CN101509047B - Watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent and preparation method thereof - Google Patents
Watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to fine chemicals and the preparation field thereof, and more particularly relates to a positive ion fluosilicic polyurethane type leather waterproof fatting agent and a preparation method thereof. The invention can overcome the problems that the function is single and the environment is polluted by the preparing technique in the prior art. The invention has the technical proposal that a aqueous positive ion fluosilicic polyurethane type leather waterproof fatting agent is prepared by the following steps: step one, polyisocyanate, dihydroxy silicon oil, hydrophilic monomer chain extender and a little diluting solvent react to prepare polyurethane prepolymer; end-capping reagent and a little catalyst are added into the polyurethane prepolymer to prepare part end-capping fluosilicic polyurethane prepolymer containing hydrophilic group; step two, acidified reagent is added into the part end-capping fluosilicic polyurethane prepolymer; after the pH value is regulated, de-ionized water is added into the mixture to prepare the aqueous positive ion fluosilicic polyurethane type leather waterproof fatting agent. Compared with the prior art, the invention has the advantages of (1) multiple functions; (2) good leather affinity; (3) excellent stability; and (4) safety and environmental protection.
Description
Technical field
The invention belongs to fine chemicals and preparation field thereof, particularly a kind of cation fluorine-silicon polyurethane type leather water-proof fatting agent and preparation method thereof.
Background technology
Fatting agent is one of maximum and requisite skin material of consumption in the tanning production; Leather quality and performance there is significant effects; Resilient feel and certain water resistance in order to give the plentiful softness of leather, this just need adopt the fatting agent stuffing with good waterproof action when stuffing.
At present, in the fatting agent commonly used, though the esters of acrylic acid waterproof currying agent has certain water-proof function, they exist a little less than the avidity, combine not by force with the leather fiber, are easy to shortcomings such as migration; The organic fluorine compounds is a leather water-proof material the most effectively, and the leather after the fluorine based compound is handled has property such as waterproof, grease proofing, anti-soil, but the leather after the stuffing is harder, and feel is bad; Though siliceous fatting agent can improve flexibility, wear resistance, smooth property of leather etc., water-repellancy is not ideal.Above-mentioned fatting agent all exists the problem of function singleness, simultaneously because most of organic fluorine and organosilicon fatting agent use a large amount of organic solvents in preparation technology, therefore also exists preparation technology's problem of environment pollution caused.
Summary of the invention
The purpose of this invention is to provide a kind of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent that integrates waterproof, stuffing and preparation method thereof, to overcome function singleness and the preparation technology's problem of environment pollution caused that prior art exists.
Above-mentioned purpose of the present invention is achieved in that
A kind of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent is prepared by following method, and said method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1: 0.8～5.5: 0.05～0.5: 0.08～0.3; Said POLYMETHYLENE POLYPHENYLISOCYANATE is the compound that contains 2 NCOs at least; Reaction conditions is: temperature of reaction is 50～90 ℃, and the reaction times is 1～5 hour, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～10 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 0.5～2.5: 0.001～0.005: 1; Temperature of reaction is 50～90 ℃; Reaction times is 1～6 hour, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 10～50 ℃; Add acidizing reagent; Regulation system pH value is 4～6.5, and back adding temperature is 10～90 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1: 1.5～9; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
Above-mentioned preferred version is:
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1: 0.8～2.5: 0.08～0.25: 0.08～0.15; Reaction conditions is: temperature of reaction is 65～80 ℃; Reaction times is 3～4 hours, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～8 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 1.0～1.5: 0.002～0.003: 1; Temperature of reaction is 70～80 ℃; Reaction times is 2～4 hours, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 25～40 ℃; Add acidizing reagent; Regulation system pH value is 5～6, and back adding temperature is 20～40 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1: 1.5～4; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
POLYMETHYLENE POLYPHENYLISOCYANATE in the above-mentioned steps one can be the polymer of aliphatic polyisocyante, aromatic polyisocyanate or these POLYMETHYLENE POLYPHENYLISOCYANATE; Aliphatic polyisocyante; Particularly 1; Hexamethylene-diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tetramethylene diisocyanate (TMXDI); Aromatic polyisocyanate, particularly tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI).
In the above-mentioned steps one:
Described dihydroxyl silicone oil is that molecular weight is the dihydroxyl silicone oil of 1000-4000;
Described hydrophilic monomer chain extender can be the trolamine in the tertiary amine-type polyhydric alcohol amine, N methyldiethanol amine or N-sec.-propyl diethylolamine;
Described diluting solvent can be selected from acetone, butanone, ETHYLE ACETATE or THF.
Described perfluoroalkyl alcohol end-capping reagent can be perfluor alkyl ethide hexanol, perfluor alkyl ethide octanol or perfluor alkyl ethide decyl alcohol.
Described catalyzer is dibutyl tin laurate, cobalt naphthenate, stannous octoate, zinc naphthenate, lead octoate 36, phthalic acid lead or zinc octoate.
Described acidizing reagent described in the above-mentioned steps two can be organic or inorganic acid, particularly hydrochloric acid, sulfuric acid or Glacial acetic acid min. 99.5.
A kind of preparation method of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1: 0.8～5.5: 0.05～0.5: 0.08～0.3; Said POLYMETHYLENE POLYPHENYLISOCYANATE is the compound that contains 2 NCOs at least; Reaction conditions is: temperature of reaction is 50～90 ℃, and the reaction times is 1～5 hour, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～10 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 0.5～2.5: 0.001～0.005: 1; Temperature of reaction is 50～90 ℃; Reaction times is 1～6 hour, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 10～50 ℃; Add acidizing reagent; Regulation system pH value is 4～6.5, and back adding temperature is 10～90 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1: 1.5～9; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
Above-mentioned preferred version is:
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1: 0.8～2.5: 0.08～0.25: 0.08～0.15; Reaction conditions is: temperature of reaction is 65～80 ℃; Reaction times is 3～4 hours, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～8 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 1.0～1.5: 0.002～0.003: 1; Temperature of reaction is 70～80 ℃; Reaction times is 2～4 hours, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 25～40 ℃; Add acidizing reagent; Regulation system pH value is 5～6, and back adding temperature is 20～40 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1: 1.5～4; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
POLYMETHYLENE POLYPHENYLISOCYANATE in the above-mentioned steps one can be the polymer of aliphatic polyisocyante, aromatic polyisocyanate or these POLYMETHYLENE POLYPHENYLISOCYANATE; Aliphatic polyisocyante; Particularly 1; Hexamethylene-diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tetramethylene diisocyanate (TMXDI); Aromatic polyisocyanate, particularly tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI).
In the above-mentioned steps one:
Described dihydroxyl silicone oil is that molecular weight is the dihydroxyl silicone oil of 1000-4000;
Described hydrophilic monomer chain extender can be the trolamine in the tertiary amine-type polyhydric alcohol amine, N methyldiethanol amine or N-sec.-propyl diethylolamine;
Described diluting solvent can be selected from acetone, butanone, ETHYLE ACETATE or THF.
Described perfluoroalkyl alcohol end-capping reagent can be perfluor alkyl ethide hexanol, perfluor alkyl ethide octanol or perfluor alkyl ethide decyl alcohol.
Described catalyzer is dibutyl tin laurate, cobalt naphthenate, stannous octoate, zinc naphthenate, lead octoate 36, phthalic acid lead or zinc octoate.
Described acidizing reagent described in the above-mentioned steps two can be organic or inorganic acid, particularly hydrochloric acid, sulfuric acid or Glacial acetic acid min. 99.5.
Compared with prior art, advantage of the present invention is:
(1) multi-functional: product of the present invention integrates the advantage of fluorine silicon, promptly integrates waterproof and softish performance, both can make to have toughness in the leather softness after the stuffing, have elasticity in plentiful, has excellent waterproof, grease proofing, antifouling performance simultaneously.
(2) good with leather avidity: final institute synthetic aqueous polyurethane macromole has cationic; There is static to combine with electronegative leather fiber; And isocyanate groups can form chemical bond with leather fiber and combines; Increased the avidity of polyurethane macromolecular and base material, strong with the leather fibrous binding force.
(3) good stability: because product of the present invention has self emulsifiable quaternary ammonium salt group, the water-dispersion ability is strong, can form stable trickle emulsion, can give better pleasant softness of leather and ventilation property after the stuffing.
(4) safety and environmental protection: in the process of preparation watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent, do not contain or only contain a spot of solvent; Be main dispersing medium during the stuffing of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent in use, reduced pollution and infringement environment and operator with water.
Embodiment
To combine embodiment that the present invention is done explanation at length below.
Embodiment 1, and a kind of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: put into 112g isophorone diisocyanate (IPDI), 233g dihydroxyl silicone oil (molecular weight 2000) and 26gN-methyldiethanolamine in the reactor drum successively; After feeding the nitrogen deoxygenation; Stir; Add ethyl acetate solvent 10g, 90 ℃ of reactions of constant temperature 1 hour form polyurethane prepolymer.This polyurethane prepolymer is cooled to 60 ℃, adds 66g perfluor alkyl ethide decyl alcohol and carry out end capping, and add the 0.3g dibutyltin dilaurate catalyst, reacted 1 hour, make the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group.
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 45 ℃;, adding the glacial acetic acid acidifying, regulation system pH value is 4.5; Under agitation; With temperature is that 15 ℃ 1746g deionized water joins in the system and stirs, and ethyl acetate solvent is removed out in distillation at last, obtains total solids level and be 20% white emulsion
Embodiment 2, and a kind of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: with 125g diphenylmethanediisocyanate (MDI), 117g dihydroxyl silicone oil (molecular weight 1000; Dry) and the 26gN-methyldiethanolamine put in the reactor drum successively; After feeding the nitrogen deoxygenation, stir, add tetrahydrofuran solvent 15g; 70 ℃ of reactions of constant temperature 4 hours form polyurethane prepolymer.This polyurethane prepolymer is warming up to 75 ℃, adds 155g perfluor alkyl ethide octanol and carry out end capping, and add 0.3g zinc naphthenate catalyzer, reacted 3.5 hours, make the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group.
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 40 ℃; Add hcl acidifying; Regulation system pH value is 5.5, under agitation, is that 20 ℃ 786g deionized water joins in the system and stirs with temperature; Tetrahydrofuran solvent is removed out in distillation at last, obtains total solids level and be 35% white emulsion
Embodiment 3, and a kind of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: put into 87g tolylene diisocyanate (TDI), 466g dihydroxyl silicone oil (molecular weight 4000) and 11gN-sec.-propyl diethylolamine in the reactor drum successively; After feeding the nitrogen deoxygenation; Stir; Add tetrahydrofuran solvent 20g, 70 ℃ of reactions of constant temperature 4 hours form polyurethane prepolymer.This polyurethane prepolymer is warming up to 80 ℃, adds 188g perfluor alkyl ethide octanol and carry out end capping, and add 0.4g lead octoate 36 catalyzer, reacted 4.5 hours, make the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group.
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 20 ℃; Add the glacial acetic acid acidifying; Regulation system pH value is 4, under agitation, is that 70 ℃ 1128g deionized water joins in the system and stirs with temperature; Tetrahydrofuran solvent is removed out in distillation at last, obtains total solids level and be 40% white emulsion.
Embodiment 4, and a kind of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: put into 112g isophorone diisocyanate (IPDI), 233g dihydroxyl silicone oil (molecular weight 2000) and 11gN-sec.-propyl diethylolamine in the reactor drum successively; After feeding the nitrogen deoxygenation; Stir; Add butanone solvent 10g, 65 ℃ of reactions of constant temperature 3 hours form polyurethane prepolymer.This polyurethane prepolymer is warming up to 75 ℃, adds 170g perfluor alkyl ethide hexanol and carry out end capping, and add the 0.3g stannous octoate catalyst, reacted 2.5 hours, make the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group.
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 35 ℃; Add sulfuric acid acidation; Regulation system pH value is 5.5, under agitation, is that 35 ℃ 1116g deionized water joins in the system and stirs with temperature; Butanone is removed out in distillation at last, obtains total solids level and be 30% white emulsion.
Embodiment 5, and a kind of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: put into 84g hexamethylene diisocyanate (HDI), 350g dihydroxyl silicone oil (molecular weight 3000) and 22g trolamine in the reactor drum successively; After feeding the nitrogen deoxygenation; Stir; Add acetone solvent 15g, 60 ℃ of reactions of constant temperature 2 hours form polyurethane prepolymer.This polyurethane prepolymer is warming up to 70 ℃, adds 188g perfluor alkyl ethide decyl alcohol and carry out end capping, and add the 0.3g dibutyltin dilaurate catalyst, reacted 3 hours, make the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group.
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 50 ℃; Add the glacial acetic acid acidifying; Regulation system pH value is 6.5, under agitation, is that 90 ℃ 1932g deionized water joins in the system and stirs with temperature; Acetone is removed out in distillation at last, obtains total solids level and be 25% white emulsion.
Above-mentioned preferred embodiment is: instance 2 and instance 4.
Claims (10)
1. a watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent is prepared by following method, and said method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1:0.8～5.5:0.05～0.5:0.08～0.3; Said POLYMETHYLENE POLYPHENYLISOCYANATE is the compound that contains 2 NCOs at least; Reaction conditions is: temperature of reaction is 50～90 ℃, and the reaction times is 1～5 hour, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～10 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 0.5～2.5:0.001～0.005:1; Temperature of reaction is 50～90 ℃; Reaction times is 1～6 hour, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Described hydrophilic monomer chain extender is trolamine, N methyldiethanol amine or the N-sec.-propyl diethylolamine in the tertiary amine-type polyhydric alcohol amine;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 10～50 ℃; Add acidizing reagent; Regulation system pH value is 4～6.5, and back adding temperature is 10～90 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1:1.5～9; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
2. watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 1 is characterized in that: prepared by following method, said method comprises the steps: successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1:0.8～2.5:0.08～0.25:0.08～0.15; Reaction conditions is: temperature of reaction is 65～80 ℃; Reaction times is 3～4 hours, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～8 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 1.0～1.5:0.002～0.003:1; Temperature of reaction is 70～80 ℃; Reaction times is 2～4 hours, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 25～40 ℃; Add acidizing reagent; Regulation system pH value is 5～6, and back adding temperature is 20～40 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1:1.5～4; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
3. watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 2 is characterized in that: the POLYMETHYLENE POLYPHENYLISOCYANATE in the said step 1 is the polymer of aliphatic polyisocyante, aromatic polyisocyanate or these POLYMETHYLENE POLYPHENYLISOCYANATE; Aliphatic polyisocyante is a hexamethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tetramethylene diisocyanate (TMXDI); Aromatic polyisocyanate is tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI).
4. watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 3 is characterized in that: in the said step 1,
Described dihydroxyl silicone oil is that molecular weight is the dihydroxyl silicone oil of 1000-4000;
Described diluting solvent is acetone, butanone, ETHYLE ACETATE or THF;
Described perfluoroalkyl alcohol end-capping reagent is perfluor alkyl ethide hexanol or perfluor alkyl ethide octanol;
Described catalyzer is dibutyl tin laurate, cobalt naphthenate, stannous octoate, zinc naphthenate, lead octoate 36, phthalic acid lead or zinc octoate.
5. watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 4 is characterized in that: the acidizing reagent in the said step 2 is hydrochloric acid, sulfuric acid or Glacial acetic acid min. 99.5.
6. the preparation method of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 1 is characterized in that: comprise the steps successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1:0.8～5.5:0.05～0.5:0.08～0.3; Said POLYMETHYLENE POLYPHENYLISOCYANATE is the compound that contains 2 NCOs at least; Reaction conditions is: temperature of reaction is 50～90 ℃, and the reaction times is 1～5 hour, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～10 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 0.5～2.5:0.001～0.005:1; Temperature of reaction is 50～90 ℃; Reaction times is 1～6 hour, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Described hydrophilic monomer chain extender is trolamine, N methyldiethanol amine or the N-sec.-propyl diethylolamine in the tertiary amine-type polyhydric alcohol amine;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 10～50 ℃; Add acidizing reagent; Regulation system pH value is 4～6.5, and back adding temperature is 10～90 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1:1.5～9; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
7. the preparation method of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 6 is characterized in that: comprise the steps successively
Step 1: preparation contains the partially end-blocked fluorine-silicon polyurethane prepolymer of hydrophilic group: made by POLYMETHYLENE POLYPHENYLISOCYANATE, dihydroxyl silicone oil, hydrophilic monomer chain extender and little diluting solvent reaction; Its weight ratio is respectively 1:0.8～2.5:0.08～0.25:0.08～0.15; Reaction conditions is: temperature of reaction is 65～80 ℃; Reaction times is 3～4 hours, makes polyurethane prepolymer; The perfluoroalkyl alcohol that will have 6～8 carbon atoms again joins in this polyurethane prepolymer as end-capping reagent and little amount of catalyst; The weight ratio of perfluoroalkyl alcohol, catalyzer and the POLYMETHYLENE POLYPHENYLISOCYANATE that is added is: 1.0～1.5:0.002～0.003:1; Temperature of reaction is 70～80 ℃; Reaction times is 2～4 hours, makes the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group;
Step 2: preparation watersoluble cation fluorine-silicon polyurethane emulsion: the partially end-blocked fluorine-silicon polyurethane prepolymer that contains hydrophilic group that step 1 is obtained is cooled to 25～40 ℃; Add acidizing reagent; Regulation system pH value is 5～6, and back adding temperature is 20～40 ℃ a deionized water, and wherein the mass ratio of acidifying fluorine-silicon polyurethane prepolymer and deionized water is 1:1.5～4; Under agitation in water, disperse; Distillation desolventizes, and makes the watersoluble cation fluorine-silicon polyurethane emulsion, i.e. the watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent.
8. the preparation method of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 7 is characterized in that: the POLYMETHYLENE POLYPHENYLISOCYANATE in the said step 1 is the polymer of aliphatic polyisocyante, aromatic polyisocyanate or these POLYMETHYLENE POLYPHENYLISOCYANATE; Aliphatic polyisocyante is a hexamethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tetramethylene diisocyanate (TMXDI); Aromatic polyisocyanate is tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI).
9. the preparation method of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 8 is characterized in that: in the said step 1,
Described dihydroxyl silicone oil is that molecular weight is the dihydroxyl silicone oil of 1000-4000;
Described diluting solvent is acetone, butanone, ETHYLE ACETATE or THF;
Described perfluoroalkyl alcohol end-capping reagent is perfluor alkyl ethide hexanol or perfluor alkyl ethide octanol;
Described catalyzer is dibutyl tin laurate, cobalt naphthenate, stannous octoate, zinc naphthenate, lead octoate 36, phthalic acid lead or zinc octoate.
10. the preparation method of watersoluble cation fluorine-silicon polyurethane type leather water-proof fatting agent as claimed in claim 9 is characterized in that: the acidizing reagent in the said step 2 is hydrochloric acid, sulfuric acid or Glacial acetic acid min. 99.5.
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| CN101696457B (en) * | 2009-10-21 | 2012-10-03 | 陕西科技大学 | Organic long-chain fluorine-alcohol modified ASA leather waterproof fat liquoring agent and preparation method thereof |
| CN102504193A (en) * | 2011-11-01 | 2012-06-20 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for fluorine-containing enclosed polyurethane crosslinking agent |
| CN102702465B (en) * | 2012-06-09 | 2014-04-02 | 东华大学 | Preparation method for silicofluoride-contained polyurethane water repellent finishing agent |
| CN102863904B (en) * | 2012-09-18 | 2014-04-02 | 江苏雪豹日化有限公司 | Moldproof softening and brightening agent for cleaning leather and preparation method thereof |
| CN103030774A (en) * | 2012-12-07 | 2013-04-10 | 青岛文创科技有限公司 | Preparation method of organic silicon modified cationic waterborne polyurethane |
| CN103059797B (en) * | 2012-12-31 | 2014-10-22 | 东莞市粤泰高分子材料有限公司 | Two-component waterborne binding agent with low-surface energy material and preparation method thereof |
| CN105330813B (en) * | 2015-11-03 | 2017-10-20 | 淮安凯悦科技开发有限公司 | A kind of synthetic method of process hides organic silicon modified aqueous polyurethane |
| CN109385199A (en) * | 2018-10-22 | 2019-02-26 | 陕西科技大学 | A kind of preparation method of cation end fluoroalkyl hyper branched polyurethane leather coating agent |
| CN110128616A (en) * | 2019-05-27 | 2019-08-16 | 嘉兴禾大科技有限公司 | A kind of fluorine silicon is total to the preparation method of modified aqueous polyurethane |
| CN114106942B (en) * | 2020-08-31 | 2024-06-25 | 万华化学集团股份有限公司 | Leather microemulsion cleaning agent composition containing aqueous polyurethane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068342A (en) * | 1991-07-08 | 1993-01-27 | 江苏化工学院 | Preparation process of cation-type water-thinned polyurethane for tanning |
| CN101157750A (en) * | 2007-10-19 | 2008-04-09 | 东华大学 | Fluorine-containing polyether graft modified aqueous polyurethane and preparation and application thereof |
-
2009
- 2009-03-11 CN CN2009100214885A patent/CN101509047B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1068342A (en) * | 1991-07-08 | 1993-01-27 | 江苏化工学院 | Preparation process of cation-type water-thinned polyurethane for tanning |
| CN101157750A (en) * | 2007-10-19 | 2008-04-09 | 东华大学 | Fluorine-containing polyether graft modified aqueous polyurethane and preparation and application thereof |
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