CN106632969B - Hydroxyl polyurethane aqueous dispersion body and its preparation method and application - Google Patents
Hydroxyl polyurethane aqueous dispersion body and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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Abstract
The invention discloses a kind of hydroxyl polyurethane aqueous dispersion bodies and its preparation method and application.Hydroxyl polyurethane aqueous dispersion body obtains the polyurethane prepolymer containing carboxyl and carbon-carbon double bond by polyaddition, is first added in neutralizer and carboxyl is to alkalescent, obtain carbon-carbon double bonds polyurethane prepolymer；It adds and is further reacted containing mercaptoalcohol with photoinitiator, obtain hydroxyl base polyurethane prepolymer for use as, deionized water progress water dispersion is then added and obtains.Defoaming agent, thickener and water are added in obtained hydroxyl polyurethane aqueous dispersion body, is mixed evenly, and dye sand base paint is used to prepare；Aqueous color paste, polyisocyanate curing agent, wetting agent and white sand are added in base paint, are mixed evenly, 60~80 DEG C dry to obtain aqueous color sand.It is 1.32~6.11Wt% that the present invention, which can control hydroxy radical content, and the position of hydroxyl is controllable, and high with isocyanates reactivity, dried coating film speed is fast, and the wearability of artificial color sand can be improved.
Description
Technical field
The present invention relates to polyurethane-type high molecular materials, in particular to a kind of hydroxyl polyurethane aqueous dispersion body and its preparation
Methods and applications.
Background technique
Artificial color sand is by having the characteristics of bright-colored, color great variety of goods made of natural sand dye system.It is artificial color
Sand is mainly used for building inside and outside wall lacquer, and market demand is very big.
The technology of preparing of artificial color sand currently on the market mainly has high temperature sintering and resin to coat two kinds of fixation.High temperature is burnt
Color sand lovely luster, the good weatherability of preparation are tied, but production process need to use more raw material, process is complicated, and production efficiency is low, energy consumption
It is high.Resin coats the method for fixation then mainly by the single, double component acrylic resin of solvent type, epoxy resin or Organic fluoride, silicon
Resin carrys out fixation, and this preparation method is needed during the preparation of resin and dye sand with a large amount of based on solvent-based system
Solvent, VOC emission amount is high, is unfavorable for environmental protection.
To adapt to environmental requirement, artificial color sand is prepared using water-base resin and has Primary Study and exploration, is mainly had aqueous
Acrylic resin and aqueous epoxy resins, the application study to water-based hydroxyl polyurethane resin in this field have not been reported, and gather
Urethane has the advantages that the protrusions such as wearability is good, flexibility is good, is highly suitable for the fixation of aqueous color sand.But existing aqueous hydroxyl
Based polyurethanes naval stores less varieties and price height are more generally using polyol such as pentaerythrite as hydroxyl source
The hydroxy compounds extent of reaction more difficult to control during the preparation process easily forms gel and reaction is caused to fail.
Summary of the invention
Present invention aim to overcome the shortcomings of the prior art, it is scattered to provide a kind of hydroxyl polyurethane aqueous
Body and its preparation method and application.
To achieve the above object, the present invention provides a kind of hydroxyl polyurethane aqueous dispersion bodies, its special feature is that: it
It is that the polyurethane prepolymer of carboxyl and carbon-carbon double bond is obtained by polyaddition, is first added in neutralizer and carboxyl to weak base
Property, obtain carbon-carbon double bonds polyurethane prepolymer；It adds and is further reacted containing mercaptoalcohol with photoinitiator, it is poly- to obtain hydroxyl
Then urethane performed polymer is added deionized water and carries out water dispersion, obtains hydroxyl polyurethane aqueous dispersion body.
The preparation method of above-mentioned hydroxyl polyurethane aqueous dispersion body, comprising the following steps:
1) preparation of carbon-carbon double bonds polyurethane prepolymer:
The oligomer dihydric alcohol of 25~50 parts by weight, the diisocyanate of 10~25 parts by weight, 1~10 parts by weight are contained
The dihydric alcohol of carbon-carbon double bond, the hydrophilic chain extender of 2~5 parts by weight, the acetone of 26~45 parts by weight, 0.01~0.1 parts by weight have
Machine tin catalyst is added in reaction kettle, is warming up to 70~80 DEG C under stiring, and after reacting 1~3h, 3~10 parts by weight are added
Carbon-carbon double bonds monohydric alcohol and the acetone of 26~45 parts by weight the reaction was continued 1~3h, obtain the poly- ammonia containing carboxyl and carbon-carbon double bond
Ester prepolymer, the neutralizer for adding 5~10 parts by weight carry out neutralization reaction, obtain the polyurethane prepolymer of carbon-carbon double bonds；
2) preparation of hydroxyl polyurethane aqueous dispersion body:
3~15 parts by weight are added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1) contains mercaptoalcohol, 0.1
The photoinitiator of~3 parts by weight further reacts 3~20h under the irradiation of UV light, obtains the base polyurethane prepolymer for use as of hydroxyl,
The deionized water that 200~320 parts by weight are added under high-speed stirred carries out water dispersion, obtains hydroxyl polyurethane water after removing acetone
Dispersion.
In the present invention, the average molecular weight of the oligomer dihydric alcohol is 500~3000, hydroxyl average functionality is 2~
2.5, wherein the parts by weight of polybutadiene dihydric alcohol are the 5%~30% of oligomer dihydric alcohol.
In the present invention, the diisocyanate is 1, and hexamethylene-diisocyanate, isophorone diisocyanate, toluene two are different
The mixture of one or more of cyanate, methyl diphenylene diisocyanate.
In the present invention, the dihydric alcohol of the carbon-carbon double bonds is selected from cis-2-butene-Isosorbide-5-Nitrae-glycol, hexadiene -3 1,5'-,
4- glycol, 5,5'- diallyl -2,2'- '-biphenyl diphenol or bis- (the methylol) -1,3- propylene glycol diacrylates of 2,2'-.
In the present invention, the carbon-carbon double bonds monohydric alcohol is selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, acrylic acid
Hydroxypropyl acrylate, 3- (acryloxy) -2- hydroxy propyl methacrylate or pentaerythritol triacrylate.
In the present invention, the hydrophilic chain extender is selected from dihydromethyl propionic acid or dimethylolpropionic acid；It is described organotin catalyzed
Agent is dibutyl tin dilaurate or stannous octoate.
In the present invention, the neutralizer be one of triethylamine, triethanolamine, ammonium hydroxide, potassium hydroxide, sodium hydroxide or
It is several.
In the present invention, it is described containing mercaptoalcohol be selected from 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 3- sulfydryl -1,2-PD,
3- sulfydryl -1- hexanol, 6- sulfydryls hexanol, any one or a few in 4- sulfydryl-n-butyl alcohol mixture.
In the present invention, the photoinitiator is selected from dimethoxybenzoin or 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Application the present invention also provides above-mentioned hydroxyl polyurethane aqueous dispersion body in manually dye sand field.Hydroxyl is gathered
Urethane aqueous dispersion is used for the colouring method of aqueous color sand, comprising the following steps:
1) defoaming agent, thickener and water are added in obtained hydroxyl polyurethane aqueous dispersion body, are mixed evenly,
It is used to prepare dye sand base paint, the parts by weight of each component are as follows:
2) aqueous color paste, polyisocyanate curing agent, wetting agent and white sand are added in base paint, are mixed evenly,
60~80 DEG C dry to obtain aqueous color sand, and the parts by weight of each component are as follows:
The beneficial effects of the present invention are: the controllable hydroxy radical content of present invention gained hydroxyl polyurethane aqueous dispersion body is
1.32~6.11Wt%, and the position of hydroxyl is controllable, the hydroxyl that can design water-based hydroxyl polyurethane resin is secondary hydroxyl, and different
Cyanate has very high reactivity, and dried coating film speed is fast；Polybutadiene diol is accessed on hydroxyl polyurethane structural
It is modified, reinforced resin wearability, to improve the wearability of artificial color sand.Hydroxyl polyurethane aqueous dispersion body is being prepared and is being applied
In the process, VOC content is substantially zeroed, extremely friendly to environment；Using hydroxyl polyurethane aqueous dispersion body prepared by the present invention
For the preparation of aqueous artificial color sand, being prepared into aqueous artificial color sand has preferable wearability and water-fast solvent resistance, can
For paint field.
Specific embodiment
In order to better explain the present invention, below in conjunction with specific embodiment, the present invention is described in further detail, but
Limiting the invention for they.
Embodiment 1
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 25.5g average molecular weight be 1000 polyether Glycols, 6.6g average molecular weight be 1000 polybutadiene two
Band is added in alcohol, 17g toluene di-isocyanate(TDI), 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g acetone
In the reaction flask of stirring, 0.02g dibutyl tin dilaurate is added dropwise, is warming up to 75 DEG C, it, first will be by 3.98g third after reacting 2.5h
The solution of olefin(e) acid hydroxyl ethyl ester and 10g acetone composition is slowly dropped into reaction flask, and keeping temperature, that the reaction was continued is anti-to isocyanate group
After answering, system is cooled to 28 DEG C, adds 2.17g triethylamine neutralization reaction 35min, it is pre- to obtain carbon-carbon double bonds polyurethane
Polymers；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2- hydroxy-2-methyl -1- the phenyl-of 0.5g is added into the resulting carbon-carbon double bonds polyurethane prepolymer of step 1)
The 2 mercapto ethanol of 1- acetone and 3.68g, reaction system are placed in 1.8mW/Cm2After reacting at room temperature 4h under ultraviolet light irradiation, it is added
90g deionized water, after high speed dispersion 40min, it is 1.32Wt% that de- acetone, which obtains hydroxy radical content, solid containing the poly- ammonia of hydroxyl for being 40%
Ester aqueous dispersion.
Embodiment 2
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 24.5g average molecular weight be 1000 polyester diol, 5.6g average molecular weight be 1000 polybutadiene two
Band is added in alcohol, 17g toluene di-isocyanate(TDI), 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g acetone
In the reaction flask of stirring, 0.02g dibutyl tin dilaurate is added dropwise, is warming up to 75 DEG C, it, first will be by 3.98g third after reacting 2.5h
The solution of olefin(e) acid hydroxyl ethyl ester and 10g acetone composition is slowly dropped into reaction flask, and keeping temperature, that the reaction was continued is anti-to isocyanate group
After answering, system is cooled to 28 DEG C, adds 2.17g triethylamine neutralization reaction 35min, obtains the polyurethane of carbon-carbon double bonds
Prepolymer；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2.27g photoinitiator 2- hydroxyl -2- first is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
3- sulfydryl -1,2 propylene glycol of base -1- phenyl -1- acetone and 5.09g, reaction system are placed in 1.8mW/Cm2Room under ultraviolet light irradiation
After temperature reaction 7h, 70g deionized water is added, after high speed dispersion 40min, it is 2.21Wt% that de- acetone, which obtains hydroxy radical content, it is solid contain be
40% hydroxyl polyurethane aqueous dispersion body.
Embodiment 3
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 50g average molecular weight be 2000 polyether Glycols, 5.6g average molecular weight be 1000 polybutadiene diol,
22.4g isophorone diisocyanate, 2.49g cis-2-butene -1,4- glycol, 2.89g dihydromethyl propionic acid and 20g acetone add
Enter in the reaction flask with stirring, 0.02g dibutyl tin dilaurate is added dropwise, is warming up to 75 DEG C, it, first will be by after reacting 2.5h
The solution of 3- (acryloxy) -2- hydroxy propyl methacrylate and 10g the acetone composition of 6.56g is slowly dropped into reaction flask
In, keep temperature the reaction was continued 2h to isocyanate group after completion of the reaction, system is cooled to 28 DEG C, adds 2.17g triethylamine
Neutralization reaction 35min obtains the polyurethane prepolymer of carbon-carbon double bonds；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2.33g photoinitiator 2- hydroxyl -2- first is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
The 2 mercapto ethanol of base -1- phenyl -1- acetone and 5.59g, reaction system are placed in 1.8mW/Cm2It is reacted at room temperature under ultraviolet light irradiation
After 6h, 160g deionized water is added, after high speed dispersion 40min, it is 1.53Wt% that de- acetone, which obtains hydroxy radical content, solid containing being 38%
Hydroxyl polyurethane aqueous dispersion body.
Embodiment 4
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 24.5g average molecular weight be 1000 polyester diol, 5.6g average molecular weight be 1000 polybutadiene two
Alcohol, 24.6g methyl diphenylene diisocyanate, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g third
Ketone is added in the reaction flask with stirring, and 0.01g stannous octoate is added dropwise, and is warming up to 75 DEG C, first will be by 6.56g's after reacting 2.5h
The solution of 3- (acryloxy) -2- hydroxy propyl methacrylate and 10g acetone composition is slowly dropped into reaction flask, is kept
After completion of the reaction to isocyanate group, system is cooled to 28 DEG C to temperature the reaction was continued 2h, adds 2.17g triethylamine neutralization reaction
35min obtains the polyurethane prepolymer of carbon-carbon double bonds；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2.33g photoinitiator 2- hydroxyl -2- first is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
3- sulfydryl -1,2-PD of base -1- phenyl -1- acetone and 7.75g, reaction system are placed in 1.8mW/Cm2Under ultraviolet light irradiation
After reacting at room temperature 10h, 130g deionized water is added, after high speed dispersion 40min, it is 3.26Wt% that de- acetone, which obtains hydroxy radical content, Gu
Containing the hydroxyl polyurethane aqueous dispersion body for 36%.
Embodiment 5
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 27.6g average molecular weight be 1000 polyether Glycols, 2.8g average molecular weight be 1000 polybutadiene two
Band is added in alcohol, 16.5g hexamethylene diisocyanate, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g acetone
In the reaction flask of stirring, 0.02g dibutyl tin dilaurate is added dropwise, is warming up to 75 DEG C, it, first will be by 9.13g season after reacting 2.5h
The solution of penta tetrol triacrylate and 10g acetone composition is slowly dropped into reaction flask, keeps temperature the reaction was continued 2h to isocyanide
After completion of the reaction, system is cooled to 28 DEG C to perester radical, adds 2.17g triethylamine neutralization reaction 35min, obtains carbon-carbon double bonds
Polyurethane prepolymer；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2.46g photoinitiator 2- hydroxyl -2- first is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
The 2 mercapto ethanol of base -1- phenyl -1- acetone and 7.49g, reaction system are placed in 1.8mW/Cm2It is reacted at room temperature under ultraviolet light irradiation
After 8h, 100g deionized water is added, after high speed dispersion 40min, it is 2.02Wt% that de- acetone, which obtains hydroxy radical content, solid containing being 36%
Hydroxyl polyurethane aqueous dispersion body.
Embodiment 6
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 27.6g average molecular weight be 1000 polyether Glycols, 2.8g average molecular weight be 1000 polybutadiene two
Band is added in alcohol, 16.5 hexamethylene diisocyanates, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g acetone
In the reaction flask of stirring, 0.01g stannous octoate is added dropwise, is warming up to 75 DEG C, it, first will be by 9.13g pentaerythrite three after reacting 2.5h
The solution of acrylate and 10g acetone composition is slowly dropped into reaction flask, and keeping temperature, the reaction was continued that 2h is anti-to isocyanate group
After answering, system is cooled to 28 DEG C, and 2.17g triethylamine neutralization reaction 35min is added, and the polyurethane for obtaining carbon-carbon double bonds is pre-
Polymers；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2.46g photoinitiator 2- hydroxyl -2- first is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
The 2 mercapto ethanol of base -1- phenyl -1- acetone and 8.9g, reaction system are placed in 1.8mW/Cm2It is reacted at room temperature under ultraviolet light irradiation
After 8h, 100g deionized water is added, after high speed dispersion 40min, it is 2.41Wt% that de- acetone, which obtains hydroxy radical content, solid containing being 36%
Hydroxyl polyurethane aqueous dispersion body.
Embodiment 7
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 27.6g average molecular weight be 1000 polyester diol, 2.8g average molecular weight be 1000 polybutadiene two
Band is added in alcohol, 17g toluene di-isocyanate(TDI), 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g acetone
In the reaction flask of stirring, 0.02g dibutyl tin dilaurate is added dropwise, is warming up to 75 DEG C, it, first will be by 9.13g season after reacting 2.5h
The solution of penta tetrol triacrylate and 10g acetone composition is slowly dropped into reaction flask, keeps temperature the reaction was continued 2h to isocyanide
After completion of the reaction, system is cooled to 28 DEG C to perester radical, adds 2.17g triethylamine neutralization reaction 35min, obtains carbon-carbon double bonds
Polyurethane prepolymer；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2.46g photoinitiator 2- hydroxyl -2- first is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
3- sulfydryl -1,2-PD of base -1- phenyl -1- acetone and 10.38g, reaction system are placed in 1.8mW/Cm2Under ultraviolet light irradiation
After reacting at room temperature 10h, 107g deionized water is added, after high speed dispersion 40min, it is 4.14Wt% that de- acetone, which obtains hydroxy radical content, Gu
Containing the hydroxyl polyurethane aqueous dispersion body for 35%.
Embodiment 8
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 27.6g average molecular weight be 1000 polyether Glycols, 2.8g average molecular weight be 1000 polybutadiene two
Band is added in alcohol, 17g toluene di-isocyanate(TDI), 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g acetone
In the reaction flask of stirring, 0.01g stannous octoate is added dropwise, is warming up to 75 DEG C, it, will be by 9.13g pentaerythrite 3 third after reacting 2.5h
The solution of olefin(e) acid ester and 10g acetone composition is slowly dropped into reaction flask, and temperature the reaction was continued 2h is kept to react to isocyanate group
After, system is cooled to 28 DEG C, and 2.17g triethylamine neutralization reaction 35min is added, obtains the polyurethane prepolymer of carbon-carbon double bonds
Object；
2) preparation of hydroxyl polyurethane aqueous dispersion body
1.65g photoinitiator dimethoxybenzoin is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
With the 2 mercapto ethanol of 9.36g, reaction system is placed in 1.8mW/Cm2Under ultraviolet light irradiation react at room temperature 7h after, be added 88g go from
Sub- water, after high speed dispersion 40min, it is 2.53Wt% that de- acetone, which obtains hydroxy radical content, solid containing the hydroxyl polyurethane aqueous for being 38%
Granular media.
Embodiment 9
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By 27.6g average molecular weight be 1000 polyether Glycols, 2.8g average molecular weight be 1000 polybutadiene two
Band is added in alcohol, 17g toluene di-isocyanate(TDI), 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acid and 20g acetone
In the reaction flask of stirring, 0.02g dibutyl tin dilaurate is added dropwise, is warming up to 75 DEG C, it, first will be by 9.13g season after reacting 2.5h
The solution of penta tetrol triacrylate and 10g acetone composition is slowly dropped into reaction flask, keeps temperature the reaction was continued 2h to isocyanide
After completion of the reaction, system is cooled to 28 DEG C to perester radical, adds 2.17g triethylamine neutralization reaction 35min, obtains carbon-carbon double bonds
Polyurethane prepolymer；
2) preparation of hydroxyl polyurethane aqueous dispersion body
2.46g photoinitiator 2- hydroxyl -2- first is added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1)
3- sulfydryl -1,2-PD of base -1- phenyl -1- acetone and 12.33g, reaction system are placed in 1.8mW/Cm2Under ultraviolet light irradiation
After reacting at room temperature 11h, 140g deionized water is added, after high speed dispersion 40min, it is 4.85Wt% that de- acetone, which obtains hydroxy radical content, Gu
Containing the hydroxyl polyurethane aqueous dispersion body for 35%.
In following application examples 1~9, defoaming agent is Akzo Nobel SF-208, and thickener is Tao Shi PUR2020, wetting
Agent is Tao Shi EH-40, and aqueous blue mill base comes from bauhinia painting, and polyisocyanate curing agent is Bayer Bayhydur XP
2655。
Application examples 1
Take hydroxyl polyurethane aqueous dispersion body prepared by 80g embodiment 1 as components, be added 0.1g defoaming agent,
0.07g thickener and 4.5g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, it is aqueous that 0.5g is then added
After mixing evenly by the two 0.79g polyisocyanate curing agent and 3g wetting agent is added in blue mill base, and above-mentioned material is abundant
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing evenly.Dyeing sand is placed in again
Dry 15min must dry dyeing sand at 80 DEG C.
Application examples 2
Take hydroxyl polyurethane aqueous dispersion body prepared by 97g embodiment 2 as components, be added 0.1g defoaming agent,
0.08g thickener and 1g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, 0.5g aqueous blue is then added
Color mill base after mixing evenly by the two is added 0.50g polyisocyanate curing agent and 3g wetting agent, above-mentioned material is sufficiently stirred
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing uniformly.Dyeing sand is placed in 80 again
Dry 15min must dry dyeing sand at DEG C.Application examples 3
It takes hydroxyl polyurethane aqueous dispersion body prepared by 94.5g embodiment 3 as components, 0.1g defoaming is added
Agent, 0.2g thickener and 1.5g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, 0.5g water is then added
Property blue mill base 0.34g polyisocyanate curing agent and 3g wetting agent after mixing evenly by the two is added, above-mentioned material is filled
Divide and poured into 486g white sand after mixing evenly, is stirred continuously with pallette knife until white sand is dyed to blue entirely.Dyeing sand is set again
Dry 15min must dry dyeing sand at 80 DEG C.
Application examples 4
Take hydroxyl polyurethane aqueous dispersion body prepared by 102g embodiment 4 as components, be added 0.1g defoaming agent,
0.06g thickener and 1g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, 0.5g aqueous blue is then added
Color mill base after mixing evenly by the two is added 0.746g polyisocyanate curing agent and 3g wetting agent, above-mentioned material is sufficiently stirred
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing uniformly.Dyeing sand is placed in 80 again
Dry 15min must dry dyeing sand at DEG C.
Application examples 5
Take hydroxyl polyurethane aqueous dispersion body prepared by 103g embodiment 5 as components, be added 0.1g defoaming agent,
0.08g thickener and 1.2g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, it is aqueous that 0.5g is then added
After mixing evenly by the two 0.45g polyisocyanate curing agent and 3g wetting agent is added in blue mill base, and above-mentioned material is abundant
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing evenly.Dyeing sand is placed in again
Dry 15min must dry dyeing sand at 80 DEG C.
Application examples 6
It takes hydroxyl polyurethane aqueous dispersion body prepared by 97.4g embodiment 6 as components, 0.1g defoaming is added
Agent, 0.06g thickener and 1g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, it is aqueous that 0.5g is then added
After mixing evenly by the two 0.57g polyisocyanate curing agent and 3g wetting agent is added in blue mill base, and above-mentioned material is abundant
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing evenly.Dyeing sand is placed in again
Dry 15min must dry dyeing sand at 80 DEG C.
Application examples 7
It takes hydroxyl polyurethane aqueous dispersion body prepared by 96.5g embodiment 7 as components, 0.1g defoaming is added
Agent, 0.06g thickener and 1g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, it is aqueous that 0.5g is then added
After mixing evenly by the two 0.99g polyisocyanate curing agent and 3g wetting agent is added in blue mill base, and above-mentioned material is abundant
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing evenly.Dyeing sand is placed in again
Dry 15min must dry dyeing sand at 80 DEG C.
Application examples 8
Take hydroxyl polyurethane aqueous dispersion body prepared by 73g embodiment 8 as components, be added 0.1g defoaming agent,
0.06g thickener and 1g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, 0.5g aqueous blue is then added
Color mill base after mixing evenly by the two is added 0.44g polyisocyanate curing agent and 3g wetting agent, above-mentioned material is sufficiently stirred
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing uniformly.Dyeing sand is placed in 80 again
Dry 15min must dry dyeing sand at DEG C.
Application examples 9
It takes hydroxyl polyurethane aqueous dispersion body prepared by 99.3g embodiment 9 as components, 0.1g defoaming is added
Agent, 0.06g thickener and 1g deionized water, stir evenly and are configured to base paint.8.5g base paint is taken, it is aqueous that 0.5g is then added
After mixing evenly by the two 0.59g polyisocyanate curing agent and 3g wetting agent is added in blue mill base, and above-mentioned material is abundant
It pours into 486g white sand, is stirred continuously with pallette knife until white sand is dyed to blue entirely after mixing evenly.Dyeing sand is placed in again
Dry 15min must dry dyeing sand at 80 DEG C.
The artificial color sand of above-mentioned preparation is subjected to solvent resistance and wearability test, test result are as shown in table 1.
Solvent resistance test operation method: water resistance takes 3g artificial color sand prepared by the present invention to be immersed in 30ml water, alcohol ester
In 12 and 1.2- propylene glycol, after placing 7 days, upper solution is poured out into observation color sand discoloration.Upper solution color with it is pure
Solvent is identical, is considered as and passes through.
Abrasion resistance test method is as follows: taking 40g artificial color sand prepared by the present invention to be put into the there-necked flask with stirring, room temperature
Under with 200r/min stir 30min, pour out pave with do not carry out wearability test color sand carry out color comparator paired observation its
Fade situation, visually observes not fade to be considered as and passes through.
Table 1: the test result of each application examples
As it can be seen from table 1 using aqueous artificial color sand made from hydroxyl polyurethane aqueous dispersion body prepared by the present invention,
Water resistance, resistance to general film forming solvent and wearability are preferable, can be used for building coating field.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within principle.
Claims (7)
1. a kind of preparation method of hydroxyl polyurethane aqueous dispersion body, it is characterised in that: method includes the following steps:
1) preparation of carbon-carbon double bonds polyurethane prepolymer:
By the oligomer dihydric alcohol of 25~50 parts by weight, the diisocyanate of 10~25 parts by weight, 1~10 parts by weight carbon containing carbon
The dihydric alcohol of double bond, the hydrophilic chain extender of 2~5 parts by weight, the acetone of 26~45 parts by weight, 0.01~0.1 parts by weight organotin
Class catalyst is added in reaction kettle, is warming up to 70~80 DEG C under stiring, and after reacting 1~3h, the carbon containing of 3~10 parts by weight is added
Carbon double bond monohydric alcohol and the acetone of 26~45 parts by weight the reaction was continued 1~3h, it is pre- to obtain the polyurethane containing carboxyl and carbon-carbon double bond
Polymers, the neutralizer for adding 5~10 parts by weight carry out neutralization reaction, obtain the polyurethane prepolymer of carbon-carbon double bonds；
2) preparation of hydroxyl polyurethane aqueous dispersion body:
3~15 parts by weight are added into the polyurethane prepolymer of the resulting carbon-carbon double bonds of step 1) contains mercaptoalcohol, 0.1~3
The photoinitiator of parts by weight further reacts 3~20h under the irradiation of UV light, the base polyurethane prepolymer for use as of hydroxyl is obtained, in high speed
The deionized water for being added with stirring 200~320 parts by weight carries out water dispersion, obtains hydroxyl polyurethane aqueous after removing acetone and dissipates
Body；
The average molecular weight of the oligomer dihydric alcohol is 500~3000, and hydroxyl average functionality is 2~2.5, wherein polybutadiene
The parts by weight of alkene dihydric alcohol are the 5%~30% of oligomer dihydric alcohol；
The dihydric alcohol of the carbon-carbon double bonds is selected from cis-2-butene -1,4- glycol, 1,5'- hexadiene -3,4- glycol, 5,5'- bis-
Allyl -2,2'- '-biphenyl diphenol or bis- (the methylol) -1,3- propylene glycol diacrylates of 2,2'-；
The carbon-carbon double bonds monohydric alcohol is selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, 3- (third
Alkene acyloxy) -2- hydroxy propyl methacrylate or pentaerythritol triacrylate.
2. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 1, it is characterised in that: two isocyanide
Acid esters is hexamethylene diisocyanate, isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate
One or more of mixture.
3. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 1, it is characterised in that: the hydrophilic expansion
Chain agent is selected from dihydromethyl propionic acid or dimethylolpropionic acid；The organotin catalysts are that dibutyl tin dilaurate or octanoic acid are sub-
Tin.
4. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 1, it is characterised in that: the neutralizer
For one or more of triethylamine, triethanolamine, ammonium hydroxide, potassium hydroxide, sodium hydroxide.
5. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 1, it is characterised in that: described to contain sulfydryl
Alcohol is selected from 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 3- sulfydryl -1,2- propylene glycol, 3- sulfydryl -1- hexanol, 6- sulfydryls hexanol, 4-
The mixture of any one or a few in sulfydryl-n-butyl alcohol.
6. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 1, it is characterised in that: described light-initiated
Agent is selected from dimethoxybenzoin or 2- hydroxy-2-methyl -1- phenyl -1- acetone.
7. a kind of hydroxyl polyurethane aqueous dispersion body according to claim 1 is in the application of manually dye sand, it is characterised in that:
Hydroxyl polyurethane aqueous dispersion body is used for the colouring method of aqueous color sand, comprising the following steps:
1) defoaming agent, thickener and water are added in obtained hydroxyl polyurethane aqueous dispersion body, are mixed evenly, are used for
Preparation dye sand base paint, the parts by weight of each component are as follows:
2) aqueous color paste, polyisocyanate curing agent, wetting agent and white sand are added in base paint, are mixed evenly, 60~
80 DEG C dry to obtain aqueous color sand, and the parts by weight of each component are as follows:
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| CN113683944B (en) * | 2021-07-30 | 2022-10-11 | 湖北众雁涂料有限公司 | Production process of water-bubble-resistant corrosion-resistant stone-like paint |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1377379A (en) * | 1999-09-30 | 2002-10-30 | 巴斯福股份公司 | Aqueous polyurethane dispersions which can be hardened with mit UV-radiation and thermally, and use thereof |
| CN101175783A (en) * | 2005-02-24 | 2008-05-07 | 巴斯福股份公司 | Radiation-curable aqueous polyurethane dispersions |
| CN102472970A (en) * | 2009-07-02 | 2012-05-23 | 太阳控股株式会社 | Photocurable heat-curable resin composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377379A (en) * | 1999-09-30 | 2002-10-30 | 巴斯福股份公司 | Aqueous polyurethane dispersions which can be hardened with mit UV-radiation and thermally, and use thereof |
| CN101175783A (en) * | 2005-02-24 | 2008-05-07 | 巴斯福股份公司 | Radiation-curable aqueous polyurethane dispersions |
| CN102472970A (en) * | 2009-07-02 | 2012-05-23 | 太阳控股株式会社 | Photocurable heat-curable resin composition |
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