CN105131239A - Water resistance solvent-free polyurethane emulsion and preparation method thereof - Google Patents
Water resistance solvent-free polyurethane emulsion and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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Abstract
The invention relates to water resistance solvent-free polyurethane emulsion and a preparation method thereof. The method includes the following steps that (1) DMBA and polyhydric alcohol are added into a reactor to be heated until the temperature is 70-100 DEG C, and the DMBA is fully dissolved in the polyhydric alcohol; a catalyst is added to be evenly stirred, then isocyanate is added slowly, reacting is conducted for 2-4 hours at the temperature of 70-100 DEG C, and accordingly a polyurethane prepolymer is obtained; (2) a salt-forming agent and an outer emulsifier are added into the prepolymer, and reacting is conducted for 5-20 minutes at the temperature of 70-100 DEG C; water with the weight being 1-3 times of the weight of the prepolymer is added, high-speed dispersion is performed for 5-10 minutes at the rotating speed of 1500 rpm and above, and pre-dispersion is conducted; (3) a polyamine post-chain extender is added into pre-dispersion emulsion drop by drop, high-speed stirring is continuously conducted for 10-20 minutes, and waterborne polyurethane emulsion is obtained. The inner and outer emulsification synergetic method is adopted, the hydrophilic chain extender which is not enough for emulsification and a surface active agent which is not enough for emulsification are added, quite stable emulsion can be obtained, and good water resistance is achieved after drying and film forming.
Description
Technical field
The present invention relates to a kind of preparation method of aqueous polyurethane, be specifically related to a kind of water tolerance no-solvent polyurethane emulsion and preparation method thereof, belong to chemical technology field.
Background technology
The technology of preparing of aqueous polyurethane is comparatively ripe, by isocyanic ester, polyvalent alcohol and hydrophilic chain extender synthesis of polyurethane performed polymer, shears dispersion form stable emulsion in water high speed.Form the key of emulsion and be hydrophilic chain extender, generally have anionic and cationic, anionic mainly contain dimethylol propionic acid (DMPA), cationic mainly contains diethanolamine etc.
The preparation technology of aqueous polyurethane is more, prevailing technology is generally acetone method, for improving the performance of aqueous polyurethane, the performed polymer of synthesis makes molecular weight high as far as possible, and makes monomer reaction complete, causes performed polymer viscosity larger, acetone viscosity reduction is progressively added in building-up process, add fashionable needs at DMPA is first dissolved in DMF solvent by solid DMPA simultaneously, for making emulsion-stabilizing, needs to add hydrophilic chain extender as far as possible.After adding emulsifying water, by distillation by most of acetone separation out, but unavoidably still there is a small amount of solvent.
Owing to adding a large amount of hydrophilic chain extender, while stability of emulsion improves, after aqueous polyurethane emulsion drying and forming-film, same wetting ability is very strong, causes water tolerance poor.For improving the water tolerance of aqueous polyurethane, have now been developed a lot of technological method, as organic-silicon-modified, epoxy resin modification, acrylate modified, aziridine is crosslinked, improves water tolerance in various degree.
The preparation method that patent application CN101759843A discloses a kind of innoxious negative ion aqueous polyurethane and the aqueous polyurethane prepared by the method, described method comprises: mixed according to mol ratio 2.5-4 with aliphatic dihydroxy alcohol by dicyclohexyl methane diisocyanate, react at 70-90 DEG C and obtain performed polymer in 3-5 hour, add the dimethylolpropionic acid containing hydrophilic radical, reaction 3-5 hour, add the aqueous solution emulsion dispersion of KOH, drip diamine chain stretching agent chain extension, obtain a kind of aqueous polyurethane emulsion.
But what adopt in the above-described techniques is still conventional internal emulsification method, and the chain extension after emulsification adopts the diamine such as quadrol, butanediamine, and polyurethane molecular chain is linear structure.The preparation of current aqueous polyurethane almost all adopts internal emulsification method, is namely reacted on polyurethane molecular chain by hydrophilic chain extender, makes polyurethane molecular chain have wetting ability.Hydrophilic chain extender just has after must reaching certain content can emulsifying property, but more hydrophilic chain extender make urethane drying after water tolerance be deteriorated.Early stage aqueous polyurethane once adopted outer emulsion process, namely in performed polymer, added tensio-active agent, prepared emulsion by high speed dispersion, but stability of emulsion prepared by outer emulsion process is poor.
Summary of the invention
The object of the invention is for the defect in aqueous polyurethane preparation method, and the problem of poor water resistance after aqueous polyurethane film forming, a kind of preparation method of water tolerance no-solvent polyurethane emulsion is provided, comprises the following steps:
(1) dimethylolpropionic acid (DMBA) and polyvalent alcohol are added in reactor, be heated to 70 DEG C-100 DEG C and DMBA is fully dissolved in polyvalent alcohol; Add catalyzer, after stirring, slowly add isocyanic ester, at 70 DEG C-100 DEG C reaction 2-4h, obtain base polyurethane prepolymer for use as;
(2) in performed polymer, add salt forming agent and outer emulsifying agent, at 70 DEG C-100 DEG C, react 5-20min; Add the water of performed polymer 1-3 times weight, high speed dispersion 5-10min under the rotating speed of more than 1500rpm, carry out pre-dispersed;
(3) chainextender after polynary amine is dropwise joined in pre-dispersed emulsion, continue high-speed stirring 10-20min, obtain aqueous polyurethane emulsion.
Described polyvalent alcohol includes but not limited to: one or more in the polyester polyol of 500-3000 molecular weight, polyether glycol, polycarbonate polyol, polybutadiene polyol; Or in the polyvalent alcohol of above-mentioned 500-3000 molecular weight one or more with lower than the mixture of the polyvalent alcohol of 400 molecular weight, the described polyvalent alcohol lower than 400 molecular weight includes but not limited to: one or more in ethylene glycol, butyleneglycol, glycol ether, glycerol, tetramethylolmethane.
Described isocyanic ester includes but not limited to: one or more in IPDI, TDI, MDI, PAPI, HDI, XDI, NDI and above-mentioned derivative.
Described catalyzer includes but not limited to: dibutyl tin laurate, stannous octoate, isocaprylic acid bismuth, one or more in lauric acid bismuth.
The consumption of described catalyzer is preferably the 0-0.05% of the total amount of polyvalent alcohol, dimethylolpropionic acid and isocyanic ester, uses when MDI can not use catalyzer at isocyanic ester.
Described salt forming agent includes but not limited to: triethylamine, NaHCO
3, KHCO
3, one or more in KOH, preferred triethylamine.
Described rear chainextender includes but not limited to: one or more in the water-soluble polyamines such as quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, hexanediamine.
Described outer emulsifying agent includes but not limited to: one or more in the anion surfactants such as fatty alcohol-polyoxyethylene ether, isomery fatty alcohol-ether, alkylphenol polyoxyethylene, and the HLB value of single or composition is 10-14.
Further, in above-mentioned steps, isocyanic ester and polyol mole ratio are 1.5-3.5:1, are preferably 2-2.5:1; The mol ratio of polyvalent alcohol and dimethylolpropionic acid is 1.2-1.8:1, is preferably 1.5-1.6:1; The mol ratio of salt forming agent and dimethylolpropionic acid is 0.9-1:1; The addition of outer emulsifying agent is the 0.3-1% of isocyanic ester, polyvalent alcohol, dimethylolpropionic acid gross weight, is preferably 0.4-0.6%; The mol ratio of isocyanic ester and polyvalent alcohol, DMBA, rear chainextender three total amount is 1.0-1.1:1, is preferably 1.02-1.05:1; The solid content of described emulsion is 25%-50%.
The present invention also provides a kind of water tolerance urethane obtained by aforesaid method, and described water tolerance urethane can be widely used in the fields such as synthetic leather dip resin, coating, tackiness agent.
The technical superiority that the present invention has and beneficial effect as follows:
(1) the present invention adopts the method that inside and outside emulsification is worked in coordination with, and adds the hydrophilic chain extender being not enough to emulsifying amount and the tensio-active agent being not enough to emulsifying amount, can obtain highly stable emulsion, and have good water tolerance after drying and forming-film.
(2) easily molten anionic hydrophilic chainextender dimethylolpropionic acid (DMBA) is adopted.Conventional dimethylol propionic acid (DMPA) very indissoluble, just can add polymerization after dissolving in a large amount of DMF or tetrahydrofuran solvent, DMF boiling point is higher, can not steam during distillation.Namely DMBA can dissolve in raw polyol, does not need to add additional solvent.
(3) chain extension after polyamine in water.Adopt mass polymerization, the base polyurethane prepolymer for use as that synthesis viscosity is lower, form emulsion after adding emulsifying water, add polyamine (as quadrol, diethylenetriamine, triethylene tetramine etc.) chain extension afterwards, molecular weight is increased, and improves water tolerance.
Accompanying drawing explanation
Fig. 1: the process route chart of preparation method of the present invention.
Embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technique means used in the present invention is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, but not limits the scope of the invention, and the spirit and scope of the invention only limited by claims.To those skilled in the art, under the prerequisite not deviating from essence of the present invention and scope, the various change carry out the material component in these embodiments and consumption or change also belong to protection scope of the present invention.
Embodiment 1:
In the there-necked flask that stirring and temperature regulating device are housed, add 160gPTMG2000 and 8.88g dimethylolpropionic acid, drip 1 dibutyltin dilaurate catalyst, be heated to 70 DEG C, after DMBA dissolves completely, add 44.4gIPDI, be warming up to 100 DEG C of reactions 3 hours.Be cooled to 70 DEG C, add 6.07g triethylamine, reaction 10min, adds 1.06g fatty alcohol-polyoxyethylene ether AEO-7, continues reaction 10min.Add 480g water, form emulsion at 1500rpm high-speed stirring 5min.3.1g diethylenetriamine is dissolved in 32g water, slowly adds in emulsion, continue high-speed stirring 20min, form half milky aqueous polyurethane emulsion.Record emulsion solid content 30%, drying and forming-film back draft intensity 35MPa, elongation at break 550%, saturated water absorption 3.0%.
Embodiment 2:
70gPTMG2000,70gPPG2000,0.9g1 is added in the there-necked flask that stirring and temperature regulating device are housed, 4-butyleneglycol, 10.4g dimethylolpropionic acid, drip 1 isocaprylic acid bismuth catalyst, be heated to 80 DEG C, add 44.4gIPDI after DMBA dissolves completely, be warming up to 100 DEG C of reactions 2 hours.Be cooled to 80 DEG C, add 6.4g triethylamine, reaction 5min, add 1g isomery fat tridecanol ether fatty alcohol and 0.25g Soxylat A 25-7 AEO-7, continue reaction 5min.Add 190g water, form emulsion at 1500rpm high-speed stirring 10min.3.1g diethylenetriamine is dissolved in 12g water, slowly adds in emulsion, continue high-speed stirring 10min, form half milky aqueous polyurethane emulsion.Record emulsion solid content 50%, drying and forming-film back draft intensity 28MPa, elongation at break 700%, saturated water absorption 3.5%.
Embodiment 3:
In the there-necked flask that stirring and temperature regulating device are housed, add 112gPPG2000,48g polyester polyol 2000 and 8.88g dimethylolpropionic acid, be heated to 70 DEG C, after DMBA dissolves completely, add 50gMDI, be warming up to 75 DEG C of reactions 3 hours.Be cooled to 70 DEG C, add 6gKHCO
3reaction 10min, adds 0.1g fatty alcohol-polyoxyethylene ether AEO-3,0.5gAEO-7,0.6g alkylphenol polyoxyethylene OP-10, continues reaction 10min.Add 480g water, form emulsion at 1500rpm high-speed stirring 5min.0.7g quadrol and 2.4g triethylene tetramine are dissolved in 32g water, slowly add in emulsion, continue high-speed stirring 20min, form half milky aqueous polyurethane emulsion.Record emulsion solid content 30%, drying and forming-film back draft intensity 37MPa, elongation at break 500%, saturated water absorption 2.6%.
Embodiment 4:
168gPPG3000,32g polycarbonate polyol 2000 and 8.88g dimethylolpropionic acid is added in the there-necked flask that stirring and temperature regulating device are housed, drip 1 isocaprylic acid bismuth catalyst, be heated to 70 DEG C, 18.8gXDI and 26.2g hydrogenation MDI is added after DMBA dissolves completely, be warming up to 90 DEG C of reactions after 3 hours, add 0.7g1,4-butyleneglycol continues reaction 0.5 hour, be cooled to 70 DEG C, add 3.4gNaHCO
3and 1.1gKOH, reaction 10min, adds 0.9g fatty alcohol-polyoxyethylene ether AEO-7 and 0.3g alkylphenol polyoxyethylene OP-10, continues reaction 10min.Add 750g water, form emulsion at 1500rpm high-speed stirring 5min.2.1g diethylenetriamine and 0.6g quadrol are dissolved in 27g water, slowly add in emulsion, continue high-speed stirring 20min, form half milky aqueous polyurethane emulsion.Record emulsion solid content 25%, drying and forming-film back draft intensity 23MPa, elongation at break 900%, saturated water absorption 3.0%.
Claims (10)
1. a preparation method for water tolerance no-solvent polyurethane emulsion, comprises the following steps:
(1) dimethylolpropionic acid and polyvalent alcohol are added in reactor, be heated to 70 DEG C-100 DEG C and dimethylolpropionic acid is fully dissolved in polyvalent alcohol; Add catalyzer, after stirring, slowly add isocyanic ester, at 70 DEG C-100 DEG C reaction 2-4h, obtain base polyurethane prepolymer for use as;
(2) in performed polymer, add salt forming agent and outer emulsifying agent, at 70 DEG C-100 DEG C, react 5-20min; Add water, high speed dispersion 5-10min under the rotating speed of more than 1500rpm, carry out pre-dispersed;
(3) chainextender after polynary amine is dropwise joined in pre-dispersed emulsion, continue high-speed stirring 10-20min, obtain aqueous polyurethane emulsion.
2. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 1, it is characterized in that, described polyvalent alcohol includes but not limited to: one or more in the polyester polyol of 500-3000 molecular weight, polyether glycol, polycarbonate polyol, polybutadiene polyol; Or in the polyvalent alcohol of above-mentioned 500-3000 molecular weight one or more with lower than the mixture of the polyvalent alcohol of 400 molecular weight, the described polyvalent alcohol lower than 400 molecular weight includes but not limited to: one or more in ethylene glycol, butyleneglycol, glycol ether, glycerol, tetramethylolmethane.
3. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 1, it is characterized in that, described isocyanic ester includes but not limited to: one or more in IPDI, TDI, MDI, PAPI, HDI, XDI, NDI and above-mentioned derivative.
4. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 1, it is characterized in that, described salt forming agent includes but not limited to: triethylamine, NaHCO
3, KHCO
3, KOH.
5. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 1, it is characterized in that, described catalyzer includes but not limited to: dibutyl tin laurate, stannous octoate, isocaprylic acid bismuth, one or more in lauric acid bismuth; The consumption of described catalyzer is: the 0-0.05% of the total amount of polyvalent alcohol, DMBA and isocyanic ester.
6. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 1, it is characterized in that, described rear chainextender includes but not limited to: one or more in the water-soluble polyamines such as quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, hexanediamine.
7. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 1, it is characterized in that, described outer emulsifying agent includes but not limited to: one or more in the anion surfactants such as fatty alcohol-polyoxyethylene ether, isomery fatty alcohol-ether, alkylphenol polyoxyethylene, and the HLB value of single or composition is at 10-14.
8. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 1, it is characterized in that, isocyanic ester and polyol mole ratio are 1.5-3.5:1; The mol ratio of polyvalent alcohol and dimethylolpropionic acid is 1.2-1.8:1; The mol ratio of salt forming agent and dimethylolpropionic acid is 0.9-1:1; Outer emulsifying agent addition is the 0.3-1% of isocyanic ester, polyvalent alcohol, dimethylolpropionic acid gross weight; The mol ratio of isocyanic ester and polyvalent alcohol, DMBA, rear chainextender three total amount is 1.0-1.1:1; Described emulsion solid content is 25%-50%.
9. the preparation method of a kind of water tolerance no-solvent polyurethane emulsion as claimed in claim 8, it is characterized in that, isocyanic ester and polyol mole ratio are 2-2.5:1; The mol ratio of polyvalent alcohol and dimethylolpropionic acid is 1.5-1.6:1; Outer emulsifying agent addition is the 0.4-0.6% of isocyanic ester, polyvalent alcohol, dimethylolpropionic acid gross weight; The mol ratio of isocyanic ester and polyvalent alcohol, DMBA, rear chainextender three total amount is 1.02-1.05:1.
10. the water tolerance no-solvent polyurethane emulsion prepared by the arbitrary described method of claim 1-9.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860025A (en) * | 2016-06-15 | 2016-08-17 | 东北林业大学 | Functional cross-linking agent isocyanate microcapsules and preparation method thereof |
| CN105968309A (en) * | 2016-06-27 | 2016-09-28 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane resin for synthetic leather fabric and preparation method thereof |
| CN106047134A (en) * | 2016-07-27 | 2016-10-26 | 上海巨峰化工有限公司 | Water-based polyurethane coating and preparation method thereof |
| CN106750149A (en) * | 2016-11-28 | 2017-05-31 | 陕西科技大学 | A kind of preparation method and application method of expansion type aqueous polyurethane |
| CN106750117A (en) * | 2016-11-28 | 2017-05-31 | 陕西科技大学 | A kind of aqueous polyurethane continuous synthesis method based on impingement mix and continuous emulsification |
| CN108424507A (en) * | 2017-02-15 | 2018-08-21 | 和友纺织股份有限公司 | The method for making aqueous polyurethane dispersing liquid with solvent-free processing procedure |
| WO2018184307A1 (en) * | 2017-04-07 | 2018-10-11 | 中国科学院长春应用化学研究所 | Waterborne polyurethane dispersion and solvent-free preparation method thereof |
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| CN109485827A (en) * | 2018-10-26 | 2019-03-19 | 湖北大学 | A kind of preparation method of aqueous polyurethane |
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| CN111662423A (en) * | 2020-06-16 | 2020-09-15 | 中国科学院山西煤炭化学研究所 | Preparation method of hydroxyl functionalized waterborne polyurethane |
| WO2022014398A1 (en) * | 2020-07-17 | 2022-01-20 | 台湾日華化学工業股▲フン▼有限公司 | Aqueous polyurethane resin composition and polyurethane film |
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| CN105968309A (en) * | 2016-06-27 | 2016-09-28 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane resin for synthetic leather fabric and preparation method thereof |
| CN105968309B (en) * | 2016-06-27 | 2018-10-26 | 合肥科天水性科技有限责任公司 | A kind of waterborne polyurethane resin and preparation method thereof for synthetic leather fabric |
| CN106047134A (en) * | 2016-07-27 | 2016-10-26 | 上海巨峰化工有限公司 | Water-based polyurethane coating and preparation method thereof |
| CN106750149A (en) * | 2016-11-28 | 2017-05-31 | 陕西科技大学 | A kind of preparation method and application method of expansion type aqueous polyurethane |
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| CN106750117B (en) * | 2016-11-28 | 2019-08-13 | 陕西科技大学 | A kind of aqueous polyurethane continuous synthesis method based on impingement mix and continuous emulsification |
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| CN108424507A (en) * | 2017-02-15 | 2018-08-21 | 和友纺织股份有限公司 | The method for making aqueous polyurethane dispersing liquid with solvent-free processing procedure |
| WO2018184307A1 (en) * | 2017-04-07 | 2018-10-11 | 中国科学院长春应用化学研究所 | Waterborne polyurethane dispersion and solvent-free preparation method thereof |
| CN110770270B (en) * | 2017-06-22 | 2021-12-07 | 东洋高分子股份有限公司 | Aqueous polyurethane dispersion, process for producing aqueous polyurethane dispersion, aqueous coating composition, and coating film |
| CN110770270A (en) * | 2017-06-22 | 2020-02-07 | 东洋高分子股份有限公司 | Aqueous polyurethane dispersion, process for producing aqueous polyurethane dispersion, aqueous coating composition, and coating film |
| CN109485827A (en) * | 2018-10-26 | 2019-03-19 | 湖北大学 | A kind of preparation method of aqueous polyurethane |
| CN109485827B (en) * | 2018-10-26 | 2021-02-19 | 湖北大学 | Preparation method of waterborne polyurethane |
| CN111662423A (en) * | 2020-06-16 | 2020-09-15 | 中国科学院山西煤炭化学研究所 | Preparation method of hydroxyl functionalized waterborne polyurethane |
| WO2022014398A1 (en) * | 2020-07-17 | 2022-01-20 | 台湾日華化学工業股▲フン▼有限公司 | Aqueous polyurethane resin composition and polyurethane film |
| CN114573780B (en) * | 2020-12-02 | 2023-12-19 | 万华化学集团股份有限公司 | Self-foaming polyurethane or polyurea water dispersion, preparation method and application |
| CN114805735A (en) * | 2022-03-31 | 2022-07-29 | 杭州海维特化工科技有限公司 | Solvent-free synthesis method of waterborne polyurethane resin emulsion |
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