CN107881266B - In-situ method for preparing layered double-metal hydroxide/polymer nano composite leather retanning agent with deepening effect and method thereof - Google Patents
In-situ method for preparing layered double-metal hydroxide/polymer nano composite leather retanning agent with deepening effect and method thereof Download PDFInfo
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- CN107881266B CN107881266B CN201711085294.2A CN201711085294A CN107881266B CN 107881266 B CN107881266 B CN 107881266B CN 201711085294 A CN201711085294 A CN 201711085294A CN 107881266 B CN107881266 B CN 107881266B
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- double hydroxide
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to a method for preparing a layered double hydroxide/polymer nano composite leather retanning agent with a deepening effect by an in-situ method. In order to eliminate the adverse effect of the retanning agent containing a large number of anionic groups on leather dyeing, the layered double hydroxide with electropositive laminate is added into the polymer retanning agent, and the obtained composite material can have good adsorption performance on anionic dye, fatliquor and the like. Firstly, under the ultrasonic condition, a monomer enters the interlayer of the layered double hydroxide through an ion exchange intercalation, and then the monomer is initiated to polymerize in situ to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect. The layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect, which is prepared by the invention, can improve the dyeing depth of leather by 23%, improve the softness by 50%, improve the tensile strength by 30% and reduce the COD of dyeing waste liquid by 15%.
Description
Technical Field
The invention relates to a leather retanning agent, in particular to a layered double-metal hydroxide/polymer nano composite leather retanning agent with a deepening effect prepared by an in-situ method and a method thereof.
Background
Retanning is a vital process for tanning, leather after being retanned has good physical properties such as fullness, grain surface compactness, dyeing uniformity and the like, and a retanning agent is diffused, absorbed and precipitated in leather fibers in the retanning process and is an important stage for improving the quality of the leather after main tanning, so that retanning is called 'gold spotting' in the tanning process. Chrome powder is mostly used for tanning during the main tanning of hides, so retanning is usually mainly aimed at chrome tanning. The essence of chrome tanning is that collagen is combined with a chromium complex, the surface of wet blue leather obtained after main tanning is positively charged, and when the wet blue leather is combined with an anionic retanning agent, the combination points of anionic dye and leather collagen during dyeing are reduced, so that the dye-uptake is influenced, the dyed crust leather is not full in color tone, and the phenomenon of so-called 'color losing' is often generated. In order to eliminate the adverse effect of the retanning agent containing a large number of anionic groups on dyeing, the development of the retanning agent with the darkening effect is particularly important.
Layered Double Hydroxides (Layered Double Hydroxides) are Layered compounds composed of negatively charged anions (interlayer anions) and positively charged metal Hydroxides (main layer plates). Due to the electropositivity of the layered double hydroxide laminate, the laminate has good adsorption performance on anionic dye, fatting agent and the like. However, because leather processing is carried out by taking water as a medium, the poor dispersibility of the layered double hydroxide in water can limit the application of the layered double hydroxide in the leather industry. The layered double hydroxide/polymer nano composite leather retanning agent obtained by adopting an in-situ polymerization method can solve the dispersion problem of the layered double hydroxide in a water system, can also solve the phenomenon of 'color losing' easily caused by applying a large amount of anionic polymer in leather, and simultaneously improves the absorption of the leather to other anionic materials, so that a leather product with excellent performance can be obtained.
Disclosure of Invention
The invention aims to provide a layered double hydroxide/polymer nano composite leather retanning agent with a darkening effect prepared by an in-situ method and a method thereof.
The technical scheme adopted by the invention is as follows:
the method for preparing the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect by the in-situ method is characterized by comprising the following steps of:
(1) adding 7.2g of acrylic acid, 0.1-0.5g of layered double hydroxide and 20g of distilled water into a beaker, uniformly mixing the substances in the beaker, adjusting the pH value to 5.0, placing the mixture in an ultrasonic cell crusher, and performing ultrasonic treatment for 5-15min to obtain an acrylic acid intercalated layered double hydroxide solution;
(2) weighing 3.65g of sodium allylsulfonate, dissolving in 8g of water, and uniformly stirring to obtain a sodium allylsulfonate aqueous solution;
(3) adding 11.3g of diallyl dimethyl ammonium chloride, 0.6-3g of ammonium persulfate and 9-15g of distilled water into the layered double hydroxide solution with the whole acrylic acid intercalation in the step (1) in a three-neck flask provided with a stirrer and a condensing device, and stirring and heating to 60-85 ℃;
(4) and (3) dropwise adding 11.65g of sodium allylsulfonate aqueous solution obtained in the step (2) into the three-neck flask obtained in the step (3) for 20-40min, reacting at a constant temperature for 3-7h, cooling, and discharging to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect.
The layered double metal hydroxide/polymer nano composite leather retanning agent with the deepening effect is prepared by the method for preparing the layered double metal hydroxide/polymer nano composite leather retanning agent with the deepening effect by the in-situ method.
The invention has the following advantages:
the invention adopts an in-situ method to prepare the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect, and the layered double hydroxide/polymer nano composite leather retanning agent has a regular intercalation structure. The layered double-metal hydroxide laminate with positive electricity is added in the leather retanning process, so that the layered double-metal hydroxide laminate with positive electricity is beneficial to the absorption of chemical materials such as anionic dye, fatting agent and the like in the later retanning period, the phenomenon of 'color losing' in the later dyeing period can be avoided, the leather performance is improved, and the organic pollution of waste liquid is reduced. After the layered double hydroxide/polymer nano composite leather retanning agent is applied to leather retanning, the dyeing depth of leather can be improved by 23%, the softness can be improved by 50%, the tensile strength can be improved by 30%, and the COD of dyeing waste liquid can be reduced by 15%.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention relates to a method for preparing a layered double hydroxide/polymer nano composite leather retanning agent with a deepening effect by an in-situ method, which is realized by the following steps:
(1) adding 7.2g of acrylic acid, 0.1-0.5g of layered double hydroxide and 20g of distilled water into a beaker, uniformly mixing the substances in the beaker, adjusting the pH value to 5.0, placing the mixture in an ultrasonic cell crusher, and performing ultrasonic treatment for 5-15min to obtain an acrylic acid intercalated layered double hydroxide solution;
(2) weighing 3.65g of sodium allylsulfonate, dissolving in 8g of water, and uniformly stirring to obtain a sodium allylsulfonate aqueous solution;
(3) adding 11.3g of diallyl dimethyl ammonium chloride, 0.6-3g of ammonium persulfate and 9-15g of distilled water into the layered double hydroxide solution with the whole acrylic acid intercalation in the step (1) in a three-neck flask provided with a stirrer and a condensing device, and stirring and heating to 60-85 ℃;
(4) and (3) dropwise adding 11.65g of sodium allylsulfonate aqueous solution obtained in the step (2) into the three-neck flask obtained in the step (3) for 20-40min, reacting at a constant temperature for 3-7h, cooling, and discharging to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect.
The layered double metal hydroxide/polymer nano composite leather retanning agent with the deepening effect is prepared by the method for preparing the layered double metal hydroxide/polymer nano composite leather retanning agent with the deepening effect by the in-situ method.
Example 1
Adding 7.2g of acrylic acid, 0.17g of layered double hydroxide and 20g of distilled water into a beaker, uniformly mixing the substances in the beaker, adjusting the pH value to 5.0, placing the mixture in an ultrasonic cell crusher, and performing ultrasonic treatment for 5min to obtain an acrylic acid intercalated layered double hydroxide solution; weighing 3.65g of sodium allylsulfonate, dissolving in 8g of water, and uniformly stirring to obtain a sodium allylsulfonate aqueous solution; adding an acrylic acid intercalated layered double hydroxide solution, 11.3g of diallyl dimethyl ammonium chloride, 0.7g of ammonium persulfate and 9g of distilled water into a three-neck flask provided with a stirrer and a condensing device, stirring and heating to 60 ℃, dropwise adding 11.65g of sodium allylsulfonate aqueous solution into the three-neck flask for 20min, then carrying out constant temperature reaction for 4h, cooling and discharging to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect.
Example 2
Adding 7.2g of acrylic acid, 0.5g of layered double hydroxide and 20g of distilled water into a beaker, uniformly mixing the substances in the beaker, adjusting the pH value to 5.0, placing the mixture in an ultrasonic cell crusher, and performing ultrasonic treatment for 15min to obtain an acrylic acid intercalated layered double hydroxide solution; weighing 3.65g of sodium allylsulfonate, dissolving in 8g of water, and uniformly stirring to obtain a sodium allylsulfonate aqueous solution; adding an acrylic acid intercalated layered double hydroxide solution, 11.3g of diallyl dimethyl ammonium chloride, 2.7g of ammonium persulfate and 15g of distilled water into a three-neck flask provided with a stirrer and a condensing device, stirring and heating to 85 ℃, dropwise adding 11.65g of sodium allylsulfonate aqueous solution into the three-neck flask for 40min, then carrying out constant temperature reaction for 7h, cooling, and discharging to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect.
Example 3
Adding 7.2g of acrylic acid, 0.34g of layered double hydroxide and 20g of distilled water into a beaker, uniformly mixing the substances in the beaker, adjusting the pH value to 5.0, placing the mixture in an ultrasonic cell crusher, and performing ultrasonic treatment for 10min to obtain an acrylic acid intercalated layered double hydroxide solution; weighing 3.65g of sodium allylsulfonate, dissolving in 8g of water, and uniformly stirring to obtain a sodium allylsulfonate aqueous solution; adding an acrylic acid intercalated layered double hydroxide solution, 11.3g of diallyl dimethyl ammonium chloride, 2g of ammonium persulfate and 18g of distilled water into a three-neck flask provided with a stirrer and a condensing device, stirring and heating to 80 ℃, dropwise adding 11.65g of sodium allylsulfonate aqueous solution into the three-neck flask for 35min, then reacting for 5h at a constant temperature, cooling and discharging to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect.
Example 4
Adding 7.2g of acrylic acid, 0.25g of layered double hydroxide and 20g of distilled water into a beaker, uniformly mixing the substances in the beaker, adjusting the pH value to 5.0, placing the mixture in an ultrasonic cell crusher, and performing ultrasonic treatment for 10min to obtain an acrylic acid intercalated layered double hydroxide solution; weighing 3.65g of sodium allylsulfonate, dissolving in 8g of water, and uniformly stirring to obtain a sodium allylsulfonate aqueous solution; adding an acrylic acid intercalated layered double hydroxide solution, 11.3g of diallyl dimethyl ammonium chloride, 2.38g of ammonium persulfate and 14g of distilled water into a three-neck flask provided with a stirrer and a condensing device, stirring and heating to 80 ℃, dropwise adding 11.65g of sodium allylsulfonate aqueous solution into the three-neck flask for 30min, then carrying out constant temperature reaction for 6h, cooling and discharging to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (2)
1. The method for preparing the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect by the in-situ method is characterized by comprising the following steps of:
(1) adding 7.2g of acrylic acid, 0.1-0.5g of layered double hydroxide and 20g of distilled water into a beaker, uniformly mixing the substances in the beaker, adjusting the pH value to 5.0, placing the mixture in an ultrasonic cell crusher, and performing ultrasonic treatment for 5-15min to obtain an acrylic acid intercalated layered double hydroxide solution;
(2) weighing 3.65g of sodium allylsulfonate, dissolving in 8g of water, and uniformly stirring to obtain a sodium allylsulfonate aqueous solution;
(3) adding 11.3g of diallyl dimethyl ammonium chloride, 0.6-3g of ammonium persulfate and 9-15g of distilled water into the layered double hydroxide solution with the whole acrylic acid intercalation in the step (1) in a three-neck flask provided with a stirrer and a condensing device, and stirring and heating to 60-85 ℃;
(4) and (3) dropwise adding 11.65g of sodium allylsulfonate aqueous solution obtained in the step (2) into the three-neck flask obtained in the step (3) for 20-40min, reacting at a constant temperature for 3-7h, cooling, and discharging to obtain the layered double hydroxide/polymer nano composite leather retanning agent with the deepening effect.
2. The layered double hydroxide/polymer nanocomposite leather retanning agent with darkening effect prepared by the method for preparing the layered double hydroxide/polymer nanocomposite leather retanning agent with darkening effect according to the in-situ method of claim 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619366A (en) * | 2009-07-21 | 2010-01-06 | 陕西科技大学 | Preparation method of amphoteric vinyl polymer/ZnO nanocomposite tanning agent |
| CN101864022A (en) * | 2010-06-17 | 2010-10-20 | 陕西科技大学 | Method for preparing vinyl polymer/inorganic nanoparticle composite tanning agent by in-situ cyclopolymerization method |
| CN105949369A (en) * | 2016-06-17 | 2016-09-21 | 陕西科技大学 | Preparation method of multi-functional hydrotalcite/polymer nano-composite additive for leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619366A (en) * | 2009-07-21 | 2010-01-06 | 陕西科技大学 | Preparation method of amphoteric vinyl polymer/ZnO nanocomposite tanning agent |
| CN101864022A (en) * | 2010-06-17 | 2010-10-20 | 陕西科技大学 | Method for preparing vinyl polymer/inorganic nanoparticle composite tanning agent by in-situ cyclopolymerization method |
| CN105949369A (en) * | 2016-06-17 | 2016-09-21 | 陕西科技大学 | Preparation method of multi-functional hydrotalcite/polymer nano-composite additive for leather |
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