WO2018184307A1 - 水性聚氨酯分散体及其无溶剂制备方法 - Google Patents

水性聚氨酯分散体及其无溶剂制备方法 Download PDF

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WO2018184307A1
WO2018184307A1 PCT/CN2017/091064 CN2017091064W WO2018184307A1 WO 2018184307 A1 WO2018184307 A1 WO 2018184307A1 CN 2017091064 W CN2017091064 W CN 2017091064W WO 2018184307 A1 WO2018184307 A1 WO 2018184307A1
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chain extender
aqueous polyurethane
polyurethane dispersion
polyol
small molecule
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PCT/CN2017/091064
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English (en)
French (fr)
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汪金
张红明
王献红
王佛松
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中国科学院长春应用化学研究所
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Publication of WO2018184307A1 publication Critical patent/WO2018184307A1/zh

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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Definitions

  • the invention belongs to the technical field of aqueous polyurethane preparation, and in particular relates to an aqueous polyurethane dispersion and a solventless preparation method thereof.
  • Polyurethane is widely used in coatings, adhesives, synthetic leathers, sealants, elastomers, etc. due to its excellent properties. Due to the increasing emphasis on environmental issues in human society, increasingly stringent ecological and other legal regulations have limited the development of traditional solvent-based polyurethanes, and have directly stimulated the development and application of waterborne polyurethanes, while in the field of coatings and adhesives. Especially remarkable.
  • the water-based polyurethane refers to a polyurethane resin formed by dissolving or dispersing polyurethane in water, and the preparation method thereof mainly includes a conventional acetone method and a prepolymer dispersion method.
  • EP373671-A describes the preparation of aqueous polyurethanes by the acetone method, mainly by reacting an excess of polyisocyanate with an oligomer polyol and a small molecular polyol having a hydrophilic group to prepare an isocyanate-terminated polyurethane prepolymer. Next, a chain extension reaction is carried out using a small molecule diol to obtain a high molecular weight polyurethane.
  • a large amount of an organic solvent such as acetone, nitromethylpyrrolidone or dimethyl sulfoxide is used to lower the viscosity of the system.
  • the neutralizing agent and a large amount of water disperse the polyurethane solution in water, and the organic solvent is removed by distillation under reduced pressure to obtain a final solventless aqueous polyurethane.
  • a method for preparing an aqueous polyurethane by a prepolymer dispersion method is described in US Pat. No. 4,591,612, A, which mainly comprises reacting an excess of polyisocyanate with an oligomer polyol and a small molecule polyol having a hydrophilic group to prepare a polyurethane prepolymer. In the meantime, add appropriate amount of organic solvent to reduce viscosity. Subsequently, the reaction temperature is lowered to 30-40 ° C, and a neutralizing agent and a large amount of water are added to form a polyurethane prepolymer dispersion. After the dispersion is completed, a polyamine chain extender is added to the isocyanate group to undergo chain extension reaction, and finally the organic component is removed. Solvent to give the final aqueous polyurethane.
  • the object of the present invention is to solve the problem of using an organic solvent in the prior art aqueous polyurethane preparation process, and to provide an aqueous polyurethane dispersion and a solventless preparation method thereof.
  • the present invention first provides a solventless preparation method of an aqueous polyurethane dispersion, the method comprising:
  • Step 1 reacting at least one polyhydroxy oligomer polyol, at least one polyisocyanate and a small molecule hydrophilic chain extender under an inert gas to obtain a polyurethane prepolymer having an NCO group at the end;
  • Step 2 reacting the polyurethane prepolymer with NCO group at the end obtained in step 1 with a small molecule neutralizing agent, then adding water at 60-100 ° C, and dispersing under stirring to reduce the temperature of the reaction system to 20 -50 ° C, then add water, after dispersion to obtain a prepolymer dispersion;
  • Step 3 reacting the prepolymer dispersion obtained in the second step with the sulfonate type polyamine hydrophilic chain extender, and then reacting with the polyamine chain extender to obtain an aqueous polyurethane dispersion;
  • the weight fraction of the polyhydroxy oligomer polyol, polyisocyanate, small molecule hydrophilic chain extender, small molecule neutralizer, sulfonate type polyamine hydrophilic chain extender and polyamine chain extender The ratio is (40-90): (8-40): (0-15): (0-15): (0-10): (0.5-8).
  • the solventless preparation of the aqueous polyurethane dispersion according to the invention is carried out under the protection of an inert gas.
  • the inert gas is selected from nitrogen or argon.
  • the inert gas is nitrogen.
  • the water used in the solventless preparation method of the aqueous polyurethane dispersion of the present invention is deionized water.
  • the polyhydroxy oligomer polyol of the first step is a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylate polyol, a polyolefin polyol, a biopolyol or a carbon dioxide group.
  • Polycarbonate-ether polyol is a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylate polyol, a polyolefin polyol, a biopolyol or a carbon dioxide group.
  • the polyisocyanate of the first step is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), benzene.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • HMDI 4,4'-dicyclohexylmethane diisocyanate
  • benzene isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • HMDI 4,4'-dicyclohexylmethane diisocyanate
  • XDI Methyl diisocyanate
  • CHDI 1,4-cyclohexane diisocyanate
  • TMXDI tetramethyl meta-xylylene diisocyanate
  • TMHDI trimethyl-1,6-hexamethylene diisocyanate
  • HXDI cyclohexane dimethylene diisocyanate
  • NB-DI norbornane diisocyanate
  • HTDI methylcyclohexy
  • the small molecule hydrophilic chain extender of the first step is dimethylolpropionic acid, dimethylol butyric acid, dihydroxy half ester, N-methyldiethanolamine, N-butyldiethanolamine, 2,2'-iminodiethanol or trishydroxyethylamine.
  • the reaction temperature when the first addition of water in the second step is 75-90 ° C.
  • the small molecule neutralizing agent of the second step is triethylamine, ammonia water, sodium hydroxide, hydrochloric acid, acetic acid, CH 3 I, (CH 3 ) 2 SO 4 , or epichlorohydrin.
  • the sulfonate-type polyamine hydrophilic chain extender of the third step is sodium 2-[(2-aminoethyl)amino]ethanesulfonate, sodium 2,4-diaminobenzenesulfonate or 3-(pentameric (1-(aminopropoxy)propyl)amino)propyl-1-sulfonic acid sodium.
  • the polyamine chain extender of the third step is ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenediamine, Triethylenetetramine or tritetraethylenepentamine.
  • the polyhydroxy oligomer polyol, polyisocyanate, small molecule hydrophilic chain extender, small molecule neutralizer, sulfonate type polyamine hydrophilic chain extender and polyamine chain extender The parts by weight ratio is (66-80):(15-25):(3-4):(1.5-2):(1.5-2):(2-3).
  • the present invention also provides an aqueous polyurethane dispersion obtained by the above production method.
  • the present invention firstly provides an aqueous polyurethane dispersion prepared by directly dispersing an aqueous polyurethane prepolymer in water at a relatively high temperature. Due to a high dispersion temperature, the preparation process overcomes the conventional process in the preparation process because Lower temperature (30-40 ° C) brings the disadvantage of higher prepolymer viscosity, and higher viscosity is also considered as the technical bottleneck of solvent-free preparation of aqueous polyurethane, achieving the retention of isocyanate groups after dispersion. more than 90 percent.
  • the viscosity of the polyurethane prepolymer at 80 ° C is reduced from 125,000 mPa ⁇ s at 40 ° C to 5,000 mPa ⁇ s, which ensures the polyurethane pre-preparation.
  • the polymer can be smoothly and uniformly dispersed in water at a low viscosity, avoiding the disadvantage of introducing a large amount of organic solvent to be diluted by high viscosity in the conventional process, having obvious environmental protection characteristics, and greatly reducing the cooling step and the solvent recovery process. Production energy consumption and preparation cycle.
  • the invention also provides the aqueous polyurethane dispersion obtained by the above preparation method, and the aqueous polyurethane dispersion prepared by the method has the same comprehensive performance as the similar products obtained by the conventional preparation method.
  • the experimental results show that the tensile strength of the product prepared by the aqueous polyurethane dispersion of the invention can be as high as 65 MPa, the elongation at break can be as high as 810%, and the bonding strength can be as high as 61N.
  • Example 1 is a nuclear magnetic hydrogen spectrum diagram of an aqueous polyurethane dispersion prepared in Example 1 of the present invention
  • Example 2 is an infrared spectrum diagram of an aqueous polyurethane dispersion prepared in Example 1 of the present invention.
  • the present invention first provides a solventless preparation method of an aqueous polyurethane dispersion, the method comprising:
  • Step 1 reacting at least one polyhydroxy oligomer polyol, at least one polyisocyanate and a small molecule hydrophilic chain extender under an inert gas to obtain a polyurethane prepolymer having an NCO group at the end;
  • Step 2 reacting the polyurethane prepolymer with NCO group at the end obtained in step 1 with a small molecule neutralizing agent, then adding water at 60-100 ° C, and dispersing under stirring to reduce the temperature of the reaction system to 20 -50 ° C, then add water, after dispersion to obtain a prepolymer dispersion;
  • Step 3 reacting the prepolymer dispersion obtained in the second step with the sulfonate type polyamine hydrophilic chain extender, and then reacting with the polyamine chain extender to obtain an aqueous polyurethane dispersion;
  • the weight fraction of the polyhydroxy oligomer polyol, polyisocyanate, small molecule hydrophilic chain extender, small molecule neutralizer, sulfonate type polyamine hydrophilic chain extender and polyamine chain extender is (40-90): (8-40): (0-15): (0-15): (0-10): (0.5-8).
  • At least one polyhydroxy oligomer polyol, at least one polyisocyanate and a small molecular chain extender are added to a reaction device to obtain a polyurethane prepolymer having an NCO group at the end;
  • the reaction temperature of the reaction is preferably from 60 to 100 ° C, more preferably from 65 to 90 ° C, most preferably from 75 to 90 ° C, and the reaction time is preferably from 3 to 6.5 hours, more preferably from 4 to 5 hours.
  • the at least one polyhydroxy oligomer polyol, at least one polyisocyanate may be added in steps as needed, and the small molecule hydrophilic chain extender It may be previously reacted with at least one polyisocyanate or after at least one polyhydroxy oligomer polyol is reacted with at least one polyisocyanate.
  • the polyhydroxy oligomer polyol is preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylate polyol, a polyolefin polyol, a biopolyol or a carbon dioxide based polymerization. Carbonate-ether polyol.
  • the polyether polyol is preferably a polyoxypropylene polyol, a polytetrahydrofuran polyol, a polyoxyethylene polyol, a polytrimethylene ether polyol or other aromatic polyether polyol.
  • the polyester polyol preferably comprises a common aliphatic polyester diol or an aromatic polyester polyol, more preferably a polycaprolactone polyol or a polybutylene adipate polyol.
  • polyhexamethylene adipate polyol the aliphatic polyester diol is obtained by polycondensation of a diol and a dicarboxylic acid, and the diol is preferably ethylene glycol, propylene glycol or butyl a diol, diethylene glycol, triethylene glycol, hexanediol or neopentyl glycol, preferably a dicarboxylic acid
  • the aromatic polyester polyol is an aromatic dicarboxylic acid or An acid anhydride obtained by reacting with a glycol.
  • the acid anhydride is preferably phthalic anhydride, terephthalic acid or isophthalic acid; the glycol is preferably ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, Hexanediol or neopentyl glycol.
  • the polycarbonate polyol is preferably obtained by transesterification of a small molecule diol with a small molecule carbonate, more preferably a polycarbonate-1,6-hexanediol diol or a monomer.
  • An ester polycarbonate polyol; the small molecule diol is preferably hexanediol, butanediol, 1,4-cyclohexanedimethylether, pentanediol or 3-methylpentanediol;
  • the small molecule carbonate described is preferably dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, ethylene carbonate or propylene carbonate.
  • the polyolefin polyol is preferably a hydroxyl terminated polybutadiene, a hydroxyl terminated hydrogenated polybutadiene, a terminal hydroxyl epoxidized polybutadiene, a hydroxyl terminated polybutadiene-acrylonitrile, a polyphenylene. Ethylene polyol or hydroxyl terminated polyisoprene.
  • the biopolyol is preferably a castor oil polyol and a derivative thereof, a soybean oil polyol or a palm oil polyol.
  • the carbon dioxide-based polycarbonate-ether polyols are preferably prepared according to the process described in the publications CN102432857A, CN102617844A and CN105061746A.
  • the polyurethane product prepared by the carbon dioxide-based polycarbonate-ether polyol exhibits excellent hydrolysis resistance, oxidation resistance and high mechanical properties, and has a significant cost advantage.
  • the polyhydroxy oligomer polyol preferably has a molar mass of from 300 g/mol to 8000 g/mol, more preferably from 500 g/mol to 6000 g/mol, most preferably from 1000 g/mol to 4000 g/mol.
  • the polyhydroxy oligomer polyol exhibits a functionality of preferably from 2 to 6, more preferably from 2 to 4, most preferably from 2 to 3.
  • the polyisocyanate is a polyisocyanate well known to those skilled in the art, preferably a low activity polyisocyanate selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), benzodimethyl diisocyanate (XDI), 1,4-cyclohexane diisocyanate (CHDI), tetramethylm-xylylene dimethylene diisocyanate (TMXDI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), cyclohexane dimethylene diisocyanate (HXDI), norbornane diisocyanate (NB-DI) or methylcyclohexyl Isocyanate (HTDI).
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • the high-activity aromatic diisocyanate is preferably toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and Liquefied product (L-MDI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), dimethylbiphenyl diisocyanate (TODI) or dimethyldiphenylmethane diisocyanate (DMMDI).
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • L-MDI Liquefied product
  • NDI naphthalene diisocyanate
  • PPDI p-phenylene diisocyanate
  • TODI dimethylbiphenyl diisocyanate
  • DMMDI dimethyldiphenylmethane diisocyanate
  • polyisocyanates having a functionality higher than 2 may be added.
  • the polyisocyanates having a functionality higher than 2 are preferably modified HDI trimers, TDI trimers, TDI-TMP adducts, IPDI trimers. , decane triisocyanate or triphenylmethane 4,4',4"-triisocyanate.
  • the low activity polyisocyanate, high activity aromatic diisocyanate and polyisocyanate having a functionality higher than 2 are in parts by weight. (8-40): (5-10): (3-10).
  • the small molecule hydrophilic chain extender is a small molecule hydrophilic chain extender well known to those skilled in the art, preferably a cationic small molecule polyol hydrophilic chain extender or an anionic small molecule hydrophilic extension.
  • Chain agent more preferably dimethylolpropionic acid, dimethylolbutanoic acid, dihydroxy half ester, N-methyldiethanolamine, N-butyldiethanolamine, 2,2'-iminodiethanol or three Hydroxyethylamine; most preferred is dimethylolpropionic acid or N-methyldiethanolamine.
  • the cationic small molecule polyol hydrophilic chain extender is preferably N-methyldiethanolamine, N-butyldiethanolamine, 2,2'-iminodiethanol, trishydroxyethylamine or diethylenetriamine.
  • the reaction product of chloropropane; the anionic small molecule hydrophilic chain extender is preferably dimethylolpropionic acid or dimethylolbutanoic acid.
  • the polyurethane prepolymer having an NCO group at the end and the small molecule neutralizing agent are neutralized, and then a small amount of deionized water is rapidly added at 65-95 ° C, preferably within 30 seconds. After initial dispersion for 0.5-2 minutes under stirring, the temperature of the reaction system is lowered to 20-50 ° C, and then a large amount of deionized water is added, and after dispersing for 3-5 minutes, a prepolymer dispersion is obtained;
  • the neutralization reaction temperature is preferably from 60 to 100 ° C, more preferably from 75 to 90 ° C, and the reaction time is preferably from 0.3 to 0.5 hours
  • the small molecule neutralizing agent is preferably a cationic small molecule neutralized.
  • the cationic small molecule neutralizing agent is preferably triethylamine, ammonia or sodium hydroxide; the anionic small molecule neutralizing agent is preferably hydrochloric acid, acetic acid, CH 3 I, CH 3 ) 2 Alkylation reagent such as SO 4 or epichlorohydrin.
  • the polyurethane prepolymer having an NCO group at the above end is directly dispersed in water at a high temperature of 60 to 100 ° C, more preferably 65 to 95 ° C, and most preferably 75 -90 ° C, when the temperature is below 60 ° C, the reaction system will lead to higher viscosity (> 100,000 mPa ⁇ s) due to too low temperature, directly leading to uneven dispersion or even failure; when the temperature is higher than 100 ° C In the above, a large amount of isocyanate groups are consumed due to a higher dispersion temperature (retention rate ⁇ 80%), resulting in a low overall product performance; the present invention controls the high temperature to 60-100 ° C to achieve post-dispersion isocyanate groups.
  • the retention rate of the group is maintained above 90%, which ensures that the polyurethane prepolymer can be smoothly and uniformly dispersed in water at a low viscosity, thereby avoiding the disadvantage of introducing a large amount of organic solvent to be diluted due to high viscosity in the conventional process.
  • the deionized water is added in two portions, a small amount is added for the first time, and a large amount is added for the second time.
  • the polyisocyanate, the first added deionized water and the second added deionized water are added.
  • the weight ratio of water is (8-40): (30-70): (150-300).
  • the prepolymer dispersion obtained above and the sulfonate type polyamine hydrophilic chain extender are reacted, and the reaction temperature of the reaction is preferably 20 to 50 ° C, and the reaction time is preferably 0.2 to 1 hour. Preferably, it is 0.5 hour; and then reacted with a polyamine chain extender, the reaction temperature of the reaction is preferably 20 to 40 ° C, and the reaction time is preferably 0.5 to 3 hours, more preferably 1 to 1.5 hours; and an aqueous polyurethane dispersion is obtained. .
  • the sulfonate-type polyamine hydrophilic chain extender is a product well known to those skilled in the art, preferably sodium 2-[(2-aminoethyl)amino]ethanesulfonate, 2,4 Sodium diaminobenzenesulfonate or sodium 3-(penta(1-(aminopropoxy)propyl)amino)propyl-1-sulfonate.
  • the polyamine chain extender is a product well known to those skilled in the art, preferably ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, Diethylenetriamine, triethylenetetramine or tritetraethylenepentamine, more preferably ethylenediamine, 1,6-butanediamine or triethylenetetramine, most preferably ethylenediamine.
  • the weight of the hydroxy oligomer polyol, polyisocyanate, small molecule hydrophilic chain extender, small molecule neutralizer, sulfonate type polyamine hydrophilic chain extender and polyamine chain extender The ratio of parts is (40-90): (8-40): (0-15): (0-15): (0-10): (0.5-8), preferably (60-85): (12 -30): (0-5): (0-3): (0-2.5): (1.5-4), most preferably (66-80): (15-25): (3-4): ( 1.5-2): (1.5-2): (2-3).
  • the present invention also provides an aqueous polyurethane dispersion obtained by the above production method.
  • the aqueous polyurethane dispersion obtained by the above process may be a nonionic aqueous polyurethane dispersion, a semiionic aqueous polyurethane dispersion or an ionic aqueous polyurethane dispersion; when the aqueous polyurethane dispersion is a nonionic aqueous polyurethane In the case of the dispersion, the amount of the small molecule hydrophilic chain extender, the sulfonate type polyamine hydrophilic chain extender and the small molecule neutralizing agent in the process is 0; when the aqueous polyurethane dispersion is a half-ionic aqueous polyurethane dispersion, The amount of the small molecule hydrophilic chain extender and the small molecule neutralizing agent in the process is 0, or the amount of the sulfonate type polyamine hydrophilic chain extender in the process is 0; when the aqueous polyurethane dispersion is
  • the polyhydroxy oligomer polyol in the first step must have hydrophilicity, preferably polyoxidation.
  • the ethylene polyol, the hydrophilic polyhydroxy oligomer polyol may be used alone or in combination with other types of polyols, and the specific amount is designed according to the needs of the final product.
  • the polyhydroxy oligomer polyol may have hydrophilicity or other types of hydrophobic polyols, and the specific amount thereof. According to actual needs.
  • an auxiliary agent or an additive is added to the aqueous polyurethane dispersion prepared above to obtain an aqueous polyurethane product
  • the auxiliary agent and the additive are not particularly limited, and may be an auxiliary agent or an additive well known to those skilled in the art. It depends on the product of the obtained aqueous polyurethane.
  • Comparative Example 1 An aqueous polyurethane dispersion was prepared according to the conventional acetone method.
  • Comparative Example 2 An aqueous polyurethane dispersion was prepared according to a conventional prepolymer dispersion method.
  • the heating device was removed, and after the temperature of the reaction system was lowered to 30 ° C, 1.5 parts by weight of triethylamine was added to neutralize the reaction, and after half an hour, 200 parts by weight of deionized water was added under stirring to obtain To the polyurethane prepolymer dispersion. After 0.5 hours, the polyurethane prepolymer was uniformly dispersed, and 2.5 parts by weight of sodium 2,4-diaminobenzenesulfonate was dissolved in 5 parts by weight of deionized water, and then added to the reaction apparatus, and after 0.5 hours of reaction, the system was introduced into the system.
  • Neutralization reaction was carried out by adding 1.5 parts by weight of triethylamine at 80 ° C, and after 50 hours, 50 parts by weight of deionized water was quickly added under stirring for 30 seconds, and the polyurethane prepolymer was completed in 1 minute at high temperature. Pre-dispersed, and after adding the temperature to 25 ° C, 150 parts by weight of deionized water was added, and after sufficiently dispersing for 5 minutes, 2.5 parts by weight of sodium 2,4-diaminobenzenesulfonate was used with 5 parts by weight of deionized water.
  • FIG. 1 is a nuclear magnetic hydrogen spectrum diagram of an aqueous polyurethane dispersion prepared in Example 1 of the present invention
  • FIG. 2 is an infrared spectrum diagram of an aqueous polyurethane dispersion prepared in Example 1 of the present invention.
  • the present invention successfully prepared an aqueous polyurethane dispersion.
  • the preparation process of the first embodiment of the present invention does not require any organic solvent, and the temperature reduction of the prepolymer and the decompression removal process of the organic solvent in the product are omitted, which greatly reduces the process. Production costs shorten the production cycle.
  • a polyurethane prepolymer having an NCO group at the end adding 2 parts by weight of dimethylolpropionic acid to continue the reaction for 3 hours, and then rapidly adding 50 parts by weight of 0.6 parts by weight of hydrogen in 75 seconds at 75 ° C
  • Deionized water of sodium oxide the polyurethane prepolymer is pre-dispersed in 1 minute at high temperature, and the temperature is lowered to 35 ° C
  • 3 parts by weight of 1,3-propanediamine was added to the system, and the solid content was 34% and pH after 1 hour of chain extension reaction at room temperature.
  • An aqueous polyurethane dispersion of 6.8 and a viscosity of 450 mPa ⁇ s is referred to as WPU-6.
  • the WPU-6 performance test results are shown in Tables 1 and 2.
  • Neutralization reaction was carried out by adding 3 parts by weight of triethylamine at 90 ° C. After half an hour, 40 parts by weight of deionized water was quickly added under stirring for 30 seconds, and the polyurethane prepolymer was completed in 2 minutes at high temperature. Pre-dispersed, and after the temperature was lowered to 40 ° C, 180 parts by weight of deionized water was added, and after sufficiently dispersing for 5 minutes, 2 parts by weight of sodium 2-[(2-aminoethyl)amino]ethanesulfonate was used.
  • WPU-3 has similar performance compared to WPU-1 and WPU-2 in terms of appearance, particle size and stability test of aqueous polyurethane dispersion.
  • the WPU-1 aqueous polyurethane dispersion dried coating film has a combination of WPU-1 and WPU-2 in terms of elongation at break, tensile strength, 100% tensile strength, and bonding strength.
  • the aqueous polyurethane dispersion prepared by the aqueous polyurethane solvent-free preparation process based on the high-temperature dispersion technique and the dried coating film thereof have comparable properties to the similar products prepared by the conventional acetone method and the prepolymer dispersion method.
  • the aqueous polyurethane drying coating film obtained by the solvent-free preparation process of the aqueous polyurethane based on the high-temperature dispersion technology of the invention has excellent mechanical properties and bonding strength, and can satisfy the coating property thereof. And application requirements in the field of adhesives.
  • the water-based polyurethane solvent-free preparation process based on the high-temperature dispersion technology significantly shortens the preparation cycle of the water-based polyurethane, and has no solvent in the whole process, which greatly reduces resource consumption and energy waste, reduces the preparation cost, and has an alternative water-based property.
  • the superiority of traditional polyurethane preparation methods Compared with the traditional process, the water-based polyurethane solvent-free preparation process based on the high-temperature dispersion technology significantly shortens the preparation cycle of the water-based polyurethane, and has no solvent in the whole process, which greatly reduces resource consumption and energy waste, reduces the preparation cost, and has an alternative water-based property.
  • the superiority of traditional polyurethane preparation methods are widely used to prepare the preparation cycle of the water-based polyurethane, and has no solvent in the whole process, which greatly reduces resource consumption and energy waste, reduces the preparation cost, and has an alternative water-based property.

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Abstract

一种水性聚氨酯分散体及其无溶剂制备方法，属于水性聚氨酯制备技术领域。解决现有的水性聚氨酯制备工艺中使用有机溶剂的问题。该方法是将至少一种多羟基低聚物多元醇、至少一种多异氰酸酯和小分子亲水扩链剂反应，得到末端带有NCO基团的聚氨酯预聚物；然后将末端带有NCO基团的聚氨酯预聚物和小分子中和剂反应，在60-100℃下加入水，在搅拌下分散后将反应体系的温度降至20-50℃，然后再加入水，分散后得到预聚物分散液；最后将预聚物分散液和磺酸盐型多元胺亲水扩链剂反应，然后再和多元胺扩链剂反应，得到水性聚氨酯分散体。提供上述制备方法得到的水性聚氨酯分散体。该方法在制备过程中没有加入有机溶剂，具有环保性。

Description

[根据细则37.2由ISA制定的发明名称]　水性聚氨酯分散体及其无溶剂制备方法 技术领域
本发明属于水性聚氨酯制备技术领域，具体涉及一种水性聚氨酯分散体及其无溶剂制备方法。
背景技术
聚氨酯因其优异的性能被广泛用于涂料、胶黏剂、合成革、密封胶、弹性体等。而由于人类社会对环保问题的日益重视，愈加严厉的生态学及其他法律规定使得传统溶剂型聚氨酯的发展受到限制，也直接激发了水性聚氨酯的开发与应用，而涂料及粘接剂领域表现得尤为显著。
水性聚氨酯是指聚氨酯溶解或分散于水中而形成的聚氨酯树脂，其制备方法主要有传统的丙酮法及预聚体分散法。EP373671-A中描述了利用丙酮法制备水性聚氨酯，主要是将过量的多异氰酸酯与低聚物多元醇及带亲水基团的小分子多元醇反应，制备出异氰酸酯封端的聚氨酯预聚物，紧接着用小分子二元醇进行扩链反应，得到高分子量聚氨酯。过程中，大量丙酮、氮甲基吡咯烷酮、二甲基亚砜等有机溶剂被用来降低体系粘度。随后，中和剂及大量的水使聚氨酯溶液分散于水中，待减压蒸馏脱除有机溶剂后得到最终的无溶剂型水性聚氨酯。
在US4598121-A中描述了预聚体分散法制备水性聚氨酯的方法，主要是将过量的多异氰酸酯与低聚物多元醇及带亲水基团的小分子多元醇反应，制备出聚氨酯预聚物，其间加入适量有机溶剂降粘。随后将反应温度降低至30-40℃，并加入中和剂和大量水形成聚氨酯预聚物分散液，待分散完全后加入多元胺扩链剂与异氰酸酯基团发生扩链反应，最后脱除有机溶剂，得到最终的水性聚氨酯。
制备水性聚氨酯的工艺经过近七十年的发展已经趋于完善，然而其制备过程中难免使用有机溶剂降低粘度，且引入的有机溶剂通常需要加热减压蒸馏法脱除，虽然能够实现溶剂的回收，但因为回收的有机溶剂为复杂的混合物，使其再利用受到限制。显而易见，水性聚氨酯制备过程对有机溶剂的依赖性造成 了资源及能源的浪费，且制备得到的产品因难以保证完全无溶剂，限制了水性聚氨酯产品的工业生产及日常使用，成为制约其发展的技术瓶颈，至今仍未攻克。
既然有机溶剂的引入是用来降低在水性聚氨酯制备过程中反应体系较高的粘度，那么如果能够在不用有机溶剂的基础上实现反应体系粘度的控制，则能够实现水性聚氨酯的无溶剂制备。
发明内容
本发明的目的是为了解决现有的水性聚氨酯制备工艺中使用有机溶剂的问题，而提供一种水性聚氨酯分散体及其无溶剂制备方法。
本发明首先提供一种水性聚氨酯分散体的无溶剂制备方法，该方法包括：
步骤一：在惰性气体保护下，将至少一种多羟基低聚物多元醇、至少一种多异氰酸酯和小分子亲水扩链剂反应，得到末端带有NCO基团的聚氨酯预聚物；
步骤二：将步骤一得到的末端带有NCO基团的聚氨酯预聚物和小分子中和剂反应，然后在60-100℃下加入水，在搅拌下分散后将反应体系的温度降至20-50℃，然后再加入水，分散后得到预聚物分散液；
步骤三：将步骤二得到的预聚物分散液和磺酸盐型多元胺亲水扩链剂反应，然后再和多元胺扩链剂反应，得到水性聚氨酯分散体；
其中，所述的多羟基低聚物多元醇、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、磺酸盐型多元胺亲水扩链剂和多元胺扩链剂的重量份数比为(40-90)∶(8-40)∶(0-15)∶(0-15)∶(0-10)∶(0.5-8)。
根据本发明的水性聚氨酯分散体的无溶剂制备方法是在惰性气体的保护下进行的。所述惰性气体选自氮气或氩气。优选地，所述惰性气体为氮气。另外，优选地，在本发明的水性聚氨酯分散体的无溶剂制备方法中所采用的水为去离子水。
优选的是，所述步骤一的多羟基低聚物多元醇为聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚丙烯酸酯多元醇、聚烯烃多元醇、生物多元醇或二氧化碳基聚碳酸酯-醚多元醇。
优选的是，所述步骤一的多异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、1，6-己二异氰酸酯(HDI)、4，4’-二环己基甲烷二异氰酸酯(HMDI)、苯二甲基二异氰酸酯(XDI)、1，4-环己烷二异氰酸酯(CHDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)、三甲基-1，6-六亚甲基二异氰酸酯(TMHDI)、环己烷二亚甲基二异氰酸酯(HXDI)、降冰片烷二异氰酸酯(NB-DI)或甲基环己基二异氰酸酯(HTDI)。
优选的是，所述步骤一的小分子亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、二羟基半酯、N-甲基二乙醇胺、N-丁基二乙醇胺、2，2’-亚氨基二乙醇或三羟乙基胺。
优选的是，所述步骤二中第一次加入水时的反应温度为75-90℃。
优选的是，所述步骤二的小分子中和剂为三乙胺、氨水、氢氧化钠、盐酸、醋酸、CH3I、(CH3)2SO4，或环氧氯丙烷。
优选的是，所述步骤三的磺酸盐型多元胺亲水扩链剂为2-[(2-氨基乙基)氨基]乙磺酸钠盐、2，4-二氨基苯磺酸钠或3-(五聚(1-(氨丙氧基)丙基)氨基)丙基-1-磺酸钠。
优选的是，所述步骤三的多元胺扩链剂为乙二胺、1，3-丙二胺、1，4-丁二胺、1，6-己二胺、一缩二乙烯三胺、二缩三乙烯四胺或三缩四乙烯五胺。
优选的是，所述的多羟基低聚物多元醇、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、磺酸盐型多元胺亲水扩链剂和多元胺扩链剂的重量份数比为(66-80)∶(15-25)∶(3-4)∶(1.5-2)∶(1.5-2)∶(2-3)。
本发明还提供上述制备方法得到的水性聚氨酯分散体。
本发明的有益效果
本发明首先提供一种水性聚氨酯分散体，其制备方法是将水性聚氨酯预聚体在较高温度下直接分散于水中，由于较高的分散温度，该制备工艺克服了传统工艺在制备过程中因为较低温度(30-40℃)而带来的预聚体黏度较高的缺点，而较高粘度也被认为是水性聚氨酯无溶剂制备的技术瓶颈，实现了分散后异氰酸酯基团保留率维持在90％以上。相比于传统制备方法，该工艺中，80℃下聚氨酯预聚体的粘度从40℃的125,000mPa·s降低至5,000mPa·s，保证了聚氨酯预 聚物在低粘度下能够顺利且均匀地分散于水中，避免了传统工艺中因高粘度引入大量有机溶剂稀释的缺点，具有明显的环保特征，且因去除了降温步骤及溶剂回收工序，大大降低了生产能耗及制备周期。
本发明还提供上述制备方法得到的水性聚氨酯分散体，该方法制备得到的水性聚氨酯分散体和传统制备方法得到的同类产品的综合性能相当。实验结果表明：本发明的水性聚氨酯分散体制备得到的产品拉伸强度可高达65MPa，断裂伸长率可高达810％，粘接强度可高达61N。
附图说明
图1为本发明实施例1制备得到的水性聚氨酯分散体的核磁氢谱图；
图2为本发明实施例1制备得到的水性聚氨酯分散体的红外光谱图。
具体实施方式
本发明首先提供一种水性聚氨酯分散体的无溶剂制备方法，该方法包括：
步骤一：在惰性气体保护下，将至少一种多羟基低聚物多元醇、至少一种多异氰酸酯和小分子亲水扩链剂反应，得到末端带有NCO基团的聚氨酯预聚物；
步骤二：将步骤一得到的末端带有NCO基团的聚氨酯预聚物和小分子中和剂反应，然后在60-100℃下加入水，在搅拌下分散后将反应体系的温度降至20-50℃，然后再加入水，分散后得到预聚物分散液；
步骤三：将步骤二得到的预聚物分散液和磺酸盐型多元胺亲水扩链剂反应，然后再和多元胺扩链剂反应，得到水性聚氨酯分散体；
其中，所述的多羟基低聚物多元醇、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、磺酸盐型多元胺亲水扩链剂和多元胺扩链剂的重量份数(重量份)比为(40-90)∶(8-40)∶(0-15)∶(0-15)∶(0-10)∶(0.5-8)。
按照本发明，氮气保护下，将至少一种多羟基低聚物多元醇、至少一种多异氰酸酯和小分子扩链剂加入反应装置中反应，得到末端带有NCO基团的聚氨酯预聚物；所述反应的反应温度优选为60-100℃，更优选为65-90℃，最优选为75-90℃，反应时间优选为3-6.5小时，更优选为4-5小时。所述的至少一种多羟基低聚物多元醇、至少一种多异氰酸酯可按需要分步加入，小分子亲水扩链剂 可按需要预先与至少一种多异氰酸酯反应或在至少一种多羟基低聚物多元醇与至少一种多异氰酸酯反应后加入。
按照本发明，所述的多羟基低聚物多元醇优选为聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚丙烯酸酯多元醇、聚烯烃多元醇、生物多元醇或二氧化碳基聚碳酸酯-醚多元醇。
按照本发明，所述的聚醚多元醇优选为聚氧化丙烯多元醇、聚四氢呋喃多元醇、聚氧化乙烯多元醇、聚三亚甲基醚多元醇或以及其他芳香族聚醚多元醇。
按照本发明，所述的聚酯多元醇优选包含常见的脂肪族聚酯二元醇或芳香族聚酯多元醇，更优选为聚己内酯多元醇、聚己二酸丁二醇酯多元醇或聚己二酸己二醇酯多元醇；所述的脂肪族聚酯二元醇是由二元醇和二元羧酸缩聚而成，所述的二元醇优选为乙二醇、丙二醇、丁二醇、二乙二醇、三乙二醇、己二醇或新戊二醇，二元羧酸优选为己二酸；所述的芳香族聚酯多元醇是由芳香族二元羧酸或酸酐与二元醇反应得到的。所述的酸酐优选为邻苯二甲酸酐、对苯二甲酸或间苯二甲酸；所述的二元醇优选为乙二醇、丙二醇、丁二醇、二乙二醇、三乙二醇、己二醇或新戊二醇。
按照本发明，所述的聚碳酸酯多元醇优选由小分子二元醇与小分子碳酸酯发生酯交换反应得到的，更优选为聚碳酸-1，6-己二醇酯二醇或己内酯的聚碳酸酯多元醇；所述的小分子二元醇优选为己二醇、丁二醇、1，4-环己烷二甲醚、戊二醇或3-甲基戊二醇；所述的小分子碳酸酯优选为碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二苯酯、碳酸亚乙酯或碳酸亚丙酯。
按照本发明，所述的聚烯烃多元醇优选为端羟基聚丁二烯、端羟基氢化聚丁二烯、端羟基环氧化聚丁二烯、端羟基聚丁二烯-丙烯腈、聚苯乙烯多元醇或端羟基聚异戊二烯。
按照本发明，所述的生物多元醇优选为蓖麻油多元醇及其衍生物多元醇、大豆油多元醇或棕榈油多元醇。
按照本发明，所述的二氧化碳基聚碳酸酯-醚多元醇优选为根据公开号为CN102432857A、CN102617844A及CN105061746A所述方法制备得到的。由所 述的二氧化碳基聚碳酸酯-醚多元醇制备得到的聚氨酯产品表现出优异的耐水解、耐氧化性及较高的机械性能，具有显著的成本优势。
按照本发明，所述的多羟基低聚物多元醇的摩尔质量优选为300g/mol到8000g/mol，更优选为500g/mol至6000g/mol，最优选为1000g/mol至4000g/mol。
按照本发明，所述的多羟基低聚物多元醇表现出的官能度优选为2到6，更优选2到4，最优选2到3。
按照本发明，所述的多异氰酸酯为本领域技术人员熟知的多异氰酸酯，优选为低活性的多异氰酸酯，选自异佛尔酮二异氰酸酯(IPDI)、1，6-己二异氰酸酯(HDI)、4，4’-二环己基甲烷二异氰酸酯(HMDI)、苯二甲基二异氰酸酯(XDI)、1，4-环己烷二异氰酸酯(CHDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)、三甲基-1，6-六亚甲基二异氰酸酯(TMHDI)、环己烷二亚甲基二异氰酸酯(HXDI)、降冰片烷二异氰酸酯(NB-DI)或甲基环己基二异氰酸酯(HTDI)。
为了提高制品机械强度，也可以在制备过程中混合加入高活性芳香族二异氰酸酯，所述的高活性芳香族二异氰酸酯优选为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)及其液化产品(L-MDI)、萘二异氰酸酯(NDI)、对苯二异氰酸酯(PPDI)、二甲基联苯二异氰酸酯(TODI)或二甲基二苯基甲烷二异氰酸酯(DMMDI)。或者也可以加入官能度高于2的多异氰酸酯，所述的官能度高于2的多异氰酸酯优选为改性的HDI三聚体、TDI三聚体、TDI-TMP加成物、IPDI三聚体、壬烷三异氰酸酯或三苯基甲烷4，4’，4”-三异氰酸酯。所述的低活性的多异氰酸酯、高活性芳香族二异氰酸酯和官能度高于2的多异氰酸酯重量份数比为(8-40)∶(5-10)∶(3-10)。
按照本发明，所述的小分子亲水扩链剂为本领域技术人员熟知的小分子亲水扩链剂，优选为阳离子型小分子多元醇亲水扩链剂或阴离子型小分子亲水扩链剂；更优选为二羟甲基丙酸、二羟甲基丁酸、二羟基半酯、N-甲基二乙醇胺、N-丁基二乙醇胺、2，2’-亚氨基二乙醇或三羟乙基胺；最优选为二羟甲基丙酸或N-甲基二乙醇胺。所述的阳离子型小分子多元醇亲水扩链剂优选为N-甲基二乙醇胺、N-丁基二乙醇胺、2，2’-亚氨基二乙醇、三羟乙基胺或二乙烯三胺与环氧 氯丙烷的反应产物；所述的阴离子型小分子亲水扩链剂优选为二羟甲基丙酸或二羟甲基丁酸。
按照本发明，所述的将上述末端带有NCO基团的聚氨酯预聚物和小分子中和剂发生中和反应，然后在65-95℃下，优选在30秒内迅速加入少量去离子水，在搅拌下初步分散0.5-2分钟后将反应体系的温度降至20-50℃，然后再加入大量去离子水，分散3-5分钟后得到预聚物分散液；
按照本发明，所述的中和反应温度优选为60-100℃，更优选为75-90℃，反应时间优选为0.3-0.5小时，所述的小分子中和剂优选阳离子型小分子中和剂或阴离子型小分子中和剂，所述的阳离子型小分子中和剂优选为三乙胺、氨水或氢氧化钠；阴离子型小分子中和剂优选为盐酸、醋酸、CH3I、(CH3)2SO4或环氧氯丙烷等烷基化试剂。
按照本发明，所述的将上述末端带有NCO基团的聚氨酯预聚物在高温下直接分散于水中，所述的高温为60-100℃，更优选为65-95℃，最优选为75-90℃，当温度低于60℃以下时，反应体系会因为过低的温度而导致较高的粘度(＞100,000mPa·s)，直接带来分散不均甚至失败；当温度高于100℃以上时，会因为较高的分散温度而导致异氰酸酯基团的大量消耗(保留率＜80％)，使得产物综合性能低下；本发明将高温温度控制在60-100℃，实现了分散后异氰酸酯基团保留率维持在90％以上，保证了聚氨酯预聚物在低粘度下能够顺利且均匀地分散于水中，避免了传统工艺中因高粘度引入大量有机溶剂稀释的缺点。所述的去离子水是分两次加入，第一次加入少量，第二次加入多量，优选的是，所述的多异氰酸酯、第一次加入的去离子水和第二次加入的去离子水的重量份数比为(8-40)∶(30-70)∶(150-300)。
按照本发明，将上述得到的预聚物分散液和磺酸盐型多元胺亲水扩链剂反应，所述反应的反应温度优选为20-50℃，反应时间优选为0.2-1小时，更优选为0.5小时；然后再和多元胺扩链剂反应，所述反应的反应温度优选为20-40℃，反应时间优选为0.5-3小时，更优选为1-1.5小时；得到水性聚氨酯分散体。
按照本发明，所述的磺酸盐型多元胺亲水扩链剂为本领域技术人员熟知的产品，优选为2-[(2-氨基乙基)氨基]乙磺酸钠盐、2，4-二氨基苯磺酸钠或3-(五聚(1-(氨丙氧基)丙基)氨基)丙基-1-磺酸钠。
按照本发明，所述的多元胺扩链剂为本领域技术人员熟知的产品，优选乙二胺、1，3-丙二胺、1，4-丁二胺、1，6-己二胺、一缩二乙烯三胺、二缩三乙烯四胺或三缩四乙烯五胺，更优选为乙二胺、1，6-丁二胺或二缩三乙烯四胺，最优选乙二胺。
按照本发明，所述的羟基低聚物多元醇、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、磺酸盐型多元胺亲水扩链剂和多元胺扩链剂的重量份数比为(40-90)∶(8-40)∶(0-15)∶(0-15)∶(0-10)∶(0.5-8)，优选为(60-85)∶(12-30)∶(0-5)∶(0-3)∶(0-2.5)∶(1.5-4)，最优选为(66-80)∶(15-25)∶(3-4)∶(1.5-2)∶(1.5-2)∶(2-3)。
本发明还提供上述制备方法得到的水性聚氨酯分散体。
按照本发明，经上述工艺得到的水性聚氨酯分散体可以为非离子型水性聚氨酯分散体、半离子型水性聚氨酯分散体或者是离子型水性聚氨酯分散体；当水性聚氨酯分散体为非离子型水性聚氨酯分散体时，工艺中小分子亲水扩链剂、磺酸盐型多元胺亲水扩链剂和小分子中和剂用量均为0；当水性聚氨酯分散体为半离子型水性聚氨酯分散体时，工艺中小分子亲水扩链剂和小分子中和剂用量均为0，或者工艺中磺酸盐型多元胺亲水扩链剂用量为0；当水性聚氨酯分散体为离子型水性聚氨酯分散体时，工艺中小分子亲水扩链剂、磺酸盐型多元胺亲水扩链剂和小分子中和剂均有使用。相应地，当制备步骤中涉及到的物料使用量为零时，对应的制备步骤省去。
按照本发明，所述的水性聚氨酯分散体为非离子型水性聚氨酯分散体和半离子型水性聚氨酯分散体时，步骤一中的多羟基低聚物多元醇必须具有亲水性，优选为聚氧化乙烯多元醇，所述的亲水性的多羟基低聚物多元醇可以单独使用，也可以与其他类型多元醇复合使用，具体的用量根据最终产品的需要设计。
按照本发明，所述的水性聚氨酯分散体为离子型水性聚氨酯分散体时，所述的多羟基低聚物多元醇可以具有亲水性，也可以是疏水性的其他类型多元醇，具体的用量根据实际需要选用。
按照本发明，在上述制备得到的水性聚氨酯分散体中加入助剂或添加剂，得到水性聚氨酯产品，所述的助剂和添加剂没有特殊限制，为本领域技术人员熟知的助剂或添加剂即可，根据得到的水性聚氨酯的产品而定。
下面结合具体实施例对本发明做进一步详细的说明，实施例中所用材料皆为聚氨酯领域熟知的原材料，均可商购。
对比例1按照传统的丙酮法制备出了水性聚氨酯分散体
将66重量份的聚己二酸丁二醇酯二元醇(2000g/mol)、3重量份的二羟甲基丙酸加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在80℃的氮气氛围下搅拌至混合均匀后，加入25重量份的异佛尔酮二异氰酸酯，反应4小时后得到末端带有NCO基团的聚氨酯预聚物。随后将4.5重量份的乙二醇加入到反应体系进行扩链反应，并加入0.1重量份的二月桂酸二丁二基锡催化剂以保证反应速度及转化率，期间加入50重量份的丁酮以防止反应体系过高的粘度。6小时后，将反应温度降低至50℃，并加入2.5重量份的2，4-二氨基苯磺酸钠，经1小时反应后，将反应温度降低至30℃，并加入1.5重量份的中和剂三乙胺，经0.5小时中和反应后，在搅拌下向反应体系加入200重量份的去离子水，经1小时充分分散后，将产物移至减压蒸馏装置，经0.5小时后得到固含量为35％、PH值为6.5、粘度为550mPa·s的水性聚氨酯分散体，记为WPU-1。WPU-1性能测试结果如表1和2所示。
对比例2按照传统的预聚体分散法制备出了水性聚氨酯分散体
将66重量份的聚己二酸丁二醇酯二元醇(2000g/mol)、3重量份的二羟甲基丙酸加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在80℃的氮气氛围下搅拌至混合均匀后，加入25重量份的异佛尔酮二异氰酸酯，反应4小时后得到末端带有NCO基团的聚氨酯预聚物。期间，加入30重量份的丁酮降低反应物粘度。撤除加热装置，待反应体系温度降低至30℃后加入1.5重量份的三乙胺发生中和反应，半小时后在搅拌下加入200重量份的去离子水，得 到聚氨酯预聚物分散液。0.5小时后，聚氨酯预聚物分散均匀，将2.5重量份的2，4-二氨基苯磺酸钠用5重量份的去离子水溶解后加入到反应装置，经0.5小时反应后，向体系中加入3重量份的乙二胺，经1小时扩链反应后，将产物移至减压蒸馏装置，经0.5小时后得到固含量为36％、PH值为6.4、粘度为620mPa·s的水性聚氨酯分散体，记为WPU-2。WPU-2性能测试结果如表1和2所示。
实施例1
将66重量份的聚己二酸丁二醇酯二元醇(2000g/mol)、3重量份的二羟甲基丙酸加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在80℃的氮气氛围下搅拌至混合均匀后，加入25重量份的异佛尔酮二异氰酸酯，反应4小时后得到末端带有NCO基团的聚氨酯预聚物。期间，无需丁酮等有机溶剂降低反应物粘度。在80℃下加入1.5重量份的三乙胺发生中和反应，半小时后在搅拌下于30秒内迅速加入50重量份的去离子水，使聚氨酯预聚物在高温下于1分钟内完成预分散，并将温度降低至25℃后加入150重量份的去离子水，经5分钟充分分散后，将2.5重量份的2，4-二氨基苯磺酸钠用5重量份的去离子水溶解后加入到反应装置，在25℃下经0.5小时反应后，向体系中加入2重量份的乙二胺，在室温下经1小时扩链反应后得到固含量为33％、PH值为6.8、粘度为520mPa·s的水性聚氨酯分散体，记为WPU-3。WPU-3性能测试结果如表1和2所示。
图1为本发明实施例1制备得到的水性聚氨酯分散体的核磁氢谱图；图2为本发明实施例1制备得到的水性聚氨酯分散体的红外光谱图。从图1和图2可以看出，本发明成功制备得到了水性聚氨酯分散体。
本发明实施例1制备的过程相比对比例2中的预聚体分散法，无需任何有机溶剂，且省去了预聚物的降温及产品中有机溶剂的减压脱除工序，大大降低了生产成本，缩短了生产周期。
实施例2
将60重量份的二氧化碳基聚碳酸酯-醚二元醇(2000g/mol)、5重量份的二羟甲基丁酸加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在85℃的氮气氛围下搅拌至混合均匀后，加入29重量份的4，4’-二环己基甲烷二异 氰酸酯，反应4小时后得到末端带有NCO基团的聚氨酯预聚物。在80℃下加入1.5重量份的三乙胺发生中和反应，半小时后在搅拌下于30秒内迅速加入50重量份的去离子水，使聚氨酯预聚物在高温下于2分钟内完成预分散，并将温度降低至20℃后加入150重量份的去离子水，经4分钟充分分散后，将1.5重量份的3-(五聚(1-(氨丙氧基)丙基)氨基)丙基-1-磺酸钠用10重量份的去离子水溶解后加入到反应装置，在20℃下经0.5小时反应后，向体系中加入4重量份的己二胺，在室温下经1小时扩链反应后得到固含量为32％、PH值为6.7、粘度为430mPa·s的水性聚氨酯分散体，记为WPU-4。WPU-4性能测试结果如表1和2所示。
实施例3
将20重量份的聚环氧丙烷二元醇(1000g/mol)、40重量份的聚碳酸亚己酯二元醇(2000g/mol)、4重量份的N-甲基二乙醇胺加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在65℃的氮气氛围下搅拌至混合均匀后，加入30重量份的异佛尔酮二异氰酸酯，反应5小时后得到末端带有NCO基团的聚氨酯预聚物。在65℃下于30秒内加入50重量份的、溶有6重量份盐酸(30％)的去离子水，使聚氨酯预聚物在高温下于2分钟内完成预分散，并将温度降低至30℃后加入130重量份的去离子水，经5分钟充分分散后，向体系中加入3重量份的1，4-丁二胺，在室温下经1小时扩链反应后得到固含量为36％、PH值为6.6、粘度为780mPa·s的水性聚氨酯分散体，记为WPU-5。WPU-5性能测试结果如表1和2所示。
实施例4
将30重量份的聚环氧乙烷二元醇(2000g/mol)、48重量份的二氧化碳基聚碳酸酯-醚三元醇(3000g/mol)加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在75℃的氮气氛围下搅拌至混合均匀后，加入10重量份的异佛尔酮二异氰酸酯及8重量份的1，6-己基二异氰酸酯，反应5小时后得到末端带有NCO基团的聚氨酯预聚物，加入2重量份的二羟甲基丙酸继续反应3小时后，在75℃下于30秒内迅速加入50重量份的、溶有0.6重量份氢氧化钠的去离子水，使聚氨酯预聚物在高温下于1分钟内完成预分散，并将温度降低至35℃后 加入140重量份的去离子水，经5分钟充分分散后，向体系中加入3重量份的1，3-丙二胺，在室温下经1小时扩链反应后固含量为34％、PH值为6.8、粘度为450mPa·s的水性聚氨酯分散体，记为WPU-6。WPU-6性能测试结果如表1和2所示。
实施例5
将4重量份的二羟甲基丙酸加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在90℃的氮气氛围下搅拌，加入20重量份的4，4’-二环己基甲烷二异氰酸酯及7重量份的异佛尔酮二异氰酸酯三聚体，反应2小时后分三等分加入60重量份的聚己内酯二元醇(3000g/mol)，经3小时后得到末端带有NCO基团的聚氨酯预聚物。在90℃下加入3重量份的三乙胺发生中和反应，半小时后在搅拌下于30秒内迅速加入40重量份的去离子水，使聚氨酯预聚物在高温下于2分钟内完成预分散，并将温度降低至40℃后加入180重量份的去离子水，经5分钟充分分散后，将2重量份的2-[(2-氨基乙基)氨基]乙磺酸钠盐用10重量份的去离子水溶解后加入到反应装置，在40℃下经0.5小时反应后，向体系中加入3重量份的三缩四乙烯五胺，在室温下经1小时扩链反应后固含量为31％、PH值为6.5、粘度为210mPa·s的水性聚氨酯分散体，记为WPU-7。WPU-7性能测试结果如表1和2所示。
实施例6
将40重量份的聚环氧乙烷二元醇(2000g/mol)、40重量份的聚四氢呋喃二元醇(3000g/mol)加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在70℃的氮气氛围下搅拌至混合均匀后，加入5重量份的2，4-甲苯二异氰酸酯，待反应2小时后加入10重量份的异氟尔酮二异氰酸酯，反应4.5小时后得到末端带有NCO基团的聚氨酯预聚物。在70℃于搅拌下于30秒内迅速加入30重量份的去离子水，使聚氨酯预聚物在0.5分钟内完成预分散，并将温度降低至室温后加入120重量份的去离子水，经4分钟充分分散后，将1.5重量份的2-[(2-氨基乙基)氨基]乙磺酸钠盐用8重量份的去离子水溶解后加入到反应装置，在室温下经0.5小时反应后，向体系中加入3重量份的三乙烯四胺，在室温下经 1.5小时扩链反应后得到固含量为39％、PH值为6.7、粘度为690mPa·s的水性聚氨酯分散体，记为WPU-8。WPU-8性能测试结果如表1和2所示。
实施例7
将20重量份的聚环氧乙烷二元醇(1500g/mol)、65重量份的聚四氢呋喃二元醇(4000g/mol)加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在95℃的氮气氛围下搅拌至混合均匀后，加入12重量份的异氟尔酮二异氰酸酯，反应3小时后得到末端带有NCO基团的聚氨酯预聚物。在70℃搅拌下于30秒内迅速加入40重量份的去离子水，使聚氨酯预聚物在0.5分钟内完成预分散，并将温度降低至50℃后加入130重量份的去离子水，经3分钟充分分散后，将1.5重量份的2-[(2-氨基乙基)氨基]乙磺酸钠盐用10重量份的去离子水溶解后加入到反应装置，在50℃下经0.5小时反应后，向体系中加入1.5重量份的乙二胺，在室温下经1.5小时扩链反应后得到固含量为40％、PH值为6.9、粘度为750mPa·s的水性聚氨酯分散体，记为WPU-9。WPU-9性能测试结果如表1和2所示。
实施例8
将20重量份的聚环氧乙烷二元醇(1000g/mol)、60重量份的聚碳酸亚己酯二元醇(4000g/mol)加入到带有氮气接口、搅拌器、冷凝管、加热装置的三口瓶中，在65℃的氮气氛围下搅拌至混合均匀后，加入3.5重量份的4，4’-二苯基甲烷二异氰酸酯反应1小时后加入15重量份的四甲基间苯二亚甲基二异氰酸酯，反应5小时后得到末端带有NCO基团的聚氨酯预聚物。在65℃搅拌下于30秒内迅速加入30重量份的去离子水，使聚氨酯预聚物在0.5分钟内完成预分散，并将温度降低至20℃后加入90重量份的去离子水，经3分钟充分分散后，向体系中加入1.5重量份的乙二胺，经1小时扩链反应后得到固含量为45％、PH值为6.7、粘度为950mPa·s的水性聚氨酯分散体，记为WPU-10。WPU-10性能测试结果如表1和2所示。
表1水性聚氨酯分散体的性能分析结果
Figure PCTCN2017091064-appb-000001
表2水性聚氨酯分散体干燥涂膜的性能测试结果
Figure PCTCN2017091064-appb-000002
由水性聚氨酯分散体性能测试结果及其干燥涂膜性能测试结果可知，在水性聚氨酯分散体外观、粒径、稳定性测试方面，WPU-3相比于WPU-1及WPU-2具有相似的性能结果，且WPU-1水性聚氨酯分散体干燥涂膜在断裂伸长率、拉伸强度、100％拉伸强度、粘接强度方面具有不逊色于WPU-1及WPU-2的综合性能。因此，本发明基于高温分散技术的水性聚氨酯无溶剂制备工艺所制备得到的水性聚氨酯分散体及其干燥涂膜具有与传统的丙酮法及预聚体分散法制备得到的类似产品具有相当的性能。由WPU-3至WPU-10的性能测试结果可知，本发明的基于高温分散技术的水性聚氨酯无溶剂制备工艺得到的水性聚氨酯干燥涂膜具有优异的机械性能及粘接强度，能够满足其在涂料及粘接剂领域的应用要求。相比于传统工艺，基于高温分散技术的水性聚氨酯无溶剂制备工艺显著缩短了水性聚氨酯的制备周期，且因全过程无溶剂，大大降低了资源消耗及能源浪费，缩减了制备成本，具有替代水性聚氨酯传统制备方法的优越性。
以上所述仅是本发明的优选实施方案，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种水性聚氨酯分散体的无溶剂制备方法，该方法包括：
    步骤一：在惰性气体保护下，将至少一种多羟基低聚物多元醇、至少一种多异氰酸酯和小分子亲水扩链剂反应，得到末端带有NCO基团的聚氨酯预聚物；
    步骤二：将步骤一得到的末端带有NCO基团的聚氨酯预聚物和小分子中和剂反应，然后在60-100℃下加入水，在搅拌下分散后将反应体系的温度降至20-50℃，然后再加入水，分散后得到预聚物分散液；
    步骤三：将步骤二得到的预聚物分散液和磺酸盐型多元胺亲水扩链剂反应，然后再和多元胺扩链剂反应，得到水性聚氨酯分散体；
    其中，所述的多羟基低聚物多元醇、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、磺酸盐型多元胺亲水扩链剂和多元胺扩链剂的重量份数比为(40-90)∶(8-40)∶(0-15)∶(0-15)∶(0-10)∶(0.5-8)。
  2. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述步骤一的多羟基低聚物多元醇为聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚丙烯酸酯多元醇、聚烯烃多元醇、生物多元醇或二氧化碳基聚碳酸酯-醚多元醇。
  3. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述步骤一的多异氰酸酯为异佛尔酮二异氰酸酯、1，6-己二异氰酸酯、4，4’-二环己基甲烷二异氰酸酯、苯二甲基二异氰酸酯、1，4-环己烷二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯、三甲基-1，6-六亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯、降冰片烷二异氰酸酯或甲基环己基二异氰酸酯。
  4. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述步骤一的小分子亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、二羟基半酯、N-甲基二乙醇胺、N-丁基二乙醇胺、2，2’-亚氨基二乙醇或三羟乙基胺。
  5. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述步骤二中第一次加入水时的反应温度为75-90℃。
  6. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述 步骤二的小分子中和剂为三乙胺、氨水、氢氧化钠、盐酸、醋酸、CH3I、(CH3)2SO4，或环氧氯丙烷。
  7. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述步骤三的磺酸盐型多元胺亲水扩链剂为2-[(2-氨基乙基)氨基]乙磺酸钠盐、2，4-二氨基苯磺酸钠或3-(五聚(1-(氨丙氧基)丙基)氨基)丙基-1-磺酸钠。
  8. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述步骤三的多元胺扩链剂为乙二胺、1，3-丙二胺、1，4-丁二胺、1，6-己二胺、一缩二乙烯三胺、二缩三乙烯四胺或三缩四乙烯五胺。
  9. 根据权利要求1所述的水性聚氨酯分散体的无溶剂制备方法，其中所述的多羟基低聚物多元醇、多异氰酸酯、小分子亲水扩链剂、小分子中和剂、磺酸盐型多元胺亲水扩链剂和多元胺扩链剂的重量份数比为(66-80)∶(15-25)∶(3-4)∶(1.5-2)∶(1.5-2)∶(2-3)。
  10. 权利要求1-9任何一项所述的制备方法得到的水性聚氨酯分散体。
PCT/CN2017/091064 2017-04-07 2017-06-30 水性聚氨酯分散体及其无溶剂制备方法 WO2018184307A1 (zh)

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