CN102432815B - Waterborne polyurethane resin and preparation method - Google Patents
Waterborne polyurethane resin and preparation method Download PDFInfo
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- CN102432815B CN102432815B CN201110258270.9A CN201110258270A CN102432815B CN 102432815 B CN102432815 B CN 102432815B CN 201110258270 A CN201110258270 A CN 201110258270A CN 102432815 B CN102432815 B CN 102432815B
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Abstract
The invention discloses a kind of waterborne polyurethane resin and preparation method, described resin is made up of polyester diol, toluene di-isocyanate(TDI), dihydromethyl propionic acid, catalyst, triethylamine, methyl acetate, cosolvent and deionized water, and described preparation method comprises dehydration, the step such as reaction, reducing temperature twice, neutralization reaction and cooling emulsification of cooling, base polyurethane prepolymer for use as once; The invention has the advantages that: preparation technology completes under unrestricted environmentally friendly solvent dilution, has reached the standard of environmental protection; The viscosity of the polyester-type waterborne polyurethane resin that meanwhile, use methyl acetate obtains as solvent is 20.5～40.2MPas; Particle diameter is 0.102～0.140 μ m, has good dilution and dispersion effect.
Description
Technical field
The present invention relates to a kind of waterborne polyurethane resin and preparation method, specifically a kind of polyester-type waterborne polyurethane resin of preparing taking methyl acetate as solvent and preparation method thereof, is applied to aqueous woodware paint, aqueous adhesive etc., belongs to resin field.
Background technology
Aqueous polyurethane is the new polyurethane system using water to replace organic solvent as decentralized medium, also claims water dispersible polyurethane, aqueous polyurethane or water-based polyurethane. Aqueous polyurethane is taking water as solvent, have pollution-free, safe and reliable, mechanical performance is good, compatibility good, be easy to the advantages such as modification, is widely used in coating, adhesive, fabric coating and finishing agent, leather finishing agent, sheet surface treating agent and fiber surface inorganic agent. Aqueous polyurethane comprises three kinds of aqueous polyurethane, aqueous dispersions and aqueous emulsions, is binary colloidal state system, and polyurethane (PU) particle is scattered in continuous water, and also someone claims water-based PU or water base PU.
Most water-based PU is prepared by self-emulsification, taking containing the PU of hydrophilic radical as main cure component, if hydrophilic component can not effectively enter in cross-linked network when dried coating film, it is easily swelling that the dry film forming is met water. It lacks the picture bi-component solvent-borne type PU film getable crosslink density of institute and high molecular weight in addition, thereby the resistance to water of these aqueous dispersion films, solvent resistance, heat resistance and glossiness are poor, have seriously limited the scope of its use. Therefore, the normal resistance to water that adopts the crosslink density of raising film to improve emulsion film. Conventional cross-linking method has two kinds: one is in the time of synthetic PU prepolymer, and the polyol that adds degree of functionality to be greater than 2 directly generates crosslinked PU prepolymer, more above-mentioned prepolymer is dispersed in water well, and chain extension forms large molecule, finally forms emulsion. This method is also front cross-linking method, and shortcoming is easily to make prepolymer viscosity increase, and more difficult being dispersed in water, affects the stability of emulsion. Another kind method is external crosslinking method, adopts and is cross-linked with the anion PU emulsion of carboxylic, and cross-linking reaction occurs on the carboxyl of PU molecule, has aziridine, carbonization imines and metal salt compound, is cross-linked at ambient temperature. This class crosslinking agent generally adds in the time using PU emulsion, very fast because of its cross-linking reaction speed, in the short time, produces gel and breakdown of emulsion. External crosslinking method can successfully solve the hydrophily problem of PU emulsion film, but because of additional crosslink agent, composition bi-component finishing agent is made troubles to construction, and the method is used less.
Time prepared by Waterborne Polyurethane Prepolymer, viscosity is larger, for convenience of heat transfer, mass transfer, especially later stage emulsification, must add suitable solvent to be diluted, conventional solvent is generally the hydrophilic organic solvents such as acetone, butanone, dioxane, DMF, 1-METHYLPYRROLIDONE. Said method is generally referred to as acetone method. Acetone, the butanone etc. using in acetone method all belongs to the organic volatile of environmental protection restriction, and is classified as the strict limiter stage scope of application owing to relating to easy toxogen material processed in recent years, and these all bring the restriction in 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 prepared from taking methyl acetate as solvent, and methyl acetate belongs to ep-type material, do not belong to the organic pollution discharge that restriction is used, can reach coating, ink, resin, environmental protection standard that adhesive producing works is new.
57.8 DEG C of methyl acetate boiling points, similar with acetone, be easy to remove, and there is dissolving power widely, can dissolve polyurethane class, acrylic compounds, vinyl-based, NC Nitroncellulose class, epoxies, polyester, phenolic resins class etc.; Belong to VOC-ExemptRegulationStatus and exempt restricted kind, belong to environmentally friendly solvent. Meanwhile, methyl acetate and glassware for drinking water have certain dissolubility, and the viscosity of the polyester-type waterborne polyurethane resin product that use methyl acetate obtains as solvent is that 20.5～40.2MPas(adopts NDJ-1 type rotation viscosity apparatus to measure); Particle diameter is that 0.102～0.140 μ m(adopts Ma Erwen MS2000 laser diffraction particle size analyzer to measure). Show good dilution and the peptizaiton effect of methyl acetate in waterborne polyurethane resin preparation.
Technical scheme of the present invention is:
A kind of waterborne polyurethane resin, is grouped into by the following one-tenth with weight portion:
45～60 parts of polyester diol,
20～40 parts of toluene di-isocyanate(TDI)s,
5～10 parts of dihydromethyl propionic acids,
0.02～0.1 part of catalyst,
4～10 parts of triethylamines,
10～40 parts of methyl acetates,
5～10 parts of cosolvents,
200～500 parts of deionized waters.
Wherein, described polyester diol is selected from one or more in polytetrahydrofuran diol, PCDL or polycaprolactone glycol;
Described catalyst is selected from one or both in dibutyl tin laurate, stannous octoate;
Described cosolvent is one or more in ethyl acetate, butyl acetate, amyl acetate, isoamyl acetate.
A preparation method for waterborne polyurethane resin, comprises the following steps:
(1) dehydration: the polyester diol of 45～60 weight portions is stirred under 120～130 DEG C, vacuum 700～750mmHg to dehydration 1～2 hour, a certain amount of water content ensures that the water content of polyester diol reaches the requirement of reaction system, because can cause the generation of gel;
(2) once cooling: then add the dihydromethyl propionic acid of 5～10 weight portions under logical nitrogen, stir 20～30 minutes, be cooled to 40～45 DEG C, dihydromethyl propionic acid is dissolved;
(3) reaction of base polyurethane prepolymer for use as: add the toluene di-isocyanate(TDI) of 20～40 weight portions and the catalyst of 0.02～0.1 weight portion, 80～85 DEG C of stirrings of constant temperature 2～3 hours;
(4) reducing temperature twice: add the cosolvent of 5～10 weight portions, 80～85 DEG C of stirrings of constant temperature 0.5 hour, are cooled to 45～50 DEG C, reduce system viscosity;
(5) neutralization reaction: add the methyl acetate of 5～15 weight portions and the triethylamine of 4～10 parts by weight, 50～60 DEG C of insulations 35～45 minutes, add again the methyl acetate of 5～25 parts of residues, it is the speed in order to control neutralization reaction that methyl acetate adds for the first time, and adding is for the second time the viscosity of the cooling rear rising of reduction system;
(6) cooling emulsification: be cooled to below 10 DEG C, to reduce in polyurethane hydration process and the reacting of water, above-mentioned reactant is poured in the deionized water of 200～500 weight portions and used high speed dispersion mulser to carry out high speed dispersion emulsification 30～40 minutes, obtain described polyester-type waterborne polyurethane resin.
The invention has the advantages that: waterborne polyurethane resin prepared by the present invention is to complete under unrestricted environmentally friendly solvent dilution, has reached the standard of environmental protection; The viscosity of the polyester-type waterborne polyurethane resin that meanwhile, use methyl acetate obtains as solvent is 20.5～40.2MPas; Particle diameter is 0.102～0.140 μ m, has good dilution and dispersion effect.
Detailed description of the invention
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
Embodiment 1
A kind of waterborne polyurethane resin, is grouped into by the following one-tenth with weight portion:
50 parts of polyester diol,
24.7 parts of toluene di-isocyanate(TDI)s,
6 parts of dihydromethyl propionic acids,
0.05 part of catalyst,
4.5 parts of triethylamines,
30 parts of methyl acetates
7 parts of cosolvents,
350 parts of deionized waters.
Wherein, described polyester diol is PCDL, and described catalyst is dibutyl tin laurate, and described cosolvent is butyl acetate.
A method of preparing above-mentioned waterborne polyurethane resin, comprising:
By 50 parts of PCDLs at 120 DEG C, under vacuum 700mmHg, stir dehydration 2 hours, then under logical nitrogen, add 6 parts of dihydromethyl propionic acids, stir 20 minutes, be cooled to 40 DEG C, add 24.7 parts of toluene di-isocyanate(TDI)s and 0.05 part of dibutyl tin laurate, 80 DEG C of stirrings of constant temperature 3 hours, then add 7 parts of butyl acetates, 80 DEG C of stirrings of constant temperature 0.5 hour, be cooled to 45 DEG C and add 10 parts of methyl acetates and 4.5 parts of triethylamines, 55 DEG C of insulations 35 minutes, add 20 parts of methyl acetates, be cooled to below 10 DEG C, pour above-mentioned reactant into 350 parts of deionized water high speed dispersion and emulsions 30 minutes, obtain polyester-type waterborne polyurethane resin.
Result: the viscosity of product is 30.8MPas; Particle diameter is 0.129 μ m.
Embodiment 2
A kind of waterborne polyurethane resin, is grouped into by the following one-tenth with weight portion:
60 parts of polyester diol,
40 parts of toluene di-isocyanate(TDI)s,
10 parts of dihydromethyl propionic acids,
0.1 part of catalyst,
10 parts of triethylamines,
40 parts of methyl acetates,
10 parts of cosolvents,
500 parts of deionized waters.
Wherein, described polyester diol is selected from polytetrahydrofuran diol, and described catalyst is stannous octoate, and described cosolvent is amyl acetate.
A method of preparing above-mentioned waterborne polyurethane resin, comprising:
By 60 parts of polytetrahydrofuran diols at 130 DEG C, under vacuum 720mmHg, stir dehydration 1.5 hours, then under logical nitrogen, add 10 parts of dihydromethyl propionic acids, stir 25 minutes, be cooled to 42 DEG C, add 40 parts of toluene di-isocyanate(TDI)s and 0.1 part of stannous octoate, 82 DEG C of stirrings of constant temperature 2.5 hours, then add 10 parts of amyl acetates, 82 DEG C of stirrings of constant temperature 0.5 hour, be cooled to 50 DEG C and add 15 parts of methyl acetates and 10 parts of triethylamines, 60 DEG C of insulations 40 minutes, add 25 parts of methyl acetates, be cooled to below 10 DEG C, pour above-mentioned reactant into 500 parts of deionized water high speed dispersion and emulsions 35 minutes, obtain polyester-type waterborne polyurethane resin.
Result: the viscosity of product is 20.5MPas; Particle diameter is 0.102 μ m.
Embodiment 3
A kind of waterborne polyurethane resin, is grouped into by the following one-tenth with weight portion:
45 parts of polyester diol,
20 parts of toluene di-isocyanate(TDI)s,
5 parts of dihydromethyl propionic acids,
0.02 part of catalyst,
4 parts of triethylamines,
10 parts of methyl acetates,
5 parts of cosolvents,
200 parts of deionized waters.
Wherein, described polyester diol is the mixture of polytetrahydrofuran diol and polycaprolactone glycol, and described catalyst is the mixture of dibutyl tin laurate and stannous octoate, and described cosolvent is the mixture of ethyl acetate and isoamyl acetate.
A method of preparing above-mentioned waterborne polyurethane resin, comprising:
By 25 parts of polycaprolactone glycols and 20 parts of polytetrahydrofuran diols at 125 DEG C, under vacuum 750mmHg, stir dehydration 1 hour, then under logical nitrogen, add 5 parts of dihydromethyl propionic acids, stir 30 minutes, be cooled to 45 DEG C, add 20 parts of toluene di-isocyanate(TDI)s and 0.01 part of stannous octoate and 0.01 part of dibutyl tin laurate, 85 DEG C of stirrings of constant temperature 2 hours, then add 4 parts of ethyl acetates and 1 part of isoamyl acetate, 85 DEG C of stirrings of constant temperature 0.5 hour, be cooled to 48 DEG C and add 5 parts of methyl acetates and 4 parts of triethylamines, 50 DEG C of insulations 45 minutes, add 5 parts of methyl acetates, be cooled to below 10 DEG C, pour above-mentioned reactant into 200 parts of deionized water high speed dispersion and emulsions 40 minutes, obtain polyester-type waterborne polyurethane resin.
Result: the viscosity of product is 40.2MPas; Particle diameter is 0.140 μ m.
Embodiment 4
A kind of waterborne polyurethane resin, is grouped into by the following one-tenth with weight portion:
50 parts of polyester-diols,
30 parts of toluene di-isocyanate(TDI)s,
8 parts of dihydromethyl propionic acids,
0.06 part of catalyst,
7 parts of triethylamines,
25 parts of methyl acetates,
8 parts of cosolvents,
400 parts of deionized waters.
Wherein, described polyester-diol is that described polyester-diol is selected from the mixture in polytetrahydrofuran diol, PCDL and polycaprolactone glycol, described catalyst is the mixture of dibutyl tin laurate and stannous octoate, and described cosolvent is the mixture of ethyl acetate and isoamyl acetate.
A method of preparing above-mentioned waterborne polyurethane resin, comprising:
By 15 weight portion polytetrahydrofuran diols, 20 weight part polycarbonate glycol and 15 weight portion polycaprolactone glycols are at 125 DEG C, under vacuum 725mmHg, stir dehydration 1.5 hours, then under logical nitrogen, add 8 parts of dihydromethyl propionic acids, stir 25 minutes, be cooled to 43 DEG C, add 30 parts of toluene di-isocyanate(TDI)s and 0.03 part of stannous octoate and 0.03 part of dibutyl tin laurate, 83 DEG C of stirrings of constant temperature 2.5 hours, then add 2 parts of ethyl acetates, 2 parts of butyl acetates, 2 parts of amyl acetates and 2 parts of isoamyl acetates, 82 DEG C of stirrings of constant temperature 0.5 hour, be cooled to 47 DEG C and add 10 parts of methyl acetates and 7 parts of triethylamines, 55 DEG C of insulations 40 minutes, add again 15 parts of methyl acetates, be cooled to below 10 DEG C, pour above-mentioned reactant into 400 parts of deionized water high speed dispersion and emulsions 35 minutes, obtain polyester-type waterborne polyurethane resin.
Result: the viscosity of product is 27.6MPas; Particle diameter is 0.124 μ m.
In each embodiment of the present invention, chemical industry material used is material used in the production of this area, all can from market, obtain, and can not exert an influence for production result; The equipment of using in each operation, all adopts conventional equipment used in current production, there is no special feature.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement. Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (1)
1. a waterborne polyurethane resin, is characterized in that, is grouped into by the following one-tenth with weight portion:
60 parts of polyester diol,
40 parts of toluene di-isocyanate(TDI)s,
10 parts of dihydromethyl propionic acids,
0.1 part of catalyst,
10 parts of triethylamines,
40 parts of methyl acetates,
10 parts of cosolvents,
500 parts of deionized waters;
Described polyester diol is selected from polytetrahydrofuran diol, and described catalyst is stannous octoate, and described cosolvent is amyl acetate;
The preparation method of described waterborne polyurethane resin, comprises the following steps:
(1) dehydration: the polytetrahydrofuran diol of 60 weight portions is stirred under 130 DEG C, vacuum 720mmHg to dehydration 1.5 hours;
(2) once cooling: then add the dihydromethyl propionic acid of 10 weight portions under logical nitrogen, stir 25 minutes, be cooled to 42 DEG C;
(3) base polyurethane prepolymer for use as reaction: add the toluene di-isocyanate(TDI) of 40 weight portions and the stannous octoate of 0.1 weight portion, 82 DEG C of stirrings of constant temperature 2.5 hours;
(4) reducing temperature twice: add the amyl acetate of 10 weight portions, 82 DEG C of stirrings of constant temperature 0.5 hour, are cooled to 50 DEG C;
(5) neutralization reaction: add the methyl acetate of 15 weight portions and the triethylamine of 10 parts by weight, be incubated 40 minutes at 60 DEG C, then add the methyl acetate of 25 parts;
(6) cooling emulsification: be cooled to below 10 DEG C, above-mentioned reactant poured in the deionized water of 500 weight portions and used high speed dispersion mulser to carry out high speed dispersion emulsification 35 minutes, obtain described polyester-type waterborne polyurethane resin;
Described waterborne polyurethane resin, viscosity is 20.5MPas; Particle diameter is 0.102 μ m.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102977282B (en) * | 2012-12-06 | 2014-06-04 | 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 |
| 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 |
| CN107641190B (en) * | 2017-09-22 | 2020-10-09 | 常熟国和新材料有限公司 | Waterborne polyurethane resin emulsion and preparation method thereof |
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2011
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| CN1742053A (en) * | 2003-09-26 | 2006-03-01 | 大日本油墨化学工业株式会社 | Water base dispersion of polyurethaneresin, and water base adhesive and water base primer coating agent containing the same |
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| CN102046686A (en) * | 2008-05-29 | 2011-05-04 | 宇部兴产株式会社 | Aqueous polyurethane resin dispersion, manufacturing method thereof, and paint composition containing the same |
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