CN102585154B - Method for preparing waterborne polyurethane - Google Patents
Method for preparing waterborne polyurethane Download PDFInfo
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- CN102585154B CN102585154B CN2012100656685A CN201210065668A CN102585154B CN 102585154 B CN102585154 B CN 102585154B CN 2012100656685 A CN2012100656685 A CN 2012100656685A CN 201210065668 A CN201210065668 A CN 201210065668A CN 102585154 B CN102585154 B CN 102585154B
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000004814 polyurethane Substances 0.000 title claims abstract description 43
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- 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 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 25
- -1 hydroxy carboxylic acid compound Chemical class 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 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
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 229940051250 hexylene glycol Drugs 0.000 claims description 9
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-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
- 230000000630 rising effect Effects 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- 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 6
- 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 229920001748 polybutylene 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 239000003995 emulsifying agent Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 8
- 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
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 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
- 241000237502 Ostreidae Species 0.000 description 1
- 230000007547 defect 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
- YONVOYAHRUTYTG-UHFFFAOYSA-N ethyl carbamate;hydrate Chemical compound O.CCOC(N)=O YONVOYAHRUTYTG-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 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
- 239000000463 material Substances 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 preparation method of environment-friendly type macromolecule material, especially relate to a kind of method for preparing aqueous polyurethane.
Background technology
Aqueous polyurethane refers to the polyurethane dispersions system take water as dispersion medium.After the environmental protection bill was promulgated in countries in the world, aqueous polyurethane was nontoxic with it, green, and the characteristics such as solvent-free, become the focus of polyurethane field research.In preparing the aqueous polyurethane process, due to the macromole of urethane hydrophobic normally, while being dispersed into emulsion, emulsifying agent is necessary.So the preparation method of aqueous polyurethane generally is divided into for outer emulsification and self-emulsification.Wherein, outer emulsion process is that the method by additional emulsifying agent is dispersed in water urethane, and this method is usually larger due to the polyaminoester emulsion size of particles, causes stability of emulsion poor.And remaining outer emulsifying agent has certain influence to the finished product performance.Therefore, the self-emulsifying dispersion method is adopted in the preparation of aqueous polyurethane at present more, namely introduces appropriate hydrophilic radical on polymer chain, and spontaneous dispersion under certain condition forms emulsion.Different according to chain extending reaction, self-emulsification can be divided into: acetone method, melting 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 the mechanical properties such as toughness, adopt present self-emulsifying dispersion method to be difficult to the hydrophilic performed polymer of the urethane of high molecular directly is dispersed in water to prepare stable aqueous polyurethane emulsion.
In recent years, the novel method-fine emulsion polymerization of synthetic water based polyurethane in succession occurs, be applicable to the polymerization of water sensitivity monomeric diisocyanate because of the polymerization mechanism of its droplet nucleation, become domestic and international study hotspot.But existing technology generally adopts the method for additional 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 is in connection with traditional self-emulsifying dispersion method and miniemulsion method, innovative approach-self-emulsifying miniemulsion method is proposed, being about to reaction carries out in two steps, the first step is synthetic wetting ability performed polymer with certain emulsifying capacity first, second step adds low molecular weight polyols to stir evenly rear emulsion dispersion, forms stable miniemulsion, continues reaction and improves molecular weight, the part chain extending reaction is carried out in miniemulsion, thereby prepare stable aqueous polyurethane emulsion.
Summary of the invention
Purpose of the present invention is exactly that a kind of preparation method of aqueous polyurethane emulsion is provided in order to overcome the defect that above-mentioned prior art exists, and the method can not add outer emulsifying agent, does not add or add less the stable aqueous polyurethane emulsion of preparation under the condition of co-stabilizer.Disperse difficult problem thereby solved in the self-emulsifying dispersion method, the negative impact of having avoided simultaneously the outer emulsifying agent in the fine emulsion polymerization to produce.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of method for preparing aqueous polyurethane comprises the following steps:
A, under the existence without 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, oligomer polyol, do not add or add on a small quantity the strong-hydrophobicity co-stabilizer and carry out prepolymerization reaction simultaneously;
C, after stirring, the b step uses immediately high speed dispersion under deionized water low temperature;
D, reduction stirring velocity, the rising temperature, add catalyzer constant temperature to carry out rear chain extending reaction, obtains stabilized aqueous polyaminoester emulsion.
The method comprises a neutralization procedure, and this neutralization procedure can add neutralizing agent in the prepolymerization reaction later stage, can be after prepolymerization reaction is completed adds neutralizing agent before in being scattered in water, also neutralizing agent can be added to the water and disperse or with rear chain extending reaction, carry out simultaneously.
The method specifically comprises the following steps:
(1) polyvalent alcohol is warming up to 100～120 ℃, vacuum hydro-extraction 45～90min, add isocyanic ester after cooling, dropping accounts for 0.01～0.04% dibutyl tin laurate of polyvalent alcohol weight, carry out prepolymerization reaction 1.5～2.5h at 75～85 ℃, add 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 is 0.5～1.2: 1,-NCO :-OH=2～4: 1, wherein-NCO represents the isocyanate group mole number ,-OH represents 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, simultaneously according to 0～12% mass ratio that accounts for the performed polymer total amount, add strong-hydrophobicity co-stabilizer rapid stirring even, carry out prepolymerization;
(3) add deionized water in the solid materials that obtains to step (2) prepolymerization, the mass ratio of deionized water and solid materials is 1～2: 1, and controlling temperature is that 0～20 ℃ of high speed dispersion becomes emulsion;
(4) rising 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 rear chain extending reaction, obtains stable aqueous polyurethane emulsion.
The method comprises a neutralization procedure, with the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in alkali metal hydroxide or tertiary amine 90%～100% or the hydroxy-acid group of performed polymer, above-mentioned neutralization procedure can carry out simultaneously in the prepolymerization reaction later stage, carry out before also can being scattered in deionized water after prepolymerization reaction is completed, also neutralizing agent can be added in deionized water or with rear chain extending reaction and carry out simultaneously.
Described polyvalent alcohol comprises polyhutadiene, polyoxytrimethylene ether glycol of hexanodioic acid hexylene glycol 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 hexamethylene diisocyanate, and the preferred vulcabond of the present invention is isophorone diisocyanate.
Described hydrophilic chain extender is one or both mixture of dimethylol propionic acid, dimethylolpropionic acid or dihydroxymethyl half ester, and the preferred hydrophilic chain extender of the present invention is dimethylolpropionic acid.
Described small molecules polyvalent alcohol, oligomer polyol are 1,4-butyleneglycol, 1,4-cyclohexanedimethanol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, 1, the arbitrary proportion mixture of one or several in 12-dodecyl glycol, Viscotrol C, PTMG, polycaprolactone glycol, polybutylene glyool adipate, 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 not add outer emulsifying agent and not add or adding less the stable aqueous polyurethane emulsion of preparation under the condition of co-stabilizer;
(2) in preparation technology of the present invention, performed polymer easily disperses, and can prepare the solvent-free aqueous polyurethane emulsion of high solids content of solid content 45～60% under the existence without any organic solvent.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
add 150g to gather hexanodioic acid hexylene glycol ester (molecular weight is 2000) to four-hole boiling flask, after heating and melting, 110 ℃ vacuumize 1h, cool to afterwards 85 ℃, add 48.3gIPDI and 1 dibutyl tin laurate reaction 2h, cool to afterwards 80 ℃, add the 8g dimethylolpropionic acid, insulation reaction 2.5h, cool to afterwards 70 ℃, add 8g1, the 4-butyleneglycol, stir and added immediately the 140g deionized water solution that is dissolved with the 5.5g triethylamine in 1 minute, high speed dispersion (rotating speed 2500rpm) 7min, be warmed up to rapidly afterwards 60 ℃, drip 20 dibutyl tin laurates, stirring at low speed (300rpm) reaction 4h, namely obtain a stable aqueous polyurethane emulsion.
This product is 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, after heating and melting, 110 ℃ vacuumize 1h, cool to afterwards 85 ℃, add 48.3gIPDI and 1 dibutyl tin laurate reaction 2h, cool to afterwards 80 ℃, add the 7.5g dimethylolpropionic acid, insulation reaction 3h, cool to afterwards 70 ℃, add 24.4g PTMG (molecular weight is 650) and 3.6g1, 4-butyleneglycol liquid form mixt, stir and added immediately the 146g deionized water solution that is dissolved with the 5.1g triethylamine in 1 minute, high speed dispersion (rotating speed 2500rpm) 10min, be warmed up to rapidly afterwards 60 ℃, drip 20 dibutyl tin laurates, middling speed stirs (1250rpm) reaction 4h, namely obtain a stable aqueous polyurethane emulsion.
This product is milky white liquid, and its solid content is 60.2%, and viscosity is 152cp.
Embodiment 3
add 74.9g to gather hexanodioic acid hexylene glycol ester (molecular weight is 2000) to four-hole boiling flask, 24.4g PTMG (molecular weight is 650) mixture, after heating and melting, 110 ℃ vacuumize 1h, cool to afterwards 85 ℃, add 51.6gIPDI and 1 dibutyl tin laurate reaction 2h, cool to afterwards 80 ℃, add the 7.6g dimethylolpropionic acid, 0.9g1, 4-butyleneglycol insulation reaction 1.5h, cool to afterwards 70 ℃, 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 immediately the 188g deionized water solution in 1 minute, high speed dispersion (rotating speed 2500rpm) 10min, be warmed up to rapidly afterwards 60 ℃, drip 4 dibutyl tin laurates, middling speed stirs (1250rpm) reaction 4h, namely obtain a stable aqueous polyurethane emulsion.
This product is milky white liquid, and its solid content is 50%, and viscosity is 453cp.
Embodiment 4
add 150g to gather hexanodioic acid hexylene glycol ester (molecular weight is 2000) to four-hole boiling flask, after heating and melting, 110 ℃ vacuumize 1h, cool to afterwards 85 ℃, add 48.3gIPDI and 1 dibutyl tin laurate reaction 2h, cool to afterwards 80 ℃, add the 8g dimethylolpropionic acid, insulation reaction 2.5h, cool to afterwards 70 ℃, add 24.4g PTMG (molecular weight is 650) and 5g heavy liquid paraffin liquid form mixt, stir and added immediately the 193g deionized water solution that is dissolved with the 5.5g triethylamine in 1 minute, high speed dispersion (rotating speed 2500rpm) 10min, reduction of speed stirring velocity (600rpm), be warmed up to rapidly 50 ℃, drip 20 dibutyl tin laurates, reaction 4h, namely obtain a stable aqueous polyurethane emulsion.
This product is milky white liquid, and its solid content is 55%, and viscosity is 460cp.
Embodiment 5
add 74.9g to gather hexanodioic acid hexylene glycol ester (molecular weight is 2000) to four-hole boiling flask, 24.4g PTMG (molecular weight is 650) mixture, after heating and melting, 110 ℃ vacuumize 1h, cool to afterwards 85 ℃, add 51.6gIPDI and 1 dibutyl tin laurate reaction 1.5h, cool to afterwards 80 ℃, add the 7.6g dimethylolpropionic acid, 0.9g1, 4-butyleneglycol insulation reaction 1.5h, cool to afterwards 70 ℃, add 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 immediately the 229g deionized water solution in 1 minute, high speed dispersion (rotating speed 2500rpm) 10min, reduction of speed stirring velocity (600rpm), be warmed up to rapidly 50 ℃, drip 20 dibutyl tin laurates, reaction 4h, namely obtain a stable aqueous polyurethane emulsion.
This product is 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 comprises the following steps:
(1) hexanodioic acid hexylene glycol ester is warming up to 100 ℃, vacuum hydro-extraction 90min, add diphenylmethanediisocyanate after cooling, dropping accounts for 0.01% dibutyl tin laurate of hexanodioic acid hexylene glycol ester weight, carry out prepolymerization reaction 2.5h at 75 ℃, add 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 hexylene glycol ester is 0.5: 1,-NCO :-OH=2: 1, wherein-NCO represents the isocyanate group mole number,-OH represents polyvalent alcohol hydroxyl mole number,
(2) add BDO in the performed polymer that step (1) obtains, addition and remnants-NCO mol ratio is 0.3: 1, carries out prepolymerization;
(3) add deionized water in the solid materials that obtains to step (2) prepolymerization, the mass ratio of deionized water and solid materials is 1: 1, and controlling temperature is that 0 ℃ of high speed dispersion becomes emulsion;
(4) rising 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 rear chain extending reaction, obtains stable aqueous polyurethane emulsion.
In addition, the method also comprises a neutralization procedure, and with the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in 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 comprises the following steps:
(1) poly adipate succinic acid ester is warming up to 110 ℃, vacuum hydro-extraction 60min, the mixture that adds tolylene diisocyanate and isophorone diisocyanate after cooling, dropping accounts for 0.02% dibutyl tin laurate of poly adipate succinic acid ester weight, carry out prepolymerization reaction 2h at 80 ℃, the mixture that adds 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 is 1: 1,-NCO :-OH=3: 1, wherein-NCO represents the isocyanate group mole number,-OH represents 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, simultaneously according to 5% mass ratio that accounts for the performed polymer total amount, add strong-hydrophobicity co-stabilizer sweet oil, rapid stirring is even, carries out prepolymerization;
(3) add deionized water in the solid materials that obtains to step (2) prepolymerization, the mass ratio of deionized water and solid materials is 1.5: 1, and controlling temperature is that 10 ℃ of high speed dispersion become emulsion;
(4) rising 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 rear chain extending reaction, obtains stable aqueous polyurethane emulsion.
The 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 being scattered in deionized water after prepolymerization reaction is completed.
Embodiment 8
A kind of method for preparing aqueous polyurethane comprises the following steps:
(1) polyhutadiene of terminal hydroxy group is warming up to 120 ℃, vacuum hydro-extraction 45min, add hexamethylene diisocyanate after cooling, dropping accounts for 0.04% dibutyl tin laurate of the polyhutadiene weight of terminal hydroxy group, carry out prepolymerization reaction 1.5h at 85 ℃, add 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 is 1.2: 1,-NCO :-OH=4: 1, wherein-NCO represents the isocyanate group mole number ,-OH represents polyvalent alcohol hydroxyl mole number;
(2) add the mixture of polybutylene glyool adipate and polybutadiene diol in the performed polymer that step (1) obtains, addition and remnants-NCO mol ratio is 1: 1, simultaneously according to 12% mass ratio that accounts for the performed polymer total amount, add strong-hydrophobicity co-stabilizer whiteruss, rapid stirring is even, carries out prepolymerization;
(3) add deionized water in the solid materials that obtains to step (2) prepolymerization, the mass ratio of deionized water and solid materials is 2: 1, and controlling temperature is that 20 ℃ of high speed dispersion become emulsion;
(4) rising 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 rear chain extending reaction, obtains stable aqueous polyurethane emulsion.
The method comprises a neutralization procedure, and with the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in tertiary amine 100% or the hydroxy-acid group of performed polymer, above-mentioned neutralization procedure carries out simultaneously in neutralizing agent is added deionized water or with rear chain extending reaction.
Claims (7)
1. a method for preparing aqueous polyurethane, is characterized in that, the method comprises the following steps:
A, under the existence without 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, oligomer polyol, do not add or add on a small quantity the strong-hydrophobicity co-stabilizer and carry out prepolymerization reaction simultaneously;
C, after stirring, the b step uses immediately high speed dispersion under deionized water low temperature;
D, reduction stirring velocity, the rising temperature, add catalyzer constant temperature to carry out rear chain extending reaction, obtains stabilized aqueous polyaminoester emulsion;
The method comprises a neutralization procedure, and this neutralization procedure adds neutralizing agent in the prepolymerization reaction later stage, adds neutralizing agent before in being scattered in water after prepolymerization reaction is completed, or neutralizing agent is added to the water and disperses or with rear chain extending reaction, carry out simultaneously;
The method for preparing aqueous polyurethane specifically comprises the following steps:
(1) polyvalent alcohol is warming up to 100～120 ℃, vacuum hydro-extraction 45～90min, add isocyanic ester after cooling, dropping accounts for 0.01～0.04% dibutyl tin laurate of polyvalent alcohol weight, carry out prepolymerization reaction 1.5～2.5h at 75～85 ℃, add 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 is 0.5～1.2:1,-NCO:-OH=2～4:1, wherein-NCO represents the isocyanate group mole number ,-OH represents 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, simultaneously according to 0～12% mass ratio that accounts for the performed polymer total amount, add strong-hydrophobicity co-stabilizer rapid stirring even, carry out prepolymerization;
(3) add deionized water in the solid materials that obtains to step (2) prepolymerization, the mass ratio of deionized water and solid materials is 1～2:1, and controlling temperature is that 0～20 ℃ of high speed dispersion becomes emulsion;
(4) rising 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 rear chain extending reaction, obtains stable aqueous polyurethane emulsion;
The method comprises a neutralization procedure, with the hydroxy carboxylic acid compound who obtains with above-mentioned reaction in alkali metal hydroxide or tertiary amine 90%～100% or the hydroxy-acid group of performed polymer, above-mentioned neutralization procedure carried out simultaneously in the prepolymerization reaction later stage, carry out before being scattered in deionized water after prepolymerization reaction is completed, or neutralizing agent is added in deionized water or with rear chain extending reaction and carries out simultaneously.
2. a kind of method for preparing aqueous polyurethane according to claim 1, it is characterized in that, described polyvalent alcohol comprises polyhutadiene or the polyoxytrimethylene ether glycol of poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, PTMG, terminal hydroxy group.
3. a kind of method for preparing aqueous polyurethane according to claim 1, it is characterized in that, described isocyanic ester is one or both the mixture in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
4. a kind of method for preparing aqueous polyurethane according to claim 1, is characterized in that, described hydrophilic chain extender is one or both mixture of dimethylol propionic acid, dimethylolpropionic acid or dihydroxymethyl half ester.
5. a kind of method for preparing aqueous polyurethane according to claim 1, it is characterized in that, described small molecules polyvalent alcohol, oligomer polyol are 1,4-butyleneglycol, 1,4-cyclohexanedimethanol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, the arbitrary proportion mixture of one or several in 1,12-dodecyl glycol, Viscotrol C, PTMG, polycaprolactone glycol, polybutylene glyool adipate, polybutadiene diol.
6. a kind of method for preparing aqueous polyurethane according to claim 1, is characterized in that, described strong-hydrophobicity co-stabilizer is n-Hexadecane, sweet oil or whiteruss.
7. a kind of method for preparing aqueous polyurethane according to claim 1, is characterized in that, described catalyzer is dibutyl tin laurate, stannous octoate, organic zirconium or organo-bismuth.
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