CN108467465B - Preparation method of graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent - Google Patents
Preparation method of graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent Download PDFInfo
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- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
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Abstract
The invention relates to a preparation method of a graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent. According to the method, oxidized graphene reacts with a chlorinating agent and diamine respectively to prepare aminated oxidized graphene, a maleic anhydride monomer is grafted onto the aminated oxidized graphene, persulfate is used as an initiator, vinyl acetate, maleic anhydride modified oxidized graphene, acrylamide and the like are used as comonomers, and the graphene-based vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent is prepared through free radical polymerization. The modified graphene is linked with vinyl acetate-maleic anhydride copolymer macromolecules through covalent bonds, so that the modified graphene has good dispersion uniformity and stability, and when the retanning agent is used for retanning and filling leather, the flame retardance, the electric conduction performance, the heat resistance performance, the tear resistance performance, the antibacterial performance and the like of the leather can be effectively improved, and the finished product grade and the international competitiveness of leather products are improved.
Description
Technical Field
The invention belongs to the technical field of leather chemicals, and particularly relates to a preparation method of a graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent.
Background
Leather products have excellent comprehensive properties such as vapor permeability, water permeability, heat resistance, wear resistance, scratch resistance, impact resistance and the like, and are widely applied to various fields such as clothing wearing, furniture packaging, automobile interior decoration and the like. Due to the improvement of people's awareness of fire safety, the leather is required to have good flame-retardant and fireproof performances, and the development of high-efficiency flame-retardant leather becomes a hotspot of research of people. At present, the flame retardant effect of leather is mainly realized in a mode of adding a flame retardant externally in the market, for example, patent CN 104450990A discloses a preparation method of flame retardant leather, and the flame retardant leather is prepared by adding a certain amount of flame retardant in a leather-making wet treatment stage; patent CN 104488758A discloses a method for preparing flame-retardant leather, which comprises the steps of drying wet blue leather, fumigating the leather by nitrogen containing trimethyl aluminum, adding polyallylamine solution for freeze-thaw cycle, and finally adding organic silicon emulsion and nano-silica for dipping and drying to obtain the flame-retardant leather.
Graphene (Graphene) is a polymer made of carbon atoms in sp2The hybrid tracks form a hexagonal planar film in a peak-nest lattice, and the unique two-dimensional monoatomic lamellar structure of the planar film endows graphene with excellent mechanical property, thermal property and electric conductivity, thereby showing wide application prospects in various fields such as materials, energy, biomedicine, information technology and the like. The graphene is introduced into the polymer material to prepare the graphene/polymer composite material, so that the flame retardant property, the mechanical property, the electrical property, the thermal property and the like of the material can be effectively improved. However, due to strong pi-pi interaction, graphene sheets have strong binding tendency, are easy to agglomerate and precipitate in dispersion media such as water and organic solvents, are not beneficial to preparation of composite materials, and simultaneously reduce the unique excellent performance of graphene. The graphene oxide is prepared by introducing active functional groups into a graphene molecular structure by an oxidation method, wherein a large number of oxygen-containing functional groups such as hydroxyl, carboxyl, carbonyl and epoxy exist on the surface of the graphene oxide at the edge of a sheet layer, and the graphene can be functionalized by common chemical reactions by utilizing the oxygen-containing functional groups. For example, patent CN 106946246a discloses "a method for preparing aminated graphene", which utilizes the reaction of carboxyl on graphene oxide with ammonia water to generate amide, then dehydrates amidated graphene with phosphorus oxychloride to generate cyanated graphene, and then carries out catalytic hydrogenation to obtain aminated graphene.
With the research of graphene/polymer nano composite materials, the preparation of graphene-based leather chemical materials by modifying graphene becomes a research and development hotspot. Chinese patent publication No. CN 104232810B discloses a method for preparing a graphene oxide and water-soluble vinyl monomer copolymer leather tanning agent, which realizes the free radical copolymerization reaction of double bonds in a graphene oxide structure and water-soluble vinyl monomers through aqueous solution free radical polymerization reaction, and the obtained copolymer simultaneously contains a graphene oxide nanosheet layer and a water-soluble vinyl structure unit. In the method, the graphene oxide contains double bonds to be copolymerized with vinyl monomers, however, the main body part of the graphene oxide consists of relatively stable six-membered rings, the double bond reaction activity is weak, the degree of free radical copolymerization of the graphene oxide and the vinyl monomers is low, and the graphene oxide cannot be well grafted to a leather tanning agent molecular chain. Therefore, how to introduce graphene with excellent performances such as flame retardance, machinery, electricity and the like into leather fibers in a chemical bonding mode to improve the leather quality is the key technology of the method.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent aiming at the defects of the prior art.
The invention provides a preparation method of the graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent, which is characterized by comprising the following steps:
(1) preparation of maleic anhydride grafted graphene oxide by weight parts
Adding 1 part of graphene oxide and 150 parts of organic solvent into a 500mL round-bottom flask provided with a nitrogen protection device, mechanical stirring and a constant-pressure dropping funnel, and performing ultrasonic dispersion for 1.0 h; adding 4.7-6.0 parts of acid-binding agent, dripping 3.5 parts of chlorinating agent diluted by 10 parts of organic solvent into the reaction solution, reacting for 4-6h at 60 ℃, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum; mixing the dried product with 150 parts of organic solvent, ultrasonically dispersing, adding into the device again, dropwise adding 3.0-8.5 parts of diamine and 4.7-6.0 parts of acid-binding agent into the system, reacting at room temperature for 2-4h, filtering under reduced pressure, washing with anhydrous ethanol, and vacuum drying; mixing the dried product with 150 parts of organic solvent, performing ultrasonic dispersion, adding the mixture into a device, dropwise adding 5.0 parts of maleic anhydride dissolved in 15 parts of organic solvent into the system, continuing to react for 8 hours at 60-70 ℃ after the dropwise addition is finished, cooling, filtering under reduced pressure, washing with absolute ethyl alcohol, and performing vacuum drying to obtain maleic anhydride grafted graphene oxide;
(2) preparation of graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent in parts by weight
Adding 1-10 parts of maleic anhydride grafted graphene oxide prepared in the step (1) into 100 parts of ionized water, and performing ultrasonic dispersion for 0.5-1.0 h; then adding 50-60 parts of vinyl acetate, 40-50 parts of maleic anhydride, 8-10 parts of initiator and 4 parts of sodium hydroxide into a four-neck flask with a mechanical stirring device, a thermometer and a condensation reflux device, and heating to 55-57 ℃ to react for 3-4h to prepare a prepolymer; then adding 2-4 parts of initiator dissolved by 5 parts of water and 4 parts of acrylamide dissolved by 20 parts of water, and continuously reacting for 4-5h at the temperature of 55-57 ℃; adding 20 parts of sodium hydroxide dissolved by 60 parts of water, and continuously reacting for 1 hour at the temperature of 40-45 ℃ to obtain the graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant retanning agent;
the organic solvent used in the step (1) in the scheme is tetrahydrofuran,N,N-dimethylformamide,N,N-dimethylacetamide and dimethylsulfoxide.
In the scheme, the chlorinating agent in the step (1) is hexachlorocyclotriphosphazene;
in the scheme, the acid-binding agent in the step (1) is any one of triethylamine or pyridine;
in the scheme, the diamine in the step (1) is ethylenediamine,1,3-propylenediamine,1,6-any of hexamethylenediamine, p-phenylenediamine or isophoronediamine.
The maleic anhydride grafted graphene oxide in the step (1) in the above scheme has the following structural general formula:
wherein R is1Is represented by2Is ethyl, propyl, hexyl, phenyl or
。
In the scheme, the initiator in the step (2) is any one of ammonium persulfate and potassium persulfate.
Compared with the prior art, the invention has the following innovation points:
(1) the maleic anhydride grafted graphene oxide provided by the invention is obtained by reacting graphene oxide with hexachlorocyclotriphosphazene and diamine to prepare aminated graphene oxide, and grafting a maleic anhydride monomer onto the surface of the aminated graphene oxide, wherein the modified graphene oxide contains hydrophilic functional groups such as amino, carboxyl and the like, and has good dispersion stability in water;
(2) the surface and the boundary of the maleic anhydride grafted graphene oxide provided by the invention contain active double bonds, and the graphene oxide can react with vinyl monomers such as vinyl acetate and the like to permanently graft the graphene in a vinyl acetate-maleic anhydride polymer molecular chain, so that the problems that the graphene interlayer is easy to agglomerate, the compatibility with a polymer is poor, the dispersion is not uniform and the like are effectively solved;
(3) the graphene modified vinyl acetate-maleic anhydride retanning agent disclosed by the invention utilizes the synergistic flame retardant effect of the phosphorus-nitrogen compound and the graphene, the flame retardant efficiency is high, the performances of the leather, such as conductivity, mechanical strength, heat resistance, aging resistance, antibacterial property and the like, are effectively improved by the graphene, the quality grade of the leather can be greatly improved, and reference is provided for the functionalization of the leather.
Drawings
Fig. 1 is a comparative analysis diagram of fourier infrared spectra of graphene oxide and maleic anhydride grafted graphene oxide.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparation of maleic anhydride grafted graphene oxide by weight parts
Adding 1 part of graphene oxide and 150 parts of tetrahydrofuran into a 500mL round-bottom flask provided with a nitrogen protection device, mechanical stirring and a constant-pressure dropping funnel, and performing ultrasonic dispersion for 1.0 h; adding 6.0 parts of triethylamine, dropwise adding 3.5 parts of hexachlorocyclotriphosphazene diluted by 10 parts of tetrahydrofuran into the reaction solution, reacting for 4-6h at 60 ℃, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum; mixing the dried product with 150 parts of tetrahydrofuran, performing ultrasonic dispersion, adding the mixture into the device again, then dropwise adding 3.0 parts of ethylenediamine and 6.0 parts of triethylamine into the system, reacting for 2 hours at room temperature, performing reduced pressure filtration, washing with absolute ethyl alcohol, and performing vacuum drying; mixing the dried product and 150 parts of tetrahydrofuran, performing ultrasonic dispersion, adding the mixture into a device, dropwise adding 5.0 parts of maleic anhydride dissolved in 15 parts of tetrahydrofuran into the system, continuing to react for 8 hours at 60-70 ℃ after the dropwise addition is finished, cooling, filtering under reduced pressure, washing with absolute ethyl alcohol, and performing vacuum drying to obtain maleic anhydride grafted graphene oxide;
(2) preparation of graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent in parts by weight
Adding 1 part of maleic anhydride grafted graphene oxide prepared in the step (1) into 100 parts of ionized water, and performing ultrasonic dispersion for 0.5 h; then adding 50 parts of vinyl acetate, 50 parts of maleic anhydride, 8 parts of ammonium persulfate and 4 parts of sodium hydroxide into a four-neck flask with a mechanical stirring device, a thermometer and a condensation reflux device, and heating to 55-57 ℃ for reaction for 4 hours to prepare a prepolymer; then adding 4 parts of ammonium persulfate dissolved by 5 parts of water and 4 parts of acrylamide dissolved by 20 parts of water, and continuously reacting for 4 hours at the temperature of 55-57 ℃; adding 20 parts of sodium hydroxide dissolved by 60 parts of water, and continuously reacting for 1 hour at the temperature of 40-45 ℃ to obtain the graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant retanning agent;
the obtained graphene modified vinyl acetate-maleic anhydride retanning agent has the solid content of 21%, the mass fraction of graphene oxide is 1%, the Limited Oxygen Index (LOI) of leather after retanning by the retanning agent is 25.3%, and the conductivity, heat resistance, tear resistance and other properties of the leather are improved.
Example 2
(1) Preparation of maleic anhydride grafted graphene oxide by weight parts
1 part of graphene oxide and 150 parts of graphene oxideN,N-dimethylformamide was added to a 500mL round bottom flask equipped with nitrogen protection, mechanical stirring and a constant pressure dropping funnel, and dispersed ultrasonically for 1.0 h; 6.0 parts of triethylamine are added and 10 parts are takenN,NDropwise adding 3.5 parts of hexachlorocyclotriphosphazene diluted by dimethylformamide into the reaction solution, reacting for 4-6h at 60 ℃, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum; the dried product and 150 parts ofN,NAdding the mixture into the device again after the dimethyl formamide is mixed and ultrasonically dispersed, and then dropwise adding 3.7 parts of the mixture into the system1,3Propane diamine and 6.0 parts of triethylamine react for 2.5 hours at room temperature, and the reaction product is subjected to reduced pressure filtration, absolute ethyl alcohol washing and vacuum drying; the dried product and 150 parts ofN,NAdding the mixture into a device after the ultrasonic dispersion of the dimethyl formamide, and dropwise adding 15 parts of the mixture into the systemN,N5.0 parts of maleic anhydride dissolved in dimethylformamide, continuously reacting at 60-70 ℃ for 8 hours after dropwise addition, cooling, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum to obtain maleic anhydride grafted graphene oxide;
(2) preparation of graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent in parts by weight
Adding 4 parts of maleic anhydride grafted graphene oxide prepared in the step (1) into 100 parts of ionized water, and performing ultrasonic dispersion for 0.7 h; adding 55 parts of vinyl acetate, 45 parts of maleic anhydride, 10 parts of ammonium persulfate and 4 parts of sodium hydroxide into a four-neck flask with a mechanical stirring device, a thermometer and a condensation reflux device, and heating to 55-57 ℃ for reaction for 3.5 hours to prepare a prepolymer; then adding 2 parts of ammonium persulfate dissolved by 5 parts of water and 4 parts of acrylamide dissolved by 20 parts of water, and continuously reacting for 5 hours at the temperature of 55-57 ℃; adding 20 parts of sodium hydroxide dissolved by 60 parts of water, and continuously reacting for 1 hour at the temperature of 40-45 ℃ to obtain a graphene modified vinyl acetate-maleic anhydride polymer;
the obtained graphene modified vinyl acetate-maleic anhydride retanning agent has the solid content of 21%, the mass fraction of graphene oxide is 4.0%, the Limited Oxygen Index (LOI) of leather after retanning by the retanning agent is 26.5%, and the performances of the leather such as conductivity, heat resistance, tear resistance and the like are improved.
Example 3
(1) Preparation of maleic anhydride grafted graphene oxide
1 part of graphene oxide and 150 parts of graphene oxideN,NAdding dimethylacetamide into a 500mL round-bottom flask provided with a nitrogen protection device, mechanical stirring and a constant pressure dropping funnel, and ultrasonically dispersing for 1.0 h; 4.7 parts of pyridine are added and 10 parts are usedN,NDropwise adding 3.5 parts of hexachlorocyclotriphosphazene diluted by dimethylacetamide into the reaction solution, reacting for 4-6h at 60 ℃, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum; the dried product and 150 parts ofN,NAdding the mixture into the device again after the ultrasonic dispersion of the dimethylacetamide, and then dropwise adding 3.7 parts of the mixture into the system1,3Propane diamine and 4.7 parts of pyridine are reacted for 2.5 hours at room temperature, and then the reaction product is filtered under reduced pressure, washed by absolute ethyl alcohol and dried in vacuum; the dried product and 150 parts ofN,NAdding the mixture into a device after ultrasonic dispersion of dimethylacetamide, and dropwise adding 15 parts of dimethylacetamideN,N5.0 parts of maleic anhydride dissolved in dimethylacetamide, continuously reacting at 60-70 ℃ for 8 hours after dropwise addition, cooling, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum to obtain maleic anhydride grafted graphene oxide;
(2) preparation of graphene modified vinyl acetate-maleic anhydride retanning agent
Adding 8 parts of maleic anhydride grafted graphene oxide prepared in the step (1) into 100 parts of ionized water, and performing ultrasonic dispersion for 0.8 h; adding 55 parts of vinyl acetate, 45 parts of maleic anhydride, 8 parts of potassium persulfate and 4 parts of sodium hydroxide into a four-neck flask with a mechanical stirrer, a thermometer and a condensation reflux device, and heating to 55-57 ℃ for reaction for 3 hours to obtain a prepolymer; then adding 3 parts of potassium persulfate dissolved by 5 parts of water and 4 parts of acrylamide dissolved by 20 parts of water, and continuously reacting for 4.5 hours at the temperature of 55-57 ℃; adding 20 parts of sodium hydroxide dissolved by 60 parts of water, and continuously reacting for 1 hour at the temperature of 40-45 ℃ to obtain a graphene modified vinyl acetate-maleic anhydride polymer;
the obtained graphene modified vinyl acetate-maleic anhydride retanning agent has the solid content of 21%, the mass fraction of graphene oxide is 8.0%, the Limited Oxygen Index (LOI) of leather after retanning by the retanning agent is 27.8%, and meanwhile, the performances of the leather such as conductivity, heat resistance, tear resistance and the like are improved.
Example 4
(1) Preparation of maleic anhydride grafted graphene oxide
Adding 1 part of graphene oxide and 150 parts of dimethyl sulfoxide into a 500mL round-bottom flask provided with a nitrogen protection device, mechanical stirring and a constant-pressure dropping funnel, and performing ultrasonic dispersion for 1.0 h; adding 4.7 parts of pyridine, dropwise adding 3.5 parts of hexachlorocyclotriphosphazene diluted by 10 parts of dimethyl sulfoxide into the reaction solution, reacting for 4-6h at 60 ℃, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum; mixing the dried product and 150 parts of dimethyl sulfoxide, performing ultrasonic dispersion, adding the mixture into a device again, then dropwise adding 8.5 parts of isophorone diamine and 4.7 parts of pyridine into the system, reacting for 4 hours at room temperature, performing reduced pressure filtration, washing with absolute ethyl alcohol, and performing vacuum drying; mixing the dried product and 150 parts of dimethyl sulfoxide, performing ultrasonic dispersion, adding the mixture into a device, dropwise adding 5.0 parts of maleic anhydride dissolved in 15 parts of dimethyl sulfoxide into the system, continuing to react for 8 hours at 60-70 ℃ after dropwise adding is finished, cooling, filtering under reduced pressure, washing with absolute ethyl alcohol, and performing vacuum drying to obtain maleic anhydride grafted graphene oxide;
(2) preparation of graphene modified vinyl acetate-maleic anhydride retanning agent
Adding 10 parts of maleic anhydride grafted graphene oxide prepared in the step (1) into 100 parts of ionized water, and performing ultrasonic dispersion for 1.0 h; then adding 60 parts of vinyl acetate, 40 parts of maleic anhydride, 10 parts of potassium persulfate and 4 parts of sodium hydroxide into a four-neck flask with a mechanical stirring device, a thermometer and a condensation reflux device, and heating to 55-57 ℃ for reaction for 3 hours to prepare a prepolymer; then adding 2 parts of potassium persulfate dissolved by 5 parts of water and 4 parts of acrylamide dissolved by 20 parts of water, and continuously reacting for 5 hours at the temperature of 55-57 ℃; adding 20 parts of sodium hydroxide dissolved by 60 parts of water, and continuously reacting for 1 hour at the temperature of 40-45 ℃ to obtain a graphene modified vinyl acetate-maleic anhydride polymer;
the obtained graphene modified vinyl acetate-maleic anhydride retanning agent has the solid content of 21%, the mass fraction of graphene oxide is 10.0%, the Limited Oxygen Index (LOI) of leather after retanning by the retanning agent is 28.7%, and the performances of the leather such as conductivity, heat resistance, tear resistance and the like are improved.
Claims (3)
1. A preparation method of a graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent is characterized by comprising the following steps:
(1) preparing maleic anhydride grafted graphene oxide, namely adding 1 part of graphene oxide and 150 parts of organic solvent in parts by weight into a 500mL round-bottom flask provided with a nitrogen protection device, mechanical stirring and a constant-pressure dropping funnel, and performing ultrasonic dispersion for 1.0 h; adding 4.7-6.0 parts of acid-binding agent, dropwise adding 3.5 parts of hexachlorocyclotriphosphazene diluted by 10 parts of organic solvent into the reaction solution, reacting for 4-6h at 60 ℃, filtering under reduced pressure, washing with absolute ethyl alcohol, and drying under vacuum; mixing the dried product with 150 parts of organic solvent, ultrasonically dispersing, adding into the device again, dropwise adding 3.0-8.5 parts of diamine and 4.7-6.0 parts of acid-binding agent into the system, reacting at room temperature for 2-4h, filtering under reduced pressure, washing with anhydrous ethanol, and vacuum drying; mixing the dried product with 150 parts of organic solvent, performing ultrasonic dispersion, adding the mixture into a device, dropwise adding 5.0 parts of maleic anhydride dissolved in 15 parts of organic solvent into the system, continuing to react for 8 hours at 60-70 ℃ after the dropwise addition is finished, cooling, filtering under reduced pressure, washing with absolute ethyl alcohol, and performing vacuum drying to obtain maleic anhydride grafted graphene oxide;
(2) preparing a graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent, namely adding 1-10 parts by weight of maleic anhydride grafted graphene oxide prepared in the step (1) into 100 parts by weight of deionized water, and performing ultrasonic dispersion for 0.5-1.0 h; then adding 50-60 parts of vinyl acetate, 40-50 parts of maleic anhydride, 8-10 parts of initiator and 4 parts of sodium hydroxide into a four-neck flask with a mechanical stirring device, a thermometer and a condensation reflux device, and heating to 55-57 ℃ to react for 3-4h to prepare a prepolymer; then adding 2-4 parts of initiator dissolved by 5 parts of water and 4 parts of acrylamide dissolved by 20 parts of water, and continuously reacting for 4-5h at the temperature of 55-57 ℃; and adding 20 parts of sodium hydroxide dissolved by 60 parts of water, and continuously reacting for 1 hour at the temperature of 40-45 ℃ to obtain the graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant retanning agent.
2. The preparation method of the graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent according to claim 1, characterized by comprising the following steps:
in the step (1), the organic solvent is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the acid-binding agent is one of triethylamine or pyridine;
the diamine is one of ethylenediamine, 1, 3-propylenediamine, 1, 6-hexamethylenediamine, p-phenylenediamine and isophoronediamine.
3. The preparation method of the graphene modified vinyl acetate-maleic anhydride retanning agent according to claim 1, characterized by comprising the following steps:
in the step (2), the initiator is any one of ammonium persulfate and potassium persulfate.
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