CN113736929B - Method for preparing high-physical-property leather by in-situ reduction of graphene oxide - Google Patents

Method for preparing high-physical-property leather by in-situ reduction of graphene oxide Download PDF

Info

Publication number
CN113736929B
CN113736929B CN202111201469.8A CN202111201469A CN113736929B CN 113736929 B CN113736929 B CN 113736929B CN 202111201469 A CN202111201469 A CN 202111201469A CN 113736929 B CN113736929 B CN 113736929B
Authority
CN
China
Prior art keywords
graphene oxide
leather
nano graphene
dispersion liquid
reducing agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111201469.8A
Other languages
Chinese (zh)
Other versions
CN113736929A (en
Inventor
李彦春
杨新乐
杨茂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202111201469.8A priority Critical patent/CN113736929B/en
Publication of CN113736929A publication Critical patent/CN113736929A/en
Application granted granted Critical
Publication of CN113736929B publication Critical patent/CN113736929B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

The invention discloses a method for preparing high-physical-property leather by in-situ reduction of graphene oxide, belongs to the technical field of application of leather functional materials, and particularly relates to a method for preparing high-physical-property leather by adding nano graphene oxide dispersion liquid into acidified leather for dispersion, adding a certain amount of chromium powder for chrome tanning after dispersion, and adding a reducing agent for in-situ reduction of nano graphene oxide after chrome tanning is completed. According to the invention, after nano graphene oxide is added into the leather to permeate into the leather in the chrome tanning process, the reducing agent is added to reduce the graphene oxide in situ, so that the tensile strength and the tearing strength of the finished leather are obviously improved, the absorption of chrome during tanning is improved, the thermal conductivity is improved, the physical performance of the leather is obviously improved, and the method has the characteristics of simplicity in operation, less dosage, less pollution and obvious effect.

Description

Method for preparing high-physical-property leather by in-situ reduction of graphene oxide
Technical Field
The invention belongs to the technical field of leather functional material application, and particularly relates to a method for preparing high-physical-property leather by in-situ reduction of graphene oxide.
Background
The leather is made from fresh hide through several dozens of processes of soaking, degreasing, unhairing, pickling, tanning, neutralizing, fatliquoring finishing and the like, wherein the most critical process is tanning, tanning is a process of adding a tanning agent to convert the hide into cooked skin with moisture, the leather tanning agent reacts with skin collagen fibers to form chemical bonding, and a cross-linking structure is formed among natural protein fibers, so that the leather has low antimicrobial effect, good mechanical property and proper elasticity and softness. Currently, the main tanning processes are: 1) inorganic salt tanning, such as metal salts of chromium, aluminum and the like form coordinate bonds with carboxyl groups on protein fibers; 2) organic tanning, such as aldehyde compounds and phenolic compounds, forming covalent bonds with amino groups and hydroxyl groups on protein fibers; 3) vegetable tanning utilizes the action of high molecular weight substances in vegetable juice with protein fibers through hydrogen bonds and ionic bonds.
In the method, the content of aldehyde tanning formaldehyde is high, leather is not resistant to yellowing, and a vegetable tanning leather blank has poor whiteness and yellowing. Due to the special electronic layer structure of chromium, tanned leather has the characteristics of good flexibility, extensibility, heat-resistant stability and water vapor permeability, and is widely applied to leather production and always dominates the production due to the excellent properties of softness, fullness, high humidity and heat resistance and the like. However, since the utilization rate of chromium salt in the current chrome tanning method is low, a large amount of trivalent chromium is discharged without being absorbed, causing serious environmental pollution. The main way to reduce the amount of chromium solvent is to increase the absorption rate of the chrome tanning agent and thus reduce the emission of chromium containing pollutants, but at present the effect is limited.
Graphene is an ideal two-dimensional crystal, and has a perfect crystal structure, extremely high electrical and thermal conductivity, excellent optical and mechanical properties and the like. Graphene Oxide (GO) serving as a graphene derivative also has good physical properties, the graphene oxide aqueous dispersion has good stability, active groups capable of reacting with leather collagen fibers such as hydroxyl, carboxyl and carbonyl are contained on the surface and the edge of the nanosheet layer, and a nano-size effect and a small-size effect are also contained between the collagen fibers, so that the nano-graphene oxide can be used in the leather production process. Graphene can be obtained after reduction of graphene oxide, but oxygen-containing functional groups in graphene oxide cannot be completely removed, and a conjugated structure cannot be completely restored, so that the graphene oxide is generally called Reduced Graphene Oxide (RGO). The higher the degree of reduction, the closer to the original properties of graphene.
Disclosure of Invention
The invention provides a method for preparing high-physical-property leather by in-situ reduction of graphene oxide, aiming at the problems of small chromium absorption amount and poor leather physical property in the chrome tanning process in the prior art. The invention is realized by the following technical scheme:
a method for preparing high-physical-property leather by in-situ reduction of graphene oxide comprises the steps of adding nano graphene oxide dispersion liquid into acidified acid leather for dispersion, adding a certain amount of chromium powder for chrome tanning after dispersion, and adding a reducing agent for in-situ reduction of nano graphene oxide after the chrome tanning is finished.
Further, the preparation method of the nano graphene oxide dispersion liquid comprises the following steps: ultrasonically dispersing nano graphene oxide water liquid with the mass percentage concentration of 0.05-0.2% for 1-1.5 h, adding a dispersing agent with the mass percentage concentration of 0.5-2% of the nano graphene oxide water liquid, and ultrasonically treating for 1-2 h to obtain nano graphene oxide dispersion liquid.
Furthermore, the dispersant is more than one of dodecyl benzene sulfonic acid, penetrant JFC, peregal O-25 and citric acid.
The reducing agent is one or more of ascorbic acid, reducing sugar, sodium bisulfite, sodium thiosulfate and sodium sulfite.
Further, the reducing agent is ascorbic acid.
Further, the addition amount of the chromium powder is 6% of the mass of the pickled Chinese cabbage skin.
Further, the chromium powder is basic chromium sulfate.
Further, the addition amount of the reducing agent is 3-10% of the mass of the nano graphene oxide dispersion liquid.
The nano graphene oxide can be reduced to obtain graphene, but oxygen-containing functional groups in the graphene oxide cannot be completely removed, and a conjugated structure cannot be completely recovered, so that the nano graphene oxide is generally called Reduced Graphene Oxide (RGO). The higher the degree of reduction, the closer to the original properties of graphene. According to the invention, under the action of ultrasonic waves and a dispersing agent, the graphene oxide sheet layer is reduced in size and is uniformly dispersed in an aqueous solution, so that the graphene oxide sheet layer can penetrate into leather collagen fibers. The surface and the edge of the nano graphene oxide sheet layer contain active groups such as hydroxyl, carboxyl, carbonyl and the like which can react with collagen fibers of leather, and a nano size effect and a small size effect are achieved between the collagen fibers, so that the nano graphene oxide can generate a gain effect on the leather after penetrating into the leather. After the graphene oxide permeates into the skin, a reducing agent is added, so that oxygen-containing functional groups which are not combined with the graphene oxide in the skin are removed, the graphene oxide is reduced in situ, a conjugated structure is recovered, the performance of the graphene oxide is improved, and the performance of the leather is further improved.
Advantageous effects
(1) The invention reduces the size of the graphene oxide lamella by the action of ultrasonic waves and a dispersing agent, the surface and the edge of the nano graphene oxide lamella contain active groups which can react with the collagen fiber, such as hydroxyl, carboxyl, carbonyl and the like, and the nano graphene oxide lamella has a nano size effect and a small size effect among the collagen fibers, thereby generating a gain effect on the leather; (2) according to the invention, after nano graphene oxide is added into the leather to permeate into the leather in the chrome tanning process, the reducing agent is added to reduce the graphene oxide in situ, so that the tensile strength and the tearing strength of the finished leather are obviously improved, the absorption of chrome during tanning is improved, the thermal conductivity is improved, the physical performance of the leather is obviously improved, and the method has the characteristics of simplicity in operation, less dosage, less pollution and obvious effect.
Drawings
FIG. 1 is a grain and flesh map of the pickled skins of example 2 before and after reduction and of conventional chrome tanned skins.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description is provided clearly and completely, and other similar embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present application based on the embodiments in the present application.
The parts described in the following examples are parts by weight, and the kraft pickled hides used in examples 1 to 3 and comparative example 1 are kraft pickled hides of the same specification.
Example 1
(1) Preparing a nano graphene oxide dispersion liquid: taking 100 parts of nano graphene oxide dispersion liquid with the mass fraction of 0.1%, carrying out ultrasonic treatment for 1 hour, then adding 0.5 part of dispersing agent (the dispersing agent is sodium dodecyl sulfate and citric acid with the mass ratio of 5: 2), and carrying out ultrasonic treatment for 2 hours to obtain the nano graphene oxide dispersion liquid;
(2) chrome tanning and graphene oxide infiltration: adding 7% of salt into a rotary drum, adjusting the liquid ratio to be 1, the water temperature to be 33 ℃ and the pH value to be 2.5-3.0, rotating for 15 minutes, putting cowhide pickled skin, adding the nano graphene oxide dispersion liquid obtained in the step (1), rotating for 1.5 hours, adding basic chromium sulfate accounting for 6% of the mass of the pickled skin, and rotating for 1.5 hours; adjusting the pH value to 3.5-4.0 by using sodium formate and sodium bicarbonate, rotating for 1 hour, and standing overnight;
(3) in-situ reduction of graphene oxide: adjusting the liquid ratio to be 1 in a rotary drum, adding the cowhide treated in the step (2) at the water temperature of 45 ℃, adding 5 parts of sodium bisulfite, rotating for 10 hours, stopping the drum, staying overnight, neutralizing and fatting by adopting a conventional process, taking out, standing and airing.
Example 2
(1) Preparing a nano graphene oxide dispersion liquid: taking 100 parts of nano graphene oxide water solution with the mass fraction of 0.15%, carrying out ultrasonic treatment for 1 hour, then adding 0.5 part of dispersing agent (the dispersing agent is sodium dodecyl sulfate, peregal-O25 and citric acid with the mass ratio of 10:1: 2), and carrying out ultrasonic treatment for 1.5 hours to obtain nano graphene oxide dispersion liquid;
(2) chrome tanning and graphene oxide infiltration: adding 7% of salt into a rotary drum, adjusting the liquid ratio to be 1, the water temperature to be 33 ℃ and the pH value to be 2.5-3.0, rotating for 15 minutes, then adding cow leather to soak acid skin, adding the nano graphene oxide dispersion liquid obtained in the step (1), rotating for 1.5 hours, adding basic chromium sulfate accounting for 6% of the mass of the acid skin, and rotating for 1.5 hours; adjusting pH to 3.5-4.0 with sodium formate and sodium bicarbonate, rotating for 1 hr, standing overnight, and showing grain and meat surface of cow hide as shown in fig. 1 (before Go reduction);
(3) in-situ reduction of graphene oxide: adjusting the liquid ratio to be 1 in a rotary drum, adding the cowhide treated in the step (2) at the water temperature of 50 ℃, adding 10 parts of ascorbic acid, rotating for 10 hours, stopping the drum, standing overnight, neutralizing and fatting by adopting a conventional process, taking out, standing and airing, wherein the grain surface and flesh surface of the obtained cowhide leather are shown in fig. 1 (after Go reduction).
Example 3
(1) Preparing a nano graphene oxide dispersion liquid: taking 200 parts of nano graphene oxide dispersion liquid with the mass fraction of 0.2%, carrying out ultrasonic treatment for 1 hour, then adding 1 part of dispersing agent (the dispersing agent is sodium dodecyl sulfate and penetrating agent JFC with the mass ratio of 2: 1), and carrying out ultrasonic treatment for 2 hours to obtain the nano graphene oxide dispersion liquid;
(2) chrome tanning and graphene oxide infiltration: adding 7% of salt into a rotary drum, adjusting the liquid ratio to be 1, the water temperature to be 33 ℃ and the pH value to be 2.5-3.0, rotating for 15 minutes, then adding cow leather to soak acid skin, adding the nano graphene oxide dispersion liquid obtained in the step (1), rotating for 1.5 hours, adding basic chromium sulfate accounting for 6% of the mass of the acid skin, and rotating for 1.5 hours; adjusting the pH value to 3.5-4.0 by using sodium formate and sodium bicarbonate, rotating for 1 hour, and standing overnight;
(3) in-situ reduction of graphene oxide: adjusting the liquid ratio to be 1 in a rotary drum, adding the cowhide treated in the step (2) at the water temperature of 50 ℃, adding 20 parts of reducing sugar, rotating for 10 hours, stopping the drum, staying overnight, neutralizing and fatting by adopting a conventional process, taking out, standing and airing.
Comparative example 1
(1) Preparing a nano graphene oxide dispersion liquid: taking 100 parts of nano graphene oxide dispersion liquid with the mass fraction of 0.1%, carrying out ultrasonic treatment for 1 hour, then adding 0.5 part of dispersing agent (the dispersing agent is sodium dodecyl sulfate, peregal-O25 and citric acid with the mass ratio of 10:1:2, and carrying out ultrasonic treatment for 1.5 hours to obtain the nano graphene oxide dispersion liquid;
(2) chrome tanning and graphene oxide infiltration: adding salt into a rotary drum, adjusting the liquid ratio, the water temperature and the pH value, rotating for 15 minutes, then adding cowhide and pickling acid skin, adding the nano graphene oxide dispersion liquid obtained in the step (1), rotating for 1.5 hours, adding 6% chromium powder, and rotating for 1.5 hours; adjusting the pH value to 3.5-4.0 by using sodium formate and sodium bicarbonate, rotating for 1 hour, standing overnight, neutralizing by adopting a conventional process, adding fat, taking out, standing and airing.
Application examples
The physical properties (shrinkage temperature, tensile strength, elongation at break, tear strength and thermal conductivity) and the intracutaneous Gr content of the cowhide leather treated in the embodiments 1-3 and the comparative example 1 are detected, sampling detection is carried out according to national and industrial standards QB/T2710-. As can be seen from tables 1 and 2, the method of the application can obviously improve the physical properties of the finished leather, improve the heat conductivity coefficient of the leather, increase the absorption of chromium during tanning and reduce the discharge of chromium-polluted wastewater.
Table 1 shows the physical properties of the treated leathers of conventional chrome tanned leathers of examples 1 to 3 and comparative example 1
Figure DEST_PATH_IMAGE001
TABLE 2 results of thermal conductivity test of treated cow leather of conventional chrome tanned leather, example 2 and comparative example 1
Figure 357983DEST_PATH_IMAGE002
。

Claims (5)

1. A method for preparing leather with high thermal conductivity coefficient, high tensile strength and high elongation at break by in-situ reduction of graphene oxide is characterized in that nano graphene oxide dispersion liquid is added into acidified acid leather for dispersion, a certain amount of chromium powder is added for chrome tanning after dispersion, and a reducing agent is added for in-situ reduction of nano graphene oxide after chrome tanning is completed;
the preparation method of the nano graphene oxide dispersion liquid comprises the following steps: ultrasonically dispersing nano graphene oxide water liquid with the mass percentage concentration of 0.05-0.2% for 1-1.5 h, adding a dispersing agent with the mass percentage concentration of 0.5-2% of the nano graphene oxide water liquid, and ultrasonically treating for 1-2 h to obtain nano graphene oxide dispersion liquid;
the addition amount of the chromium powder is 6 percent of the mass of the pickled Chinese cabbage skin;
the addition amount of the reducing agent is 3-10% of the mass of the nano graphene oxide dispersion liquid.
2. The method according to claim 1, wherein the dispersant is one or more of dodecylbenzene sulfonic acid, penetrant JFC, peregal O-25, and citric acid.
3. The method of claim 1, wherein the reducing agent is one or more of ascorbic acid, reducing sugar, sodium bisulfite, sodium thiosulfate, and sodium sulfite.
4. The method of claim 3, wherein the reducing agent is ascorbic acid.
5. The method of claim 1 wherein said chromium powder is basic chromium sulfate.
CN202111201469.8A 2021-10-15 2021-10-15 Method for preparing high-physical-property leather by in-situ reduction of graphene oxide Active CN113736929B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111201469.8A CN113736929B (en) 2021-10-15 2021-10-15 Method for preparing high-physical-property leather by in-situ reduction of graphene oxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111201469.8A CN113736929B (en) 2021-10-15 2021-10-15 Method for preparing high-physical-property leather by in-situ reduction of graphene oxide

Publications (2)

Publication Number Publication Date
CN113736929A CN113736929A (en) 2021-12-03
CN113736929B true CN113736929B (en) 2022-05-17

Family

ID=78726723

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111201469.8A Active CN113736929B (en) 2021-10-15 2021-10-15 Method for preparing high-physical-property leather by in-situ reduction of graphene oxide

Country Status (1)

Country Link
CN (1) CN113736929B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114318889A (en) * 2021-12-14 2022-04-12 无锡市曼优丽新型复合材料有限公司 High-physical-property military belt leather and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104232808B (en) * 2014-09-23 2016-06-29 陕西科技大学 graphene oxide and trivalent chromium complex tanning agent and preparation method thereof
CN104894302B (en) * 2015-03-30 2017-04-05 陕西科技大学 Graphene oxide/ferrum nano-composite tanning agent and preparation method thereof
CN104745736B (en) * 2015-03-30 2017-01-11 陕西科技大学 Graphene/aluminium oxide nano-composite tanning agent and preparation method thereof

Also Published As

Publication number Publication date
CN113736929A (en) 2021-12-03

Similar Documents

Publication Publication Date Title
Beghetto et al. The leather industry: a chemistry insight Part I: an overview of the industrial process
CN113736929B (en) Method for preparing high-physical-property leather by in-situ reduction of graphene oxide
AU2008331353B2 (en) Method of preserving hides and skins
CN105734183B (en) Sheepskin china picture-character paper
CN100355907C (en) Composition of tanning agent containing modified tara mimosa extract, and bating method without chrome
KR20100111271A (en) Agent and method for tanning skins and pelts
CN113227407B (en) Preparation of leather auxiliary before tanning
CN102443660B (en) Fur tanning-piercing and printing process and tanning fur
CN1928123A (en) Hair-protection and hair-removing composition of organosilicon and enzyme and method for hair-protection and hair-removing animal skin by the same
CN111118235B (en) Method for tanning leather by external electric field
CN111118234B (en) Non-chrome leather tanning method
CN113999943B (en) Polysaccharide-based hydrotalcite nano composite tanning agent and preparation method and application thereof
CN106834563B (en) A method of few salt pickling, tanning leather
CN102224261B (en) Methods of preserving hides
CN106350619B (en) The method of few chromium combination tanning after a kind of immersion of complex enzyme formulation
CN106167841B (en) A kind for the treatment of process of woolfell
CN104831003A (en) Enzyme treatment method capable of softening vegetable leather
CN105543423A (en) Novel environment-friendly tanning technology
Sathish et al. Salt-free Chromium Tanning: Practical Approaches
Kopp et al. 19 Application of Cellulose
US1567644A (en) Tanning of skins and hides
US680604A (en) Process of working leather.
CN109880943A (en) A kind of salt-free not pickling Animal Skin chrome tanning method based on composite ligand synergistic effect
Zhang et al. Collagen Fiber Opening of Cattle Hides in Urea/Calcium Hydroxide Solutions
KR100288734B1 (en) Leather processing method using alum

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant