CN102585154A - Method for preparing waterborne polyurethane - Google Patents
Method for preparing waterborne polyurethane Download PDFInfo
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- CN102585154A CN102585154A CN2012100656685A CN201210065668A CN102585154A CN 102585154 A CN102585154 A CN 102585154A CN 2012100656685 A CN2012100656685 A CN 2012100656685A CN 201210065668 A CN201210065668 A CN 201210065668A CN 102585154 A CN102585154 A CN 102585154A
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000004814 polyurethane Substances 0.000 title claims abstract description 31
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 31
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 4
- 239000012948 isocyanate Substances 0.000 claims abstract description 3
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- -1 hydroxy carboxylic acid compound Chemical class 0.000 claims description 22
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011343 solid material Substances 0.000 claims description 15
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 13
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 150000001261 hydroxy acids Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical group CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 235000009508 confectionery Nutrition 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 9
- 238000009413 insulation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for preparing waterborne polyurethane. The method comprises the following steps: reacting polydiol with isocyanate; adding a hydrophilic chain extender for chain extension so as to produce a -NCO terminal group prepolymer; neutralizing by a neutralizing agent; adding one or mixture of two of small molecular diol and oligomer polyalcohol; uniformly stirring; adding a de-ionized water solution for high-speed dispersion immediately; finally heating to obtain a stable waterborne polyurethane emulsion. Compared with the prior art, the stable waterborne polyurethane emulsion can be prepared without the addition of external emulsifiers and additive stabilizers or few additive stabilizers, the prepolymer is easily dispersed in a preparation process, and a solvent-free waterborne polyurethane emulsion with high solid content of 45-60% can be prepared without any organic solvent.
Description
Technical field
The present invention relates to a kind of environment-friendly type macromolecule preparation methods, especially relate to a kind of method for preparing aqueous polyurethane.
Background technology
Aqueous polyurethane is meant with water to be the polyurethane dispersions system of dispersion medium.After countries in the world promulgations environmental protection bill, aqueous polyurethane is nontoxic with it, green, and characteristics such as solvent-free become the focus of polyurethane field research.In preparation aqueous polyurethane process, because the macromole of urethane is normally hydrophobic, when being dispersed into emulsion, emulsifying agent is necessary.So the Synthesis of Waterborne Polyurethane method generally is divided into and is outer emulsification and self-emulsification.Wherein, outer emulsion process is through the method that adds emulsifying agent urethane to be dispersed in the water, and this method because the polyaminoester emulsion size of particles is bigger, causes stability of emulsion poor usually.And remaining outer emulsifying agent has certain influence to the finished product performance.Therefore, Synthesis of Waterborne Polyurethane adopts the self-emulsifying dispersion method more at present, promptly on polymer chain, introduces an amount of hydrophilic radical, and spontaneous under certain condition dispersion forms emulsion.Different according to chain extending reaction, self-emulsification can be divided into: acetone method, fusion dispersion method, prepolymer method and ketimine process etc.Along with industrial expansion; Performance to aqueous polyurethane has had higher requirement; Intensity particularly, the requirement of mechanical properties such as toughness adopts present self-emulsifying dispersion method to be difficult to the hydrophilic performed polymer of high-molecular weight urethane directly is dispersed in the water with preparation stabilized aqueous polyaminoester emulsion.
In recent years, occurred the novel method-fine emulsion polymerization of synthetic water based polyurethane in succession, the polymerization of water sensitivity monomeric diisocyanate become domestic and international research focus because of the polymerization mechanism of its droplet nucleation is applicable to.But existing technology generally adopts the method that adds emulsifying agent to prepare stable miniemulsion, and final product comprises outer emulsifier component, thereby must the performance of product be had a negative impact.The present invention will combine traditional self-emulsifying dispersion method and miniemulsion method, propose innovative approach-self-emulsifying miniemulsion method, be about to reaction and carry out in two steps; Synthetic earlier the wetting ability performed polymer of the first step with certain emulsifying capacity; Second step added low molecular weight polyols and stirs back emulsification dispersion, formed stable miniemulsion, continued reaction and improved molecular weight; The part chain extending reaction is carried out in miniemulsion, thereby prepare the stabilized aqueous polyaminoester emulsion.
Summary of the invention
The object of the invention is exactly the preparation method that a kind of aqueous polyurethane emulsion is provided in order to overcome the defective that above-mentioned prior art exists, this method can be not adding outside emulsifying agent, do not add or add less under the condition of co-stabilizer and prepare the stabilized aqueous polyaminoester emulsion.Disperse difficult problem in the self-emulsifying dispersion method thereby solved, the negative impact of having avoided the outer emulsifying agent in the fine emulsion polymerization to produce simultaneously.
The object of the invention can be realized through following technical scheme:
A kind of method for preparing aqueous polyurethane may further comprise the steps:
A, in the presence of no any solvent, with polyvalent alcohol, hydrophilic chain extender and isocyanate reaction, the performed polymer of generation-NCO end group;
One or both mixtures in b, interpolation small molecules polyvalent alcohol, the oligomer polyol, the while does not add or adds the strong-hydrophobicity co-stabilizer on a small quantity and carry out prepolymerization reaction;
C, treat to use high speed dispersion under the deionized water low temperature immediately after the b step stirs;
D, reduction stirring velocity, elevated temperature adds catalyzer constant temperature and carries out the back chain extending reaction, obtains stabilized aqueous polyaminoester emulsion.
This method comprises a neutralization procedure, and this neutralization procedure can add neutralizing agent in the prepolymerization reaction later stage, can accomplish the back at prepolymerization reaction and add neutralizing agent before being scattered in the water, also can with neutralizing agent add disperse in the entry or with after chain extending reaction carry out simultaneously.
This method specifically may further comprise the steps:
(1) polyvalent alcohol is warming up to 100～120 ℃, vacuum hydro-extraction 45～90min, the cooling back adds isocyanic ester; 0.01～0.04% the dibutyl tin laurate that dropping accounts for polyvalent alcohol weight carries out prepolymerization reaction 1.5～2.5h at 75～85 ℃, adds hydrophilic chain extender; At 70～80 ℃ of reaction 2.5～3.5h; Generation-NCO end group performed polymer, the mole ratio of hydrophilic chain extender and polyvalent alcohol are 0.5～1.2: 1 ,-NCO :-OH=2～4: 1; Wherein-and NCO representes the NCO mole number ,-OH representes polyvalent alcohol hydroxyl mole number;
(2) add small molecules polyvalent alcohol, oligomer polyol or its blend in the performed polymer that step (1) obtains; Addition and remnants-NCO mol ratio is 0.3～1: 1; Add the strong-hydrophobicity co-stabilizer according to 0～12% mass ratio that accounts for the performed polymer total amount simultaneously and stir fast, carry out the prepolymerization reaction;
(3) in the solid materials that step (2) prepolymerization reaction obtains, add deionized water, the mass ratio of deionized water and solid materials is 1～2: 1, and controlled temperature is that 0～20 ℃ of high speed dispersion becomes emulsion;
(4) elevated temperature to 40～60 ℃, 0.03～0.08% the mass ratio of pressing the solid materials amount adds catalyzer, and constant temperature 2.5～4h carries out the back chain extending reaction, obtains the stabilized aqueous polyaminoester emulsion.
This method comprises a neutralization procedure; With the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in alkali metal hydroxide or the tertiary amine 90%～100% or the hydroxy-acid group of performed polymer; Above-mentioned neutralization procedure can carry out in the prepolymerization reaction later stage simultaneously; Carry out before also can after prepolymerization reaction is accomplished, being scattered in the deionized water, also can neutralizing agent be added in the deionized water or with the back chain extending reaction and carry out simultaneously.
Described polyvalent alcohol comprises polyhutadiene, polyoxytrimethylene ether glycol of hexanodioic acid pinakon ester, poly adipate succinic acid ester, PTMG, terminal hydroxy group etc.
Described isocyanic ester is one or both the mixture in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate, and the preferred vulcabond of the present invention is an isophorone diisocyanate.
Described hydrophilic chain extender is one or both a mixture of dimethylol propionic acid, dimethylolpropionic acid or dihydroxymethyl half ester, and the preferred hydrophilic chain extender of the present invention is a dimethylolpropionic acid.
Described small molecules polyvalent alcohol, oligomer polyol are 1; 4-butyleneglycol, 1; 4-cyclohexanedimethanol, 1,6-pinakon, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, 1; The arbitrary proportion mixture of one or several in 12-dodecyl glycol, Viscotrol C, PTMG, polycaprolactone glycol, poly adipate succinic acid ester glycol, the polybutadiene diol, the preferred small molecules polyvalent alcohol of the present invention are that molecular weight is 650 PTMG.
Described strong-hydrophobicity co-stabilizer is n-Hexadecane, sweet oil or whiteruss.
Described catalyzer is dibutyl tin laurate, stannous octoate, organic zirconium, organo-bismuth etc.
Compared with prior art, the present invention has the following advantages:
(1) the present invention can be outside not adding emulsifying agent and do not add or add less preparation stabilized aqueous polyaminoester emulsion under the condition of co-stabilizer;
(2) performed polymer disperses easily among the preparation technology of the present invention, can in the presence of no any organic solvent, prepare the solvent-free aqueous polyurethane emulsion of high solids content of solid content 45～60%.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
Add 150g to four-hole boiling flask and gather hexanodioic acid pinakon ester (molecular weight is 2000), behind the heating and melting, 110 ℃ vacuumize 1h, cool to 85 ℃ afterwards; Add 48.3gIPDI and 1 dibutyl tin laurate reaction 2h, cool to 80 ℃ afterwards, add the 8g dimethylolpropionic acid, insulation reaction 2.5h; Cool to 70 ℃ afterwards, add 8g1, the 4-butyleneglycol; Stir the 140g deionized water solution that adding immediately in 1 minute is dissolved with the 5.5g triethylamine, high speed dispersion (rotating speed 2500rpm) 7min is warmed up to 60 ℃ afterwards rapidly; Drip 20 dibutyl tin laurates, stirring at low speed (300rpm) reaction 4h promptly obtains a stabilized aqueous polyaminoester emulsion.
This product is a milky white liquid, and its solid content is 59.3%, and viscosity is 370cp.
Embodiment 2
Add 150g poly adipate succinic acid ester (molecular weight is 2000) to four-hole boiling flask, behind the heating and melting, 110 ℃ vacuumize 1h; Cool to 85 ℃ afterwards, add 48.3gIPDI and 1 dibutyl tin laurate reaction 2h, cool to 80 ℃ afterwards; Add the 7.5g dimethylolpropionic acid, insulation reaction 3h cools to 70 ℃ afterwards; Add 24.4g PTMG (molecular weight is 650) and 3.6g1,4-butyleneglycol liquid form mixt stirs the 146g deionized water solution that adding immediately in 1 minute is dissolved with the 5.1g triethylamine; High speed dispersion (rotating speed 2500rpm) 10min is warmed up to 60 ℃ afterwards rapidly, drips 20 dibutyl tin laurates; Middling speed stirs (1250rpm) reaction 4h, promptly obtains a stabilized aqueous polyaminoester emulsion.
This product is a milky white liquid, and its solid content is 60.2%, and viscosity is 152cp.
Embodiment 3
Add 74.9g to four-hole boiling flask and gather hexanodioic acid pinakon ester (molecular weight is 2000), 24.4g PTMG (molecular weight is 650) mixture, behind the heating and melting, 110 ℃ vacuumize 1h; Cool to 85 ℃ afterwards, add 51.6gIPDI and 1 dibutyl tin laurate reaction 2h, cool to 80 ℃ afterwards; Add the 7.6g dimethylolpropionic acid, 0.9g1,4-butyleneglycol insulation reaction 1.5h; Cool to 70 ℃ afterwards, add 5.2g triethylamine insulation reaction 0.5h, add 24.4g PTMG (molecular weight is 650) and 3.6g Viscotrol C liquid form mixt; Stir and added the 188g deionized water solution in 1 minute immediately, high speed dispersion (rotating speed 2500rpm) 10min is warmed up to 60 ℃ afterwards rapidly; Drip 4 dibutyl tin laurates, middling speed stirs (1250rpm) reaction 4h, promptly obtains a stabilized aqueous polyaminoester emulsion.
This product is a milky white liquid, and its solid content is 50%, and viscosity is 453cp.
Embodiment 4
Add 150g to four-hole boiling flask and gather hexanodioic acid pinakon ester (molecular weight is 2000), behind the heating and melting, 110 ℃ vacuumize 1h; Cool to 85 ℃ afterwards, add 48.3gIPDI and 1 dibutyl tin laurate reaction 2h, cool to 80 ℃ afterwards; Add the 8g dimethylolpropionic acid, insulation reaction 2.5h cools to 70 ℃ afterwards; Add 24.4g PTMG (molecular weight is 650) and 5g heavy liquid paraffin liquid form mixt, stir the 193g deionized water solution that adding immediately in 1 minute is dissolved with the 5.5g triethylamine, high speed dispersion (rotating speed 2500rpm) 10min; Reduction of speed stirring velocity (600rpm) is warmed up to 50 ℃ rapidly, drips 20 dibutyl tin laurates; Reaction 4h promptly obtains a stabilized aqueous polyaminoester emulsion.
This product is a milky white liquid, and its solid content is 55%, and viscosity is 460cp.
Embodiment 5
Add 74.9g to four-hole boiling flask and gather hexanodioic acid pinakon ester (molecular weight is 2000), 24.4g PTMG (molecular weight is 650) mixture is behind the heating and melting; 110 ℃ vacuumize 1h, cool to 85 ℃ afterwards, add 51.6gIPDI and 1 dibutyl tin laurate reaction 1.5h; Cool to 80 ℃ afterwards, add the 7.6g dimethylolpropionic acid, 0.9g1; 4-butyleneglycol insulation reaction 1.5h cools to 70 ℃ afterwards, adds 5.2g triethylamine insulation reaction 0.5h; Add 24.4g PTMG (molecular weight is 650) and 3.6g heavy liquid paraffin liquid form mixt, stir and added the 229g deionized water solution in 1 minute immediately, high speed dispersion (rotating speed 2500rpm) 10min; Reduction of speed stirring velocity (600rpm) is warmed up to 50 ℃ rapidly, drips 20 dibutyl tin laurates; Reaction 4h promptly obtains a stabilized aqueous polyaminoester emulsion.
This product is an oyster white blueing light liquid, and its solid content is 45%, and viscosity is 380cp.
Embodiment 6
A kind of method for preparing aqueous polyurethane may further comprise the steps:
(1) hexanodioic acid pinakon ester is warming up to 100 ℃, vacuum hydro-extraction 90min, the cooling back adds diphenylmethanediisocyanate; 0.01% the dibutyl tin laurate that dropping accounts for hexanodioic acid pinakon ester weight carries out prepolymerization reaction 2.5h at 75 ℃, adds the hydrophilic chain extender dimethylol propionic acid; At 70 ℃ of reaction 3.5h; Generation-NCO end group performed polymer, the mole ratio of hydrophilic chain extender dimethylol propionic acid and hexanodioic acid pinakon ester is 0.5: 1 ,-NCO :-OH=2: 1; Wherein-and NCO representes the NCO mole number ,-OH representes polyvalent alcohol hydroxyl mole number;
(2) add 1, the 4-butyleneglycol is in the performed polymer that step (1) obtains, and addition and remnants-NCO mol ratio is 0.3: 1, carries out the prepolymerization reaction;
(3) in the solid materials that step (2) prepolymerization reaction obtains, add deionized water, the mass ratio of deionized water and solid materials is 1: 1, and controlled temperature is that 0 ℃ of high speed dispersion becomes emulsion;
(4) elevated temperature to 40 ℃, 0.03% the mass ratio of pressing the solid materials amount adds the catalyzer dibutyl tin laurate, and constant temperature 2.5h carries out the back chain extending reaction, obtains the stabilized aqueous polyaminoester emulsion.
In addition, this method also comprises a neutralization procedure, and with the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in the alkali metal hydroxide 90% or the hydroxy-acid group of performed polymer, above-mentioned neutralization procedure carried out in the prepolymerization reaction later stage.
Embodiment 7
A kind of method for preparing aqueous polyurethane may further comprise the steps:
(1) poly adipate succinic acid ester is warming up to 110 ℃, vacuum hydro-extraction 60min, the cooling back adds the mixture of tolylene diisocyanate and isophorone diisocyanate; 0.02% the dibutyl tin laurate that dropping accounts for poly adipate succinic acid ester weight carries out prepolymerization reaction 2h at 80 ℃, adds the mixture of hydrophilic chain extender dimethylolpropionic acid and dihydroxymethyl half ester; At 75 ℃ of reaction 3h; Generation-NCO end group performed polymer, the mole ratio of hydrophilic chain extender and poly adipate succinic acid ester are 1: 1 ,-NCO :-OH=3: 1; Wherein-and NCO representes the NCO mole number ,-OH representes polyvalent alcohol hydroxyl mole number;
(2) adding molecular weight is that 650 PTMG is in the performed polymer that step (1) obtains; Addition and remnants-NCO mol ratio is 0.5: 1; Add strong-hydrophobicity co-stabilizer sweet oil according to 5% mass ratio that accounts for the performed polymer total amount simultaneously, stir fast, carry out the prepolymerization reaction;
(3) in the solid materials that step (2) prepolymerization reaction obtains, add deionized water, the mass ratio of deionized water and solid materials is 1.5: 1, and controlled temperature is that 10 ℃ of high speed dispersion become emulsion;
(4) elevated temperature to 50 ℃, 0.05% the mass ratio of pressing the solid materials amount adds the catalyzer organic zirconium, and constant temperature 3h carries out the back chain extending reaction, obtains the stabilized aqueous polyaminoester emulsion.
This method also comprises a neutralization procedure, and with the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in alkali metal hydroxide or 100% or the hydroxy-acid group of performed polymer, above-mentioned neutralization procedure carries out before after prepolymerization reaction is accomplished, being scattered in the deionized water.
Embodiment 8
A kind of method for preparing aqueous polyurethane may further comprise the steps:
(1) polyhutadiene with terminal hydroxy group is warming up to 120 ℃, vacuum hydro-extraction 45min, and the cooling back adds hexamethylene diisocyanate; 0.04% the dibutyl tin laurate that dropping accounts for the polyhutadiene weight of terminal hydroxy group carries out prepolymerization reaction 1.5h at 85 ℃, adds hydrophilic chain extender dihydroxymethyl half ester; At 80 ℃ of reaction 2.5h; Generation-NCO end group performed polymer, the mole ratio of the polyhutadiene of hydrophilic chain extender and terminal hydroxy group are 1.2: 1 ,-NCO :-OH=4: 1; Wherein-and NCO representes the NCO mole number ,-OH representes polyvalent alcohol hydroxyl mole number;
(2) mixture that adds poly adipate succinic acid ester glycol and polybutadiene diol is in the performed polymer that step (1) obtains; Addition and remnants-NCO mol ratio is 1: 1; Add strong-hydrophobicity co-stabilizer whiteruss according to 12% mass ratio that accounts for the performed polymer total amount simultaneously; Stir fast, carry out the prepolymerization reaction;
(3) in the solid materials that step (2) prepolymerization reaction obtains, add deionized water, the mass ratio of deionized water and solid materials is 2: 1, and controlled temperature is that 20 ℃ of high speed dispersion become emulsion;
(4) elevated temperature to 60 ℃, 0.08% the mass ratio of pressing the solid materials amount adds the catalyzer organo-bismuth, and constant temperature 4h carries out the back chain extending reaction, obtains the stabilized aqueous polyaminoester emulsion.
This method comprises a neutralization procedure, and with the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in the tertiary amine 100% or the hydroxy-acid group of performed polymer, above-mentioned neutralization procedure carries out neutralizing agent being added in the deionized water or with the back chain extending reaction simultaneously.
Claims (10)
1. a method for preparing aqueous polyurethane is characterized in that, this method may further comprise the steps:
A, in the presence of no any solvent, with polyvalent alcohol, hydrophilic chain extender and isocyanate reaction, the performed polymer of generation-NCO end group;
One or both mixtures in b, interpolation small molecules polyvalent alcohol, the oligomer polyol, the while does not add or adds the strong-hydrophobicity co-stabilizer on a small quantity and carry out prepolymerization reaction;
C, treat to use high speed dispersion under the deionized water low temperature immediately after the b step stirs;
D, reduction stirring velocity, elevated temperature adds catalyzer constant temperature and carries out the back chain extending reaction, obtains stabilized aqueous polyaminoester emulsion.
2. a kind of method for preparing aqueous polyurethane according to claim 1; It is characterized in that; This method comprises a neutralization procedure; This neutralization procedure can add neutralizing agent in the prepolymerization reaction later stage, can accomplish the back at prepolymerization reaction and add neutralizing agent before being scattered in the water, also can with neutralizing agent add disperse in the entry or with after chain extending reaction carry out simultaneously.
3. a kind of method for preparing aqueous polyurethane according to claim 1 is characterized in that this method specifically may further comprise the steps:
(1) polyvalent alcohol is warming up to 100～120 ℃, vacuum hydro-extraction 45～90min, the cooling back adds isocyanic ester; 0.01～0.04% the dibutyl tin laurate that dropping accounts for polyvalent alcohol weight carries out prepolymerization reaction 1.5～2.5h at 75～85 ℃, adds hydrophilic chain extender; At 70～80 ℃ of reaction 2.5～3.5h; Generation-NCO end group performed polymer, the mole ratio of hydrophilic chain extender and polyvalent alcohol are 0.5～1.2: 1 ,-NCO :-OH=2～4: 1; Wherein-and NCO representes the NCO mole number ,-OH representes polyvalent alcohol hydroxyl mole number;
(2) add small molecules polyvalent alcohol, oligomer polyol or its blend in the performed polymer that step (1) obtains; Addition and remnants-NCO mol ratio is 0.3～1: 1; Add the strong-hydrophobicity co-stabilizer according to 0～12% mass ratio that accounts for the performed polymer total amount simultaneously and stir fast, carry out the prepolymerization reaction;
(3) in the solid materials that step (2) prepolymerization reaction obtains, add deionized water, the mass ratio of deionized water and solid materials is 1～2: 1, and controlled temperature is that 0～20 ℃ of high speed dispersion becomes emulsion;
(4) elevated temperature to 40～60 ℃, 0.03～0.08% the mass ratio of pressing the solid materials amount adds catalyzer, and constant temperature 2.5～4h carries out the back chain extending reaction, obtains the stabilized aqueous polyaminoester emulsion.
4. a kind of method for preparing aqueous polyurethane according to claim 3; It is characterized in that; This method comprises a neutralization procedure; With the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in alkali metal hydroxide or the tertiary amine 90%～100% or the hydroxy-acid group of performed polymer; Above-mentioned neutralization procedure can carry out in the prepolymerization reaction later stage simultaneously, also can after prepolymerization reaction is accomplished, be scattered in the deionized water and carry out before, also can neutralizing agent be added in the deionized water or with the back chain extending reaction and carry out simultaneously.
5. a kind of method for preparing aqueous polyurethane according to claim 1 and 2; It is characterized in that described polyvalent alcohol comprises polyhutadiene or the polyoxytrimethylene ether glycol that gathers hexanodioic acid pinakon ester, poly adipate succinic acid ester, PTMG, terminal hydroxy group.
6. a kind of method for preparing aqueous polyurethane according to claim 1 and 2; It is characterized in that described isocyanic ester is one or both the mixture in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate.
7. a kind of method for preparing aqueous polyurethane according to claim 1 and 2 is characterized in that, described hydrophilic chain extender is one or both a mixture of dimethylol propionic acid, dimethylolpropionic acid or dihydroxymethyl half ester.
8. a kind of method for preparing aqueous polyurethane according to claim 1 and 2; It is characterized in that described small molecules polyvalent alcohol, oligomer polyol are 1,4-butyleneglycol, 1; 4-cyclohexanedimethanol, 1; 6-pinakon, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, 1, the arbitrary proportion mixture of one or several in 12-dodecyl glycol, Viscotrol C, PTMG, polycaprolactone glycol, poly adipate succinic acid ester glycol, the polybutadiene diol.
9. a kind of method for preparing aqueous polyurethane according to claim 1 and 2 is characterized in that described strong-hydrophobicity co-stabilizer is n-Hexadecane, sweet oil or whiteruss.
10. a kind of method for preparing aqueous polyurethane according to claim 1 and 2 is characterized in that described catalyzer is dibutyl tin laurate, stannous octoate, organic zirconium or organo-bismuth.
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