CN104788665A - Alcohol water-soluble modified polyester ink resin and preparation method thereof - Google Patents
Alcohol water-soluble modified polyester ink resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an alcohol water-soluble modified polyester ink resin and a preparation method thereof. The alcohol water-soluble modified polyester ink resin is prepared through the reaction of the following raw materials in parts by weight: 10-30 parts of dibasic acid I and/or dicarboxylic acid anhydrides, 10-30 parts of dihydric alcohol, 2-10 parts of a hydrophilic component I, 0.01-0.1 part of a catalyst, 2-15 parts of polyether glycol, 2-15 parts of dibasic acid II, 2-15 parts of diamine, 1-10 parts of a hydrophilic component II, 0.01-0.1 part of a stabilizer, 20-30 parts of an alcohol solvent, 20-30 parts of deionized water and 0.5-10 parts of a pH value regulator. Through the selection and constitutive modification of the raw materials, the prepared alcohol water-soluble modified polyester ink resin disclosed by the invention has good hydrolysis resistance and storage stability. The alcohol water-soluble modified polyester ink resin has the advantages that the hydrophilic functional groups are uniform in distribution, the molecular weight of resin is moderate, the re-dissolving performance is good, the color strength is high, the adhesive force on substrates is good, the film forming strength is high, and the alcohol water-soluble modified polyester ink resin belongs to new-generation environmental-friendly ink resin.
Description
Technical field
The invention belongs to ink resin preparing technical field, particularly water-soluble modified poly ester ink resin of a kind of alcohol and preparation method thereof.
Background technology
The water color ink of current exploitation generally adopts maleated rosin resin, polyacrylic resin and modified acrylic acid emulsion etc. as binder.The standby water color ink of these resin-made is adopted usually to there is rate of drying slow, the shortcomings such as water resisting property and resistance to low temperature difference.Therefore the important directions that the more superior water-based ink resin of over-all properties is the development of current water color ink is developed.
Polyester is the family macromolecule resin obtained by esterification or transesterification reaction with polyvalent alcohol by polyprotonic acid (ester), and water-soluble polyester is then in polyester chain, introduce hydrophilic radical make it possess wetting ability.Current water-soluble polyester is widely used in the numerous areas such as spinning sizing agent, water-borne coatings and water-based stoving paint, and its application in water color ink field also has a small amount of trial.Patent CN101942245B discloses a kind of water-based ink and preparation method thereof.This ink is by certain proportioning raw materials, after the amination of polyester modification macromolecule resin ammoniacal liquor being obtained water soluble resin, then mixes with pigment and water, grinding, then mixes with pure-acrylic emulsion, auxiliary agent etc. and is prepared from.
Patent CN101942246A discloses a kind of water-soluble transparent colored ink for aluminized plastic film and preparation method thereof.This ink is according to a certain ratio by after the amination of waterborne sulfonated vibrin ammoniacal liquor, even with dyestuff and water blending dispersion, after grinding, then mixes with pure-acrylic emulsion, auxiliary agent etc. and is prepared from.
As a rule, drawbacks such as storing instability, not hydrolysis can be there is in the water-soluble polyester that prepared by these class methods.
Summary of the invention
The object of the present invention is to provide a kind of water-soluble modified poly ester ink resin of alcohol with good storage stability and sticking power and water tolerance and preparation method thereof.
The water-soluble modified poly ester ink resin of alcohol of the present invention, by mass parts, it is by diprotic acid I and/or dibasic acid anhydride 10-30 part altogether, the dibasic alcohol of 10-30 part, the catalyzer of hydrophilic component I, 0.01-0.1 part of 2-10 part, the polyether Glycols of 2-15 part, the diamine of diprotic acid II, 2-15 part of 2-15 part, the hydrophilic component II of 1-10 part, the stablizer of 0.01-0.1 part, the alcoholic solvent of 20-30 part, the deionized water of 20-30 part, the pH value regulator reaction of 0.5-10 part forms.
Described diprotic acid I is selected from oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, dimeracid, 1, 2-cyclohexane cyclohexanedimethanodibasic, 1, 3-cyclohexane cyclohexanedimethanodibasic, 1, 4-cyclohexane cyclohexanedimethanodibasic, 2, down alkane dioctyl phthalate falls in 5-, terephthalic acid, phthalic acid, tetrahydrophthalic acid, interior methylene radical tetrahydrophthalic acid, methylhexahydrophthaacid acid, m-phthalic acid, 1, 4-naphthalic acid, 2, 3-naphthalic acid, 2, 5-naphthalic acid, 2, 6-naphthalic acid, 2, 7-naphthalic acid, 4, 4 '-diphenyl dicarboxylic acid, sulfosalicylic phthalate, sulfoterephthalic, one or more in sulfoisophthalic acid.
Described dibasic acid anhydride is selected from one or more in 1,2-cyclohexane cyclohexanedimethanodibasic acid anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, Nadic anhydride, methylhexahydrophthalic anhydride, 2,3-naphthalic anhydrides.
Described dibasic alcohol is selected from ethylene glycol, 1, ammediol, 2-methyl propanediol, 2, 2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2, 2, 4-trimethylammonium-1, 3-pentanediol, neopentyl glycol, 1, 6-hexylene glycol, 1, 2, 4-trimethylammonium-1, 6-hexylene glycol, 2, 2, 4-trimethylammonium-1, 6-hexylene glycol, 2, 4-dimethyl-2-ethyl hexane-1, 3-glycol, ethohexadiol, 1, 9-nonanediol, decanediol, glycol ether, dipropylene glycol, dipropylene glycol, 2, 2, 4, 4-tetramethyl--1, 3-cyclobutanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 2, two (4-hydroxy-cyclohexyl) propane of 2-, terephthalyl alcohol, 4, 4 '-dicyclohexyl glycol, 2, 6-naphthalene glycol, 2, one or more in 7-naphthalene glycol.
Described hydrophilic component I is selected from dimethyl terephthalate (DMT)-2-sodium sulfonate, diglycol terephthalate-2-potassium sulfonate, 5-sodium sulfo isophthalate, m-phthalic acid-5-potassium sulfonate, m-phthalic acid-5-Sulfonic Lithium, Sodium Dimethyl Isophthalate-5-sulfonate, dimethyl isophthalate-5-Sulfonic Lithium, dimethyl isophthalate-5-potassium sulfonate, dimethyl isophthalate-5-sodium sulfonate, the two hydroxyl ethyl ester-5-sodium sulfonate of m-phthalic acid, one or more in the two hydroxyl ethyl ester-5-potassium sulfonate of m-phthalic acid.
Described catalyzer is selected from one or more in tetrabutyl tin, Dibutyltin oxide, stannous octoate, titanium ethanolate, isopropyl titanate, butyl (tetra) titanate, iso-butyl titanate, magnesium acetate, zinc acetate, manganese acetate, antimony acetate, antimonous oxide, germanium dioxide.
Described polyether Glycols is selected from one or more in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, ethylene glycol and 1,2-propylene glycol copolymer glycols, tetrahydrofuran (THF)-propylene oxide copolymer glycols.
Described diprotic acid II is selected from one or more in propanedioic acid, succinic acid, pentanedioic acid, 3,3-dimethylated pentanedioic acids, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, phthalic acid, m-phthalic acid, terephthalic acid, cyclohexane cyclohexanedimethanodibasic.
Described diamine is selected from quadrol, 1,2-propylene diamine, 1,3-propylene diamine, 2-methyl isophthalic acid, 3-propylene diamine, 2,2-dimethyl-1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 2, one or more in 2,4-trimethylhexane diamine, piperazine, 2-methylpiperazine, isophorone diamine, dicyclohexyl methyl hydride-4,4 '-diamines.
Described hydrophilic component II is dimethylol propionic acid and/or dimethylolpropionic acid.
Described stablizer is selected from one or more in phosphoric acid, phosphoric acid ester compound, phosphorous acid, phosphorous acid ester compound, phosphonic acids, phospho acid.
Described alcoholic solvent is selected from one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol.
Described pH value regulator is selected from Trimethylamine 99, triethylamine, ethamine, Tri N-Propyl Amine, secondary propylamine, butylamine, sec-butylamine, TERTIARY BUTYL AMINE, n-amylamine, Alpha-Methyl butylamine, α-ethylpropylamine, β-ethyl butyl amine, hexylamine, octylame, decyl amine, monoisopropanolamine, hexahydroaniline, thanomin, diethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, one or more in N methyldiethanol amine.
The preparation method of the water-soluble modified poly ester ink resin of above-mentioned alcohol is:
(1) diprotic acid I and/or dibasic acid anhydride, dibasic alcohol, hydrophilic component I and catalyzer are dropped in reactor, pass into nitrogen, react by room temperature to 140-160 DEG C, then 210-220 DEG C is warming up to 5-15 DEG C/h, continue after insulation reaction 4-6 hour, be cooled to 70-90 DEG C;
(2) in the reactor of step (1), polyether Glycols, diprotic acid II and diamine, hydrophilic component II is added, then 230-270 DEG C is warming up to 5-15 DEG C/h, stablizer is added after insulation reaction 2-4 hour, open vacuum pump, increase vacuum tightness gradually, until vacuum tightness≤-0.095MPa, continue the acid number≤1mgKOH/ gram of insulation reaction to resin, cooling resin, to 50-70 DEG C, obtains modified poly ester;
(3) in dispersion reactor, alcoholic solvent and deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add pH value regulator, the pH value of adjustment solution is 7.5-8.5, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 10000-100000.
The present invention, by the selection of plurality of raw materials and structurally-modified, makes made alcohol water-soluble modified poly ester ink resin have good hydrolytic resistance and storage stability.The hydrophilic functional group of the water-soluble modified poly ester ink resin of this alcohol is evenly distributed, and molecular resin amount is moderate, and solubility is good, and color development power is strong, and good to base material sticking power, film strength is high, belongs to environment-friendly ink resin of new generation.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but should not be understood as limiting the scope of the invention.All based on above-mentioned technological thought, the amendment utilizing ordinary skill knowledge and usual technique means to make, replacement, change, all belong to scope of the present invention.Its middle-molecular-weihydroxyethyl adopts gel permeation chromatography to be that standard specimen measures with polystyrene.
Embodiment 1
(1) by 4kg oxalic acid, 6kg 1,1 of 2-cyclohexane cyclohexanedimethanodibasic acid anhydride, 14kg, ammediol, 16kg pentanediol, 2kg dimethyl terephthalate (DMT)-2-sodium sulfonate and 0.1kg tetrabutyl tin drop in reactor, pass into nitrogen, react by room temperature to 140 DEG C, then be warming up to 210 DEG C with 5 DEG C/h, continue insulation reaction after 5 hours, be cooled to 70 DEG C;
(2) in the reactor of step (1), 2kg polyoxyethylene glycol, 0.5kg propanedioic acid, 1.5kg dodecanedioic acid and 2.3kg quadrol, 1.5kg dimethylol propionic acid is added, then 230 DEG C are warming up to 5 DEG C/h, insulation reaction adds 0.05kg phosphoric acid and 0.05kg phosphorous acid after 3 hours, open vacuum pump, increase vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.5mgKOH/ gram, cooling resin to 70 DEG C, obtained modified poly ester;
(3) in dispersion reactor, 5kg ethanol, 15kg propyl carbinol and 20kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add 3kg Trimethylamine 99,7kg diethanolamine, the pH value of adjustment solution is 7.5, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 10000.
Embodiment 2
(1) by the propanedioic acid of 12kg, 2 of 8kg, the 2-methyl propanediol of 3-naphthalic acid, 9kg, 1 of 11kg, 2,4-trimethylammonium-1, in the Dibutyltin oxide of the two hydroxyl ethyl ester-5-sodium sulfonate of the diglycol terephthalate-2-potassium sulfonate of 6-hexylene glycol, 4.5kg, the m-phthalic acid of 1.5kg and 0.025kg, the antimonous oxide input reactor of 0.03kg, pass into nitrogen, react by room temperature to 150 DEG C, then 215 DEG C are warming up to 10 DEG C/h, continue insulation reaction after 4 hours, be cooled to 90 DEG C;
(2) in the reactor of step (1), 2kg polypropylene glycol is added, 0.5kg tetrahydrofuran (THF)-propylene oxide copolymer glycols, 1.5kg succinic acid, 1 of 0.5kg cyclohexane cyclohexanedimethanodibasic and 0.7kg, 2-propylene diamine, 1.3kg dicyclohexyl methyl hydride-4, 4 '-diamines, 0.935kg dimethylolpropionic acid, 1kg dimethylol propionic acid, then 250 DEG C are warming up to 10 DEG C/h, insulation reaction adds 0.005kg methyl orthophosphoric acid and 0.005kg phospho acid after 2 hours, open vacuum pump, increase vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.3mgKOH/ gram, cooling resin to 50 DEG C, obtained modified poly ester,
(3) in dispersion reactor, 20kg n-propyl alcohol and 25kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add 0.25kg triethylamine and 0.25kgN, N-diethylethanolamine, the pH value of adjustment solution is 8, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 55000.
Embodiment 3
(1) by the ethylene glycol of the sulfosalicylic phthalate of the methylhexahydrophthalic anhydride of 20kg, 10kg, 8kg, 2 of 2kg, 2-dimethyl-1, the 5-sodium sulfo isophthalate of ammediol, 4kg and the stannous octoate of 0.01kg drop in reactor, pass into nitrogen, react by room temperature to 150 DEG C, then be warming up to 220 DEG C with 15 DEG C/h, continue insulation reaction after 6 hours, be cooled to 80 DEG C;
(2) in the reactor of step (1), 3kg polytetrahydrofuran diol, 2kg pentanedioic acid and 2.685kg 1 is added, 3-propylene diamine, 2kg dimethylol propionic acid, then 270 DEG C are warming up to 15 DEG C/h, insulation reaction added 0.055kg dimethyl phosphate after 4 hours, opened vacuum pump, increased vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.6mgKOH/ gram, cooling resin to 60 DEG C, obtained modified poly ester;
(3) in dispersion reactor, 21kg Virahol and 20kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add 2kg ethamine and 3.25kg hexahydroaniline, the pH value of adjustment solution is 8.5, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 100000.
Embodiment 4
(1) by the hexanodioic acid of 10kg, 1 of 5kg, 2-ethyl-2-the butyl-1 of 3-butyleneglycol, 6kg, m-phthalic acid-5-the potassium sulfonate of ammediol, 10kg and the titanium ethanolate of 0.01kg drop in reactor, pass into nitrogen, react by room temperature to 160 DEG C, then be warming up to 214 DEG C with 12 DEG C/h, continue insulation reaction after 4.5 hours, be cooled to 75 DEG C;
(2) add in the reactor of step (1) 8.5kg ethylene glycol and 1,2-propylene glycol copolymer glycols, 2.48kg 3, the 2-methyl isophthalic acid of 3-dimethylated pentanedioic acid and 2kg, the dimethylolpropionic acid of 3-propylene diamine, 5.5kg, then 240 DEG C are warming up to 10 DEG C/h, insulation reaction added 0.04kg etherophosphoric acid after 2.5 hours, open vacuum pump, increase vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.2mgKOH/ gram, cooling resin to 55 DEG C, obtained modified poly ester;
(3) in dispersion reactor, 25kg propyl carbinol and 24.97kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add 0.5kg Tri N-Propyl Amine, the pH value of adjustment solution is 7.9, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 30000.
Embodiment 5
(1) by the 2-ethyl-2-isobutyl--1 of the sebacic acid of 12.98kg, 11kg, m-phthalic acid-5-the Sulfonic Lithium of ammediol, 2kg and the isopropyl titanate of 0.01kg drop in reactor, pass into nitrogen, react by room temperature to 154 DEG C, then 218 DEG C are warming up to 8 DEG C/h, continue insulation reaction after 5.5 hours, be cooled to 82 DEG C;
(2) in the reactor of step (1), 2kg tetrahydrofuran (THF)-propylene oxide copolymer glycols, 2kg hexanodioic acid and 8.5kg 2 is added, 2-dimethyl-1, the dimethylol propionic acid of 3-propylene diamine, 3kg, the dimethylolpropionic acid of 7kg, then 260 DEG C are warming up to 7 DEG C/h, insulation reaction added 0.01kg diethyl phosphoric acid after 3.5 hours, open vacuum pump, increase vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.7mgKOH/ gram, cooling resin to 65 DEG C, obtained modified poly ester;
(3) in dispersion reactor, 30kg sec-butyl alcohol and 21kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add the secondary propylamine of 0.5kg, the pH value of adjustment solution is 8.2, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 60000.
Embodiment 6
(1) by the dimeracid of 13kg, 1 of 10kg, the Sodium Dimethyl Isophthalate-5-sulfonate of 3-butyleneglycol, 2kg and the butyl (tetra) titanate of 0.09kg drop in reactor, pass into nitrogen, react by room temperature to 147 DEG C, then 216 DEG C are warming up to 14 DEG C/h, continue insulation reaction after 5.5 hours, be cooled to 83 DEG C;
(2) in the reactor of step (1), 15kg polyoxyethylene glycol, 2.9kg suberic acid and 15kg 1 is added, 4-butanediamine, 1kg dimethylolpropionic acid, then 262 DEG C are warming up to 12 DEG C/h, insulation reaction added 0.01kg phosphorous acid after 3.6 hours, opened vacuum pump, increased vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.3mgKOH/ gram, cooling resin to 68 DEG C, obtained modified poly ester;
(3) in dispersion reactor, 20kg isopropylcarbinol and 20kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add 1kg butylamine, the pH value of adjustment solution is 7.6, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 21000.
Embodiment 7
(1) by 1 of 10kg, 1 of 2-cyclohexane cyclohexanedimethanodibasic, 11.43kg, dimethyl isophthalate-5-the Sulfonic Lithium of 4-butyleneglycol, 2kg and the iso-butyl titanate of 0.06kg drop in reactor, pass into nitrogen, react by room temperature to 148 DEG C, then be warming up to 213 DEG C with 6 DEG C/h, continue insulation reaction 4.8 hours, be cooled to 76 DEG C;
(2) in the reactor of step (1), 6kg polypropylene glycol, 15kg nonane diacid and 2kg 1 is added, 5-pentamethylene diamine, 1kg dimethylol propionic acid, then 265 DEG C are warming up to 14 DEG C/h, insulation reaction added 0.01kg methyl phosphite after 2.4 hours, opened vacuum pump, increased vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.5mgKOH/ gram, cooling resin to 57 DEG C, obtained modified poly ester;
(3) in dispersion reactor, 20kg ethanol and 30kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add 2.5kg sec-butylamine, the pH value of adjustment solution is 8.1, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 83000.
Embodiment 8
(1) by 2 of 11kg, the magnesium acetate that down alkane dioctyl phthalate, the pentanediol of 12kg, the dimethyl isophthalate-5-potassium sulfonate of 2kg and 0.01kg fall in 5-drops in reactor, pass into nitrogen, react by room temperature to 159 DEG C, then 217 DEG C are warming up to 9 DEG C/h, continue insulation reaction after 5.3 hours, be cooled to 79 DEG C;
(2) in the reactor of step (1), 12kg polytetrahydrofuran diol, 8.5kg sebacic acid and 4kg 1 is added, 6-hexanediamine, 7kg dimethylolpropionic acid, then 247 DEG C are warming up to 6 DEG C/h, insulation reaction added 0.01kg phosphonic acids after 2.9 hours, opened vacuum pump, increased vacuum tightness gradually, until vacuum tightness≤-0.095MPa, when to continue insulation reaction to the acid number of resin be 0.4mgKOH/ gram, cooling resin to 59 DEG C, obtained modified poly ester;
(3) in dispersion reactor, 21kg n-propyl alcohol and 20kg deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add 2.48kg TERTIARY BUTYL AMINE, the pH value of adjustment solution is 8.4, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 76000.
Claims (10)
1. the water-soluble modified poly ester ink resin of alcohol, is characterized in that, by mass parts, it is by diprotic acid I and/or dibasic acid anhydride 10-30 part altogether, the dibasic alcohol of 10-30 part, the hydrophilic component I of 2-10 part, the catalyzer of 0.01-0.1 part, the polyether Glycols of 2-15 part, the diprotic acid II of 2-15 part, the diamine of 2-15 part, the stablizer of hydrophilic component II, 0.01-0.1 part of 1-10 part, the alcoholic solvent of 20-30 part, the deionized water of 20-30 part, the pH value regulator reaction of 0.5-10 part forms.
2. the water-soluble modified poly ester ink resin of alcohol according to claim 1, it is characterized in that, described diprotic acid I is selected from oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, dimeracid, 1, 2-cyclohexane cyclohexanedimethanodibasic, 1, 3-cyclohexane cyclohexanedimethanodibasic, 1, 4-cyclohexane cyclohexanedimethanodibasic, 2, down alkane dioctyl phthalate falls in 5-, terephthalic acid, phthalic acid, tetrahydrophthalic acid, interior methylene radical tetrahydrophthalic acid, methylhexahydrophthaacid acid, m-phthalic acid, 1, 4-naphthalic acid, 2, 3-naphthalic acid, 2, 5-naphthalic acid, 2, 6-naphthalic acid, 2, 7-naphthalic acid, 4, 4 '-diphenyl dicarboxylic acid, sulfosalicylic phthalate, sulfoterephthalic, one or more in sulfoisophthalic acid,
Described dibasic acid anhydride is selected from one or more in 1,2-cyclohexane cyclohexanedimethanodibasic acid anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, Nadic anhydride, methylhexahydrophthalic anhydride, 2,3-naphthalic anhydrides.
3. the water-soluble modified poly ester ink resin of alcohol according to claim 1, it is characterized in that, described dibasic alcohol is selected from ethylene glycol, 1,3-PD, 2-methyl propanediol, 2，2-dimethyl-1，3-propanediol, 2-ethyl-2-butyl-1,3-PD, 2-ethyl-2-isobutyl--1,3-PD, 1,3 butylene glycol, BDO, pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,2,4-trimethylammonium-1,6-hexylene glycol, 2,2,4-trimethylammonium-1,6-hexylene glycol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, ethohexadiol, 1,9-nonanediol, decanediol, glycol ether, dipropylene glycol, dipropylene glycol, TMCD, 1,2-CHDM, 1,3-CHDM, 1,4 cyclohexane dimethanol, two (4-hydroxy-cyclohexyl) propane of 2,2-, terephthalyl alcohol, 4,4 '-dicyclohexyl glycol, 2,6-naphthalene glycol, one or more in 2,7-naphthalene glycol.
4. the water-soluble modified poly ester ink resin of alcohol according to claim 1, it is characterized in that, described hydrophilic component I is selected from dimethyl terephthalate (DMT)-2-sodium sulfonate, diglycol terephthalate-2-potassium sulfonate, 5-sodium sulfo isophthalate, m-phthalic acid-5-potassium sulfonate, m-phthalic acid-5-Sulfonic Lithium, Sodium Dimethyl Isophthalate-5-sulfonate, dimethyl isophthalate-5-Sulfonic Lithium, dimethyl isophthalate-5-potassium sulfonate, dimethyl isophthalate-5-sodium sulfonate, the two hydroxyl ethyl ester-5-sodium sulfonate of m-phthalic acid, one or more in the two hydroxyl ethyl ester-5-potassium sulfonate of m-phthalic acid,
Described catalyzer is selected from one or more in tetrabutyl tin, Dibutyltin oxide, stannous octoate, titanium ethanolate, isopropyl titanate, butyl (tetra) titanate, iso-butyl titanate, magnesium acetate, zinc acetate, manganese acetate, antimony acetate, antimonous oxide, germanium dioxide.
5. the water-soluble modified poly ester ink resin of alcohol according to claim 1, it is characterized in that, described polyether Glycols is selected from one or more in polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, ethylene glycol and 1,2-propylene glycol copolymer glycols, tetrahydrofuran (THF)-propylene oxide copolymer glycols.
6. the water-soluble modified poly ester ink resin of alcohol according to claim 1, it is characterized in that, described diprotic acid II is selected from one or more in propanedioic acid, succinic acid, pentanedioic acid, 3,3-dimethylated pentanedioic acids, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, phthalic acid, m-phthalic acid, terephthalic acid, cyclohexane cyclohexanedimethanodibasic.
7. the water-soluble modified poly ester ink resin of alcohol according to claim 1, it is characterized in that, described diamine is selected from quadrol, 1,2-propylene diamine, 1,3-propylene diamine, 2-methyl isophthalic acid, 3-propylene diamine, 2,2-dimethyl-1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 2, one or more in 2,4-trimethylhexane diamine, piperazine, 2-methylpiperazine, isophorone diamine, dicyclohexyl methyl hydride-4,4 '-diamines.
8. the water-soluble modified poly ester ink resin of alcohol according to claim 1, is characterized in that, described hydrophilic component II is dimethylol propionic acid and/or dimethylolpropionic acid.
9. the water-soluble modified poly ester ink resin of alcohol according to claim 1, is characterized in that, described stablizer is selected from one or more in phosphoric acid, phosphoric acid ester compound, phosphorous acid, phosphorous acid ester compound, phosphonic acids, phospho acid;
Described alcoholic solvent is selected from one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol;
Described pH value regulator is selected from Trimethylamine 99, triethylamine, ethamine, Tri N-Propyl Amine, secondary propylamine, butylamine, sec-butylamine, TERTIARY BUTYL AMINE, n-amylamine, Alpha-Methyl butylamine, α-ethylpropylamine, β-ethyl butyl amine, hexylamine, octylame, decyl amine, monoisopropanolamine, hexahydroaniline, thanomin, diethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, one or more in N methyldiethanol amine.
10., according to the preparation method of the arbitrary described water-soluble modified poly ester ink resin of alcohol of claim 1-9, it is characterized in that, its concrete operation step is:
(1) diprotic acid I and/or dibasic acid anhydride, dibasic alcohol, hydrophilic component I and catalyzer are dropped in reactor, pass into nitrogen, react by room temperature to 140-160 DEG C, then 210-220 DEG C is warming up to 5-15 DEG C/h, continue after insulation reaction 4-6 hour, be cooled to 70-90 DEG C;
(2) in the reactor of step (1), polyether Glycols, diprotic acid II and diamine, hydrophilic component II is added, then 230-270 DEG C is warming up to 5-15 DEG C/h, stablizer is added after insulation reaction 2-4 hour, open vacuum pump, increase vacuum tightness gradually, until vacuum tightness≤-0.095MPa, continue the acid number≤1mgKOH/ gram of insulation reaction to resin, cooling resin, to 50-70 DEG C, obtains modified poly ester;
(3) in dispersion reactor, alcoholic solvent and deionized water is added, after mixing and stirring, the modified poly ester that step (2) is obtained is put in dispersion reactor under whipped state, after stirring and dissolving is even, add pH value regulator, the pH value of adjustment solution is 7.5-8.5, and discharging obtains the water-soluble modified poly ester ink resin of alcohol that number-average molecular weight is 10000-100000.
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