CN102702471A - Method for preparing solvent-free aqueous polyurethane dispersion - Google Patents
Method for preparing solvent-free aqueous polyurethane dispersion Download PDFInfo
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Abstract
The invention relates to a method for preparing solvent-free aqueous polyurethane dispersion, and aims to provide the method for preparing the aqueous polyurethane dispersion without using complex solubilizer and solvent during the preparing process; the technical key points of the method sequentially comprises the following steps of: 1) preparing prepolymer which contains end isocyanate group; 2) adding 20-50% of hot water at the temperature of 60-90 DEG C, and stirring for 3-10 minutes; 3) uniformly mixing tertiary amine which accounts for 1-5% of the mass of the prepolymer with water which accounts for 40-60% of the mass of the prepolymer, adding the material which is obtained in step 2) under the stirring condition, and continuously stirring for 10-30 minutes; and 4) uniformly mixing amine chain extender which accounts for 1-5% of the mass of the prepolymer with the water which accounts for 5-15% of the mass of the prepolymer, adding the material which is obtained in the step 3) into the mixture under the stirring condition, and stirring for 60-120 minutes at the temperature of 40-60 DEG C, thus obtaining the solvent-free aqueous polyurethane dispersion. The method belongs to the technical field of the production of a chemical disperse system.
Description
Technical field
The present invention relates to a kind of preparation method of dispersion system, specifically, is a kind of preparation method of solvent-free aqueous polyurethane water dispersion, belongs to chemical industry dispersion system preparing technical field.
Background technology
Traditional Synthesis of Waterborne Polyurethane mode is that the alcohol that contains the carboxylated hydrophilic group, polyvalent alcohol and vulcabond are carried out prepolymerization reaction at a small amount of high boiling organic solvent under as the condition of solubility promoter; Re-use the tertiary amine neutralization; Be that performed polymer has ionic, thereby possess hydrophilic property is used an amount of solvent cut with this performed polymer with ionic; Disperse again to carry out in the water emulsification and chain extending reaction; Can make aqueous polyurethane-polyurea dispersions or, add a large amount of low boiling point solvents, carry out chain extension emulsification with the polyamine (like sulfamate) that contains hydrophilic radical at low temperatures polyvalent alcohol and vulcabond prepolymerization reaction; Deviate from low boiling point solvent at last, obtain aqueous polyurethane-polyurea dispersions.Need in the production process to add a certain amount of solubility promoter, like acetone, butanone, N, SL 1332, production or use meeting discharge a certain amount of VOC, cause environmental pollution.
CN1869091 has disclosed a kind of solvent-free Synthesis of Waterborne Polyurethane method, the concrete steps of this method be POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol with 1.2～2: the ratio of 1 (mol ratio) contains the oligopolymer of terminal isocyanate group in 60～110 ℃ of reactions preparation in 2～4 hours down.Be cooled to room temperature, with water: prepolymer=4～2: add the aqueous solution that is dissolved with an amount of triethylamine and chainextender (quadrol or diethylenetriamine) under 1 the ratio vigorous stirring, it is 20～30% aqueous polyurethane that the chain extension dispersion obtains solid content.US 12/961; 256 have disclosed the solvent-free Synthesis of Waterborne Polyurethane method of a kind of high temperature emulsifying process; Its main points are to contain at least a kind of isocyanic ester chain terminator reaction performed polymer emulsifying soln with room temperature water and neutralizing agent under 80 ~ 90 ℃ of conditions, the aqueous pu dispersions of chain extension production at last.Above technology all exists performed polymer viscosity very high, to disadvantages such as equipment requirements height.
Summary of the invention
To above-mentioned deficiency, the present invention discloses a kind of preparation method that in the preparation process, need not use the aqueous pu dispersions that solubility promoter and solvent can obtain.
For achieving the above object, the present invention adopts following technical scheme: the preparation method of solvent-free aqueous pu dispersions, it comprises the steps: successively
1) takes by weighing 20 ~ 55% POLYMETHYLENE POLYPHENYLISOCYANATE, 2 ~ 10% carboxylic small molecules divalent alcohol, 0 ~ 5% small molecules divalent alcohol by weight percentage; 40 ~ 80% polyvalent alcohol; 0.1 ~ 0.5% organo-metallic catalyst mixes; 60 ~ 110 ℃ of following stirring reactions 2 ~ 5 hours, obtain containing the performed polymer of terminal isocyanate group;
2) at the water that in the performed polymer of step 1) gained, adds performed polymer quality 20 ~ 50% under 60 ~ 90 ℃, water temperature is controlled at 60 ~ 90 ℃, stirs 3 ~ 10 minutes;
3) tertiary amine of performed polymer quality 1 ~ 5% and the water of performed polymer quality 40 ~ 60% are mixed, under agitation condition, add step 2) in the material of gained, continued stirring reaction 10 ~ 30 minutes;
4) amine chain extender of performed polymer quality 1 ~ 5% and the water of performed polymer quality 5 ~ 15% are mixed; Under agitation condition, add in the material in the material of adding step 3) gained; Stirring reaction is 60 ~ 120 minutes under 40 ~ 60 ℃ of conditions, promptly gets this aqueous pu dispersions.
The preparation method of above-mentioned a kind of solvent-free aqueous pu dispersions is characterized in that, described polyisocyanate compound is one of aliphatic polyisocyante, alicyclic polyisocyanates or their combination.
The preparation method of above-mentioned a kind of solvent-free aqueous polyurethane-polyurea dispersions; Wherein, described polymer polyatomic alcohol is one of them of polyether glycol, THF homopolymer polyvalent alcohol and copolymer polyols thereof, polyester polyol, polycaprolactone polyol, polycarbonate polyol, polyacrylate polyol, polyolefin polyhydric alcohol, castor oil polyhydric alcohol, epoxy resin or rosin ester polyvalent alcohol or their combination.
The preparation method of above-mentioned a kind of solvent-free aqueous pu dispersions; Wherein, described low molecular polylol is one of them of unit's alcohol such as terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether, Diethylene Glycol, pentanediol, NSC 6366, TriMethylolPropane(TMP), USP Kosher, tetramethylolmethane or their combination.
The preparation method of above-mentioned a kind of solvent-free aqueous pu dispersions, wherein, described carboxylic small molecules divalent alcohol is dimethylol propionic acid, one of them perhaps their combination of dimethylolpropionic acid.
The preparation method of above-mentioned a kind of solvent-free aqueous pu dispersions; Wherein, described organo-metallic catalyst is one of them of organic tin catalyzer, metal carboxylate catalyzer, titanate ester catalyzer, organic zirconium class catalyzer, organo-bismuth class catalyzer.
The preparation method of above-mentioned a kind of solvent-free aqueous pu dispersions, wherein, described tertiary amine is one of triethylamine, trolamine, methyl glycol amine, dimethylethanolamine or their combination.
The preparation method of above-mentioned a kind of solvent-free aqueous pu dispersions, wherein, described amine chain extender is quadrol, diethylenetriamine, 1, one of 6-hexanediamine, isophorone diamine, cyclohexanediamine, Hydrazine Hydrate 80 or its compsn.
The preparation method of above-mentioned a kind of solvent-free aqueous pu dispersions is characterized in that, described stirring velocity is 600 ~ 1200r/min.
Compared with prior art, the present invention's advantage specific as follows:
1. the present invention is under hot conditions, earlier with performed polymer directly with the hot water dilution, neutralization reduces the viscosity of system significantly again, be convenient to the later stage in the emulsification chain extension, make and need not use any organic solvent in process of production, economic environmental protection.
2. adopt the aqueous pu dispersions performance of this invention preparation to meet or exceed the performance of the like product of acetone method or the preparation of performed polymer (containing acetone) method, and reduce formulation cost significantly and simplify technology.
Embodiment
The present invention confirms to build on the basis of a large amount of simultaneous tests and screening about the design of aqueous polyurethane and each component and usage quantity thereof; Specific embodiments more given below are part preferred version further explain the present invention of the present invention, but do not limit the invention to the scope of following embodiment.Preparing method who adopts among the embodiment and use together can be with reference to laboratory, present technique field ordinary method, concrete preparation process is exemplified below:
Embodiment 1
In being furnished with the 1000M there-necked flask of TM, heating and whipping appts, add through dehydration place THF homopolymer polyethers PTMEG (molecular weight 2000) 200g; Dimethylol propionic acid (DMPA) 15g; Isophorone diamine (IPDI) 85g; Organic bismuth catalyst (effectively bismuth 20%) 0.2g, 95 ± 2 ℃ of stirring reactions are 3 hours under the nitrogen protection; Be cooled to 80 ℃, add 80 ℃ of deionized water 90g, stirred 5 minutes, stir the mixture of adding 11g triethylamine (TEA) and 300g room temperature water down at 1000r/min again, stir and made translucent homogeneous latex emulsion in 10 minutes with the speed of 600r/min; Under 1100r/min stirs, add the mixture of 22g isophorone diamine (IPDI) and 70g room temperature water, stirred 10 minutes, be warming up to 50 ± 2 ℃ at last, stirred 1 hour with 650r/min speed; Be cooled to room temperature, filter discharging, get translucent aqueous pu dispersions, solids content 40.1%, viscosity 300mpa.s, PH=7.8.
Embodiment 2
In being furnished with the 1000Ml there-necked flask of TM, heating and whipping appts, add through dehydration place THF homopolymer polyethers PTMEG (molecular weight 2000) 200g; Dimethylol propionic acid (DMPA) 15g; 100g dicyclohexyl methane diisocyanate (HMDI); Organic bismuth catalyst (effectively bismuth 20%) 0.2g, 95 ± 2 ℃ of stirring reactions are 3 hours under the nitrogen protection.Be cooled to 80 ℃, add 80 ℃ of deionized water 90g, stirred 5 minutes, stir the mixture of adding 11g triethylamine (TEA) and 300g room temperature water down, stir and made translucent homogeneous latex emulsion in 10 minutes at 1200r/min with the stirring velocity of 600r/min; Under the 1200r/min agitation condition, add the mixture of 22g isophorone diamine (IPDI) and 70g room temperature water, stirred 10 minutes, be warming up to 50 ± 2 ℃ at last, stirred 1 hour with 650r/min speed; Be cooled to room temperature, filter discharging, get translucent aqueous pu dispersions, solids content 41.5%, viscosity 100mpa.s, PH=8.2.
Embodiment 3
In being furnished with the 1000Ml there-necked flask of TM, heating and whipping appts, add through dehydration place polyoxypropyleneglycol (GE220, molecular weight 2000) 200g, 1; 4-butyleneglycol 10g; Dimethylol propionic acid (DMPA) 15g, 1,6-hexamethylene diisocyanate (HDI) 100g; Organic bismuth catalyst (effectively bismuth 20%) 0.2g, 95 ± 2 ℃ of stirring reactions are 3 hours under the nitrogen protection.Be cooled to 80 ℃, add 80 ℃ of deionized water 80g, stirred 5 minutes, stir the mixture of adding 11g triethylamine (TEA) and 480g room temperature water down, stir and made translucent homogeneous latex emulsion in 10 minutes in stirring velocity with 1000r/min with the stirring velocity of 600r/min.The mixture that under the 1200r/min agitation condition, adds 30g isophorone diamine (IPDI) and 100g room temperature water with the stirring velocity of 600r/min 10 minutes, was warming up to 55 ± 2 ℃ of stirring at low speed 1 hour at last.Be cooled to room temperature, filter discharging, get translucent aqueous pu dispersions, solids content 35.1%, viscosity 370mpa.s, PH=8.2.
Embodiment 4
In being furnished with the 1000Ml there-necked flask of TM, heat and whipping appts, add and (gather 1 through the polyester polyol CMA-1024 of processed; 4-butyleneglycol glycol ester, molecular weight 1000, hydroxyl value 112mgKOH/g); Dimethylolpropionic acid (DMBA) 14g; Isophorone diamine (IPDI) 115g, organic bismuth catalyst (effectively bismuth 20%) 0.1g, 95 ± 2 ℃ of stirring reactions are 3 hours under the nitrogen protection.Be cooled to 85 ℃, add 85 ℃ of deionized water 100g, stirred 5 minutes, stir the mixture of adding 9g triethylamine (TEA) and 340g room temperature water down, stir and made translucent homogeneous latex emulsion in 10 minutes in stirring velocity with 1000r/min with the stirring velocity of 700r/min.Stirring velocity with 1100r/min stirs adding 19g1 down, and the mixture of 6-hexanediamine and 60g room temperature water stirred 10 minutes, was warming up to 55 ± 2 ℃ of stirring at low speed at last 1 hour.Be cooled to room temperature, filter discharging, must be with little band blue light aqueous pu dispersions, solids content 40.5%, viscosity 100mpa.s, PH=8.1.
Embodiment 5
In being furnished with the 1000Ml there-necked flask of TM, heating and whipping appts, add and (gather 1 through the polyester polyol CMA-24 of processed; 4-butyleneglycol glycol ester, molecular weight 2000, hydroxyl value 56mgKOH/g); Dimethylol propionic acid (DMPA) 12g; Sym.-diisopropylideneacetone diamines (IPDI) 95g, organic bismuth catalyst (effectively bismuth 20%) 0.15g, 95 ± 2 ℃ of stirring reactions are 3 hours under the nitrogen protection.Be cooled to 80 ℃; Add 80 ℃ of deionized water 100g, stirred 5 minutes, stir the mixture of adding 9g triethylamine (TEA) and 200g room temperature water down in stirring velocity with 1200r/min with the stirring velocity of 800r/min; Stir and made translucent homogeneous latex emulsion in 10 minutes; Stirring velocity with 1200r/min stirs the mixture that adds 10g quadrol (DEA) and 50g room temperature water down, stirs 10 minutes, is warming up to 55 ± 2 ℃ of stirring at low speed at last 1 hour.Be cooled to room temperature, filter discharging, must be with the blue light aqueous pu dispersions, solids content 47.5%, viscosity 100mpa.s, PH=7.9.
Embodiment 6
In being furnished with the 1000Ml there-necked flask of TM, heating and whipping appts, add through the PCDL PCDL of processed (hydroxyl value 56mgKOH/g); Dimethylol propionic acid (DMPA) 16g; Isophorone diisocyanate (IPDI) 90g; Organic bismuth catalyst (effectively bismuth 20%) 0.10g, 95 ± 2 ℃ of stirring reactions are 3 hours under the nitrogen protection.Be cooled to 85 ℃; Add 85 ℃ of deionized water 100g; Stirring at low speed 5 minutes, the mixture of adding 12g triethylamine (TEA) and 400g room temperature water stirs and made translucent homogeneous latex emulsion in 10 minutes under violent stirring. add the mixture of 10g Hydrazine Hydrate 80 (80% effective constituent) and 50g room temperature water under the high degree of agitation; Stirred 10 minutes, be warming up to 55 ± 2 ℃ of stirring at low speed at last 1 hour.Be cooled to room temperature, filter discharging, get transparent blue light based polyurethane dispersion-s, solids content 35.9%, viscosity 390mpa.s, the PH=7.4 of having a little.
Comparative Examples 1
The 1000Ml there-necked flask is furnished with TM, heating and whipping appts.Add in the there-necked flask through dehydration place THF homopolymer polyethers PTMEG (molecular weight 2000) 200g, isophorone diamine (IPDI) 85g, organic bismuth catalyst (effectively bismuth 20%) 0.2g, 90 ± 2 ℃ of stirring reactions are 2 hours under the nitrogen protection; Be cooled to 60 ℃, add anhydrous propanone 50g, dimethylol propionic acid 15g (is dissolved in 30Gn; In the N-Methyl pyrrolidone), in 60 ℃ of reactions 2 hours, be cooled to 50 ℃; Add triethylamine 11g, reacted 30 minutes, be cooled to 30 ± 2 ℃.Under high degree of agitation, count deionized water 500g, emulsification 10 minutes adds the mixture of 22g isophorone diamine (IPDI) and 70g room temperature water under the high degree of agitation, stirred 60 minutes, is warming up to 50 ± 2 ℃ of stirring at low speed reduce pressure acetone 1 hour at last.Be cooled to room temperature, filter discharging, get translucent aqueous pu dispersions, solids content 36.1%, viscosity 380mpa.s, PH=7.6.
Comparative Examples 2: the performance comparison test of aqueous pu dispersions
Get above-mentioned aqueous pu dispersions 50 grams, drying and forming-film on the tetrafluoroethylene plate of 20cm*20cm, seasoning was tested after seven days.
Elongation at break test: carry out according to " GB/T 1040-2:2006 film material and sheet material tensile strength, tensile modulus, elongation at break detect ".
Freeze-thaw stability property testing: carry out according to " mensuration of GB/T9268-2008 rubber-emulsion paint freeze-thaw resistance "
The emulsion particle diameter test: water intaking based polyurethane dispersion-s is diluted to solid content 0.5%, with BI-900AI type photon spectrometry particle diameter.
Test result sees the following form 1:
Table 1
| Dispersion-s | The film forming outward appearance | Elongation at break | Freeze-thaw stability | Median size |
| Embodiment 1 | Homogeneous transparent | 1300% | Through | 45nm |
| Embodiment 2 | Homogeneous transparent | 1050% | Through | 72nm |
| Embodiment 3 | Homogeneous transparent | 1600% | Through | 38nm |
| Embodiment 4 | Homogeneous transparent | 1100% | Through | 135nm |
| Embodiment 5 | Homogeneous transparent | 1050% | Through | 83nm |
| Comparative Examples 6 | Homogeneous transparent | 1200% | Through | 50nm |
| Comparative Examples 1 | Homogeneous transparent | 1400% | Through | 40nm |
Through above-mentioned contrast, adopt the aqueous pu dispersions performance of this invention preparation to meet or exceed the performance of the like product of acetone method or the preparation of performed polymer (containing acetone) method, and reduce formulation cost significantly and simplify technology, and alleviated environmental stress.
Adopt the aqueous pu dispersions of this invention preparation to can be used for top coat or stickers such as textiles, leather, synthetic leather, woodenware, plastic cement.
Claims (9)
1. the preparation method of a solvent-free aqueous pu dispersions is characterized in that, comprises the steps: successively
1) takes by weighing 20 ~ 55% POLYMETHYLENE POLYPHENYLISOCYANATE, 2 ~ 10% carboxylic small molecules divalent alcohol, 0 ~ 5% small molecules divalent alcohol by weight percentage; 40 ~ 80% polyvalent alcohol; 0.1 ~ 0.5% organo-metallic catalyst mixes; 60 ~ 110 ℃ of following stirring reactions 2 ~ 5 hours, obtain containing the performed polymer of terminal isocyanate group;
2) at the water that in the performed polymer of step 1) gained, adds performed polymer quality 20 ~ 50% under 60 ~ 90 ℃, water temperature is controlled at 60 ~ 90 ℃, stirs 3 ~ 10 minutes;
3) tertiary amine of performed polymer quality 1 ~ 5% and the water of performed polymer quality 40 ~ 60% are mixed, under agitation condition, add step 2) in the material of gained, continued stirring reaction 10 ~ 30 minutes;
4) amine chain extender of performed polymer quality 1 ~ 5% and the water of performed polymer quality 5 ~ 15% are mixed; Under agitation condition, add in the material in the material of adding step 3) gained; Stirring reaction is 60 ~ 120 minutes under 40 ~ 60 ℃ of conditions, promptly gets this aqueous pu dispersions.
2. the preparation method of a kind of solvent-free aqueous pu dispersions according to claim 1 is characterized in that, described polyisocyanate compound is one of aliphatic polyisocyante, alicyclic polyisocyanates or their combination.
3. the preparation method of a kind of solvent-free aqueous polyurethane-polyurea dispersions according to claim 1; It is characterized in that described polymer polyatomic alcohol is one of them of polyether glycol, THF homopolymer polyvalent alcohol and copolymer polyols thereof, polyester polyol, polycaprolactone polyol, polycarbonate polyol, polyacrylate polyol, polyolefin polyhydric alcohol, castor oil polyhydric alcohol, epoxy resin or rosin ester polyvalent alcohol or their combination.
4. the preparation method of a kind of solvent-free aqueous pu dispersions according to claim 1; It is characterized in that described low molecular polylol is one of them of unit's alcohol such as terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether, Diethylene Glycol, pentanediol, NSC 6366, TriMethylolPropane(TMP), USP Kosher, tetramethylolmethane or their combination.
5. the preparation method of a kind of solvent-free aqueous pu dispersions according to claim 1 is characterized in that, described carboxylic small molecules divalent alcohol is dimethylol propionic acid, one of them perhaps their combination of dimethylolpropionic acid.
6. the preparation method of a kind of solvent-free aqueous pu dispersions according to claim 1; It is characterized in that described organo-metallic catalyst is one of them of organic tin catalyzer, metal carboxylate catalyzer, titanate ester catalyzer, organic zirconium class catalyzer, organo-bismuth class catalyzer.
7. the preparation method of a kind of solvent-free aqueous pu dispersions according to claim 1 is characterized in that, described tertiary amine is one of triethylamine, trolamine, methyl glycol amine, dimethylethanolamine or their combination.
8. the preparation method of a kind of solvent-free aqueous pu dispersions according to claim 1; It is characterized in that; Described amine chain extender is quadrol, diethylenetriamine, 1, one of 6-hexanediamine, isophorone diamine, cyclohexanediamine, Hydrazine Hydrate 80 or its compsn.
9. the preparation method of a kind of solvent-free aqueous pu dispersions according to claim 1 is characterized in that, described stirring velocity is 600 ~ 1200r/min.
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