CN105418853A - Hydroxyl type water-borne cationic polyurethane-acrylic acid resin and preparation method thereof - Google Patents
Hydroxyl type water-borne cationic polyurethane-acrylic acid resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of hydroxyl type water-borne cationic polyurethane-acrylic acid resin. The method comprises the following steps that 1, hydroxyl telechelic polyester containing an unsaturated double bond is obtained through a reaction; 2, a product obtained in the first step serves as the raw material, dihydric alcohol, isocyanate, a hydrophilic monomer, a catalyst, an end-capped reagent, neutralizer and the like are added according to the ratio of a designed formula, and the unsaturated water-borne cationic polyurethane is obtained; 3, a product obtained in the second step serves as the raw material to be reacted with an acrylate monomer according to the ratio of a designed formula, and the hydroxyl type water-borne cationic polyurethane-acrylic acid resin is obtained. The end-capped reagent is added in the second step, double bond monomer end-capping is conducted on a water-borne cationic polyurethane resin prepolymer, and the grafting rate of acrylic acid resin is further increased; the reaction condition is mild, water-borne cationic polyurethane-hydroxyl type acrylic acid resin with improved performance is obtained without adding emulsifier, and the application field of the resin is greatly enlarged.
Description
Technical field:
The present invention relates to resin art, be specifically related to the preparation method of hydroxyl aqueous cation polyurethane-acrylic resin.
Background technology:
Aqueous polyurethane is 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, application at present on the market for anion aqueous polyurethane is more, reason be quaternary ammonium salt cationic 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; Compared to anion-type water-thinned polyurethane, research report cationic is at present less, and waterborne cation polyurethane exists the shortcomings such as poor water resistance, gloss is low, poor solvent resistance, rate of drying are slow simultaneously; But 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; Water based acrylic resin has that physical strength is high, ageing-resistant, the advantage such as good weatherability and water-tolerant, but it exists the shortcoming of hot sticky cold crisp equally; Hydroxy acrylate is carried out modification to waterborne cation polyurethane, just can accomplish to maximize favourable factors and minimize unfavourable ones, obtain waterborne cation polyurethane-Hydroxylated acrylic resin that performance is improved; And this resin is convenient composite with aminoresin, prepares waterborne cation amino-stoving varnish; Also can be composite with aqueous polyisocyanate curing agent, prepare the two components resin of normal temperature self-drying type waterborne cation polyurethane, the resin after composite can significantly improve the performances such as its hardness, water-fast, shock resistance, expands the Application Areas of resin cation (R.C.) greatly.
Traditional solvent-borne type cation polyurethane-acrylic resin is all use acetone or butanone method simultaneously, the use of organic solvent need be removed by distillation method, technique is loaded down with trivial details, has a large amount of organic solvents to evaporate in air simultaneously, easily cause the pollution of environment in construction process.
Summary of the invention:
The invention provides a kind of method preparing hydroxyl aqueous cation polyurethane-acrylic 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 the hydroxyl aqueous cation polyurethane-acrylic resin of preparation, adopt the method for soap-free polymerization, introduce hydroxyl acrylic 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 acrylic resin is high, ageing-resistant, good weatherability and water-tolerant.This resin and water-compatible amino resin or aqueous polyisocyanate curing agent composite after, excellent combination property, ageing-resistant performance is given prominence to, and has exceeded domestic like product, reduce the gap of two component resin cation (R.C.) with oiliness, there is extraordinary market-oriented prospect in environmental friendliness society.
Preparation process of the present invention is as follows:
A) under the protection of nitrogen, by the polyvalent alcohol of component design ratio, polyprotonic acid, solvent xylene, stoppers etc. add 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), 210 DEG C of insulation reaction after 0.5 hour, start to measure acid number, when acid number is down to 5mgKOH/g resin, dimethylbenzene is deviate from about 100 DEG C vacuum, at vacuum tightness >=0.045Kpa, vacuum decompression drying 1 ~ 2 hour, temperature is 50 ~ 80 DEG C, namely unsaturated hydroxyl telechelic polyester is obtained.
B) by mass parts, by the above-mentioned steps of 400 ~ 600 parts, a) reaction vessel put into by the middle unsaturated hydroxyl telechelic polyester of preparation and the dibasic alcohol of 200 ~ 300 parts, under vacuum tightness >=0.060Kpa, first vacuum is drawn water 0.5 ~ 1.5h, cool to 55 ~ 65 DEG C, add 650 ~ 850 parts of butanone and 1150 ~ 1450 parts of isocyanic ester, reaction 0.5 ~ 1.5h, cool to 50 ~ 40 DEG C, drip 150 ~ 300 parts of hydrophilic monomers again, reaction 0.5 ~ 1.5h, be warmed up to 65 ~ 80 DEG C, add 4 ~ 10 parts of organometallic catalysts to NCO content≤4.6% in system, cool to 55 ~ 63 DEG C again, add 150 ~ 400 parts of end-capping reagents, react to NCO content in system close to 0, cool to 40 ~ 50 DEG C again, add 70 ~ 150 parts of neutralizing agents, stir 0.5 ~ 1h, add acetone adjusting viscosity, cool to 30 ~ 40 DEG C, under whipped state, add 3800 ~ 4500 parts of deionized waters, butanone is sloughed in decompression and acetone just obtains unsaturated waterborne cation polyurethane,
C) get the above-mentioned steps b of mass parts 1300 ~ 2200) in preparation unsaturated waterborne cation polyurethane put into reaction vessel, at 40 ~ 60 DEG C, first add 600 ~ 1200 acrylic ester monomers, the cross-linking monomer of 15 ~ 20, in the mixing solutions of 14 ~ 25 initiators total mass part 5% ~ 40%, then be warmed up to 80 ~ 90 DEG C, drip remaining mixing solutions, reaction 0.5 ~ 2h, just obtains hydroxyl aqueous cation polyurethane-acrylic resin.
Stopper of the present invention is preferably methylol methyl-phenoxide.
End-capping reagent of the present invention is the one in senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, methacrylic acid-β-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy-propyl, methacrylic acid-β-hydroxypropyl acrylate; Neutralizing agent is the one in acetic acid, propionic acid, butyric acid.
Polyvalent alcohol of the present invention to be carbonatoms be 1 ~ 12 dibasic alcohol and TriMethylolPropane(TMP), in TriMethylolPropane(TMP) mono allyl ether at least two kinds; Polyprotonic acid is one or more 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.
Isocyanate-monomer of the present invention is tolylene diisocyanate, 1, one or more in hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, two cyclohexyl methane diisocyanates, Methylcyclohexyl diisocyanate, ditan-4,4-vulcabond; Hydrophilic monomer is for being diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanolamine, N butyl diethanol amine, tertiarybutyldiethanolamine, dimethylethanolamine, N, one in N-dihydroxy ethyl aniline, N, N-dihydroxypropyl aniline.
Acrylic ester monomer of the present invention comprises the acrylate monomer of not hydroxyl, the acrylate monomer of hydroxyl, and hydroxy acryl acid ester monomer is not vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, n-propyl, Isooctyl acrylate monomer, lauryl acrylate, lauryl methacrylate(LMA), vinylbenzene, vinylformic acid octadecyl, methacrylic acid octadecyl, lauryl methacrylate, phenyl methacrylate, benzyl methacrylate, at least one in acrylamide, and consumption is 60 ~ 98% of acrylic ester monomer quality, hydroxy acryl acid ester monomer is senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy-propyl, at least one in methacrylic acid-β-hydroxypropyl acrylate, its consumption is 2 ~ 40% of acrylic ester monomer quality.
Cross-linking monomer of the present invention is vinyltrimethoxy silane, vinyltriethoxysilane, 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, at least one in vinyl trichloro silane, and its consumption is 2 ~ 20% of acrylic ester monomer quality, initiator is at least one 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, and consumption is 0.1 ~ 5% of acrylic ester monomer quality.
The present invention is by means of only 3 steps, just hydroxy acrylate is incorporated in urethane resin, the method is simple to operate, be convenient to implement, the chemical property of Hydroxylated acrylic resin excellence is introduced simultaneously, avoid the distinct disadvantage such as waterborne cation polyurethane resin poor water resistance, gloss is low, obtain low-temperature impact resistance, ageing-resistant, good weatherability, water-tolerant and the hydroxyl of chemical stability waterborne cation polyurethane-acrylic resin, and this resin is easy and aminoresin is composite, prepares waterborne cation amino-stoving varnish; Also can be composite with aqueous polyisocyanate curing agent, prepare the two components resin of normal temperature self-drying type waterborne cation polyurethane, the resin after composite can significantly improve the performances such as its hardness, water-fast, shock resistance, expands the Application Areas of resin cation (R.C.) greatly.
Embodiment:
Below in conjunction with specific embodiment, technical scheme of the present invention is described
Embodiment 1
(1) under nitrogen protection, by 120 parts of maleic anhydrides, 130 parts of TriMethylolPropane(TMP)s; 480 parts of hexanodioic acids; 550 parts of hexylene glycols, put into stirring to methylol methyl-phenoxide for 6 parts, 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 5h).After 210 DEG C of insulation 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resin, vacuum deviates from dimethylbenzene, and vacuum tightness is 0.045Kpa, and the dry 1h of vacuum decompression, obtains unsaturated hydroxyl telechelic polyester.
(2) by 500 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 230 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, and under 110 DEG C of conditions, first vacuum is drawn water 1h, makes vacuum tightness be 0.060Kpa; Then be cooled to 60 DEG C, add 740 parts of butanone, pass into nitrogen protection, start to drip 1300 parts of isophorone diisocyanates, 1h dropwises; Then be cooled to 50 DEG C, start to drip 190 parts of N methyldiethanol amines, 1h dropwises, insulation 1h; Then be warmed up to 70 DEG C, add 6 parts of dibutyl tin laurates, make NCO content be 4.5% (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 60 DEG C, add 316 parts of Propylene glycol monoacrylates, insulation reaction, make system NCO content close to 0; Be cooled to 50 DEG C, add 95 parts of acetic acid; After stirring 0.5h; Be cooled to 40 DEG C, under the state of rapid stirring, drip 4145 parts of deionized waters, continue dispersion 0.5h, acetone and 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 1035 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get butyl acrylate 210 parts, methyl methacrylate 588 parts, vinyltrimethoxy silane 16.8 parts, hydroxyethyl methylacrylate 25.2 parts mixes with 16.8 parts of Diisopropyl azodicarboxylates, get 171 parts of above-mentioned mixing solutionss and add reactor, temperature controls at 40 DEG C, stir 0.5h swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, 3h dropwises, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1h is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain hydroxyl aqueous cation polyurethane-acrylic resin (A) (solid content about 40%).
Embodiment 2:
(1) under nitrogen protection, by 120 parts of maleic anhydrides, 300 parts of TriMethylolPropane(TMP) mono allyl ethers, 480 parts of hexanodioic acids, 650 parts of 2-ethyl-2-butyl 1,3-PDs, put into stirring to methylol methyl-phenoxide for 8 parts, 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 5h); After 210 DEG C of insulation 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resin, vacuum deviates from dimethylbenzene, and after having reacted, vacuum tightness is 0.045Kpa, and vacuum decompression 1.5h obtains unsaturated hydroxyl telechelic polyester.
(2) by 400 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 280 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, and under 110 DEG C of conditions, first vacuum is drawn water 1h, and vacuum tightness is 0.060Kpa; Then be cooled to 60 DEG C, add 803 parts of butanone; Pass into nitrogen protection, start to drip 1460 parts of isophorone diisocyanates, 1h dropwises; Then be cooled to 50 DEG C, start to drip 210 parts of N methyldiethanol amines, 1h dropwises, insulation 1h; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content be 4.4% (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 60 DEG C, add 341 parts of Propylene glycol monoacrylates, insulation reaction, make system NCO content close to 0; Be cooled to 45 DEG C, add 105 parts of acetic acid; After stirring 0.5h; Be cooled to 40 DEG C, 4410 parts of deionized waters are dripped under the state of rapid stirring, continue dispersion 0.5h, acetone and butanone are deviate from 60 DEG C of decompressions, obtain the unsaturated waterborne cation polyurethane of translucent yellowish brown (B) (solid content about 35%).
(3) above-mentioned 1500 parts of waterborne cation polyurethanes are got and 1258 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get butyl acrylate 236 parts, methyl methacrylate 662 parts, vinyltrimethoxy silane 18.9 parts, Propylene glycol monoacrylate 28.4 parts mixes with 18.9 parts of Diisopropyl azodicarboxylates, 193 parts that get above-mentioned mixing solutions add reactor, temperature controls at 40 DEG C, stir 0.5h swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, within 3 hours, dropwise, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1h is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain hydroxyl aqueous cation polyurethane-acrylic resin (solid content about 40%).
Embodiment 3:
(1) under nitrogen protection, by 90 parts of maleic anhydrides, 270 parts of TriMethylolPropane(TMP) mono allyl ethers; 500 parts of hexanodioic acids, 670 parts of 2-ethyl-2-butyl 1,3-PDs; put into stirring to methylol methyl-phenoxide for 8 parts; 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 5h).After 210 DEG C of insulation 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resin, vacuum deviates from dimethylbenzene, and after having reacted, vacuum tightness is 0.045Kpa, and dry 2 hours of vacuum decompression, obtains unsaturated hydroxyl telechelic polyester.
(2) by 560 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 230 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, and under 110 DEG C of conditions, first vacuum is drawn water 1h, and vacuum tightness is 0.060Kpa; Then be cooled to 60 DEG C, add 813 parts of butanone; Pass into nitrogen protection, start to drip 1410 parts of isophorone diisocyanates, 1h dropwises; Then be cooled to 50 DEG C, start to drip 240 parts of N methyldiethanol amines, 1h dropwises, and is incubated 1 hour; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content be 4.25% (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 60 DEG C, add 249 parts of hydroxyethyl methylacrylates, insulation reaction, make system NCO content close to 0; Be cooled to 50 DEG C, add 120 parts of acetic acid; After stirring 0.5h; Be cooled to 40 DEG C, under the state of rapid stirring, drip 4403 parts of deionized waters, continue dispersion 0.5h, 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 1258 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 595 parts, vinyltriethoxysilane 18.9 parts, hydroxyethyl methylacrylate 94.5 parts mixes with 18.9 parts of Diisopropyl azodicarboxylates, get 193 parts and add reactor, temperature controls at 40 DEG C, stir 0.5h swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, 3h dropwises, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1h is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain hydroxyl aqueous cation polyurethane-acrylic resin (solid content about 40%).
Embodiment 4:
(1) under nitrogen protection, by 90 parts of maleic anhydrides, 270 parts of TriMethylolPropane(TMP) mono allyl ethers; 500 parts of hexanodioic acids; 460 parts of hexylene glycols, put into stirring to methylol methyl-phenoxide for 7 parts, 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 5h).After 210 DEG C of insulation 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resin, vacuum deviates from dimethylbenzene, and after having reacted, vacuum tightness is 0.045Kpa, and the dry 2h of vacuum decompression, obtains unsaturated hydroxyl telechelic polyester.
(2) by 480 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 210 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, and under 110 DEG C of conditions, first vacuum is drawn water 1h, and vacuum tightness is 0.060Kpa; Then be cooled to 60 DEG C, add 740 parts of butanone; Pass into nitrogen protection, start to drip 1290 parts of isophorone diisocyanates, 1h dropwises; Then be cooled to 50 DEG C, start to drip 240 parts of N methyldiethanol amines, 1h dropwises, insulation 1h; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content be 3.77% (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 60 DEG C, add 201 parts of hydroxyethyl methylacrylates, insulation reaction, make system NCO content close to 0; Be cooled to 50 DEG C, add 120 parts of acetic acid; After stirring 0.5h; Be cooled to 40 DEG C, under the state of rapid stirring, drip 3979 parts of deionized waters, continue dispersion 0.5h, 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 1510 parts of deionized waters add with whipping appts, thermometer, in four mouthfuls of reactors of prolong and constant pressure funnel, get Isooctyl acrylate monomer 284 parts, methyl methacrylate 714 parts, vinyltriethoxysilane 22.6 parts, Hydroxyethyl acrylate 11.3 parts mixes with 22.7 parts of Diisopropyl azodicarboxylates, get 231 parts and add reactor, temperature controls at 40 DEG C, stir 0.5h swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, 3h dropwises, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1h is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain hydroxyl aqueous cation polyurethane-acrylic resin (solid content about 40%).
Embodiment 5:
(1) under nitrogen protection, by 90 parts of maleic anhydrides, 270 parts of TriMethylolPropane(TMP)s; 530 parts of hexanodioic acids; 430 parts of hexylene glycols, put into stirring to methylol methyl-phenoxide for 7 parts, 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 5h).After 210 DEG C of insulation 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resin, vacuum deviates from dimethylbenzene, and after having reacted, vacuum tightness is 0.045Kpa, and the dry 1h of vacuum decompression, obtains unsaturated hydroxyl telechelic polyester.
(2) by 420 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 190 parts of BDOs, add in four mouthfuls of reactors with agitator, thermometer, nitrogen airway, prolong, and under 110 DEG C of conditions, first vacuum is drawn water 1h, and vacuum tightness is 0.060Kpa; Then be cooled to 60 DEG C, add 690 parts of butanone; Pass into nitrogen protection, start to drip 1230 parts of isophorone diisocyanates, 1h dropwises; Then be cooled to 50 DEG C, start to drip 230 parts of N methyldiethanol amines, 1h dropwises, insulation 1h; Then be warmed up to 70 DEG C, add 5 parts of dibutyl tin laurates.Make NCO content be 4.43% (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 60 DEG C, add 220 parts of hydroxyethyl methylacrylates, insulation reaction, make system NCO content close to 0; Be cooled to 50 DEG C, add 115 parts of acetic acid; After stirring 0.5h; Be cooled to 40 DEG C, under the state of rapid stirring, drip 3778 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 1215 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, methyl methacrylate 595 parts, vinyltriethoxysilane 18.9 parts, hydroxyethyl methylacrylate 94.5 parts mixes with 15.2 parts of Diisopropyl azodicarboxylates, get 192 parts and add reactor, temperature controls at 40 DEG C, stir 0.5h swelling micelle, residual monomer and initiator mixing solutions is dripped from dropping funnel, temperature controls at 85 DEG C, 3h dropwises, rate of addition is controlled depending on monomers flow back speed in prolong, reaction 1h is continued at 85 DEG C, finally be cooled to 40 DEG C, 300 order net filtrations, namely obtain hydroxyl aqueous cation polyurethane-acrylic resin (solid content about 40%).
Claims (10)
1. a preparation method for hydroxyl aqueous cation polyurethane-acrylic resin, is characterized in that comprising the steps:
A) by mass parts, 550 ~ 650 parts of polyprotonic acids, 600 ~ 1000 parts of polyvalent alcohols and 5 ~ 9 parts, to the reaction of methylol methyl-phenoxide, obtain unsaturated hydroxyl telechelic polyester;
B) by mass parts, get 400 ~ 600 parts of above-mentioned steps a) in the unsaturated hydroxyl telechelic polyester, 200 ~ 300 parts of dibasic alcohol that prepare put into reaction vessel, add 650 ~ 850 parts of butanone, 1150 ~ 1450 parts of isocyanic ester, 150 ~ 300 parts of hydrophilic monomers, 4 ~ 10 parts of organometallic catalysts reactions successively, add 150 ~ 400 parts of end-capping reagents, 70 ~ 150 parts of neutralizing agents and 3800-4500 part deionized water again, butanone is sloughed in decompression, obtains unsaturated waterborne cation polyurethane;
C) get 1300 ~ 2200 parts of above-mentioned steps b) in the unsaturated waterborne cation polyurethane for preparing put into reaction vessel, add 600 ~ 1200 parts of acrylic ester monomers, 15 ~ 20 parts of cross-linking monomers, 14 ~ 25 parts of initiators, are obtained by reacting hydroxyl aqueous cation polyurethane-acrylic resin.
2. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, it is characterized in that: step b) in temperature of reaction be 55 ~ 65 DEG C, add end-capping reagent, in insulation reaction to system, NCO content is 0, is cooled to 40 ~ 50 DEG C, adds neutralizing agent, be cooled to 30 ~ 40 DEG C, under whipped state, drip deionized water, butanone is sloughed in decompression, obtains unsaturated waterborne cation polyurethane.
3. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, it is characterized in that: step c) in temperature of reaction be 40 ~ 60 DEG C, add acrylic ester monomer, cross-linking monomer, 5% ~ 40% of initiator mixing solutions, then temperature is elevated to 80 ~ 90 DEG C, dropwise remaining mixing solutions, after reaction 0.5 ~ 2h, be cooled to 35 ~ 45 DEG C, obtain hydroxyl aqueous cation polyurethane-acrylic resin.
4. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1 and 2, is characterized in that: described end-capping reagent is the one in senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, methacrylic acid-β-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy-propyl, methacrylic acid-β-hydroxypropyl acrylate; Neutralizing agent is the one in acetic acid, propionic acid, butyric acid.
5. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, it is characterized in that: step c) described in acrylic ester monomer comprise the not acrylate monomer of hydroxyl and the acrylate monomer of hydroxyl, hydroxy acryl acid ester monomer is not methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, n-propyl, Isooctyl acrylate monomer, lauryl acrylate, lauryl methacrylate(LMA), vinylformic acid octadecyl, methacrylic acid octadecyl, lauryl methacrylate, phenyl methacrylate, benzyl methacrylate and acrylamide, at least one in vinylbenzene, its consumption is 60 ~ 98% of acrylic ester monomer quality, hydroxy acryl acid ester monomer is at least one in senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, vinylformic acid-2-hydroxyl-3-phenoxy-propyl, methacrylic acid-β-hydroxypropyl acrylate, and its consumption is 2 ~ 40% of acrylic ester monomer quality.
6. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, is characterized in that: step a) described in polyvalent alcohol be carbonatoms from 1 ~ 12 dibasic alcohol, TriMethylolPropane(TMP), TriMethylolPropane(TMP) mono allyl ether at least two kinds.
7. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, it is characterized in that: step a) described in polyprotonic acid be one or more 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.
8. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, it is characterized in that: step b) described in isocyanate-monomer be tolylene diisocyanate, 1, one or more in hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, two cyclohexyl methane diisocyanates, Methylcyclohexyl diisocyanate, ditan-4,4-vulcabond.
9. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, it is characterized in that: step b) described in hydrophilic monomer for for diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanolamine, N butyl diethanol amine, tertiarybutyldiethanolamine, dimethylethanolamine, N, one in N-dihydroxy ethyl aniline, N, N-dihydroxypropyl aniline.
10. the hydroxyl aqueous cation polyurethane-acrylic resin of one according to claim 1, it is characterized in that: step c) described in cross-linking monomer be vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane, γ-methacryloxy Trimethoxy silane, 3-methacryloxypropyl trimethoxy silane, triple phenoxyl vinyl silanes, the rare acryloxypropylethoxysilane Trimethoxy silane of γ-methyl-prop, vinyl silane triisopropoxide, at least one in vinyl trichloro silane, its consumption is 2 ~ 20% of acrylic ester monomer quality, described initiator is at least one 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, and its consumption is 0.1 ~ 5% of acrylic ester monomer quality.
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| CN109680521A (en) * | 2018-12-17 | 2019-04-26 | 江苏丽王科技股份有限公司 | A kind of Networks of Polyurethane/Polystyrene-acrlylonitrile-acrylate emulsion binding agent and preparation method thereof |
| CN110627967A (en) * | 2019-09-04 | 2019-12-31 | 湖北大学 | Preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane |
| CN112778834A (en) * | 2021-02-22 | 2021-05-11 | 昆明凌润科技有限公司 | Nanoscale weak cation acrylate emulsion for water-based transparent ink and preparation method thereof |
| CN113913077A (en) * | 2021-08-23 | 2022-01-11 | 广东深展实业有限公司 | Scratch-resistant water-based vacuum coating film-plating matte paint and preparation method thereof |
| CN115160916A (en) * | 2022-06-30 | 2022-10-11 | 上海回天新材料有限公司 | High-temperature-resistant high-humidity-resistant solvent-free insulating paint and preparation method thereof |
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