CN109651945A - A kind of preparation method and applications method of the graphene-based leather finishing agent of high physical property - Google Patents
A kind of preparation method and applications method of the graphene-based leather finishing agent of high physical property Download PDFInfo
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- CN109651945A CN109651945A CN201811383945.0A CN201811383945A CN109651945A CN 109651945 A CN109651945 A CN 109651945A CN 201811383945 A CN201811383945 A CN 201811383945A CN 109651945 A CN109651945 A CN 109651945A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/16—Esters of inorganic acids
- C09D101/18—Cellulose nitrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to tanning chemistries and field of engineering technology, a kind of preparation method and applications method of graphene-based leather finishing agent of high physical property is provided, using graphene oxide as modified material, oxygen-containing group existing for graphene oxide, keep its water solubility, reactivity good, it can be not easily to fall off with hydroxyl, carboxyl or the amino reaction in polyacrylate, polyurethane resin, polysiloxanes or in conjunction with the hydroxyl of leather collagen fiber, carboxyl or amino.Using polyacrylate, polyurethane resin, polysiloxanes as carrier, prepare the graphene-based leather finishing agent for stablizing homogeneous system, dispersion stabilization of the graphene oxide in polyacrylate, polyurethane resin, polysiloxanes is effectively improved, polyacrylate, polyurethane resin, polysiloxanes and graphene are had complementary advantages；Gained leather finishing agent is coated on leather surface, one layer of uniform containing graphene film is formed in leather surface, to improve the performance of leather coating.
Description
Technical field
The present invention relates to tanning chemistry and field of engineering technology, in particular to a kind of graphene-based leather finishing agent of high physical property
Preparation method and applications method.
Background technique
Leather finish is a very important workshop section in leather making processes, and the leather without covering with paint, feel is coarse,
Easy damaged forms thin film in leather surface after covering with paint, lacquer, colour wash, etc., and feel is smooth, and has certain intensity, not easy damaged.Due to
It is limited by leather chemicals, there are the skills such as strength of coating, wearability, resistance to ag(e)ing difference for the leather products being widely used at present
Art defect, this status seriously restricts China's leather products in the competitiveness of international market, therefore increases the high property of leather products
Conventional leather industry is transformed using new and high technology in the research and development of energy key technology, is to improve China's leather products technology content
And competitiveness in the international market, it is ensured that the key of China's leather industry advantage and industry value chain.
It is existing to use ethylene glycol ethyl ether as decentralized medium at present to solve aforementioned technical problem, prepare graphene content
For 0.1% graphene dispersing solution, then physical blending process is used to be added in leather finishing agent to match graphene dispersing solution
It makes graphene-based leather finishing agent, and ox is applied to using the method for spraying and receives the covering with paint workshop section of pa vamp.Although graphene
It is the highest two-dimension nano materials of nature intensity, there is extraordinary toughness, being applied in leather finishing agent facilitates
Improve intensity, the wearability etc. for covering with paint, lacquer, colour wash, etc. coating；But there are following problems in existing method:
1, graphene is using ethylene glycol ethyl ether as decentralized medium in existing method, and ethylene glycol ethyl ether is organic solvent, meeting
VOC is generated, harm is generated to human health, does not meet environmentally friendly process hides demand；Moreover, there is graphene the technology of reactionlessness to lack
It falls into, is difficult to react with leather finishing agent component or leather collagen fiber, as ethylene glycol ethyl ether gradually volatilizees, graphene
It can reunite and be deposited on leather surface, be unevenly distributed, and is easily peelable, show leather surface different parts coating wear-resistant strength
Different defects reduces finishing agent film forming stability, reduces and covers with paint, lacquer, colour wash, etc. practical function；Finishing agent obtained is heterogeneous system,
Stability is poor, intolerant to storage；
2, leather finishing agent is multicomponent mixture, includes polyacrylate, polyurethane resin and other non-resin groups
Point, directly graphene dispersing solution is added with leather finishing agent in existing method and is mixed, will cause graphene both with poly- third
Olefin(e) acid ester, polyurethane resin absorption, and with non-resin component adsorb the phenomenon that, and coating wear resistance depend primarily on leather painting
The performance of polyacrylate, polyurethane resin in decorations agent, the then graphene for being adsorbed in non-resin component fail to play effective work
With causing graphene effective rate of utilization low, increase the production problem such as cost.
3, there are the technological deficiencies such as easy to reunite, reactionlessness for graphene, accordingly, it is difficult to which graphene to be directly dispersed into polymerization
In objects system, being difficult to the active force to its functional modification, between graphene and polymer using graphene, there is only van der
Walls power, to the physical and chemical performance of material without being obviously improved；And relative to graphene, though graphene oxide can be preferably dispersed in
In polymeric system, but since its two-dimensional structure has been destroyed, therefore under opposite graphene is mixed with obviously on physical and chemical performance
Drop.
4, compound mixing is carried out using physical blending process, passed through between graphene or graphene oxide and polymer
Van der walls power realizes mixed binding, and the main chain of leather finishing agent polymer is all made of singly-bound, singly-bound flexibility
Preferably, therefore between polymer space conformation the barrier potential Δ μ b changed is much smaller than outer field action energy, therefore polymer monomer is in space
It is randomly curled in Coiling-type, and polymer segment can constantly change its conformation.Since intermolecular force is much weaker than covalent bond
Bonding, polymer segment flexibility is too strong, and dependence van der walls power is difficult to graphene or graphene oxide is good
On polymer, causing graphene or graphene oxide, dispersibility is excessively weak in the polymer for anchor, is promoted more to physical and chemical performance
It is limited, and precipitating easy to form or suspension, the comprehensive performance of composite material is greatly reduced, practicability is low.
Summary of the invention
Therefore, for above-mentioned problem, the present invention proposes a kind of preparation method of graphene-based leather finishing agent of high physical property
And its application method.Graphene oxide is used in the preparation method of the graphene-based leather finishing agent of high physical property, aoxidizes stone
Black alkene has oxygen-containing group, and water solubility, reactivity are good, can be with the hydroxyl in polyacrylate, polyurethane resin, polysiloxanes
Base, carboxyl or amino react or in conjunction with the hydroxyl of leather collagen fiber, carboxyl or amino, not easily to fall off.With polyacrylic acid
Ester, polyurethane resin, polysiloxanes are carrier, prepare the leather finishing agent for stablizing homogeneous system, effectively improve graphite oxide
Dispersion stabilization of the alkene in polyacrylate, polyurethane resin, polysiloxanes, by polyacrylate, polyurethane resin, poly- silicon
Oxygen alkane and graphene have complementary advantages；Gained leather finishing agent is coated on leather surface, forms one layer uniformly in leather surface
Containing graphene film, to improve the performance of leather coating.
To realize above-mentioned technical problem, a kind of solution that the present invention takes are as follows: high graphene-based leather finish of physical property
The preparation method of agent, by graphene-based polysiloxane emulsion, graphene oxide based polyacrylic acid ester resin emulsion, graphene oxide
Based polyurethanes resin emulsion, finish auxiliary are soluble in water, and graphene-based leather finishing agent is made in ultrasonic wave dispersion；Wherein, graphite
Alkenyl polysiloxane emulsion is using graphene oxide graft modification polysiloxanes through solgel reaction, reduction, again through emulsifying
Gained after compounding；Graphene oxide based polyacrylic acid ester resin emulsion is using graphene oxide graft modification polypropylene acid esters tree
Obtained by rouge；Graphene oxide based polyurethanes resin emulsion is using obtained by graphene oxide graft modification polyurethane resin.
The preparation method of the graphene-based leather finishing agent of high physical property, specifically comprises the following steps:
Step 1, modified polyorganosiloxane preparation: siloxanyl monomers, silane coupling agent, end-capping reagent, catalyst, crosslinking agent are existed
3-8h is reacted at 70-140 DEG C, obtains modified polyorganosiloxane；
The preparation of step 2, modified graphene oxide: adding graphene oxide into solvent, and N, bis- ring of N- is then added
Hexyl carbodiimide, ultrasonic disperse 20-270min obtain modified graphene oxide forerunner's dispersion liquid, are transferred in reactor and add
Enter modifying agent and react 12-96h at 50-150 DEG C, the dehydrated alcohol with the solvent equivalent is added, stands 6- at 0-50 DEG C
48h is filtered, washed, is dried in vacuo and obtains solid powder, then obtains modified graphene oxide after carrying out reduction；
The preparation of step 3, graphene-based polysiloxanes: step 2 gained modified graphene oxide is added in deionized water,
Ultrasonic disperse 20-200min, obtains modified graphene oxide dispersion liquid；Modified oxygen is added in step 1 gained modified polyorganosiloxane
In graphite alkene dispersion liquid, triethylamine is added, colloidal sol is made in 3-8h under 10-50 DEG C of reaction, is then warming up to 60-100 DEG C
It reacts 1-5h and gel solution is made；Gel is obtained after gel solution is dried in vacuo, then is obtained after carrying out reduction graphene-based
Polysiloxanes；
Step 4, the preparation of graphene-based polysiloxane emulsion: dispersion stirring 5- after two kinds and the above different emulsifiers are mixed
120min obtains emulsifier mixed solution；Step 3 gained graphene modified polyorganosiloxane is uniformly mixed with polysiloxanes, is obtained
Polysiloxanes mixed solution；Polysiloxanes mixed solution is added in emulsifier mixed solution, dispersion stirring 5-120min is obtained
Reaction mixture；By reaction mixture in the case where dispersing stirring 5-15 times of deionized water dropwise, obtain lotion；In lotion
Middle addition 0-20% helps emulsion, and graphene-based polysiloxane emulsion can be obtained after being dispersed stirring 5-120min；
Step 5, the preparation of graphene oxide based polyacrylic acid ester resin emulsion: graphene oxide powder is soluble in water, surpass
Sound wave dispersion, then adjusts pH to 6.5-9 with 2-4% ammonium hydroxide, graphene oxide dispersion is obtained, by graphene oxide dispersion
It is mixed with polyacrylate resin lotion, ultrasonic wave dispersion prepares the graphite oxide that graphene oxide concentration is 0.05-0.1%
Alkenyl polyacrylate resin lotion；
Step 6, the preparation of graphene oxide based polyurethanes resin emulsion: graphene oxide powder is soluble in water, ultrasonic wave
Then dispersion adjusts pH to 6.5-9 with 2-4% ammonium hydroxide, obtains graphene oxide dispersion, by graphene oxide dispersion and gather
The mixing of urethane resin emulsion, ultrasonic wave dispersion prepare the graphite oxide alkenyl that graphene oxide mass fraction is 0.05-0.1%
Ester-polyurethane resin emulsion；
Step 7, the preparation of graphene-based leather finishing agent: by weight, by 0-160 parts of graphene oxide based polyacrylic acids
Ester resin emulsion, 0-125 parts of graphene oxide based polyurethanes resin emulsions, 0-15 parts of graphene-based polysiloxane emulsions, coverings with paint
Auxiliary agent is soluble in water, and graphene-based leather finishing agent is made in ultrasonic wave dispersion.
Wherein, siloxanyl monomers described in step 1 are octamethylcy-clotetrasiloxane.
Wherein, silane coupling agent described in step 1 is at least 3- chloropropyl triethoxysilane, 3- aminopropyl-triethoxy
One of silane, 3- (2,3 the third oxygen of epoxy) propyl-triethoxysilicane, triethoxysilane.
Wherein, end-capping reagent described in step 1 is at least 1,3- bis- (3- glycydoxy) -1,1,3,3- tetra-
One of tetramethyldisiloxane, hexamethyldisiloxane.
Wherein, catalyst described in step 1 is at least one of potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide.
Wherein, crosslinking agent described in step 1 is at least one of epoxy prapanol, third chlorine of epoxy.
Wherein, the concentration of silane coupling agent described in step 1 is 0.1-5%, and the end-capping reagent concentration is 0.1-1%,
The catalyst concn is 0.01-0.2%, and the crosslinker concentration is 0-4%.
Wherein, modifying agent described in step 2 is polyethylene polyamine or silane coupling agent；The solvent be organic solvent or
Silane coupling agent.
The polyethylene polyamine is at least ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine at least one,
The silane coupling agent is 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, 3- (2,3 the third oxygen of epoxy) third
One of ethyl triethoxy silicane alkane, triethoxysilane.
It is at least one that the organic solvent is at least N,N-dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone；
The silane coupling agent is 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, 3- (2,3 the third oxygen of epoxy)
One of propyl-triethoxysilicane, triethoxysilane.
Wherein, the concentration of graphene oxide described in step 2 in a solvent is 0.5-10g/L, the N, N- dicyclohexyl
The concentration of carbodiimide in a solvent is 1-15g/L, and the concentration of the modifying agent in a solvent is 0-500g/L.
Wherein, the concentration of modified graphene oxide described in step 3 in deionized water is 0.5-10g/L；The modification
Concentration of the polysiloxanes in modified graphene oxide dispersion liquid is 100-1000g/L, and the triethylamine is in modified oxidized stone
Concentration in black alkene dispersion liquid is 0.005-0.025g/L.
Wherein, emulsifier described in step 4 is at least TWEEN 20, TWEEN 40, TWEEN 60, TWEEN 80, SPAN
20, one of SPAN 40, SPAN 60, SPAN 80, OP 10, OP40, TX 10, TX100.
Wherein, polysiloxanes described in step 4 is at least the poly- silicon oxygen of hydroxyl polysiloxane, amino silicones, epoxy group
One of alkane, methyl polysiloxane；The viscosity of the polysiloxanes is 100-10000mPas.
Wherein, accounting of the polysiloxanes described in step 4 in graphene modified polyorganosiloxane is 0-100%；It is described poly-
Siloxanes mixed solution is 10-90% in the concentration of emulsifier mixed solution.
Wherein, helped described in step 4 emulsion be at least methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, in n-amyl alcohol
It is a kind of.
Wherein, finish auxiliary described in step 7 includes casein, auxiliary agent, pigment paste, graphene-based leather made from step 7
Finishing agent is the graphene-based leather finishing agent in middle layer；
The graphene-based leather finishing agent preparation of step 7 are as follows: by weight, by 125-160 parts of graphite oxide alkenyls poly- third
Olefin(e) acid ester resin emulsion, 85-100 parts of graphene oxide based polyurethanes resin emulsions, 45-60 parts of caseins, 85-100 auxiliary agent, 65-
80 parts of pigment pastes are dissolved in 300-450 parts of water, and the graphene-based leather finishing agent in middle layer is made in ultrasonic wave dispersion.
Wherein, finish auxiliary described in step 7 includes nitrocotton brightener, polyurethane brightener, oily wax assistant, crosslinking
Agent, graphene-based leather finishing agent made from step 7 are the graphene-based leather finishing agent in upper layer；
The graphene-based leather finishing agent preparation of step 7 are as follows: by weight, by 0-150 parts of nitrocotton brighteners, 0-150
Part polyurethane brightener, 5-20 parts of oily wax assistants, 5-20 parts of graphene-based polysiloxane emulsions, 2-7 parts of crosslinking agents are dissolved in 100-
In 200 parts of water, the graphene-based leather finishing agent in upper layer is made in ultrasonic wave dispersion.
Wherein, graphene-based leather finishing agent made from step 7 is top layer graphene base leather finishing agent；
The graphene-based leather finishing agent preparation of step 7 are as follows: by weight, by 7-12 parts of graphene-based polysiloxane emulsions
It is dissolved in 80-150 parts of water, top layer graphene base leather finishing agent is made in ultrasonic wave dispersion.
A kind of graphene-based leather finishing agent application method of high physical property, which is characterized in that successively comprise the following steps: crust leather
The graphene-based leather finishing agent in the graphene-based leather finishing agent covering with paint → ironing → upper layer in back cover covering with paint → ironing → middle layer is covered with paint, lacquer, colour wash, etc.
→ drying → ironing → oscillation is drawn soft → falls soft → oscillation and draws soft → toggling → ironing → top layer graphene base leather finish
Agent covering with paint → drying → ironing → dry vacuum；Wherein, the graphene-based leather finishing agent in the middle layer is by following parts by weight component group
At: 125-160 parts of graphene oxide based polyacrylic acid ester resin emulsions, 85-100 parts of graphene oxide based polyurethanes resin creams
Liquid, 45-60 part casein, 85-100 auxiliary agent, 65-80 parts of pigment pastes and 300-450 parts of water；The graphene-based leather finish in upper layer
Agent is made of following parts by weight component:, 0-150 parts of nitrocotton brighteners, by 0-150 parts of polyurethane brighteners, 5-20 parts of oily waxes
Auxiliary agent, 5-20 parts of graphene-based polysiloxane emulsions, 2-7 parts of crosslinking agents and 100-200 parts of water；The top layer graphene base leather
Finishing agent is made of following parts by weight component: 7-12 parts of graphene-based polysiloxane emulsions and 80-150 parts of water.
Wherein, the coated weight that the graphene-based leather finishing agent in the middle layer is covered with paint, lacquer, colour wash, etc. is 10-15g/sf；The upper layer graphene
The coated weight that base leather finishing agent is covered with paint, lacquer, colour wash, etc. is 5-10g/sf；The coated weight that the top layer graphene base leather finishing agent is covered with paint, lacquer, colour wash, etc. is 2-
5g/sf；The condition of the ironing is 120-130 DEG C/10-40kgf；It is 5-6 grades that soft intensity is drawn in the oscillation；It is described fall it is soft
Time is 8-12h；The condition of the toggling is 45-50 DEG C/4-6cm/20-25min, the condition 65-80 of the dry vacuum
DEG C/15-30 seconds/vacuum degree-(0.05-0.1) MPa.
By using preceding solution, the beneficial effects of the present invention are: the graphene-based leather finishing agent of high physical property
Preparation method have the advantage that compared with the existing technology
1, using water as decentralized medium, VOC is not generated, it is environmentally protective, meet environmentally friendly process hides demand；And graphene oxide
Reactivity material, can be reacted with hydroxyl, carboxyl or the amino in polyacrylate, polyurethane resin, polysiloxanes or
Not easily to fall off in conjunction with the hydroxyl of leather collagen fiber, carboxyl or amino, obtained graphene-based leather finishing agent is homogeneous body
System, stability is good, resistance to storage；Finishing agent is coated on leather surface as moisture gradually volatilizees, and graphene oxide can be in leather
Surface is evenly distributed, and is firmly combined, and shows the consistent feature of leather surface different parts coating performance.
2, graphene oxide forms stable homogeneous system using polyacrylate, polyurethane resin as carrier, and effect is aobvious
It writes, and graphene oxide dispersion is first compounded with polyacrylate, ester-polyurethane resin emulsion, then be added to finishing agent
In, the effective rate of utilization of graphene oxide can be increased substantially, cost is reduced.
3, using after graphene oxide covalent bond functional modification and as active site, chemical grafting polyacrylic acid
Ester, polyurethane resin, polysiloxanes.It not only can be further improved its lamella each by the graphene oxide of functional modification
Dispersion stabilization in class solvent, polymer, and the graphene oxide after covalent bond functional modification introduces functionalization point
The compatibility of graphene oxide and polymer can be significantly improved after son, polymer, group, so that graphene oxide can be
More preferable, dispersion more evenly in the matrixes such as function chemoattractant molecule, polymer.
4, using chemical graft process on graphene oxide graft polypropylene acid esters, polyurethane resin, polysiloxanes, pass through
Chemical bond is by graphene oxide and polymer-bound, so that graphene oxide is uniformly dispersed in polymer, simultaneous oxidation stone
Active site on black alkene makes polymer branching to a certain extent, hinders the interior rotation of chain, and introduced by modifying agent
Active group, so that being able to form the intermolecular forces such as conjugatedπbond, hydrogen bond between polymer and graphene oxide, further
Promote the dispersion stabilization of graphene oxide in the polymer.
5, modified graphene oxide is restored, so that graphene oxide is restored the structure of script graphene, is only side
There are still a small amount of oxygen-containing functional group, this method to obtain good dispersion effect while promoting its physical and chemical performance edge.
6, leather finish is carried out using the graphene-based leather finishing agent, greatly improves the intensity of leather coating, it is resistance to
Mill property and ageing-resistant performance, leather coating tearing strength promote 8-12%, and elongation at break reduces 6-8%；Leather coating is wear-resisting
Performance boost 16-18%；Leather coating ageing-resistant performance promotes 4-8%, and waterproof performance 48h is waterproof.
Specific embodiment
The present invention is specifically described below by specific embodiment, whereby to the present invention how applied technology method
Technical problem is solved, and the realization process for reaching technical effect can fully understand and implement, it is necessary to indicated herein
It is that the present embodiment is served only for that invention is further explained, should not be understood as limiting the scope of the invention, the neck
The person skilled in the art in domain can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
Unless otherwise specified, the conventional hand that technological means employed in embodiment is well known to those skilled in the art
Section, used reagent and product are also available commercial.The various processes and method being not described in detail are in this field
Well known conventional method, the source of agents useful for same, trade name and it is necessary to list its constituent person, on the first appearance
It indicates.
Embodiment 1
A kind of preparation method of the graphene-based leather finishing agent of high physical property, includes the following steps:
Step 1, modified polyorganosiloxane preparation: by siloxanyl monomers (octamethylcy-clotetrasiloxane), silane coupling agent (3- ammonia
Propyl-triethoxysilicane), end-capping reagent (two silicon oxygen of 1,3- bis- (3- glycydoxy) -1,1,3,3- tetramethyl
Alkane), catalyst (tetramethylammonium hydroxide) react 6h at 90 DEG C, obtain modified polyorganosiloxane；Wherein, the silane coupling agent
Concentration is 2%, and the end-capping reagent concentration is 0.8%, and the catalyst concn is 0.06%；
The preparation of step 2, modified graphene oxide: graphene oxide (single-layer graphene oxide) is added to silane coupled
In agent (3- chloropropyl triethoxysilane), concentration of the graphene oxide in silane coupling agent is 7.5g/L, and N is then added,
N- dicyclohexylcarbodiimide, the N, concentration of the N- dicyclohexylcarbodiimide in silane coupling agent are 7.5g/L, ultrasound
Disperse 90min (it is 60W that ultrasonic wave, which disperses power), obtains graphene oxide dispersion, be transferred in reactor and reacted at 70 DEG C
Reaction mixture is obtained solid through filtration washing vacuum drying (vacuum drying temperature is 35 DEG C, drying time 60h) by 36h
Powder, then restored (restoring method be obtain modified graphene oxide after 2.5% hydrazine hydrate solution reduction treatment 8h)；
The preparation of step 3, graphene-based polysiloxanes: step 2 gained modified graphene oxide is added in deionized water,
The concentration of modified graphene oxide in deionized water is 2g/L, and ultrasonic disperse 90min (it is 60W that ultrasonic wave, which disperses power) is obtained
To modified graphene oxide dispersion liquid；Step 1 gained modified polyorganosiloxane is added in modified graphene oxide dispersion liquid, it is modified
Concentration of the polysiloxanes in modified graphene oxide dispersion liquid is 350g/L, adds triethylamine, triethylamine is modified oxidized
Concentration in graphene dispersing solution is 0.02g/L, and colloidal sol is made in 3h under 25 DEG C of reactions, is then warming up to 80 DEG C of reaction 3h systems
Gel solution is obtained, will be coagulated after gel solution vacuum drying (vacuum drying temperature is 35 DEG C, drying time 60h)
Glue, then graphene-based polysiloxanes is obtained after being restored (restoring method is using 2.5% hydrazine hydrate solution reduction treatment 8h)；
Step 4, the preparation of graphene-based polysiloxane emulsion: by 65 parts of emulsifier TWEEN20 and 35 parts of emulsifier SPAN80
Simultaneously ultrasonic disperse 10min (ultrasonic wave operating power is 600W) is mixed, emulsifier mixed solution is obtained；It will be aoxidized obtained by step 3
Graphene modified polyorganosiloxane and polysiloxanes (methyl polysiloxane, viscosity 500mPas) are uniformly mixed, and obtain poly- silicon oxygen
Alkane mixed solution, wherein accounting of the polysiloxanes in graphene oxide modified polyorganosiloxane is 85%；By polysiloxanes
Mixed solution is added in emulsifier mixed solution, and polysiloxanes mixed solution is 65% in the concentration of emulsifier mixed solution, surpasses
Sound disperses 60min (ultrasonic wave operating power is 600W), obtains reaction mixture；Reaction mixture is stirred into shape in dispersion
9 times of deionized waters dropwise under state, obtain lotion；5% is added in lotion to help emulsion (n-amyl alcohol), ultrasonic disperse 60min is (super
Sound wave effect power is 600W), graphene-based polysiloxane emulsion can be obtained；
Step 5, the preparation of graphene oxide based polyacrylic acid ester resin emulsion:
10.0 parts of graphene oxide powders are dissolved in 1000 parts of water, ultrasonic wave disperses 30min, and ultrasonic power is
300W, pH to 7.5 then is adjusted with 2% ammonium hydroxide, graphene oxide dispersion is made；
1. by 8 parts of graphene oxide dispersions and 500 parts of polyacrylate resin lotions (RA-2356, solid content 20%,
The fine coating of this tal fibre (Suzhou) Co., Ltd) mixing, ultrasonic wave disperses 30min, ultrasonic power 450W, obtained to aoxidize stone
The graphene oxide based polyacrylic acid ester resin emulsion RA-2356 that black alkene mass fraction is 0.08%；
2. by 14 parts of graphene oxide dispersions and 500 parts of polyacrylate resin lotions (RA-1079, solid content 35%,
The fine coating of this tal fibre (Suzhou) Co., Ltd) mixing, ultrasonic wave disperses 30min, ultrasonic power 500W, obtained to aoxidize stone
The graphene oxide based polyacrylic acid ester resin emulsion RA-1079 that black alkene mass fraction is 0.08%；
Step 6, the preparation of graphene oxide based polyurethanes resin emulsion:
10.0 parts of graphene oxide powders are dissolved in 1000 parts of water, ultrasonic wave disperses 30min, and ultrasonic power is
300W, pH to 7.5 then is adjusted with 2% ammonium hydroxide, graphene oxide dispersion is made；
1. by 14 parts of step 1 gained graphene oxide dispersions and 500 parts of ester-polyurethane resin emulsions (RU-3910, admittedly contain
Amount 35%, the fine coating of this tal fibre (Suzhou) Co., Ltd) it mixes, ultrasonic dispersing time 30min, ultrasonic power is
The graphene oxide based polyurethanes resin emulsion RU-3910 that graphene oxide mass fraction is 0.08% is made in 500W；
2. by 14 parts of step 1 gained graphene oxide dispersions and 500 parts of ester-polyurethane resin emulsion (Aqualen Top
LN.A, solid content 35%, the fine coating of this tal fibre (Suzhou) Co., Ltd) mixing, ultrasonic wave dispersion 30min, ultrasonic power
For 500W, the graphene oxide based polyurethanes resin emulsion Aqualen Top that graphene oxide mass fraction is 0.08% is made
LN.A；
Step 7, the preparation of graphene-based leather finishing agent:
1. by 60 parts of graphene oxide based polyacrylic acid ester resin emulsions, 80 parts of graphene oxide based polyacrylic acid ester resins
Lotion RA-1079,100 parts of graphene oxide based polyurethanes resin emulsions, 60 parts of caseins (RODA bind TU688/B, De Ruipi
Change Co., Ltd), 40 parts of wax assistants (48416-GAA, Shanghai Pierre's Ka Lefu benefit Chemical Co., Ltd.), 50 parts of soft additives
(EUDERM Nappa SoftS-C, Lang Sheng group), 80 parts of pigment pastes (PPE DEEP BLACK A-ID, the fine coating of this tal fibre
(Suzhou) Co., Ltd) it is dissolved in 400 parts of water, 8min, speed of agitator 950r/min are stirred, the graphene-based leather in middle layer is made
Finishing agent；
2. by 100 parts of nitrocotton brighteners (WL-8119, the upper positive Wan Wei leather chemical corporation, Ltd. in Haifeng county), 10 parts of oily waxes
Auxiliary agent (KO 2311, Xiamen Hao Deya trade Co., Ltd), 10 parts of graphene-based polysiloxane emulsions, 5 parts of crosslinking agents
(Aqualen AKU liq, the fine coating of this tal fibre (Suzhou) Co., Ltd) is dissolved in 150 parts of water, is stirred 8min, stirring
Revolving speed is 950r/min, and the graphene-based leather finishing agent in upper layer is made.
3. 10 parts of graphene-based polysiloxane emulsions are dissolved in 100 parts of water, it is stirred 8min, speed of agitator is
Top layer graphene base leather finishing agent is made in 950r/min.
Application examples 1
A kind of application method of the graphene-based leather finishing agent of high physical property, successively comprises the following steps: crust leather back cover is covered with paint, lacquer, colour wash, etc.
The graphene-based leather finishing agent covering with paint → 1 gained upper layer of ironing → embodiment in 1 gained middle layer of → ironing → embodiment is graphene-based
Leather finishing agent covering with paint → drying → ironing → oscillation is drawn soft → falls soft → oscillation and draws soft → toggling → ironing → embodiment 1
Gained top layer graphene base leather finishing agent covering with paint → drying → ironing → dry vacuum；Wherein, the graphene-based leather in the middle layer
The coated weight that finishing agent is covered with paint, lacquer, colour wash, etc. is 15g/sf；The coated weight that the graphene-based leather finishing agent in middle layer is covered with paint, lacquer, colour wash, etc. is 8g/sf；It is described
The coated weight that top layer graphene base leather finishing agent is covered with paint, lacquer, colour wash, etc. is 3g/sf；The condition of the ironing is 120 DEG C/30kgf；The vibration
Swinging the soft intensity of drawing is 5 grades；It is described to fall the soft time as 10h；The condition of the toggling is 50 DEG C/4cm/25min, described
80 DEG C of the condition of dry vacuum/15 seconds/vacuum degree -0.1MPa.
After the graphene-based leather finishing agent coating, leather coating tearing strength promotes 8-12%, elongation at break drop
Low 6-8%；Leather coating wear-resisting property promotes 16-18%；Leather coating ageing-resistant performance promotes 4-8%, and waterproof performance 48h is not
It is permeable.
In conclusion the preparation method and application method of the graphene-based leather finishing agent of high physical property, for traditional skin
Strength of coating, wearability, the technological deficiency of resistance to ag(e)ing difference are removed from office, increasing of the stannic oxide/graphene nano material as leather coating is introduced
Strong agent, graphene oxide specific surface area with higher, more rich oxygen-containing functional group can be with polypropylene under ultrasonic wave effect
The graphene-based leather finish that acid esters, polyurethane resin, polysiloxanes leather film forming agent are blended preparation uniformity, have good stability
Film forming agent；Since graphene oxide has excellent intensity and toughness, it can enhance, tenacity-increased profax acid esters, polyurethane resin, gather
The mechanical property of siloxanes leather film forming agent, to obtain high performance leather coating.
The foregoing descriptions are merely the embodiment using this origination techniques content, any those skilled in the art use this wound
Make done modifications and changes, all belong to the scope of the patents of this creation opinion, and is not limited to those disclosed embodiments.
Claims (21)
1. a kind of preparation method of the graphene-based leather finishing agent of high physical property, it is characterised in that: by graphene-based polysiloxanes cream
Liquid, graphene oxide based polyacrylic acid ester resin emulsion, graphene oxide based polyurethanes resin emulsion, finish auxiliary are dissolved in water
In, graphene-based leather finishing agent is made in ultrasonic wave dispersion；Wherein, graphene-based polysiloxane emulsion is using graphite oxide
Alkene graft modification polysiloxanes is through solgel reaction, reduction, the again gained after emulsification compounding；Graphene oxide based polyacrylic acid
Ester resin emulsion is using obtained by graphene oxide graft modification polypropylene acid ester resin；Graphene oxide based polyurethanes resin cream
Liquid is using obtained by graphene oxide graft modification polyurethane resin.
2. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 1, it is characterised in that:
Step 1, modified polyorganosiloxane preparation: by siloxanyl monomers, silane coupling agent, end-capping reagent, catalyst, crosslinking agent in 70-
3-8h is reacted at 140 DEG C, obtains modified polyorganosiloxane；
The preparation of step 2, modified graphene oxide: adding graphene oxide into solvent, and N, N- dicyclohexyl is then added
Carbodiimide, ultrasonic disperse 20-270min obtain modified graphene oxide forerunner's dispersion liquid, are transferred to addition in reactor and change
Property agent react 12-96h at 50-150 DEG C, the dehydrated alcohol with the solvent equivalent is added, 6-48h is stood at 0-50 DEG C,
It is filtered, washed, is dried in vacuo and obtains solid powder, then obtain modified graphene oxide after carrying out reduction；
The preparation of step 3, graphene-based polysiloxanes: step 2 gained modified graphene oxide is added in deionized water, ultrasound
Disperse 20-200min, obtains modified graphene oxide dispersion liquid；Modified oxidized stone is added in step 1 gained modified polyorganosiloxane
In black alkene dispersion liquid, triethylamine is added, colloidal sol is made in 3-8h under 10-50 DEG C of reaction, is then warming up to 60-100 DEG C of reaction
Gel solution is made in 1-5h；Gel is obtained after gel solution is dried in vacuo, then obtains graphene-based poly- silicon after carrying out reduction
Oxygen alkane；
Step 4, the preparation of graphene-based polysiloxane emulsion: dispersion stirring 5- after two kinds and the above different emulsifiers are mixed
120min obtains emulsifier mixed solution；Step 3 gained graphene modified polyorganosiloxane is uniformly mixed with polysiloxanes, is obtained
Polysiloxanes mixed solution；Polysiloxanes mixed solution is added in emulsifier mixed solution, dispersion stirring 5-120min is obtained
Reaction mixture；By reaction mixture in the case where dispersing stirring 5-15 times of deionized water dropwise, obtain lotion；In lotion
Middle addition 0-20% helps emulsion, and graphene-based polysiloxane emulsion can be obtained after being dispersed stirring 5-120min；
Step 5, the preparation of graphene oxide based polyacrylic acid ester resin emulsion: graphene oxide powder is soluble in water, ultrasonic wave
Then dispersion adjusts pH to 6.5-9 with 2-4% ammonium hydroxide, obtains graphene oxide dispersion, by graphene oxide dispersion and gather
Acrylate resin emulsion mixing, ultrasonic wave dispersion prepare the graphite oxide alkenyl that graphene oxide concentration is 0.05-0.1%
Polyacrylate resin lotion；
Step 6, the preparation of graphene oxide based polyurethanes resin emulsion: graphene oxide powder is soluble in water, ultrasonic wave dispersion,
Then pH to 6.5-9 is adjusted with 2-4% ammonium hydroxide, graphene oxide dispersion is obtained, by graphene oxide dispersion and polyurethane
Resin emulsion mixing, ultrasonic wave dispersion prepare the poly- ammonia of graphite oxide alkenyl that graphene oxide mass fraction is 0.05-0.1%
Ester resin emulsion；
Step 7, the preparation of graphene-based leather finishing agent: by weight, by 0-160 parts of graphene oxide based polyacrylic acid ester trees
Fat liquor, 0-125 parts of graphene oxide based polyurethanes resin emulsions, 0-15 parts of graphene-based polysiloxane emulsions, finish auxiliaries
Soluble in water, graphene-based leather finishing agent is made in ultrasonic wave dispersion.
3. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 1
Described in siloxanyl monomers be octamethylcy-clotetrasiloxane.
4. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 1
Described in silane coupling agent be at least 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, 3- (2,3 epoxies third
Oxygen) propyl-triethoxysilicane, one of triethoxysilane.
5. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 1
Described in end-capping reagent be at least 1,3- bis- (3- glycydoxy) -1,1,3,3- tetramethyl disiloxane, hexamethyl
One of disiloxane.
6. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 1
Described in catalyst be at least one of potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide.
7. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 1
Described in crosslinking agent be at least one of epoxy prapanol, third chlorine of epoxy.
8. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 1
Described in the concentration of silane coupling agent be 0.1-5%, the end-capping reagent concentration is 0.1-1%, and the catalyst concn is
0.01-0.2%, the crosslinker concentration are 0-4%.
9. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 2
Described in modifying agent be polyethylene polyamine or silane coupling agent；The solvent is organic solvent or silane coupling agent.
10. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 9, it is characterised in that: described
Polyethylene polyamine is at least ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine at least one, described silane coupled
Agent is 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, 3- (2,3 the third oxygen of epoxy) propyl-triethoxysilicane
One of alkane, triethoxysilane.
11. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 9, it is characterised in that: described
It is at least one that organic solvent is at least N,N-dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone；The silane is even
Connection agent is 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, 3- (2,3 the third oxygen of epoxy) propyl-triethoxysilicane
One of alkane, triethoxysilane.
12. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 2
Described in the concentration of graphene oxide in a solvent be 0.5-10g/L, the N, N- dicyclohexylcarbodiimide is in a solvent
Concentration is 1-15g/L, and the concentration of the modifying agent in a solvent is 0-500g/L.
13. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 3
Described in the concentration of modified graphene oxide in deionized water be 0.5-10g/L；The modified polyorganosiloxane is modified oxidized
Concentration in graphene dispersing solution is 100-1000g/L, and the triethylamine is in the concentration in modified graphene oxide dispersion liquid
For 0.005-0.025g/L.
14. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 4
Described in emulsifier be at least TWEEN 20, TWEEN 40, TWEEN 60, TWEEN 80, SPAN 20, SPAN 40, SPAN
60, one of SPAN 80, OP 10, OP40, TX 10, TX100.
15. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 4
Described in polysiloxanes be at least hydroxyl polysiloxane, amino silicones, epoxy based polysiloxane, in methyl polysiloxane
It is a kind of；The viscosity of the polysiloxanes is 100-10000mPas.
16. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 4
Described in accounting of the polysiloxanes in graphene modified polyorganosiloxane be 0-100%；The polysiloxanes mixed solution is in cream
The concentration of agent mixed solution is 10-90%.
17. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 4
Described in help emulsion to be at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, n-amyl alcohol.
18. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 7
Described in finish auxiliary include casein, auxiliary agent, pigment paste, graphene-based leather finishing agent made from step 7 is middle layer graphene
Base leather finishing agent；
The graphene-based leather finishing agent preparation of step 7 are as follows: by weight, by 125-160 parts of graphene oxide based polyacrylic acids
Ester resin emulsion, 85-100 parts of graphene oxide based polyurethanes resin emulsions, 45-60 parts of caseins, 85-100 auxiliary agent, 65-80 parts
Pigment paste is dissolved in 300-450 parts of water, and the graphene-based leather finishing agent in middle layer is made in ultrasonic wave dispersion.
19. the preparation method of the graphene-based leather finishing agent of high physical property according to claim 2, it is characterised in that: step 7
Described in finish auxiliary include nitrocotton brightener, polyurethane brightener, oily wax assistant, crosslinking agent, graphene made from step 7
Base leather finishing agent is the graphene-based leather finishing agent in upper layer；
The graphene-based leather finishing agent preparation of step 7 are as follows: by weight, by 0-150 parts of nitrocotton brighteners, 0-150 parts poly-
Urethane brightener, 5-20 parts of oily wax assistants, 5-20 parts of graphene-based polysiloxane emulsions, 2-7 parts of crosslinking agents are dissolved in 100-200 parts
In water, the graphene-based leather finishing agent in upper layer is made in ultrasonic wave dispersion.
20. the preparation of the graphene-based leather finishing agent of high physical property according to claim 2 and application method, feature exist
In: graphene-based leather finishing agent made from step 7 is top layer graphene base leather finishing agent；
The graphene-based leather finishing agent preparation of step 7 are as follows: by weight, 7-12 parts of graphene-based polysiloxane emulsions are dissolved in
In 80-150 parts of water, top layer graphene base leather finishing agent is made in ultrasonic wave dispersion.
21. a kind of graphene-based leather finishing agent application method of high physical property, which is characterized in that successively comprise the following steps: crust leather
The graphene-based leather finishing agent in the graphene-based leather finishing agent covering with paint → ironing → upper layer in back cover covering with paint → ironing → middle layer is covered with paint, lacquer, colour wash, etc.
→ drying → ironing → oscillation is drawn soft → falls soft → oscillation and draws soft → toggling → ironing → top layer graphene base leather finish
Agent covering with paint → drying → ironing → dry vacuum；Wherein, the graphene-based leather finishing agent in the middle layer is by following parts by weight component group
At: 125-160 parts of graphene oxide based polyacrylic acid ester resin emulsions, 85-100 parts of graphene oxide based polyurethanes resin creams
Liquid, 45-60 part casein, 85-100 auxiliary agent, 65-80 parts of pigment pastes and 300-450 parts of water；The graphene-based leather finish in upper layer
Agent is made of following parts by weight component: 0-150 parts of nitrocotton brighteners, and 0-150 parts of polyurethane brighteners, 5-20 parts of oily waxes are helped
Agent, 5-20 parts of graphene-based polysiloxane emulsions, 2-7 parts of crosslinking agents and 100-200 parts of water；The top layer graphene base leather applies
Decorations agent is made of following parts by weight component: 7-12 parts of graphene-based polysiloxane emulsions and 80-150 parts of water.
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