CN100569887C - A kind of method for preparing water polyurethane binder for shoe - Google Patents
A kind of method for preparing water polyurethane binder for shoe Download PDFInfo
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- CN100569887C CN100569887C CNB2007101220757A CN200710122075A CN100569887C CN 100569887 C CN100569887 C CN 100569887C CN B2007101220757 A CNB2007101220757 A CN B2007101220757A CN 200710122075 A CN200710122075 A CN 200710122075A CN 100569887 C CN100569887 C CN 100569887C
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Abstract
The present invention relates to a kind of preparation method of water polyurethane binder for shoe, belong to technical field of polymer materials.First polyvalent alcohol, second polyvalent alcohol, the 3rd polyvalent alcohol and the 4th polyvalent alcohol are mixed mutually, make polyurethane prepolymer; Add the triethylamine neutralization, the polyurethane prepolymer that obtains is distributed in the deionized water, add tensio-active agent again, obtain aqueous polyurethane dispersion; In aqueous polyurethane dispersion, add quadrol and carry out chain extending reaction, make aqueous polyurethane; Slough acetone with the vacuum decompression method, mix mutually with oxidation inhibitor, uv-absorbing agent, flow agent, defoamer, wetting agent, thickening material and silane coupling agent and water cross-linking agent at last, obtain water polyurethane binder for shoe.The inventive method, technology is simple, and consumption of organic solvent is few, and solid content is higher than 50%, and the production process energy consumption is low, and various footwear materials such as polyvinyl chloride, urethane, leather, SBS, canvas, rubber are had excellent bonding strength and good heat resistance.
Description
Technical field
The present invention relates to a kind of method for preparing water polyurethane binder for shoe, belong to the shoemaking industry technical field.
Background technology
Aqueous polyurethane is a dispersion medium with water, has advantages such as pollution-free, environmentally friendly, anti-storage, transportation safety, no hidden fire-fighting danger, saving resource, in field widespread uses such as fabric coating, leather limit oil, tackiness agent.Comparatively active to the research of aqueous polyurethane in recent years, but the general solid content of aqueous polyurethane of preparation is all about 40%, the method of producing water dispersion of polyurethane resin can be referring to U.S. Pat 3,036,998, US3,756,992 etc., its solid content of water dispersion of polyurethane resin of these patent preparations is lower.The low-solid content aqueous polyurethane adhesive exists that moisture evaporation speed is slow, gluing often, problems such as storage and transportation cost height, therefore limited the use of aqueous polyurethane on shoemaking industry always.
Japanese Patent 2894494 discloses a kind of production and has had carboxylate radical and/or sulfonate radical as the aqueous solution of the polyisocyanate polyaddition compound of hydrophilic radical or the method for water dispersion.Describe in this patent, these reactivate that are applied to the tackiness agent on the base material can be undertaken by subzero treatment.But the adhesiveproperties of these tackiness agents is unsatisfactory.
Concerning aqueous polyurethane, improve solid content and can reduce the volatilization time, increase work efficiency.High solids content and low viscosity be contradiction often.Prepare high-solid content water-based polyurethane, must increase emulsion particle diameter, make it to be polymolecularity, and make the attenuation of particle hydration layer as far as possible, spacing of particle shortens in addition, and this may make stability of emulsion descend again.The present invention has taked all to introduce hydrophilic radical in soft segment of polyurethane and hard section for improving the stability of high solid aquosity polyurethane dispersions, and some tensio-active agents have stablized emulsion, has obtained the high aqueous polyurethane adhesive that contains (〉=50%) admittedly.
Summary of the invention
An object of the present invention is to propose a kind of method for preparing water polyurethane binder for shoe, to solve the moisture evaporation slow-footed problem of aqueous polyurethane when solid content low (less than 40%).
The preparation method of the water polyurethane binder for shoe that the present invention proposes may further comprise the steps:
(1) with first polyvalent alcohol, second polyvalent alcohol, the 3rd polyvalent alcohol and the 4th polyvalent alcohol mix mutually, drying is 1～3 hour under 100 ℃～140 ℃ rough vacuum, be cooled to 70 ℃～90 ℃, the mixing quality ratio of above-mentioned four kinds of polyvalent alcohols is: first polyvalent alcohol: second polyvalent alcohol: the 3rd polyvalent alcohol: the 4th polyvalent alcohol=1: 0.2～2: 0.01～0.2: 0～0.05, add the isocyanic ester that accounts for said mixture mass percent 3～20% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.01～0.001% of said mixture mass percent 20～80%, reacted 2～5 hours, and made polyurethane prepolymer;
(2) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 80-120%, the polyurethane prepolymer after obtaining neutralizing;
(3) polyurethane prepolymer after the above-mentioned neutralization is evenly spread in the deionized water under high speed shear, the mass ratio of polyurethane prepolymer and deionized water is: polyurethane prepolymer: deionized water=1: 0.8～1.1, add the tensio-active agent that accounts for above-mentioned polyurethane prepolymer mass percent 0.1～2% again, this tensio-active agent is made up of first surface promoting agent and second surface promoting agent, wherein, the mass ratio of first surface promoting agent and second surface promoting agent is: the first surface promoting agent: second surface promoting agent=1: 0.3～2, emulsion reaction 20-40 minute, temperature of reaction maintains 40 ℃～60 ℃, obtains aqueous polyurethane dispersion;
(4) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 0.5～2 hour, temperature of reaction is 40 ℃～60 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 0.6～1.2 make aqueous polyurethane;
(5) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(6) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, defoamer, wetting agent, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of aqueous polyurethanes
0.01～0.05 part in oxidation inhibitor
0.01～0.05 part of uv-absorbing agent
0.01～0.2 part of flow agent
0.01～0.2 part of defoamer
0.01～0.2 part of wetting agent
0.01～0.2 part of thickening material
0.2～1.0 part of silane coupling agent;
(7) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 1～10.
The method for preparing water polyurethane binder for shoe that the present invention proposes, the method that combines with inside and outside emulsification has been made the water polyurethane binder for shoe of high solids content, and technology is simple, and consumption of organic solvent is few, and solid content is higher than 50%, and the production process energy consumption is low; With it is that high-performance water polyurethane binder for shoe composition of main component preparation has faster rate of drying, initial bonding strength is big, and just sticking and final bonding strength all surpasses the adhesive for shoe use national standard.The inventive method has obtained being suitable for the aqueous polyurethane adhesive that shoemaking industry is used by to the adjustment of aqueous polyurethane adhesive main component polyester polyol structure and the adjustment of some chemical assistants, has improved the production efficiency of aqueous polyurethane bonding shoemaking.The tackiness agent of the inventive method preparation, since have faster rate of drying, can be after being applied on the base material rapid drying and under 50-60 ℃ activation temperature, adhering to, and various footwear materials such as polyvinyl chloride, urethane, leather, SBS, canvas, rubber are had excellent bonding strength and thermotolerance.
Embodiment
The preparation method of the water polyurethane binder for shoe that the present invention proposes may further comprise the steps:
(1) with first polyvalent alcohol, second polyvalent alcohol, the 3rd polyvalent alcohol and the 4th polyvalent alcohol mix mutually, drying is 1～3 hour under 100 ℃～140 ℃ rough vacuum, be cooled to 70 ℃～90 ℃, the mixing quality ratio of above-mentioned four kinds of polyvalent alcohols is: first polyvalent alcohol: second polyvalent alcohol: the 3rd polyvalent alcohol: the 4th polyvalent alcohol=1: 0.2～2: 0.01～0.2: 0～0.05, add the isocyanic ester that accounts for said mixture mass percent 3～20% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.01～0.001% of said mixture mass percent 20～80%, reacted 2～5 hours, and made polyurethane prepolymer;
(2) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 80-120%, the polyurethane prepolymer after obtaining neutralizing;
(3) polyurethane prepolymer after the above-mentioned neutralization is evenly spread in the deionized water under high speed shear, the mass ratio of polyurethane prepolymer and deionized water is: polyurethane prepolymer: deionized water=1: 0.8～1.1, add the tensio-active agent that accounts for above-mentioned polyurethane prepolymer mass percent 0.1～2% again, this tensio-active agent is made up of first surface promoting agent and second surface promoting agent, wherein, the mass ratio of first surface promoting agent and second surface promoting agent is: the first surface promoting agent: second surface promoting agent=1: 0.3～2, emulsion reaction 20-40 minute, temperature of reaction maintains 40 ℃～60 ℃, obtains aqueous polyurethane dispersion;
(4) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 0.5～2 hour, temperature of reaction is 40 ℃～60 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 0.6～1.2 make aqueous polyurethane;
(5) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(6) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, defoamer, wetting agent, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of aqueous polyurethanes
0.01～0.05 part in oxidation inhibitor
0.01～0.05 part of uv-absorbing agent
0.01～0.2 part of flow agent
0.01～0.2 part of defoamer
0.01～0.2 part of wetting agent
0.01～0.2 part of thickening material
0.2～1.0 part of silane coupling agent;
(7) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 1～10.
The preparation method of first polyvalent alcohol in the aforesaid method may further comprise the steps:
(1) in nitrogen atmosphere, monomer polyvalent alcohol, hydrophilic monomer and tetrabutyl titanate to be mixed mutually, the mol ratio of each component is: the monomer polyvalent alcohol: the mass percent that hydrophilic monomer=1: 0.05～0.2, tetrabutyl titanate account for the monomer polyvalent alcohol is 0.01%;
(2) stir on intensification limit in limit, adds polyprotonic acid and be warming up to 180 ℃～210 ℃ after temperature reaches 160 ℃～210 ℃, and constant temperature refluxed 20～30 minutes, and wherein, the mol ratio of monomer polyvalent alcohol and polyprotonic acid is: the monomer polyvalent alcohol: polyprotonic acid=1: 0.5～0.8;
(3) under 180 ℃～210 ℃, reacted 2～3 hours, dealcoholysis is 30～60 minutes under 500Pa pressure, and obtaining hydroxyl value is 37.4～113 milligrams of potassium hydroxide/gram, and acid number is less than first polyvalent alcohol of 1 milligram of potassium hydroxide/gram.
In the preparation of first polyvalent alcohol, used monomer polyvalent alcohol is: any in ethylene glycol, butyleneglycol, hexylene glycol or the neopentyl glycol; Described polyprotonic acid is: hexanodioic acid or sebacic acid.Used hydrophilic monomer is any in dimethyl isophthalate-5-sodium sulfonate, m-phthalic acid binaryglycol ester-5-sodium sulfonate or the 5-sodium sulfo isophthalate.
Second polyvalent alcohol in the aforesaid method can be hexanodioic acid hexylene glycol, hexanodioic acid butyleneglycol or the adipate glycol of molecular mass between 1000-3000.
The 3rd polyvalent alcohol in the aforesaid method can be dimethylol propionic acid or dimethylolpropionic acid.
The 4th polyvalent alcohol in the aforesaid method can be butyleneglycol or hexylene glycol.
Isocyanic ester in the aforesaid method can be: isophorone diisocyanate, two-(4-isocyanate group cyclohexyl) methane, '-diphenylmethane diisocyanate, tolylene diisocyanate or 1, any in the 6-hexamethylene diisocyanate.
First surface promoting agent in the aforesaid method can be any in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or the sodium lauryl sulphate.The second surface promoting agent can be fatty alcohol-polyoxyethylene ether, structural formula: RO (C2H4O)
nH, or aliphatic acid polyethenoxy ether, structural formula: RCOO (C2H4O)
nH, wherein R represents long chain alkane or has the long chain alkane of phenyl ring, and the numerical value of n is: 1～50.
Oxidation inhibitor in the aforesaid method can be any among Irganox 1010, Irganox 1076, Irganox 1098 or the Irgafos168.Uv-absorbing agent can be any among Chimassorb 944, Tinuvin 327, Tinuvin622 or the Tinuvin770.Silane coupling agent can be any among WD50, WD52 or the WD60.Wetting agent can for:
Any among Wet KL 245, BYK-345 or the BYK-346.Flow agent can for:
Glide 410 or BYK-348.Thickening material can for:
Any among ViscoPlus3000 or the Borchigel L75.Defoamer can be BYK-028 or BYK-019.
Below introduce embodiments of the invention.In the embodiment of the invention, used Irganox 1010, Irganox 1076, Irganox 1098, Irgafos 168, Chimassorb 944, Tinuvin 327, Tinuvin622, Tinuvin770 are produced by Switzerland Ciba company; BYK-028, BYK-019, BYK-345, BYK-346, BYK-348 are produced by German BYK Chemie company; WD50, WD52, WD60 are produced by the military big organosilicon limited liability company in Chinese Hubei;
Wet KL 245,
Glide 410,
ViscoPlus3000 is produced by German Degussa company; Borchigel L75 is produced by U.S. Borchers company.
Embodiment 1
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol ethylene glycol, hydrophilic monomer dimethyl isophthalate-5-sodium sulfonate and tetrabutyl titanate.Wherein, the mol ratio of ethylene glycol and dimethyl isophthalate-5-sodium sulfonate is: ethylene glycol: dimethyl isophthalate-5-sodium sulfonate=1: 0.05.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 210 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid sebacic acid and also was warming up to 200 ℃, and wherein, the mol ratio of ethylene glycol and sebacic acid is: ethylene glycol: sebacic acid=1: 0.5.In 210 ℃ of isothermal reactions 3 hours, dealcoholysis 60 minutes under 210 ℃ and 500Pa pressure at last.The hydroxyl value of products therefrom is that 37.4 milligrams of potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.7 milligram of potassium hydroxide/gram.
(2) with 100 parts of the above first polyvalent alcohol massfractions, 20 parts of the second polyvalent alcohol hexanodioic acid hexylene glycol massfractions of molecular weight 1000,20 parts of the 3rd polyvalent alcohol dimethylol propionic acid massfractions and the 4th polyvalent alcohol butyleneglycol massfraction mix for 5 parts mutually, drying is 2 hours under 130 ℃ rough vacuum, be cooled to 80 ℃, add the isophorone diisocyanate that accounts for said mixture mass percent 15% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.001% of said mixture mass percent 50%, reacted 4 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 110%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 100 parts of deionized waters of massfraction under high speed shear, the second surface promoting agent fatty alcohol-polyoxyethylene ether that adds the first surface promoting agent Sodium dodecylbenzene sulfonate and the mass percent 0.03% that account for above-mentioned polyurethane prepolymer mass percent 0.08% again, emulsion reaction 30 minutes, temperature of reaction maintains 50 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 1 hour, temperature of reaction is 55 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1.2: 1 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (5) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
1,010 0.05 parts of oxidation inhibitor: Irganox
944 0.01 parts of uv-absorbing agent: Chimassorb
0.01 part of wetting agent: BYK-346
0.01 part of defoamer: BYK-028
0.05 part of flow agent: BYK-348
0.05 part of thickening material Borchigel L75
0.4 part of silane coupling agent: WD50;
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 1.
Embodiment 2
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol butyleneglycol, hydrophilic monomer 5-sodium sulfo isophthalate and tetrabutyl titanate.Wherein, the mol ratio of butyleneglycol and dimethyl isophthalate-5-sodium sulfonate is: butyleneglycol: dimethyl isophthalate-5-sodium sulfonate=1: 0.15.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 180 ℃, constant temperature refluxed 30 minutes, added hexanodioic acid and also was warming up to 200 ℃, and wherein, the mol ratio of butyleneglycol and hexanodioic acid is: butyleneglycol: hexanodioic acid=1: 0.8.In 210 ℃ of isothermal reactions, treated out the water of theoretical amount 98% after, at last in the dehydration 60 minutes down of 210 ℃ and 500Pa pressure.The hydroxyl value of products therefrom is that 52.1mg milligram potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.9 milligram of potassium hydroxide/gram.
(2) 60 parts of the second polyvalent alcohol hexanodioic acid butyleneglycol massfractions, the 3rd polyvalent alcohol dimethylol propionic acid massfraction with 100 parts of the above first polyvalent alcohol massfractions, molecular weight 2000 mixes for 1 part mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add two-(the 4-isocyanate group cyclohexyl) methane account for said mixture mass percent 7% again, account for the acetone of said mixture mass percent 50% and account for the dibutyl tin laurate of said mixture mass percent 0.001%, reacted 3 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 100%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 100 parts of deionized waters of massfraction under high speed shear, add first surface promoting agent sodium laurylsulfonate and the mass percent 1.33% second surface promoting agent aliphatic acid polyethenoxy ether that accounts for above-mentioned polyurethane prepolymer mass percent 0.66% again, emulsion reaction 30 minutes, temperature of reaction maintains 55 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 1.5 hours, temperature of reaction is 55 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 1 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (5) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
1,076 0.01 parts of oxidation inhibitor: Irganox
327 0.05 parts of uv-absorbing agent: Tinuvin
0.2 part of wetting agent: BYK-345
0.2 part of defoamer: BYK-019
0.01 part of flow agent: BYK-348
0.01 part of thickening material ViscoPlus3000
0.2 part of silane coupling agent: WD50;
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 2.
Embodiment 3
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol butyleneglycol, hydrophilic monomer 5-sodium sulfo isophthalate and tetrabutyl titanate.Wherein, the mol ratio of butyleneglycol and dimethyl isophthalate-5-sodium sulfonate is: butyleneglycol: dimethyl isophthalate-5-sodium sulfonate=1: 0.1.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 180 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid hexanodioic acid and heated up, and wherein, the mol ratio of butyleneglycol and hexanodioic acid is: butyleneglycol: hexanodioic acid=1: 0.7.In 210 ℃ of isothermal reactions 3 hours, at last in 210 ℃ and the following dehydration of 500Pa pressure 60min.The hydroxyl value of products therefrom is that 113 milligrams of potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.9 milligram of potassium hydroxide/gram.
(2) with 100 parts of the above first polyvalent alcohol massfractions, 150 parts of the second polyvalent alcohol adipate glycol massfractions of molecular weight 3000,12 parts of the 3rd polyvalent alcohol dimethylolpropionic acid massfractions and the 4th polyvalent alcohol butyleneglycol massfraction mix for 1 part mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add the '-diphenylmethane diisocyanate that accounts for said mixture mass percent 20% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.001% of said mixture mass percent 50%, reacted 3 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 100%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 100 parts of deionized waters of massfraction under high speed shear, add again and account for above-mentioned polyurethane prepolymer mass percent 0.25% first surface promoting agent sodium lauryl sulphate and mass percent 0.25% second surface promoting agent aliphatic acid polyethenoxy ether, emulsion reaction 30 minutes, temperature of reaction maintains 60 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 1.5 hours, temperature of reaction is 60 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 1 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (5) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
1,076 0.02 parts of oxidation inhibitor: Irganox
327 0.1 parts of uv-absorbing agent: Tinuvin
0.05 part of wetting agent: BYK-346
0.1 part of defoamer: BYK-019
410 0.09 parts of flow agent: Glide
0.1 part of thickening material ViscoPlus3000
0.4 part of silane coupling agent: WD52;
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 3.
Embodiment 4
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol hexylene glycol, hydrophilic monomer m-phthalic acid binaryglycol ester-5-sodium sulfonate and tetrabutyl titanate.Wherein, the mol ratio of hexylene glycol and m-phthalic acid binaryglycol ester-5-sodium sulfonate is: hexylene glycol: m-phthalic acid binaryglycol ester-5-sodium sulfonate=1: 0.2.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 210 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid hexanodioic acid and heated up, and wherein, the mol ratio of hexylene glycol and hexanodioic acid is: hexylene glycol: hexanodioic acid=1: 0.65.In 200 ℃ of isothermal reactions 3 hours, at last in 210 ℃ and the following dehydration of 500Pa pressure 60min.The hydroxyl value of products therefrom is that 55.1 milligrams of potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.5 milligram of potassium hydroxide/gram.
(2) with 100 parts of the above first polyvalent alcohol massfractions, 60 parts of the second polyvalent alcohol adipate glycol massfractions of molecular weight 2900,11 parts of the 3rd polyvalent alcohol dimethylol propionic acid massfractions and the 4th polyvalent alcohol butyleneglycol massfraction mix for 3 parts mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add again and account for 1 of said mixture mass percent 6%, the 6-hexamethylene diisocyanate, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.001% of said mixture mass percent 50%, reacted 3 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 80%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 90 parts of deionized waters of massfraction under high speed shear, add again and account for above-mentioned polyurethane prepolymer mass percent 0.9% ten first surface promoting agent dialkyl group sodium sulfonate and mass percent 1.0% second surface promoting agent aliphatic acid polyethenoxy ether, emulsion reaction 30 minutes, temperature of reaction maintains 55 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 1.5 hours, temperature of reaction is 55 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 0.8 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
1,098 0.03 parts of oxidation inhibitor: Irganox
622 0.03 parts of uv-absorbing agent: Tinuvin
Wetting agent: 245 0.15 parts of Wet KL
0.05 part of defoamer: BYK-019
410 0.2 parts of flow agent: Glide
0.2 part of thickening material Vi scoPlus3000
1.0 parts of silane coupling agent: WD60;
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 4.
Embodiment 5
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol neopentyl glycol, hydrophilic monomer m-phthalic acid binaryglycol ester-5-sodium sulfonate and tetrabutyl titanate.Wherein, the mol ratio of neopentyl glycol and m-phthalic acid binaryglycol ester-5-sodium sulfonate is: neopentyl glycol: m-phthalic acid binaryglycol ester-5-sodium sulfonate=1: 0.2.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 210 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid hexanodioic acid and heated up, and wherein, the mol ratio of neopentyl glycol and hexanodioic acid is: neopentyl glycol: hexanodioic acid=1: 0.6.In 210 ℃ of isothermal reactions 3 hours, at last in 210 ℃ and the following dehydration of 500Pa pressure 60min.The hydroxyl value of products therefrom is that 45.1 milligrams of potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.5 milligram of potassium hydroxide/gram.
(2) with 100 parts of the above first polyvalent alcohol massfractions, 200 parts of the second polyvalent alcohol adipate glycol massfractions of molecular weight 3000,8 parts of the 3rd polyvalent alcohol dimethylol propionic acid massfractions and the 4th polyvalent alcohol hexylene glycol massfraction mix for 3 parts mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add the tolylene diisocyanate that accounts for said mixture mass percent 8% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.001% of said mixture mass percent 50%, reacted 3 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 100%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 110 parts of deionized waters of massfraction under high speed shear, add again and account for above-mentioned polyurethane prepolymer mass percent 0.75% first surface promoting agent sodium laurylsulfonate and mass percent 0.25% second surface promoting agent aliphatic acid polyethenoxy ether, emulsion reaction 30 minutes, temperature of reaction maintains 55 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 1.5 hours, temperature of reaction is 55 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1:, make aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
168 0.01 parts of oxidation inhibitor: Irgafos
327 0.01 parts of uv-absorbing agent: Tinuvin
Wetting agent: 245 0.05 parts of Wet KL
0.15 part of defoamer: BYK-028
410 0.2 parts of flow agent: Glide
0.2 part of thickening material ViscoPlus3000
0.8 part of silane coupling agent: WD50
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 5.
Embodiment 6
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol butyleneglycol, hydrophilic monomer m-phthalic acid binaryglycol ester-5-sodium sulfonate and tetrabutyl titanate.Wherein, the mol ratio of butyleneglycol and m-phthalic acid binaryglycol ester-5-sodium sulfonate is: butyleneglycol: m-phthalic acid binaryglycol ester-5-sodium sulfonate=1: 0.12.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 210 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid hexanodioic acid and heated up, and wherein, the mol ratio of butyleneglycol and hexanodioic acid is: butyleneglycol: hexanodioic acid=1: 0.6.In 180 ℃ of isothermal reactions 3 hours, at last in 200 ℃ and the following dehydration of 500Pa pressure 90min.The hydroxyl value of products therefrom is that 75.1 potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.6 potassium hydroxide/gram.
(2) with 100 parts of the above first polyvalent alcohol massfractions, 100 parts of the second polyvalent alcohol adipate glycol massfractions of molecular weight 1500,13 parts of the 3rd polyvalent alcohol dimethylol propionic acid massfractions and the 4th polyvalent alcohol hexylene glycol massfraction mix for 4 parts mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add the isophorone diisocyanate that accounts for said mixture mass percent 11% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.002% of said mixture mass percent 50%, reacted 3 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 90%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 100 parts of deionized waters of massfraction under high speed shear, add again and account for above-mentioned polyurethane prepolymer mass percent 0.7% first surface promoting agent sodium lauryl sulphate and mass percent 0.8% second surface promoting agent fatty alcohol-polyoxyethylene ether, emulsion reaction 30 minutes, temperature of reaction maintains 50 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 2 hours, temperature of reaction is 50 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 1 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
168 0.02 parts of oxidation inhibitor: Irgafos
622 0.04 parts of uv-absorbing agent: Tinuvin
0.05 part of wetting agent: BYK-346
0.05 part of defoamer: BYK-028
0.15 part of flow agent: BYK-348
0.15 part of thickening material ViscoPlus3000
0.6 part of silane coupling agent: WD52
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 6.
Embodiment 7
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol butyleneglycol, hydrophilic monomer m-phthalic acid binaryglycol ester-5-sodium sulfonate and tetrabutyl titanate.Wherein, the mol ratio of butyleneglycol and m-phthalic acid binaryglycol ester-5-sodium sulfonate is: butyleneglycol: m-phthalic acid binaryglycol ester-5-sodium sulfonate=1: 0.06.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 210 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid hexanodioic acid and heated up, and wherein, the mol ratio of butyleneglycol and hexanodioic acid is: butyleneglycol: hexanodioic acid=1: 0.7.In anti-3 hours of 180 ℃ of constant temperature, at last in 200 ℃ and 500Pa pressure dehydration 90min down.The hydroxyl value of products therefrom is that 40.1 milligrams of potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.8 milligram of potassium hydroxide/gram.
(2) 30 parts of the second polyvalent alcohol adipate glycol massfractions, the 3rd polyvalent alcohol dimethylol propionic acid massfraction with 100 parts of the above first polyvalent alcohol massfractions, molecular weight 3000 mixes for 5 parts mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add the isophorone diisocyanate account for said mixture mass percent 3% again, account for the acetone of said mixture mass percent 50% and account for the dibutyl tin laurate of said mixture mass percent 0.003%, reacted 3.5 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 90%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 100 parts of deionized waters of massfraction under high speed shear, add again and account for above-mentioned polyurethane prepolymer mass percent 0.5% first surface promoting agent sodium lauryl sulphate and mass percent 0.4% second surface promoting agent fatty alcohol-polyoxyethylene ether, emulsion reaction 30 minutes, temperature of reaction maintains 50 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 2 hours, temperature of reaction is 50 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 1 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
168 0.02 parts of oxidation inhibitor: Irgafos
327 0.04 parts of uv-absorbing agent: Tinuvin
0.05 part of wetting agent: BYK-345
0.11 part of defoamer: BYK-019
0.04 part of flow agent: BYK-348
0.05 part of thickening material Vi scoPlus3000
0.5 part of silane coupling agent: WD60
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 7.
Embodiment 8
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol hexylene glycol, hydrophilic monomer m-phthalic acid binaryglycol ester-5-sodium sulfonate and tetrabutyl titanate.Wherein, the mol ratio of hexylene glycol and m-phthalic acid binaryglycol ester-5-sodium sulfonate is: hexylene glycol: m-phthalic acid binaryglycol ester-5-sodium sulfonate=1: 0.13.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 210 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid sebacic acid and heated up, and wherein, the mol ratio of hexylene glycol and sebacic acid is: hexylene glycol: sebacic acid=1: 0.6.In anti-3 hours of 180 ℃ of constant temperature, at last in 200 ℃ and 500Pa pressure dehydration 90min down.The hydroxyl value of products therefrom is that 64.1 milligrams of potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.8 milligram of potassium hydroxide/gram.
(2) with 100 parts of the above first polyvalent alcohol massfractions, 80 parts of the second polyvalent alcohol adipate glycol massfractions of molecular weight 2000,7 parts of the 3rd polyvalent alcohol dimethylol propionic acid massfractions and the 4th polyvalent alcohol hexylene glycol massfraction mix for 2 parts mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add the tolylene diisocyanate that accounts for said mixture mass percent 10% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.003% of said mixture mass percent 50%, reacted 3.5 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 90%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 100 parts of deionized waters of massfraction under high speed shear, add again and account for above-mentioned polyurethane prepolymer mass percent 0.6% first surface promoting agent sodium lauryl sulphate and mass percent 0.9% second surface promoting agent fatty alcohol-polyoxyethylene ether, emulsion reaction 30 minutes, temperature of reaction maintains 50 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 2 hours, temperature of reaction is 50 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 1 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
168 0.04 parts of oxidation inhibitor: Irgafos
770 0.1 parts of uv-absorbing agent: Tinuvin
0.08 part of wetting agent: BYK-345
0.12 part of defoamer: BYK-019
0.11 part of flow agent: BYK-348
0.03 part of thickening material ViscoPlus3000
0.4 part of silane coupling agent: WD52
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 8.
Embodiment 9
(1) reflux condensing tube, thermometer, agitator and N are being housed
2In the four-hole boiling flask of inlet, add monomer polyvalent alcohol butyleneglycol, hydrophilic monomer m-phthalic acid binaryglycol ester-5-sodium sulfonate and tetrabutyl titanate.Wherein, the mol ratio of butyleneglycol and m-phthalic acid binaryglycol ester-5-sodium sulfonate is: butyleneglycol: m-phthalic acid binaryglycol ester-5-sodium sulfonate=1: 0.12.Tetrabutyl titanate accounts for 0.01% of monomer polyvalent alcohol.At N
2Heat up under the atmosphere, stir, when temperature reaches 210 ℃, constant temperature refluxed 30 minutes, added the polyprotonic acid hexanodioic acid and heated up, and wherein, the mol ratio of butyleneglycol and hexanodioic acid is: butyleneglycol: hexanodioic acid=1: 0.6.In 180 ℃ of isothermal reactions 3 hours, at last in 200 ℃ and the following dehydration of 500Pa pressure 90min.The hydroxyl value of products therefrom is that 75.1 potassium hydroxide/gram and acid number are first polyvalent alcohol of 0.6 potassium hydroxide/gram.
(2) with 100 parts of the above first polyvalent alcohol massfractions, 100 parts of the second polyvalent alcohol adipate glycol massfractions of molecular weight 1500,13 parts of the 3rd polyvalent alcohol dimethylol propionic acid massfractions and the 4th polyvalent alcohol hexylene glycol massfraction mix for 4 parts mutually, drying is 2 hours under 120 ℃ rough vacuum, be cooled to 70 ℃, add the isophorone diisocyanate that accounts for said mixture mass percent 11% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.002% of said mixture mass percent 50%, reacted 3 hours, and made polyurethane prepolymer;
(3) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 90%, the polyurethane prepolymer after obtaining neutralizing;
(4) polyurethane prepolymer of 100 parts of massfractions after the above-mentioned neutralization is evenly spread in 100 parts of deionized waters of massfraction under high speed shear, add again and account for above-mentioned polyurethane prepolymer mass percent 0.7% first surface promoting agent sodium lauryl sulphate and mass percent 0.8% second surface promoting agent fatty alcohol-polyoxyethylene ether, emulsion reaction 30 minutes, temperature of reaction maintains 50 ℃, obtains aqueous polyurethane dispersion;
(5) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 2 hours, temperature of reaction is 50 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 1 makes aqueous polyurethane;
(6) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(7) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, wetting agent, defoamer, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of above-mentioned aqueous polyurethanes
168 0.02 parts of oxidation inhibitor: Irgafos
622 0.04 parts of uv-absorbing agent: Tinuvin
0.05 part of wetting agent: BYK-346
0.05 part of defoamer: BYK-019
0.15 part of flow agent: BYK-348
0.15 part of thickening material Borchigel L75
0.6 part of silane coupling agent: WD52
(8) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 10.
Claims (5)
1, a kind of preparation method of water polyurethane binder for shoe is characterized in that this method may further comprise the steps:
(1) with first polyvalent alcohol, second polyvalent alcohol, the 3rd polyvalent alcohol and the 4th polyvalent alcohol mix mutually, drying is 1～3 hour under 100 ℃～140 ℃ rough vacuum, be cooled to 70 ℃～90 ℃, the mixing quality ratio of above-mentioned four kinds of polyvalent alcohols is: first polyvalent alcohol: second polyvalent alcohol: the 3rd polyvalent alcohol: the 4th polyvalent alcohol=1: 0.2～2: 0.01～0.2: 0～0.05, add the isocyanic ester that accounts for said mixture mass percent 3～20% again, account for the acetone and the dibutyl tin laurate that accounts for said mixture mass percent 0.01～0.001% of said mixture mass percent 20～80%, reacted 2～5 hours, and made polyurethane prepolymer;
The preparation method of wherein said first polyvalent alcohol may further comprise the steps:
(1-1) in nitrogen atmosphere, monomer polyvalent alcohol, hydrophilic monomer and tetrabutyl titanate to be mixed mutually, the mol ratio of each component is: the monomer polyvalent alcohol: the mass percent that hydrophilic monomer=1: 0.05～0.2, tetrabutyl titanate account for the monomer polyvalent alcohol is 0.01%;
(1-2) stir on intensification limit in limit, when temperature reaches 160 ℃～210 ℃, add polyprotonic acid after constant temperature refluxed 20～30 minutes and be warming up to 180 ℃～210 ℃, wherein, the mol ratio of monomer polyvalent alcohol and polyprotonic acid is: the monomer polyvalent alcohol: polyprotonic acid=1: 0.5～0.8;
(1-3) under 180 ℃～210 ℃, reacted 2～3 hours, dealcoholysis is 30～60 minutes under 500Pa pressure, and obtaining hydroxyl value is 37.4～113 milligrams of potassium hydroxide/gram, and acid number is less than first polyvalent alcohol of 1 milligram of potassium hydroxide/gram;
Wherein said second polyvalent alcohol is hexanodioic acid hexylene glycol, hexanodioic acid butyleneglycol or adipate glycol;
Wherein said the 3rd polyvalent alcohol is dimethylol propionic acid or dimethylolpropionic acid;
Wherein said the 4th polyvalent alcohol is butyleneglycol or hexylene glycol;
(2) with above-mentioned prepolymer that makes and triethylamine generation neutralization reaction, make wherein carboxylate radical or sulfonate radical in and salify, degree of neutralization is 80-120%, the polyurethane prepolymer after obtaining neutralizing;
(3) polyurethane prepolymer after the above-mentioned neutralization is evenly spread in the deionized water under high speed shear, the mass ratio of polyurethane prepolymer and deionized water is: polyurethane prepolymer: deionized water=1: 0.8～1.1, add the tensio-active agent that accounts for above-mentioned polyurethane prepolymer mass percent 0.1～3% again, this tensio-active agent is made up of first surface promoting agent and second surface promoting agent, wherein, the mass ratio of first surface promoting agent and second surface promoting agent is: the first surface promoting agent: second surface promoting agent=1: 0.3～2, emulsion reaction 20-40 minute, temperature of reaction maintains 40 ℃～60 ℃, obtains aqueous polyurethane dispersion;
(4) in the above-mentioned aqueous polyurethane dispersion that makes, add quadrol and carry out chain extending reaction, reaction times is 0.5～2 hour, temperature of reaction is 40 ℃～60 ℃, the adding mol ratio of quadrol is: the amido in the quadrol (NH): the isocyano in the aqueous polyurethane dispersion=1: 0.6～1.2 make aqueous polyurethane;
(5) slough acetone in the aqueous polyurethane that step (4) makes with the vacuum decompression method, the content that makes acetone wherein is below 1%;
(6) aqueous polyurethane with above-mentioned preparation mixes mutually with oxidation inhibitor, uv-absorbing agent, flow agent, defoamer, wetting agent, thickening material and silane coupling agent, makes first component, and wherein each composition blended mass fraction is:
100 parts of aqueous polyurethanes
0.01～0.05 part in oxidation inhibitor
0.01～0.05 part of uv-absorbing agent
0.01～0.2 part of flow agent
0.01～0.2 part of defoamer
0.01～0.2 part of wetting agent
0.01～0.2 part of thickening material
0.2～1.0 part of silane coupling agent;
(7) above-mentioned first component is mixed mutually with water cross-linking agent, obtain water polyurethane binder for shoe, blending ratio is: the mass ratio of first component and water cross-linking agent is: first component: water cross-linking agent=100: 1～10.
2, the method for claim 1 is characterized in that wherein said monomer polyvalent alcohol is: any in ethylene glycol, butyleneglycol, hexylene glycol or the neopentyl glycol; Described polyprotonic acid is: hexanodioic acid or sebacic acid; Described hydrophilic monomer is any in dimethyl isophthalate-5-sodium sulfonate, m-phthalic acid binaryglycol ester-5-sodium sulfonate or the 5-sodium sulfo isophthalate.
3, the method for claim 1, it is characterized in that wherein said isocyanic ester is isophorone diisocyanate, two-(4-isocyanate group cyclohexyl) methane, '-diphenylmethane diisocyanate, tolylene diisocyanate or 1, any in the 6-hexamethylene diisocyanate.
4, the method for claim 1 is characterized in that wherein said first surface promoting agent is any in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or the sodium lauryl sulphate; Described second surface promoting agent is a fatty alcohol-polyoxyethylene ether, structural formula: RO (C
2H
4O)
nH, or aliphatic acid polyethenoxy ether, structural formula: RCOO (C
2H
4O)
nH, wherein R represents long chain alkane or has the long chain alkane of phenyl ring, and the numerical value of n is: 1～50.
5, the method for claim 1 is characterized in that wherein said oxidation inhibitor is any among Irganox 1010, Irganox1076, Irganox 1098 or the Irgafos 168; Described uv-absorbing agent is any among Chimassorb 944, Tinuvin 327, Tinuvin622 or the Tinuvin770; Described silane coupling agent is any among WD50, WD52 or the WD60; Described wetting agent is
Any among Wet KL 245, BYK-345 or the BYK-346; Described flow agent is
Glide 410 or BYK-348; Described thickening material is
Any among ViscoPlus3000 or the Borchigel L75; Described defoamer is BYK-028 or BYK-019.
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| CN108531129A (en) * | 2018-04-28 | 2018-09-14 | 福建华夏蓝新材料科技有限公司 | One kind is except aqueous adhesive for shoes of formaldehyde and preparation method thereof |
| US11014347B2 (en) * | 2019-06-27 | 2021-05-25 | Bemis Associates, Inc. | Methods of bonding a textile |
| CN111518257B (en) * | 2020-05-29 | 2021-11-23 | 骏能化工（龙南）有限公司 | Water-based polyurethane shoe adhesive and preparation method thereof |
| CN113736370B (en) * | 2021-09-06 | 2022-05-06 | 汕头市松炀新材料特种纸有限公司 | Preparation process of water-soluble glue for curtain type coated non-setting adhesive label |
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2007
- 2007-09-21 CN CNB2007101220757A patent/CN100569887C/en not_active Expired - Fee Related
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