CN102432815A - Waterborne polyurethane resin and preparation method thereof - Google Patents
Waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- CN102432815A CN102432815A CN2011102582709A CN201110258270A CN102432815A CN 102432815 A CN102432815 A CN 102432815A CN 2011102582709 A CN2011102582709 A CN 2011102582709A CN 201110258270 A CN201110258270 A CN 201110258270A CN 102432815 A CN102432815 A CN 102432815A
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Abstract
The invention discloses waterborne polyurethane resin and a preparation method thereof. The waterborne polyurethane resin consists of polyester glycol, toluene diisocyanate, dimethylolpropionic acid, a catalyst, triethylamine, methyl acetate, latent solvent and deionized water. The preparation method comprises the steps of dehydration, primary temperature reduction, reaction of polyurethane prepolymer, secondary temperature reduction, neutralization reaction, temperature reduction and emulsification and the like. The waterborne polyurethane resin and the preparation method thereof have the advantages that a preparation process is finished by diluting an environment-friendly solvent without being limited, so that the standard of environment friendliness is met; and meanwhile, the polyester type waterborne polyurethane resin taking the methyl acetate as the solvent has the viscosity of 20.5-40.2MPa s and the particle size of 0.102-0.140mum as well as favorable diluting and dispersing effects.
Description
Technical field
The present invention relates to a kind of waterborne polyurethane resin and preparation method, specifically a kind of is the polyester type waterborne polyurethane resin and preparation method thereof of solvent preparation with the ritalin, is applied to aqueous woodware paint, aqueous adhesive etc., belongs to the resin field.
Background technology
Aqueous polyurethane is with the new polyurethane system of water to replace organic solvent as dispersion medium, also claims water dispersible polyurethane, aqueous polyurethane or waterbased urethane.Aqueous polyurethane is solvent with water; Have pollution-free, safe and reliable, mechanical property is good, consistency good, be easy to advantages such as modification, is widely used in coating, tackiness agent, fabric coating and finishing composition, hide finishes, sheet surface treating agent and fiber surface treatment agent.Aqueous polyurethane comprises three kinds of aqueous polyurethane, aqueous dispersions and water miscible liquids, is binary colloidal state system, and urethane (PU) particle is scattered in the successive aqueous phase, and also the someone claims water-based PU or water base PU.
Present most of water-based PU mainly is by the self-emulsification preparation, is main cure component with the PU that contains hydrophilic radical, if hydrophilic component can not effectively get in the cross-linked network, the dry chance water of filming that forms is prone to swelling during dried coating film.It lacks film institute getable cross-linking density and high molecular weight as two-pack solvent-borne type PU in addition, thereby water tolerance, solvent resistance, thermotolerance and glossiness that these water dispersions are filmed are relatively poor, have seriously limited the scope of its use.Therefore, the normal employing improved the water tolerance that the cross-linking density of filming improves emulsion film.Cross-linking method commonly used has two kinds: a kind of is when synthetic PU prepolymer, adds functionality greater than 2 polyol, directly generates crosslinked PU prepolymer, more above-mentioned prepolymer is dispersed in the water well, and chain extension formation macromole, form emulsion at last.This method also is preceding crosslinking, and shortcoming is to be prone to make the prepolymer viscosity to increase, and difficulty is dispersed in the water, influences the stability of emulsion.Another kind method is the external crosslinking method, and it is crosslinked to adopt the negatively charged ion PU emulsion of being with carboxylic to carry out, and crosslinking reaction occurs on the carboxyl of PU molecule, and Soluol XC 100, carbonization imines and metal salt compound are arranged, and carries out crosslinked at ambient temperature.This type linking agent generally adds when using the PU emulsion, and is very fast because of its crosslinking reaction speed, produces gel and breakdown of emulsion in the short period of time.The external crosslinking method can successfully solve the wetting ability problem of PU emulsion film, but because of additional crosslink agent, forms the two-pack finish and make troubles to construction, and this method is used less.
Viscosity was bigger when the aqueous polyurethane performed polymer prepared; For convenient heat transfer, mass transfer, especially later stage emulsification, must add appropriate solvent and dilute; Solvent commonly used is generally acetone, butanone, dioxane, N, hydrophilic organic solvents such as dinethylformamide, N-Methyl pyrrolidone.Aforesaid method generally is referred to as acetone method.The acetone that uses in the acetone method, butanone etc. all belong to the organic volatile of environmental protection restriction, and are classified as strict limiter stage use range owing to relating to easy system toxogen material in recent years, and these all bring the restriction in the use.
Summary of the invention
In order to address the above problem; The invention provides a kind of waterborne polyurethane resin and preparation method; Described waterborne polyurethane resin is that solvent is prepared from the ritalin; And ritalin belongs to ep-type material, does not belong to the organic pollutant discharging that restriction is used, and can reach coating, printing ink, resin, the new environmental protection standard of tackiness agent factory.
57.8 ℃ of ritalin boiling points, similar with acetone, be easy to remove, and have solvency power widely, can the dissolve polyurethane class, acrylic acid or the like, vinyl-based, Nitrocellulose class, epoxies, polyester, resol class etc.; Belong to VOC-Exempt Regulation Status and exempt restricted kind, belong to environmentally friendly solvent.Simultaneously, ritalin and glassware for drinking water have certain dissolubility, and the use ritalin is 20.5～40.2 MPas (adopting NDJ-1 type rotation viscosity apparatus to measure) as the viscosity of the polyester type waterborne polyurethane resin product that solvent obtains; Particle diameter is 0.102～0.140 μ m (adopting Ma Erwen MS2000 laser diffraction granularity appearance to measure).Show preferably dilution and the dissemination effect of ritalin in the waterborne polyurethane resin preparation.
Technical scheme of the present invention is:
A kind of waterborne polyurethane resin is grouped into by following one-tenth with weight part:
45～60 parts of polyester diol,
20～40 parts of tolylene diisocyanates,
5～10 parts of dimethylol propionic acids,
0.02～0.1 part of catalyzer,
4～10 parts of triethylamines,
10～40 parts of ritalins,
5～10 parts of solubility promoters,
200～500 parts of deionized waters.
Wherein, said polyester diol is selected from one or more in polytetrahydrofuran diol, polycarbonate diol or the polycaprolactone glycol;
Said catalyzer is selected from one or both in dibutyl tin laurate, the stannous octoate;
Said solubility promoter is one or more in vinyl acetic monomer, N-BUTYL ACETATE, amyl acetate-n, the isoamyl acetate.
A kind of preparation method of waterborne polyurethane resin comprises the following steps:
(1) dehydration: the polyester diol of 45～60 weight parts is stirred down and dewatered 1～2 hour at 120～130 ℃, vacuum tightness 700～750mmHg; A certain amount of water cut guarantees that the water cut of polyester diol reaches the requirement of reaction system, because can cause the generation of gel;
(2) once cooling: under logical nitrogen, add the dimethylol propionic acid of 5～10 weight parts then, stirred 20～30 minutes, be cooled to 40～45 ℃, make dimethylol propionic acid obtain dissolving;
(3) reaction of base polyurethane prepolymer for use as: add the tolylene diisocyanate of 20～40 weight parts and catalyzer, the constant temperature of 0.02～0.1 weight part and stirred 2～3 hours for 80～85 ℃;
(4) reducing temperature twice: add the solubility promoter of 5～10 weight parts, constant temperature stirred 0.5 hour for 80～85 ℃, was cooled to 45～50 ℃, reduced system viscosity;
(5) neutralization reaction: add the ritalin of 5～15 weight parts and the triethylamine of 4～10 parts by weight; 50～60 ℃ of insulations 35～45 minutes; The ritalin that adds 5～25 parts of residues again; It is in order to control the speed of neutralization reaction that ritalin adds for the first time, and adding for the second time is the viscosity that rises in reduction system cooling back;
(6) cooling emulsification: be cooled to below 10 ℃; To reduce in the urethane hydration process reaction with water; Above-mentioned reactant is poured into used the high speed dispersion mulser to carry out high speed dispersion emulsification 30～40 minutes in the deionized water of 200～500 weight parts, obtain said polyester type waterborne polyurethane resin.
The invention has the advantages that: the waterborne polyurethane resin of the present invention's preparation is under the environmentally friendly solvent dilution that does not receive any restriction, to accomplish, and has reached the standard of environmental protection; Simultaneously, using the viscosity of the polyester type waterborne polyurethane resin that ritalin obtains as solvent is 20.5～40.2 MPas; Particle diameter is 0.102～0.140 μ m, has good dilution and dispersion effect.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for explanation and explains the present invention, and be not used in qualification the present invention.
Embodiment 1
A kind of waterborne polyurethane resin is grouped into by following one-tenth with weight part:
50 parts of polyester diol,
24.7 parts of tolylene diisocyanates,
6 parts of dimethylol propionic acids,
0.05 part of catalyzer,
4.5 parts of triethylamines,
30 parts of ritalins
7 parts of solubility promoters,
350 parts of deionized waters.
Wherein, said polyester diol is a polycarbonate diol, and said catalyzer is a dibutyl tin laurate, and said solubility promoter is a N-BUTYL ACETATE.
A kind of method for preparing above-mentioned waterborne polyurethane resin comprises:
50 parts of polycarbonate diols are stirred dehydration 2 hours under 120 ℃, vacuum tightness 700mmHg, then at logical nitrogen 6 parts of dimethylol propionic acids of adding down, stir 20 minutes, be cooled to 40 ℃; Add 24.7 parts of tolylene diisocyanates and 0.05 part of dibutyl tin laurate, constant temperature stirred 3 hours for 80 ℃, added 7 parts of N-BUTYL ACETATEs then, constant temperature stirred 0.5 hour for 80 ℃; Be cooled to 45 ℃ and add 10 parts of ritalins and 4.5 parts of triethylamines; 55 ℃ of insulations 35 minutes, add 20 parts of ritalins, be cooled to below 10 ℃; Pour above-mentioned reactant into 350 parts of deionized water high speed dispersion and emulsions 30 minutes, obtain the polyester type waterborne polyurethane resin.
The result: the viscosity of product is 30.8 MPas; Particle diameter is 0.129 μ m.
Embodiment 2
A kind of waterborne polyurethane resin is grouped into by following one-tenth with weight part:
60 parts of polyester diol,
40 parts of tolylene diisocyanates,
10 parts of dimethylol propionic acids,
0.1 part of catalyzer,
10 parts of triethylamines,
40 parts of ritalins,
10 parts of solubility promoters,
500 parts of deionized waters.
Wherein, said polyester diol is selected from polytetrahydrofuran diol, and said catalyzer is a stannous octoate, and said solubility promoter is an amyl acetate-n.
A kind of method for preparing above-mentioned waterborne polyurethane resin comprises:
60 parts of polytetrahydrofuran diols are stirred dehydration 1.5 hours under 130 ℃, vacuum tightness 720mmHg, then at logical nitrogen 10 parts of dimethylol propionic acids of adding down, stir 25 minutes, be cooled to 42 ℃; Add 40 parts of tolylene diisocyanates and 0.1 part of stannous octoate, constant temperature stirred 2.5 hours for 82 ℃, added 10 parts of amyl acetate-ns then, constant temperature stirred 0.5 hour for 82 ℃; Be cooled to 50 ℃ and add 15 parts of ritalins and 10 parts of triethylamines; 60 ℃ of insulations 40 minutes, add 25 parts of ritalins, be cooled to below 10 ℃; Pour above-mentioned reactant into 500 parts of deionized water high speed dispersion and emulsions 35 minutes, obtain the polyester type waterborne polyurethane resin.
The result: the viscosity of product is 20.5 MPas; Particle diameter is 0.102 μ m.
Embodiment 3
A kind of waterborne polyurethane resin is grouped into by following one-tenth with weight part:
45 parts of polyester diol,
20 parts of tolylene diisocyanates,
5 parts of dimethylol propionic acids,
0.02 part of catalyzer,
4 parts of triethylamines,
10 parts of ritalins,
5 parts of solubility promoters,
200 parts of deionized waters.
Wherein, said polyester diol is the mixture of polytetrahydrofuran diol and polycaprolactone glycol, and said catalyzer is the mixture of dibutyl tin laurate and stannous octoate, and said solubility promoter is the mixture of vinyl acetic monomer and isoamyl acetate.
A kind of method for preparing above-mentioned waterborne polyurethane resin comprises:
25 parts of polycaprolactone glycols and 20 parts of polytetrahydrofuran diols are stirred dehydration 1 hour under 125 ℃, vacuum tightness 750mmHg; Add 5 parts of dimethylol propionic acids down at logical nitrogen then, stir 30 minutes, be cooled to 45 ℃, add 20 parts of tolylene diisocyanates and 0.01 part of stannous octoate and 0.01 part of dibutyl tin laurate, 85 ℃ of stirrings of constant temperature 2 hours; Add 4 parts of vinyl acetic monomers and 1 part of isoamyl acetate then; Constant temperature stirred 0.5 hour for 85 ℃, was cooled to 48 ℃ and added 5 parts of ritalins and 4 parts of triethylamines, 50 ℃ of insulations 45 minutes; Add 5 parts of ritalins; Be cooled to below 10 ℃, poured above-mentioned reactant into 200 parts of deionized water high speed dispersion and emulsions 40 minutes, obtain the polyester type waterborne polyurethane resin.
The result: the viscosity of product is 40.2 MPas; Particle diameter is 0.140 μ m.
Embodiment 4
A kind of waterborne polyurethane resin is grouped into by following one-tenth with weight part:
50 parts of polyester glycols,
30 parts of tolylene diisocyanates,
8 parts of dimethylol propionic acids,
0.06 part of catalyzer,
7 parts of triethylamines,
25 parts of ritalins,
8 parts of solubility promoters,
400 parts of deionized waters.
Wherein, Said polyester glycol is that said polyester glycol is selected from the mixture in polytetrahydrofuran diol, polycarbonate diol and the polycaprolactone glycol; Said catalyzer is the mixture of dibutyl tin laurate and stannous octoate, and said solubility promoter is the mixture of vinyl acetic monomer and isoamyl acetate.
A kind of method for preparing above-mentioned waterborne polyurethane resin comprises:
15 weight part polytetrahydrofuran diols, 20 weight part polycarbonates, two pure and mild 15 weight part polycaprolactone glycols are stirred dehydration 1.5 hours under 125 ℃, vacuum tightness 725mmHg; Add 8 parts of dimethylol propionic acids down at logical nitrogen then, stir 25 minutes, be cooled to 43 ℃, add 30 parts of tolylene diisocyanates and 0.03 part of stannous octoate and 0.03 part of dibutyl tin laurate, 83 ℃ of stirrings of constant temperature 2.5 hours; Add 2 parts of vinyl acetic monomers, 2 parts of N-BUTYL ACETATEs, 2 parts of amyl acetate-ns and 2 parts of isoamyl acetates then; Constant temperature stirred 0.5 hour for 82 ℃, was cooled to 47 ℃ and added 10 parts of ritalins and 7 parts of triethylamines, 55 ℃ of insulations 40 minutes; Add 15 parts of ritalins again; Be cooled to below 10 ℃, poured above-mentioned reactant into 400 parts of deionized water high speed dispersion and emulsions 35 minutes, obtain the polyester type waterborne polyurethane resin.
The result: the viscosity of product is 27.6 MPas; Particle diameter is 0.124 μ m.
Among each embodiment of the present invention, used chemical industry material is used material in the production of this area, all can from market, obtain, and can not exert an influence for the production result; The equipment of in each operation, using all adopts conventional equipment used in the current production, does not have special feature.
What should explain at last is: the above is merely the preferred embodiments of the present invention; Be not limited to the present invention; Although the present invention has been carried out detailed explanation with reference to previous embodiment; For a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a waterborne polyurethane resin is characterized in that, is grouped into by following one-tenth with weight part:
45～60 parts of polyester diol,
20～40 parts of tolylene diisocyanates,
5～10 parts of dimethylol propionic acids,
0.02～0.1 part of catalyzer,
4～10 parts of triethylamines,
10～40 parts of ritalins,
5～10 parts of solubility promoters,
200～500 parts of deionized waters.
2. waterborne polyurethane resin according to claim 1 is characterized in that: described polyester diol is selected from one or more in polytetrahydrofuran diol, polycarbonate diol or the polycaprolactone glycol.
3. waterborne polyurethane resin according to claim 1 is characterized in that: described catalyzer is selected from one or both in dibutyl tin laurate, the stannous octoate.
4. waterborne polyurethane resin according to claim 1 is characterized in that: described solubility promoter is one or more in vinyl acetic monomer, N-BUTYL ACETATE, amyl acetate-n, the isoamyl acetate.
5. the preparation method of waterborne polyurethane resin as claimed in claim 1 comprises the following steps:
(1) dehydration: the polyester diol of 45～60 weight parts is stirred down and dewatered 1～2 hour at 120～130 ℃, vacuum tightness 700～750mmHg;
(2) once cooling: under logical nitrogen, add the dimethylol propionic acid of 5～10 weight parts then, stirred 20～30 minutes, be cooled to 40～45 ℃;
(3) base polyurethane prepolymer for use as reaction: add the tolylene diisocyanate of 20～40 weight parts and catalyzer, the constant temperature of 0.02～0.1 weight part and stirred 2～3 hours for 80～85 ℃;
(4) reducing temperature twice: add the solubility promoter of 5～10 weight parts, constant temperature stirred 0.5 hour for 80～85 ℃, was cooled to 45～50 ℃;
(5) neutralization reaction: add the ritalin of 5～15 weight parts and the triethylamine of 4～10 parts by weight,, add 5～25 parts ritalin again 50～60 ℃ of insulations 35～45 minutes;
(6) cooling emulsification: be cooled to below 10 ℃, above-mentioned reactant poured into used the high speed dispersion mulser to carry out high speed dispersion emulsification 30～40 minutes in the deionized water of 200～500 weight parts, obtain said polyester type waterborne polyurethane resin.
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Cited By (6)
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| CN102977282A (en) * | 2012-12-06 | 2013-03-20 | 陕西科技大学 | Preparation method of anionic organic-solvent-free and emulsifier-free polyurethane microemulsion |
| CN102995466A (en) * | 2012-11-23 | 2013-03-27 | 青岛文创科技有限公司 | Preparation method of waterborne polyurethane printing adhesive |
| CN104497949A (en) * | 2014-12-02 | 2015-04-08 | 佛山铭乾科技有限公司 | Preparation method of novel high-solid-content waterborne polyurethane adhesive for shoes |
| CN104829811A (en) * | 2015-04-30 | 2015-08-12 | 安吉县广泰化工纸业有限公司 | Preparation process for aqueous polyurethane resin |
| CN106995521A (en) * | 2017-05-11 | 2017-08-01 | 佛山市尚峰高分子科技有限公司 | A kind of waterborne polyurethane resin |
| CN107641190A (en) * | 2017-09-22 | 2018-01-30 | 常熟国和新材料有限公司 | A kind of aqueous polyurethane resin emulsion and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995466A (en) * | 2012-11-23 | 2013-03-27 | 青岛文创科技有限公司 | Preparation method of waterborne polyurethane printing adhesive |
| CN102977282A (en) * | 2012-12-06 | 2013-03-20 | 陕西科技大学 | Preparation method of anionic organic-solvent-free and emulsifier-free polyurethane microemulsion |
| CN104497949A (en) * | 2014-12-02 | 2015-04-08 | 佛山铭乾科技有限公司 | Preparation method of novel high-solid-content waterborne polyurethane adhesive for shoes |
| CN104829811A (en) * | 2015-04-30 | 2015-08-12 | 安吉县广泰化工纸业有限公司 | Preparation process for aqueous polyurethane resin |
| CN104829811B (en) * | 2015-04-30 | 2017-09-01 | 安吉县广泰化工纸业有限公司 | A kind of preparation technology of waterborne polyurethane resin |
| CN106995521A (en) * | 2017-05-11 | 2017-08-01 | 佛山市尚峰高分子科技有限公司 | A kind of waterborne polyurethane resin |
| CN107641190A (en) * | 2017-09-22 | 2018-01-30 | 常熟国和新材料有限公司 | A kind of aqueous polyurethane resin emulsion and preparation method thereof |
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