CN107881266A - In-situ method prepares layered double hydroxide/polymer nanocomposite composite leather retanning agent and its method with hyperchromic effect - Google Patents
In-situ method prepares layered double hydroxide/polymer nanocomposite composite leather retanning agent and its method with hyperchromic effect Download PDFInfo
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- CN107881266A CN107881266A CN201711085294.2A CN201711085294A CN107881266A CN 107881266 A CN107881266 A CN 107881266A CN 201711085294 A CN201711085294 A CN 201711085294A CN 107881266 A CN107881266 A CN 107881266A
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- Prior art keywords
- layered double
- double hydroxide
- retanning agent
- polymer nanocomposite
- hyperchromic effect
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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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to the method that in-situ method prepares layered double hydroxide/polymer nanocomposite composite leather retanning agent with hyperchromic effect.Adversely affected to eliminate caused by the Retanning Agent on Leather dyeing containing a large amount of anionic groups, there is electropositive layered double hydroxide to be added in polymer retanning agent laminate, obtained composite can play good absorption property to anionic dye, fatting agent etc..Monomer is entered layered double hydroxide interlayer by the present invention first under ultrasound condition by ion exchange intercalation, triggers monomer in situ polymerization to obtain the layered double hydroxide/polymer nanocomposite composite leather retanning agent with hyperchromic effect afterwards.Layered double hydroxide with hyperchromic effect prepared by the present invention/polymer nanocomposite composite leather retanning agent, the dye level of leather can be made to improve 23%, pliability and improve 50%, tensile strength raising 30%, dyeing the COD of waste liquid reduces by 15%.
Description
Technical field
The present invention relates to a kind of leather composite tanning agent, and in particular to a kind of in-situ method prepares the double gold of the stratiform with hyperchromic effect
Belong to hydroxide/polymer nanocomposite composite leather retanning agent and its method.
Background technology
Retanning is the vital process of process hides, and the leather after retanning has good physical property, as fullness,
The grain degree of packing, dyeing uniformity etc., retanning agent is diffused in leather fiber, absorbs, precipitated during retanning, is main tan
The important stage of leather quality-improving afterwards, therefore retanning is referred to as " Golden Touch " in leather making process.In the main tan process of rawhide
In mostly using chromium powder carry out tanning, it is usually the case that retanning is primarily directed to chrome leather.The essence of chrome tanning is collagen egg
Combined in vain with chromic compound, the wet blue leather surface obtained after main tan is positively charged, after it is combined with anionic property retanning agent, subtracts
The binding site of anionic dye and collagen when having lacked dyeing, so as to influence the dye-uptake of dyestuff, makes the crust leather tone after dyeing
It is not full, often produce so-called " losing colour " phenomenon.For eliminate the retanning agent containing a large amount of anionic groups to dyeing caused by not
Profit influences, and retanning agent of the exploitation with hyperchromic effect is particularly important.
Layered double hydroxide（Layered Double Hydroxides）Be one kind by negatively charged anion
（Interlayer anion）With positively charged metal hydroxides（Main layer board）The lamellar compound formed.Due to the double gold of stratiform
Belong to the electropositive of hydroxide laminate, make it that there is good absorption property for anionic dye, fatting agent etc..But due to
Leather processing is carried out by medium of water, and dispersive property difference of the layered double hydroxide in water can limit it in skin
Remove from office the application of industry.Layered double hydroxide/polymer nanocomposite composite leather retanning agent had been obtained both using situ aggregation method
Can solve scattering problem of the layered double hydroxide in aqueous systems, can solve to exist containing a large amount of anionic polymers again
Using " losing colour " phenomenon being also easy to produce in leather, while absorption of the leather to other anion materials is improved, available can be excellent
Different leather and fur products.
The content of the invention
It is an object of the invention to provide a kind of in-situ method to prepare layered double hydroxide/polymerization with hyperchromic effect
Thing nano composite leather retanning agent and its method, the application of the retanning agent can improve the dyeability, pliability and machine of leather
Tool performance, and reduce the COD value of dyeing waste liquid.
The technical solution adopted in the present invention is：
In-situ method prepares the side of layered double hydroxide/polymer nanocomposite composite leather retanning agent with hyperchromic effect
Method, it is characterised in that comprise the following steps：
（1）Acrylic acid 7.2g, layered double hydroxide 0.1-0.5g, distilled water 20g are added in beaker, above-mentioned substance is existed
Adjust pH to be placed in ultrasonic 5-15min under ultrasonic cell disruptor for 5.0 after being well mixed in beaker, obtain acrylic acid intercalation
Layered double hydroxide solution；
（2）Weigh ALS 3.65g to be dissolved in 8g water, allyl sulphonic acid sodium water solution is obtained after stirring；
（3）The step is added in the three-necked flask equipped with agitator and condensing unit（1）Whole acrylic acid intercalations layer
Shape double-metal hydroxide solution, diallyldimethylammonium chloride 11.3g, ammonium persulfate 0.6-3g, distilled water 9-15g, is stirred
Mix and be warming up to 60-85 DEG C；
（4）By the step（2）Obtained 11.65g allyl sulphonic acids sodium water solution is to step（3）Dripped in described three-necked flask
Add 20-40min, afterwards isothermal reaction 3-7h, cool down, discharging, the layered double hydroxide for obtaining that there is hyperchromic effect/gather
Compound nano composite leather retanning agent.
Described in-situ method prepares layered double hydroxide/polymer nanocomposite composite leather with hyperchromic effect and answered
Obtained layered double hydroxide/polymer nanocomposite composite leather the retanning agent with hyperchromic effect of the method for tanning agent.
The present invention has advantages below：
The present invention prepares layered double hydroxide/polymer nanocomposite composite leather with hyperchromic effect using in-situ method and answered
Regular intercalation configuration is presented in tanning agent.It is added during leather retanning, the layered double hydroxide laminate of positive electricity
Be advantageous to absorption of the retanning later stage to materials such as anionic dye, fatting agents, can avoid dyeing later stage appearance " losing colour " phenomenon, carry
High Leather Properties, reduce the Organic Pollution of waste liquid.Layered double hydroxide/polymer nanocomposite composite leather retanning agent exists
After being applied in leather retanning, the dye level of leather can be made to improve 23%, pliability and improve 50%, tensile strength raising 30%, dye
The COD of color waste liquid reduces by 15%.
Embodiment
With reference to embodiment, the present invention will be described in detail.
It is compound that in-situ method of the present invention prepares layered double hydroxide/polymer nanocomposite with hyperchromic effect
The method of leather composite tanning agent, is realized by following steps：
（1）Acrylic acid 7.2g, layered double hydroxide 0.1-0.5g, distilled water 20g are added in beaker, above-mentioned substance is existed
Adjust pH to be placed in ultrasonic 5-15min under ultrasonic cell disruptor for 5.0 after being well mixed in beaker, obtain acrylic acid intercalation
Layered double hydroxide solution；
（2）Weigh ALS 3.65g to be dissolved in 8g water, allyl sulphonic acid sodium water solution is obtained after stirring；
（3）The step is added in the three-necked flask equipped with agitator and condensing unit（1）Whole acrylic acid intercalations layer
Shape double-metal hydroxide solution, diallyldimethylammonium chloride 11.3g, ammonium persulfate 0.6-3g, distilled water 9-15g, is stirred
Mix and be warming up to 60-85 DEG C；
（4）By the step（2）Obtained 11.65g allyl sulphonic acids sodium water solution is to step（3）Dripped in described three-necked flask
Add 20-40min, afterwards isothermal reaction 3-7h, cool down, discharging, the layered double hydroxide for obtaining that there is hyperchromic effect/gather
Compound nano composite leather retanning agent.
Described in-situ method prepares layered double hydroxide/polymer nanocomposite composite leather with hyperchromic effect and answered
Obtained layered double hydroxide/polymer nanocomposite composite leather the retanning agent with hyperchromic effect of the method for tanning agent.
Embodiment 1
Acrylic acid 7.2g, layered double hydroxide 0.17g, distilled water 20g are added in beaker, by above-mentioned substance in beaker
Adjust pH to be placed in ultrasonic 5min under ultrasonic cell disruptor for 5.0 after well mixed, obtain the double gold of stratiform of acrylic acid intercalation
Belong to hydroxide solution；Weigh ALS 3.65g to be dissolved in 8g water, ALS water is obtained after stirring
Solution；The layered double hydroxide that acrylic acid intercalation is added in the three-necked flask equipped with agitator and condensing unit is molten
Liquid, diallyldimethylammonium chloride 11.3g, ammonium persulfate 0.7g, distilled water 9g, stir pi-allyl sulphur after being warming up to 60 DEG C
20min is added dropwise into three-necked flask by acid sodium aqueous solution 11.65g, afterwards isothermal reaction 4h, cools down, discharging, obtains having the deep effect of increasing
The layered double hydroxide answered/polymer nanocomposite composite leather retanning agent.
Embodiment 2
Acrylic acid 7.2g, layered double hydroxide 0.5g, distilled water 20g are added in beaker, by above-mentioned substance in beaker
Adjust pH to be placed in ultrasonic 15min under ultrasonic cell disruptor for 5.0 after well mixed, obtain the double gold of stratiform of acrylic acid intercalation
Belong to hydroxide solution；Weigh ALS 3.65g to be dissolved in 8g water, ALS water is obtained after stirring
Solution；The layered double hydroxide that acrylic acid intercalation is added in the three-necked flask equipped with agitator and condensing unit is molten
Liquid, diallyldimethylammonium chloride 11.3g, ammonium persulfate 2.7g, distilled water 15g, stir pi-allyl after being warming up to 85 DEG C
40min is added dropwise into three-necked flask by sulfonic acid sodium water solution 11.65g, afterwards isothermal reaction 7h, cools down, discharging, obtains having increasing deep
The layered double hydroxide of effect/polymer nanocomposite composite leather retanning agent.
Embodiment 3
Acrylic acid 7.2g, layered double hydroxide 0.34g, distilled water 20g are added in beaker, by above-mentioned substance in beaker
Adjust pH to be placed in ultrasonic 10min under ultrasonic cell disruptor for 5.0 after well mixed, obtain the double gold of stratiform of acrylic acid intercalation
Belong to hydroxide solution；Weigh ALS 3.65g to be dissolved in 8g water, ALS water is obtained after stirring
Solution；The layered double hydroxide that acrylic acid intercalation is added in the three-necked flask equipped with agitator and condensing unit is molten
Liquid, diallyldimethylammonium chloride 11.3g, ammonium persulfate 2g, distilled water 18g, stir pi-allyl sulphur after being warming up to 80 DEG C
35min is added dropwise into three-necked flask by acid sodium aqueous solution 11.65g, afterwards isothermal reaction 5h, cools down, discharging, obtains having the deep effect of increasing
The layered double hydroxide answered/polymer nanocomposite composite leather retanning agent.
Embodiment 4
Acrylic acid 7.2g, layered double hydroxide 0.25g, distilled water 20g are added in beaker, by above-mentioned substance in beaker
Adjust pH to be placed in ultrasonic 10min under ultrasonic cell disruptor for 5.0 after well mixed, obtain the double gold of stratiform of acrylic acid intercalation
Belong to hydroxide solution；Weigh ALS 3.65g to be dissolved in 8g water, ALS water is obtained after stirring
Solution；The layered double hydroxide that acrylic acid intercalation is added in the three-necked flask equipped with agitator and condensing unit is molten
Liquid, diallyldimethylammonium chloride 11.3g, ammonium persulfate 2.38g, distilled water 14g, stir pi-allyl after being warming up to 80 DEG C
30min is added dropwise into three-necked flask by sulfonic acid sodium water solution 11.65g, afterwards isothermal reaction 6h, cools down, discharging, obtains having increasing deep
The layered double hydroxide of effect/polymer nanocomposite composite leather retanning agent.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is that claim of the invention is covered.
Claims (2)
1. in-situ method prepares the side of layered double hydroxide/polymer nanocomposite composite leather retanning agent with hyperchromic effect
Method, it is characterised in that comprise the following steps：
（1）Acrylic acid 7.2g, layered double hydroxide 0.1-0.5g, distilled water 20g are added in beaker, above-mentioned substance is existed
Adjust pH to be placed in ultrasonic 5-15min under ultrasonic cell disruptor for 5.0 after being well mixed in beaker, obtain acrylic acid intercalation
Layered double hydroxide solution；
（2）Weigh ALS 3.65g to be dissolved in 8g water, allyl sulphonic acid sodium water solution is obtained after stirring；
（3）The step is added in the three-necked flask equipped with agitator and condensing unit（1）Whole acrylic acid intercalations layer
Shape double-metal hydroxide solution, diallyldimethylammonium chloride 11.3g, ammonium persulfate 0.6-3g, distilled water 9-15g, is stirred
Mix and be warming up to 60-85 DEG C；
（4）By the step（2）Obtained 11.65g allyl sulphonic acids sodium water solution is to step（3）Dripped in described three-necked flask
Add 20-40min, afterwards isothermal reaction 3-7h, cool down, discharging, the layered double hydroxide for obtaining that there is hyperchromic effect/gather
Compound nano composite leather retanning agent.
2. in-situ method as claimed in claim 1 prepares layered double hydroxide/polymer nanocomposite with hyperchromic effect
Obtained layered double hydroxide/polymer nanocomposite the composite leather with hyperchromic effect of the method for composite leather retanning agent
Retanning agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711085294.2A CN107881266B (en) | 2017-11-07 | 2017-11-07 | In-situ method for preparing layered double-metal hydroxide/polymer nano composite leather retanning agent with deepening effect and method thereof |
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| CN201711085294.2A CN107881266B (en) | 2017-11-07 | 2017-11-07 | In-situ method for preparing layered double-metal hydroxide/polymer nano composite leather retanning agent with deepening effect and method thereof |
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| CN107881266A true CN107881266A (en) | 2018-04-06 |
| CN107881266B CN107881266B (en) | 2020-05-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358877A (en) * | 2019-06-04 | 2019-10-22 | 陕西科技大学 | Acrylic/hydrotalcite-like nano tanning agent with layer structure and preparation method thereof and tannage |
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 |
-
2017
- 2017-11-07 CN CN201711085294.2A patent/CN107881266B/en active Active
Patent 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358877A (en) * | 2019-06-04 | 2019-10-22 | 陕西科技大学 | Acrylic/hydrotalcite-like nano tanning agent with layer structure and preparation method thereof and tannage |
| CN110358877B (en) * | 2019-06-04 | 2021-10-26 | 陕西科技大学 | Hydrotalcite-like nano tanning agent with layered structure and preparation method and tanning method thereof |
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| CN107881266B (en) | 2020-05-19 |
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