CN104745736A - 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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- CN104745736A CN104745736A CN201510144047.XA CN201510144047A CN104745736A CN 104745736 A CN104745736 A CN 104745736A CN 201510144047 A CN201510144047 A CN 201510144047A CN 104745736 A CN104745736 A CN 104745736A
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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/aluminium nano-composite 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 that tanning agent and materials with hide glue fibril there occurs chemical reaction, the process of tanning agent and collagen generation chemical reaction is called tanning, tanned rawhide become there is certain mechanical strength, resistance toly to deposit, the leather of soft and certain purposes.What can be used as leather retanning agent in theory has chrome tanning agent, zirconium tanning agent, titanium tannage agent, aluminum tanning agent, iron tannage agent, vegetable tanning agent, aldehyde tanning agent, synthetic tanning agent etc., in fact the over-all properties due to chrome tanning agent tan leather is best, only have chrome tanning agent to obtain to apply widely, current chrome tanning leather accounts for about 90% (Wang Wei outstanding person of leather output, Liao Xuepin, Shi Bi. the extraction of tea-polyphenol and the application in tanning thereof in the secondary tea of green tea. Chinese leather, 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 ofthe society ofleather technologists and chemists, 2012,96 (4): 133-140).A large amount of uses of chrome tanning agent create another one problem, the waste water containing chromium, mud, the scrap leather bits that are difficult in a large number administer can be produced exactly in Chrome Tanning Process, in addition tanning agent and the trivalent chromium contained in chromium pollutant can be converted into the larger sexavalent chrome of harm under certain condition, therefore the domestic and international use to chrome tanning agent proposes restriction (Li Dongling at present, Dan Zhihua, Yang Meng, Deng. plant the research of aldehyde combination tannage rigid matrix ageing resistance. Chinese leather, 2014,43 (13): 27-30).Therefore, the focus that chrome-free tanning agent etc. becomes research is researched and developed at present.There is the object that affluent resources and the little aluminum tanning agent, iron tannage agent etc. of pollution hazard degree become research again.The subject matter that aluminum tanning agent exists is the shrinkage temperature lower (70 ~ 75 DEG C) of tan leather, and the leather of tanning is not water-fast, and after dipped water, tanning successful goes down, and tan leather plate is hard, flat thin etc.Tanning agent or vegetable tanning agent, glutaraldehyde tanning agent, the synthetic tanning agent etc. of the current chromium mainly good with tanning performance for the improvement of aluminum tanning agent, zirconium, titanium carry out in conjunction with tanning (Liu Zilong, Zhang Hui, Qiang Xihuai, Li Meng. the preparations and applicatio of sial fitting-type tanning agent. Chinese leather, 2014,43 (21): 223-27; Xu Xiaoying, Tian Cheng, Guo Cheng, etc. organic acid covers the application of aluminum complex tanning agent in less chrome tannage of limiting. Chinese leather, 2013,42 (7): 1-7; He Qing, but defend China, but time, Deng. a kind of less chrome tannage totally enclosed circulating technology coordinating tanning agent based on Zirconium-aluminum-titanium. Chinese leather, 2013,42 (7): 5-9), but the effect of these modifications still improve limited, result in aluminum current tanning agent and still cannot be applied to tanning production, can not substitute chromium tanning agent.We find that forming nano-composite tanning agent by GO and aluminium can significantly improve aluminum tanning agent tanning effect, can be used as tanning agent under study for action.
Summary of the invention
For solving the technical problem of existing existence, the embodiment of the present invention provides a kind of graphene oxide/aluminium nano-composite tanning agent and preparation method thereof, gained tanning agent by trivalent aluminium with coordinate bond, covalent linkage etc. form nano-composite tanning agent with stannic oxide/graphene nano lamella, when with graphene oxide/aluminium nano-composite tanning agent tan leather, the multiple spot chemical bonds that on GO nanoscale twins, active group and aluminum tanning agent and collagen are formed and nano effect and produce tanning effect, the participation of GO nanoscale twins improves the tanning effect of aluminum tanning agent, improve the wash durability of tan leather and the stability of tan leather performance.
For achieving the above object, 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/aluminium nano-composite tanning agent, is made up according to mass parts of following material:
Stannic oxide/graphene nano lamella dispersion liquid 40 ~ 50 parts, 25 ~ 30 parts, aluminum chloride, tosic acid 0.5 ~ 1 part, basifier solution 20 ~ 25 parts, dispersion agent 0.5 ~ 1 part.
In such scheme, containing graphene oxide lamella massfraction in described stannic oxide/graphene nano lamella dispersion liquid is 1%, and described graphene oxide lamella is of a size of 5 ~ 30 nanometers.
In such scheme, described basifier solution is that 10 parts of sodium bicarbonates are dissolved in 20 parts of deionized waters or 8 parts of sodium carbonate and are dissolved in the solution that 20 parts of deionized waters are formed.
In such scheme, described dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, and the weight ratio of described dodecyl hydroxypropyl sultaine and penetrating agent JFC is 0.5 ~ 0.8:1 ~ 1.5.
The embodiment of the present invention also provides the preparation method of a kind of graphene oxide/aluminium nano-composite tanning agent, this preparation method is: get stannic oxide/graphene nano lamella dispersion liquid 40 ~ 50 parts and 25 ~ 30 parts, aluminum chloride according to mass parts and stir in reactor and regulate pH to be 2.0 ~ 3.0, be heated to 85 ~ 95 DEG C, add tosic acid 0.5 ~ 1 part, insulation reaction 1 ~ 2 hour, then 70 ~ 80 DEG C are cooled to, under agitation slowly add basifier 6 ~ 12 parts, insulation reaction 3 ~ 4 hours, cool to 25 ~ 30 DEG C, the pH value of regulator solution is 3.5 ~ 4.0, add the dispersion agent of 0.5 ~ 1 part, ultrasonic wave dispersion 1 ~ 1.5 hour, products therefrom is graphene oxide/aluminium nano-composite tanning agent, wherein the content of aluminium is 20% ~ 25% according to the massfraction of aluminium sesquioxide, graphene oxide massfraction is 0.4 ~ 0.6%.
In such scheme, containing graphene oxide lamella massfraction in described stannic oxide/graphene nano lamella dispersion liquid is 1%, and described graphene oxide lamella is of a size of 5 ~ 30 nanometers.
In such scheme, described basifier solution is that 10 parts of sodium bicarbonates are dissolved in 20 parts of deionized waters or 8 parts of sodium carbonate and are dissolved in the solution that 20 parts of deionized waters are formed.
In such scheme, described dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, and the weight ratio of described dodecyl hydroxypropyl sultaine and penetrating agent JFC is 0.5 ~ 0.8:1 ~ 1.5.
Compared with prior art, beneficial effect of the present invention:
The present invention forms nano-complex by the carboxyl of stannic oxide/graphene nano lamella, hydroxyl and the coordination formed between epoxy group(ing) and aluminum chloride, covalent bonds, by suitable regulation and control pH value to increase the hydrolysis of aluminum chloride and to join cumulative power, impel the title complex being formed and there is the multinuclear aluminium that GO nanoscale twins participates in, also dispersion effect is produced to stannic oxide/graphene nano lamella simultaneously.Tanning effect derives from the active group on GO lamella and the active group on materials with hide glue fibril forms chemical bonding effect, multinuclear aluminium joins polyacetylene compound tanning effect and stannic oxide/graphene nano lamella nanometer size effect.
The multiple spot chemical bonds that the nano-composite tanning agent of gained of the present invention is formed by active group and collagen on multinuclear polymerize aluminum chloride and stannic oxide/graphene nano lamella and stannic oxide/graphene nano dimensional effect reach the object of tan leather.When graphene oxide/aluminium nano-composite tanning agent is 5% of tare weight according to solid consumption, the shrinkage temperature of its tan leather reaches 112 DEG C, the specific absorption of aluminum tanning agent reaches 95%, tan leather is washed 10 its shrinkage temperatures and is not almost reduced, wash 20 shrinkage temperatures and reduce 5%, the flexibility of tan leather, elasticity and fullness etc. are close to chrome tanning leather.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The embodiment of the present invention provides a kind of graphene oxide/aluminium nano-composite tanning agent, is made up according to mass parts of following material:
Stannic oxide/graphene nano lamella dispersion liquid 40 ~ 50 parts, 25 ~ 30 parts, aluminum chloride, tosic acid 0.5 ~ 1 part, basifier solution 20 ~ 25 parts, dispersion agent 0.5 ~ 1 part.
The preparation method of described stannic oxide/graphene nano lamella dispersion liquid is: the Graphite Powder 99 of 3 ~ 5 parts slowly being joined 80 ~ 100 parts of massfractions is in 98% vitriol oil, the temperature of the hierarchy of control 0 ~ 5 DEG C, the potassium permanganate slowly adding 10 ~ 15 parts after stirring reacts 3 ~ 4 hours, and then be warmed up to 30 ~ 40 DEG C of continuation reactions 2 ~ 2.5 hours, slowly add 150 ~ 180 parts of deionized waters again, be warming up to 80 ~ 90 DEG C of reactions 1 ~ 2 hour; Then the superoxol that 30 DEG C ~ 35 drip 35 ~ 40 parts of massfractions 30% is cooled to, react 1 ~ 1.5 hour, stannic oxide/graphene nano lamella dispersion liquid is prepared in ultrasonic wave dispersion for 1 ~ 1.5 hour, and containing graphene oxide lamella massfraction in stannic oxide/graphene nano lamella dispersion liquid is 1%; Because the preparation process of described stannic oxide/graphene nano lamella dispersion liquid is comparatively complicated, therefore generally once prepare more consumption, in order to taking as required in preparation process.
Described basifier solution is that 10 parts of sodium bicarbonates are dissolved in 20 parts of deionized waters or 8 parts of sodium carbonate and are dissolved in the solution that 20 parts of deionized waters are formed.
Described dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, and the weight ratio of described dodecyl hydroxypropyl sultaine and penetrating agent JFC is 0.5 ~ 0.8:1 ~ 1.5.
The embodiment of the present invention also provides the preparation method of a kind of graphene oxide/aluminium nano-composite tanning agent, this preparation method is: get stannic oxide/graphene nano lamella dispersion liquid 40 ~ 50 parts and 25 ~ 30 parts, aluminum chloride according to mass parts and stir in reactor and regulate pH to be 2.0 ~ 3.0, be heated to 85 ~ 95 DEG C, add tosic acid 0.5 ~ 1 part, insulation reaction 1 ~ 2 hour, then 70 ~ 80 DEG C are cooled to, under agitation slowly add basifier 6 ~ 12 parts, insulation reaction 3 ~ 4 hours, cool to 25 ~ 30 DEG C, the pH value of regulator solution is 3.5 ~ 4.0, add the dispersion agent of 0.5 ~ 1 part, ultrasonic wave dispersion 1 ~ 1.5 hour, products therefrom is graphene oxide/aluminium nano-composite tanning agent, the massfraction controlling aluminium sesquioxide is 20% ~ 25%, controlled oxidization Graphene massfraction is 0.4 ~ 0.6%.
The tanning agent of invention has the advantage that consumption is few, specific absorption is high, chromium from waste chromium compound residual quantity is low when tanning, and production technique is unique, and technological process easily operates, and has good application prospect.
The present invention is acted on from aluminum chloride by the structural carboxyl of graphene oxide, hydroxyl and epoxy group(ing) etc. under different pH environment, at the nano combined beyond the region of objective existence that formation aluminum chloride is connected with the coordinate bond formed between active group on graphene oxide, covalent linkage, also aluminum chloride polyreaction has been carried out, what make defines graphene oxide/aluminium nano-composite tanning agent, is also that the degree of scatter of stannic oxide/graphene nano lamella increases simultaneously.The active group that tanning effect derives from stannic oxide/graphene nano lamella can form chemical bonding effect, the tanning effect of polymerize aluminum chloride and the nanometer size effect of stannic oxide/graphene nano lamella with the active group on materials with hide glue fibril.
Use graphene oxide/aluminium nano-composite tanning agent tan leather time graphene oxide/aluminium nano-composite tanning agent consumption (with chromium sesquioxide calculate) for tare weight 5%, graphene oxide (solid consumption) consumption be tare weight 0.20% time, the shrinkage temperature of tan leather can be made to reach 112 DEG C, and the specific absorption of aluminum tanning agent reaches 95%.
Embodiment one:
Step one: the preparation of stannic oxide/graphene nano lamella dispersion liquid:
The Graphite Powder 99 of 3 parts slowly being joined 80 parts of massfractions is in 98% vitriol oil, the temperature of the hierarchy of control 0 DEG C, the potassium permanganate slowly adding 10 parts after stirring reacts 3 hours, and then be warmed up to 30 DEG C of continuation reactions 2 hours, slowly add 150 parts of deionized waters again, be warming up to 80 DEG C of reactions 1 hour; Then the superoxol that 30 DEG C drip 35 parts of massfractions 30% is cooled to, react 1 hour, ultrasonic wave disperses within 1 hour, to prepare stannic oxide/graphene nano lamella dispersion liquid, and containing graphene oxide lamella massfraction in controlled oxidization graphene nano lamella dispersion liquid is 1%.
Step 2: the preparation of basifier solution:
Basifier solution is the solution that 10 parts of sodium bicarbonates are dissolved in 20 parts of deionized waters formation.
Step 3: the preparation of dispersion agent:
Dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, and the weight ratio of described material is 0.5:1.
Step 4: the preparation method of graphene oxide/aluminium nano-composite tanning agent:
Get stannic oxide/graphene nano lamella dispersion liquid 40 parts and 25 parts, aluminum chloride according to mass parts to stir in reactor and regulate pH to be 2.0, be heated to 85 DEG C, add tosic acid 0.5 part, insulation reaction 1 hour, then 70 DEG C are cooled to, under agitation slowly add basifier 6 parts, insulation reaction 3 hours, cool to 25 DEG C, the pH value of regulator solution is 3.5, add the dispersion agent of 0.5 part, ultrasonic wave disperses 1 hour, products therefrom is graphene oxide/aluminium nano-composite tanning agent, control the massfraction of aluminium sesquioxide be 20% and graphene oxide massfraction be 0.4%.
Embodiment two:
Step one: the preparation method of stannic oxide/graphene nano lamella dispersion liquid:
The Graphite Powder 99 of 5 parts slowly being joined 100 parts of massfractions is in 98% vitriol oil, the temperature of the hierarchy of control 5 DEG C, the potassium permanganate slowly adding 15 parts after stirring reacts 4 hours, and then be warmed up to 40 DEG C of continuation reactions 2.5 hours, slowly add 180 parts of deionized waters again, be warming up to 90 DEG C of reactions 2 hours; Then the superoxol that 35 DEG C drip 40 parts of massfractions 30% is cooled to, react 1.5 hours, ultrasonic wave disperses within 1.5 hours, to prepare stannic oxide/graphene nano lamella dispersion liquid, and containing graphene oxide lamella massfraction in controlled oxidization graphene nano lamella dispersion liquid is 1%.
Step 2: the preparation of basifier solution:
Basifier solution is the solution that 8 parts of sodium carbonate are dissolved in 20 parts of deionized waters formation.
Step 3: the preparation of dispersion agent:
Dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, and the weight ratio of described material is 0.8:1.5.
Step 4: the preparation method of graphene oxide/aluminium nano-composite tanning agent:
Get stannic oxide/graphene nano lamella dispersion liquid 50 parts and 30 parts, aluminum chloride according to mass parts to stir in reactor and regulate pH to be 3.0, be heated to 95 DEG C, add tosic acid 1 part, insulation reaction 2 hours, then 80 DEG C are cooled to, under agitation slowly add basifier 12 parts, insulation reaction 4 hours, cool to 30 DEG C, the pH value of regulator solution is 4.0, add the dispersion agent of 1 part, ultrasonic wave disperses 1.5 hours, products therefrom is graphene oxide/aluminium nano-composite tanning agent, control the massfraction of aluminium sesquioxide be 25% and graphene oxide massfraction be 0.6%.
Embodiment three:
Step one: the preparation method of stannic oxide/graphene nano lamella dispersion liquid:
The Graphite Powder 99 of 4 parts slowly being joined 90 parts of massfractions is in 98% vitriol oil, the temperature of the hierarchy of control 3 DEG C, the potassium permanganate slowly adding 12 parts after stirring reacts 3.5 hours, and then be warmed up to 35 DEG C of continuation reactions 2 hours, slowly add 170 parts of deionized waters again, be warming up to 85 DEG C of reactions 1.5 hours; Then the superoxol that 30 DEG C drip 35 parts of massfractions 30% is cooled to, react 1.5 hours, ultrasonic wave disperses within 1.5 hours, to prepare stannic oxide/graphene nano lamella dispersion liquid, containing graphene oxide lamella massfraction 1% in controlled oxidization graphene nano lamella dispersion liquid.
Step 2: the preparation of basifier solution:
Basifier solution is the solution that 10 parts of sodium bicarbonates are dissolved in 20 parts of deionized waters formation.
Step 3: the preparation of dispersion agent:
Dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, and the weight ratio of described material is 0.6:1.3.
Step 4: the preparation method of graphene oxide/aluminium nano-composite tanning agent:
Get stannic oxide/graphene nano lamella dispersion liquid 45 parts and 28 parts, aluminum chloride according to mass parts to stir in reactor and regulate pH to be 2.5, be heated to 90 DEG C, add tosic acid 0.8 part, insulation reaction 1.5 hours, then 75 DEG C are cooled to, under agitation slowly add basifier 10 parts, insulation reaction 3.5 hours, cool to 30 DEG C, the pH value of regulator solution is 3.5, add 1 part of dispersion agent, ultrasonic wave disperses 1 hour, products therefrom is graphene oxide/aluminium nano-composite tanning agent, control the massfraction of aluminium sesquioxide be 23% and graphene oxide massfraction be 0.5%.
Claims (8)
1. graphene oxide/aluminium nano-composite tanning agent, is characterized in that, is made up according to mass parts of following material:
Stannic oxide/graphene nano lamella dispersion liquid 40 ~ 50 parts, 25 ~ 30 parts, aluminum chloride, tosic acid 0.5 ~ 1 part, basifier solution 20 ~ 25 parts, dispersion agent 0.5 ~ 1 part.
2. graphene oxide according to claim 1/aluminium nano-composite tanning agent, is characterized in that: containing graphene oxide lamella massfraction in described stannic oxide/graphene nano lamella dispersion liquid is 1%, and described graphene oxide lamella is of a size of 5 ~ 30 nanometers.
3. graphene oxide according to claim 1/aluminium nano-composite tanning agent, is characterized in that: described basifier solution is that 10 parts of sodium bicarbonates are dissolved in 20 parts of deionized waters or 8 parts of sodium carbonate and are dissolved in the solution that 20 parts of deionized waters are formed.
4. graphene oxide according to claim 1/aluminium nano-composite tanning agent, it is characterized in that: described dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, the weight ratio of described dodecyl hydroxypropyl sultaine and penetrating agent JFC is 0.5 ~ 0.8:1 ~ 1.5.
5. the preparation method of graphene oxide/aluminium nano-composite tanning agent, it is characterized in that, this preparation method is: get stannic oxide/graphene nano lamella dispersion liquid 40 ~ 50 parts and 25 ~ 30 parts, aluminum chloride according to mass parts and stir in reactor and regulate pH to be 2.0 ~ 3.0, be heated to 85 ~ 95 DEG C, add tosic acid 0.5 ~ 1 part, insulation reaction 1 ~ 2 hour, then 70 ~ 80 DEG C are cooled to, under agitation slowly add basifier 6 ~ 12 parts, insulation reaction 3 ~ 4 hours, cool to 25 ~ 30 DEG C, the pH value of regulator solution is 3.5 ~ 4.0, add the dispersion agent of 0.5 ~ 1 part, ultrasonic wave dispersion 1 ~ 1.5 hour, products therefrom is graphene oxide/aluminium nano-composite tanning agent, wherein the content of aluminium is 20% ~ 25% according to the massfraction of aluminium sesquioxide, graphene oxide massfraction is 0.4 ~ 0.6%.
6. the preparation method of graphene oxide according to claim 5/aluminium nano-composite tanning agent, it is characterized in that: containing graphene oxide lamella massfraction in described stannic oxide/graphene nano lamella dispersion liquid is 1%, and described graphene oxide lamella is of a size of 5 ~ 30 nanometers.
7. the preparation method of graphene oxide according to claim 6/aluminium nano-composite tanning agent, is characterized in that: described basifier solution is that 10 parts of sodium bicarbonates are dissolved in 20 parts of deionized waters or 8 parts of sodium carbonate and are dissolved in the solution that 20 parts of deionized waters are formed.
8. the preparation method of graphene oxide according to claim 5/aluminium nano-composite tanning agent, it is characterized in that: described dispersion agent is made up of dodecyl hydroxypropyl sultaine and penetrating agent JFC, the weight ratio of described dodecyl hydroxypropyl sultaine and penetrating agent JFC is 0.5 ~ 0.8:1 ~ 1.5.
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| CN105755185A (en) * | 2016-03-29 | 2016-07-13 | 陕西科技大学 | Titanium tanning agent/graphene-oxide nanometer composite tanning agent and preparing method thereof |
| CN105779668A (en) * | 2016-03-29 | 2016-07-20 | 陕西科技大学 | Zirconium tanning agent/oxidized graphene nano-composite tanning agent and preparation method thereof |
| CN108359753A (en) * | 2018-04-17 | 2018-08-03 | 白银普瑞特化工有限公司 | A kind of preparation method and application for the aluminium tanningagent complex that can polymerize in collagen |
| CN108929923A (en) * | 2018-02-08 | 2018-12-04 | 陕西科技大学 | Modified graphene oxide small size nanoscale twins water phase uniform dispersion and its preparation method and application for leather agent |
| CN110957058A (en) * | 2019-12-25 | 2020-04-03 | 陕西科技大学 | Conductive leather and preparation method thereof |
| CN113736929A (en) * | 2021-10-15 | 2021-12-03 | 齐鲁工业大学 | Method for preparing high-physical-property leather by in-situ reduction of graphene oxide |
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| CN105779668A (en) * | 2016-03-29 | 2016-07-20 | 陕西科技大学 | Zirconium tanning agent/oxidized graphene nano-composite tanning agent and preparation method thereof |
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| CN110957058A (en) * | 2019-12-25 | 2020-04-03 | 陕西科技大学 | Conductive leather and preparation method thereof |
| CN113736929A (en) * | 2021-10-15 | 2021-12-03 | 齐鲁工业大学 | Method for preparing high-physical-property leather by in-situ reduction of graphene oxide |
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