leather fatliquor with good market applicability.

The goat skin blue wet leather was fatliquored by using the prepared nano-composite fatliquor based on the synergistic anti-mildew of the alkyl glycoside and the nano-silver. The test results of the mildew resistance of the leather to Aspergillus flavus and Trichoderma viride were shown in Fig. 1. And 2 are shown. It can be seen from Fig. 1 and 2 that the antifungal property of the leather after fatliquoring without the addition of alkyl glycoside and nanosilver is obviously stronger than that of the leather after adding the nanocomposite fatliquor with alkyl glycoside and nanosilver. Mildew performance is relatively poor. In the culture environment of high-concentration mold, the nano-composite fatliquor based on alkyl glycoside and nano-silver has a small inhibition zone after fatliquoring, and no mold is proliferated on the surface of the crust. Has good mold resistance.

The content of the present invention is not limited to the embodiments, and any equivalent changes to the technical solutions of the present invention will be covered by the claims of the present invention.

Claims

A method for preparing a nano-composite fatliquor based on synergistic mildew resistance between an alkyl glycoside and nano-silver, characterized in that:

Includes the following steps:

Step 1: Preparation of nano silver-alkyl glycoside solution:

Take 10 parts by volume and a molar volume fraction of 0.01 mol·L -1 silver nitrate solution in a beaker. Add 10 to 20 parts by volume and a molar volume fraction of 0.01 mol·L -1 under magnetic stirring. After the alkyl glycoside is fully mixed, slowly add 25-25 parts by volume, a molar volume fraction of 0.02 mol·L -1 sodium borohydride solution, and react in an ice bath for 30-60 min to obtain a stable nano-silver-alkane. Glycoside solution;

Step 2: Preparation of polyhydroxy soybean phospholipid fatliquor:

The mass fraction is 45-50 parts of soybean phospholipid in a three-necked flask, and then 1 to 1.5 parts by mass of 1-allyloxy-2,3-epoxypropane is added, and the temperature is raised to 50 ° C, and the temperature is reacted for 3 hours. Then, a mass fraction of 1.7-2.2 parts of formic acid, 0.48 parts of concentrated sulfuric acid is added, and 23 to 26 parts by mass of hydrogen peroxide is slowly added dropwise to the three-necked flask, and the temperature is raised to 60 ° C for 4 hours; For the pH adjuster, adjust the pH to 7.5, add 23-25 parts by volume, 40% by volume of sodium bisulfite solution, and raise the temperature to 80 ° C for 2 h; use a volume fraction of 40%. The pH of the sodium hydroxide system is adjusted to 6-7, and the polyhydroxy soybean phospholipid fatliquor is obtained after stirring for 30 minutes;

Step 3: Obtain a mold-proof nanocomposite fatliquor:

Take 50 parts by mass of polyhydroxy soybean phospholipid fatliquor in a three-necked flask and add The mass fraction is 20-30 parts of nano silver-alkyl glycoside solution, the temperature is 50 ° C, and the mixture is stirred for 30 min to prepare a mold-proof nano composite fatliquor.
The nanocomposite fatliquor prepared by the method for preparing a nanocomposite fatliquor based on synergistic mildew prevention of an alkyl glycoside and nanosilver according to claim 1.