CN104745736B - Graphene/aluminium oxide nano-composite tanning agent and preparation method thereof - Google Patents
Graphene/aluminium oxide nano-composite tanning agent and preparation method thereof Download PDFInfo
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- CN104745736B CN104745736B CN201510144047.XA CN201510144047A CN104745736B CN 104745736 B CN104745736 B CN 104745736B CN 201510144047 A CN201510144047 A CN 201510144047A CN 104745736 B CN104745736 B CN 104745736B
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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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- 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
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Abstract
The invention discloses a graphene/aluminium oxide nano-composite tanning agent. The graphene/aluminium oxide nano-composite tanning agent is prepared from the following materials in parts by mass: 40-50 parts of a graphene oxide nano-slice dispersion liquid, 25-30 parts of aluminium chloride, 0.5-1 parts of p-toluenesulfonic acid, 20-25 parts of alkalizer solution and 0.5-1 parts of a dispersant. The invention further discloses a preparation method for the graphene/aluminium oxide nano-composite tanning agent, wherein when the solid dosage of the graphene/aluminium oxide nano-composite tanning agent is 5% of a tare, the shrinkage temperature of leather tanned by the graphene/aluminium oxide nano-composite tanning agent achieves 112 DEG C, the absorption rate of the tanning agent achieves 95%, the shrinkage temperature is hardly lowered when the tanned leather is washed for 10 times, and lowered by 5% when the tanned leather is washed for 20 times, and the softness, elasticity, fullness and the like of the tanned leather approximate to those of chrome-tanned leather.
Description
Technical field
The invention belongs to the preparing technical field of leather retanning agent, be specifically related to a kind of graphene oxide/aluminum nanometer multiple
Close tanning agent and preparation method thereof.
Background technology
Leather retanning agent is a kind of chemical substance that rawhide can be made to become leather, its essence is tanning agent and hide glue fibril
Dimension there occurs that chemical reaction, tanning agent are referred to as tanning, tanned life with the process of collagen generation chemical reaction
Skin become have certain mechanical strength, resistance to deposit, the leather of soft and certain purposes.Can be used as in theory
Leather retanning agent have chrome tanning agent, zirconium tanning agent, titanium tannage agent, aluminium tanningagent, iron tannage agent, vegetable tanning agent, aldehyde tanning agent,
Syntanses etc., actually best due to the combination property of chrome tanning agent tan leather, only chrome tanning agent obtains
Apply widely, current chrome tanning leather account for leather yield about 90% (Wang Wei is outstanding, Liao Xuepin, Shi Bi. green tea
In secondary tea, tea polyphenols extracts and application in tanning. Chinese leather, and 2014,43 (1): 11-14；
Chattopadhyay B,Aich A,Mukhopadhyay S K.Chromium in the Tanning Industry:
An Odyssey from Cradle to Grave[J].Journal of the society of leather technologists
and chemists,2012,96(4):133-140).The a large amount of use of chrome tanning agent creates another one problem,
Be exactly can produce in Chrome Tanning Process be difficult in a large number to administer the waste water containing chromium, mud, scrap leather bits, tan in addition
Agent and the trivalent chromium contained in chromium pollutant can be converted into the Cr VI that harm is bigger, therefore mesh under certain condition
Before use to chrome tanning agent both at home and abroad propose restriction (Li Dongling, Dan Zhihua, Yang Meng, etc. plant aldehyde combination tannage firm
Property module resistance to ag(e)ing research. Chinese leather, 2014,43 (13): 27-30).Therefore, nothing is researched and developed at present
Chrome tanning agents etc. become the focus of research.There is affluent resources and the little aluminium tanningagent of contamination hazard degree, iron tannage
Agent etc. become the object of research again.Aluminium tanningagent exist subject matter be the shrinkage temperature of tan leather relatively
Low (70～75 DEG C), the leather of tanning is the most water-fast, and after dipped water, tanning effect substantially goes down, tan leather plate
Firmly, flat thin etc..At present aluminium tanningagent is improved and be mainly the chromium the best with tanning performance, zirconium, the tanning agent of titanium
Or vegetable tanning agent, glutaraldehyde tanning agent, syntans etc. be combined tanning (Liu Zilong, Zhang Hui, Qiang Xihuai,
Li Meng. the preparation of sial fitting-type tanning agent and application. Chinese leather, 2014,43 (21): 223-27；Xu Xiaoying, Tian Cheng,
Guo Cheng, etc. organic acid covers aluminum complex tanning agent application in less chrome tannage of limiting. Chinese leather, and 2013,
42(7):1-7；He Qing, but defend China, but time, etc. a kind of less chrome tannage based on Zirconium-aluminum-titanium cooperation tanning agent is complete
Enclosed circulation technology. Chinese leather, 2013,42 (7): 5-9), but what the effect of these modifications still improved
Limited, result in aluminum current tanning agent and still cannot be applied to tanning production, it is impossible to substitute chrome tanning agent.We
Research finding, forming nano-composite tanning agent by GO with aluminum can significantly improve aluminium tanningagent tanning effect, can
For use as tanning agent.
Summary of the invention
For solving the technical problem of existing existence, the embodiment of the present invention provides a kind of graphene oxide/aluminum nanometer multiple
Closing tanning agent and preparation method thereof, gained tanning agent passes through trivalent aluminium with coordinate bond, covalent bond etc. and graphene oxide
Nanoscale twins forms nano-composite tanning agent, when with graphene oxide/aluminum nano-composite tanning agent tan leather, GO
Multiple spot chemical bonds and nano effect that on nanoscale twins, active group and aluminium tanningagent are formed with collagen and produce
Raw tanning effect, the participation of GO nanoscale twins improves the tanning effect of aluminium tanningagent, improves tan leather
Wash durability and the stability of tan leather performance.
For reaching above-mentioned purpose, the technical scheme of the embodiment of the present invention is achieved in that
The embodiment of the present invention provides a kind of graphene oxide/aluminum nano-composite tanning agent, by following material according to quality
Part is made:
Stannic oxide/graphene nano lamella dispersion liquid 40～50 parts, aluminum chloride 25～30 parts, p-methyl benzenesulfonic acid 0.5～1
Part, basifier solution 20～25 parts, dispersant 0.5～1 part.
In such scheme, containing graphene oxide lamella quality in described stannic oxide/graphene nano lamella dispersion liquid
Mark is 1%, and the size of described graphene oxide lamella is 5～30 nanometers.
In such scheme, described basifier solution be 10 parts of sodium bicarbonate be dissolved in 20 parts of deionized waters or
8 parts of sodium carbonate are dissolved in the solution that 20 parts of deionized waters are formed.
In such scheme, described dispersant is made up of dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC,
The weight ratio of described dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC is 0.5～0.8:1～1.5.
The embodiment of the present invention also provides for the preparation method of a kind of graphene oxide/aluminum nano-composite tanning agent, and this is prepared
Method is: take stannic oxide/graphene nano lamella dispersion liquid 40～50 parts and aluminum chloride 25～30 parts according to mass parts
The regulation pH that stirs in reactor is 2.0～3.0, is heated to 85～95 DEG C, adds p-methyl benzenesulfonic acid 0.5～1
Part, insulation reaction 1～2 hours, then cool to 70～80 DEG C, be added slowly with stirring basifier 6～12
Part, insulation reaction 3～4 hours, cool to 25～30 DEG C, the pH value of regulation solution is 3.5～4.0, adds
The dispersant of 0.5～1 part, ultrasound wave disperses 1～1.5 hour, and products therefrom is that graphene oxide/aluminum nanometer is multiple
Closing tanning agent, wherein the content of aluminum is 20%～25% according to the mass fraction of aluminium sesquioxide, graphene oxide matter
Amount mark is 0.4～0.6%.
In such scheme, containing graphene oxide lamella quality in described stannic oxide/graphene nano lamella dispersion liquid
Mark is 1%, and the size of described graphene oxide lamella is 5～30 nanometers.
In such scheme, described basifier solution be 10 parts of sodium bicarbonate be dissolved in 20 parts of deionized waters or
8 parts of sodium carbonate are dissolved in the solution that 20 parts of deionized waters are formed.
In such scheme, described dispersant is made up of dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC,
The weight ratio of described dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC is 0.5～0.8:1～1.5.
Compared with prior art, beneficial effects of the present invention:
The present invention is by the carboxyl of stannic oxide/graphene nano lamella, formation between hydroxyl and epoxy radicals and aluminum chloride
Coordination, covalent bond combine formed nano-complex, by suitable regulation and control pH value to increase aluminum chloride
Hydrolysis and join cumulative power, promote to be formed the coordination compound with the multinuclear aluminum that GO nanoscale twins participates in, simultaneously
Also stannic oxide/graphene nano lamella is produced dispersion effect.Tanning effect derives from the active group on GO lamella
Group and the active group on materials with hide glue fibril form chemical bonding effect, multinuclear aluminum joins polyacetylene compound tanning effect
And the nanometer size effect of stannic oxide/graphene nano lamella.
The nano-composite tanning agent of gained of the present invention is by multinuclear aluminium polychlorid and stannic oxide/graphene nano lamella
Multiple spot chemical bonds and stannic oxide/graphene nano dimensional effect that active group is formed with collagen reach tanning
The purpose of leather.Its tan when graphene oxide/aluminum nano-composite tanning agent is according to 5% that solid consumption is tare weight
The shrinkage temperature of leather processed has reached 112 DEG C, and the absorbance of aluminium tanningagent has reached 95%, and tan leather is washed
10 its shrinkage temperatures, almost without reduction, are washed 20 shrinkage temperatures and are reduced 5%, tan leather soft
Soft, elastic and fullness etc. is close to chrome tanning leather.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
The embodiment of the present invention provides a kind of graphene oxide/aluminum nano-composite tanning agent, by following material according to quality
Part is made:
Stannic oxide/graphene nano lamella dispersion liquid 40～50 parts, aluminum chloride 25～30 parts, p-methyl benzenesulfonic acid 0.5～1
Part, basifier solution 20～25 parts, dispersant 0.5～1 part.
The preparation method of described stannic oxide/graphene nano lamella dispersion liquid is: slowly added by the graphite powder of 3～5 parts
Entering to 80～100 parts of mass fractions is in 98% concentrated sulphuric acid, and the temperature 0 of control system～5 DEG C, after stirring
The potassium permanganate being slowly added to 10～15 parts reacts 3～4 hours, is warmed up to 30～40 DEG C the most again and continues reaction
2～2.5 hours, it is slow added into 150～180 parts of deionized waters, is warming up to 80～90 DEG C and reacts 1～2 hour；
Then it is cooled to 30 DEG C～the hydrogenperoxide steam generator of 35 35～40 parts of mass fractions 30% of dropping, reacts 1～1.5
Hour, stannic oxide/graphene nano lamella dispersion liquid is prepared in ultrasound wave dispersion for 1～1.5 hour, and graphene oxide is received
Containing graphene oxide lamella mass fraction in rice lamella dispersion liquid is 1%；Due to described stannic oxide/graphene nano
The preparation process of lamella dispersion liquid is complex, therefore typically once prepares more consumption, in case preparing
On-demand in journey take.
Described basifier solution is that 10 parts of sodium bicarbonate are dissolved in 20 parts of deionized waters or 8 parts of sodium carbonate
It is dissolved in the solution that 20 parts of deionized waters are formed.
Described dispersant is made up of dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC, described dodecane
The weight ratio of base hydroxypropyl sulfobetaines and penetrating agent JFC is 0.5～0.8:1～1.5.
The embodiment of the present invention also provides for the preparation method of a kind of graphene oxide/aluminum nano-composite tanning agent, and this is prepared
Method is: take stannic oxide/graphene nano lamella dispersion liquid 40～50 parts and aluminum chloride 25～30 parts according to mass parts
The regulation pH that stirs in reactor is 2.0～3.0, is heated to 85～95 DEG C, adds p-methyl benzenesulfonic acid 0.5～1
Part, insulation reaction 1～2 hours, then cool to 70～80 DEG C, be added slowly with stirring basifier 6～12
Part, insulation reaction 3～4 hours, cool to 25～30 DEG C, the pH value of regulation solution is 3.5～4.0, adds 0.5～1
The dispersant of part, ultrasound wave disperses 1～1.5 hour, and products therefrom is graphene oxide/aluminum nano-composite tanning agent,
The mass fraction controlling aluminium sesquioxide is 20%～25%, controls graphene oxide mass fraction and is
0.4～0.6%.
The tanning agent of invention has when tanning that consumption is few, absorbance is high, chromium from waste chromium compound residual quantity is low
Advantage, and production technology is unique, and technical process easily operates, and has good application prospect.
The present invention passes through carboxyl, hydroxyl and the epoxy radicals etc. in graphene oxide structure from aluminum chloride at different pH
Act under environment, forming coordinate bond, the covalency formed between active group on aluminum chloride and graphene oxide
Bonded nano combined beyond the region of objective existence, has been also carried out aluminum chloride polyreaction, make define graphene oxide/
Aluminum nano-composite tanning agent, is also that the degree of scatter of stannic oxide/graphene nano lamella increases simultaneously.Tanning is made
Can be formed with the active group on materials with hide glue fibril with the active group derived from stannic oxide/graphene nano lamella
The nano-scale effect of chemical bonding effect, the tanning effect of aluminium polychlorid and stannic oxide/graphene nano lamella
Should.
Graphene oxide/aluminum nano-composite tanning agent when using graphene oxide/aluminum nano-composite tanning agent tan leather
Consumption (calculating with chromic oxide) is that tare weight 5%, graphene oxide (solid consumption) consumption are as tare weight
When 0.20%, the shrinkage temperature of tan leather can be made to reach 112 DEG C, the absorbance of aluminium tanningagent has reached 95%.
Embodiment one:
Step one: the preparation of stannic oxide/graphene nano lamella dispersion liquid:
It is in 98% concentrated sulphuric acid that the graphite powder of 3 parts is slowly added to 80 parts of mass fractions, controls the temperature of system
Spending 0 DEG C, the potassium permanganate being slowly added to 10 parts after stirring reacts 3 hours, is warmed up to 30 DEG C the most again
Continue reaction 2 hours, be slow added into 150 parts of deionized waters, be warming up to 80 DEG C and react 1 hour；Then
It is cooled to the hydrogenperoxide steam generator of 35 parts of mass fractions 30% of 30 DEG C of droppings, reacts 1 hour, ultrasonic wavelength-division
Dissipate and within 1 hour, prepare stannic oxide/graphene nano lamella dispersion liquid, control in stannic oxide/graphene nano lamella dispersion liquid
It is 1% containing graphene oxide lamella mass fraction.
Step 2: the preparation of basifier solution:
Basifier solution is the solution that 10 parts of sodium bicarbonate are dissolved in that 20 parts of deionized waters are formed.
Step 3: the preparation of dispersant:
Dispersant is made up of dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC, the weight of described material
Ratio is 0.5:1.
Step 4: the preparation method of graphene oxide/aluminum nano-composite tanning agent:
Stannic oxide/graphene nano lamella dispersion liquid 40 parts and 25 parts of aluminum chloride is taken in reactor according to mass parts
The regulation pH that stirs is 2.0, is heated to 85 DEG C, adds p-methyl benzenesulfonic acid 0.5 part, and insulation reaction 1 is little
Time, then cool to 70 DEG C, be added slowly with stirring basifier 6 parts, insulation reaction 3 hours, cooling
To 25 DEG C, the pH value of regulation solution is 3.5, adds the dispersant of 0.5 part, and ultrasound wave disperses 1 hour, institute
Product be graphene oxide/aluminum nano-composite tanning agent, control aluminium sesquioxide mass fraction be 20% and
Graphene oxide mass fraction is 0.4%.
Embodiment two:
Step one: the preparation method of stannic oxide/graphene nano lamella dispersion liquid:
It is in 98% concentrated sulphuric acid that the graphite powder of 5 parts is slowly added to 100 parts of mass fractions, controls system
Temperature 5 DEG C, the potassium permanganate being slowly added to 15 parts after stirring reacts 4 hours, is warmed up to 40 DEG C the most again
Continue reaction 2.5 hours, be slow added into 180 parts of deionized waters, be warming up to 90 DEG C and react 2 hours；So
After be cooled to 35 DEG C dropping 40 parts of mass fractions 30% hydrogenperoxide steam generators, react 1.5 hours, ultrasound wave
Disperse to prepare for 1.5 hours stannic oxide/graphene nano lamella dispersion liquid, control the dispersion of stannic oxide/graphene nano lamella
Containing graphene oxide lamella mass fraction in liquid is 1%.
Step 2: the preparation of basifier solution:
Basifier solution is the solution that 8 parts of sodium carbonate are dissolved in that 20 parts of deionized waters are formed.
Step 3: the preparation of dispersant:
Dispersant is made up of dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC, the weight of described material
Ratio is 0.8:1.5.
Step 4: the preparation method of graphene oxide/aluminum nano-composite tanning agent:
Stannic oxide/graphene nano lamella dispersion liquid 50 parts and 30 parts of aluminum chloride is taken in reactor according to mass parts
The regulation pH that stirs is 3.0, is heated to 95 DEG C, addition p-methyl benzenesulfonic acid 1 part, insulation reaction 2 hours,
Then cool to 80 DEG C, be added slowly with stirring basifier 12 parts, insulation reaction 4 hours, cool to
30 DEG C, the pH value of regulation solution is 4.0, adds the dispersant of 1 part, and ultrasound wave disperses 1.5 hours, gained
Product is graphene oxide/aluminum nano-composite tanning agent, and the mass fraction controlling aluminium sesquioxide is 25% and oxygen
Functionalized graphene mass fraction is 0.6%.
Embodiment three:
Step one: the preparation method of stannic oxide/graphene nano lamella dispersion liquid:
It is in 98% concentrated sulphuric acid that the graphite powder of 4 parts is slowly added to 90 parts of mass fractions, controls the temperature of system
Spending 3 DEG C, the potassium permanganate being slowly added to 12 parts after stirring reacts 3.5 hours, is warmed up to 35 DEG C the most again
Continue reaction 2 hours, be slow added into 170 parts of deionized waters, be warming up to 85 DEG C and react 1.5 hours；So
After be cooled to 30 DEG C dropping 35 parts of mass fractions 30% hydrogenperoxide steam generators, react 1.5 hours, ultrasound wave
Disperse to prepare for 1.5 hours stannic oxide/graphene nano lamella dispersion liquid, control the dispersion of stannic oxide/graphene nano lamella
Containing graphene oxide lamella mass fraction 1% in liquid.
Step 2: the preparation of basifier solution:
Basifier solution is the solution that 10 parts of sodium bicarbonate are dissolved in that 20 parts of deionized waters are formed.
Step 3: the preparation of dispersant:
Dispersant is made up of dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC, the weight of described material
Ratio is 0.6:1.3.
Step 4: the preparation method of graphene oxide/aluminum nano-composite tanning agent:
Stannic oxide/graphene nano lamella dispersion liquid 45 parts and 28 parts of aluminum chloride is taken in reactor according to mass parts
The regulation pH that stirs is 2.5, is heated to 90 DEG C, adds p-methyl benzenesulfonic acid 0.8 part, insulation reaction 1.5
Hour, then cool to 75 DEG C, be added slowly with stirring basifier 10 parts, insulation reaction 3.5 hours,
Cooling to 30 DEG C, the pH value of regulation solution is 3.5, adds 1 part of dispersant, and ultrasound wave disperses 1 hour,
Products therefrom is graphene oxide/aluminum nano-composite tanning agent, control aluminium sesquioxide mass fraction be 23% with
And graphene oxide mass fraction is 0.5%.
Claims (4)
- null1. the preparation method of graphene oxide/aluminum nano-composite tanning agent，It is characterized in that，This preparation method is: take stannic oxide/graphene nano lamella dispersion liquid 40 ~ 50 parts according to mass parts and 25 ~ 30 parts of the aluminum chloride regulation pH that stirs in reactor is 2.0 ~ 3.0，It is heated to 85 ~ 95 DEG C，Add p-methyl benzenesulfonic acid 0.5 ~ 1 part，Insulation reaction 1 ~ 2 hour，Then 70 ~ 80 DEG C are cooled to，It is added slowly with stirring basifier 6 ~ 12 parts，Insulation reaction 3 ~ 4 hours，Cool to 25 ~ 30 DEG C，The pH value of regulation solution is 3.5 ~ 4.0，Add the dispersant of 0.5 ~ 1 part，Ultrasound wave disperses 1 ~ 1.5 hour，Products therefrom is graphene oxide/aluminum nano-composite tanning agent，Wherein the content of aluminum is 20% ~ 25% according to the mass fraction of aluminium sesquioxide，Graphene oxide mass fraction is 0.4 ~ 0.6%.
- The preparation method of graphene oxide the most according to claim 1/aluminum nano-composite tanning agent, it is characterized in that: containing graphene oxide lamella mass fraction in described stannic oxide/graphene nano lamella dispersion liquid is 1%, and the size of described graphene oxide lamella is 5 ~ 30 nanometers.
- The preparation method of graphene oxide the most according to claim 2/aluminum nano-composite tanning agent, it is characterised in that: described basifier is that 10 parts of sodium bicarbonate are dissolved in 20 parts of deionized waters or 8 parts of sodium carbonate are dissolved in the solution that 20 parts of deionized waters are formed.
- The preparation method of graphene oxide the most according to claim 1/aluminum nano-composite tanning agent, it is characterized in that: described dispersant is made up of dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC, the weight ratio of described dodecyl hydroxypropyl sulfobetaines and penetrating agent JFC is 0.5 ~ 0.8:1 ~ 1.5.
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| CN105779668B (en) * | 2016-03-29 | 2017-10-20 | 陕西科技大学 | Zirconium tanning agent/stannic oxide/graphene nano composite tanning agent and preparation method thereof |
| CN105755185B (en) * | 2016-03-29 | 2017-10-24 | 陕西科技大学 | Titanium tannage agent/stannic oxide/graphene nano composite tanning agent and preparation method thereof |
| CN108929923B (en) * | 2018-02-08 | 2020-10-27 | 陕西科技大学 | Modified graphene oxide small-size nanosheet layer water-phase uniform dispersion liquid for leather auxiliary agent and preparation method and application thereof |
| CN108359753B (en) * | 2018-04-17 | 2020-07-17 | 白银普瑞特化工有限公司 | Preparation method and application of aluminum tanning agent complex capable of polymerizing in skin collagen |
| CN110957058B (en) * | 2019-12-25 | 2022-09-16 | 陕西科技大学 | Conductive leather and preparation method thereof |
| CN113736929B (en) * | 2021-10-15 | 2022-05-17 | 齐鲁工业大学 | Method for preparing high-physical-property leather by in-situ reduction of graphene oxide |
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| US20080229511A1 (en) * | 2007-03-23 | 2008-09-25 | Council Of Scientific & Industrial Research | Process for the Preparation of Synthetic Tanning Agent for Improved Leather Characteristics |
| CN102321771B (en) * | 2011-08-22 | 2015-03-11 | 温州大学 | Chrome-free metal composite tanning agent and preparation method thereof |
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