CN110358877A - Acrylic/hydrotalcite-like nano tanning agent with layer structure and preparation method thereof and tannage - Google Patents
Acrylic/hydrotalcite-like nano tanning agent with layer structure and preparation method thereof and tannage Download PDFInfo
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- CN110358877A CN110358877A CN201910480143.XA CN201910480143A CN110358877A CN 110358877 A CN110358877 A CN 110358877A CN 201910480143 A CN201910480143 A CN 201910480143A CN 110358877 A CN110358877 A CN 110358877A
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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
- C14C3/28—Multi-step processes
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Abstract
Acrylic/hydrotalcite-like nano tanning agent that the invention discloses a kind of with layer structure and preparation method thereof and tannage, technical solution are as follows: magnesium, aluminium, the nitrate of X and water is taken to be mixed and made into solution A respectively, X is one of chromium, iron, zirconium, zinc, sodium carbonate and water are mixed and made into solution B, and sodium hydroxide and water are mixed and made into solution C；Under conditions of 300 r/min stirring, solution A, solution C are added dropwise in solution B simultaneously, after being added dropwise to complete, 10 h of crystallization at 80 DEG C, gained sediment centrifugation is drying to obtain the acrylic/hydrotalcite-like nano tanning agent with layer structure.Using acrylic/hydrotalcite-like nano tanning agent tanning prepared by the present invention, gained crust leather shrinkage temperature can promote being absorbed and utilized for the anion dyeing and finishing chemicals such as dyestuff, fatting agent in after-tanning wet operation, finished leather made to have good dyeing uniformity and flexibility up to 75 DEG C or more.
Description
Technical field
The invention belongs to leather tanning process fields, and in particular to a kind of acrylic/hydrotalcite-like nano tanning agent with layer structure
And its tannage.
Background technique
Chrome tanning is one of leather tanning most mature in current leather industry, and it is good comprehensive can to assign leather
Can, it occupies an leading position in global leather industry all the time, but traditional chrome tanning is in after-tanning wet process, storage and use process
Cr (III) is easily oxidized to the Cr (VI) with potential carcinogenic risk, and the chromed leather wastes generated in leather making process are deposited
In certain processing pressure.Therefore, the use of chrome tanning agent how is avoided or reduced, the pollution that chrome tanning generates is reduced, is realized clear
Clean tanning, it has also become the important directions of leather industry sustainable development.
In recent years, researchers are conceived to Application of micron in tanning technology, realize cleaning tanning.According to document report
Road, layered nanoclay can improve the hydrothermal stability of leather in conjunction with materials with hide glue fibril.But such as montmorillonite, lithium soap soil
It is negatively charged etc. natural or synthetic layered nanoclay surface, it is unfavorable for the anion dyeing and finishing such as tanning later period dyestuff, fatting agent
The absorption of product.Houghite is a kind of layer dihydroxy formed by interlayer anion and positively charged laminate ordered fabrication
Complex metal hydroxide forms adjustable, main layer board charge density with main layer board metal ion and its distribution is adjustable
The features such as, it is biomedical, in terms of be widely used.It has been reported that houghite can
A kind of organosilicon/inorganic nano-hybrid material is formed by hydrogen bond, electrostatic interaction etc. between protein and other,
And collagen is a kind of natural polymer with polyampholyte property, this makes houghite shape in conjunction with collagenous fibres
It is possibly realized at leather matrix.
Summary of the invention
The invention aims to provide a kind of acrylic/hydrotalcite-like nano tanning agent and its tannage with layer structure, the tanning agent
It is raw materials used cheap and easy to get and preparation is simple, crust leather shrinkage temperature obtained by tanning is used for up to 75 DEG C or more；
The thermal stability of finished leather can be improved, promote the absorption benefit of the anion dyeing and finishing chemicals such as dyestuff, fatting agent in after-tanning wet operation
With, make finished leather have good dyeing uniformity and flexibility.
A kind of preparation method of the acrylic/hydrotalcite-like nano tanning agent with layer structure, take respectively magnesium, aluminium, X nitrate with
Water is mixed and made into solution A, magnesium, aluminium, X molar ratio be 20:9 ~ 5:1 ~ 5, X is one of chromium, iron, zirconium, zinc, sodium carbonate and water
It is mixed and made into solution B, sodium hydroxide and water are mixed and made into solution C；Under conditions of 300 r/min stirring, by solution A, solution C
It is added dropwise in solution B simultaneously, after being added dropwise to complete, 10 h of crystallization at 80 DEG C, gained sediment is centrifuged, is drying to obtain with layer
The acrylic/hydrotalcite-like nano tanning agent of shape structure.
The nitrate anion substance withdrawl syndrome of above-mentioned solution A is 1 mol/L, and the substance withdrawl syndrome of solution B is 1 mol/L,
The substance withdrawl syndrome of solution C is 2 mol/L.
Above-mentioned solution A, solution B, the volume ratio of solution C are 1:1:1.
Softening Pi Yushui is added in rotary drum first, softens the quality of Pi Yushui by a kind of tannage using above-mentioned tanning agent
Than for 1:1 ~ 1.5, adding 7% ~ 8% sodium chloride of tare weight, rotate 30 min, later with formic acid solution adjust bath foam pH value to
2.5 ~ 3.5, continue to rotate 30 min；It is subsequently added into the acrylic/hydrotalcite-like nano tanning agent of the 0.5% ~ 8% of tare weight, rotates 3 ~ 8 h, then
Bath foam pH value is adjusted to 4.0 ~ 6.0 with sodium bicarbonate solution, continues to rotate 30 min；Stop drum and stands 24 h, next day rotation 30
Min, washing.
The tanning endpoint pH of above-mentioned tannage is 4.0 ~ 6.0.
The mass ratio of formic acid and water in above-mentioned formic acid solution is 1:10, the matter of sodium bicarbonate and water in sodium bicarbonate solution
Amount is than being 1:10.
Compared with prior art, the beneficial effects of the present invention are:
1) present invention introduces the metal salts with certain flexibility, and acrylic/hydrotalcite-like nano is made by coprecipitation under given conditions
Tanning agent provides a kind of acrylic/hydrotalcite-like nano tanning agent with layer structure；
2) the acrylic/hydrotalcite-like nano tanning agent tanning is used, gained crust leather shrinkage temperature is up to 75 DEG C or more；
3) the permanent electropositive of houghite plate layer assigns leather fiber positive charge, can promote dyestuff, fatting agent in after-tanning wet operation
Equal anion dyeing and finishing chemicals is absorbed and utilized, and finished leather is made to have good dyeing uniformity and flexibility.
Detailed description of the invention
Fig. 1 is acrylic/hydrotalcite-like nano tanning agent tanning crust leather shrinkage temperature；
Fig. 2 is acrylic/hydrotalcite-like nano tanning agent and negatively charged natural clay and the dye-uptake for synthesizing clay.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but embodiments of the present invention include
But it is not limited to the range of following embodiment expression.
Embodiment 1:
The preparation of acrylic/hydrotalcite-like nano tanning agent:
Take magnesium, aluminium, the nitrate of zirconium and water to be mixed and made into solution A respectively, magnesium, aluminium, zirconium molar ratio be 20:8:2, sodium carbonate with
Water is mixed and made into solution B, and sodium hydroxide and water are mixed and made into solution C；Then under conditions of 300 r/min are stirred, by solution
A, C simultaneously be added dropwise in the reaction vessel containing solution B, after being added dropwise to complete at 80 DEG C 10 h of crystallization, gained sediment pass through from
The heart is drying to obtain the acrylic/hydrotalcite-like nano tanning agent with layer structure；
The nitrate anion substance withdrawl syndrome of above-mentioned solution A is 1 mol/L, and the substance withdrawl syndrome of solution B is 1 mol/L, solution C
Substance withdrawl syndrome be 2 mol/L.
Above-mentioned solution A, solution B, the volume ratio of solution C are 1:1:1.
Tanning:
Softening Pi Yushui is added in rotary drum first, the mass ratio for softening Pi Yushui is 1:1, adds 8% chlorine of tare weight
Change sodium, rotate 30 min, adjusts bath foam pH value to 2.5 with formic acid solution later, continue to rotate 30 min；Then to above-mentioned bath foam
It is middle be added tare weight 3% according to acrylic/hydrotalcite-like nano tanning agent made from above-mentioned preparation method, rotate 3 h, then use sodium bicarbonate
Solution adjusts bath foam pH value to 4.5, continues to rotate 30 min；Stop drum and stand 24 h, next day rotates 30 min, washing.
Embodiment 2:
The preparation of acrylic/hydrotalcite-like nano tanning agent:
Take magnesium, aluminium, the nitrate of chromium and water to be mixed and made into solution A respectively, magnesium, aluminium, chromium molar ratio be 20:7:3, sodium carbonate with
Water is mixed and made into solution B, and sodium hydroxide and water are mixed and made into solution C；Then under conditions of 300 r/min are stirred, by solution
A, C simultaneously be added dropwise in the reaction vessel containing solution B, after being added dropwise to complete at 80 DEG C 10 h of crystallization, gained sediment pass through from
The heart is drying to obtain the acrylic/hydrotalcite-like nano tanning agent with layer structure；
The nitrate anion substance withdrawl syndrome of above-mentioned solution A is 1 mol/L, and the substance withdrawl syndrome of solution B is 1 mol/L, solution C
Substance withdrawl syndrome be 2 mol/L.
Above-mentioned solution A, solution B, the volume ratio of solution C are 1:1:1.
Tanning:
Softening Pi Yushui is added in rotary drum first, the mass ratio for softening Pi Yushui is 1:1.5, adds the 8% of tare weight
Sodium chloride rotates 30 min, adjusts bath foam pH value to 3.0 with formic acid solution later, continues to rotate 30 min；Then to above-mentioned bath
Be added in liquid the 5% of tare weight according to acrylic/hydrotalcite-like nano tanning agent made from above-mentioned preparation method, rotate 8 h, then use bicarbonate
Sodium solution adjusts bath foam pH value to 6.0, continues to rotate 30 min；Stop drum and stand 24 h, next day rotates 30 min, washing.
Embodiment 3:
The preparation of acrylic/hydrotalcite-like nano tanning agent:
Take zinc, aluminium, the nitrate of zirconium and water to be mixed and made into solution A respectively, magnesium, aluminium, iron molar ratio be 20:6:4, sodium carbonate with
Water is mixed and made into solution B, and sodium hydroxide and water are mixed and made into solution C；Then under conditions of 300 r/min are stirred, by solution
A, C simultaneously be added dropwise in the reaction vessel containing solution B, after being added dropwise to complete at 80 DEG C 10 h of crystallization, gained sediment pass through from
The heart is drying to obtain the acrylic/hydrotalcite-like nano tanning agent with layer structure；
The nitrate anion substance withdrawl syndrome of above-mentioned solution A is 1 mol/L, and the substance withdrawl syndrome of solution B is 1 mol/L, solution C
Substance withdrawl syndrome be 2 mol/L.
Above-mentioned solution A, solution B, the volume ratio of solution C are 1:1:1.
Tanning:
Softening Pi Yushui is added in rotary drum first, the mass ratio for softening Pi Yushui is 1:1.3, adds the 8% of tare weight
Sodium chloride rotates 30 min, adjusts bath foam pH value to 3.0 with formic acid solution later, continues to rotate 30 min；Then to above-mentioned bath
Be added in liquid the 8% of tare weight according to acrylic/hydrotalcite-like nano tanning agent made from above-mentioned preparation method, rotate 5 h, then use bicarbonate
Sodium solution adjusts bath foam pH value to 5.0, continues to rotate 30 min；Stop drum and stand 24 h, next day rotates 30 min, washing.
Referring to Fig. 1, in Fig. 1,0#For pure crust leather, 1#For embodiment 1,2#For embodiment 2,3#For embodiment 3, implementation is used
Acrylic/hydrotalcite-like nano tanning agent tanning made from example, gained crust leather shrinkage temperature is up to 75 DEG C or more.
Etc. quality use the negatively charged natural clay and conjunction of acrylic/hydrotalcite-like nano tanning agent and surface respectively with position pickled skin
After clay tanning, the wet ornamenting process of table 1 is first passed around, then measurement dyeing front and back dyestuff absorbance, contaminates thereon to calculate
Rate.Dye-uptake can be obtained by following formula:
R=C
0
-C/C
0
=A
0
-A/A
0
Wherein R is dye-uptake,C 0 It is dye liquor concentration before contaminating,CIt is dye liquor concentration after contaminating,A 0 It is dye liquor absorbance before contaminating,AAfter being dye
Dye liquor absorbance.
Table 1: the negatively charged natural clay of acrylic/hydrotalcite-like nano tanning agent and surface and the synthesis wet finishing process of clay
| Process | Material | Dosage/% | Temperature/DEG C | Time/min | Remarks |
| Washing | Water | 300 | Room temperature | 10 | Drain |
| Retanning, dyeing | Water | 150 | 30 | ||
| Acrylic acid double tanning agent | 12 | 10 | |||
| Orchil | 3 | 90 | Drain | ||
| It is fixed | Water | 150 | 45 | 10 | |
| Formic acid | 1.5~2 | 20*3 | PH ~ 4.0-4.5, drain | ||
| Stuffing | Water | 150 | 45 | ||
| NCS lecithin fatting agent | 12 | 90 | |||
| Fixation | Formic acid | 2.0 | 20*3 | PH ~ 3.5 are washed out and are roused |
By calculating, the data in Fig. 2 are obtained, acrylic/hydrotalcite-like nano tanning agent dye-uptake is 82.41%, higher than negatively charged day
Right clay and synthesis clay illustrate that acrylic/hydrotalcite-like nano tanning agent produced by the present invention can promote dyestuff, stuffing in after-tanning wet operation
The anion dyeing and finishing chemicals such as agent is absorbed and utilized, and finished leather is made to have good dyeing uniformity and flexibility.
Claims (7)
1. a kind of preparation method of the acrylic/hydrotalcite-like nano tanning agent with layer structure, it is characterised in that:
Magnesium, aluminium, the nitrate of X and water is taken to be mixed and made into solution A respectively, X is one of chromium, iron, zirconium, zinc, and magnesium, aluminium, X rub
, than being mixed and made into solution B for 20:9 ~ 5:1 ~ 5, sodium carbonate and water, sodium hydroxide and water are mixed and made into solution C for you；In 300 r/
Under conditions of min stirring, solution A, solution C are added dropwise in solution B simultaneously, after being added dropwise to complete, 10 h of crystallization at 80 DEG C, institute
Sediment is obtained to be centrifuged, be drying to obtain the acrylic/hydrotalcite-like nano tanning agent with layer structure.
2. the preparation method of the acrylic/hydrotalcite-like nano tanning agent according to claim 1 with layer structure, it is characterised in that:
The nitrate anion substance withdrawl syndrome of the solution A is 1 mol/L, and the substance withdrawl syndrome of solution B is 1 mol/L, solution C
Substance withdrawl syndrome be 2 mol/L.
3. a kind of preparation method of acrylic/hydrotalcite-like nano tanning agent with layer structure according to claim 2, feature
It is:
The solution A, solution B, the volume ratio of solution C are 1:1:1.
4. a kind of acrylic/hydrotalcite-like nano tanning agent with layer structure being prepared as described in claim 1-3.
5. a kind of tannage using claim 4 tanning agent, it is characterised in that:
First softening Pi Yushui is added in rotary drum, the mass ratio for softening Pi Yushui is 1:1 ~ 1.5, adds the 7% ~ 8% of tare weight
Sodium chloride, rotate 30 min, later with formic acid solution adjust bath foam pH value to 2.5 ~ 3.5, continue to rotate 30 min；Then plus
Enter the acrylic/hydrotalcite-like nano tanning agent of the 0.5% ~ 8% of tare weight, rotate 3 ~ 8 h, then with sodium bicarbonate solution adjust bath foam pH value to
4.0 ~ 6.0, continue to rotate 30 min；Stop drum and stand 24 h, next day rotates 30 min, washing.
6. a kind of tannage according to claim 5, it is characterised in that:
The tanning endpoint pH of the tannage is 4.0 ~ 6.0.
7. a kind of tannage according to claim 6, it is characterised in that:
The mass ratio of formic acid and water in the formic acid solution is 1:10, the mass ratio of sodium bicarbonate and water in sodium bicarbonate solution
For 1:10.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004877A (en) * | 2019-12-30 | 2020-04-14 | 陕西科技大学 | Nano tanning agent based on structure memory effect and preparation method and application thereof |
| CN112094962A (en) * | 2020-09-11 | 2020-12-18 | 陕西科技大学 | Method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid |
| CN113073160A (en) * | 2021-04-29 | 2021-07-06 | 陕西科技大学 | Carboxylic acid ligand MOFs nano tanning agent with stable framework structure and preparation method and application thereof |
| CN113999943A (en) * | 2021-11-15 | 2022-02-01 | 陕西科技大学 | Polysaccharide-based hydrotalcite nano composite tanning agent and preparation method and application thereof |
| CN114164308A (en) * | 2021-11-18 | 2022-03-11 | 陕西科技大学 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
| CN114350860A (en) * | 2022-01-20 | 2022-04-15 | 陕西科技大学 | Non-chromium tanning process based on hydrotalcite and zirconium sulfate |
| CN114369690A (en) * | 2022-01-20 | 2022-04-19 | 陕西科技大学 | Preparation method and tanning method of supermolecular intercalation structure nano tanning agent |
| CN116219086A (en) * | 2023-02-07 | 2023-06-06 | 陕西科技大学 | Flame-retardant ecological automobile leather and production process thereof |
| CN116287488A (en) * | 2023-03-20 | 2023-06-23 | 浙江理工大学 | Method for protecting soft-back of cracked hard leather cultural relics |
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Cited By (13)
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| CN111004877B (en) * | 2019-12-30 | 2021-10-26 | 陕西科技大学 | Nano tanning agent based on structure memory effect and preparation method and application thereof |
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| CN112094962A (en) * | 2020-09-11 | 2020-12-18 | 陕西科技大学 | Method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid |
| CN113073160A (en) * | 2021-04-29 | 2021-07-06 | 陕西科技大学 | Carboxylic acid ligand MOFs nano tanning agent with stable framework structure and preparation method and application thereof |
| CN113999943A (en) * | 2021-11-15 | 2022-02-01 | 陕西科技大学 | Polysaccharide-based hydrotalcite nano composite tanning agent and preparation method and application thereof |
| CN114164308A (en) * | 2021-11-18 | 2022-03-11 | 陕西科技大学 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
| CN114164308B (en) * | 2021-11-18 | 2023-12-22 | 陕西科技大学 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
| CN114350860A (en) * | 2022-01-20 | 2022-04-15 | 陕西科技大学 | Non-chromium tanning process based on hydrotalcite and zirconium sulfate |
| CN114369690A (en) * | 2022-01-20 | 2022-04-19 | 陕西科技大学 | Preparation method and tanning method of supermolecular intercalation structure nano tanning agent |
| CN116219086A (en) * | 2023-02-07 | 2023-06-06 | 陕西科技大学 | Flame-retardant ecological automobile leather and production process thereof |
| CN116219086B (en) * | 2023-02-07 | 2024-01-19 | 陕西科技大学 | Flame-retardant ecological automobile leather and production process thereof |
| CN116287488A (en) * | 2023-03-20 | 2023-06-23 | 浙江理工大学 | Method for protecting soft-back of cracked hard leather cultural relics |
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