CN109627409A - A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method - Google Patents

A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method Download PDF

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Publication number
CN109627409A
CN109627409A CN201811566688.4A CN201811566688A CN109627409A CN 109627409 A CN109627409 A CN 109627409A CN 201811566688 A CN201811566688 A CN 201811566688A CN 109627409 A CN109627409 A CN 109627409A
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aqueous polyurethane
parts
added
dumb light
polyurethane
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鲁明友
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Zhejiang Chengxun New Materials Co Ltd
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Zhejiang Chengxun New Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • C08G18/3275Hydroxyamines containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/34Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348Hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/36Hydroxylated esters of higher fatty acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00Surface finishing of leather
    • C14C11/003Surface finishing of leather using macromolecular compounds
    • C14C11/006Surface 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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to the technical fields of high molecular material, more particularly to a kind of aqueous polyurethane, including the following raw material: polynary amino alcohol, isocyanic acid, thermoplastic polyurethane elastomer, chain extender, neutralizer, deionized water and hydrazine hydrate, polynary amino alcohol is diethylaminoethanol, 3- amino -1,2- propylene glycol or 3- lignocaine -1- propyl alcohol, the dosage of neutralizer is that the pH of control mixed liquor is 7.5-9, has the advantages that wear-resisting, water resistance is good and wellability is good;The aqueous polyurethane that castor oil is added is additionally provided, the wellability of aqueous polyurethane is further improved;Additionally provide the preparation method of dumb light aqueous polyurethane after two kinds of aqueous polyurethanes to be added to flatting silicas and preparation method thereof and two kinds of aqueous polyurethanes, the dumb light aqueous polyurethane made, while improving leather surface gloss, delustering agent can be made not to be stripped out from film, extend the effective acting time of flatting silica.

Description

A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method
Technical field
The present invention relates to the technical fields of high molecular material, and in particular to a kind of aqueous polyurethane, dumb light aqueous polyurethane And preparation method.
Background technique
A large amount of leathers are used in automobile, luggage and shoe-making field, to improve leather surface aesthetics, corrosion resistance and wear-resisting Performance often uses coating and carries out top finishing.
Synthetic Leather is the most promising natural leather substitute after artificial polyvinyl chloride leather.Synthetic Leather It compensates for artificial polyvinyl chloride leather and substrate adhesive fastness is poor, be easy to peel off, the disadvantages of feel is stiff has gloss naturally soft With, adhesive property is good, it is wear-resistant the advantages that.
Existing low gloss leather finishing agent mostly uses greatly waterborne polyurethane resin, and aqueous polyurethane is a kind of plastic particle Evenly dispersed thinlyfluid in water forms the sequential like being evenly distributed by fusion between polymer particles and applies when in use Film;When film forming, show especially with the volatilization of solvent, the thinning silica dioxide granule for shrinking, being suspended in resin of film in film item Layer forms a micro-roughened surface, which can make incident light, thus obtain low gloss effect with Soft sense of touch.But it is monomer that current aqueous polyurethane, which mostly uses polyether polyol, water resistance is poor with wearability;And its Wellability is poor, although can obtain low gloss effect by the delustering agent for adding such as silica etc, with pushing away for time It moves, these duller particles are easy to be stripped out from film, thus bring to the weatherability of film and ultraviolet-resistant performance Negative effect.
Summary of the invention
In view of the deficienciess of the prior art, the first purpose of this invention is that providing one kind has wear-resisting, water resistance The good aqueous polyurethane of energy.
The first purpose of this invention is achieved through the following technical solutions:
A kind of aqueous polyurethane, the raw material including following parts by weight: polynary amino alcohol 40-60 parts, 35-55 parts of isocyanic acid, thermoplastic 15-30 parts of polyurethane elastomer of property, 8-15 parts of chain extender, neutralizer, 5-15 parts of deionized water and 1-3 parts of hydrazine hydrate are described more First amino alcohol is diethylaminoethanol, 3- amino -1,2-PD or 3- lignocaine -1- propyl alcohol, the dosage of the neutralizer It is 7.5-9 to control the pH of mixed liquor.
By using above-mentioned technical proposal, diethylaminoethanol (English name Diethylaminoethanol) also known as 2- (diethylin) ethyl alcohol [2- (diethylamino)-Ethano1].It is colourless liquid under room temperature, has ammonia taste, there is hygroscopicity.It is main To be used as sour gas in medicine intermediate, softening agent, emulsifier, curing agent etc. and organic synthesis raw material and natural gas Scavenger.3- amino -1,2-PD (3-Amino-1,2-propanediol) is used as emulsifier, organic intermediate.3- bis- Ethylamino -1- propyl alcohol, nickname N, N- diethylpropanolamine, 3- diethyl amino -1- propyl alcohol, 3- (lignocaine) -1- propyl alcohol are colourless To yellow liquid.Hydrazine hydrate is also known as hydrazine hydrate, is a kind of important fine chemical material.Thermoplastic polyurethane elastomer is also known as Thermoplastic polyurethane rubber, with the comprehensive performance that high intensity, high tenacity, wear-resisting, oil resistant etc. are excellent, processing performance is good.Pass through Polynary amino alcohol and isocyanate reaction obtain polyurethane, compared to using polyether polyol as the polyurethane of monomer, water resistance with Wear-resisting property is greatly improved.And the introducing of hydrazine hydrate, by the polymer of polynary amino alcohol and isocyanate reaction with High-intensitive, high tenacity and the crosslinking of the thermoplastic polyurethane elastomer of wear-resisting property mix, and have the two by chemical bond Machine combines, and further improves the wear-resisting property of aqueous polyurethane.
Preferably, the chain extender is 1-4- butanediol or 2,2- dihydromethyl propionic acid.
By using above-mentioned technical proposal, chain extender is also known as chain extender, and being can be with the functional group on linear polymer chain The substance for reacting and increasing strand extension, molecular weight.It is usually used in improving the mechanical property and work of the products such as polyurethane, polyester Skill performance.2,2- dihydromethyl propionic acids are both chain extender in aqueous polyurethane manufacture and make polyurethane obtained from emulsibility Can, it can be made into the self-emulsifying aqueous polyurethane of excellent in stability.
Second object of the present invention is to provide a kind of preparation method of the aqueous polyurethane of first goal of the invention, packet Include following operating procedure:
Isocyanic acid is added after polynary amino alcohol is carried out vacuum dehydration processing, at 75-85 DEG C, reacts 1-3h;Chain extender is added, At 80-90 DEG C, 2-4h is reacted;Add neutralizer at salt, deionized water and hydrazine hydrate is added, is dispersed with the revolving speed of 2000r/min 3-5min is stirred, later at 20-50 DEG C, reacts 30-40min;It is down to 20-25 DEG C, stirs 40-60min, stands 30- 48h obtains aqueous polyurethane.
Third object of the present invention is to provide a kind of wearability and the high aqueous polyurethane of wetting property.
Third object of the present invention is achieved through the following technical solutions:
A kind of aqueous polyurethane, the raw material including each parts by weight in first goal of the invention further include 5-15 parts of castor oil.
By using above-mentioned technical proposal, castor oil is the polyol compound of natural reproducible, longer non-in component Polarity aliphatic chain has good hydrophobic effect, can further improve the water resistance and flexibility of water-base polyurethane material.And And it further can make aqueous polyurethane preferably spread in substrate surface, to further increase the infiltration of aqueous polyurethane Property, to improve the wear-resisting property of film.
Fourth object of the present invention is to provide a kind of preparation method of the aqueous polyurethane of third goal of the invention, wrap Include following operating procedure:
Isocyanic acid and castor oil is added after polynary amino alcohol is carried out vacuum dehydration processing, at 80-85 DEG C, reacts 1-3h;Add Enter chain extender, at 80-90 DEG C, reacts 2-4h: neutralizer being added to be neutralized into salt, deionized water and hydrazine hydrate is added, with 2000r/ The revolving speed dispersion stirring 3-5min of min reacts 30-40min later at 20-50 DEG C;It is down to 20-25 DEG C, stirs 40- 60min stands 30-48h, obtains aqueous polyurethane.
Fifth object of the present invention is to provide a kind of dumb light aqueous polyurethanes, for that can make leather in leather paint The softer beauty of the gloss on surface, and cooperate the aqueous polyurethane in the present invention, remove delustering agent will not from film Out.
5th purpose of the invention is realized by following technical solution:
A kind of dumb light aqueous polyurethane, the raw material including following parts by weight: first or third goal of the invention aqueous polyurethane 85-95 parts, 20-40 parts of deionized water, 1-3 parts of flatting silica, 5-10 parts of thermoplastic polyurethane elastomer, 0.1-1 parts of levelling agent, profit 0.1-1 parts of hygroscopic water powder, 0.1-1 parts of defoaming agent and 0.5-1.5 parts of thickener.
It is good with the high-wearing feature, high waterproofness and wetting property prepared in the present invention by using above-mentioned technical proposal Aqueous polyurethane, flatting silica and auxiliary agent in addition, to obtain the leather finishing agent with photoextinction;Due to the present invention Aqueous polyurethane wetting property it is good, duller particle can be very good infiltration in finally obtained film, to be not easy It is stripped out from film, to realize the delustring treatment effect to leather products surface long term.
Preferably, the flatting silica is the silica that partial size is 5-10 μm.
By using above-mentioned technical proposal, the fineness of silica is controlled, improves its square dispersing uniformity in film, from And further avoid it and detached from film, improve the delustring stability of dumb light aqueous polyurethane.
Of the invention the 6th is designed to provide a kind of preparation side of the dumb light aqueous polyurethane of 5th goal of the invention Method, including following operating procedure: the aqueous polyurethane in first or third goal of the invention, deionized water are sufficiently mixed It is even, flatting silica is added and stirs 25-35min, thermoplastic polyurethane elastomer is added and stirs 25-35min, levelling agent, wetting is added Dispersing agent stirs 15-20min, and defoaming agent is added and thickener stirs 5-15min, obtains dumb light aqueous polyurethane.
In conclusion the invention has the following beneficial effects:
(1) polymer for obtaining polynary amino alcohol and isocyanate reaction, cooperation hydrazine hydrate and high-intensitive, high tenacity and wearability The thermoplastic polyurethane elastomer crosslinking of energy mixes, and the polymer and thermoplastic polyurethane elastomer is made to pass through chemical bond It organically combines, while improving the wetting property of aqueous polyurethane, further improves the wear-resisting property of aqueous polyurethane;
(2) by the way that the polyol compound castor oil of natural reproducible is added, obtained it is a kind of have better water resistance and Flexible water-base polyurethane material;The material can make aqueous polyurethane preferably spread in substrate surface, to further mention The wellability of high aqueous polyurethane;
(3) by the way that two kinds of above-mentioned aqueous polyurethanes are added upper flatting silica and auxiliary agent, obtain having the leather of photoextinction to apply Agent is adornd, since the wetting property of two kinds of aqueous polyurethanes is good, duller particle can be very good infiltration in finally obtained painting In film, to be not easy to be stripped out from film, to realize the delustring treatment effect to leather products surface long term.
Specific embodiment
Each raw material and chemical reagent used in the present invention are commercial product.Wherein thermoplastic polyurethane elastomer is selected Polyester-type spherical particle.Wetting dispersing agent is nonionic surface active agent, and nonionic surface active agent, which can improve, to be helped Agent dispersion performance, the present invention in wetting dispersing agent select Air Prod & Chem, the U.S. the trade mark be Surfynol 104 table Face activating agent.Defoaming agent selects silicone emulsion, and thickener selects hydroxypropyl methyl cellulose.
Embodiment 1
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, be heated under vacuum conditions 110 DEG C be carried out dehydrating 1.5h (dehydration for this The conventional technical means in field), isocyanic acid 35g is then added, at 75 DEG C, reacts 1h, obtains mixed liquor A;
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 80 DEG C, reacts 2h, obtains To the mixed liquid B of polymerization reaction;
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 7.5, and deionized water 5g, hydrazine hydrate is added 1g, and be dispersed with stirring under the mixing speed of 2000r/min, emulsify 3min, then at 20 DEG C, 30min is reacted, is mixed Liquid C;
(4) by mixed liquor C at 20 DEG C, the mixing speed of 2400r/min stirs 40min, stands 30h and is hardened, obtains water Property polyurethane.
Embodiment 2
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, it is heated to 110 DEG C under vacuum conditions and is carried out dehydrating 2h (dehydration is ability The conventional technical means in domain), isocyanic acid 35g is then added, at 80 DEG C, reacts 2h, obtains mixed liquor A;
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 85 DEG C, reacts 3h, obtains To mixed liquid B;
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 8.5, and deionized water 5g, hydrazine hydrate is added 1g, and the stirring and emulsifying 5min under the mixing speed of 2000r/min react 40min, obtain mixed liquor C then at 35 DEG C;
(4) by mixed liquor C at 25 DEG C, the mixing speed of 4000r/min stirs 50min, stands 48h, obtains aqueous poly- ammonia Ester.
Embodiment 3
A kind of aqueous polyurethane is made by the steps to obtain:
(1) by diethylaminoethanol 40g, be heated under vacuum conditions 110 DEG C be carried out dehydrating 1.5h (dehydration for this The conventional technical means in field), isocyanic acid 35g is then added, at 85 DEG C, reacts 3h, obtains mixed liquor A;
(2) thermoplastic polyurethane elastomer 15g and 1-4- butanediol 8g are added into mixed liquor A, at 90 DEG C, reacts 4h, obtains To mixed liquid B;
(3) add neutralizer at salt into mixed liquid B, select ammonium hydroxide herein, adjusting pH is 9, and deionized water 5g, hydrazine hydrate is added 1g, and the stirring and emulsifying 4min under the mixing speed of 2000r/min react 30min, obtain mixed liquor C then at 50 DEG C;
(4) by mixed liquor C at 25 DEG C, the mixing speed of 5000r/min stirs 60min, stands 48h, obtains aqueous poly- ammonia Ester.
Embodiment 4
Embodiment 4 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: 3- Amino -1,2-PD 50g, isocyanic acid 40g, thermoplastic polyurethane elastomer 25g, 2,2- dihydromethyl propionic acid 10g, deionization Water 10g and hydrazine hydrate 2g.
Embodiment 5
Embodiment 5 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: 3- Lignocaine -1- propyl alcohol 55g, isocyanic acid 45g, thermoplastic polyurethane elastomer 20g, methyl pyrrolidone 12g, deionized water 13g and hydrazine hydrate 2.5g.
Embodiment 6
Embodiment 6 is identical as the operating procedure of embodiment 2, and difference is that the raw material components being added and content are different, specifically: two Ethylaminoethanol 45g, isocyanic acid 50g, thermoplastic polyurethane elastomer 25g, methyl pyrrolidone 15g, deionized water 15g and water Close hydrazine 3g.
Embodiment 7
Embodiment 7 is identical as the operating procedure of embodiment 1, and difference is only that, in step (1), while isocyanic acid is added, adds Enter 5g castor oil, at 80 DEG C, reacts 1h, obtain mixed liquor A;Remaining is same as Example 1.
Embodiment 8
Embodiment 8 is identical as the operating procedure of embodiment 2, and difference is only that, in step (1), while isocyanic acid is added, adds Enter 5g castor oil, remaining is same as Example 2.
Embodiment 9
Embodiment 9 is identical as the operating procedure of embodiment 3, and difference is only that, in step (1), while isocyanic acid is added, adds Enter 5g castor oil, remaining is same as Example 3.
Embodiment 10
Embodiment 10 is identical as the operating procedure of embodiment 4, and difference is only that, in step (1), while isocyanic acid is added, 8g castor oil is added, remaining is same as Example 4.
Embodiment 11
Embodiment 11 is identical as the operating procedure of embodiment 5, and difference is only that, in step (1), while isocyanic acid is added, 12g castor oil is added, remaining is same as Example 5.
Embodiment 12
Embodiment 12 is identical as the operating procedure of embodiment 6, and difference is only that, in step (1), while isocyanic acid is added, 15g castor oil is added, remaining is same as Example 6.
Embodiment 13
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared 85g, deionized water 20g are sufficiently mixed uniformly, and the 1g silica that partial size is 5-10 μm, the revolving speed stirring of 1000r/min is added Thermoplastic polyurethane elastomer 5g is added in 25min, stirs 25min, and carboxymethyl cellulose 0.1g, wetting dispersing agent 0.1g is added, 15min is stirred, defoaming agent 0.1g and thickener 0.5g is added, 5min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 14
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared 90g, deionized water 30g are sufficiently mixed uniformly, and the 2g silica that partial size is 5-10 μm, the revolving speed stirring of 1300r/min is added Thermoplastic polyurethane elastomer 8g is added in 30min, stirs 30min, and carboxymethyl cellulose 0.5g, wetting dispersing agent 0.5g is added, 15min is stirred, defoaming agent 0.5g and thickener 1g is added, 10min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 15
A kind of dumb light aqueous polyurethane, is prepared by following operating procedure, the aqueous polyurethane that embodiment 5 is prepared 95g, deionized water 40g are sufficiently mixed uniformly, and the 3g silica that partial size is 5-10 μm, the revolving speed stirring of 1500r/min is added Thermoplastic polyurethane elastomer 10g is added in 35min, stirs 35min, and carboxymethyl cellulose 1g, wetting dispersing agent 1g is added, stirs 20min is mixed, defoaming agent 1g and thickener 1.5g is added, 15min is stirred, obtains dumb light aqueous polyurethane.
Embodiment 16
Embodiment 16 and the difference of embodiment 13 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation Example 13 is identical.
Embodiment 17
Embodiment 17 and the difference of embodiment 14 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation Example 14 is identical.
Embodiment 18
Embodiment 18 and the difference of embodiment 15 be, the aqueous polyurethane being prepared using embodiment 11, remaining and implementation Example 15 is identical.
Comparative example 1
Comparative example 1 and the difference of embodiment 5 are do not have thermoplastic polyurethane elastomer in the raw material in comparative example 1, remaining with Embodiment 5 is identical.
Comparative example 2
Comparative example 2 and the difference of embodiment 5 are do not have hydrazine hydrate in the raw material in comparative example 2, remaining is same as Example 5.
Comparative example 3
Comparative example 3 and the difference of embodiment 5 are do not have polynary amino alcohol and isocyanic acid in the raw material in comparative example 3, also without The operation step of the two, remaining is same as Example 5.
Comparative example 4
Comparative example 4 and the difference of embodiment 17 are do not have thermoplastic polyurethane elastomer in the raw material in comparative example 4, remaining It is identical as embodiment 17.
Performance test
According to following test method to embodiment 1-18, comparative example the 1-4 aqueous polyurethane prepared or dumb light aqueous polyurethane into Row test, test result are shown in Tables 1 and 2.Wherein blank group is the sample without smearing any leather finishing agent.
Film rub resistance: according to GB/T8949-2008 " polyurethane dry method artificial leather " in Scott type rubbing test machine Upper measurement.Experimental method is as follows: unidirectional 2 pieces of sample cloth covers being overlapped, being then charged into grip separation is 30mm's In rubbing test machine clamp.The distance for gradually reducing fixture applies load, spacing contracting after contacting the cloth cover of 2 pieces of samples gently It is small to load be 1kg until.It is 120 times/min in frequency, under conditions of stroke 50mm, reciprocal 1000 times, observes artificial leather table Face whether there is or not glossiness variation, crackle, damage or Bu Ji and apply UF membrane phenomena such as.If there is having above-mentioned phenomenon on 1 piece of sample, then The rub resistance for sentencing the sample is unqualified.Experimental sample is in (23 ± 2) DEG C, the standard environment and one of relative humidity (50 ± 10) % As carry out the sample status adjustment of no less than 4h in deviation range, and tested with this condition.
Film wearability: carrying out according to QB/T2537-2001 " leather color fastness test reciprocating friction color fastness ", this mark Standard is equal to ISO11640.The wear-resisting property of film is with leather surface colour fastness test tester to the resistance to dry of each finished leather film Wet rubbing is tested, and then determines its grade by regulation with gray scale.Experiment condition is 20 DEG C of temperature, relative humidity 80%, Measuring head gross mass is 1000g, and xerotripsis number is 50 times, and wet rubbing number is 200 times.
Water-resistance property of coating: materialsing 2 pieces, is put into the water that temperature is 25 DEG C, and water all submerges sample, if sample floating is difficult Then apply external force with submergence to guarantee in sample immersion water.Observe variation of the sample in 72h.
Apply it is film modified after leather glossiness: with the daylight light irradiation specimen surface of 30W, observe gloss.
The performance test results of each aqueous polyurethane of table 1
The performance test results of each dumb light aqueous polyurethane of table 2
By Tables 1 and 2 it is found that aqueous polyurethane prepared by the present invention and dumb light aqueous polyurethane all have good wearability And water resistance, and rub resistance can be strong, it, can be right using the aqueous polyurethane and dumb light aqueous polyurethane in the present invention Leather and fur products plays preferable protective effect, and the raising of wear-resisting property can further improve the defect that flatting silica is easily detached from. And the wear-resisting property for being added to the aqueous polyurethane of castor oil is better than un-added.By comparative example 1-3 in table 1 it is found that Thermoplastic polyurethane elastomer, hydrazine hydrate, polynary amino alcohol and isocyanic acid have water resistance, wear-resisting property very big in the present invention Influence;Lack three's any component, then will lead to it is water-fast, wear-resisting property substantially reduce or even effect is equal to blank group, Prove that thermoplastic polyurethane elastomer in the present invention, hydrazine hydrate, polynary amino alcohol and isocyanic acid mutual cooperation play synergistic effect, Improve the wear-resisting and water resistance of aqueous polyurethane of the present invention.As shown in Table 2, the delustring of dumb light aqueous polyurethane of the invention Effect is obvious, can effectively improve the appearance and gloss of product using leather and fur products.By comparative example 4 in table 2 it is found that the present invention Thermoplastic polyurethane elastomer in dumb light aqueous polyurethane has the wear-resisting and waterproof performance of dumb light aqueous polyurethane very big just To effect.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as All by the protection of Patent Law in scope of the presently claimed invention.

Claims (8)

1. a kind of aqueous polyurethane, which is characterized in that the raw material including following parts by weight: polynary amino alcohol 40-60 parts, isocyanic acid 35-55 parts, 15-30 parts of thermoplastic polyurethane elastomer, 8-15 parts of chain extender, neutralizer, 5-15 parts of deionized water and hydrazine hydrate 1-3 parts, the polynary amino alcohol be diethylaminoethanol, 3- amino -1,2-PD or 3- lignocaine -1- propyl alcohol, it is described The dosage of neutralizer is that the pH of control mixed liquor is 7.5-9.
2. aqueous polyurethane according to claim 1, it is characterised in that: the chain extender is 1-4- butanediol or 2,2- bis- Hydroxymethyl propionic acid.
3. a kind of preparation method of aqueous polyurethane of any of claims 1 or 2, which is characterized in that including following operating procedure:
Isocyanic acid is added after polynary amino alcohol is carried out vacuum dehydration processing, at 75-85 DEG C, reacts 1-3h;Chain extender is added, At 80-90 DEG C, 2-4h is reacted;Add neutralizer at salt, deionized water and hydrazine hydrate is added, is dispersed with the revolving speed of 2000r/min 3-5min is stirred, later at 20-50 DEG C, reacts 30-40min;It is down to 20-25 DEG C, stirs 40-60min, stands 30- 48h obtains aqueous polyurethane.
4. aqueous polyurethane according to claim 1, it is characterised in that: further include 5-15 parts of castor oil.
5. a kind of preparation method of aqueous polyurethane as claimed in claim 4, which is characterized in that including following operating procedure:
Isocyanic acid and castor oil is added after polynary amino alcohol is carried out vacuum dehydration processing, at 80-85 DEG C, reacts 1-3h;Add Enter chain extender, at 80-90 DEG C, reacts 2-4h;Add neutralizer to be neutralized into salt, deionized water and hydrazine hydrate is added, with 2000r/ The revolving speed dispersion stirring 3-5min of min reacts 30-40min later at 20-50 DEG C;It is down to 20-25 DEG C, stirs 40- 60min stands 30-48h, obtains aqueous polyurethane.
6. a kind of dumb light aqueous polyurethane, which is characterized in that the raw material including following parts by weight: claim 1 or 4 it is aqueous poly- 85-95 parts of urethane, 20-40 parts of deionized water, 1-3 parts of flatting silica, 5-10 parts of thermoplastic polyurethane elastomer, levelling agent 0.1-1 Part, 0.1-1 parts of wetting dispersing agent, 0.1-1 parts of defoaming agent and 0.5-1.5 parts of thickener.
7. dumb light aqueous polyurethane according to claim 6, it is characterised in that: the flatting silica is that partial size is 5-10 μm Silica.
8. a kind of preparation method of dumb light aqueous polyurethane as claimed in claim 6, which is characterized in that including operating step as follows It is rapid: the aqueous polyurethane of claim 1 or 4, deionized water being sufficiently mixed uniformly, flatting silica is added and stirs 25-35min, adds Enter thermoplastic polyurethane elastomer stirring 25-35min, levelling agent is added, wetting dispersing agent stirs 15-20min, addition defoaming agent 5-15min is stirred with thickener, obtains dumb light aqueous polyurethane.
CN201811566688.4A 2018-12-20 2018-12-20 A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method Pending CN109627409A (en)

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CN115851056A (en) * 2022-12-21 2023-03-28 江苏德威涂料有限公司 Water-based acrylic coating and preparation method and application thereof

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Application publication date: 20190416