CN1335328A - Process for producing water-base polyurethane emulsion - Google Patents
Process for producing water-base polyurethane emulsion Download PDFInfo
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- CN1335328A CN1335328A CN 01127791 CN01127791A CN1335328A CN 1335328 A CN1335328 A CN 1335328A CN 01127791 CN01127791 CN 01127791 CN 01127791 A CN01127791 A CN 01127791A CN 1335328 A CN1335328 A CN 1335328A
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Abstract
During the preparation of water-base polyurethane emulsion, prepolymer is first prepared through dewatering of polyesterglycol at 60-150 deg.c and 10-1000 Pa vacuum, reaction with diisocyanate in the amount of 1.5-2.5 times polyesterglycol weight at 70-100 deg.c for 1-4 hr, reaction with acetone solution of tartaric acid at 40-60 deg.c for 1-6 hr. The prepolymer is then produced into the polyurethane emulsion through neutralization reaction with caustic alkali or trialkylamine at 40-60 deg.c for 10-60 min, emulsified with water solution of emulsifier and eliminating organic solvent. The polyurethane emulsion is used in adhesive, paint and composite polymer/inorganic material.
Description
The present invention relates to chemical field, particularly the preparation method of water-base polyurethane emulsion.
Urethane is a kind of macromolecular material of excellent combination property.Macromole design according to different can obtain satisfying multi-purpose material, as plastics, rubber, coating and tackiness agent etc.Eighties of last century is since mid-term, and the solvent borne polyurethane that is used for coating and tackiness agent is used widely.Because the solid content of solvent-borne type product is lower, solvent all will enter construction operation regional environment and atmospheric environment in the use, also environment be brought very big pollution like this in grievous injury operating personnel healthy.Along with the enhancing of people's environmental consciousness, the shortcoming of solvent-borne type product becomes increasingly conspicuous.
The objective of the invention is to be used for the preparation method of the water-base polyurethane emulsion of the good stability of tackiness agent, coating and polymer/inorganic composite materials and excellent property.
The preparation method of water-base polyurethane emulsion of the present invention comprises:
(1) preparation performed polymer, being polyester diol carries out processed under 60-150 ℃ and 10-1000Pa vacuum condition, adding consumption is polyester diol 1.5-2.5 times of weight diisocyanate resin, 70-100 ℃ of reaction 1-4 hour, adding concentration was the tartaric acetone soln of 4-10% weight, 40-60 ℃ of reaction 1-6 hour;
The top condition of processed is 100～120 ℃, 200～400Pa.
(2) in and salify, promptly in the performed polymer of (1) gained, add caustic alkali that consumption is a tartrate 0.5-2.5 times weight or tertiary amine 40-60 ℃ of reaction 10-50 minute down;
(3) it is that 40-80 ℃, concentration are the chainextender aqueous solution of 0.5-5% that chain extension emulsification, the reaction product that is about to (2) are dispersed in temperature, and described chainextender is a polyamine;
(4) desolventizing promptly presses down in the decompression power of 50-200mmHg and steams organic solvent, obtains the water-base polyurethane emulsion of organic solvent content less than 5% weight.
The diisocyanate resin that is used to prepare performed polymer can be aliphatic, also can be aromatic, or their mixture.
The most suitable aliphatics diisocyanate resin has wherein one or more mixtures of different fluorine diketone diisocyanate resin (IPDI), pentamethylene diisocyanate resin, six methyne diisocyanate resins (HDI), dicyclohexyl methyl hydride diisocyanate resin;
The most suitable aromatic diisocyanate resin has wherein one or more mixtures of diphenylmethane diisocyanate fat (MDI), toluene diisocyanate (TDI), two phenyl diisocyanate resin and phenyl diisocyanate resin.
The polyvalent alcohol that is used to prepare performed polymer can be the polyether-type or the polyester type dibasic alcohol of different hydroxyl values.In order to increase intermolecular reactive force, preferably select polyester type dibasic alcohol for use, it is the reaction product of dibasic alcohol and diprotic acid.Diprotic acid can be hexanodioic acid or terephthalic acid, and dibasic alcohol can be ethylene glycol or 1, the 4-butyleneglycol.
The polyhydroxy-acid that is used to prepare performed polymer generally has following chemical structure:
(HO)
2R(COOH)
X
X=1～4R is the hydrocarbon group that contains 1～10 carbon atom of straight or branched.Compounds suitable for use is 2,2-dimethylol propionic acid, 2, and 2-dihydroxymethyl acetate, 2,2-dimethylolpropionic acid and tartrate is one or more mixtures wherein.
In order to make the polyamine fat that makes that high molecular weight be arranged, when performed polymer is scattered in water, carry out chain extension with chainextender.The speed that increases for Quality Initiative, suppressing the generation of gel, the diamine of handy sealing is made chainextender.Diamine can be wherein one or more mixtures of quadrol, butanediamine, hexanediamine, diethylenetriamine or triethylene tetramine.Encapsulant can be wherein one or more mixtures of acetone, butanone or methyl ethyl ketone.The preparation of dead front type chainextender is diamine to be mixed by 2: 1 weight with ketone placed 1.5-5 hour.
Under comparatively high temps, disperse chain extension, also help the appearance that high-molecular weight formed and suppressed gel.The temperature of disperseing chain extension preferably is 45～60 ℃, and wherein 50 ℃ is best.
Polyaminoester emulsion that finally obtains and solid content can be adjusted between the 20-30% by the water yield as required.
When the inventive method products obtained therefrom is used as the component of tackiness agent, coating or polymer/inorganic composite materials, can comprise tensio-active agent.Tensio-active agent is an anionic, and consumption is the 0.5-2% of total solid content.
Major advantage of the present invention is: the starting material source fully helps domestic industry production; The processing technology routine process is easy to control.The stability of product is high; The excellent property of product can directly be used as the composition of tackiness agent, coating or polymer/inorganic composite materials.
The invention will be further described below by embodiment.
Embodiment 1
23.1g (0.0233mol) polyester dihydric alcohol is packed in the four-hole ground reaction flask, agitator, thermometer are housed on the reaction flask, connect the nitrogen ball flatly, clog with ground glass plug flatly.Heat temperature raising to 100 ℃ at vacuum (300Pa) dehydration 40min down, is cooled to 50 ℃ then, fills nitrogen to make pressure of the inside of a bottle return to 1atm, adds 8.1gTDI, is warming up to ℃, reacts 1.5h under nitrogen protection, is cooled to 45 ℃ then.Load onto reflux condensing tube again on reaction flask, add the solution that is made by 30g acetone and 1.74g tartrate, be warming up to 50 ℃ then, reaction 3.5h gets performed polymer.In performed polymer, add by 3.0gEt
3The solution that N and 20g acetone are formed stirs 10min, pours into then in 50 ℃ the 120g water under the high-speed stirring, disperses 10min, slowly adds the hexanediamine of 3.40g by the butanone sealing then, continues to stir 2h.Last underpressure distillation, acetone reclaims through condensation, just obtains the oyster white solid content and be 23.2% water base polyamine fat liquor.Emulsion viscosity is 150mPa.S, and the particle diameter of average emulsion particle is 290nm, and the molecular-weight average of polyamine fat is 8.2 ten thousand.
Embodiment 2
25.46g (0.025mol) polyester dihydric alcohol is packed in the four-hole ground reaction flask, agitator, thermometer are housed on the reaction flask, connect the nitrogen ball flatly, clog with ground glass plug flatly.Heat temperature raising to 110 ℃ at vacuum (200Pa) dehydration 40min down, is cooled to 50 ℃ then, fills nitrogen to make pressure of the inside of a bottle return to 1atm, adds 8.89gTDI, is warming up to 90 ℃, and nitrogen protection is reaction 1.5h down, is cooled to 45 ℃ then.Load onto reflux condensing tube again on reaction flask, add the solution that is made by 35g acetone and the acid of 1.92g stone, be warming up to 55 ℃ then, reaction 3.5h gets performed polymer.In performed polymer, add by 3.0gEt
3The solution that N and 20g acetone are formed stirs 10min, pours 55 ℃ water 110g under the high-speed stirring then into, disperses 10min, slowly adds the hexanediamine of 3.50g by the butanone sealing then, continues to stir 2h.Last underpressure distillation, acetone reclaims through condensation, just obtains the oyster white solid content and be 25.1% water base polyamine fat liquor.Emulsion viscosity is 165mPa.S, and the particle diameter of average emulsion particle is 240nm, and the molecular-weight average of polyamine fat is 9.2 ten thousand.
Embodiment 3
23.49g (0.024mol) polyester dihydric alcohol is packed in the four-hole ground reaction flask, agitator, thermometer are housed on the reaction flask, connect the nitrogen ball flatly, clog with ground glass plug flatly.Heat temperature raising to 110 ℃ at vacuum (200Pa) dehydration 40min down, is cooled to 50 ℃ then, fills nitrogen to make pressure of the inside of a bottle return to 1atm, adds 8.21gTDI, is warming up to 90 ℃, reacts 1.5h under nitrogen protection, is cooled to 45 ℃ then.Load onto reflux condensing tube again on reaction flask, add the solution that is made by 30g acetone and 1.77g tartrate, be warming up to 55 ℃ then, reaction 3.5h gets performed polymer.In performed polymer, add by 3.0gEt
3The solution that N and 20g acetone are formed stirs 10min, pours 50 ℃ the aqueous solution 110g that contains the 1g sodium laurylsulfonate under the high-speed stirring then into, disperses 10min, slowly adds the hexanediamine of 3.10g by the butanone sealing then, continues to stir 2h.Last underpressure distillation, acetone reclaims through condensation, just obtains the oyster white solid content and be 24.5% water base polyamine fat liquor.Emulsion viscosity is 115mPa.S, and the particle diameter of average emulsion particle is 210nm, and the molecular-weight average of polyamine fat is 8.3 ten thousand.
Embodiment 4
25.54g (0.026mol) polyester dihydric alcohol is packed in the four-hole ground reaction flask, agitator, thermometer are housed on the reaction flask, connect the nitrogen ball flatly, clog with ground glass plug flatly.Heat temperature raising to 110 ℃ at vacuum (300Pa) dehydration 40min down, is cooled to 50 ℃ then, fills nitrogen to make pressure of the inside of a bottle return to 1atm, adds 8.91gTDI, is warming up to 90 ℃, reacts 1.5h under nitrogen protection, is cooled to 45 ℃ then.Load onto reflux condensing tube again on reaction flask, add the solution that is made by 20g acetone and 1.91g tartrate, be warming up to 55 ℃ then, reaction 3h gets performed polymer.In performed polymer, add by 3.5gEt
3The solution that N and 20g acetone are formed stirs 10min, pours 50 ℃ the aqueous solution 100g that contains the 1g sodium laurylsulfonate under the high-speed stirring then into, disperses 10min, slowly adds the diethylenetriamine of 3.20g by the butanone sealing then.Continue to stir 2.5h.Last underpressure distillation, acetone reclaims through condensation, just obtains the oyster white solid content and be 28% water base polyamine fat liquor.Emulsion viscosity is 235mPa.S, and the particle diameter of average emulsion particle is 270nm, and the molecular-weight average of polyamine fat is 8.7 ten thousand.
Embodiment 5
Agitator, thermometer are being housed; connect flatly the nitrogen ball, flatly in the four-hole ground reaction flask that clogs with ground glass plug, the 25.26g that packs into (0.025mol) polyester diamine; heat temperature raising to 110 ℃; dehydration 40min is cooled to 50 ℃ then under vacuum (200Pa), fills nitrogen to make pressure of the inside of a bottle return to 1atm; add 8.81gTDI; be warming up to 90 ℃, under nitrogen protection, react 1.5h, be cooled to 45 ℃ then.Load onto reflux condensing tube again on reaction flask, add the solution that is made by 20g acetone and 1.91g tartrate, be warming up to 55 ℃ then, reaction 3h gets performed polymer.In performed polymer, add by 3.0gEt
3The solution that N and 20g acetone are formed stirs 10min, pours 50 ℃ the aqueous solution 120g that contains the 1g sodium laurylsulfonate under the high-speed stirring then into, disperses 10min, slowly adds the diethylenetriamine of 3.14g by the butanone sealing then.Continue to stir 2.5h.Last underpressure distillation, acetone reclaims through condensation, and just obtaining the oyster white solid content is 24.3% water base polyamine fat liquor.Emulsion viscosity is 220mPa.S, and the particle diameter of average emulsion particle is 210nm, and the molecular-weight average of polyamine fat is 8.5 ten thousand.
Embodiment 6
Agitator, thermometer are being housed; connect flatly the nitrogen ball, flatly in the four-hole ground reaction flask that clogs with ground glass plug, the 25.32g that packs into (0.0254mol) polyester diamine; heat temperature raising to 110 ℃; dehydration 40min is cooled to 50 ℃ then under vacuum (300Pa), fills nitrogen to make pressure of the inside of a bottle return to 1atm; add 8.8gTDI; be warming up to 90 ℃, under nitrogen protection, react 1.5h, be cooled to 45 ℃ then.Load onto reflux condensing tube again on reaction flask, add the solution that is made by 20g acetone and 1.90g tartrate, be warming up to 55 ℃ then, reaction 3.5h gets performed polymer.In performed polymer, add by 3.0gEt
3The solution that N and 20g acetone are formed stirs 10min, pours 50 ℃ the aqueous solution 120g that contains the 0.5g sodium laurylsulfonate under the high-speed stirring then into, disperses 10min, slowly adds the diethylenetriamine of 3.20g by the butanone sealing then.Continue to stir 2.5h.Last underpressure distillation, acetone reclaims through condensation, and just obtaining the oyster white solid content is 30% water base polyamine fat liquor.Emulsion viscosity is 250mPa.S, and the particle diameter of average emulsion particle is 280nm, and the molecular-weight average of polyamine fat is 9.3 ten thousand.
Claims (10)
1, a kind of preparation method of water-base polyurethane emulsion is characterized in that comprising:
(1) preparation performed polymer, being polyester diol carries out processed under 60-150 ℃ and 10-1000Pa vacuum condition, adding consumption is polyester diol 1.5-2.5 times of weight diisocyanate resin, 70-100 ℃ of reaction 1-4 hour, adding concentration was the tartaric acetone soln of 4-10% weight, 40-60 ℃ of reaction 1-6 hour;
(2) in and salify, promptly in the performed polymer of (1) gained, add caustic alkali that consumption is a tartrate 0.5-2.5 times weight or tertiary amine 40-60 ℃ of reaction 10-60 minute down;
(3) it is that 40-80 ℃, concentration are the chainextender aqueous solution of 0.5-5% that chain extension emulsification, the reaction product that is about to (2) are dispersed in temperature, and described chainextender is a polyamine;
(4) desolventizing promptly presses down in the decompression power of 50-200mmHg and steams organic solvent.
2, the preparation method of water-base polyurethane emulsion according to claim 1 is characterized in that in (1) that polyester diol carries out processed under 100～120 ℃, 200～400Pa vacuum condition.
3, the preparation method of water-base polyurethane emulsion according to claim 1, the diisocyanate resin that it is characterized in that being used to preparing performed polymer can be aliphatic, also can be aromatic, or their mixture.
4, the preparation method of water-base polyurethane emulsion according to claim 3 is characterized in that described aliphatics diisocyanate resin is wherein one or more mixtures of different fluorine diketone diisocyanate resin (IPDI), pentamethylene diisocyanate resin, six methyne diisocyanate resins (HDI), dicyclohexyl methyl hydride diisocyanate resin;
5, the preparation method of water-base polyurethane emulsion according to claim 3 is characterized in that described aromatic diisocyanate resin is wherein one or more mixtures of diphenylmethane diisocyanate fat (MDI), toluene diisocyanate (TDI), two phenyl diisocyanate resin and phenyl diisocyanate resin.
6, the preparation method of water-base polyurethane emulsion according to claim 1, the polyvalent alcohol that it is characterized in that being used to preparing performed polymer can be the polyether-type or the polyester type dibasic alcohol of different hydroxyl values.
7, the preparation method of water-base polyurethane emulsion according to claim 6 is characterized in that selecting for use polyester type dibasic alcohol, and it is the reaction product of dibasic alcohol and diprotic acid.Diprotic acid can be hexanodioic acid or terephthalic acid, and dibasic alcohol can be ethylene glycol or 1, the 4-butyleneglycol.
8, the preparation method of water-base polyurethane emulsion according to claim 1, the polyhydroxy-acid that it is characterized in that being used to preparing performed polymer has following chemical structure: (HO)
2R (COOH)
X(X=1～4), R is the hydrocarbon group that contains 1～10 carbon atom of straight or branched.
9, the preparation method of water-base polyurethane emulsion according to claim 1 is characterized in that adopting the diamine of sealing to make chainextender.
10, the preparation method of water-base polyurethane emulsion according to claim 9 is characterized in that diamine can be wherein one or more mixtures of quadrol, butanediamine, hexanediamine, diethylenetriamine or triethylene tetramine; Encapsulant can be wherein one or more mixtures of acetone, butanone or methyl ethyl ketone.
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| CNB011277912A CN1159360C (en) | 2001-08-30 | 2001-08-30 | Process for producing water-base polyurethane emulsion |
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| CNB011277912A CN1159360C (en) | 2001-08-30 | 2001-08-30 | Process for producing water-base polyurethane emulsion |
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-
2001
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| CN105423173A (en) * | 2014-10-29 | 2016-03-23 | 中山市四维家居照明有限公司 | American retro LED floor lamp |
| CN105423182A (en) * | 2014-10-29 | 2016-03-23 | 中山市四维家居照明有限公司 | European type wall lamp with good heat dissipation effect |
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| CN105605501A (en) * | 2014-10-29 | 2016-05-25 | 中山市四维家居照明有限公司 | Three-layer European pendant lamp |
| CN115594808A (en) * | 2022-10-31 | 2023-01-13 | 亚士防水科技（滁州）有限公司（Cn） | Bio-based anionic waterborne polyurethane and preparation method and application thereof |
| CN115594808B (en) * | 2022-10-31 | 2024-03-29 | 亚士防水科技(滁州)有限公司 | Bio-based anionic waterborne polyurethane and preparation method and application thereof |
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