CN102504527A - Ultraviolet curing cationic aqueous polyurethane dispersion liquid with ion-containing soft segment, and preparation method thereof - Google Patents
Ultraviolet curing cationic aqueous polyurethane dispersion liquid with ion-containing soft segment, and preparation method thereof Download PDFInfo
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Abstract
The invention provides an ultraviolet-curing cationic aqueous polyurethane dispersion liquid with an ion-containing soft segment, and a preparation method thereof. The aqueous polyurethane dispersion liquid comprises, by mass, 25-45% of an ultraviolet-curing cationic aqueous polyurethane prepolymer, 0-1% of a catalyst, 0-2% of an antifoaming agent, 0.5-5% of an aqueous photoinitiator, and 47-74.5% of water, wherein the soft segment polyol for forming the prepolymer is the polyol with an ion-containing soft segment, the number average molecular weight of the soft segment polyol is 500-3000, and the soft segment polyol is prepared by the following steps: carrying out a reaction of diisocyanate with a symmetrical structure and a cationic hydrophilic chain extender according to a molar ratio of 2:1, and adopting a small molecular weight polyol to carry out end capping to prepare the soft segment polyol. The ultraviolet-curing cationic aqueous polyurethane dispersion liquid of the present invention has characteristics of high solid content, small particle size, low viscosity, stable storage, and fast curing, and can provide the following advantages under the condition of the less use amount of the materials, wherein the advantages comprise that: the mechanical performance is maintained, the raw materials are saved, and the excellent properties are provided. In addition, the advantages of simple operation, no requirement of complex equipment are provided.
Description
Technical field
The present invention relates to a kind of UV-curable water-borne cation polyurethane dispersion liquid and preparation method thereof, particularly soft section cation polyvalent alcohol and preparation method thereof.
Background technology
Urethane is a kind of soft section block polymer that alternately is connected with hard section, and wherein oligomer polyol has constituted soft section of polymkeric substance, and isocyanic ester and small molecule chain extender react hard section that has constituted polymkeric substance.Because environmental requirement, the range of application of aqueous polyurethane (WPU) is more and more wider.Aqueous polyurethane with water as dispersion medium, have nontoxic, do not fire, environmental protection, characteristics such as energy-conservation.Aqueous polyurethane is different according to the group charging property of its introducing, can be divided into anionic, cationic, non-ionic type and amphoteric.The hydrophilic radical of introducing is carboxyl and sulfonic genus anionic; Hydrophilic radical is that the genus of tertiary amine groups is cationic; Hydrophilic radical is the genus non-ionic type that water miscible polyoxyethylene glycol or employing contain the hydrophilic polymerized ether of ethylene oxide chain link.((particle diameter is at 0.001um～0.1um), aqueous polyurethane (particle diameter＜0.001um) for particle diameter＞0.1um), polyurethane dispersing liquid can be divided into polyaminoester emulsion according to the dispersion state aqueous polyurethane.
For aqueous polyurethane; Present domestic and international research mainly is placed on hard section and contains on ionic polyaminoester emulsion and the method for modifying thereof; But there are problems such as vaporization heat is high, rate of drying is slow, poor to the non-polar substrate wettability, original viscosity is low, poor water resistance, and thermotolerance is bad in the synthetic aqueous polyurethane more.
Research report for anion aqueous polyurethane is very many, and its product has also been realized industriallization, but also less relatively to the research report of cation aqueous polyurethane.This mainly is that with the operation more complicated that performed polymer carries out the quaternary ammonium salinization, cost is higher because cation aqueous polyurethane is generally quaternary, and sometimes emulsifying product is stable inadequately, so bring difficulty to suitability for industrialized production.
Have positively charged ion on the skeleton of cation-type water-thinned polyurethane, make it have particular performances, have in fields such as leather, coating, textile and papers preferably and use.In addition, cation aqueous polyurethane is insensitive to water hardness, can under acidic conditions, use.Therefore, develop excellent performance, the cation aqueous polyurethane that emulsifying product is stable, its market outlook are boundless.
Summary of the invention
The problem that the present invention will solve is to provide soft section of a kind of uV curable to contain ionic cation aqueous polyurethane dispersion liquid and preparation method thereof to the problems referred to above.This soft section contains the positive aqueous polyurethane of ionic and has the characteristics of solid content height, emulsion-stabilizing, quick solidifying, water-tolerant, good heat resistance, can under the thinner situation of material, guarantee mechanical property, saves material, and has excellent performance.
The present invention addresses the above problem the solution that is adopted to contain ionic ultraviolet light polymerization cation aqueous polyurethane dispersion liquid for having prepared a kind of soft section.
The composition of ultraviolet light polymerization cation aqueous polyurethane dispersion liquid provided by the invention comprises:
Described percentage ratio is mass percent
For synthetic described ultraviolet light polymerization cation aqueous polyurethane prepolymer, provide a series of novel soft section to contain the ionic oligomer polyol, its structure can be for shown in following A, the B general structure:
A：
R wherein
1, R
2And R
3Be one or more (down together) in the following structure;
R
1For:
Again or
R
2For:
Again or
A=2 wherein, 4,6.N >=1 is integer.
R
3Be H, or be C
1-C
6Straight chained alkyl, or end group is hydroxyl (C OH)
1-C
6Straight chain primary alcohol, or end group is a benzyl
C
1-C
6Straight chained alkyl.
B：
Soft section polyvalent alcohol of above-mentioned ion among the present invention is through vulcabond that will have symplex structure and the reaction of cationic small molecules hydrophilic chain extender; Acquisition is with the polymkeric substance of-NCO group end capping; Further prepare again, it is characterized in that including following steps with the oligomer polyol of small molecular weight oligomer polyol reaction generations-OH group end capping:
1) gets and have above-mentioned R
1The vulcabond of structure joins in the reaction vessel that whisking appliance, TM and constant pressure funnel are housed, and reaction unit places water-bath, and other gets has aforementioned R
3The cationic small molecules hydrophilic chain extender of structure adds in the constant pressure funnel, splashes in the reaction vessel, dropwises in 30-60 minute.Wherein the mol ratio of vulcabond and cationic small molecules hydrophilic chain extender is 2: 1.
2) treat that cationic hydrophilic chain extender dropwises after, the temperature of reaction in the reaction vessel is risen to 65 ℃, be incubated 1 hour; Then rise to 75 ℃; Be incubated 2-8 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use.
3) get in addition and have aforementioned R
2The small molecular weight oligomer polyol of structure joins in another reaction vessel that whisking appliance, TM and constant pressure funnel are housed; Temperature of reaction in the reaction vessel is risen to 40 ℃; Get 2) in the synthetic oligopolymer add in the constant pressure funnel; Splash in the reaction vessel, dropwised in 30-60 minute.Be warming up to 85 ℃ of reactions 2-8 hour after being added dropwise to complete.Small molecular weight oligomer polyol and 2 wherein) mol ratio of synthetic oligopolymer is 2: 1.
4) determination step 3) free isocyanate content of gained oligopolymer, when NCO% stopped reaction near 0 time, vacuum defoamation 30 minutes is cooled to room temperature, and discharging promptly gets soft section polyvalent alcohol of ionic.
Described ultraviolet light polymerization cation aqueous polyurethane prepolymer can be shown in following C, D, the E general structure:
C：
D：
E：
In the formula, R is soft section of an aforementioned synthetic ionic, it is characterized in that the molecular weight ranges that is had is: 500≤number-average molecular weight≤3000; R
4Be neutralizing agent, like sulfuric acid, hydrochloric acid, Glacial acetic acid min. 99.5, methyl sulfate, oxyacetic acid etc.; R
5Be the cationic hydrophilic chainextender, like N methyldiethanol amine, trolamine, diethylolamine, N-propyl group diethylolamine, N-benzyl diethylolamine, tertiary butyl diethylolamine, benzylaniline etc.; R
6Be vulcabond; As 2,4 toluene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 1; 6-hexyl diisocyanate, 4; 4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, 1,4-phenylene diisocyanate, 2,4 '-diphenylmethanediisocyanate, Methylcyclohexyl diisocyanate etc. and composition thereof; R
7For containing the small molecule chain extender of active hydrogenate, comprise small molecules two pure and mild small molecules diamines, comprise the part anhydride compound in addition, the small molecules glycol is like terepthaloyl moietie, Ucar 35, NSC 6366,1,4-butyleneglycol, 1,6-pinakon etc.; The small molecules diamines is like quadrol, 1,4-tetramethylenediamine, cyclohexanediamine, 1,6-hexanediamine, tn, your ketone diamines of different fluorine etc.; Anhydride compound such as pyromellitic dianhydride etc.; R
8Be end-capping reagent such as Hydroxyethyl acrylate, Rocryl 400 etc.; NR
3' be tertiary amine compound.
Described catalyzer is dibutyl tin laurate, stannous octoate, triethylamine, diethylenetriamine, sodium methylate etc., can be single a kind of or above-mentioned multiple mixture;
Described skimmer is one or more the mixture among BYK-141, BYK-065/066,201 methyl-silicone oils, Perenol S4, Perenol S43, the Perenol E1 etc.;
Described water-soluble photoinitiator is one or more the mixture among Irgacure1173, Irgacure2959, Irgacure184, the Irgacure500.
A kind of soft section provided by the invention to contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid preparation process following:
1) soft section that gets in the aforementioned ultraviolet light polymerization cation aqueous polyurethane prepolymer general structure contains ion polyvalent alcohol R; In 100～120 ℃ under 0.09MPa decompression dehydration 1-2 hour; Be cooled to 40 ℃, under agitation condition, add vulcabond R in the said structure formula
6With 0～1% catalyzer, system slowly is warming up to 80 ℃ of reactions 2-6 hour, measure system free isocyanate content and reach after the theoretical value stopped reaction and be cooled to 30 ℃ of left and right sides for use;
2) the cationic hydrophilic chainextender R among the dropping general structure C in the oligopolymer after above-mentioned cooling
5Or the chainextender among the general structure D 2, the 3-dibromo-succinic acid, the organic solvent of adding 5～10% was warming up to 50 ℃ of insulation reaction 1-3 hours; Add the active hydrogenate small molecule chain extender R that contains in the general structure
7, 65 ℃ the reaction 1 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use.If do not add hydrophilic chain extender and directly do not adopt the small molecule chain extender chain extension, and then by following 3) end-blocking then obtains structure E and contains ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid for said soft section;
3) in above-mentioned product, add the end-capping reagent R described in the general structure
8, being dissolved with 0.5～4% stopper of end-capping reagent quality in the end-capping reagent, end-capping reagent slightly excessive (end-blocking rate 1.02～1.10) is warming up to 85 ℃ of reactions 2 hours, measures the system free isocyanate content near 0 back stopped reaction, is cooled to 40 ℃;
4) add the neutralization reagent R described in the general structure
4Or NR
3', under high-speed stirring in 30 minutes, promptly obtain soft section shown in above-mentioned three kinds of general structures and contain ion ultraviolet light polymerization cation aqueous polyurethane prepolymer;
5) in above-mentioned prepolymer, add the deionized water that measures, disperseed fast 5～15 minutes, use high-shear emulsifying appearance emulsification 15～30 minutes again, obtain white emulsion, add 0～2% skimmer;
6) above-mentioned emulsion is warming up to 30～50 ℃ of vacuum removal organic solvents under 0.09MPa, adds 0.5～5% water-soluble photoinitiator, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
According to such scheme, the preparation method of soft section polyvalent alcohol of described ionic is characterized in that described free isocyanate content is measured to measure by HG/T 2409-1992 " different propylhomoserin ester group Determination on content in the base polyurethane prepolymer for use as ";
Described organic solvent is one or more in acetone, butanone, ETHYLE ACETATE, the YLENE;
Described stopper is Resorcinol, p methoxy phenol or 2,6 di tert butyl 4 methyl phenol.
Positive progressive effect of the present invention is:
Soft section of ultraviolet light polymerization provided by the present invention contains that ion cation aqueous polyurethane dispersion liquid has the solid content height, particle diameter is little, viscosity is little, the characteristics of shelf-stable, quick solidifying; And can under material usage situation still less, guarantee mechanical property; Save material, have excellent performance.Have simple to operately simultaneously, do not need the advantage of complex apparatus.
Soft section of ultraviolet light polymerization of the present invention contains ion cation aqueous polyurethane dispersion liquid and can be used as tackiness agent, coating-forming agent etc. and be applied to industries such as leather, weaving, coating, sizing agent, woodenware, building, printing and dyeing, papermaking.
Embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to ordinary method and condition, or is selected according to catalogue.
Embodiment 1
(a) 336g hexamethylene diisocyanate (HDI) adding is equipped with in the container of whisking appliance, TM and constant pressure funnel, feeds nitrogen protection, under the water bath condition 119gN-methyldiethanolamine (MDEA) is added constant pressure funnel and in 30-60 minute, drip to advance among the HDI; Be warming up to 65 ℃ after being added dropwise to complete; Be incubated 1 hour, then rise to 75 ℃, be incubated 2-8 hour; Stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, be cooled to 40 ℃ for use;
(b) in the container that whisking appliance, TM and constant pressure funnel are housed, adding the 900g number-average molecular weight is 450 PTMG (PTMG-450); Logical nitrogen protection is stirred and is warming up to 40 ℃, and mixture solution in (a) is transferred in the constant pressure funnel; Drop in the reaction vessel in 30-60 minute; Be warming up to after being added dropwise to complete 85 ℃ the reaction 2-8 hour, treat the isocyanate groups complete reaction in the system after, the structural formula that contains soft section of ion that obtains the A structure is:
(c) soft section of above-mentioned ion is cooled to 40 ℃, adds 1048g4,4 '-dicyclohexyl methane diisocyanate (H
12MDI), add 0.72g dibutyl tin laurate (DBTDL), temperature in the system is risen to 80 ℃, insulation reaction 2-6 hour, the free isocyanate content reached after the theoretical value stopped reaction and is cooled to 30 ℃ in the mensuration system;
(d) add the 294g butanone, drip 238gMDEA and go in the above-mentioned oligopolymer, be warming up to 50 ℃ of insulation reaction 1-3 hours; Add 45g1, the 4-butyleneglycol is warming up to 65 ℃ of reactions 1 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use;
(e) the 1.03g Resorcinol being dissolved in the middle dropping of 68.3g Rocryl 400 (HEMA) advances in (d) product; Slowly be warming up to 85 ℃ of reactions of its structure 2 hours; Mensuration system free isocyanate content is cooled to 40 ℃ near 0 back stopped reaction, obtains blocked prepolymer;
(f) the 180g Glacial acetic acid min. 99.5 is added in (e) end-blocking thing, under 900 rev/mins high-speed stirring in 30 minutes, promptly get soft section prepolymer of the positively charged ion of ultra-violet curing shown in the structure C, its structural formula is:
(g) in above-mentioned prepolymer, add the 4571g deionized water, in 1200 rev/mins of high-speed stirring, disperseed 5-15 minute fast, use high-shear emulsifying appearance emulsification 15-30 minute again, obtain white emulsion, add the 31gBYK-141 froth breaking;
(f) above-mentioned emulsion is warming up to 45 ℃ of vacuum removal organic solvent butanone under 0.09MPa, adds 2.73gIrgacure1173, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
Embodiment 2
(a) 336g hexamethylene diisocyanate (HDI) adding is equipped with in the container of whisking appliance, TM and constant pressure funnel, feeds nitrogen protection, under the water bath condition 119gN-methyldiethanolamine (MDEA) is added constant pressure funnel and in 30-60 minute, drip to advance among the HDI; Be warming up to 65 ℃ after being added dropwise to complete; Be incubated 1 hour, then rise to 75 ℃, be incubated 2-8 hour; Stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, be cooled to 40 ℃ for use;
(b) in the container that whisking appliance, TM and constant pressure funnel are housed, adding the 800g number-average molecular weight is 400 polyoxypropyleneglycol (PPG-400); Logical nitrogen protection is stirred and is warming up to 40 ℃, and mixture solution in (a) is transferred in the constant pressure funnel; Drop in the reaction vessel in 30-60 minute; Be warming up to after being added dropwise to complete 85 ℃ the reaction 2-8 hour, treat the isocyanate groups complete reaction in the system after, the structural formula that contains soft section of ion that obtains the A structure is:
(c) soft section of above-mentioned ion is cooled to 40 ℃, adds 1048g4,4 '-dicyclohexyl methane diisocyanate (H
12MDI), add the 0.69g stannous octoate, temperature in the system is risen to 80 ℃, insulation reaction 2-6 hour, the free isocyanate content reached after the theoretical value stopped reaction and is cooled to 30 ℃ in the mensuration system;
(d) add the 284g butanone, drip 238gMDEA and go in the above-mentioned oligopolymer, be warming up to 50 ℃ of insulation reaction 1-3 hours; Add 58g1,6-hexanediamine ice bath reaction 1 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use;
(e) with 0.93g2; The 6-di-tert-butyl-4-methy phenol is dissolved in the 60.9g Hydroxyethyl acrylate (HEA) and drips in (d) product, slowly is warming up to 85 ℃ of reactions of its structure 2 hours, measures the system free isocyanate content near 0 back stopped reaction; Be cooled to 40 ℃, obtain blocked prepolymer;
(f) the 180g Glacial acetic acid min. 99.5 is added in (e) end-blocking thing, under 900 rev/mins high-speed stirring in 30 minutes, promptly get soft section prepolymer of the positively charged ion of ultra-violet curing shown in the structure C, its structural formula is:
(g) in above-mentioned prepolymer, add the 4294g deionized water, in 1200 rev/mins of high-speed stirring, disperseed 5-15 minute fast, use high-shear emulsifying appearance emulsification 15-30 minute again, obtain white emulsion, add 29g201 methyl-silicone oil froth breaking;
(f) above-mentioned emulsion is warming up to 45 ℃ of vacuum removal organic solvent butanone under 0.09MPa, adds 1.9gIrgacure2959, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
Embodiment 3
(a) with 332g1,4-cyclohexyl diisocyanate (CHDI) adding is equipped with in the container of whisking appliance, TM and constant pressure funnel, feeds nitrogen protection; Under the water bath condition 119gN-methyldiethanolamine (MDEA) is added constant pressure funnel and in 30-60 minute, drip to advance among the CHDI, be warming up to 65 ℃ after being added dropwise to complete, be incubated 1 hour; Then rise to 75 ℃; Be incubated 2-8 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, be cooled to 40 ℃ for use;
(b) in the container that whisking appliance, TM and constant pressure funnel are housed, adding the 800g number-average molecular weight is 400 polyoxypropyleneglycol (PPG-400); Logical nitrogen protection is stirred and is warming up to 40 ℃, and mixture solution in (a) is transferred in the constant pressure funnel; Drop in the reaction vessel in 30-60 minute; Be warming up to after being added dropwise to complete 85 ℃ the reaction 2-8 hour, treat the isocyanate groups complete reaction in the system after, the structural formula that contains soft section of ion that obtains the A structure is:
(c) soft section of above-mentioned ion is cooled to 40 ℃, adds 786g4,4 '-dicyclohexyl methane diisocyanate (H
12MDI), add the 0.61g stannous octoate, temperature in the system is risen to 80 ℃, insulation reaction 2-6 hour, the free isocyanate content reached after the theoretical value stopped reaction and is cooled to 30 ℃ in the mensuration system;
(d) add the 231g butanone, be added dropwise to 90g1 in 30 minutes, the 4-butyleneglycol is warming up to 65 ℃ of reactions 1 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use;
(e) the 1.83g p methoxy phenol being dissolved in the middle dropping of 121.8g Hydroxyethyl acrylate (HEA) advances in (d) product; Slowly be warming up to 85 ℃ of reactions of its structure 2 hours; Mensuration system free isocyanate content is cooled to 40 ℃ near 0 back stopped reaction, obtains blocked prepolymer;
(f) the 60g Glacial acetic acid min. 99.5 is added in (e) end-blocking thing, under 900 rev/mins high-speed stirring in 30 minutes, promptly get soft section prepolymer of ultra-violet curing positively charged ion shown in the structure E, its structural formula is:
(g) in above-mentioned prepolymer, add the 4289g deionized water, in 1200 rev/mins of high-speed stirring, disperseed 5-15 minute fast, use high-shear emulsifying appearance emulsification 15-30 minute again, obtain white emulsion, add the 23gBYK-065 froth breaking;
(f) above-mentioned emulsion is warming up to 45 ℃ of vacuum removal organic solvent butanone under 0.09MPa, adds 3.8gIrgacure184, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
Embodiment 4
(a) with 332g1,4-cyclohexyl diisocyanate (CHDI) adding is equipped with in the container of whisking appliance, TM and constant pressure funnel, feeds nitrogen protection; Under the water bath condition 119gN-methyldiethanolamine (MDEA) is added constant pressure funnel and in 30-60 minute, drip to advance among the CHDI, be warming up to 65 ℃ after being added dropwise to complete, be incubated 1 hour; Then rise to 75 ℃; Be incubated 2-8 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, be cooled to 40 ℃ for use;
(b) in the container that whisking appliance, TM and constant pressure funnel are housed, adding the 1000g number-average molecular weight is 500 polycaprolactone glycol (PCL-500); Logical nitrogen protection is stirred and is warming up to 40 ℃, and mixture solution in (a) is transferred in the constant pressure funnel; Drop in the reaction vessel in 30-60 minute; Be warming up to after being added dropwise to complete 85 ℃ the reaction 2-8 hour, treat the isocyanate groups complete reaction in the system after, the structural formula that contains soft section of ion that obtains the A structure is:
(c) soft section of above-mentioned ion is cooled to 40 ℃; Add 666g isoflurane chalcone diisocyanate (IPDI), add 0.64gDBTDL, temperature in the system is risen to 80 ℃; Insulation reaction 2-6 hour, the free isocyanate content reached after the theoretical value stopped reaction and is cooled to 30 ℃ in the mensuration system;
(d) add the 236g butanone, be added dropwise to 62g terepthaloyl moietie in 30 minutes and be warming up to 65 ℃ of reactions 1 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use;
(e) the 1.83g p methoxy phenol being dissolved in the middle dropping of 121.8g Hydroxyethyl acrylate (HEA) advances in (d) product; Slowly be warming up to 85 ℃ of reactions of its structure 2 hours; Mensuration system free isocyanate content is cooled to 40 ℃ near 0 back stopped reaction, obtains blocked prepolymer;
(f) the 60g Glacial acetic acid min. 99.5 is added in (e) end-blocking thing, under 900 rev/mins high-speed stirring in 30 minutes, promptly get soft section prepolymer of ultra-violet curing positively charged ion shown in the structure E, its structural formula is:
(g) in above-mentioned prepolymer, add the 4389g deionized water, in 1200 rev/mins of high-speed stirring, disperseed 5-15 minute fast, use high-shear emulsifying appearance emulsification 15-30 minute again, obtain white emulsion, add 23gPerenol S4 froth breaking;
(f) above-mentioned emulsion is warming up to 45 ℃ of vacuum removal organic solvent butanone under 0.09MPa, adds 3.8gIrgacure500, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
Embodiment 5
(a) with 528.58g3,3 '-dimethyl--4,4 '-biphenyl diisocyanate (TODI) adds and to be equipped with in the container of whisking appliance, TM and constant pressure funnel; Feed nitrogen protection, with 275.88g2, the 3-dibromo-succinic acid adds constant pressure funnel and in 30-60 minute, drips to advance among the TODI under the water bath condition; Be warming up to 65 ℃ after being added dropwise to complete; Be incubated 1 hour, then rise to 75 ℃, be incubated 2-8 hour; Stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, be cooled to 40 ℃ for use;
(b) in the container that whisking appliance, TM and constant pressure funnel are housed, adding the 1000g number-average molecular weight is 500 polycaprolactone glycol (PCL-500); Logical nitrogen protection is stirred and is warming up to 40 ℃, and mixture solution in (a) is transferred in the constant pressure funnel; Drop in the reaction vessel in 30-60 minute; Be warming up to after being added dropwise to complete 85 ℃ the reaction 2-8 hour, treat the isocyanate groups complete reaction in the system after, the structural formula that contains soft section of ion that obtains the B structure is:
(c) soft section of above-mentioned ion is cooled to 40 ℃; Add 666g isoflurane chalcone diisocyanate (IPDI), add 0.73gDBTDL, temperature in the system is risen to 80 ℃; Insulation reaction 2-6 hour, the free isocyanate content reached after the theoretical value stopped reaction and is cooled to 30 ℃ in the mensuration system;
(d) add the 291g butanone, be added dropwise to 118g1 in 30 minutes, 6-pinakon (HDO) is warming up to 65 ℃ of reactions 1-2 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use;
(e) the 1.83g Resorcinol being dissolved in the middle dropping of 121.8g Hydroxyethyl acrylate (HEA) advances in (d) product; Slowly be warming up to 85 ℃ of reactions of its structure 2 hours; Mensuration system free isocyanate content is cooled to 40 ℃ near 0 back stopped reaction, obtains blocked prepolymer;
(f) the 202g triethylamine is added in (e) end-blocking thing, under 900 rev/mins high-speed stirring in 30 minutes, promptly get soft section prepolymer of ultra-violet curing positively charged ion shown in the structure D, its structural formula is:
(g) in above-mentioned prepolymer, add the 5413g deionized water, in 1200 rev/mins of high-speed stirring, disperseed 5-15 minute fast, use high-shear emulsifying appearance emulsification 15-30 minute again, obtain white emulsion, add the 29gBYK-141 froth breaking;
(f) above-mentioned emulsion is warming up to 45 ℃ of vacuum removal organic solvent butanone under 0.09MPa, adds 3.8gIrgacure1173, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
Embodiment 6
(a) with 528.58g3,3 '-dimethyl--4,4 '-biphenyl diisocyanate (TODI) adds and to be equipped with in the container of whisking appliance, TM and constant pressure funnel; Feed nitrogen protection, with 275.88g2, the 3-dibromo-succinic acid adds constant pressure funnel and in 30-60 minute, drips to advance among the TODI under the water bath condition; Be warming up to 65 ℃ after being added dropwise to complete; Be incubated 1 hour, then rise to 75 ℃, be incubated 2-8 hour; Stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, be cooled to 40 ℃ for use;
(b) in the container that whisking appliance, TM and constant pressure funnel are housed, adding the 1000g number-average molecular weight is 500 poly adipate succinic acid ester glycol; Logical nitrogen protection is stirred and is warming up to 40 ℃, and mixture solution in (a) is transferred in the constant pressure funnel; Drop in the reaction vessel in 30-60 minute; Be warming up to after being added dropwise to complete 85 ℃ the reaction 2-8 hour, treat the isocyanate groups complete reaction in the system after, the structural formula that contains soft section of ion that obtains the B structure is:
(c) soft section of above-mentioned ion is cooled to 40 ℃; Add 888g isoflurane chalcone diisocyanate (IPDI), add 0.81gDBTDL, temperature in the system is risen to 80 ℃; Insulation reaction 2-6 hour, the free isocyanate content reached after the theoretical value stopped reaction and is cooled to 30 ℃ in the mensuration system;
(d) add 382g ETHYLE ACETATE; With 275.88g2, the 3-dibromo-succinic acid adds in the above-mentioned oligopolymer, is warming up to 50 ℃ of insulation reaction 1-3 hours; Again with 218g pyromellitic dianhydride (PMDA) and 1.68g sodium methylate; Be warming up to 75 ℃ the reaction 1-3 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use;
(e) the 1.83g p methoxy phenol being dissolved in the middle dropping of 121.8g Hydroxyethyl acrylate (HEA) advances in (d) product; Slowly be warming up to 85 ℃ of reactions of its structure 2 hours; Mensuration system free isocyanate content is cooled to 40 ℃ near 0 back stopped reaction, obtains blocked prepolymer;
(f) the 404g triethylamine is added in (e) end-blocking thing, under 900 rev/mins high-speed stirring in 30 minutes, promptly get soft section prepolymer of ultra-violet curing positively charged ion shown in the structure D, its structural formula is:
(g) in above-mentioned prepolymer, add the 5730g deionized water, in 1200 rev/mins of high-speed stirring, disperseed 5-15 minute fast, use high-shear emulsifying appearance emulsification 15-30 minute again, obtain white emulsion, add the 39gBYK-141 froth breaking;
(f) above-mentioned emulsion is warming up to 45 ℃ of vacuum removal organic solvent butanone under 0.09MPa, adds 3.8gIrgacure2959, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
Soft section performance test that contains ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid among above-mentioned each embodiment realizes through following steps:
1. the dispersion liquid outward appearance is measured: adopt GB/T 1721-2008 " varnish, edible vegetable oil and thinner outward appearance and diaphanometry " to measure;
2. dispersion liquid viscosity measurement: adopt rotational viscosimeter press GB/T2794-1995 " mensuration of sizing agent viscosity " mensuration, wherein bath temperature is (30 ± 1) ℃, test result such as table 1;
3. thermostability: place 60 ℃ of baking ovens, observed whether deposition is arranged, and measured result such as table 1 in 3 days;
4. cold stability: place-10 ± 0.5 ℃ of refrigerators, observed whether deposition is arranged, and measured result such as table 1 in 3 days;
5. the test of solid content: press GB/T 2793-1995 " mensuration of tackiness agent non-volatile content " and measure, wherein the Constant Temp. Oven thermostat temperature is 105 (± 2) ℃, measures result such as table 1;
6. particle diameter test: adopt German ALV company (ALV-Laser Vertriebsgesellschaft m.b.H) ALV/CGS-5022F type laser light scattering instrument to measure, measure result such as table 1;
7. leave standstill stability: normal temperature is preserved, and whether every two weeks is observed has deposition, measures result such as table 1.
Effect embodiment
The product that embodiment 1-6 is obtained carries out each item performance test, and the result sees table 1.
Table 1 embodiment performance table
Can be known that by table 1 soft section of the present invention contains ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid and have the solid content height, viscosity is little, and particle diameter is little, shelf-stable, hot and cold advantage such as stable.
And uV curable of the present invention adopts the 1000w ultra violet lamp, can in 60 seconds, solidify, and compares the great curing efficiency that improved with traditional method, more can further promote each item performances such as water tolerance, thermotolerance, mechanical property of product after the curing.
Claims (4)
1. one kind soft section contains ionic ultraviolet light polymerization cation aqueous polyurethane dispersion liquid, and the composition of this dispersion liquid and mass percent are:
Described ultraviolet light polymerization cation aqueous polyurethane prepolymer can be shown in following C, D, the E general structure:
C：
D：
E：
In the formula, R is soft section an of ionic, it is characterized in that the molecular weight ranges that is had is: 500≤number-average molecular weight≤3000; R
4Be neutralizing agent, like sulfuric acid, hydrochloric acid, Glacial acetic acid min. 99.5, methyl sulfate, oxyacetic acid etc.; R
5Be the cationic hydrophilic chainextender, like N methyldiethanol amine, trolamine, diethylolamine, N-propyl group diethylolamine, N-benzyl diethylolamine, tertiary butyl diethylolamine, benzylaniline etc.; R
6Be vulcabond; As 2,4 toluene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 1; 6-hexyl diisocyanate, 4; 4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, 1,4-phenylene diisocyanate, 2,4 '-diphenylmethanediisocyanate, Methylcyclohexyl diisocyanate etc. and composition thereof; R
7For containing the small molecule chain extender of active hydrogenate, comprise small molecules two pure and mild small molecules diamines, comprise the part anhydride compound in addition, the small molecules glycol is like terepthaloyl moietie, Ucar 35, NSC 6366,1,4-butyleneglycol, 1,6-pinakon etc.; The small molecules diamines is like quadrol, 1,4-tetramethylenediamine, cyclohexanediamine, 1,6-hexanediamine, tn, your ketone diamines of different fluorine etc.; Anhydride compound such as pyromellitic dianhydride etc.; R
8Be end-capping reagent such as Hydroxyethyl acrylate, Rocryl 400 etc.; NR
3' be tertiary amine compound.
Described catalyzer is dibutyl tin laurate, stannous octoate, triethylamine, diethylenetriamine, sodium methylate etc., can be single a kind of or above-mentioned multiple mixture;
Described skimmer is one or more the mixture among BYK-141, BYK-065/066,201 methyl-silicone oils, Perenol S4, Perenol S43, the Perenol E1 etc.;
Described water-soluble photoinitiator is one or more the mixture among Irgacure1173, Irgacure2959, Irgacure184, the Irgacure500.
2. the soft section preparation method who contains ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid as claimed in claim 1 is characterized in that including following steps:
1) get soft section and contain ion polyvalent alcohol R, in 100～120 ℃ under 0.09MPa decompression dehydration 1-2 hour, be cooled to 40 ℃, under agitation condition, add vulcabond R
6With 0～1% catalyzer, system slowly is warming up to 80 ℃ of reactions 2-6 hour, measure system free isocyanate content and reach after the theoretical value stopped reaction and be cooled to 30 ℃ of left and right sides for use;
2) the cationic hydrophilic chainextender R among the dropping general structure C in the oligopolymer after above-mentioned cooling
5Or the chainextender among the general structure D 2, the 3-dibromo-succinic acid, the organic solvent of adding 5～10% was warming up to 50 ℃ of insulation reaction 1-3 hours; Add the active hydrogenate small molecule chain extender R that contains in the general structure
7, 65 ℃ the reaction 1 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use.If do not add hydrophilic chain extender and directly do not adopt the small molecule chain extender chain extension, and then by following 3) end-blocking then obtains structure E and contains ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid for said soft section;
3) in above-mentioned product, add the end-capping reagent R described in the general structure
8, being dissolved with 0.5～4% stopper of end-capping reagent quality in the end-capping reagent, end-capping reagent slightly excessive (end-blocking rate 1.02～1.10) is warming up to 85 ℃ of reactions 2 hours, measures the system free isocyanate content near 0 back stopped reaction, is cooled to 40 ℃;
4) add the neutralization reagent R described in the general structure
4Or NR
3', under high-speed stirring in 30 minutes, promptly obtain soft section shown in above-mentioned three kinds of general structures and contain ion ultraviolet light polymerization cation aqueous polyurethane prepolymer;
5) in above-mentioned prepolymer, add the deionized water that measures, disperseed fast 5～15 minutes, use high-shear emulsifying appearance emulsification 15～30 minutes again, obtain white emulsion, add 0～2% skimmer;
6) above-mentioned emulsion is warming up to 30～50 ℃ of vacuum removal organic solvents under 0.09MPa, adds 0.5～5% water-soluble photoinitiator, remove by filter insolubles, promptly get soft section and contain ion ultraviolet light polymerization cation aqueous polyurethane dispersion liquid.
3. soft section described in claim 1 and claim 2 contains ion polyvalent alcohol R, and its structure can be for shown in following A, the B general structure:
A：
R wherein
1, R
2And R
3Be one or more (down together) in the following structure;
R
1For:
Again or
R
2For:
Again or
A=2 wherein, 4,6.N >=1 is integer.R
3Be H, or be C
1-C
6Straight chained alkyl, or end group is hydroxyl (C OH)
1-C
6Straight chain primary alcohol, or end group is a benzyl
C
1-C
6Straight chained alkyl.
B：
4. like the preparation method of soft section polyvalent alcohol of the said ion of claim 3, it is characterized in that including following steps:
1) gets the above-mentioned R of having
1The vulcabond of structure joins in the reaction vessel that whisking appliance, TM and constant pressure funnel are housed, and reaction unit places water-bath, and other gets has aforementioned R
3The cationic small molecules hydrophilic chain extender of structure adds in the constant pressure funnel, splashes in the reaction vessel, dropwises in 30-60 minute.Wherein the mol ratio of vulcabond and cationic small molecules hydrophilic chain extender is 2: 1.
2) treat that cationic hydrophilic chain extender dropwises after, the temperature of reaction in the reaction vessel is risen to 65 ℃, be incubated 1 hour; Then rise to 75 ℃; Be incubated 2-8 hour, stopped reaction when the free isocyanate content reaches theoretical value in the mensuration system, with above-mentioned polymkeric substance be cooled to 40 ℃ for use.
3) get the aforementioned R of having in addition
2The small molecular weight oligomer polyol of structure joins in another reaction vessel that whisking appliance, TM and constant pressure funnel are housed; Temperature of reaction in the reaction vessel is risen to 40 ℃; Get 2) in the synthetic oligopolymer add in the constant pressure funnel; Splash in the reaction vessel, dropwised in 30-60 minute.Be warming up to 85 ℃ of reactions 2-8 hour after being added dropwise to complete.Small molecular weight oligomer polyol and 2 wherein) mol ratio of synthetic oligopolymer is 2: 1.
4) determination step 3) free isocyanate content of gained oligopolymer, when NCO% stopped reaction near 0 time, vacuum defoamation 30 minutes is cooled to room temperature, and discharging promptly gets soft section polyvalent alcohol of ionic.
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