CN108456482A - A kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent and preparation method thereof - Google Patents

A kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent and preparation method thereof Download PDF

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Publication number
CN108456482A
CN108456482A CN201810035278.0A CN201810035278A CN108456482A CN 108456482 A CN108456482 A CN 108456482A CN 201810035278 A CN201810035278 A CN 201810035278A CN 108456482 A CN108456482 A CN 108456482A
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agent
aqueous polyurethane
parts
graphene
leather finishing
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胡剑青
邹滔
涂伟萍
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South China University of Technology SCUT
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South China University of Technology SCUT
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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
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

The invention belongs to the technical field of polyurethane decorative paint for leather, a kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent and preparation method thereof is disclosed.The leather finishing agent is made of the two parts separately stored, and first part and second part are all according to mass fraction meter；First part includes following components：25 55 parts of polyalcohol, 29 45 parts of diisocyanate, 3 15 parts of hydrophily glycol chain extender, dihydric alcohol/5 25 parts of trihydroxylic alcohol chain extender, 0.05 1 parts of catalyst, 3 20 parts of neutralizer, 250 450 parts of water, 1 15 parts of graphene, 0.05 3 parts of silane coupling agent；Second part is curing agent；5 15 parts of curing agent.The present invention Aqueous Polyurethane Leather Finishing Agent is with preferable storage stability and water-fast, solvent resistance and polyurethane coating is with preferable mechanics and heat conductivility.

Description

A kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent and preparation method thereof
Technical field
The invention belongs to the technical fields of polyurethane decorative paint for leather, and in particular to a kind of graphene modified double components are aqueous Polyurethane decorative paint for leather and preparation method thereof.
Background technology
Aqueous polyurethane is the new polyurethane system that organic solvent is substituted using water as decentralized medium, also referred to as water base poly- Urethane.Compared with traditional solvent borne polyurethane, not only have many advantages, such as pollution-free, Environmental Safety, it is fire-retardant, while having resistance to Mill, the features such as mechanical strength is excellent, are widely used in the fields such as coating, adhesive, ink, leather finish.With leather finish For：Covering with paint is one of important procedure in leather manufacture production, it can make leather surface form color, style and different outer of gloss Table increases leather aesthetic measure and assigns and remove from office certain water resistance and easy maintenance, expands use scope.Wherein polyurethane skin Finishing agent is removed from office due to itself excellent mechanical property and covering power, the quality and grade of leather can be obviously improved, therefore obtain Extensive use is arrived.Polyurethane decorative paint for leather on the market is mainly single-component water-based polyurethane at present, with isocyanates Base blocks, then by being that hydrophilic radical carries out internal emulsification method synthesis with carboxylate or sulfonate etc..But isocyanates is deposited Making such product that there is higher reactivity at normal temperatures so that storage stability is bad.
For one-component leather finishing agent, two-component leather finishing agent storage stability of the invention is more preferable, and And by modified so that the storage stability of aqueous polyurethane further improves in leather finishing agent；And pass through different molecular Being used cooperatively between weight polyalcohol can meet unlike material with good adhesive force while film is with high glaze Leather finish demand.
Graphene be it is a kind of be made of single layer of carbon atom, only there are one carbon atom thickness honeycomb crystal lattice material.It is Be currently known in the world most it is frivolous it is also most hard, conduction/thermal coefficient is most strong, the highest novel nano-material of intensity uses stone Black alkene is modified double-component polyurethane decorative paint for leather, changes while improving water-fast aqueous polyurethane, solvent resistance The mechanical property of kind finishing agent makes it obtain widely application.
Invention content
The shortcomings that in order to overcome aqueous polyurethane in existing one-component leather finishing agent and leather finishing agent and deficiency, this Invention is designed to provide a kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent.The present invention is by graphene dispersion It is modified in the aqueous polyurethane emulsion blocked to hydroxyl, is handed over by the isocyanate-based curing agent added after cooperation Connection uses, and improves the mechanics and thermal conductivity of polyurethane coating while improving its storage stability and water-fast, solvent resistance Energy.
Another object of the present invention is to provide the systems of above-mentioned graphene modified double components Aqueous Polyurethane Leather Finishing Agent Preparation Method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent, is made of, first the two parts separately stored Part and second part are all according to mass fraction meter；
First part includes following components：
Second part is curing agent；
5-15 parts of curing agent.
The first part further includes moistening flatting agent and hand feeling agent, the mass fraction of the moistening flatting agent and hand feeling agent For：
The first part further includes organic solvent, the organic solvent be n,N-Dimethylformamide, neutralizer with have The mass ratio of solvent is (3-20)：(5-12).
The polyalcohol is in PCL1000, PCL2000, PCL3000, PPG400, PPG1000, PPG2000, PBA3000 More than one, it is preferably two or more.
The diisocyanate is isophorone diisocyanate (IPDI), methyl diphenylene diisocyanate (MDI), six One in methylene diisocyanate (HDI) tripolymer, hexamethylene diisocyanate (HDI), toluene di-isocyanate(TDI) (TDI) Kind or more.
The hydrophily glycol chain extender is one in dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA) Kind or more.
The dihydric alcohol/trihydroxylic alcohol chain extender is 1,4- butanediols, 1,3- propylene glycol, 1,6-HD, neopentyl glycol, three One or more of hydroxymethyl-propane, glycerine.
The catalyst is dibutyl tin dilaurate or stannous octoate.
The neutralizer is one or more of triethanolamine, triethylamine, sodium hydroxide.
The moistening flatting agent be Si Luoke Sliok-8333, one or more of Sliok-8858 or Sliok-8035, Preferably Sliok-8858.
The hand feeling agent be Si Luoke Sliok-9151, Sliok-3300, one or more of Sliok-9148, preferably Sliok-3300。
The curing agent is one or more of Bai Situo WT2102, XD803.
The silane coupling agent is one or more of KH-560, KH-570, KH-164, preferably KH-164.
The dosage of the graphene is preferably 1-10 parts, more preferably 1-6 parts.
The preparation method of the graphene modified double components Aqueous Polyurethane Leather Finishing Agent, includes the following steps：
(1) it by polyalcohol vacuum dehydration, is then reacted, is reacted under the action of partial catalyst with diisocyanate Temperature be 60-80 DEG C, the reaction time be 1-3 hours, obtain performed polymer；
(2) hydrophily glycol chain extender is added into performed polymer, dihydric alcohol/trihydroxylic alcohol is added in insulation reaction 1-3 hours Chain extender and residual catalyst, are warming up to 70-85 DEG C, polymerisation 2-4 hours, cooling, be added neutralizer and organic solvent into Row neutralizes, and obtains base polyurethane prepolymer for use as；
(3) it under moderate-speed mixer, adds water in base polyurethane prepolymer for use as, water increases speed after adding, emulsification, obtains containing hydroxyl The aqueous polyurethane emulsion of base sealing end；
(4) graphene is mixed with water, silane coupling agent is added dropwise, ultrasonic disperse obtains graphene dispersing solution；By graphene Dispersion liquid is uniformly mixed with the aqueous polyurethane emulsion that hydroxyl blocks, and obtains modified aqueous polyurethane emulsion；
(5) when in use, modified aqueous polyurethane emulsion is uniformly mixed with moistening flatting agent, hand feeling agent, is finally added Enter curing agent, obtains Aqueous Polyurethane Leather Finishing Agent.
The condition of vacuum dehydration described in step (1) is to be dried in vacuo 0.5-1 hours at 90-110 DEG C, and the part is urged Agent is the 30-70% of catalyst total amount；
The temperature of insulation reaction described in step (2) is 60-80 DEG C；The temperature of the cooling is 35-45 DEG C, the neutralization The time of reaction is 20-45 minutes；
The rotating speed of middling speed described in step (3) is 800-1200r/min；It is described that increase speed refer to increasing to rotating speed 3000-4000r/min；The addition of the water is：The mass ratio of water and hydrophily glycol chain extender is (150-350)：(3- 15), i.e., the addition of the described water is 150-350 mass parts；The time of emulsification is 15-30min；
The dosage relation of graphene and water described in step (4) is that 1-15 mass parts graphite is added in every 100 mass parts water Alkene；The time of the ultrasonic disperse is 30-60min, and described be uniformly mixed refers to disperseing under the rotating speed of 400-1000r/min It is even.
The polyurethane that the present invention is blocked by synthesizing hydroxyl, improves the bin stability of aqueous polyurethane；It adopts simultaneously The mechanical property (such as adhesive force) of polyurethane is adjusted with different chain extenders；Wherein hydrophilic chain extender is in order in polyurethane chain Middle introducing hydrophilic radical, promotes the synthesis of aqueous polyurethane emulsion, while controlling water-resistance property of coating, and dihydric alcohol/trihydroxylic alcohol expands The use of chain agent is then linear/build chain extension in order to make polyurethane chain form part, adjusts its mechanical property；And different molecular The polyalcohol collocation of amount is using can make finished product polyurethane decorative paint for leather be kept between good adhesive force and tacky performance Balance；The effect of silane coupling agent is that graphene is made to be dispersed in water phase under ultrasonication, finally under low speed dispersion It is evenly distributed in polyaminoester emulsion；Silane coupling agent as a kind of surfactant, as organic phase (polyaminoester emulsion) and The bridge that inorganic phase (graphene) is connected with each other, can be such that graphene uniform is dispersed in aqueous polyurethane emulsion.
Compared with prior art, the present invention has the following advantages and beneficial effects：
The present invention will be modified in aqueous polyurethane emulsion that graphene dispersion to hydroxyl blocks, by adding after cooperation The isocyanate-based curing agent added carries out crosslinking use, changes while improving its storage stability and water-fast, solvent resistance The mechanics and heat conductivility of kind polyurethane coating.The storage stability of the Aqueous Polyurethane Leather Finishing Agent of the present invention is to pass through water Property polyaminoester emulsion storage stability is embodied.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to This.
Embodiment 1
(1) be added in the reaction vessel 6.2 mass parts molecular weight be 1000 polycaprolactone diols (PCL1000) and The polycaprolactone diols (PCL2000) that 37.1 mass parts molecular weight are 2000,105 DEG C of vacuum pumps are dried 30 minutes, drop 35.7 mass parts isophorone diisocyanate and 0.05 mass parts of catalyst dibutyl tin dilaurate are added after temperature to room temperature, Kept for 80 DEG C react 1 hour；
(2) 7 mass parts dihydromethyl propionic acids are added in above-mentioned reactant, are warming up to 80 DEG C, react 1.5 hours；Again plus Enter 8.5 mass parts 1,4-butanediol (prior drying and dehydrating processing), in 85 DEG C of polymerisations 3.5 hours, be then cooled to 42 DEG C, It is added 5.5 mass parts triethylamines and n,N-Dimethylformamide that 8 mass parts remove water in advance is neutralized, the reaction time is 25 points Base polyurethane prepolymer for use as is made in clock；
(4) under the rotating speed of dispersion machine 1000r/min, polyurethane prepolymer is gently added in the deionized water of 200 mass parts In body, rotating speed is then promoted to 3500r/min, emulsifies 20min, the aqueous polyurethane emulsion for obtaining hydroxyl sealing end is (penetrating The aqueous polyurethane emulsion of the hydroxyl sealing end of blueing light)；
(5) 1 mass parts graphene is placed in 100 mass parts deionized waters, 1 mass parts silane coupling agent (KH- is added dropwise 164), ultrasonic disperse 45min obtains the graphene dispersing solution of stable dispersion；Graphene dispersing solution and hydroxyl are blocked poly- Urethane lotion 400r/min dispersion machine effect under be uniformly mixed, obtain modified polyurethane emulsion (graphene be modified contain hydroxyl The aqueous polyurethane emulsion of base sealing end)；
(6) by 100 mass parts modified polyurethane emulsions, 3 mass parts moistening flatting agent Sliok-8858 and 2 mass parts feels Agent Sliok-3300 is uniformly mixed, and 2 mass parts water-based polyurethane curing agent Bai Situo WT2102 are added, after stirring 30 minutes, i.e., Obtain double-component waterborne polyurethane leather finishing agent.
N,N-Dimethylformamide can dissolve the macromolecule polyurethane chain that reaction is formed after the completion, reduce the viscosity of product, It mixes well and is neutralized with resin convenient for neutralizer triethylamine.
The performance test results of Aqueous Polyurethane Leather Finishing Agent manufactured in the present embodiment are as shown in table 1.
Embodiment 2
(1) polypropylene glycol (PPG1000) and 35.6 mass that 6.6 mass parts molecular weight are 1000 are added in the reaction vessel The polycaprolactone diols (PCL2000) that part molecular weight is 2000,105 DEG C of vacuum pumps are dried 30 minutes, are cooled to room temperature After be added 35.7 mass parts isophorone diisocyanate and 0.05 mass parts of catalyst dibutyl tin dilaurate, kept for 80 DEG C Reaction 1 hour；
(2) 6.6 mass parts dimethylolpropionic acids are added in above-mentioned reactant, are warming up to 80 DEG C, react 2 hours；Again plus Enter 8.9 mass parts 1,4-butanediol (prior drying and dehydrating processing), in 80 DEG C of polymerisations 3.5 hours, be then cooled to 42 DEG C, It is added 5 mass parts triethylamines and n,N-Dimethylformamide that 8 mass parts remove water in advance is neutralized, the reaction time is 25 points Base polyurethane prepolymer for use as is made in clock；
(4) under the rotating speed of dispersion machine 1000r/min, polyurethane prepolymer is gently added in the deionized water of 200 mass parts In body, rotating speed is then promoted to 3000r/min, emulsifies 20min, the aqueous polyurethane emulsion for obtaining hydroxyl sealing end is (penetrating The aqueous polyurethane emulsion of the hydroxyl sealing end of blueing light)；
(5) 1 mass parts graphene is placed in 100 mass parts deionized waters, 1 mass parts silane coupling agent (KH- is added dropwise 164, the triumphant chemical industry of Guangzhou dragon), ultrasonic disperse 45min obtains the graphene dispersing solution of stable dispersion；By graphene dispersing solution with The polyaminoester emulsion of hydroxyl sealing end is uniformly mixed under the dispersion machine effect of 400r/min, obtains modified polyurethane emulsion (stone The aqueous polyurethane emulsion for the hydroxyl sealing end that black alkene is modified)；
(6) by 100 mass parts modified polyurethane emulsions, 3 mass parts moistening flatting agent Sliok-8858 and 2 mass parts feels Agent Sliok-3300 is uniformly mixed, and 2 mass parts water-based polyurethane curing agent Bai Situo WT2102 are added, after stirring 30 minutes, i.e., Obtain double-component waterborne polyurethane leather finishing agent.The performance test results of Aqueous Polyurethane Leather Finishing Agent manufactured in the present embodiment As shown in table 1.
Embodiment 3
(1) polypropylene glycol (PPG1000) and 35.1 mass that 6.5 mass parts molecular weight are 1000 are added in the reaction vessel The polycaprolactone diols (PCL2000) that part molecular weight is 2000,105 DEG C of vacuum pumps are dried 30 minutes, are cooled to room temperature After be added 36.9 mass parts isophorone diisocyanate and 0.05 mass parts of catalyst dibutyl tin dilaurate, kept for 80 DEG C Reaction 1 hour；
(2) 6.5 mass parts dimethylolpropionic acids are added in above-mentioned reactant, are warming up to 80 DEG C, react 2 hours；Again plus Enter 8.8 mass parts 1,4-butanediol (prior drying and dehydrating processing) and 1.4 mass parts trimethylolpropanes, in 80 DEG C of polymerisations 3.5 hours, 42 DEG C are then cooled to, the n,N-Dimethylformamide that 4.9 mass parts triethylamines of addition and 8 mass parts remove water in advance It is neutralized, the reaction time is 25 minutes, and base polyurethane prepolymer for use as is made；
(4) under the rotating speed of dispersion machine 1000r/min, polyurethane prepolymer is gently added in the deionized water of 200 mass parts In body, rotating speed is then promoted to 3000r/min, emulsifies 20min, the aqueous polyurethane emulsion for obtaining hydroxyl sealing end is (penetrating The aqueous polyurethane emulsion of the hydroxyl sealing end of blueing light)；
(5) 1 mass parts graphene is placed in 100 mass parts deionized waters, 1 mass parts silane coupling agent (KH- is added dropwise 164), ultrasonic disperse 45min obtains the graphene dispersing solution of stable dispersion；Graphene dispersing solution and hydroxyl are blocked poly- Urethane lotion 400r/min dispersion machine effect under be uniformly mixed, obtain modified polyurethane emulsion (graphene be modified contain hydroxyl The aqueous polyurethane emulsion of base sealing end)；
(6) by 100 mass parts modified polyurethane emulsions, 3 mass parts moistening flatting agent Sliok-8858 and 2 mass parts feels Agent Sliok-3300 is uniformly mixed, and 2 mass parts water-based polyurethane curing agent Bai Situo WT2102 are added, after stirring 30 minutes, i.e., Obtain double-component waterborne polyurethane leather finishing agent.The performance test results of Aqueous Polyurethane Leather Finishing Agent manufactured in the present embodiment As shown in table 1.
Embodiment 4
(1) be added in the reaction vessel 7.2 mass parts molecular weight be 1000 polycaprolactone diols (PCL1000) and The polycaprolactone diols (PCL2000) that 38.9 mass parts molecular weight are 2000,105 DEG C of vacuum pumps are dried 30 minutes, drop 35.8 mass parts isophorone diisocyanate and 5.1 mass parts hexamethylene diisocyanate trimers are added after temperature to room temperature With 0.05 mass parts of catalyst dibutyl tin dilaurate, kept for 80 DEG C react 1 hour；
(2) 5.1 mass parts dimethylolpropionic acids are added in above-mentioned reactant, are warming up to 80 DEG C, react 2 hours；Again plus Enter 9.2 mass parts 1,4-butanediol (prior drying and dehydrating processing), in 80 DEG C of polymerisations 3.5 hours, be then cooled to 42 DEG C, It is added 3.9 mass parts triethylamines and n,N-Dimethylformamide that 8 mass parts remove water in advance is neutralized, the reaction time is 25 points Base polyurethane prepolymer for use as is made in clock；
(4) under the rotating speed of dispersion machine 1000r/min, polyurethane prepolymer is gently added in the deionized water of 200 mass parts In body, rotating speed is then promoted to 3500r/min, emulsifies 20min, the aqueous polyurethane emulsion for obtaining hydroxyl sealing end is (penetrating The aqueous polyurethane emulsion of the hydroxyl sealing end of blueing light)；
(5) 1 mass parts graphene is placed in 100 mass parts deionized waters, 1 mass parts silane coupling agent (KH- is added dropwise 164), ultrasonic disperse 45min obtains the graphene dispersing solution of stable dispersion；Graphene dispersing solution and hydroxyl are blocked poly- Urethane lotion 400r/min dispersion machine effect under be uniformly mixed, obtain modified polyurethane emulsion (graphene be modified contain hydroxyl The aqueous polyurethane emulsion of base sealing end)；
(6) by 100 mass parts modified polyurethane emulsions, 3 mass parts moistening flatting agent Sliok-8858 and 2 mass parts feels Agent Sliok-3300 is uniformly mixed, and 2 mass parts water-based polyurethane curing agent Bai Situo WT2102 are added, after stirring 30 minutes, i.e., Obtain double-component waterborne polyurethane leather finishing agent.The performance test results of Aqueous Polyurethane Leather Finishing Agent manufactured in the present embodiment As shown in table 1.
Embodiment 5
(1) be added in the reaction vessel 8.3 mass parts molecular weight be 1000 polycaprolactone diols (PCL1000) and The polycaprolactone diols (PCL3000) that 40.4 mass parts molecular weight are 3000,105 DEG C of vacuum pumps are dried 30 minutes, drop 29.4 mass parts isophorone diisocyanate and 0.05 mass parts of catalyst dibutyl tin dilaurate are added after temperature to room temperature, Kept for 80 DEG C react 1 hour；
(2) 6.4 mass parts dihydromethyl propionic acids are added in above-mentioned reactant, are warming up to 80 DEG C, react 2 hours；Again plus Enter 8.7 mass parts 1,4-butanediol (prior drying and dehydrating processing) and 1.8 mass parts trimethylolpropanes, in 80 DEG C of polymerisations 3.5 hours, 42 DEG C are then cooled to, the n,N-Dimethylformamide that 4.9 mass parts triethylamines of addition and 8 mass parts remove water in advance It is neutralized, the reaction time is 25 minutes, and base polyurethane prepolymer for use as is made；
(4) under the rotating speed of dispersion machine 1000r/min, polyurethane prepolymer is gently added in the deionized water of 200 mass parts In body, rotating speed is then promoted to 3500r/min, emulsifies 20min, the aqueous polyurethane emulsion for obtaining hydroxyl sealing end is (penetrating The aqueous polyurethane emulsion of the hydroxyl sealing end of blueing light)；
(5) 1 mass parts graphene is placed in 100 mass parts deionized waters, 1 mass parts silane coupling agent (KH- is added dropwise 164), ultrasonic disperse 45min obtains the graphene dispersing solution of stable dispersion；Graphene dispersing solution and hydroxyl are blocked poly- Urethane lotion 400r/min dispersion machine effect under be uniformly mixed, obtain modified polyurethane emulsion (graphene be modified contain hydroxyl The aqueous polyurethane emulsion of base sealing end)；
(6) by 100 mass parts modified polyurethane emulsions, 3 mass parts moistening flatting agent Sliok-8858 and 2 mass parts feels Agent Sliok-3300 is uniformly mixed, and 2 mass parts water-based polyurethane curing agent Bai Situo WT2102 are added, after stirring 30 minutes, i.e., Obtain double-component waterborne polyurethane leather finishing agent.The performance test results of Aqueous Polyurethane Leather Finishing Agent manufactured in the present embodiment As shown in table 1.
Performance test：
(1) solid content is tested：Take 2g (m0) Examples 1 to 5 prepare hydroxyl sealing end aqueous polyurethane emulsion be placed in In culture dish, dries in 75 DEG C of baking ovens and weigh for 24 hours, quality is denoted as m1.Solid content is calculated using following equation：
Solid content (%)=(m1/m0) * 100%.
(2) water absorption rate test：Weigh length and width be 2*2cm, quality maLatex film (modification prepared by Examples 1 to 5 is poly- Urethane emulsion film forming), it immerses in deionized water, wiping surface moisture away with blotting paper after placement 48h at room temperature is weighed as mb, inhale Water rate is calculated using following equation：
Water absorption rate (%)=[(mb-ma)/ma] * 100%.
(3) adhesive force is tested：Finishing agent prepared by Examples 1 to 5 is uniformly coated on spreading rod on soft leather, 105 DEG C of dry 45s, using GB/T 9286-1998 as standard, using cross-hatching testing coating adhesive force.
(4) bin stability is tested：Lotion (aqueous polyurethane emulsion of hydroxyl sealing end prepared by Examples 1 to 5) Stability test is carried out according to GB/T 6753.3-1986；Using CENTRIFUGAL ACCELERATING sedimentation experiment simulating storage stability, centrifuging Centrifugal sedimentation 15min is carried out to lotion with 3000r/min in machine, is recognized as if without precipitation with 6 months or more Storage periods.
(5) resistant to acetone is tested：Weigh film (modified polyurethane emulsion film forming prepared by Examples 1 to 5) M0；It is immersed in third It is taken out afterwards for 24 hours in ketone, wipes the M that weighs after the liquid on dry surface1, measure weight rate (%)=[(M after sample impregnates0-M1)/ M0] * 100%.
(6) elongation at break is tested：Dumbbell shaped film (finishing agent film forming prepared by Examples 1 to 5) is prepared, according to GB/T 508-1998, is 0.01N with minimum force, and rate of extension is that 300mm/min is tested.
Aqueous polyurethane emulsion and finishing agent the performance test results prepared by each embodiment is as shown in table 1.
Aqueous polyurethane emulsion and finishing agent the performance test results prepared by 1 Examples 1 to 5 of table：
Above several case study on implementation are the preferable several embodiments of the present invention, described in the above content to illustrate the invention Basic principle, therefore the present invention is not limited to the above embodiments.Under the premise of the basic principle and range of the present invention, can also There is various change and improve, these changes and improvements both fall within scope of the claimed invention.

Claims (8)

1. a kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent, it is characterised in that：By the two parts separately stored Composition, first part and second part are all according to mass fraction meter；
First part includes following components：
Second part is curing agent；
5-15 parts of curing agent；
The polyalcohol is one in PCL1000, PCL2000, PCL3000, PPG400, PPG1000, PPG2000, PBA3000 Kind or more；
The hydrophily glycol chain extender is one or more of dihydromethyl propionic acid or dimethylolpropionic acid；
The dihydric alcohol/trihydroxylic alcohol chain extender is 1,4- butanediols, 1,3- propylene glycol, 1,6-HD, neopentyl glycol, three hydroxyl first One or more of base propane, glycerine.
2. graphene modified double components Aqueous Polyurethane Leather Finishing Agent according to claim 1, it is characterised in that：Described A part further includes moistening flatting agent and hand feeling agent, and the mass fraction of the moistening flatting agent and hand feeling agent is：
3-15 parts of moistening flatting agent
3-15 parts of hand feeling agent.
3. graphene modified double components Aqueous Polyurethane Leather Finishing Agent according to claim 2, it is characterised in that：Described A part further includes organic solvent, and the organic solvent is n,N-Dimethylformamide.
4. graphene modified double components Aqueous Polyurethane Leather Finishing Agent according to claim 1, it is characterised in that：It is described more First alcohol is two or more in PCL1000, PCL2000, PCL3000, PPG400, PPG1000, PPG2000, PBA3000；
The diisocyanate is isophorone diisocyanate, methyl diphenylene diisocyanate, hexa-methylene diisocyanate One or more of ester tripolymer, hexamethylene diisocyanate, toluene di-isocyanate(TDI).
5. graphene modified double components Aqueous Polyurethane Leather Finishing Agent according to claim 1, it is characterised in that：It is described to urge Agent is dibutyl tin dilaurate or stannous octoate；
The neutralizer is one or more of triethanolamine, triethylamine, sodium hydroxide；
The moistening flatting agent is Si Luoke Sliok-8333, one or more of Sliok-8858 or Sliok-8035；
The hand feeling agent is Si Luoke Sliok-9151, Sliok-3300, one or more of Sliok-9148；
The curing agent is one or more of Bai Situo WT2102, XD803；
The silane coupling agent is one or more of KH-560, KH-570, KH-164.
6. according to the preparation side of any one of Claims 1 to 5 graphene modified double components Aqueous Polyurethane Leather Finishing Agent Method, it is characterised in that：Include the following steps：
(1) it by polyalcohol vacuum dehydration, is then reacted under the action of partial catalyst with diisocyanate, the temperature of reaction Degree is 60-80 DEG C, and the reaction time is 1-3 hours, obtains performed polymer；
(2) hydrophily glycol chain extender is added into performed polymer, dihydric alcohol/trihydroxylic alcohol chain extension is added in insulation reaction 1-3 hours Agent and residual catalyst are warming up to 70-85 DEG C, and polymerisation 2-4 hours, cooling is added in neutralizer and organic solvent progress With obtain base polyurethane prepolymer for use as；
(3) it under moderate-speed mixer, adds water in base polyurethane prepolymer for use as, water increases speed after adding, emulsification, obtains hydroxyl envelope The aqueous polyurethane emulsion at end；
(4) graphene is mixed with water, silane coupling agent is added dropwise, ultrasonic disperse obtains graphene dispersing solution；By graphene dispersion Liquid is uniformly mixed with the aqueous polyurethane emulsion that hydroxyl blocks, and obtains modified aqueous polyurethane emulsion；
(5) when in use, modified aqueous polyurethane emulsion is uniformly mixed with moistening flatting agent, hand feeling agent, is eventually adding solid Agent obtains Aqueous Polyurethane Leather Finishing Agent.
7. the preparation method of graphene modified double components Aqueous Polyurethane Leather Finishing Agent according to claim 6, feature It is：The rotating speed of middling speed described in step (3) is 800-1200r/min；It is described that increase speed refer to that rotating speed is increased to 3000- 4000r/min；The addition of the water is：The mass ratio of water and hydrophily glycol chain extender is (150-350)：(3-15)； The time of the emulsification is 15-30min；
The temperature of insulation reaction described in step (2) is 60-80 DEG C；The temperature of the cooling is 35-45 DEG C, the neutralization reaction Time be 20-45 minutes.
8. the preparation method of graphene modified double components Aqueous Polyurethane Leather Finishing Agent according to claim 6, feature It is：The condition of vacuum dehydration described in step (1) is to be dried in vacuo 0.5-1 hours at 90-110 DEG C, the partially catalyzed Agent is the 30-70% of catalyst total amount；
The dosage relation of graphene and water described in step (4) is that 1-15 mass parts graphenes are added in every 100 mass parts water；Institute The time for stating ultrasonic disperse is 30-60min, and described be uniformly mixed refers to being uniformly dispersed under the rotating speed of 400-1000r/min.
CN201810035278.0A 2018-01-15 2018-01-15 A kind of graphene modified double components Aqueous Polyurethane Leather Finishing Agent and preparation method thereof Pending CN108456482A (en)

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Application publication date: 20180828