CN102050931B - Preparation method of alkali resistant waterborne polyurethane emulsion - Google Patents
Preparation method of alkali resistant waterborne polyurethane emulsion Download PDFInfo
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Abstract
The invention relates to a preparation method of alkali resistant waterborne polyurethane emulsion. The preparation method comprises pre-polymerizing polyisocyanate and polyol in the presence of catalyst and solvent, adding ionic group compound, reacting, sequentially adding chain expander for chain expansion, blocking ends with hydroxyl-containing unsaturated monomer, neutralizing with salt forming agent to obtain pre-polymer solution, adding water for emulsion, vacuuming, and removing solvent to obtain waterborne polyurethane pre-polymer dispersion; and allowing self polymerization of the waterborne polyurethane pre-polymer dispersion in the presence of colloid protectant, reacting with unsaturated monomer pre-emulsion, cooling, and filtering to obtain alkali resistant waterborne polyurethane emulsion. The inventive alkali resistant waterborne polyurethane emulsion has no condensation product in strongly alkaline condition (pH 13), and can be stably stored for 30 days; and greatly improves the toughness of concrete and improves the flexural strength of concrete by up to 13%.
Description
Technical field
The present invention relates to a kind of preparation method of alkali resistance aqueous polyurethane emulsion.
Background technology
Use polymer emulsion modified sand-cement slurry and concrete to have and reach the history in 80 years, polymer emulsion can effectively improve sand-cement slurry and concrete anti-permeability performance, adhesive property, prevent performances such as carbonation properties, freezing and thawing performance and toughness.Especially along with modern architecture to large span, high stratification development, the research of sand-cement slurry and toughness of concrete is become the field of extensively being paid close attention to, make polymer emulsion in increasing engineering, obtain application.The polymer emulsion that is used for sand-cement slurry and concrete modifying at present is mainly acrylic ester emulsion, styrene-butadiene emulsion and aqueous polyvinyl acetate emulsion; Because their mechanical moduli volume low, in sand-cement slurry and concrete is big, when improving sand-cement slurry and toughness of concrete its intensity is descended by a relatively large margin.
Urethane (polyurethane) is to be made through step-reaction polymerization by POLYMETHYLENE POLYPHENYLISOCYANATE, polyvalent alcohol or polyamine; On the molecular chain except carbamate groups; Contain groups such as ether, ester group, urea groups, carboxamido-group toward contact, form hydrogen bond easily, form microphase-separated; Have extremely strong force of cohesion, have superior mechanical property and molecular designing property flexibly.
For can be in sand-cement slurry and concrete system good dispersion, need to use aqueous polyurethane.That aqueous polyurethane commonly used is divided into is cationic, three kinds of anionic and non-ion aqueous polyurethanes.Be characterized on molecular backbone chain, introducing hydrophilic radical, introduced quaternary amines like cation-type water-thinned polyurethane, anion-type water-thinned polyurethane has been introduced carboxylate radical, sulfonate radical negative ion, and non-ion aqueous polyurethane has been introduced the Soxylat A 25-7 segment.Through the effect of hydrophilic radical, self-emulsifying forms the aqueous dispersions of urethane in water.Because sand-cement slurry and concrete are strong basicity systems, when mix, a large amount of hydroxyl radical negative ions makes aqueous polyurethane that flocculation take place to the polyurethane particles effect of self-emulsifying to reunite.Have only the investigator of only a few that the alkali resistance of aqueous polyurethane dispersing liquid was carried out research at present, for example Japanese Patent JP 2006022222 has introduced the cation quaternary ammonium salt group, strengthens the alkali resistance of aqueous polyurethane dispersing liquid; U.S. Pat 4108814 and US5071578 have introduced the alkali resistance that sulfonate groups strengthens polyurethane aqueous dispersion.But introduce cationic quaternary ammonium salt group, synthetic difficulty is difficult to stably manufactured, and contains few, the expensive of polyvalent alcohol kind of sulfonic acid group, not suitable for mass production; Simultaneously, its alkali resistance is just compared the carboxylic acid type aqueous polyurethane and is slightly improved, and in strong base solution, still serious flocculation can take place.Therefore, solving the scattering problem of aqueous polyurethane in strong basicity is to guarantee the gordian technique of low-dosage aqueous polyurethane at sand-cement slurry and concrete performance modified effect.
Summary of the invention
The technical problem that the present invention will solve provides a kind of preparation method of alkali resistance aqueous polyurethane emulsion.
Its concrete scheme may further comprise the steps:
1). the preparation of aqueous polyurethane prepolymer dispersion liquid: under 60-80 ℃; The mixture that in the reaction vessel of the solvent of the POLYMETHYLENE POLYPHENYLISOCYANATE that 50-60 part is housed and 10-30 part, adds the polyvalent alcohol of catalyzer and 50-80 part carries out pre-polymerization; Reaction 2-3h; Adding accounts for the ionic groups compound of POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol total mass 5-10% and the solvent of 5-30 part again, reaction 1-2h, and the chainextender that then adds 0.26-10 part successively carries out chain extending reaction 0.5-1h; The hydroxyl unsaturated monomer of 1-12 part reaction 1-2h, cool to then 30-50 ℃ with the salt forming agent of mol ratio such as ionic groups compound in after make pre-polymer solution; The back chainextender of pre-polymer solution and water and 0-8.6 part is carried out emulsification, remove solvent acquisition aqueous polyurethane prepolymer dispersion liquid through vacuumizing;
2). prepare initiator solution and the pre-emulsion that contains 100-302 part ethylenically unsaturated monomers respectively; In the aqueous polyurethane prepolymer dispersion liquid that step 1) makes, add colloid protective agent; Be warming up to 70-85 ℃; Splash into the 10%-20% of initiator solution total mass in the 5-15min; React 15-30min, in 3-4h, add the pre-emulsion and the remaining initiator solution of ethylenically unsaturated monomers then, insulation reaction 2h; The cooling after-filtration makes the alkali resistance aqueous polyurethane emulsion;
Above umber all is mass fractions.
Catalyzer is selected organotin catalysts for use in the preceding text, preferred dibutyl tin laurate, and stannous octoate or its mixture, preferred especially dibutyl tin laurate, consumption is the 0.05%-0.2% of the total mass of POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol.
As a kind of preferred version, said ethylenically unsaturated monomers is the mixture of one or more arbitrary proportions in TEB 3K, vinyl acetate, vinylformic acid, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi and the vinylbenzene.The independent use of above-mentioned substance also can reach identical effect, the embodiment that its combination selection is not limited in the embodiment to be lifted, and embodiment is the better optimal way of effect.
In order to make aqueous polyurethane emulsion have the good mechanical performance, improve plasticization effect to sand-cement slurry and concrete system, said ethylenically unsaturated monomers be hard monomer with soft monomer with 1: 1-1: the mixture of 2 mass ratioes composition; Wherein, TEB 3K, vinyl acetate, vinylformic acid, methyl acrylate and vinylbenzene are hard monomer, and Bing Xisuandingzhi and ethyl propenoate are soft monomer.
Step 1) prepares in the pre-polymer solution process, and the mol ratio of NCO/OH is 1.02-2.
As a kind of preferred version, said POLYMETHYLENE POLYPHENYLISOCYANATE is 4,4 '-diphenylmethanediisocyanate; 2,4 toluene diisocyanate and 2,6-tolylene diisocyanate mass ratio are 80: 20 mixture; Isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate; 1, the mixture of one or more arbitrary proportions in 5-naphthalene diisocyanate and the dicyclohexyl methane diisocyanate.Two or more combinations are used and also can be reached identical effect in the above-mentioned substance, the embodiment that its selection is not limited in the embodiment to be lifted, and embodiment is the better optimal way of effect.
As a kind of preferred version, said polyvalent alcohol is that molecular weight is 400,600,1000,1500,2000, the mixture of one or more arbitrary proportions in the polyoxypropyleneglycol of 3000g/mol and the polyoxytrimethylene triol that molecular weight is 3000g/mol.Two or more combinations are used and also can be reached identical effect in the above-mentioned substance, the embodiment that its selection is not limited in the embodiment to be lifted, and embodiment is the better optimal way of effect.
Said ionic groups compound is a dimethylol propionic acid, dimethylolpropionic acid or its mixture.
Said salt forming agent is triethylamine, Trimethylamine 99, trolamine, tri-n-butylamine, potassium hydroxide aqueous solution or aqueous sodium hydroxide solution.
Said chainextender is 1,4-butyleneglycol, terepthaloyl moietie, Ucar 35, Diethylene Glycol, 1,6-pinakon or cyclohexanedimethanol.
Said back chainextender is quadrol, terepthaloyl moietie, 1,4-tetramethylenediamine, TEPA, diethylenetriamine, piperazine, isophorone diamine or Hydrazine Hydrate 80.
As a kind of preferred version, said back chainextender consumption is the 0-6.5 mass parts.
Said solvent is acetone, butanone, THF, N, dinethylformamide or N-Methyl pyrrolidone.
Said initiator is ammonium persulphate or Potassium Persulphate.
Said colloid protective agent is ZX-I, PVP K120 or TX10.
Said emulsifying agent be nonionic emulsifying agent and anionic emulsifier with 1: 1-1: 2 quality are than blended mixture, and consumption is the 1%-5% of ethylenically unsaturated monomers quality; Nonionic emulsifying agent is that the oxyethane adduct number is the polyoxyethylene octylphenol ether of 8-50, and the oxyethane adduct number is that polyoxyethylene nonylphenol or the oxyethane adduct number of 8-50 is the alkyl polyoxyethylene ether of 8-50; Anionic emulsifier is a sodium lauryl sulphate, and the oxyethane adduct number is alkyl phenol polyethenoxy ether sodium sulfate or the Fatty Alcohol(C12-C14 and C12-C18) succsinic acid sodium salt of 8-50.
The present invention at first prepares with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid, this aqueous polyurethane prepolymer dispersion liquid elder generation autohemagglutination, and then make the alkali resistance aqueous polyurethane emulsion through letex polymerization with ethylenically unsaturated monomers.The alkali resistance aqueous polyurethane emulsion of the present invention's preparation; With the aqueous polyurethane is nuclear; With the ethylenically unsaturated monomers polymkeric substance is shell, through ethylenically unsaturated monomers polymkeric substance " shell " aqueous polyurethane " nuclear " is protected, and has strengthened the alkaline resistance properties of aqueous polyurethane emulsion; Be that no condensation prod occurs under 13 the strong alkaline condition in the pH value, but and stably stored reach 30 days; Obviously improved concrete toughness, concrete flexural strength improves can reach 13%, and the maximal destruction power of concrete fracture improves can reach 40%.
Description of drawings
Fig. 1 is that 6# is the transmission electron microscope picture under 8.2 at pH value.
Fig. 2 is that 6# is the transmission electron microscope picture under 13 at pH value.
Fig. 3 is that 5# is the transmission electron microscope picture under 8.2 at pH value.
Fig. 4 is that 5# is the transmission electron microscope picture under 13 at pH value.
Fig. 5 is concrete disruptive force-deformation relationship figure.
Embodiment
Below in conjunction with embodiment the preparation of alkali resistance aqueous polyurethane emulsion is described, the main raw material(s) trade mark, abbreviation and manufacturer used among the embodiment are as shown in table 1.
The table 1 main raw material(s) trade mark, abbreviation and manufacturer
Embodiment 1
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 60 ℃, in reaction vessel, add the MDI and the 20 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 70 mass parts PPG1000 and 0.065 mass parts T-12, insulation reaction 3h.The DMPA and the 20 mass parts acetone that add 13 mass parts then, reaction 1h; Then in 20min, splash into 1 of 0.66 mass parts, 4-butyleneglycol, reaction 1h.The last EHA that in 20min, splashes into 6.7 mass parts, reaction 1h.Wherein, NCO/OH=1.02 in the reaction of this step.
After reaction finishes; Cool to 40 ℃, the triethylamine that in 20min, splashes into 9.8 mass parts neutralizes, and stirs 10min; Then under the 400rpm rotating speed; Pre-polymer solution is slowly added in the 300 mass parts water, continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 3.4 mass parts 155C and 30 parts of water of 1.7 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the MMA of 68 mass parts and the BA mixture of 34 mass parts, obtains the monomer pre-emulsion; Water with 40 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.6 mass parts.Add the LCN407 of 0.2 mass parts and the water of 150 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of red facies tract blue-fluorescence, and solid content is 34wt%.
Embodiment 2
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 70 ℃, in reaction vessel, add the MDI and the 20 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 50 mass parts PPG1000 and 0.11 mass parts T-12, insulation reaction 3h.The DMPA and the 10 mass parts acetone that add 8.8 mass parts then, reaction 1h; Then in 20min, splash into 1 of 2.8 mass parts, 4-butyleneglycol, reaction 1h.The last EHA that in 20min, splashes into 12 mass parts, reaction 2h.Wherein, NCO/OH=1.2 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 6.6 mass parts neutralizes; Stir 10min; Then under the 400rpm rotating speed, pre-polymer solution is slowly added in the 250 mass parts water, then 10min splashes into the solution that the water by 1.9 mass parts quadrols and 1.9 mass parts is made into; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 4 mass parts K12 and 50 parts of water of 2 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the MMA of 76.5 mass parts and the BA mixture of 76.5 mass parts, obtains the monomer pre-emulsion; Water with 40 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.6 mass parts.Add the LCN407 of 0.28 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 70 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 40wt%.
Embodiment 3
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 60 ℃, in reaction vessel, add the MDI and the 30 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 80 mass parts PPG1000 and 0.3 mass parts T-12, insulation reaction 3h.The DMPA and the 20 mass parts acetone that add 9 mass parts then, reaction 1h; Then in 20min, splash into 1 of 0.26 mass parts, 4-butyleneglycol, reaction 0.5h.The last EHA that in 20min, splashes into 5 mass parts, reaction 2h.Wherein, NCO/OH=1.3 in the reaction of this step.
After reaction finishes, cool to 30 ℃, the triethylamine that in 20min, splashes into 4 mass parts neutralizes; Stir 10min; Then under the 400rpm rotating speed, pre-polymer solution is slowly added in the 250 mass parts water, then 10min splashes into the solution that the water by 2.65 mass parts quadrols and 2.65 mass parts is made into; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 10 mass parts 155C and 80 parts of water of 5 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the MMA of 204 mass parts and the EA mixture of 102 mass parts, obtains the monomer pre-emulsion; Water with 80 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 1.8 mass parts.Add the X-405 of 0.6 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 85 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 48wt%.
Embodiment 4
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, butanone with 4
molecular sieve soaks stagnant processed.
Under 65 ℃, in reaction vessel, add the MDI and the 30 mass parts butanone of 60 mass parts, then in 30min, splash into the mixture of 60 mass parts PPG1000 and 0.3 mass parts T-12, insulation reaction 3h.Add the DMPA of 9.6 mass parts and the butanone of 20 mass parts then, reaction 1h; Then in 20min, splash into 1 of 1.57 mass parts, 4-butyleneglycol, reaction 1h.The last EHA that in 20min, splashes into 8 mass parts, reaction 1.5h.Wherein, NCO/OH=1.1 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 7.2 mass parts neutralizes; Stir 10min; Then under the 400rpm rotating speed, pre-polymer solution is slowly added in the 250 mass parts water, then 10min splashes into the solution that the water by 1.5 mass parts diethylenetriamines and 1.5 mass parts is made into; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 1.6 mass parts 155C and 80 parts of water of 0.8 mass parts NP-10 adding; Adopt mechanical stirring; Rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of BA of VAC and 60 mass parts of MA, 30 mass parts of 30 mass parts, obtains the monomer pre-emulsion; Water with 80 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.48 mass parts.Add the X-405 of 0.24 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 5min, splash into 15% initiator solution then, reaction 20min; Then in 3.5h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 35wt%.
Embodiment 5
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 60 ℃, in reaction vessel, add the MDI and the 30 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 72 mass parts PPG1000 and 0.13 mass parts T-12, insulation reaction 2h.Add the DMPA of 13.2 mass parts and the acetone of 30 mass parts then, reaction 1h; Then in 20min, splash into 1 of 0.66 mass parts, 4-butyleneglycol, reaction 0.5h.The last EHA that in 20min, splashes into 6.68 mass parts, reaction 2h.Wherein, NCO/OH=1.02 in the reaction of this step.
After reaction finishes; Cool to 35 ℃, the tri-n-butylamine that in 20min, splashes into 19 mass parts neutralizes, and stirs 10min; Then under the 400rpm rotating speed; Pre-polymer solution is slowly added in the 400 mass parts water, continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 10 mass parts 155C and 60 parts of water of 5 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the MMA of 204 mass parts and the BA mixture of 102 mass parts, obtains the monomer pre-emulsion; Water with 80 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 1.8 mass parts.Add the LCN407 of 0.61 mass parts and the water of 600 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 85 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 30wt%.
Embodiment 6
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 60 ℃, in reaction vessel, add the MDI and the 30 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 72 mass parts PPG1000 and 0.13 mass parts T-12, insulation reaction 2h.Add the DMPA of 13.2 mass parts and the acetone of 30 mass parts then, reaction 1h; Then in 20min, splash into 1 of 0.66 mass parts, 4-butyleneglycol, reaction 0.5h.The last EHA that in 20min, splashes into 6.68 mass parts, reaction 1h.Wherein, NCO/OH=1.02 in the reaction of this step.
After reaction finishes; Cool to 50 ℃, the triethylamine that in 20min, splashes into 10.4 mass parts neutralizes, and stirs 10min; Then under the 400rpm rotating speed; Pre-polymer solution is slowly added in the 300 mass parts water, continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 5 mass parts 155C and 30 parts of water of 2.5 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the MMA of 102 mass parts and the BA mixture of 51 mass parts, obtains the monomer pre-emulsion; Water with 80 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.9 mass parts.Add the LCN407 of 0.3 mass parts and the water of 200 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of red facies tract blue-fluorescence, and solid content is 35wt%.
Embodiment 7
PPG1000, terepthaloyl moietie and DMPA are carried out vacuum hydro-extraction respectively under 100-150 ℃ handle; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 70 ℃, in reaction vessel, add the MDI and the 30 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 72 mass parts PPG1000 and 0.13 mass parts T-12, insulation reaction 3h.Add the DMPA of 13.2 mass parts and the acetone of 30 mass parts then, reaction 2h; Then in 20min, splash into the terepthaloyl moietie of 1.82 mass parts, reaction 1h.The last EHA that in 20min, splashes into 2 mass parts, reaction 1h.Wherein, NCO/OH=1.1 in the reaction of this step.
After reaction finishes, cool to 45 ℃, the tri-n-butylamine that in 20min, splashes into 19 mass parts neutralizes; Stir 10min; Then under the 400rpm rotating speed, pre-polymer solution is slowly added in the 300 mass parts water, in 10min, splash into the solution that the water by 1 mass parts terepthaloyl moietie and 1 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 1.25 mass parts 403C, 2 mass parts 155C, 30 parts of water of 0.5 mass parts SB10 adding; Adopt mechanical stirring; Rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the vinylbenzene of 102 mass parts and the BA mixture of 51 mass parts, obtains the monomer pre-emulsion; Water with 80 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.9 mass parts.Add the PVP K120 of 0.3 mass parts and the water of 200 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 15min, splash into 20% initiator solution then, reaction 15min; Then in 3h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 35wt%.
Embodiment 8
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 70 ℃, in reaction vessel, add the TDI-80 and the 20 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 60 mass parts PPG1000 and 0.24 mass parts T-12, insulation reaction 3h.Add the DMPA of 9.6 mass parts and the acetone of 30 mass parts then, reaction 1h; Then in 20min, splash into 1 of 10 mass parts, 4-butyleneglycol, reaction 1h.The last EHA that in 20min, splashes into 8.35 mass parts, reaction 2h.Wherein, NCO/OH=1.1 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 7.23 mass parts neutralizes; Stir 10min; Then under the 400rpm rotating speed, pre-polymer solution is slowly added in the 300 mass parts water, in 10min, splash into the solution that the water by 1.5 mass parts quadrols and 1.5 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 0.9 mass parts 403C, 30 parts of water of 0.9 mass parts SB10 adding; Adopt mechanical stirring; Rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into MA, the 90 mass parts EA of 86.4 mass parts, the mixture of 3.6 mass parts AA, obtains the monomer pre-emulsion; Water with 60 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.36 mass parts.Add the ZX-I of 0.15 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 70 ℃, in 10min, splash into 10% initiator solution then, reaction 15min; Then in 3h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 40wt%.
Embodiment 9
With PPG1000,1; 2-Ucar 35 and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 70 ℃, in reaction vessel, add the TDI-80 and the 20 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 60 mass parts PPG1000 and 0.24 mass parts T-12, insulation reaction 3h.Add the DMPA of 12 mass parts and the acetone of 30 mass parts then, reaction 1h; Then in 20min, splash into 1 of 1.66 mass parts, 2-Ucar 35, reaction 1h.The last HPA that in 20min, splashes into 7.6 mass parts, reaction 1h.Wherein, NCO/OH=1.5 in the reaction of this step.
After reaction finishes, cool to 35 ℃, the triethylamine that in 20min, splashes into 9 mass parts neutralizes; Stir 10min; Then under the 400rpm rotating speed, pre-polymer solution is slowly added in the 200 mass parts water, in 10min, splash into the solution that the water by the quadrol of 5.5 mass parts and 5.5 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 0.9 mass parts NP-10 and 40 parts of water of 0.9 mass parts K12 adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the BA of 70 mass parts VAC, 50 mass parts, obtains the monomer pre-emulsion; Water with 80 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.48 mass parts.Add the PVP K120 of 0.24 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 40wt%.
Embodiment 10
With PPG1000,1; 4-butyleneglycol and DMBA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 80 ℃, in reaction vessel, add the TDI-80 and the 20 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 50 mass parts PPG2000 and 0.22 mass parts T-9, insulation reaction 2h.Add the DMBA of 7.8 mass parts and the acetone of 30 mass parts then, reaction 1h; Then in 20min, splash into 1 of 3 mass parts, 4-butyleneglycol, reaction 1h.The last HEMA that in 20min, splashes into 8 mass parts, reaction 2h.Wherein, NCO/OH=2 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 5.32 mass parts neutralizes; Stir 10min; Then under the 400rpm rotating speed, pre-polymer solution is slowly added in the 200 mass parts water, in 10min, splash into the solution that the water by 8.6 mass parts terepthaloyl moietie and 8.6 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 1.8 mass parts 155C and 30 parts of water of 1.2 mass parts OP-10 adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the EA of 60 mass parts MMA, 40 mass parts, obtains the monomer pre-emulsion; Water with 60 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.4 mass parts.Add the X-405 of 0.2 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 15% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 38wt%.
Embodiment 11
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 80 ℃, in reaction vessel, add the IPDI and the 5 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 50 mass parts PPG1000 and 0.22 mass parts T-12, insulation reaction 2h.Add the DMPA of 5.5 mass parts and the acetone of 10 mass parts then, reaction 1h; Then in 20min, splash into 1 of 3.89 mass parts, 4-butyleneglycol, reaction 1h.The last EHA that in 20min, splashes into 5.5 mass parts, reaction 2h.Wherein, NCO/OH=1.2 in the reaction of this step.
After reaction finishes; Cool to 50 ℃, under the 400rpm rotating speed, will add pre-polymer solution with the solution of 2.3 parts of water fast and stir 2min; And then slowly add pre-polymer solution in the 200 mass parts water; In 10min, splash into the solution that the water by 4.2 mass parts quadrols and 4.2 mass parts is made into then, continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 1.92 mass parts NP-10 and 30 parts of water of 2.88 mass parts SB10 adding; Adopt mechanical stirring; Rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the BA of 80 mass parts MMA, 40 mass parts, obtains the monomer pre-emulsion; Water with 60 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.6 mass parts.Add the LCN407 of 0.24 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 10% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 40wt%.
Embodiment 12
PPG2000, terepthaloyl moietie and DMPA are carried out vacuum hydro-extraction respectively under 100-150 ℃ handle; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 80 ℃, in reaction vessel, add the IPDI and the 5 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 70 mass parts PPG2000 and 0.22 mass parts T-12, insulation reaction 3h.Add the DMPA of 6.5 mass parts and the acetone of 5 mass parts then, reaction 1h; Then in 20min, splash into the terepthaloyl moietie of 2.2 mass parts, reaction 1h.The last HEMA that in 20min, splashes into 8 mass parts, reaction 2h.Wherein, NCO/OH=1.5 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 4.9 mass parts neutralizes; Stir 10min; Under the 400rpm rotating speed, pre-polymer solution is slowly added in the 250 mass parts water, in 10min, splash into the solution that the water by 4.3 mass parts quadrols and 4.3 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 10 mass parts 155C and 60 parts of water of 5 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the BA of 200 mass parts MMA, 100 mass parts, obtains the monomer pre-emulsion; With the water of 60 mass parts the Potassium Persulphate initiator dissolving of 1.8 mass parts is obtained initiator solution.Add the LCN407 of 0.6 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 50wt%.
Embodiment 13
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 80 ℃, in reaction vessel, add the IPDI and the 5 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 50 mass parts PPG1000 and 0.22 mass parts T-12, insulation reaction 3h.Add the DMPA of 6 mass parts and the acetone of 10 mass parts then, reaction 1h; Then in 20min, splash into 1 of 3.13 mass parts, 4-butyleneglycol, reaction 1h.The last HPMA that in 20min, splashes into 8 mass parts, reaction 1h.Wherein, NCO/OH=2 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 4.5 mass parts neutralizes; Stir 10min; Under the 400rpm rotating speed, pre-polymer solution is slowly added in the 250 mass parts water, in 10min, splash into the solution that the water by 6.48 mass parts quadrols and 6.48 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 2.6 mass parts 155C and 60 parts of water of 1.3 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the BA of 100 mass parts MA, 100 mass parts, obtains the monomer pre-emulsion; Water with 60 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.8 mass parts.Add the LCN407 of 0.4 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 10% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h then.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 35wt%.
Embodiment 14
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 80 ℃, in reaction vessel, add the IPDI and the 5 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 50 mass parts PPG1000 and 0.22 mass parts T-12, insulation reaction 3h.Add the DMPA of 6 mass parts and the acetone of 10 mass parts then, reaction 1h; Then in 20min, splash into 1 of 3.13 mass parts, 4-butyleneglycol, reaction 1h.The last HPMA that in 20min, splashes into 8 mass parts, reaction 1h.Wherein, NCO/OH=2 in the reaction of this step.
After reaction finishes, cool to 40 ℃, in 20min, splash into 2.5 mass parts Pottasium Hydroxide and 2.5 mass parts water neutralize; Stir 10min; Under the 400rpm rotating speed, pre-polymer solution is slowly added in the 250 mass parts water, in 10min, splash into the solution that the water by 6.48 mass parts quadrols and 6.48 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 2.6 mass parts 155C and 60 parts of water of 1.3 mass parts 403C adding, adopt mechanical stirring, rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the BA of 100 mass parts MA, 100 mass parts, obtains the monomer pre-emulsion; Water with 60 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.8 mass parts.Add the LCN407 of 0.4 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 15% initiator solution then, reaction 15min; Then in 3h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 35wt%.
Embodiment 15
With PPG2000,1; 4-butyleneglycol and DMBA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 80 ℃, in reaction vessel, add the IPDI and the 20 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 70 mass parts PPG2000 and 0.26 mass parts T-12, insulation reaction 3h.Add the DMBA of 7.8 mass parts and the acetone of 20 mass parts then, reaction 1h; Then in 20min, splash into 1 of 8 mass parts, 4-butyleneglycol, reaction 1h.The last EHA that in 20min, splashes into 3 mass parts, reaction 1h.Wherein, NCO/OH=1.2 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 5.32 mass parts neutralizes; Stir 10min; Under the 400rpm rotating speed, pre-polymer solution is slowly added in the 250 mass parts water, in 10min, splash into the solution that the water by 2.16 mass parts quadrols and 2.16 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
The NP-10 of 0.4 mass parts 403C, 0.3 mass parts and 1.4 mass parts 155C are added in 20 parts of water be mixed with solution; Adopt mechanical stirring; Rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the BA of 70 mass parts MMA, 35 mass parts, obtains the monomer pre-emulsion; Water with 60 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.84 mass parts.Add the LCN407 of 0.2 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 70 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 38wt%.
Embodiment 16
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 60 ℃, in reaction vessel, add the MDI and the 30 mass parts acetone of 50 mass parts, then in 30min, splash into the mixture of 80 mass parts PPG1000 and 0.12 mass parts T-12, insulation reaction 3h.Add the DMPA of 10.4 mass parts and the acetone of 30 mass parts then, reaction 1h; Then in 20min, splash into 1 of 2.16 mass parts, 4-butyleneglycol, reaction 1h.The last EHA that in 20min, splashes into 1 mass parts, reaction 1h.Wherein, NCO/OH=1.05 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 7.84 mass parts neutralizes; Stir 10min; Under the 400rpm rotating speed, pre-polymer solution is slowly added in the 300 mass parts water, in 10min, splash into the solution that the water by 0.45 mass parts quadrol and 0.45 mass parts is made into then; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 1.25 mass parts 403C, 2 mass parts 155C, 30 parts of water of 0.5 mass parts SB10 adding; Adopt mechanical stirring; Rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the vinylbenzene of 92 mass parts, the mixture of 61 mass parts BA, obtains the monomer pre-emulsion; Water with 80 mass parts dissolves the acquisition initiator solution with the ammonium persulfate initiator of 0.9 mass parts.Add the PVP K120 of 0.1 mass parts and the water of 200 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 80 ℃, in 10min, splash into 20% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 34wt%.
Embodiment 17
With PPG2000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 70 ℃, in reaction vessel, add the MDI and the 30 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 80 mass parts PPG2000 and 0.22 mass parts T-12, insulation reaction 2h.Add the DMPA of 11.2 mass parts and the acetone of 20 mass parts then, reaction 1h; Then in 20min, splash into 1 of 1 mass parts, 4-butyleneglycol, reaction 0.5h.The last HPMA that in 20min, splashes into 12 mass parts, reaction 1h.Wherein, NCO/OH=1.1 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 8.4 mass parts neutralizes; Stir 10min; Under the 400rpm rotating speed, pre-polymer solution is added in the 250 mass parts water, in 10min, splash into the solution that is made into of water then by 1 mass parts quadrol and 1 amount part; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain with the end capped aqueous polyurethane prepolymer of hydroxyl unsaturated monomer dispersion liquid.
With being mixed with solution in 2.6 mass parts 155C and 30 parts of water of 1.3 mass parts NP-10 adding; Adopt mechanical stirring; Rotating speed is 100rpm, in 30min, in the solution for preparing, splashes into the mixture of the BA of 100 mass parts VAC, 100 mass parts, obtains the monomer pre-emulsion; With the water of 60 mass parts the Potassium Persulphate initiator dissolving of 0.8 mass parts is obtained initiator solution.Add the LCN407 of 0.2 mass parts and the water of 100 mass parts in hydrotropisms's polyurethane prepolymer dispersion liquid, mix, be warming up to 85 ℃, in 10min, splash into 10% initiator solution then, reaction 30min; Then in 4h, splash into remaining initiator solution and whole monomer pre-emulsions, insulation reaction 2h.After reaction finishes, be cooled to 40 ℃, feed liquid filtered promptly get target product, outward appearance is the milky white liquid of being with blue-fluorescence, and solid content is 44wt%.
Embodiment 18
For the aqueous polyurethane emulsion that the present invention's preparation better is described has extremely strong alkali resistance, present embodiment prepares common aqueous polyurethane dispersing liquid as a comparison according to general method.
With PPG1000,1; 4-butyleneglycol and DMPA carry out vacuum hydro-extraction respectively under 100-150 ℃ handles; Guarantee that water cut is lower than 0.5%, acetone with 4
molecular sieve soaks stagnant processed.
Under 60 ℃, in reaction vessel, add the MDI and the 30 mass parts acetone of 60 mass parts, then in 30min, splash into the mixture of 70 mass parts PPG1000 and 0.06 mass parts T-12, insulation reaction 3h.Add the DMPA of 13 mass parts and the acetone of 30 mass parts then, reaction 1h; Then in 20min, splash into 1 of 6.21 mass parts, 4-butyleneglycol, reaction 1h.Wherein, NCO/OH=1.02 in the reaction of this step.
After reaction finishes, cool to 40 ℃, the triethylamine that in 20min, splashes into 9.8 mass parts neutralizes; Stir 10min; Under the 400rpm rotating speed, pre-polymer solution is added in the 300 mass parts water, in 10min, splash into the solution that is made into of water then by 1 mass parts quadrol and 1 amount part; Continue to stir 1h, vacuumize then and remove solvent and promptly obtain common aqueous polyurethane dispersing liquid.
Application examples
With embodiment 5,6 and 18 is that example describes, and shows that the aqueous polyurethane dispersing liquid of the present invention's preparation has fabulous alkali resistance and the increasing tougheness fabulous to concrete.
Because cement and concrete are the highly basic systems, before the concrete coagulation sclerosis, the polymer emulsion that mixes wherein must can keep good dispersiveness, and flocculation or reunion can not take place in strong base solution.Embodiment 5,6 and 18 synthetic emulsions (being labeled as 5#, 6# and 18# respectively), recording its pH through glass electrode method is 7-8.5.For the strong basicity environment of simulation concrete, under agitation condition, the NaOH solution with 30% slowly is added dropwise in the emulsion and reaches 13 until pH, continues vigorous stirring 12h then, and the different pH values of each emulsion state are down seen table 2.
Accumulation shape in the different pH environment of table 2
| Sample | PH is the original solution of 7-8.5 | PH is 13 solution after the alkaline purification |
| 18# | The turn blue translucent emulsion of look fluorescence | The white condensation prod |
| 6# | The red mutually milky white liquid of look fluorescence turns blue | White emulsion stores 30 days |
| 5# | The white emulsion of look fluorescence turns blue | White emulsion stores 7 days |
Utilize the test of ALV-7004 type sound attitude light scattering apparatus in different pH environment, the hydrodynamic radius (R of emulsion
h), all square rotation radius (R
g) changing conditions as shown in table 3.
The change of size of the different pH values of table 3
Can find out from table 2 and table 3, the increase of pH, 6# and 5# still exist with emulsion form, and its Rg and Rh all increase, and particle is assembled in the emulsion; 18# initially adds fashionable at NaOH solution, occur the agglomerate condensation prod immediately and stir it is disperseed, and the aqueous polyurethane emulsion that this explanation the present invention makes is alkaline-resisting stable.Wherein, 6# is in pH is 13 environment, and Rg and Rh are all less than 150nm, and it is little that particle diameter increases amplitude, has excellent alkaline resistance properties, can stably stored 30 days.
Utilize the observation of Hitachi H-7650III type transmission electron microscope 5# and the form of 6# under different pH values, its transmission electron microscope (TEM) is shown in Fig. 1-4.Can find out clearly that from Fig. 1 and Fig. 3 when pH=8.2,6# and 5# all have complete globosity; Can find out clearly that from Fig. 2 and Fig. 4 when pH=13, the particle diameter of 6# and 5# all has increase, still not be spheroidal particle structure more clearly but bigger particle aggregation phenomenon, especially 6# occur.This aqueous polyurethane emulsion that further proves the present invention's preparation has alkaline resistance properties preferably.
The purpose that in concrete, adds aqueous polyurethane is that (especially ultimate compression strength) improves concrete toughness under the negative effect situation concrete strength not being produced.According to following method 18# and 6# emulsion are carried out testing concrete performance: the mensuration of concrete slump and air content is carried out according to GB/T 50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard "; The mensuration of concrete formation, maintenance, ultimate compression strength and bending strength is carried out according to GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete "; The mensuration of fracture energy of concrete is split daraf(reciprocal of farad) according to wedging among the DL/T5332-2005 " concrete for hydraulic structure tearing test rules " and is carried out, and it calculates " daraf(reciprocal of farad) research fracture energy of concrete is split in wedging " of then publishing with reference to [water power journal] the 4th phase in 2003.In experiment, the concrete design slump is 20cm, and the volume of polymkeric substance is the 1wt% of gel material content.When 18# added concrete mortar, the slurry that has certain degree of mobilization originally became very sticky immediately, can't accomplish the dress mould; 6# then can make concrete keep the high-ductility state until sclerosis in long-time, and the concrete intensity of its toughening modifying is as shown in table 4.
Concrete ultimate compression strength of table 4 toughening modifying and bending strength
| Sample | 28d ultimate compression strength (MPa) | 28d folding strength (MPa) |
| Blank concrete | 68.9 | 6.06 |
| The 6# modified concrete | 68.1 | 6.88 |
By finding out in the table 4, the interpolation of 6# emulsion is to the almost not influence of concrete ultimate compression strength, and the folding strength raising reaches 13%.Fig. 5 is concrete fracture power-deformation relationship figure, and peak value is represented maximal destruction power, the energy that the complete fracture specimen of the cartographic represenation of area of entire curve is required.The energy-to-break of 6# modified concrete is by 97Nm
-1Bring up to 213Nm
-1, maximal destruction power has improved 40%.Toughness of concrete has obtained obvious raising.
Claims (13)
1. the preparation method of an alkali resistance aqueous polyurethane emulsion is characterized in that may further comprise the steps:
1). the preparation of aqueous polyurethane prepolymer dispersion liquid: under 60-80 ℃; The mixture that in the reaction vessel of the solvent of the POLYMETHYLENE POLYPHENYLISOCYANATE that 50-60 part is housed and 10-30 part, adds the polyvalent alcohol of catalyzer and 50-80 part carries out pre-polymerization; Reaction 2-3h; Adding accounts for the ionic groups compound of POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol total mass 5-10% and the solvent of 5-30 part again, reaction 1-2h, and the chainextender that then adds 0.26-10 part successively carries out chain extending reaction 0.5-1h; The hydroxyl unsaturated monomer of 1-12 part reaction 1-2h, cool to then 30-50 ℃ with the salt forming agent of mol ratio such as ionic groups compound in after make pre-polymer solution; The back chainextender of pre-polymer solution and water and 0-8.6 part is carried out emulsification, remove solvent acquisition aqueous polyurethane prepolymer dispersion liquid through vacuumizing;
Aforementioned ionic groups compound is a dimethylol propionic acid, dimethylolpropionic acid or its mixture;
2) prepare initiator solution and the pre-emulsion that contains 100-302 part ethylenically unsaturated monomers respectively; In the aqueous polyurethane prepolymer dispersion liquid that step 1) makes, add colloid protective agent; Be warming up to 70-85 ℃; Splash into the 10%-20% of initiator solution total mass in the 5-15min; React 15-30min, in 3-4h, add the pre-emulsion and the remaining initiator solution of ethylenically unsaturated monomers then, insulation reaction 2h; The cooling after-filtration makes the alkali resistance aqueous polyurethane emulsion;
Aforementioned ethylenically unsaturated monomers is the mixture of one or more arbitrary proportions in TEB 3K, vinyl acetate, vinylformic acid, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi and the vinylbenzene;
Above umber all is mass fractions.
2. by the preparation method of the described alkali resistance aqueous polyurethane emulsion of claim 1, it is characterized in that: said ethylenically unsaturated monomers is the mixture that hard monomer and soft monomer are formed with the 1:1-1:2 mass ratio; Wherein, methacrylic methyl esters, vinyl acetate, vinylformic acid, methyl acrylate and vinylbenzene are hard monomer, and Bing Xisuandingzhi and ethyl propenoate are soft monomer.
3. by the preparation method of the described alkali resistance aqueous polyurethane emulsion of claim 1, it is characterized in that: step 1) prepares in the pre-polymer solution process, and the mol ratio of NCO/OH is 1.02-2.
4. by the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions, it is characterized in that: said POLYMETHYLENE POLYPHENYLISOCYANATE is 4,4 '-diphenylmethanediisocyanate; 2; 4-tolylene diisocyanate and 2,6-tolylene diisocyanate mass ratio are 80: 20 mixture, isophorone diisocyanate; Hexamethylene diisocyanate; Xylylene diisocyanate, 1, the mixture of one or more arbitrary proportions in 5-naphthalene diisocyanate and the dicyclohexyl methane diisocyanate.
5. by the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions, it is characterized in that: said polyvalent alcohol is that molecular weight is 400,600,1000,1500,2000, the mixture of one or more arbitrary proportions in the polyoxypropyleneglycol of 3000g/mol and the polyoxytrimethylene triol that molecular weight is 3000g/mol.
6. by the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions, it is characterized in that: said salt forming agent is triethylamine, Trimethylamine 99, trolamine, tri-n-butylamine, potassium hydroxide aqueous solution or aqueous sodium hydroxide solution.
7. by the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions, it is characterized in that: said chainextender is 1,4-butyleneglycol, terepthaloyl moietie, Ucar 35, Diethylene Glycol, 1,6-pinakon or cyclohexanedimethanol.
8. press the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions; It is characterized in that: said back chainextender is quadrol, terepthaloyl moietie, 1,4-tetramethylenediamine, TEPA, diethylenetriamine, piperazine, isophorone diamine or Hydrazine Hydrate 80.
9. by the preparation method of the described alkali resistance aqueous polyurethane emulsion of claim 1, it is characterized in that: said back chainextender consumption is the 0-6.5 mass parts.
10. by the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions, it is characterized in that: said solvent is acetone, butanone, THF, N, dinethylformamide or N-Methyl pyrrolidone.
11. by the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions, it is characterized in that: said initiator is ammonium persulphate or Potassium Persulphate.
12. by the preparation method of claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions, it is characterized in that: said colloid protective agent is ZX-I, PVP K120 or TX10.
13. preparation method by claim 1 or 2 or 3 described alkali resistance aqueous polyurethane emulsions; It is characterized in that: step 2) emulsifying agent that uses when preparation contains the pre-emulsion of ethylenically unsaturated monomers be nonionic emulsifying agent and anionic emulsifier with the 1:1-1:2 quality than blended mixture, consumption is the 1%-5% of ethylenically unsaturated monomers quality; Nonionic emulsifying agent is that the oxyethane adduct number is the polyoxyethylene octylphenol ether of 8-50, and the oxyethane adduct number is that polyoxyethylene nonylphenol or the oxyethane adduct number of 8-50 is the alkyl polyoxyethylene ether of 8-50; Anionic emulsifier is a sodium lauryl sulphate, and the oxyethane adduct number is alkyl phenol polyethenoxy ether sodium sulfate or the Fatty Alcohol(C12-C14 and C12-C18) succsinic acid sodium salt of 8-50.
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| CN102617812B (en) * | 2012-03-27 | 2014-01-15 | 合肥工业大学 | Preparation method of anionic water-based polyurethane/poly (phenethylene-acrylate-acrylonitrile) hybrid emulsion |
| CN102786654B (en) * | 2012-08-23 | 2014-06-11 | 蚌埠金黄山凹版印刷有限公司 | Nano waterborne ink binder and preparation method thereof |
| CN102786651B (en) * | 2012-08-23 | 2013-12-11 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN104591634B (en) * | 2015-01-21 | 2016-09-28 | 中铁大桥局集团第二工程有限公司 | Microdilatancy fiber reinforced concrete and preparation method thereof |
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| CN108529957B (en) * | 2018-05-17 | 2021-01-19 | 浙江省通用砂浆研究院 | Preparation method of biogel-reinforced high-viscosity special mortar for fabricated building |
| CN111289687B (en) * | 2018-12-06 | 2022-05-17 | 宝辰联合(廊坊)科技有限公司 | Method for adjusting and testing alkali resistance of polymer emulsion for architectural coating |
| CN109667175A (en) * | 2018-12-21 | 2019-04-23 | 南通江天化学股份有限公司 | A kind of synthetic method of water-borne polyurethane color fixing agent |
| CN112341035B (en) * | 2020-09-24 | 2022-02-11 | 鹤壁宝来化工科技有限公司 | Concrete rheology regulator and preparation method thereof |
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| CN101100500B (en) * | 2006-07-07 | 2011-06-08 | 西安工程大学 | Polyurethane shape memory macromolecule material and synthetic technique thereof |
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| CN100506872C (en) * | 2007-03-15 | 2009-07-01 | 黄山市圣雷特化学有限公司 | Preparation of water-base polyurethane adhesive |
| CN101157749B (en) * | 2007-09-10 | 2011-08-10 | 浙江新力化工有限公司 | Polyurethane modified acrylic acid emulsion and preparation method thereof |
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