CN104232810B - Graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent and preparation method thereof - Google Patents
Graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, be made up according to mass parts of following material: stannic oxide/graphene nano lamella dispersion liquid 20 ~ 30 parts, 0.5 ~ 1 part, oxygenant, monomer mixture solution 60 ~ 80 parts, initiator 20 ~ 30 parts, the invention also discloses the preparation method of a kind of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, the present invention achieves double bond and water-soluble vinyl monomer in graphene oxide structure by aqueous free radical polyreaction and carries out free radical copolymerization, simultaneously containing stannic oxide/graphene nano lamella and aqueous vinyl structural unit in gained multipolymer, also make the size of stannic oxide/graphene nano lamella less, be more evenly distributed, penetrating into after between leather collagen fiber, produce chemical bonding effect and nanometer size effect, thus the tanning effect obtained leather fiber, can separately as leather retanning agent.
Description
Technical field
The invention belongs to green Chrome-free leather retanning agent technical field, be specifically related to a kind of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent and preparation method thereof.
Background technology
Current China is leather production and trade big country in the world, and leather industry is being created huge material wealth for country and while creating job opportunities for people, also created serious pollution problem.Reason is the process of manufacture of leather is the process that a fur to natural animal carries out chemical modification, its basic feature is that the consumption of the leather chemicals when producing is large, specific absorption is low, causes producing a large amount of waste water, mud and scrap leather bits containing various chemical in leather processing procedure.The pollution that wherein leather tanning process produces is the most serious and reluctant.Although leather retanning agent can be used as chrome tanning agent, vegetable tanning agent, aldehyde tanning agent, synthetic tanning agent etc., due to chrome tanning agent tan leather over-all properties preferably and process for tanning easily operate, chrome tanning agent is widely applied.
At present, chrome tanning leather account for leather output about 90% (see Li Chenying, Chen Hualin, Luo Rong, Liu Bailing, Liu Minghua. the application forecast of hyperbranched polymer in high-absorption chrome tanning agent. Chinese leather, 2012,41 (17): 48-52; ChattopadhyayB, AichA, MukhopadhyaySK.ChromiumintheTanningIndustry:AnOdysseyfro mCradletoGrave [J] .Journalofthesocietyofleathertechnologistsandchemists, 2012,96 (4): 133-140).The chromate waste water, chromium-bearing sludge, chrome leather wastes etc. that are difficult in a large number administer can be produced in Chrome Tanning Process, in addition the trivalent chromium in leather may be converted into the larger sexavalent chrome of harm under certain condition, makes many countries in the world make strict regulation to content of 6-valence Cr ions in leatherware.
At present, the consistent viewpoint of domestic and international leather circle reduces the consumption of chrome tanning agent as much as possible, development chrome-free tanning agent and green tanning agent, Main is the specific absorption improving chrome tanning agent, reduce the consumption of chrome tanning agent, reduce containing chromium pollutant, but the effect acquired by this way is very limited, current chrome tanning leather has still accounted for 90% of leather output.Although whole world leather researchist at non-chromium metal tanning agents if iron tannage agent, aluminum tanning agent, zirconium tanning agent, zinc tanning agent and organic tanning agent are as carried out many explorations in organic phosphine tanning agent etc., also do not find at present the novel tanning agent that can compare favourably with chrome tanning agent in tanning performance, these non-chrome tanning agents also also exist the problem of large usage quantity, specific absorption is low and easy generation is new pollution in addition.
From tanning effect and effect, tanning agent can be divided into tanning agent (main tanning agent) and retanning agent, their effect is distinguishing, generally can be used as retanning agent, as chrome tanning agent, aldehyde tanning agent etc. as main tanning agent, but can not necessarily can as main tanning agent as retanning agent, as synthetic tanning agent, acrylic resin retanning agent, aminoresin retanning agent etc. (see " tanning chemistry ", Chen Wuyong etc., China Light Industry Press, 179-181 page, 2008).
Current synthetic tanning agent, acrylic resin retanning agent etc. can only can not as main tanning agents as retanning agent, because the chemical action of this kind of tanning agent and hide fiber does not reach the requirement of main tanning agent from far away.The effect of main tanning agent is that skin is become leather, leather shrinkage temperature being only had the raw animal skin of about 50 DEG C to be converted into shrinkage temperature exactly to reach more than 90 DEG C, have certain mechanical property and practical value; And the main purpose of retanning and retanning agent be exactly supplement tanning, filling targetedly according to the purposes of leather and improve flexibility etc. (see " composition principle of leather China chemical and utilisation technology ", horse is built medium, China Light Industry Press, 100-102 page, 2009).
Summary of the invention
For solving the technical problem of existing existence, the embodiment of the present invention provides a kind of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent and preparation method thereof, gained tanning agent reaches the object of tan leather by the multiple spot chemical bonds that formed with collagen and nanometer size effect, and tanning agent is had, and tanning is effective and specific absorption is high.
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 and water-soluble vinyl monomer multipolymer leather retanning agent, it is characterized in that: be made up according to mass parts of following material:
Stannic oxide/graphene nano lamella dispersion liquid 20 ~ 30 parts, 0.5 ~ 1 part, oxygenant, monomer mixture solution 60 ~ 80 parts, initiator 20 ~ 30 parts.
In such scheme, described oxygenant is mass fraction is 30% hydrogen peroxide or ammonium persulphate.
In such scheme, described monomer mixture solution is the mixing solutions of methacrylic acid, methylene-succinic acid, sodium allyl sulfonate and deionized water, and its weight ratio is followed successively by 10:4:1:15; Or described monomer mixture solution is the mixing solutions of vinylformic acid, maleic acid, methylpropene sodium sulfonate and deionized water, and its weight ratio is followed successively by 10:5:1:16.
In such scheme, described initiator solution is obtained by ammonium persulphate or Potassium Persulphate or Sodium Persulfate and deionized water mixed dissolution; The weight ratio of described material is 1:30.
The embodiment of the present invention also provides the preparation method of a kind of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, the method is: get stannic oxide/graphene nano lamella dispersion liquid 20 ~ 30 parts according to mass parts in reactor, be heated to 80 ~ 90 DEG C, add 0.5 ~ 1 part of oxygenant and carry out preoxidation 30 ~ 60 minutes, under agitation slowly add 60 ~ 80 parts of monomer mixture solutions and 20 ~ 30 parts of initiator solutions respectively again, time for adding is 1 ~ 2 hour, be added dropwise to complete follow-up continuous insulation reaction 2 ~ 3 hours, then less than 40 DEG C are cooled to, be 5.5 ~ 6.0 by the sodium hydroxide solution regulation system pH value that mass fraction is 40%, products therefrom is graphene oxide and ethylene monomer copolymer type leather tanning agent.
In such scheme, in the graphene oxide of described preparation and water-soluble vinyl monomer multipolymer leather retanning agent, the thickness of stannic oxide/graphene nano lamella is at 8 ~ 15nm, and length and width are at 12 ~ 30nm.
Compared with prior art, beneficial effect of the present invention:
The present invention can improve degree of scatter and the degree of oxidation of stannic oxide/graphene nano lamella, enable to penetrate in leather fiber and go, chemical bonding effect is formed with the active group on materials with hide glue fibril, GO nanoscale twins produces nanometer size effect between the fibers simultaneously, and the synergy of chemical bonding effect and nano effect creates tanning effect;
It is about 30% that modified graphene oxide leather retanning agent solid content prepared by the present invention controls, wherein graphene oxide content about 1%, the tanning (main tanning agent) of leather can be used for as main tanning agent, when graphene oxide and water-soluble vinyl monomer multipolymer consumption are 10% of tare weight, (wherein graphene oxide content 0.1%) can make the shrinkage temperature of goat leather for garment bring up to the shrinkage temperature of leather can be made to bring up to 91 DEG C, the tensile strength of the leather of tanning, tear strength and extension at break reach use standard, and it is soft, smooth, specific absorption is high, in waste liquid, remaining quantity is little, be applicable to goatskin, the tanning of the leathers such as lamb skin, there is good application prospect.
Accompanying drawing explanation
Fig. 1 is preparation process and the structural representation of graphene oxide of the present invention and ethylene monomer copolymer tanning agent.
Embodiment
Below in conjunction with the drawings and specific embodiments mode, the present invention is described in detail.
The embodiment of the present invention provides a kind of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, is made up according to mass parts of following material:
Stannic oxide/graphene nano lamella dispersion liquid 20 ~ 30 parts, 0.5 ~ 1 part, oxygenant, monomer mixture solution 60 ~ 80 parts, initiator 20 ~ 30 parts.
Described stannic oxide/graphene nano lamella dispersion liquid obtains by the following method: the Graphite Powder 99 of 1 part slowly to be joined 30 parts of mass fractions be 98% vitriol oil and 3 parts of mass fractions is in the mixture of 85% strong phosphoric acid, the temperature of the hierarchy of control 5 DEG C, add after being uniformly mixed at the potassium permanganate slowly adding 5 parts, react 3 hours at this temperature, and then be warmed up to 35 DEG C of continuation reactions 1 hour, slowly add 150 parts of deionized waters again, be warming up to 90 DEG C of reactions 4 hours, then the superoxol that 50 DEG C drip 20 parts of mass fractions 30% is cooled to, after reacting 30 points of kinds, then lower the temperature and centrifugation carried out to product, by the method for deionized water wash until the pH of washing water is 6.0, disperse within 1 hour, to obtain stannic oxide/graphene nano lamella dispersion liquid by ultrasonic wave, and the massfraction of controlled oxidization Graphene is about 4%, the gauge control of stannic oxide/graphene nano lamella is 8 ~ 15nm, length and width are 16 ~ 30nm, because the preparation process of described stannic oxide/graphene nano lamella dispersion liquid is comparatively complicated, therefore generally once prepare more consumption, choose applicable consumption in order to follow-up flow process and carry out other operations again, certainly, also above-mentioned materials can be followed successively by according to weight ratio the consumption that 1:30:3:5:150:20 directly makes the stannic oxide/graphene nano lamella dispersion liquid that subsequent handling needs, the number 150 of deionized water here just needs the amount added first in system in preparation process, owing to needing use deionized water wash repeatedly before obtaining final stannic oxide/graphene nano lamella dispersion liquid, therefore the water consumption in final system should be the water yield needing in system when being 4% with controlled oxidization Graphene massfraction to add.
Described oxygenant is mass fraction is 30% hydrogen peroxide or ammonium persulphate.
Described monomer mixture solution is the mixing solutions of methacrylic acid, methylene-succinic acid, sodium allyl sulfonate and 15 parts of deionized waters, and its weight ratio is followed successively by 10:4:1:15;
Or described monomer mixture solution is the mixing solutions of vinylformic acid, maleic acid, methylpropene sodium sulfonate and deionized water, and its weight ratio is followed successively by 10:5:1:16.
Described initiator solution is obtained by ammonium persulphate or Potassium Persulphate or Sodium Persulfate and deionized water mixed dissolution, and its weight ratio is 1:30.
The embodiment of the present invention also provides the preparation method of a kind of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, the method is: get stannic oxide/graphene nano lamella dispersion liquid 20 ~ 30 parts according to mass parts in reactor, be heated to 80 ~ 90 DEG C, add 0.5 ~ 1 part of oxygenant and carry out preoxidation 30 ~ 60 minutes, under agitation slowly add 60 ~ 80 parts of monomer mixture solutions and 20 ~ 30 parts of initiator solutions respectively again, time for adding is 1 ~ 2 hour, be added dropwise to complete follow-up continuous insulation reaction 2 ~ 3 hours, then less than 40 DEG C are cooled to, be 5.5 ~ 6.0 by the sodium hydroxide solution regulation system pH value that mass fraction is 40%, products therefrom is graphene oxide and ethylene monomer copolymer type leather tanning agent.
Be about 30% by mass fraction shared by solid matter in aforesaid method products therefrom, wherein mass fraction shared by graphene oxide is about 1%.
In the graphene oxide of described preparation and water-soluble vinyl monomer multipolymer leather retanning agent, the thickness of stannic oxide/graphene nano lamella is at 4 ~ 8nm, and length and width are at 8 ~ 20nm.
The present invention is carrying out on preoxidation basis to stannic oxide/graphene nano lamella, achieve double bond and water-soluble vinyl monomer in graphene oxide structure by aqueous free radical polyreaction and carry out free radical copolymerization, simultaneously containing stannic oxide/graphene nano lamella and aqueous vinyl structural unit in gained multipolymer, also make the size of stannic oxide/graphene nano lamella less, distribution evenly, penetrating into after between leather collagen fiber, produce chemical bonding effect and nanometer size effect simultaneously, thus the tanning effect obtained leather fiber, can tan as leather retanning agent and for the master of leather separately.
Graphene oxide prepared by the present invention and water-soluble vinyl monomer multipolymer, mainly as main tanning agent, have basic difference with usually crylic acid resin tanning agent in structure and tanning effect.The preparation of graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent and structure are as shown in Figure 1.
Embodiment one:
Step one: the preparation of graphene oxide.
The Graphite Powder 99 of 1 part slowly to be joined 40 parts of mass fractions be 98% vitriol oil and 3 parts of mass fractions is in the mixture of 85% strong phosphoric acid, the temperature of the hierarchy of control 5 DEG C, add after being uniformly mixed at the potassium permanganate slowly adding 5 parts, react 3 hours at this temperature, and then be warmed up to 35 DEG C of continuation reactions 1 hour, slowly add 150 parts of deionized waters again, be warming up to 90 DEG C of reactions 4 hours; Then the superoxol that 50 DEG C drip 20 parts of mass fractions 30% is cooled to, after reacting 30 points of kinds, then lower the temperature and centrifugation carried out to product, by the method for deionized water wash until the pH of washing water is 6.0, disperse within 1 hour, to obtain stannic oxide/graphene nano lamella dispersion liquid by ultrasonic wave, and the massfraction of controlled oxidization Graphene is about 4%, the thickness of stannic oxide/graphene nano lamella in 8 ~ 15nm, length and width at 12 ~ 30nm;
Step 2: the preparation of aqueous vinyl monomer.
Used monomer mixture solution is 10 parts of methacrylic acids, 4 parts of methylene-succinic acids, 1 part of sodium allyl sulfonate and 15 parts of deionized water mixing solutionss.
Step 3: the configuration of initiator solution.
Initiator solution is obtained by the ammonium persulphate of 1 part and 30 parts of deionized water mixed dissolutions;
Step 4: the preparation of graphene oxide and water-soluble vinyl monomer multipolymer tanning agent.
Get stannic oxide/graphene nano lamella dispersion liquid 20 parts according to mass fraction in reactor, be heated to 80 DEG C, the ammonium persulphate or the mass fraction that add 0.5 part are 30% hydrogen peroxide preoxidation 30 minutes, and then under agitation slowly add 60 parts of monomer mixture solutions and 20 parts of initiator solutions respectively, time for adding is 1 hour, be added dropwise to complete follow-up continuous insulation reaction 2 hours, then cooling to less than 40 DEG C by the sodium hydroxide solution regulation system pH value that mass fraction is 40% is 5.5, products therefrom is graphene oxide and ethylene monomer copolymer type leather tanning agent, wherein mass fraction shared by solid matter is about 30%, wherein mass fraction shared by graphene oxide is about 1%, in graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, the thickness of stannic oxide/graphene nano lamella is at 6 ~ 8nm, length and width are at 10 ~ 15nm.
Embodiment two:
Step one: the preparation of graphene oxide.
The Graphite Powder 99 of 1 part slowly to be joined 40 parts of mass fractions be 98% vitriol oil and 3 parts of mass fractions is in the mixture of 85% strong phosphoric acid, the temperature of the hierarchy of control 5 DEG C, add after being uniformly mixed at the potassium permanganate slowly adding 5 parts, react 3 hours at this temperature, and then be warmed up to 35 DEG C of continuation reactions 1 hour, slowly add 150 parts of deionized waters again, be warming up to 90 DEG C of reactions 4 hours; Then the superoxol that 50 DEG C drip 20 parts of mass fractions 30% is cooled to, react 30 points of kinds, then lower the temperature and centrifugation carried out to product, by the method for deionized water wash until the pH of washing water is 6.0, disperse within 1 hour, to obtain stannic oxide/graphene nano lamella dispersion liquid by ultrasonic wave, and the massfraction of controlled oxidization Graphene is about 4%, the gauge control of stannic oxide/graphene nano lamella is 8 ~ 15nm, length and width are 16 ~ 30nm;
Step 2: the preparation of aqueous vinyl monomer.
Used monomer mixture solution is by 10 parts of vinylformic acid, 5 parts of maleic acids, 1 part of methylpropene sodium sulfonate and 16 parts of deionized water mixing solutionss;
Step 3: the configuration of initiator solution.
Initiator solution is obtained by the Sodium Persulfate of 1 part and 30 parts of deionized water mixed dissolutions;
Step 4: the preparation of graphene oxide and water-soluble vinyl monomer multipolymer tanning agent.
Get stannic oxide/graphene nano lamella dispersion liquid 30 parts according to mass fraction in reactor, be heated to 90 DEG C, the ammonium persulphate or the mass fraction that add 1 part are 30% hydrogen peroxide preoxidation 60 minutes, and then under agitation slowly add 80 parts of monomer mixture solutions and 30 parts of initiator solutions respectively, time for adding is 2 hours, be added dropwise to complete follow-up continuous insulation reaction 3 hours, then cooling to less than 40 DEG C by the sodium hydroxide solution regulation system pH value that mass fraction is 40% is 6.0, products therefrom is graphene oxide and ethylene monomer copolymer type leather tanning agent, wherein mass fraction shared by solid matter is about 30%, wherein mass fraction shared by graphene oxide is about 1%, in graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, the thickness of stannic oxide/graphene nano lamella is at 4 ~ 6nm, length and width are at 10 ~ 15nm.
Embodiment three:
Step one: the preparation of graphene oxide.
The Graphite Powder 99 of 1 part slowly to be joined 40 parts of mass fractions be 98% vitriol oil and 3 parts of mass fractions is in the mixture of 85% strong phosphoric acid, the temperature of the hierarchy of control 5 DEG C, add after being uniformly mixed at the potassium permanganate slowly adding 5 parts, react 3 hours at this temperature, and then be warmed up to 35 DEG C of continuation reactions 1 hour, slowly add 150 parts of deionized waters again, be warming up to 90 DEG C of reactions 4 hours; Then the superoxol that 50 DEG C drip 20 parts of mass fractions 30% is cooled to, react 30 points of kinds, then cooling to carrying out centrifugation to product, by the method for deionized water wash until the pH of washing water is 6.0, disperse within 1 hour, to obtain stannic oxide/graphene nano lamella dispersion liquid by ultrasonic wave, and the massfraction of controlled oxidization Graphene is about 4%, the gauge control of stannic oxide/graphene nano lamella is 8 ~ 15nm, length and width are 16 ~ 30nm;
Step 2: the preparation of aqueous vinyl monomer.
Used monomer mixture solution is 10 parts of methacrylic acids, 4 parts of methylene-succinic acids, 1 part of sodium allyl sulfonate and 15 parts of deionized water mixing solutionss;
Step 3: the configuration of initiator solution.
Initiator solution is obtained by the Potassium Persulphate of 1 part and 30 parts of deionized water mixed dissolutions;
Step 4: the preparation of graphene oxide and water-soluble vinyl monomer multipolymer tanning agent.
Get stannic oxide/graphene nano lamella dispersion liquid 25 parts according to mass fraction in reactor, be heated to 85 DEG C, the ammonium persulphate or the mass fraction that add 0.8 part are 30% hydrogen peroxide preoxidation 40 minutes, and then under agitation slowly add 70 parts of monomer mixture solutions and 25 parts of initiator solutions respectively, time for adding is 1.5 hours, be added dropwise to complete follow-up continuous insulation reaction 2.5 hours, then cooling to less than 40 DEG C by the sodium hydroxide solution regulation system pH value that mass fraction is 40% is 5.5, products therefrom is graphene oxide and ethylene monomer copolymer type leather tanning agent, wherein mass fraction shared by solid matter is about 30%, wherein mass fraction shared by graphene oxide is about 1%, in graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, the thickness of stannic oxide/graphene nano lamella is at 5 ~ 7nm, length and width are at 8 ~ 16nm.
Application result:
Conveniently process for tanning carries out tanning test on goat acid skin, and shrinkage temperature and mechanical property are carried out sampling according to country and industry standard and detected.The performance index of graphene oxide and water-soluble vinyl monomer multipolymer leather tanning agent are in table 1, and application result is in table 2.As can be seen from application result, graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent have good tanning effect, and the mechanical property of tan leather is close to chrome tanning leather, and independent acrylic resin can not use as leather retanning agent.
Table 1 is graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent performance index
Table 2 is application result
Claims (4)
1. graphene oxide and a water-soluble vinyl monomer multipolymer leather retanning agent, is characterized in that: be made up according to mass parts of following material:
Stannic oxide/graphene nano lamella dispersion liquid 20 ~ 30 parts, 0.5 ~ 1 part, oxygenant, monomer mixture solution 60 ~ 80 parts, initiator 20 ~ 30 parts; Described oxygenant is mass fraction is 30% hydrogen peroxide or ammonium persulphate
;described monomer mixture solution is the mixing solutions of methacrylic acid, methylene-succinic acid, sodium allyl sulfonate and deionized water, and its weight ratio is followed successively by 10:4:1:15; Or described monomer mixture solution is the mixing solutions of vinylformic acid, maleic acid, methylpropene sodium sulfonate and deionized water, and its weight ratio is followed successively by 10:5:1:16.
2. graphene oxide according to claim 1 and water-soluble vinyl monomer multipolymer leather retanning agent, is characterized in that: described initiator solution is obtained by ammonium persulphate or Potassium Persulphate or Sodium Persulfate and deionized water mixed dissolution; The weight ratio of described material is 1:30.
3. the preparation method of a graphene oxide and water-soluble vinyl monomer multipolymer leather retanning agent, it is characterized in that, the method is: get stannic oxide/graphene nano lamella dispersion liquid 20 ~ 30 parts according to mass parts in reactor, be heated to 80 ~ 90 DEG C, add 0.5 ~ 1 part of oxygenant and carry out preoxidation 30 ~ 60 minutes, under agitation slowly add 60 ~ 80 parts of monomer mixture solutions and 20 ~ 30 parts of initiator solutions respectively again, time for adding is 1 ~ 2 hour, be added dropwise to complete follow-up continuous insulation reaction 2 ~ 3 hours, then less than 40 DEG C are cooled to, be 5.5 ~ 6.0 by the sodium hydroxide solution regulation system pH value that mass fraction is 40%, products therefrom is graphene oxide and ethylene monomer copolymer type leather tanning agent.
4. graphene oxide according to claim 3 and water-soluble vinyl monomer multipolymer leather retanning agent, it is characterized in that: in the graphene oxide of described preparation and water-soluble vinyl monomer multipolymer leather retanning agent, the thickness of stannic oxide/graphene nano lamella is at 8 ~ 15nm, and length and width are at 12 ~ 30nm.
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| CN105483298B (en) * | 2016-01-20 | 2017-08-08 | 陕西科技大学 | Epoxy resin-matrix stannic oxide/graphene nano leather retanning agent and preparation method |
| 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 |
| 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 |
| CN108467465B (en) * | 2018-03-14 | 2020-06-12 | 四川大学 | Preparation method of graphene modified vinyl acetate-maleic anhydride copolymer flame-retardant leather retanning agent |
| CN112210245A (en) * | 2020-10-12 | 2021-01-12 | 福建格林春天新材料股份有限公司 | Water-based ink for sanitary packaging material and preparation method thereof |
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