CN101435159B - Cation type aqueous full fluorine polyurethane textile finishing agent and preparing method thereof - Google Patents
Cation type aqueous full fluorine polyurethane textile finishing agent and preparing method thereof Download PDFInfo
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Abstract
The invention belongs to the filed of fine chemicals and preparation technology thereof, more particularly relates to a cationoid aqueous perfluorinated polyurethane textile finishing agent and a preparation method thereof. The invention aims at overcoming the problems in the prior art that product stability is poor, the combination between the product and fiber textile with negative charge is poorer and the washability of the textile is poorer, simultaneously overcoming the problem of environment pollution existing in the preparation technology. The aim of the invention is realized as follows: the cationoid aqueous perfluorinated polyurethane textile finishing agent is prepared by the following method which sequentially comprises the following steps of: (1) preparing a tertiary amine type polyurethane prepolymer containing hydrophilic group; (2) preparing perfluorinated alkyl end capping polyurethane; and (3) preparing perfluorinated alkyl end capping quaternary ammonium salt type cation aqueous polyurethane. The invention has the advantages of good water proof property, good stability, good hydrophobic and oleophobic property and environment-friendly and simple and convenient preparation technology.
Description
Technical field:
The invention belongs to fine chemicals and preparing technical field thereof, relate in particular to a kind of cation type aqueous full fluorine polyurethane textile finishing agent and preparation method thereof.
Background technology:
Fluorine-containing textile finishing agent is the outstanding fabric finishing agent of generally acknowledging in the world, comparing with traditional common finishing agent in each side such as hydrophobic and lyophobic property, soil resistance, resistance to water, rub resistance, corrosion resistances all has remarkable advantages, have development prospect and promotional value, attracted attention by common people.
Fluorochemical urethane is a kind of novel fabric finishing agent functional material, it be by various means of different with fluorine element modify, modification preparation comes.On the polyurethane molecular chain, introduce full-fluorine group, not only kept the original characteristic of polyurethane-type fabric finishing agent, and make solvent resistance, resistance to water, oil resistivity and the pollution resistance of its excellence that has, be one of approach that improves polyurethane-type fabric finishing agent performance.
Common several fluorine modifications, modification polyurethane loomage finishing agent comprise following several: by the modification of mechanical-physical blending method, its principle is to use forces the method for blend that some fluoropolymers and polyurethane are carried out physical blending and introduce fluorine (1).But have consistency problem usually, because fluoropolymer and polyurethane solubility parameter differ too big, the fluorochemical urethane globality of gained is bad.(2) fluoro-acrylate monomer is introduced method, and its principle is to utilize polyurethane macromolecular monomer and fluorinated acrylate monomer or fluorinated monomer monomer and mixture of vinyl monomer grafting, copolymerization introducing fluorine.But the course of reaction complexity that this fluorinated acrylate and polyurethane macromolecular monomer copolymerization method relate to reacts wayward, and conversion ratio is not high.(3) flexible polyurethane section, hard section introducing method, soft section is introduced principle is to utilize PFPE, half perfluoroalkyl polyether, full polyurethane or above fluorine-containing polyalcohol and common polyol blends to introduce fluorine as the flexible polyurethane section; It is to utilize to fluoridize polyisocyanates, micromolecule glycol/diamines that hard section is introduced a ratio juris, or above-mentioned fluoride and common isocyanates, micromolecule glycol/two amine blends are as hard section introducing fluorine.Though this method has solved the problem of compatibility, reaction controllability and conversion ratio among preceding two kinds of preparation methods, but prior preparation method generally needs high speed shear or adds a large amount of solvents and could disperse in water, has product stability difference and environmental pollution problems; And the fabric finishing agent neutral of preparing or electronegative, be unfavorable for combining with electronegative fabric fibre, be unfavorable for improving the washability of fabric.
Summary of the invention:
The objective of the invention is to provide a kind of cation type aqueous full fluorine polyurethane textile finishing agent and preparation method thereof, with overcome the product stability that prior art exists poor, combine problem relatively poor and that the fabric washability is relatively poor with electronegative fabric fibre, also to overcome the problem of environment pollution caused that preparation technology exists simultaneously.
Above-mentioned purpose of the present invention is achieved in that
A kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and described method comprises the steps: successively
Step 1: preparation contains the tertiary amine-type polyurethane prepolymer of hydrophilic group: made by polyisocyanates, polyalcohol, hydrophilic monomer chain extender and a little diluting solvent reaction, its weight ratio is respectively 1: 0.3～0.7: 0.03～0.07: 0.05～0.2, reaction condition is: reaction temperature is 50～90 ℃, reaction time is 1～5 hour, makes polyurethane prepolymer;
Step 2: preparation perfluoroalkyl blocked polyurethane: the perfluoroalkyl alcohol that will have 2～21 carbon atoms joins in the polyurethane prepolymer that step 1 obtains as end-capping reagent and little amount of catalyst, the weight ratio of perfluoroalkyl alcohol, catalyst and the polyisocyanates that adds is: 1.5～2.8: 0.001～0.005: 1, reaction temperature is 50～90 ℃, reaction time is 1～6 hour, isocyanate end to prepolymer is carried out end-blocking, makes perfluoroalkyl end-sealed type polyurethane;
Step 3: preparation perfluoroalkyl end-blocking quaternary ammonium salt cationic aqueous polyurethane: the weight ratio of ionization reagent and polyisocyanates is 0.02～0.09: 1, adding ionization reagent in the perfluoroalkyl end-sealed type polyurethane that step (2) obtains neutralizes, reaction temperature is 40～60 ℃, reaction time is 0.5～2 hour, makes cation type polyurethane; Adding acidizing reagent then in cation type polyurethane carries out acidifying and regulates after the pH value is 4～6.5, add deionized water, wherein the volume ratio of cation type aqueous full fluorine polyurethane and deionized water is 1: 1.5～9, under agitation in water, disperse, distillation desolventizes, and makes cation type aqueous full fluorine polyurethane textile finishing agent.
Polyisocyanates in the above-mentioned steps one is the compound that contains 2 isocyanate group at least, can be the polymer of aliphatic polyisocyante, aromatic polyisocyanate or these polyisocyanates.Aliphatic polyisocyante, particularly hexamethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tetramethylene diisocyanate (TMXDI); Aromatic polyisocyanate, particularly toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI);
Described polyalcohol is one or more the mixture in polyester polyol, polyether polyol, Merlon and the polycaprolactone.
Described hydrophilic monomer chain extender can be the tertiary amine-type polyhydric alcohol amine, can be triethanolamine, N methyldiethanol amine, N-isopropyl diethanol amine;
Described retarder thinner can be selected from acetone, butanone, ethyl acetate or oxolane.
End-capping reagent in the above-mentioned steps two is the perfluoroalkyl alcohol with 2～21 carbon atoms; Described catalyst is dibutyl tin laurate, cobalt naphthenate, stannous octoate, zinc naphthenate, lead octoate, phthalic acid lead or zinc octoate.
End-capping reagent in the above-mentioned steps two can be the mixed alcohol of any or they in perfluor alkyl ethide butanols, perfluor alkyl ethide hexanol, perfluor alkyl ethide octanol, the perfluor alkyl ethide decyl alcohol especially.
The carbon atom number of above-mentioned perfluoroalkyl alcohol is 3～12.
The carbon atom number of above-mentioned perfluoroalkyl alcohol is 4～10.Better effects if.
Above-mentioned steps three intermediate ion reagent can be dimethyl carbonate, ethylene dimethyl, dimethyl malenate, dimethyl succinate or dimethyl glutarate; Described acidizing reagent can be organic or inorganic acid, particularly hydrochloric acid, sulfuric acid or glacial acetic acid.
Such scheme also comprises the optimization step: cation type aqueous full fluorine polyurethane textile finishing agent and crosslinking agent and stannous octoate catalyst are mixed, wherein cation type aqueous full fluorine polyurethane textile finishing agent: crosslinking agent: the weight ratio of catalyst is 1: 0.05～0.3: 0.005～0.01.Better through the product property after this step.
Above-mentioned crosslinking agent can be selected from triethanolamine, diethanol amine, glycerine or trimethylolpropane.
A kind of preparation method of cation type aqueous full fluorine polyurethane textile finishing agent comprises the steps: successively
Step 1: preparation contains the tertiary amine-type polyurethane prepolymer of hydrophilic group: made by polyisocyanates, polyalcohol, hydrophilic monomer chain extender and a little diluting solvent reaction, its weight ratio is respectively 1: 0.3～0.7: 0.03～0.07: 0.05～0.2, reaction condition is: reaction temperature is 50～90 ℃, reaction time is 1～5 hour, makes polyurethane prepolymer;
Step 2: preparation perfluoroalkyl blocked polyurethane: the perfluoroalkyl alcohol that will have 2～21 carbon atoms joins in the polyurethane prepolymer that step 1 obtains as end-capping reagent and little amount of catalyst, the weight ratio of perfluoroalkyl alcohol, catalyst and the polyisocyanates that adds is: 1.5～2.8: 0.001～0.005: 1, reaction temperature is 50～90 ℃, reaction time is 1～6 hour, isocyanate end to prepolymer is carried out end-blocking, makes perfluoroalkyl end-sealed type polyurethane;
Step 3: preparation perfluoroalkyl end-blocking quaternary ammonium salt cationic aqueous polyurethane: the weight ratio of ionization reagent and polyisocyanates is 0.02～0.09: 1, adding ionization reagent in the perfluoroalkyl end-sealed type polyurethane that step (2) obtains neutralizes, reaction temperature is 40～60 ℃, reaction time is 0.5～2 hour, makes cation type polyurethane; Adding acidizing reagent then in cation type polyurethane carries out acidifying and regulates after the pH value is 4～6.5, add deionized water, wherein the volume ratio of cation type aqueous full fluorine polyurethane and deionized water is 1: 1.5～9, under agitation in water, disperse, distillation desolventizes, and makes cation type aqueous full fluorine polyurethane textile finishing agent.
The present invention adopts flexible polyurethane section, hard section introducing legal system to be equipped with the full fluorine polyurethane fabric finishing agent, but but the quaternary ammonium salt cationic group of introducing self-emulsifying in the preparation process, because it has good water-solubility and self-emulsifying, make the dispersion and stable in water easily of the big molecule of full fluorine polyurethane, form trickle emulsion, the fabric after the processing has good hand feeling and excellent sucting wet air permeability; And full fluorine polyurethane and the fiber binding ability of band cationic are strong, combine with fiber formation chemical bond easily and improve water-wash resistance.Can improve greatly like this by soft section, hard section and introduce the method that legal system is equipped with the fluorochemical urethane fabric finishing agent.Compared with prior art, the advantage of product of the present invention is:
(1) water-wash resistance is good: the big molecule of the final aqueous polyurethane that synthesizes has cationic, has increased the affinity of polyurethane macromolecular and base material, combines by force with electronegative fabric fibre, and the fabric water-wash resistance is largely increased.
(2) good stability: because product of the present invention has self emulsifiable quaternary ammonium salt group, the aqueous dispersion ability is strong, can form stable trickle emulsion, can give better sucting wet air permeability of fabric and pleasant softness after the arrangement.
(3) the hydrophobic and oil repellent performance is good: by the perfluoroalkyl end-blocking, make textile finshing agent have lower surface energy, increased its hydrophobic and lyophobic property; In the aqueous dispersion process, do not need additionally to add emulsifying agent, eliminated the influence of small-molecular emulsifier, improved the effect of product more result of use.
(4) preparation technology's environmental protection: in the process of preparation cation type aqueous full fluorine polyurethane textile finishing agent, do not contain or only contain a spot of solvent, cation type aqueous full fluorine polyurethane textile finishing agent is a main dispersing medium with water in use, has reduced pollution and infringement to environment and operating personnel.
The specific embodiment:
Below in conjunction with embodiment the present invention is done and to explain.
Embodiment 1, and a kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: polyurethane preformed polymer: with 90g hexamethylene diisocyanate (HDI), 33g polypropylene glycol (molecular weight 2000, dry) and the 5g triethanolamine put in the reactor successively, after feeding the nitrogen deoxygenation, stir, add acetone solvent 10g, 60 ℃ of reactions of constant temperature 2 hours form polyurethane prepolymer.
Step 2: preparation perfluoroalkyl blocked polyurethane: polyurethane prepolymer is warming up to 70 ℃, add 150g perfluor alkyl ethide butanols and carry out end capping reaction, and add the 0.4g dibutyltin dilaurate catalyst, and reacted 3 hours, form perfluoroalkyl end-sealed type polyurethane.
Step 3: be cooled to 50 ℃, add the ionization of 4.5g dimethyl carbonate, the reaction time is 1 hour, makes cationic polyurethane; Add the glacial acetic acid acidifying again, regulation system pH value is 6.5, under agitation, is that 90 ℃ 879g deionized water joins in the system and stirs with temperature, and acetone is removed out in distillation at last, obtains total solids content and be 25% white emulsion.
Embodiment 2, and a kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: polyurethane preformed polymer: with 120g isophorone diisocyanate (IPDI), 40g PTMG (molecular weight 2000, dry) and 8gN-isopropyl diethanol amine put in the reactor successively, after feeding the nitrogen deoxygenation, stir, add butanone solvent 10g, 65 ℃ of reactions of constant temperature 3 hours form polyurethane prepolymer.
Step 2: preparation perfluoroalkyl blocked polyurethane: polyurethane prepolymer is warming up to 75 ℃, adds 170g perfluor alkyl ethide hexanol and carries out end capping reaction, and add the 0.4g stannous octoate catalyst, reacts 2.5 hours, forms perfluoroalkyl end-sealed type polyurethane.
Step 3: be cooled to 45 ℃, add the ionization of 6.5g dimethyl succinate, the reaction time is 1.5 hours, makes cationic polyurethane; Add sulfuric acid acidation again, regulation system pH value is 5.5, under agitation, is that 70 ℃ 805g deionized water joins in the system and stirs with temperature, and butanone is removed out in distillation at last, obtains total solids content and be 30% white emulsion.
Embodiment 3, and a kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: polyurethane preformed polymer: with 133g methyl diphenylene diisocyanate (MDI), 65g polycaprolactone (molecular weight 4000, dry) and the 6gN-methyl diethanolamine put in the reactor successively, after feeding the nitrogen deoxygenation, stir, add tetrahydrofuran solvent 15g, 70 ℃ of reactions of constant temperature 5 hours form polyurethane prepolymer.
Step 2: preparation perfluoroalkyl blocked polyurethane: polyurethane prepolymer is warming up to 75 ℃, adds 216g perfluor alkyl ethide octanol and carries out end capping reaction, and add 0.5g zinc naphthenate catalyst, reacts 3.5 hours, forms perfluoroalkyl end-sealed type polyurethane.
Step 3: be cooled to 55 ℃, add the ionization of 6.5g dimethyl malenate, the reaction time is 1.5 hours, makes cationic polyurethane; Add hcl acidifying again, regulation system pH value is 5.5, under agitation, is that 50 ℃ 781g deionized water joins in the system and stirs with temperature, and tetrahydrofuran solvent is removed out in distillation at last, obtains total solids content and be 35% white emulsion.
Embodiment 4, and a kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: polyurethane preformed polymer: with 93g toluene di-isocyanate(TDI) (TDI), 65g Merlon (molecular weight 4000, dry) and the 6gN-methyl diethanolamine put in the reactor successively, after feeding the nitrogen deoxygenation, stir, add ethyl acetate solvent 17g, 90 ℃ of reactions of constant temperature 1 hour form polyurethane prepolymer.
Step 2: preparation perfluoroalkyl blocked polyurethane: polyurethane prepolymer is warming up to 60 ℃, adds 250g perfluor alkyl ethide decyl alcohol and carries out end capping reaction, and add 0.3g zinc naphthenate catalyst, reacts 1 hour, forms perfluoroalkyl end-sealed type polyurethane.
Step 3: be cooled to 55 ℃, add the ionization of 4.5g dimethyl carbonate, the reaction time is 1 hour, makes cationic polyurethane; Add the glacial acetic acid acidifying again, regulation system pH value is 4.5, under agitation, is that 40 ℃ 2932g deionized water joins in the system and stirs with temperature, and ethyl acetate solvent is removed out in distillation at last, obtains total solids content and be 10% white emulsion.
Embodiment 5, and a kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: polyurethane preformed polymer: with 93g toluene di-isocyanate(TDI) (TDI), 17g Merlon (molecular weight 4000, dry), 24g PTMG (molecular weight 2000, dry) and the 6gN-methyl diethanolamine put in the reactor successively, after feeding the nitrogen deoxygenation, stir, add tetrahydrofuran solvent 15g, 70 ℃ of reactions of constant temperature 4 hours form polyurethane prepolymer.
Step 2: preparation perfluoroalkyl blocked polyurethane: polyurethane prepolymer is warming up to 80 ℃, add 129.6g perfluor alkyl ethide decyl alcohol and 92g perfluor alkyl ethide octanol and carry out end capping reaction, and add 0.3g lead octoate catalyst, and reacted 4.5 hours, form perfluoroalkyl end-sealed type polyurethane.
Step 3: be cooled to 55 ℃, add the ionization of 4.5g dimethyl carbonate, the reaction time is 1 hour, makes cationic polyurethane; Add the glacial acetic acid acidifying again, regulation system pH value is 4, under agitation, is that 30 ℃ 550g deionized water joins in the system and stirs with temperature, and tetrahydrofuran solvent is removed out in distillation at last, obtains total solids content and be 40% white emulsion.
Embodiment 6, and a kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: polyurethane preformed polymer: with 120g isophorone diisocyanate (IPDI), 28g PTMG (molecular weight 2000, dry), 12g polycaprolactone glycol (molecular weight 2000, dry) and 8gN-isopropyl diethanol amine put in the reactor successively, after feeding the nitrogen deoxygenation, stir, add butanone solvent 15g, 50 ℃ of reactions of constant temperature 4.5 hours form polyurethane prepolymer.
Step 2: preparation perfluoroalkyl blocked polyurethane: polyurethane prepolymer is warming up to 50 ℃, adds 250g perfluor alkyl ethide octanol and carries out end capping reaction, and add the plumbous catalyst of 0.3g phthalic acid, reacts 6 hours, forms perfluoroalkyl end-sealed type polyurethane.
Step 3: be cooled to 55 ℃, add the ionization of 4.5g dimethyl carbonate, the reaction time is 1 hour, makes cationic polyurethane; Add the glacial acetic acid acidifying again, regulation system pH value is 4.5, under agitation, is that 40 ℃ 2932g deionized water joins in the system and stirs with temperature, and butanone solvent is removed out in distillation at last, obtains total solids content and be 15% white emulsion.
Embodiment 7, and a kind of cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and this preparation method comprises the steps: successively
Step 1: polyurethane preformed polymer: with 120g isophorone diisocyanate (IPDI), 40g PTMG (molecular weight 2000, dry) and 8gN-isopropyl diethanol amine put in the reactor successively, after feeding the nitrogen deoxygenation, stir, add acetone solvent 10g, 75 ℃ of reactions of constant temperature 2 hours form polyurethane prepolymer.
Step 2: preparation perfluoroalkyl blocked polyurethane: polyurethane prepolymer is warming up to 90 ℃, add 194g perfluor alkyl ethide octanol and 30g perfluor alkyl ethide butanols and carry out end capping reaction, and add 0.3g zinc octoate catalyst, and reacted 1 hour, form perfluoroalkyl end-sealed type polyurethane.
Step 3: be cooled to 55 ℃, add the ionization of 4.5g dimethyl carbonate, the reaction time is 1 hour, makes cationic polyurethane; Add sulfuric acid acidation again, regulation system pH value is 4.5, under agitation, is that 45 ℃ 1190g deionized water joins in the system and stirs with temperature, and acetone solvent is removed out in distillation at last, obtains total solids content and be 25% white emulsion.
Embodiment 8: the solid content of getting embodiment 3 is that 35% cation type aqueous full fluorine polyurethane textile finishing agent is optimized processing, promptly is by weight to add triethanolamine crosslinking agent and stannous octoate catalyst at 1: 0.05: 0.005, mixes to get final product.Product property is better than the product of embodiment 3.
Embodiment 9: the solid content of getting embodiment 6 is that 15% cation type aqueous full fluorine polyurethane textile finishing agent is optimized processing, promptly is by weight to add triethanolamine crosslinking agent and stannous octoate catalyst at 1: 0.3: 0.008, mixes to get final product.Product property is better than the product of embodiment 6.
But product of the present invention is self-emulsifying and the aqueous polyurethane that contains the perfluoroalkyl closed-end structure, and it is a cation emulsion, and it is controlled that its emulsion particle is distributed in 50～200nm, and the solid content of polyurethane is 10～40%.
During use, can be directly dilute with the deionized water of 60～120 times of weight.
For example:
The solid content of getting embodiment 1 is 25% cation type aqueous full fluorine polyurethane textile finishing agent, with the deionized water dilution of 80 times of weight, will treat that finish fabric is dipped in the dressing liquid, soaks two mutual aid system devised for poor peasants skill with two and puts in order.
Get the textile finshing agent of the optimization process of embodiment 8,, will treat that finish fabric is dipped in the dressing liquid, soak two mutual aid system devised for poor peasants skill with two and put in order with 100 times deionized water dilution.
Claims (8)
1. a cation type aqueous full fluorine polyurethane textile finishing agent is prepared by following method, and described method comprises the steps: successively
Step 1: preparation contains the tertiary amine-type polyurethane prepolymer of hydrophilic group: made by polyisocyanates, polyalcohol, hydrophilic monomer chain extender and a little diluting solvent reaction, its weight ratio is respectively 1: 0.3～0.7: 0.03～0.07: 0.05～0.2, reaction condition is: reaction temperature is 50～90 ℃, reaction time is 1～5 hour, makes polyurethane prepolymer;
Step 2: preparation perfluoroalkyl blocked polyurethane: the perfluoroalkyl alcohol that will have 2～21 carbon atoms joins in the polyurethane prepolymer that step 1 obtains as end-capping reagent and little amount of catalyst, the weight ratio of perfluoroalkyl alcohol, catalyst and the polyisocyanates that adds is: 1.5～2.8: 0.001～0.005: 1, reaction temperature is 50～90 ℃, reaction time is 1～6 hour, isocyanate end to prepolymer is carried out end-blocking, makes perfluoroalkyl end-sealed type polyurethane;
Step 3: preparation perfluoroalkyl end-blocking quaternary ammonium salt cationic aqueous polyurethane: the weight ratio of ionization reagent and polyisocyanates is 0.02～0.09: 1, adding ionization reagent in the perfluoroalkyl end-sealed type polyurethane that step 2 obtains neutralizes, reaction temperature is 40～60 ℃, reaction time is 0.5～2 hour, makes cation type polyurethane; Adding acidizing reagent then in cation type polyurethane carries out acidifying and regulates after the pH value is 4～6.5, add deionized water, wherein the volume ratio of cation type aqueous full fluorine polyurethane and deionized water is 1: 1.5～9, under agitation in water, disperse, distillation desolventizes, and makes cation type aqueous full fluorine polyurethane textile finishing agent.
2. a kind of cation type aqueous full fluorine polyurethane textile finishing agent as claimed in claim 1 is characterized in that: the polyisocyanates in the described step 1 is the polymer of aliphatic polyisocyante, aromatic polyisocyanate or these polyisocyanates; Aliphatic polyisocyante is a hexamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or tetramethylene diisocyanate; Aromatic polyisocyanate is toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate;
Described polyalcohol is a kind of in polyester polyol, the polyether polyol or both mixtures;
Described hydrophilic monomer chain extender is triethanolamine, N methyldiethanol amine or N-isopropyl diethanol amine;
Described retarder thinner is selected from acetone, butanone, ethyl acetate or oxolane.
3. a kind of cation type aqueous full fluorine polyurethane textile finishing agent as claimed in claim 1 or 2 is characterized in that: the end-capping reagent in the described step 2 is the perfluoroalkyl alcohol with 2～21 carbon atoms; Described catalyst is dibutyl tin laurate, cobalt naphthenate, stannous octoate, zinc naphthenate, lead octoate, phthalic acid lead or zinc octoate.
4. a kind of cation type aqueous full fluorine polyurethane textile finishing agent as claimed in claim 3 is characterized in that: the carbon atom number of described perfluoroalkyl alcohol is 3～12.
5. a kind of cation type aqueous full fluorine polyurethane textile finishing agent as claimed in claim 4 is characterized in that: described step 3 intermediate ion reagent is dimethyl carbonate, ethylene dimethyl, dimethyl malenate, dimethyl succinate or dimethyl glutarate; Described acidizing reagent is hydrochloric acid, sulfuric acid or glacial acetic acid.
6. a kind of cation type aqueous full fluorine polyurethane textile finishing agent as claimed in claim 5, it is characterized in that: described scheme also comprises the optimization step: cation type aqueous full fluorine polyurethane textile finishing agent and crosslinking agent and stannous octoate catalyst are mixed, wherein cation type aqueous full fluorine polyurethane textile finishing agent: crosslinking agent: the weight ratio of catalyst is 1: 0.05～0.3: 0.005～0.01.
7. a kind of cation type aqueous full fluorine polyurethane textile finishing agent as claimed in claim 6 is characterized in that: described crosslinking agent is selected from triethanolamine, diethanol amine, glycerine and trimethylolpropane.
8. the preparation method of a kind of cation type aqueous full fluorine polyurethane textile finishing agent as claimed in claim 1 comprises the steps: successively
Step 1: preparation contains the tertiary amine-type polyurethane prepolymer of hydrophilic group: made by polyisocyanates, polyalcohol, hydrophilic monomer chain extender and a little diluting solvent reaction, its weight ratio is respectively 1: 0.3～0.7: 0.03～0.07: 0.05～0.2, reaction condition is: reaction temperature is 50～90 ℃, reaction time is 1～5 hour, makes polyurethane prepolymer;
Step 2: preparation perfluoroalkyl blocked polyurethane: the perfluoroalkyl alcohol that will have 2～21 carbon atoms joins in the polyurethane prepolymer that step 1 obtains as end-capping reagent and little amount of catalyst, the weight ratio of perfluoroalkyl alcohol, catalyst and the polyisocyanates that adds is: 1.5～2.8: 0.001～0.005: 1, reaction temperature is 50～90 ℃, reaction time is 1～6 hour, isocyanate end to prepolymer is carried out end-blocking, makes perfluoroalkyl end-sealed type polyurethane;
Step 3: preparation perfluoroalkyl end-blocking quaternary ammonium salt cationic aqueous polyurethane: the weight ratio of ionization reagent and polyisocyanates is 0.02～0.09: 1, adding ionization reagent in the perfluoroalkyl end-sealed type polyurethane that step 2 obtains neutralizes, reaction temperature is 40～60 ℃, reaction time is 0.5～2 hour, makes cation type polyurethane; Adding acidizing reagent then in cation type polyurethane carries out acidifying and regulates after the pH value is 4～6.5, add deionized water, wherein the volume ratio of cation type aqueous full fluorine polyurethane and deionized water is 1: 1.5～9, under agitation in water, disperse, distillation desolventizes, and makes cation type aqueous full fluorine polyurethane textile finishing agent.
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| CN102010584B (en) * | 2010-09-21 | 2012-04-25 | 盐城东邦化工有限公司 | Normal-temperature self-crosslinking fluorine-containing aqueous PU dispersion liquid and preparation method and application 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 |
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| CN102417575A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of fluorine-containing waterborne polyurethane water-repellent and oil-repellent finishing agent |
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| CN101435159A (en) | 2009-05-20 |
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