CN105779668B - Zirconium tanning agent/stannic oxide/graphene nano composite tanning agent and preparation method thereof - Google Patents
Zirconium tanning agent/stannic oxide/graphene nano composite tanning agent and preparation method thereof Download PDFInfo
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- CN105779668B CN105779668B CN201610185613.6A CN201610185613A CN105779668B CN 105779668 B CN105779668 B CN 105779668B CN 201610185613 A CN201610185613 A CN 201610185613A CN 105779668 B CN105779668 B CN 105779668B
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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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Abstract
The invention discloses a kind of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, it is made up of following material according to mass parts：60 ~ 70 parts of 30 ~ 40 parts of zirconium sulfate, 40 ~ 50 parts of stannic oxide/graphene nano lamella suspension, 10 ~ 20 parts of dispersant and deionized water；The invention also discloses a kind of preparation method of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, tanning agent of the present invention may be used as tanning agent, when zirconium tanning agent/stannic oxide/graphene nano composite tanning agent solid consumption is the 5% of tare weight, the shrinkage temperature of tan leather has reached 111 DEG C, the absorptivity of zirconium tanning agent has reached 96%, graphene oxide alkene yield has reached 99%, and tan leather has good flexibility, elasticity and fullness.
Description
Technical field
The invention belongs to the preparing technical field of leather retanning agent, and in particular to a kind of zirconium tanning agent/stannic oxide/graphene nano material
Expect composite tanning agent and preparation method thereof.
Background technology
Research and development chrome-free tanning agent etc. becomes the focus of research at present, and reason is that chrome tanning agent has good tanning
Effect, but exist that absorptivity is low, produce be difficult to administer containing chromium pollutant, to the with serious pollution defect of environment（Hubei Province
Great waves, Yang Shuyi, Ma Hongrui, etc., citric acid is studied trivalent chromium sedimentation function influence in leather-making waste water, Chinese leather, and 2015,4
（15）：21-24）.Other metal tanning agents such as aluminium tanningagent, iron tannage agent, titanium tannage agent and zirconium tanning agent due to its resource extensively, small toxicity,
The features such as environmental pollution is small becomes the object of research again, but these tanning agents have process for tanning compared with chrome tanning agent and answered
There is certain in miscellaneous, tan leather, hinder their application（Yang Meng, Li Rui, Dan Zhihua, etc. conventional Chrome-free knot
Close the application of tannage, leather science and engineering, 2015,25（2）：27-31）.In these non-chromium metal tanning agents, the tan of zirconium tanning agent
Preferably, the shrinkage temperature of such as zirconium tanning agent tan leather may be up to 96 DEG C to performance processed, and tan leather color is pure white, is suitable for system
Make white leather and light color leather, plentiful consolidation.Have the disadvantage：Zirconium tanning leather compares plate firmly, and water imbibition is strong.It is easily deformed；During zirconium tanning
PH is less than 3, and easily precipitation causes infiltration uneven（Li Feng, He Qing, but time, etc. chrome-free tanning agent New research progress, west
Portion's leather, 2012,34（10）：33-37；Lan Yunjun, perhaps Xiao Hong, Zhou Jianfei, the flexibility analysis of zirconates and its development prospect, leather
Scientific and engineering, 2009,19（4）：21-24）.Therefore, current zirconium tanning agent is also applied in leather tanning without substantial amounts of.
The content of the invention
To solve existing technical problem, the present invention provides a kind of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent
And preparation method thereof, gained tanning agent improves zirconium tanning by zirconium tanning agent and stannic oxide/graphene nano lamella formation nano-composite tanning agent
The resistance to alkali ability of agent and stability and permeability in tanning, zirconium tanning agent/stannic oxide/graphene nano composite tanning agent pass through active group
The multiple spot chemical bonds and nanometer size effect of group and collagen formation reach the purpose of tan leather, compared with simple zirconium tanning agent
Tanning effect increase significantly.
To reach above-mentioned purpose, what the technical scheme of the embodiment of the present invention was realized in：
The embodiment of the present invention provides a kind of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, by following material according to quality
Part is made：
40 ~ 50 parts of stannic oxide/graphene nano lamella suspension, 30 ~ 40 parts of zirconium sulfate, 10 ~ 20 parts of deionized waters 80 of dispersant
~ 100 parts.
In such scheme, in the stannic oxide/graphene nano lamella dispersion liquid containing graphite oxide mass fraction be 0.5% ~
0.6%, the size of graphene oxide layer is 5 ~ 30 nanometers.
In such scheme, the dispersant is made by following preparation method：100 ~ 150 parts of deionized water, it is heated to 80 ~
90 DEG C, while 10 ~ 20 parts of 40 ~ 50 parts of monomer mixture solution and initiator solution are added dropwise respectively, feed time is 30 ~ 40 points
Sodium hydroxide solution that then insulation reaction 1 ~ 2 hour after the completion of clock, charging is 20% with mass fraction regulation product pH is 6 ~
7, the mass fraction of product is controlled 20% ~ 25%.
In such scheme, the monomer mixture solution be hydroxypropyl acrylate, diallyldimethylammonium chloride and go from
Sub- water is according to mass ratio 15:10:10 mix.
In such scheme, the initiator solution is that 2 parts of ammonium persulfates or potassium peroxydisulfate or sodium peroxydisulfate are dissolved in
Obtained in 20 parts of deionized waters.
The embodiment of the present invention also provides a kind of preparation method of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, the preparation
Method is：30 ~ 40 parts of 40 ~ 50 parts of stannic oxide/graphene nano lamella dispersion liquid and zirconium sulfate is taken to be stirred in reactor according to mass parts
It is 1.0 ~ 2.0 to mix even regulation pH, is heated to 55 ~ 65 DEG C, adds 10 ~ 20 parts of dispersant, and then insulation reaction 1 ~ 2 hour drops
Temperature is to 30 ~ 40 DEG C, and the pH value for adjusting solution by basifier is 3.5 ~ 4.0, and ultrasonic wave is scattered 0.5 ~ 1.0 hour, products therefrom
For zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, the wherein content of zirconium is 20% ~ 25% according to zirconium sulfate mass fraction, oxidation
Graphene mass fraction is 0.2 ~ 0.3%.
In such scheme, the alkalization agent solution is that 15 parts of monoethanolamines or diethanol amine are dissolved in 25 parts of deionized waters.
Compared with prior art, beneficial effects of the present invention：
The present invention passes through multiple groups in the carboxyl of stannic oxide/graphene nano lamella, hydroxyl and epoxy radicals and dispersant
The coordination that is formed between zirconates, Covalent bonding together form nano-complex, improve the resistance to alkali ability of zirconates, by a relatively large margin
Ground improves pH scopes during zirconium tanning agent tanning, adds penetrating power of the zirconium tanning agent between materials with hide glue fibril, reduces zirconium
Tanning agent coordination is acted on, and is reduced the deposition between materials with hide glue fibril, is improved the tanning effect of zirconium tanning agent.Tanning is acted on
The effect of active group formation chemical bonding, the tanning of zirconium tanning agent on the active group and materials with hide glue fibril on GO lamellas
Effect and the nanometer size effect of stannic oxide/graphene nano lamella.
Nano-composite tanning agent obtained by the present invention passes through active group and skin on zirconium tanning agent and stannic oxide/graphene nano lamella
The multiple spot chemical bonds and stannic oxide/graphene nano dimensional effect of collagen formation reach the purpose of tan leather.When zirconium tanning agent/
Stannic oxide/graphene nano composite tanning agent has reached 111 according to the shrinkage temperature of its tan leather during 5% that solid consumption is tare weight
DEG C, the absorptivity of aluminium tanningagent has reached 96%, and the defect of the water suction deformation of leather disappears, the flexibility of tan leather, elastic and rich
The highly significants such as full property.
Embodiment
With reference to embodiment, the present invention is described in detail.
The embodiment of the present invention provides a kind of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, by following material according to quality
Part is made：
40 ~ 50 parts of stannic oxide/graphene nano lamella suspension, 30 ~ 40 parts of zirconium sulfate, 10 ~ 20 parts of deionized waters 80 of dispersant
~ 100 parts.
The stannic oxide/graphene nano lamella dispersion liquid is made by the following method:By 8 ~ 10 parts of concentrated phosphoric acids and 60 ~ 90 parts
The concentrated sulfuric acid is added sequentially in three-necked flask the stirring reaction half an hour at 0 ~ 5 DEG C, then by 2 ~ 3 parts of powdery graphites and 10 ~ 15
The mixture of part potassium permanganate was added in three-necked flask by several times in 1 hour, isothermal reaction 3 hours under being stirred at 0 ~ 5 DEG C
Afterwards, solution is changed into blackish green, rise temperature to 50 DEG C, reaction 5 hours after, rise temperature to 80 DEG C, add 150 ~ 200 parts go from
Sub- water, continues to react 30 minutes, is cooled to after 25 DEG C, be slowly added to 8 ~ 14 parts of the hydrogen peroxide of mass fraction 30%, add the time
For 30 minutes, continue to react obtaining graphite oxide ene product in 30 minutes after solution is changed into golden yellow.Then product is carried out from
Heart precipitation, the method being washed with deionized are 6.5 ~ 7.0 until the pH of washings, and ultrasonic disperse obtains graphite oxide in 1 hour
Alkene dispersion liquid, and the mass fraction for controlling graphene oxide is 0.5%, obtains product for graphene oxide dispersion, nano-scale exists
5~30 nm。
The preparation method of the zirconium tanning agent/stannic oxide/graphene nano composite tanning agent dispersant, it is characterised in that：Deionized water
100 ~ 150 parts, 80 ~ 90 DEG C are heated to, while 10 ~ 20 parts of 40 ~ 50 parts of monomer mixture solution and initiator solution is added dropwise, plus
The material time is 30 ~ 40 minutes, insulation reaction 1 ~ 2 hour after the completion of charging, then with the sodium hydroxide solution that mass fraction is 20%
It is 6 ~ 7 to adjust product pH, controls the mass fraction of product 20% ~ 25%.
The monomer mixture solution is hydroxypropyl acrylate, diallyldimethylammonium chloride and deionized water according to quality
Than 15:10:10 mix.
The initiator initiator solution is that 2 parts of ammonium persulfates or potassium peroxydisulfate or sodium peroxydisulfate are dissolved in 20 parts and gone
Obtained in ionized water.
The preparation method of the zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, it is characterised in that：Oxygen is taken according to mass parts
30 ~ 40 parts of 40 ~ 50 parts of graphite alkene nanoscale twins dispersion liquid and zirconium sulfate stirred in reactor regulation pH be 1.0 ~
2.0,55 ~ 65 DEG C are heated to, 10 ~ 20 parts of dispersant is added, then insulation reaction 1 ~ 2 hour cools to 30 ~ 40 DEG C, add alkali
Agent, the pH value of regulation solution is 3.5 ~ 4.0, and ultrasonic wave is scattered 0.5 ~ 1.0 hour, and products therefrom is zirconium tanning agent/graphite oxide
The content of alkene nano-composite tanning agent, wherein zirconium is 20% ~ 25% according to zirconium sulfate mass fraction, and graphene oxide mass fraction is
0.2~0.3%。
The alkalization agent solution is that 15 parts of monoethanolamines or diethanol amine are dissolved in 25 parts of deionized waters.
Embodiment one
Step one：The preparation of stannic oxide/graphene nano lamella suspension
The stannic oxide/graphene nano lamella suspension is made by the following method:By 8 parts of concentrated phosphoric acids and 60 parts of concentrated sulfuric acids
The stirring reaction half an hour at 0 DEG C is added sequentially in three-necked flask, then by the mixed of 2 parts of powdery graphites and 10 parts of potassium permanganate
Compound was added in three-necked flask by several times in 1 hour, and under being stirred at 0 DEG C after isothermal reaction 3 hours, solution is changed into blackish green
Color, rise temperature is to 50 DEG C, after reacting 5 hours, and rise temperature adds 150 parts of deionized waters to 80 DEG C, continues to react 30 points
Clock, is cooled to after 25 DEG C, is slowly added to 8 parts of the hydrogen peroxide of mass fraction 30%, and it is 30 minutes to add the time, treats that solution is changed into
Continue to react after golden yellow to obtain graphite oxide ene product in 30 minutes.Then centrifugation is carried out to product, be washed with deionized water
The method washed is 6.5 ~ 7.0 until the pH of washings, uses BaSO4Solution is examined in cleaning solution without SO4 2-, ultrasonic disperse 1 hour must
To graphene oxide dispersion, and the mass fraction for controlling graphene oxide is 0.5%, obtains product for graphene oxide dispersion,
Nano-scale is in 5 ~ 30 nm
Step 2：The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent dispersant
（1）The preparation of monomer mixture solution
Hydroxypropyl acrylate, diallyldimethylammonium chloride and deionized water are according to mass ratio 15:10:10 mixing and
Into.
（2）The preparation of initiator solution
Initiator solution is that 2 parts of ammonium persulfates or potassium peroxydisulfate or sodium peroxydisulfate are dissolved in 20 parts of deionized waters and obtained
.
（3）The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent dispersant
100 parts of deionized water, is heated to 80 DEG C, while 10 parts of 40 parts of monomer mixture solution and initiator solution is added dropwise,
Feed time is 30 minutes, insulation reaction 1 hour after the completion of charging, is then adjusted with mass fraction for 30% ethanolamine solutions
Product pH is 6 ~ 7, controls the mass fraction of product 20% ~ 25%.
Step 3：The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent
30 parts of 40 parts of stannic oxide/graphene nano lamella dispersion liquid and zirconium sulfate is taken to be stirred in reactor according to mass parts
Even section pH is 1.0 ~ 2.0, is heated to 55 ~ 65 DEG C, adds 10 parts of dispersant, and then insulation reaction 1 hour cools to 30 DEG C,
It is 3.5 with the pH value that mass fraction is 20% monoethanolamine regulation solution, ultrasonic wave is scattered 30 minutes, and products therefrom is zirconium tanning agent/oxygen
Graphite alkene nano-composite tanning agent, the wherein content of zirconium are 20% ~ 25% according to zirconium sulfate mass fraction, graphene oxide quality point
Number is 0.2 ~ 0.3%.
Embodiment two
Step one：The preparation of stannic oxide/graphene nano lamella suspension
The stannic oxide/graphene nano lamella suspension is made by the following method:By 10 parts of concentrated phosphoric acids and 90 parts of dense sulphur
Acid is added sequentially in three-necked flask the stirring reaction half an hour at 0 ~ 5 DEG C, then by 3 parts of powdery graphites and 15 parts of potassium permanganate
Mixture be added to by several times in three-necked flask in 1 hour, after lower isothermal reaction being stirred at 5 DEG C 3 hours, solution is changed into ink
Green, rise temperature is to 50 DEG C, after reacting 5 hours, and rise temperature adds 200 parts of deionized waters to 80 DEG C, continues to react 30 points
Clock, is cooled to after 25 DEG C, is slowly added to 14 parts of the hydrogen peroxide of mass fraction 30%, and it is 30 minutes to add the time, treats that solution is changed into
Continue to react after golden yellow to obtain graphite oxide ene product in 30 minutes.Then centrifugation is carried out to product, be washed with deionized water
The method washed is 6.5 ~ 7.0 until the pH of washings, and ultrasonic disperse obtains graphene oxide dispersion for 1 hour, and controls oxidation
The mass fraction of graphene obtains product for graphene oxide dispersion, nano-scale is in 5 ~ 30 nm 0.5%
Step 2：The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent dispersant
（3）The preparation of monomer mixture solution
Hydroxypropyl acrylate, diallyldimethylammonium chloride and deionized water are according to mass ratio 15:10:10 mixing and
Into.
（4）The preparation of initiator solution
Initiator initiator solution is that 2 parts of ammonium persulfates or potassium peroxydisulfate or sodium peroxydisulfate are dissolved in 20 parts of deionizations
Obtained in water.
（3）The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent dispersant
150 parts of deionized water, is heated to 90 DEG C, while 20 parts of 50 parts of monomer mixture solution and initiator solution is added dropwise,
Feed time is 40 minutes, insulation reaction 2 hours after the completion of charging, is then adjusted with mass fraction for 30% ethanolamine solutions
Product pH is 6 ~ 7, controls the mass fraction of product 20% ~ 25%.
Step 3：The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent
40 parts of 50 parts of stannic oxide/graphene nano lamella dispersion liquid and zirconium sulfate is taken to be stirred in reactor according to mass parts
Even section pH is 2.0, is heated to 65 DEG C, adds 20 parts of dispersant, and then insulation reaction 2 hours cools to 40 DEG C, with quality point
Number is that the pH value of 20% diethanol amine regulation solution is 4.0, and ultrasonic wave is scattered 1.0 hours, and products therefrom is zirconium tanning agent/oxidation stone
Black alkene nano-composite tanning agent, the wherein content of zirconium are 20% ~ 25% according to zirconium sulfate mass fraction, and graphene oxide mass fraction is
0.2~0.3%。
Embodiment three
Step one：The preparation of stannic oxide/graphene nano lamella suspension
The stannic oxide/graphene nano lamella suspension is made by the following method:By 9 parts of concentrated phosphoric acids and 75 parts of concentrated sulfuric acids
The stirring reaction half an hour at 3 DEG C is added sequentially in three-necked flask, then by 2.5 parts of powdery graphites and 13 parts of potassium permanganate
Mixture was added in three-necked flask by several times in 1 hour, and under being stirred at 3 DEG C after isothermal reaction 3 hours, solution is changed into blackish green
Color, rise temperature is to 50 DEG C, after reacting 5 hours, and rise temperature adds 180 parts of deionized waters to 80 DEG C, continues to react 30 points
Clock, is cooled to after 25 DEG C, is slowly added to 11 parts of the hydrogen peroxide of mass fraction 30%, and it is 30 minutes to add the time, treats that solution is changed into
Continue to react after golden yellow to obtain graphite oxide ene product in 30 minutes.Then centrifugation is carried out to product, be washed with deionized water
The method washed is 6.5 ~ 7.0 until the pH of washings, and ultrasonic disperse obtains graphene oxide dispersion for 1 hour, and controls oxidation
The mass fraction of graphene obtains product for graphene oxide dispersion, nano-scale is in 5 ~ 50 nm 0.5%
Step 2：The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent dispersant
（1）The preparation of monomer mixture solution
Hydroxypropyl acrylate, diallyldimethylammonium chloride and deionized water are according to mass ratio 15:10:10 mixing and
Into.
（2）The preparation of initiator solution
Initiator initiator solution is that 2 parts of ammonium persulfates or potassium peroxydisulfate or sodium peroxydisulfate are dissolved in 20 parts of deionizations
Obtained in water.
（3）The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent dispersant
130 parts of deionized water, is heated to 85 DEG C, while 15 parts of 45 parts of monomer mixture solution and initiator solution is added dropwise,
Feed time is 35 minutes, insulation reaction 1.5 hours after the completion of charging, is then adjusted with mass fraction for 30% ethanolamine solutions
It is 6 ~ 7 to save product pH, controls the mass fraction of product 20% ~ 25%.
Step 3：The preparation of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent
35 parts of 45 parts of stannic oxide/graphene nano lamella dispersion liquid and zirconium sulfate is taken to be stirred in reactor according to mass parts
Even section pH is 1.5, is heated to 60 DEG C, adds 15 parts of dispersant, and then insulation reaction 1.5 hours cools to 35 DEG C, use quality
Fraction is that the pH value of 20% monoethanolamine regulation solution is 3.5 ~ 4.0, and ultrasonic wave is scattered 1.0 hours, and products therefrom is zirconium tanning agent/oxygen
Graphite alkene nano-composite tanning agent, the wherein content of zirconium are 20% ~ 25% according to zirconium sulfate mass fraction, graphene oxide quality point
Number is 0.2 ~ 0.3%.
Claims (5)
1. a kind of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, it is characterised in that be made up of following material according to mass parts：
40 ~ 50 parts of stannic oxide/graphene nano lamella suspension, 30 ~ 40 parts of zirconium sulfate, 10 ~ 20 parts of dispersant, deionized water 80 ~
100 parts；The dispersant is made by following preparation method：100 ~ 150 parts of deionized water, is heated to 80 ~ 90 DEG C, respectively simultaneously
10 ~ 20 parts of 40 ~ 50 parts of monomer mixture solution and initiator solution is added dropwise, feed time is 30 ~ 40 minutes, after the completion of charging
The sodium hydroxide solution regulation product pH that then insulation reaction 1 ~ 2 hour is 20% with mass fraction is 6 ~ 7, controls the matter of product
Fraction is measured 20% ~ 25%；The monomer mixture solution is hydroxypropyl acrylate, diallyldimethylammonium chloride and deionization
Water is according to mass ratio 15:10:10 mix.
2. zirconium tanning agent according to claim 1/stannic oxide/graphene nano composite tanning agent, it is characterised in that：The oxidation stone
It is 0.5% ~ 0.6% to contain graphene oxide mass fraction in black alkene nanoscale twins suspension, and the size of graphene oxide layer is 5
~ 30 nanometers.
3. zirconium tanning agent according to claim 1 or 2/stannic oxide/graphene nano composite tanning agent, it is characterised in that：It is described to trigger
Agent solution is that 2 parts of ammonium persulfates or potassium peroxydisulfate or sodium peroxydisulfate are dissolved in 20 parts of deionized waters and obtained.
4. a kind of preparation method of zirconium tanning agent/stannic oxide/graphene nano composite tanning agent, it is characterised in that the preparation method is：Press
30 ~ 40 parts of 40 ~ 50 parts of stannic oxide/graphene nano lamella suspension and zirconium sulfate is taken to be stirred in reactor tune according to mass parts
It is 1.0 ~ 2.0 to save pH, is heated to 55 ~ 65 DEG C, adds 10 ~ 20 parts of dispersant, and then insulation reaction 1 ~ 2 hour cools to 30 ~ 40
DEG C, the pH value for adjusting solution by the agent solution that alkalizes is 3.5 ~ 4.0, and ultrasonic wave is scattered 0.5 ~ 1.0 hour, and products therefrom is zirconium tanning
Agent/stannic oxide/graphene nano composite tanning agent, the wherein content of zirconium are 20% ~ 25%, graphene oxide according to zirconium sulfate mass fraction
Mass fraction is 0.2 ~ 0.3%；The dispersant is made by following preparation method：100 ~ 150 parts of deionized water, it is heated to 80 ~
90 DEG C, while 10 ~ 20 parts of 40 ~ 50 parts of monomer mixture solution and initiator solution are added dropwise respectively, feed time is 30 ~ 40 points
Sodium hydroxide solution that then insulation reaction 1 ~ 2 hour after the completion of clock, charging is 20% with mass fraction regulation product pH is 6 ~
7, the mass fraction of product is controlled 20% ~ 25%；The monomer mixture solution is hydroxypropyl acrylate, diallydimethyl
Ammonium chloride and deionized water are according to mass ratio 15:10:10 mix.
5. the preparation method of zirconium tanning agent according to claim 4/stannic oxide/graphene nano composite tanning agent, it is characterised in that：
The alkalization agent solution is that 15 parts of monoethanolamines or diethanol amine are dissolved in 25 parts of deionized waters.
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