CN105461862A - One-component water-based cationic polyurethane-fluorinated acrylate resin and preparation method thereof - Google Patents
One-component water-based cationic polyurethane-fluorinated acrylate resin and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
- C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention relates to one-component water-based cationic polyurethane-fluorinated acrylate resin and a preparation method thereof. The preparation process comprises three main steps as follows: (1), double-bond-containing polyhydric alcohol and polybasic acid have condensation polymerization reaction to synthesize unsaturated hydroxyl-terminated polyester; (2), diol, butanone, a capping agent and the like are added to the unsaturated hydroxyl-terminated polyester for reaction, finally, an acidic neutralizing agent is added for neutralization, and unsaturated water-based cationic polyurethane is prepared; (3), fluorinated acrylate monomers and acrylate monomers are added to water-based cationic polyurethane containing unsaturated double bonds, and the one-component water-based cationic polyurethane-fluorinated acrylate resin is synthesized with a soap-free polymerization method. The water-based polyurethane resin and the fluorinated acrylate resin are mutually complemented, and the acquired resin has wide application in the fields of leather, water paint, an aqueous binder, a fabric and textile finishing agent, papermaking and the like.
Description
Technical field:
The present invention relates to a kind of single-component water-based cation polyurethane-perfluoroalkyl acrylate resin for fields such as leather, water-borne coatings, aqueous binder, fabric weaving finishing composition, papermaking and preparation method thereof.The present invention by introducing unsaturated double-bond on polyester, one-step synthesis of going forward side by side contains the waterborne cation polyurethane of unsaturated double-bond, last and acrylate containing fluorine monomer copolymerization, has synthesized a kind of single-component water-based cation polyurethane-perfluoroalkyl acrylate resin with nucleocapsid structure.
Background technology:
Aqueous polyurethane is a kind of environmentally friendly macromolecular material, possesses excellent cohesiveness, elasticity, winter hardiness, high gloss and soft durometer and varies with temperature the advantages such as little, have good environment friendly and versatility.Aqueous polyurethane can be divided into single-component and two component two class by type of service, and the aqueous polyurethane that can obtain required use properties without the need to linking agent is called monocomponent waterborne polyurethane.Be divided into ionic and non-ionic type according to whether dispersed particle is charged, and ionic aqueous polyurethane can be divided into anionic, cationic and amphoteric ion type according to the charged character in polyurethane backbone.At present, be more common in anion aqueous polyurethane about aqueous polyurethane research report, and cationic less.Cation-type water-thinned polyurethane generally refers to the aqueous polyurethane containing ammonium ion (being generally quaternary ammonium ion) or sulfonium cation on main chain or side chain, and most situation is quaternary ammonium cation.Due on the molecular chain of cation-type water-thinned polyurethane with positive electricity, it has good wetting property to hydrophobic polyester, fabric fibre, simultaneously insensitive to water hardness, can use in acid condition, therefore it is with a wide range of applications in fields such as weaving, leather, woodwork coating and papermaking.In addition, when cation aqueous polyurethane is applied on timber, can have an effect with coloring matters such as Weibull, stoping it to move, is the important filmogen of wooden ware sealing priming paint.But cation aqueous polyurethane in preparation process by the operation more complicated of performed polymer quaternization, cost is higher, and the positively charged ion product of preparation stores instability sometimes, there is the shortcomings such as poor water resistance, gloss is low, poor solvent resistance, rate of drying are slow in addition.
Polyacrylate(s) macromolecular material has the plurality of advantages such as higher, ageing-resistant, the weather-proof and water-tolerant of physical strength, but it exists the shortcoming of hot sticky cold crisp.Can see and show that this bi-material exists good complementarity.Fluoropolymer is due to the property (as low polarity and high electronegativity) of fluorine atom, and it has excellent surface property, resistance to medium, thermotolerance and weathering resistance.Thus waterborne cation polyurethane resin and fluoroacrylic resin are passed through the method compound of chemical graft, respective shortcoming can be overcome, accomplish to maximize favourable factors and minimize unfavourable ones, particularly make film performance be significantly improved.
Summary of the invention:
The object of the invention is to synthesize a kind of excellent performance and widely used single-component water-based cation polyurethane-perfluoroalkyl acrylate resin.For the shortcoming of the above waterborne cation polyurethane resin, by perfluoroalkyl acrylate resin, modification is carried out to waterborne cation polyurethane resin, introduce the performance that it is good, avoid the distinct disadvantage such as waterborne cation polyurethane resin poor water resistance, gloss is low.Synthesize the single-component water-based cation polyurethane-perfluoroalkyl acrylate resin obtained and there is remarkable low-temperature impact resistance, chemical stability, elasticity, snappiness, weathering resistance and water tolerance, and physical strength is high, thus expand the Application Areas of waterborne cation polyurethane resin.
The present invention is based on waterborne cation polyurethane, utilize the characteristic of aqueous polyurethane cats product, when carrying out perfluoroalkyl acrylate class monomer polymerization, need not additional emulsifying agent, adopt the method for soap-free polymerization to make perfluoroalkyl acrylate class monomer carry out copolymerization well in urethane inside.Synthesize a kind of single-component water-based cation polyurethane-perfluoroalkyl acrylate resin with nucleocapsid structure.Invention not only avoids and use poisonous fluorine-containing emulsifier, and reaction conditions is gentle, owing to not having emulsifying agent in product, resin property also improves a lot.
Single-component water-based cation polyurethane-perfluoroalkyl acrylate resin of the present invention, the main raw material of its synthesis is:
A () at least comprises a kind of unsaturated waterborne cation polyurethane;
B () at least comprises one (fluorine) Acrylic Acid Monomer;
C () at least comprises a kind of initiator, its consumption accounts for 0.1% ~ 5.0% of (fluorine) Acrylic Acid Monomer quality.
Unsaturated waterborne cation polyurethane of the present invention, synthesis material and raw materials quality per-cent are: unsaturated hydroxyl telechelic polyester 4.5% ~ 7%, dibasic alcohol 2.5% ~ 4%, butanone 9.5% ~ 12%, isocyanic ester 17.5% ~ 19%, hydrophilic monomer 2.5% ~ 3.5%, catalyzer 0.1%, end-capping reagent 2.5% ~ 4%, acetic acid 1.3% ~ 1.7%, deionized water 53.5% ~ 55.5%.Dibasic alcohol recited above comprises following: 1,4-butyleneglycol, ethylene glycol, 2-ethyl-2-butyl 1, ammediol, 1,6-hexylene glycol, 2,2,4-trimethylammoniums-1,3-pentanediol, 2-methyl isophthalic acid, ammediol, glycol ether, ethohexadiol, neopentyl glycol, 1,3 propylene glycol, 1,4 cyclohexane dimethanol etc.This kind of raw material can be used alone also can be used in combination, wherein 2-ethyl-2-butyl 1,3-PD, 1,4-cyclohexanedimethanols etc. are owing to having very long carbochain, therefore there is good water tolerance, but this type of dibasic alcohol price is higher, preferably with the lower dibasic alcohol of other prices with the use of.Hydrophilic monomer comprises: at least one such as diethanolamine, trolamine, N methyldiethanol amine (N-MDEA), N-ethyldiethanolamine (N-EDEA), N-propyl group diethanolamine (N-PDEA), N butyl diethanol amine (N-BDEA), tertiarybutyldiethanolamine (t-BDEA), dimethylethanolamine, two (2-hydroxyethyl) aniline (BHBA), two (2-hydroxypropyl) aniline (BHPA), preferentially selects N methyldiethanol amine (N-MDEA).Isocyanate-monomer comprises: tolylene diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, two cyclohexyl methane diisocyanates, Methylcyclohexyl diisocyanate, ditan-4,4-vulcabond, preferentially select tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or its mixture.End-capping reagent is the acrylate monomer containing hydroxy functional group: at least one such as (methyl) senecioate-hydroxyl ethyl ester, (methyl) senecioate-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy-propyl, methacrylic acid-β-hydroxypropyl acrylate, preferable methyl senecioate-hydroxyl ethyl ester.
Unsaturated hydroxyl telechelic polyester described in the present invention, synthesis material and raw materials quality per-cent are: maleic anhydride 6% ~ 10%, dibasic alcohol 32% ~ 44%, diprotic acid 30% ~ 41%, TriMethylolPropane(TMP) 9% ~ 21%, stopper 0.5%.Polyvalent alcohol is: 1,4-butyleneglycol, ethylene glycol, 2-ethyl-2-butyl 1, ammediol, 1,6-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, 2-methyl isophthalic acid, ammediol, glycol ether, ethohexadiol, neopentyl glycol, 1,3 propylene glycol, 1,4-cyclohexanedimethanol, TriMethylolPropane(TMP), TriMethylolPropane(TMP) mono allyl ether etc., at least containing 2 kinds of polyvalent alcohols.Wherein, TriMethylolPropane(TMP) is with three primary hydroxyls, and the space steric effect of the ethyl on it can shield ester group, improves hydrolytic resistance, and be commonly used to introduce branch, neopentyl glycol is also well used due to same characteristic.Diprotic acid is: maleic anhydride, 1,4 cyclohexanedicarboxylic acid, FUMARIC ACID TECH GRADE, phthalic anhydride, m-phthalic acid, terephthalic acid, tetrahydrophthalic anhydride, succinic acid, pentanedioic acid, oxalic acid, fumaric acid, dimeracid, HHPA and hexanodioic acid.Phthalic anhydride Main Function is used to reduce costs; The unsaturated dibasic acids such as maleic anhydride are mainly used for introducing unsaturated double-bond; The diprotic acid such as m-phthalic acid are mainly used for improving hydrolytic resistance; Above-mentioned diprotic acid can be used in combination.
Single-component water-based cation polyurethane-perfluoroalkyl acrylate resin of the present invention, synthesis material and raw materials quality per-cent are: waterborne cation polyurethane resin, acrylate monomer, fluoroacrylate monomers, vinylsiloxane, initiator and deionized water etc. adopt the method for emulsifier-free emulsion polymerization to synthesize.Acrylate monomer is: one or more in (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, cyclohexyl acrylate, n-propyl, Isooctyl acrylate monomer, (methyl) lauryl acrylate, vinylbenzene, (methyl) vinylformic acid octadecyl, lauryl methacrylate, phenyl methacrylate, benzyl methacrylate, acrylamide.Fluoroacrylate monomers is: (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, (methyl) perfluoroethyl octyl group ethyl ester, perfluoroethyl is base ethyl ester, (methyl) vinylformic acid tetrafluoro propyl ester, perfluoro capryl propyl acrylate, (methyl) dodecafluorhe-ptylacrylate, N-hydroxyethyl perfluoro-octanoyl amine acrylate, methacrylic acid trifluoroacetyl 2-ethoxyethyl acetate, trifluoromethyl acrylate, (methyl) vinylformic acid octafluoro pentyl ester, perfluoroalkyl acrylic methyl esters, N-propyl group perfluoro capryl (alkylsulfonyl) amido ethyl propenoate, 2-(N-methyl perfluoro octyl alkylsulfonyl) ethyl propylene acid esters, one or more in perfluoroalkyl methacrylate, its consumption is the 2%-40% of acrylic ester monomer quality.Vinylsiloxane (N) is: vinyl trimethoxy (oxyethyl group) silane, propenyl Trimethoxy silane, γ-methacryloxy Trimethoxy silane, 3-methacryloxypropyl trimethoxy silane, triple phenoxyl vinyl silanes, vinyl three (2-methoxy ethoxy) silane, the rare acryloxypropylethoxysilane Trimethoxy silane of γ-methyl-prop, vinyl silane triisopropoxide, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, one or more in vinyl trichloro silane, its consumption is the 1%-20% of acrylic ester monomer quality.Initiator is: one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, Potassium Persulphate, tertbutyl peroxide, ammonium persulphate, ferrous salt, isopropyl benzene hydroperoxide, sodium bisulfite, Sulfothiorine, rongalite.Preferentially select Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, its consumption is 0.1% ~ 5% of acrylic ester monomer quality.
The preparation method of single-component water-based cation polyurethane-perfluoroalkyl acrylate resin of the present invention, its technique comprises:
1) synthesis of unsaturated hydroxyl telechelic polyester
Under the protection of nitrogen, by the polyvalent alcohol of component design ratio, polyprotonic acid, solvent xylene, stopper etc. add and thermometer are housed, water trap and prolong, with in the four mouthfuls of reactors stirred.Be heated in prolong, start there is backflow with electric mantle, and when starting there is the globule in water trap, insulation reaction 1 hour, then be slowly warming up to 210 DEG C (heating-up time is 5 hours),, start to measure acid number after 0.5 hour 210 DEG C of insulation reaction, when acid number is down to 5mgKOH/g resin, dimethylbenzene is deviate from about 100 DEG C vacuum, after having reacted, vacuum decompression dry 1-2 hour, vacuum tightness >=0.045Kpa, temperature is 50-80 DEG C, obtains unsaturated hydroxyl telechelic polyester.
2) synthesis of unsaturated waterborne cation polyurethane
By unsaturated hydroxyl telechelic polyester, small molecules dibasic alcohol adds in the reactor that agitator, dropping funnel, thermometer, prolong are housed, and under 110 DEG C of conditions, first vacuum is drawn water 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 60 DEG C, add butanone, pass into nitrogen protection, start to drip isocyanic ester, within 1 hour, drip off, be then cooled to 50 DEG C, start to drip hydrophilic monomer, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 70 DEG C, add catalyzer, continue insulation reaction, make NCO content reach theoretical value, period is by acetone regulation system viscosity; Be cooled to about 60 DEG C, add end-capping reagent, insulation reaction, make system NCO content close to 0; Be cooled to less than 50 DEG C, add neutralizing agent; Stir after 0.5 hour; Be cooled to 40 DEG C, under the state of rapid stirring, drip deionized water, continue dispersion 0.5 hour, acetone, butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown.
Comprise organometallic compound and trimethylamine class by suitable catalyzer in described the present invention above, organometallic compound comprises: stannous octoate, dibutyl tin laurate, lead octoate 36, iron octoate etc.; Trimethylamine comprises: triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine, N, N-dimethyl benzylamine, N, N-dimethyl butylamine etc.Organometallic compound class catalyzer is preferably used, as dibutyl tin laurate in the present invention.Neutralizing agent suitable in described the present invention is generally acetic acid, and its consumption is generally 90% ~ 120% of hydrophilic monomer mole number.
3) synthesis of single-component water-based cation polyurethane-perfluoroalkyl acrylate resin
Unsaturated waterborne cation polyurethane, portions of de-ionized water is added in four mouthfuls of reactors that agitator, thermometer, prolong are housed, stirring is warming up to 60 DEG C, add the initiator of 5% ~ 40% and the mixing solutions of perfluoroalkyl acrylate esters monomer, stir 0.5 hour swelling micelle; Be warming up to 85 DEG C, add remaining mixing solutions from dropping funnel, within 3-4 hour, dropwise, control rate of addition depending on monomers flow back speed in prolong; Continue reaction 1 hour at 85 DEG C, be finally cooled to 40 DEG C, 300 order hole nylon net filters, obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin.
The present invention is due in the process preparing waterborne cation polyurethane resin, first the hydroxyl telechelic polyester containing unsaturated double-bond has been synthesized, double bond monomer end-blocking is carried out to waterborne cation polyurethane resin prepolymer simultaneously, improved the percentage of grafting of acrylic resin further; When preparation single-component water-based cation polyurethane-perfluoroalkyl acrylate resin, adopt the method for soap-free polymerization, introduce fluorine (silicon) acrylate resin and modification has been carried out to it, while maintenance waterborne cation polyurethane intrinsic excellent properties, the advantages such as the physical strength introducing water-based perfluoroalkyl acrylate resin is high, ageing-resistant, good weatherability and water-tolerant.Waterborne cation polyurethane component after this resin solidification is high, excellent combination property, ageing-resistant performance, film performance are given prominence to, and have exceeded domestic like product, reduce the gap with oiliness resin cation (R.C.), there is extraordinary market-oriented prospect in environmental friendliness society.
Embodiment:
Below in conjunction with embodiment, the present invention is described further:
Embodiment 1:
(1) under nitrogen protection; by 100 parts of maleic anhydrides; 200 parts of TriMethylolPropane(TMP)s, 420 parts of 1,4 cyclohexanedicarboxylic acids; 480 parts of 2-ethyl-2-butyl 1; ammediol, 6 parts of stoppers (to methylol methyl-phenoxide) put into four mouthfuls of reactors with stirring, thermometer, nitrogen airway, prolong and water trap, are slowly warmed up to 140 DEG C; start stirring, be slowly warming up to 210 DEG C (heating-up time is 5 hours)., start to measure acid number, when acid number is down to 5mgKOH/g resin after 0.5 hour 210 DEG C of insulations, dimethylbenzene is deviate from about 100 DEG C vacuum, after having reacted, the dry 1-2 hour of vacuum decompression, vacuum tightness >=0.045Kpa, temperature is 50-80 DEG C, obtains unsaturated hydroxyl telechelic polyester.
(2) by 507 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 233 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, under 110 DEG C of conditions, first vacuum is drawn water 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 60 DEG C, add 780 parts of butanone.Pass into nitrogen protection, start to drip 1360 parts of isophorone diisocyanates, within 1 hour, dropwise; Then be cooled to 50 DEG C, start to drip 260 parts of N methyldiethanol amines, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 70 DEG C, add 6 parts of dibutyl tin laurates.Make NCO content≤3.05% (experimentally design, the NCO content in raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount), period is by acetone regulation system viscosity; Be cooled to about 60 DEG C, add 223 parts of Propylene glycol monoacrylates, insulation reaction, make system NCO content close to 0; Be cooled to less than 50 DEG C, add 130 parts of acetic acid; Stir after 0.5 hour; Be cooled to 40 DEG C, under the state of rapid stirring, drip 4252 parts of deionized waters, continue dispersion 0.5 hour, acetone, butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown (solid content about 35%).
(3) above-mentioned 2000 parts of waterborne cation polyurethanes are got and 1024 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get butyl acrylate 252 parts, methyl methacrylate 546 parts, vinyltrimethoxy silane 16.8 parts, trifluoroethyl methacrylate 25.2 parts mixes with 9.6 parts of Potassium Persulphates, get 170 parts and add reactor, temperature controls at 40-60 DEG C, stir 0.5 hour swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, within 3-4 hour, dropwise, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1 hour is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin (solid content about 40%).
Embodiment 2:
(1) under nitrogen protection, by 120 parts of maleic anhydrides, 270 parts of TriMethylolPropane(TMP)s; 420 parts of hexanodioic acids, 520 parts of 2-ethyl-2-butyl 1,3-PDs; 7 parts of stoppers (to methylol methyl-phenoxide) are put into stirring; thermometer, nitrogen airway, prolong; in four mouthfuls of reactors of water trap; slowly be warmed up to 140 DEG C, start stirring, be slowly warming up to 210 DEG C (heating-up time is 5 hours)., start to measure acid number, when acid number is down to 5mgKOH/g resin after 0.5 hour 210 DEG C of insulations, dimethylbenzene is deviate from about 100 DEG C vacuum, after having reacted, the dry 1-2 hour of vacuum decompression, vacuum tightness >=0.045Kpa, temperature is 50-80 DEG C, obtains unsaturated hydroxyl telechelic polyester.
(2) by 527 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 213 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, under 110 DEG C of conditions, first vacuum is drawn water 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 60 DEG C, add 803 parts of butanone.Pass into nitrogen protection, start to drip 1430 parts of isophorone diisocyanates, within 1 hour, dropwise; Then be cooled to 50 DEG C, start to drip 240 parts of N-ethyldiethanolamine, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content≤5.38% (experimentally design, the NCO content in raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount), period is by acetone regulation system viscosity; Be cooled to about 60 DEG C, add 312 parts of Propylene glycol monoacrylates, insulation reaction, make system NCO content close to 0; Be cooled to less than 50 DEG C, add 120 parts of acetic acid; Stir after 0.5 hour; Be cooled to 40 DEG C, under the state of rapid stirring, drip 4473 parts of deionized waters, continue dispersion 0.5 hour, acetone, butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown (solid content about 35%).
(3) above-mentioned 2000 parts of waterborne cation polyurethanes are got and 1349 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get butyl acrylate 315 parts, methyl methacrylate 683 parts, vinyltrimethoxy silane 21 parts, trifluoroethyl methacrylate 31.5 parts mixes with 15.8 parts of ammonium persulphates, get 213 parts and add reactor, temperature controls at 40-60 DEG C, stir 0.5 hour swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, within 3-4 hour, dropwise, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1 hour is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin (solid content about 40%).
Embodiment 3:
(1) under nitrogen protection, by 80 parts of maleic anhydrides, 250 parts of TriMethylolPropane(TMP) mono allyl ethers; 500 parts of hexanodioic acids; 400 parts of neopentyl glycol, 6 parts of stoppers (to methylol methyl-phenoxide) are put into stirring, thermometer; nitrogen airway; prolong, in four mouthfuls of reactors of water trap, is slowly warmed up to 140 DEG C; start stirring, be slowly warming up to 210 DEG C (heating-up time is 5 hours)., start to measure acid number, when acid number is down to 5mgKOH/g resin after 0.5 hour 210 DEG C of insulations, dimethylbenzene is deviate from about 100 DEG C vacuum, after having reacted, the dry 1-2 hour of vacuum decompression, vacuum tightness >=0.045Kpa, temperature is 50-80 DEG C, obtains unsaturated hydroxyl telechelic polyester.
(2) by 320 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 253 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, under 110 DEG C of conditions, first vacuum is drawn water 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 60 DEG C, add 803 parts of butanone.Pass into nitrogen protection, start to drip 1310 parts of isophorone diisocyanates, within 1 hour, dropwise; Then be cooled to 50 DEG C, start to drip 220 parts of N methyldiethanol amines, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content≤3.72% (experimentally design, the NCO content in raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount), period is by acetone regulation system viscosity; Be cooled to about 60 DEG C, add 188 parts of methacrylic acid-beta-hydroxy ethyl esters, insulation reaction, make system NCO content close to 0; Be cooled to less than 50 DEG C, add 110 parts of acetic acid; Stir after 0.5 hour; Be cooled to 40 DEG C, under the state of rapid stirring, drip 3758 parts of deionized waters, continue dispersion 0.5 hour, acetone, butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown (solid content about 35%).
(3) above-mentioned 1500 parts of waterborne cation polyurethanes are got and 1011 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get Isooctyl acrylate monomer 236 parts, vinylbenzene 512 parts, vinyltriethoxysilane 15.7 parts, Hexafluorobutyl mathacrylate 23.6 parts mixes with 11.8 parts of Diisopropyl azodicarboxylates, get 159.8 parts and add reactor, temperature controls at 40-60 DEG C, stir 0.5 hour swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, within 3-4 hour, dropwise, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1 hour is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin (solid content about 40%).
Embodiment 4:
(1) under nitrogen protection, by 120 parts of maleic anhydrides, 130 parts of TriMethylolPropane(TMP) mono allyl ethers; 500 parts of hexanodioic acids; 590 parts of hexylene glycols, 7 parts of stoppers (to methylol methyl-phenoxide) are put into stirring, thermometer; nitrogen airway; prolong, in four mouthfuls of reactors of water trap, is slowly warmed up to 140 DEG C; start stirring, be slowly warming up to 210 DEG C (heating-up time is 5 hours)., start to measure acid number, when acid number is down to 5mgKOH/g resin after 0.5 hour 210 DEG C of insulations, dimethylbenzene is deviate from about 100 DEG C vacuum, after having reacted, the dry 1-2 hour of vacuum decompression, vacuum tightness >=0.045Kpa, temperature is 50-80 DEG C, obtains unsaturated hydroxyl telechelic polyester.
(2) by 400 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 230 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, under 110 DEG C of conditions, first vacuum is drawn water 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 60 DEG C, add 717 parts of butanone.Pass into nitrogen protection, start to drip 1330 parts of isophorone diisocyanates, within 1 hour, dropwise; Then be cooled to 50 DEG C, start to drip 190 parts of N methyldiethanol amines, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content≤5.67% (experimentally design, the NCO content in raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount), period is by acetone regulation system viscosity; Be cooled to about 60 DEG C, add 293 parts of methacrylic acid-beta-hydroxy ethyl esters, insulation reaction, make system NCO content close to 0; Be cooled to less than 50 DEG C, add 95 parts of acetic acid; Stir after 0.5 hour; Be cooled to 40 DEG C, under the state of rapid stirring, drip 3996 parts of deionized waters, continue dispersion 0.5 hour, acetone, butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown (solid content about 35%).
(3) above-mentioned 1800 parts of waterborne cation polyurethanes are got and 1028 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get Isooctyl acrylate monomer 205 parts, methyl methacrylate 573 parts, vinyltriethoxysilane 16.4 parts, Hexafluorobutyl mathacrylate 24.6 parts mixes with 16.4 parts of Diisopropyl azodicarboxylates, get 167 parts and add reactor, temperature controls at 40-60 DEG C, stir 0.5 hour swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, within 3-4 hour, dropwise, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1 hour is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin (solid content about 40%).
Embodiment 5:
(1) under nitrogen protection, by 120 parts of maleic anhydrides, 130 parts of TriMethylolPropane(TMP)s; 480 parts of hexanodioic acids; 560 parts of hexylene glycols, 6 parts of stoppers (to methylol methyl-phenoxide) are put into stirring, thermometer; nitrogen airway; prolong, in four mouthfuls of reactors of water trap, is slowly warmed up to 140 DEG C; start stirring, be slowly warming up to 210 DEG C (heating-up time is 5 hours)., start to measure acid number, when acid number is down to 5mgKOH/g resin after 0.5 hour 210 DEG C of insulations, dimethylbenzene is deviate from about 100 DEG C vacuum, after having reacted, the dry 1-2 hour of vacuum decompression, vacuum tightness >=0.045Kpa, temperature is 50-80 DEG C, obtains unsaturated hydroxyl telechelic polyester.
(2) by 500 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 260 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, under 110 DEG C of conditions, first vacuum is drawn water 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 60 DEG C, add 760 parts of butanone.Pass into nitrogen protection, start to drip 1330 parts of isophorone diisocyanates, within 1 hour, dropwise; Then be cooled to 50 DEG C, start to drip 190 parts of N methyldiethanol amines, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content≤3.76% (experimentally design, the NCO content in raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount), period is by acetone regulation system viscosity; Be cooled to about 60 DEG C, add 205 parts of methacrylic acid-beta-hydroxy ethyl esters, insulation reaction, make system NCO content close to 0; Be cooled to less than 50 DEG C, add 95 parts of acetic acid; Stir after 0.5 hour; Be cooled to 40 DEG C, under the state of rapid stirring, drip 4031 parts of deionized waters, continue dispersion 0.5 hour, acetone, butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown (solid content about 35%).
(3) above-mentioned 2000 parts of waterborne cation polyurethanes are got and 1142 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get Isooctyl acrylate monomer 228 parts, methyl methacrylate 637 parts, vinyltriethoxysilane 18.2 parts, Hexafluorobutyl mathacrylate 27.3 parts mixes with 18.2 parts of Diisopropyl azodicarboxylates, get 186 parts and add reactor, temperature controls at 40-60 DEG C, stir 0.5 hour swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, within 3-4 hour, dropwise, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1 hour is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin (solid content about 40%).
Embodiment 6:
(1) under nitrogen protection, by 120 parts of maleic anhydrides, 198 parts of TriMethylolPropane(TMP)s; 420 parts of hexanodioic acids; 456 parts of hexylene glycols, 6 parts of stoppers (to methylol methyl-phenoxide) are put into stirring, thermometer; nitrogen airway; prolong, in four mouthfuls of reactors of water trap, is slowly warmed up to 140 DEG C; start stirring, be slowly warming up to 210 DEG C (heating-up time is 5 hours)., start to measure acid number, when acid number is down to 5mgKOH/g resin after 0.5 hour 210 DEG C of insulations, dimethylbenzene is deviate from about 100 DEG C vacuum, after having reacted, the dry 1-2 hour of vacuum decompression, vacuum tightness >=0.045Kpa, temperature is 50-80 DEG C, obtains unsaturated hydroxyl telechelic polyester.
(2) by 520 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 238 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, under 110 DEG C of conditions, first vacuum is drawn water 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 60 DEG C, add 742 parts of butanone.Pass into nitrogen protection, start to drip 1300 parts of tolylene diisocyanates, within 1 hour, dropwise; Then be cooled to 50 DEG C, start to drip 260 parts of N methyldiethanol amines, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 70 DEG C, add 7 parts of dibutyl tin laurates.Make NCO content≤4.18% (experimentally design, the NCO content in raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount), period is by acetone regulation system viscosity; Be cooled to about 60 DEG C, add 222 parts of methacrylic acid-beta-hydroxy ethyl esters, insulation reaction, make system NCO content close to 0; Be cooled to less than 50 DEG C, add 149 parts of acetic acid; Stir after 0.5 hour; Be cooled to 40 DEG C, under the state of rapid stirring, drip 3989 parts of deionized waters, continue dispersion 0.5 hour, acetone, butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown (solid content about 35%).
(3) above-mentioned 2000 parts of waterborne cation polyurethanes are got and 904 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get Isooctyl acrylate monomer 269 parts, methyl methacrylate 615 parts, vinyltriethoxysilane 15 parts, Hexafluorobutyl mathacrylate 27 parts mixes with 15 parts of Diisopropyl azodicarboxylates, get 188 parts and add reactor, temperature controls at 40-60 DEG C, stir 0.5 hour swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, within 3-4 hour, dropwise, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1 hour is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin (solid content about 40%).
Claims (10)
1. single-component water-based cation polyurethane-perfluoroalkyl acrylate resin, it is characterized in that: it is polymerized in deionized water by unsaturated waterborne cation polyurethane resin, acrylate monomer, vinylsiloxane, fluoroacrylate monomers and initiator, described unsaturated waterborne cation polyurethane resin is polymerized in deionized water by unsaturated hydroxyl telechelic polyester, dibasic alcohol, butanone, isocyanic ester, hydrophilic monomer, adds catalyzer, end-capping reagent and acid acceptor during polymerization.
2. single-component water-based cation polyurethane-perfluoroalkyl acrylate resin according to claim 1, it is characterized in that: by weight percentage, synthesize unsaturated waterborne cation polyurethane resin in the raw material of single-component water-based cation polyurethane-perfluoroalkyl acrylate resin and account for 45% ~ 52%, deionized water 23% ~ 31%, acrylate monomer 20% ~ 23%, vinylsiloxane 0.2% ~ 4.5%, fluoroacrylate monomers 0.4 ~ 9.2%, initiator 0.2% ~ 0.4%.
3. single-component water-based cation polyurethane-perfluoroalkyl acrylate resin according to claim 1, it is characterized in that: by weight percentage, synthesize unsaturated hydroxyl telechelic polyester accounting 4.5% ~ 7% in the raw material of unsaturated waterborne cation polyurethane resin, dibasic alcohol accounting 2.5% ~ 4%, butanone 9.5% ~ 12%, isocyanic ester 17.5% ~ 19%, hydrophilic monomer 2.5% ~ 3.5%, catalyzer 0.06% ~ 0.12%, end-capping reagent 2.5% ~ 4%, deionized water 53.5% ~ 55.5%, described acid acceptor is acetic acid, accounting 1.3% ~ 1.7%.
4. single-component water-based cation polyurethane-perfluoroalkyl acrylate resin according to claim 1, is characterized in that: described unsaturated hydroxyl telechelic polyester is polymerized in a solvent by maleic anhydride, polyvalent alcohol, polyprotonic acid, TriMethylolPropane(TMP) and stopper.
5. single-component water-based cation polyurethane-perfluoroalkyl acrylate resin according to claim 1, it is characterized in that: described dibasic alcohol is 1,4-butyleneglycol, ethylene glycol, 2-ethyl-2-butyl 1,3-PD, 1,6-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, 2-methyl isophthalic acid, ammediol, glycol ether, ethohexadiol, neopentyl glycol, 1, at least one in 3 propylene glycol, 1,4 cyclohexane dimethanol; Described polyprotonic acid is at least one in maleic anhydride, 1,4 cyclohexanedicarboxylic acid, FUMARIC ACID TECH GRADE, phthalic anhydride, m-phthalic acid, terephthalic acid, tetrahydrophthalic anhydride, succinic acid, pentanedioic acid, oxalic acid, fumaric acid, dimeracid, HHPA and hexanodioic acid; Described stopper is to methylol methyl-phenoxide; Described hydrophilic monomer is the one in diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanolamine, N butyl diethanol amine, tertiarybutyldiethanolamine, dimethylethanolamine, two (2-hydroxyethyl) aniline, two (2-hydroxypropyl) aniline; Described isocyanic ester is tolylene diisocyanate, 1, at least one in hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, two cyclohexyl methane diisocyanates, Methylcyclohexyl diisocyanate, ditan-4,4-vulcabond.
6. single-component water-based cation polyurethane-perfluoroalkyl acrylate resin according to claim 4, it is characterized in that: described polyvalent alcohol is 1,4-butyleneglycol, ethylene glycol, 2-ethyl-2-butyl 1,3-PD, 1,6-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, 2-methyl isophthalic acid, ammediol, glycol ether, ethohexadiol, neopentyl glycol, 1, two kinds are had at least in 3 propylene glycol, 1,4 cyclohexane dimethanol, TriMethylolPropane(TMP) and TriMethylolPropane(TMP) mono allyl ether.
7. the single-component water-based cation polyurethane-perfluoroalkyl acrylate resin according to claim 1 or 3, is characterized in that: described end-capping reagent is the acrylate monomer containing hydroxy functional group: at least one in (methyl) senecioate-hydroxyl ethyl ester, (methyl) senecioate-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy-propyl, methacrylic acid-β-hydroxypropyl acrylate.
8. single-component water-based cation polyurethane-perfluoroalkyl acrylate process for preparing resins, comprises the steps:
1) unsaturated hydroxyl telechelic polyester is synthesized
Under protective atmosphere, maleic anhydride, polyvalent alcohol, polyprotonic acid, TriMethylolPropane(TMP) and stopper are put into solvent-laden reaction vessel, dry after heating up, stir, be incubated and deviating from solvent, obtain unsaturated hydroxyl telechelic polyester;
2) unsaturated waterborne cation polyurethane resin is synthesized
Unsaturated hydroxyl telechelic polyester, dibasic alcohol, butanone, isocyanic ester, hydrophilic monomer, catalyzer, end-capping reagent and acid acceptor are added in reaction vessel successively, through heating, insulation, catalyzed reaction and adjustment potential of hydrogen, obtain unsaturated waterborne cation polyurethane;
3) single-component water-based cation polyurethane-perfluoroalkyl acrylate resin is synthesized
Aqueous cation polyurethane and deionized water add in reactor; get acrylate monomer, vinylsiloxane, fluoroacrylate monomers mix with initiator; and be divided into two portions; a wherein part is accounted for 5% ~ 40% of mixture total mass and add reactor and stir swelling micelle, then add remaining mixing solutions polyreaction and obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin.
9. single-component water-based cation polyurethane-perfluoroalkyl acrylate process for preparing resins according to claim 8, it is characterized in that: described unsaturated waterborne cation polyurethane resin preparation process is, unsaturated hydroxyl telechelic polyester, dibasic alcohol are added in reactor, first under 100 ~ 110 DEG C of conditions, vacuum is drawn water 0.8 ~ 1 hour, vacuum tightness >=0.060Kpa; Then be cooled to 55 ~ 65 DEG C, add butanone.Pass into protection gas, start to drip isocyanic ester, within 50 ~ 70 minutes, dropwise; Then be cooled to 45 ~ 55 DEG C, start to drip hydrophilic monomer, within 1 hour, dropwise, be incubated 1 hour; Then be warmed up to 65 ~ 70 DEG C, add catalyzer, make NCO content reach theoretical value, period is by acetone regulation system viscosity; Be cooled to 55 ~ 60 DEG C, add end-capping reagent, insulation reaction, make system NCO content close to 0; Be cooled to 45 ~ 50 DEG C, add acetic acid; Stir after 30 ~ 35 minutes; Be cooled to 35 ~ 40 DEG C and drip deionized water, continue dispersion 30 ~ 40 minutes, deviate from acetone, butanone 55 ~ 60 DEG C of decompressions, obtain unsaturated waterborne cation polyurethane.
10. single-component water-based cation polyurethane-perfluoroalkyl acrylate process for preparing resins according to claim 8, it is characterized in that: the technique of described synthesis single-component water-based cation polyurethane-perfluoroalkyl acrylate resin is, first waterborne cation polyurethane and deionized water are added in reactor, stir and be warming up to 55 ~ 60 DEG C; Get acrylate monomer, vinylsiloxane, fluoroacrylate monomers mix with initiator, and be divided into two portions, wherein a part accounts for 20% of mixture total mass, first this part is added reactor, temperature controls at 40 ~ 60 DEG C, stirs 30 ~ 40 minutes swelling micelles, drip remaining mixing solutions again, temperature controls at 80 ~ 85 DEG C, within 3 ~ 4 hours, dropwises, and controls rate of addition depending on monomers flow back speed in prolong; Reaction more than 1 hour is continued at 80 ~ 85 DEG C; Finally be cooled to 40 ~ 45 DEG C, filter and namely obtain single-component water-based cation polyurethane-perfluoroalkyl acrylate resin.
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