CN1425726A - Polyurethane water dispersion and its preparing method - Google Patents
Polyurethane water dispersion and its preparing method Download PDFInfo
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Abstract
The present invention relates to paint and is especially aqueous polyurethane dispersion and its preparation process. The preparation process includes: vacuum dewatering of polyol at 90-120 deg.c vacuum degree 0.05-0.1 MPa for 1.0-2.0 hr before cooling; adding polyol and diisocyanate monomer, heating to 60-100 deg.c for 1.0-2.0 hr, adding small molecular dibasic alcohol as chain expander, reaction at 60-80 deg.c until reaching required NCO group content, adding hydrophilic chain expander and reaction at 50-70 deg.c to unchanged NCO group content to obtain polyurethane prepolymer; cooling the prepolymer, neutralizing with neutralizing agent, transferring the product to emulsifying reactor, high speed emulsifying while adding deionized water, adding amine to expand chain, adding NCO group collecting agent and defoaming agent for stabilizing treatment, and eliminating acetone.
Description
Technical field
The present invention relates to paint field, particularly polyurethane aqueous dispersions.
The invention still further relates to the preparation method of described polyurethane aqueous dispersions.
Technical background
The main component of AQUEOUS POLYURETHANE DISPERSION COATINGS, existing polyurethane aqueous dispersion body chemical resistant properties and solvent resistance are bad, hardness is lower, surface gloss is not high, and polyurethane aqueous dispersions poor from thickening property, solid content is low, the poor water resistance of latex film etc., has limited its widespread use.Common method of modifying polysiloxane modification and acrylate modified etc. is described as U.S. Pat P6063861 (2000), USP6239209 (calendar year 2001) and USP6197874 (calendar year 2001) etc.The polysiloxane-modified needs has active amino or hydroxyl on the siloxane molecule structure, be incorporated into to compare difficulty on the aqueous polyurethane structure, and siloxanes can accumulate in film coated surface after the modified aqueous polyurethane film forming, reduces to be coated with intermembranous ply adhesion.Acrylic modified waterborne urethane reduces the film formation at low temp performance of modified resin, and appearance of film is not good, synthesis technique complexity, unstable product quality.The cross-linking modified mechanical property and the chemical resistance that can improve AQUEOUS POLYURETHANE DISPERSION COATINGS.At first, select the synthetic raw material such as the synthetic aqueous polyurethane dispersion such as polyvalent alcohol, polyamine chainextender and polyisocyanate crosslinker of polyfunctionality for use, have the shortcomings such as package stability difference of synthesis technique instability, product emulsion with little crosslinking structure.Secondly, add internal crosslinker, as carbodiimide, azomethine and ethylenimine compounds, quite stable under alkaline condition, energy stable existence in polyaminoester emulsion is filmed in drying process because the volatilization of water and neutralizing agent, make the pH value in the glued membrane descend, crosslinking reaction is carried out, and has the cost height, deficiencies such as toxicity is big, storage requirement harshness.Also have in addition that add that linking agent is crosslinked, thermal activation is crosslinked outward, ultraviolet light cross-linking and autoxidation are crosslinked etc.Add outside cross-linking agent and have shortcomings such as pot-life is short, other cross-linking modified, ultraviolet light cross-linkings crosslinked as thermal activation need drying plant etc.
Summary of the invention
The objective of the invention is to problem at the prior art existence, a kind of polyurethane aqueous dispersions is provided, adopt the back to add chainextender and prepare the polyurethane aqueous dispersions of self-crosslinking modification with crosslinking structure, this dispersion has excellent film-forming properties, lower temperature resistance, water tolerance, chemical placidness resistance, anti-doing/wet rubbing, sticking power is good, hardness is adjustable, is widely used.
It is composed as follows that the present invention prepares the raw material of polyurethane aqueous dispersions:
---polyvalent alcohol, number average relative molecular mass are 300-10000, and hydroxyl value is 30-200mgKOH/g, account for 20～60% of total solids quality;
---diisocyanate monomer accounts for the 20-60% of total solids quality;
---chainextender, consumption are the 2-15% of total solids quality;
---linking agent, consumption are the 1-5% of total solids quality;
---NCO group trapping agent, consumption are the 0.5-2.0% of total solids quality;
---neutralizing agent, consumption are the 1-10% of total solids quality;
---defoamer, consumption are the 0.01-0.5% of total solids quality;
Above-mentioned polyvalent alcohol can be a polyester polyol, as CMA-1044, the CMA-1042 of east, Shandong major company, the T-1136 of Huels AG; Can be polyether glycol, as N210, N220, N330, Diol1000, Diol2000, also Viscotrol C and derivative thereof; It can be one or more mixture of polyester-polyether glycol, polycarbonate polyol, polytetrahydrofuran polyvalent alcohol, polyurethane polyol, polyacrylate polyol, polyolefin polyhydric alcohol (polybutadiene polyol), polycaprolactone (PCL) polyvalent alcohol.
Above-mentioned vulcabond can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and six cyclohexyl diisocyanate (H
6MDI), one or more mixture of xylylene diisocyanate.
Described chainextender is small molecules diol chain-extension agent and/or hydrophilic chain extender.
Above-mentioned small molecules diol chain-extension agent can be ethylene glycol, propylene glycol, 1,4 butyleneglycol, 1,6 hexylene glycol, one or more mixture such as 1,4 cyclohexanediol, Diethylene Glycol, glycol ether.
Above-mentioned hydrophilic chain extender is the dihydroxyl alkyl acid, can be dihydroxymethyl acetate, dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), one or more mixtures of dihydroxymethyl valeric acid and sulfonate.
Above-mentioned linking agent can be TriMethylolPropane(TMP) (TMP), trimethylolethane, Resins, epoxy (comprising E-20, E-12, E-44, E-51) or polyacrylate polyol.
Above-mentioned NCO group trapping agent, for single functionality or polyfunctionality very easily with the material of NCO radical reaction, can be ammoniacal liquor, hydrazine, quadrol, different phorone diamines etc.
Above-mentioned defoamer can be BYK-019, the BYK-034 etc. of BYK company, TEGO800, TEGO805, TEGO810 and TEGO825 etc. and other company's similar products like of Di Gao company.
The preparation method of polyurethane aqueous dispersions of the present invention may further comprise the steps:
(1) raw-material preparation and processing: be that 90-120 ℃, vacuum tightness are vacuum hydro-extraction 1.0-2.0h under the 0.05-0.1Mpa with polyvalent alcohol in temperature in reactor, it is standby to lower the temperature then;
(2) preparation of base polyurethane prepolymer for use as: in the reactor that stirring arm, thermometer and condenser are housed, add polyvalent alcohol and diisocyanate monomer, be warming up to 60-100 ℃, be incubated 1.0-2.0 hour, the NCO group content is (9-20%) when reaching prescribed value, adds small molecules dibasic alcohol chainextender, reacts to the NCO group content at 60-80 ℃ and reaches prescribed value (5-15%), add hydrophilic chain extender, 50-70 ℃ react to NCO base content when constant till.Adopt the back to add linking agent and introduce crosslinking structure, in reaction process,, obtain containing the polyurethane prepolymer of end NCO group with acetone conditioned reaction thing viscosity.
(3) above-mentioned polyurethane prepolymer is cooled to about 30-60 ℃, add in the neutralizing agent stirring and after 5-30 minute, neutralized reaction product is moved in the emulsification still, deionized water is joined the emulsification of emulsification still high speed, add amine chain extender simultaneously and carry out chain extension, adding NCO group trapping agent and defoamer simultaneously and carry out stabilization treatment, is that 50-60 ℃ and vacuum tightness (absolute pressure) remove acetone under the condition of 0.02-0.1Mpa in temperature then.
Adding technology can add when adding small molecule chain extender behind the above-mentioned linking agent, also can add when adding hydrophilic chain extender, can also add in emulsion process.
Above-mentioned polyurethane aqueous dispersions solids content is 15.0-45.0%, and pH value is 5.0-10.0, and emulsion particle diameter is 10-200nm, and viscosity is 10-2000cps; Minimum film-forming temperature is less than 10 ℃; The mechanical property of above-mentioned polyurethane laminate is: tensile strength is 0.5-50Mpa, and elongation at break is 100-1500%, and shore hardness (Shao Shi D) is 20-100, temperature limit of brittleness is-and 40-0 ℃.
The performance that the present invention is prepared polyurethane aqueous dispersions can characterize with the following method: the particle size of emulsion size and the automatic particle diameter instrument of employing Autosizer Lo-c that distributes are measured; Being coated with film dynamic performance tests with the Instron electronic tension tester; The emulsion polymer structure is measured with Fourier infrared spectrograph (FTIR); The emulsion second-order transition temperature is measured with the minimum film-forming temperature instrument with differential scanning calorimeter (DSC), minimum film-forming temperature; The latex particle form of emulsion has scanning electron microscope (TEM) to measure; The emulsion latex film is crosslinked to be measured by MEK (methyl ethyl ketone) reflux method of extraction; The pencil hardness of filming is measured by ASTM-3364; Sticking power is pressed GB/T9286-88 cross cross-hatching and is measured; The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The present invention's advantage compared with prior art: the present invention selects polymer polyatomic alcohol and polyisocyanates prepared in reaction polyurethane prepolymer for use, by introducing hydrophilic ion and hydrophilic polymer segment, preparation contains the polyurethane prepolymer of hydrophilic radical and end NCO base, in and can emulsification be distributed in the water behind the salify.Add Viscotrol C, TriMethylolPropane(TMP), Resins, epoxy, tetrem alkene triamine etc. and have cross-linking monomer, polyaminoester emulsion is filmed and is had crosslinking structure, can significantly improve the rate of growth of the degree of crosslinking of latex film, particularly hardness of film, improve the final hardness of filming, increased the water tolerance of filming.Linking agent adopts the back adding technology, both can guarantee that linking agent fully participated in reaction, and the viscosity of not obvious again increase reaction product makes reaction steadily to carry out.NCO group trapping agent is added in employing in emulsion process, eliminate the residual NCO group of emulsion, avoid the too much and water reaction of emulsion NCO group in storage process, generate polyureas and carbon dioxide, make that emulsion is flocculated, phenomenons such as layering and the jar that rises, guarantee the package stability of modified polyurethane emulsion.The emulsion particle diameter very little (less than 100nm) of the present invention's preparation, and surface tension is very low, emulsion has bilayer structure, moisture content is contained in emulsion particle inside, and moisture content has plastification, can help polyaminoester emulsion Cheng Mo, so they have fabulous film-forming properties, perviousness, wettability and levelling property, can infiltrate in atomic thin bump maps line, the fine capillary channel and the unusual complicated matrix surface of geometrical shape, can improve coating film gloss and improve the outward appearance of filming, have the ornamental of excellence.So self-crosslinking remodeling polyurethane aqueous dispersions of the present invention's preparation, the technology simple and stable, the product period of storage is long, do not contain the outer emulsifying agent that adds, at room temperature can the self-crosslinking film forming, have good film-forming properties, excellent in water resistance, scrub resistance, chemical solvent resistance, contamination resistance, be widely used in high-grade water-borne wood coating, waterproof paint and waterborne metallic paint and aqueous adhesive and printing ink etc.
The coating performance index such as the following table 1 of self-crosslinking modified polyurethane emulsion woodwork coating of the present invention.
The translucent viscous emulsion of film performance project aqueous polyurethane dispersion outward appearance of the present invention of table 1 self-crosslinking modified polyurethane emulsion woodwork coating, there is not mechanical impurity solids content, % 20-45 viscosity, cp 30-100 appearance of film light, smooth surface drying time, h 0.5 does solid work the time, (immersion 48h) is non-foaming for h 48 pendulum-rocker hardnesss 0.70 water tolerance, the solvent resistance that do not come off (soaking newborn industrial spirit 24h) is non-foaming, does not come off
Embodiment
Under be specific embodiments of the invention, but be not limited only to for embodiment.
Embodiment 1
Polyurethane aqueous dispersions, its component is listed in table 2.
Table 2 self-crosslinking remodeling aqueous polyurethane emulsion constituent mass percentage ratio 1 polyether glycol, (N210) 242 polyester polyols, (T1136) 103 tolylene diisocyanates, (TDI) 454 dimethylol propionic acids, (DMPA) 65 glycol ethers, (DEG) 66 trishydroxymethyl propionic acid, (TMP) 27 triethylamines, (TEA) 4.08 quadrols, (EDA) 0.89 trapping agent, (hydrazine) 0.410 deionized water 150.0
Under the drying nitrogen protection; the polyether glycol N210 that dewatered and polyester glycol T1136 and TDI are joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; 70 ℃-80 ℃ reactions 2 hours; add glycol ether then 75 ℃ of reactions 1 hour, judge reaction end with the n-butylamine titration method.Add nmp solution and the TriMethylolPropane(TMP) that is dissolved with dimethylol propionic acid (DMPA) after reaching terminal point, react to the NCO base at 60 ℃-65 ℃ and to reach prescribed value (about NCO%=3.5%), be cooled to 40 ℃ then, add the triethylamine neutralization, add acetone diluted, the quadrol chain extension is used in emulsification in normal-temperature water, add trapping agent and defoamer (TEGO-810) stirring at low speed 30 minutes, last vacuum is sloughed acetone and is obtained polyurethane aqueous dispersions.
Above-mentioned polyurethane aqueous dispersions solids content is 35%, and pH value is 7.0, and emulsion particle diameter is 50nm, and viscosity is 80cps; 5 ℃ of minimum film-forming temperatures; The mechanical property of above-mentioned polyurethane laminate is: tensile strength is 34Mpa, and elongation at break is 260%, and shore hardness is 90, and temperature limit of brittleness is-15 ℃.
Embodiment 2
Use the pure and mild aliphatic diisocyanate prepared in reaction of polyester polyols self-crosslinking modified polyurethane emulsion, used starting material are listed in table 3.
Table 3 self-crosslinking remodeling aqueous polyurethane emulsion constituent mass percentage 1 PEPA (T1136) 46.32 different phorone vulcabond (IPDI) 35.93 butanediols (BDO) 6.04 dihydromethyl propionic acids (DMPA) 5.05 epoxy resin (E-44) 6.06N methyl pyrrolidone 10.07 triethylamines (TEA) 4.08 ethylenediamines (EDA) 0.89 capturing agents (hydrazine) 0.410 deionized water 150.0
Under the drying nitrogen protection; the polyester glycol and the IPDI that dewatered are joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; 70 ℃-80 ℃ reactions 2 hours; add butyleneglycol then 70 ℃-80 ℃ reactions 1 hour, judge reaction end with the n-butylamine titration method.Add nmp solution and the Resins, epoxy that is dissolved with dimethylol propionic acid (DMPA) after reaching terminal point, react to the NCO base at 60 ℃-65 ℃ and to reach prescribed value, be cooled to 40 ℃ then, add the triethylamine neutralization, add acetone diluted, the quadrol chain extension is used in emulsification in normal-temperature water, and last vacuum is sloughed acetone and obtained aqueous polyurethane dispersion (WPU).This emulsion is mixed with leather gloss agent, advantage such as have that feel nature, winter hardiness are good, the anti-bending of folding, water-fast and anti-doing/wet rubbing are good.
The performance of the aqueous polyurethane dispersion leather gloss agent of above-mentioned example and offshore company's product performance are relatively as table 4
Table 4 water-based leather gloss agent performance is test item Italy Holland this project development outward appearance uniform liquid relatively, no condensation product pH value 7.0 6.5 7.0 solid contents, 22.5 20.5 21.5105 ℃ ± 2 ℃ of % (being not less than), 4h viscosity, cp 17 26 22.0 sticking power, level, (being not more than) 221 gloss, %, the slight check crack of (being not less than) 103 90 117 winter hardiness (20 ℃ complications 1000 times) is no change after tackiness (40 or not, kept 10 minutes), level 221 Bearable dry and wet wipes, inferior 88 10
The polyurethane aqueous dispersion body leather gloss agent of table 4 explanation the present invention preparation is better than external product at aspects such as sticking power, gloss and winter hardiness.
Embodiment 3
Adopt Viscotrol C and MDI prepared in reaction self-crosslinking modified aqueous polyurethane emulsion.Raw materials used and component is listed in table 5.
Table 5 self-crosslinking remodeling aqueous polyurethane emulsion constituent mass percentage ratio 1 Viscotrol C 352 diphenylmethanediisocyanates, (MDI) 423 hexylene glycols, (HDO) 454 dimethylol propionic acids, (DMPA) 65 triethylamines, (TEA) 4.06 quadrols, (EDA) 0.87 trapping agent, (hydrazine) 0.48 deionized water 150.0
Under the drying nitrogen protection; the Viscotrol C and the MDI that dewatered are joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; 70 ℃-80 ℃ reactions 2 hours, add hexylene glycol then 70 ℃-80 ℃ reactions 1 hour, judge reaction end with the n-butylamine titration method.Add nmp solution and the TriMethylolPropane(TMP) that is dissolved with dimethylol propionic acid (DMPA) after reaching terminal point, react to the NCO base at 60 ℃-65 ℃ and to reach prescribed value, be cooled to 40 ℃ then, add the triethylamine neutralization, add acetone diluted, the quadrol chain extension is used in emulsification in normal-temperature water, add trapping agent and defoamer (TEGO-810) stirring at low speed 30 minutes, last vacuum is sloughed acetone and is obtained self-crosslinking modified aqueous polyurethane dispersoid (WPU).
Above-mentioned formulated is become water-borne wood coating, detect film performance, and compare, the results are shown in table 6 with the product performance of certain company of Germany.
Certain aqueous wooden ware example 1 example 3 of table 6 aqueous polyurethane dispersion performance index project Germany
60 ° of gloss of coating, % 87 93 95 pencil hardness HB H H film forming situations are snappiness carefully well, 111 sticking power, level 421 water-intake rates, % (48h) 10 7.5 4.3 ethanol-tolerant performances, 24h is carefully bad
The performance of all multifunctional polyurethane aqueous dispersion of table 6 explanation the present invention preparation is compared with external performance has better hardness and water tolerance, and appearance of film is fine, has bigger prospects for commercial application.
Claims (7)
1, a kind of preparation method of polyurethane aqueous dispersions is characterized in that its raw material is composed as follows:
---polyvalent alcohol, number average relative molecular mass are 300-10000, and hydroxyl value is 30-200mgKOH/g, account for 20～60% of total solids quality;
-diisocyanate monomer accounts for the 20-60% of total solids quality;
-chainextender, consumption are the 2-15% of total solids quality;
-linking agent, consumption are the 1-5% of total solids quality;
-NCO group trapping agent, consumption are the 0.5-2.0% of total solids quality;
-neutralizing agent, consumption are the 1-10% of total solids quality;
-defoamer, consumption are the 0.01-0.5% of total solids quality; The preparation method of polyurethane aqueous dispersions of the present invention may further comprise the steps:
(1 is that 90-120 ℃, vacuum tightness are vacuum hydro-extraction 1.0-2.0h under the 0.05-0.1Mpa with polyvalent alcohol in temperature in reactor, and it is standby to lower the temperature then;
(2) add polyvalent alcohol and diisocyanate monomer, be warming up to 60-100 ℃, be incubated 1.0-2.0 hour, add small molecules dibasic alcohol chainextender, react to the NCO group content at 60-80 ℃ and to reach prescribed value, add hydrophilic chain extender, 50-70 ℃ react to NCO base content when constant till, obtain containing the polyurethane prepolymer of end NCO group;
(3) above-mentioned polyurethane prepolymer is cooled to about 30-60 ℃, add in the neutralizing agent stirring and after 5-30 minute, neutralized reaction product is moved in the emulsification still, deionized water is joined the emulsification of emulsification still high speed, add amine chain extender simultaneously and carry out chain extension, adding NCO group trapping agent and defoamer simultaneously and carry out stabilization treatment, is that 50-60 ℃ and vacuum tightness (absolute pressure) remove acetone under the condition of 0.02-0.1Mpa in temperature then.
2, the preparation method of polyurethane aqueous dispersions according to claim 1 is characterized in that described polyvalent alcohol is wherein one or more a mixture of polyester polyol, polyether glycol, Viscotrol C and derivative thereof, polyester-polyether glycol, polycarbonate polyol, polytetrahydrofuran polyvalent alcohol, polyurethane polyol, polyacrylate polyol, polyolefin polyhydric alcohol (polybutadiene polyol), polycaprolactone (PCL) polyvalent alcohol.
3, the preparation method of polyurethane aqueous dispersions according to claim 1 and 2 is characterized in that described vulcabond is tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), di-isocyanate (HDI), isophorone diisocyanate (IPDI) and six cyclohexyl diisocyanate (H
6MDI), xylylene diisocyanate one or more mixture wherein.
4, according to the preparation method of claim 1 or 2 or 3 described polyurethane aqueous dispersions, it is characterized in that described chainextender is small molecules diol chain-extension agent and/or hydrophilic chain extender, the small molecules diol chain-extension agent is ethylene glycol, propylene glycol, 1,4 butyleneglycols, 1,6 hexylene glycols, one or more mixture such as 1,4 cyclohexanediol, Diethylene Glycol, glycol ether; Hydrophilic chain extender is dihydroxymethyl acetate, dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), one or more mixtures of dihydroxymethyl valeric acid and sulfonate.
5,, it is characterized in that described linking agent is TriMethylolPropane(TMP) (TMP), trimethylolethane, Resins, epoxy or polyacrylate polyol according to the preparation method of claim 1 or 2 or 3 or 4 described polyurethane aqueous dispersions.
6,, it is characterized in that described NCO group trapping agent is ammoniacal liquor, hydrazine, quadrol or different phorone diamines according to the preparation method of claim 1 or 2 or 3 or 4 described polyurethane aqueous dispersions.
7, the polyurethane aqueous dispersions of the described method preparation of claim 1.
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