CN106632969A - Aqueous dispersion containing hydroxyl polyurethane and preparation method and application thereof - Google Patents
Aqueous dispersion containing hydroxyl polyurethane and preparation method and application thereof 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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses an aqueous dispersion containing hydroxyl polyurethane and a preparation method and application thereof. A polyurethane prepolymer containing carboxyl groups and carbon-carbon double bonds is obtained by polyaddition, a neutralizing agent is added to neutralize the carboxyl groups to weak basicity, and a polyurethane prepolymer containing carbon-carbon double bonds is obtained; then, mercaptoalcohol and a photoinitiator are added to conduct a next reaction, a polyurethane prepolymer containing hydroxyl polyurethane is obtained, then deionized water is added to conduct water dispersing, and the aqueous dispersion containing hydroxyl polyurethane is obtained. An antifoaming agent, a thickening agent and water are added into the obtained aqueous dispersion containing hydroxyl polyurethane to be evenly mixed and stirred, and the mixture is used for preparing a basic paint for sand dyeing; a water-based color paste, a polyisocyanates curing agent, a wetting agent and white sand are added into the basic paint to be evenly mixed and stirred, and the mixture is dried at the temperature of 60 DEG C to 80 DEG C to obtain water-based color sand. The method can control the hydroxyl content to be 1.32-6.11 wt.%, and the aqueous dispersion has controllable hydroxyl positions, high reactivity with isocyanates and fast speed of coating drying. Meanwhile, the method can improve the wear resistance of the water-based color sand.
Description
Technical field
The present invention relates to polyurethane-type macromolecular material, in particular to a kind of hydroxyl polyurethane aqueous dispersion body and its preparation
Methods and applications.
Background technology
Artificial coloured silk sand is formed through natural sand dye system, with bright-colored, the characteristics of color great variety of goods.It is artificial color
Sand is mainly used in the true mineral varnish of building inside and outside wall, and market demand is very big.
The technology of preparing of artificial color sand in the market mainly has two kinds of high temperature sintering and resin-coating fixation.High temperature burns
Color sand lovely luster, good weatherability prepared by knot, but production process need to use more raw material, and process is complicated, low production efficiency, energy consumption
It is high.The method of resin-coating fixation is then mainly by the single, double component acrylic resin of solvent-borne type, epoxy resin or Organic fluoride, silicon
Resin carrys out fixation, and this preparation method is needed with substantial amounts of based on solvent-based system during the preparation of resin and dye sand
Solvent, VOC emission amount is high, is unfavorable for environmental protection.
To adapt to environmental requirement, the existing Primary Study of artificial coloured silk sand and exploration are prepared using water-base resin, mainly had aqueous
Acrylic resin and aqueous epoxy resins, to application study of the water-based hydroxyl polyurethane resin in this field report is had no, is gathered
Urethane has the advantages that the protrusions such as wearability is good, pliability is good, is highly suitable for the fixation of aqueous color sand.But existing aqueous hydroxyl
Based polyurethanes naval stores kind is few and price is high, many typically using polyol such as pentaerythrite as hydroxyl source
Hydroxy compounds more difficult control extent of reaction in preparation process, easily forms gel and causes reaction failure.
The content of the invention
Present invention aim to overcome the shortcomings of existing for prior art, there is provided a kind of hydroxyl polyurethane aqueous dissipate
Body and its preparation method and application.
For achieving the above object, the invention provides a kind of hydroxyl polyurethane aqueous dispersion body, it is particular in that:It
It is the polyurethane prepolymer that carboxyl and carbon-carbon double bond are obtained by polyaddition, is initially charged in nertralizer and carboxyl is to weak base
Property, obtain carbon-carbon double bonds polyurethane prepolymer;Add and further reacted with light trigger containing mercaptoalcohol, obtain hydroxyl and gather
Urethane performed polymer, be subsequently adding deionized water carry out moisture dissipate, obtain hydroxyl polyurethane aqueous dispersion body.
The preparation method of above-mentioned hydroxyl polyurethane aqueous dispersion body, comprises the following steps:
1) preparation of carbon-carbon double bonds polyurethane prepolymer:
The oligomer dihydroxylic alcohols of 25~50 weight portions, the diisocyanate of 10~25 weight portions, 1~10 weight portion are contained
The dihydroxylic alcohols of carbon-carbon double bond, the hydrophilic chain extender of 2~5 weight portions, the acetone of 26~45 weight portions, 0.01~0.1 weight portion have
Machine tin catalyst is added in reactor, and 70~80 DEG C are warming up under agitation, after 1~3h of reaction, adds 3~10 weight portions
The acetone of carbon-carbon double bonds monohydric alcohol and 26~45 weight portions continues to react 1~3h, obtains the poly- ammonia containing carboxyl and carbon-carbon double bond
Ester prepolymer, the nertralizer for adding 5~10 weight portions is neutralized reaction, obtains the polyurethane prepolymer of carbon-carbon double bonds;
2) preparation of hydroxyl polyurethane aqueous dispersion body:
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 3~15 weight portions containing mercaptoalcohol, 0.1
The light trigger of~3 weight portions, under UV light irradiation further 3~20h of reaction, obtain the base polyurethane prepolymer for use as of hydroxyl,
Under high-speed stirred add 200~320 weight portions deionized water carry out moisture dissipate, removing acetone after obtain hydroxyl polyurethane water
Dispersion.
In the present invention, the mean molecule quantity of the oligomer dihydroxylic alcohols is 500~3000, hydroxyl average functionality is 2~
2.5, the wherein weight portion of polybutadiene dihydroxylic alcohols is the 5%~30% of oligomer dihydroxylic alcohols.
In the present invention, the diisocyanate is 1, and hexamethylene-diisocyanate, IPDI, toluene two are different
The mixture of one or more in cyanate, methyl diphenylene diisocyanate.
In the present invention, the dihydroxylic alcohols of the carbon-carbon double bonds is selected from cis-2-butene-Isosorbide-5-Nitrae-glycol, 1,5'- hexadiene -3,
Double (the methylol) -1,3- propylene glycol diacrylates of 4- glycol, 5,5'- diallyl -2,2'- '-biphenyl diphenols or 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 methacrylates 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 laurate or stannous octoate.
In the present invention, the nertralizer be triethylamine, triethanolamine, ammoniacal liquor, potassium hydroxide, NaOH in one kind or
It is several.
In the present invention, it is described containing mercaptoalcohol selected from 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 3- sulfydryls -1,2-PD,
Any one or a few mixture in 3- sulfydryl -1- hexanols, 6- sulfydryl hexanols, 4- sulfydryls-n-butyl alcohol.
In the present invention, the light trigger is selected from dimethoxybenzoin or 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Present invention also offers application of the above-mentioned hydroxyl polyurethane aqueous dispersion body in artificial dye sand field.Hydroxyl is gathered
Urethane aqueous dispersion is used for the colouring method of aqueous color sand, comprises the following steps:
1) addition defoamer, thickener and water in obtained hydroxyl polyurethane aqueous dispersion body, mixing and stirring,
For preparing dye sand base paint, the weight portion of each component is as follows:
2) addition aqueous color paste, polyisocyanate curing agent, wetting agent and white sand in base paint, mixing and stirring,
60~80 DEG C dry to obtain aqueous color sand, and the weight portion of each component is as follows:
The beneficial effects of the present invention is:Gained hydroxyl polyurethane aqueous dispersion body of the invention can control hydroxy radical content and be
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, so as to improve the wearability of artificial coloured silk sand.Hydroxyl polyurethane aqueous dispersion body is being prepared and applied
During, its VOC content is substantially zeroed, extremely friendly to environment;The hydroxyl polyurethane aqueous dispersion body prepared using the present invention
For the preparation of aqueous artificial color sand, it is prepared into aqueous artificial color sand and there is preferable wearability and water-fast solvent resistance, can
For paint field.
Specific embodiment
In order to preferably explain the present invention, below in conjunction with specific embodiment, the present invention is described in further detail, but
They do not constitute to the present invention and limit.
Embodiment 1
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By polyether Glycols, the polybutadiene two that 6.6g mean molecule quantities are 1000 that 25.5g mean molecule quantities are 1000
Alcohol, 17g toluene di-isocyanate(TDI)s, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g acetone add band
In the reaction bulb of stirring, 0.02g dibutyl tin laurates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, first will be by 3.98g third
Olefin(e) acid hydroxyl ethyl ester is slowly dropped in reaction bulb with the solution of 10g acetone composition, and keeping temperature continues to react anti-to NCO
After should finishing, system is cooled to 28 DEG C, adds 2.17g triethylamine neutralization reaction 35min, obtains carbon-carbon double bonds polyurethane pre-
Polymers;
2) preparation of hydroxyl polyurethane aqueous dispersion body
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 0.5g 2- hydroxy-2-methyl -1- phenyl -
The 2 mercapto ethanol of 1- acetone and 3.68g, reaction system is placed in 1.8mW/Cm2Under ultra violet lamp after room temperature reaction 4h, add
90g deionized waters, at a high speed after dispersion 40min, it is 1.32Wt% that de- acetone obtains hydroxy radical content, Gu containing the poly- ammonia of hydroxyl for 40%
Ester aqueous dispersion.
Embodiment 2
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By polyester diol, the polybutadiene two that 5.6g mean molecule quantities are 1000 that 24.5g mean molecule quantities are 1000
Alcohol, 17g toluene di-isocyanate(TDI)s, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g acetone add band
In the reaction bulb of stirring, 0.02g dibutyl tin laurates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, first will be by 3.98g third
Olefin(e) acid hydroxyl ethyl ester is slowly dropped in reaction bulb with the solution of 10g acetone composition, and keeping temperature continues to react anti-to NCO
After should finishing, 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
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 2.27g light trigger 2- hydroxyl -2- first
3- sulfydryl -1 of base -1- phenyl -1- acetone and 5.09g, 2 propane diols, reaction system is placed in 1.8mW/Cm2Room under ultra violet lamp
It is warm to react after 7h, 70g deionized waters are added, at a high speed after dispersion 40min, it is 2.21Wt% that de- acetone obtains hydroxy radical content, Gu contain be
40% hydroxyl polyurethane aqueous dispersion body.
Embodiment 3
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By polyether Glycols that 50g mean molecule quantities are 2000, the polybutadiene diol that 5.6g mean molecule quantities are 1000,
22.4g IPDIs, 2.49g cis-2-butene -1,4- glycol, 2.89g dihydromethyl propionic acids and 20g acetone add
In entering the reaction bulb with stirring, 0.02g dibutyl tin laurates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, first will be by
3- (the acryloxy) -2- hydroxy propyl methacrylates of 6.56g are slowly dropped into reaction bulb with the solution of 10g acetone composition
In, to NCO after completion of the reaction, system is cooled to 28 DEG C to keeping temperature continuation reaction 2h, adds 2.17g triethylamines
Neutralization reaction 35min, obtains the polyurethane prepolymer of carbon-carbon double bonds;
2) preparation of hydroxyl polyurethane aqueous dispersion body
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 2.33g light trigger 2- hydroxyl -2- first
The 2 mercapto ethanol of base -1- phenyl -1- acetone and 5.59g, reaction system is placed in 1.8mW/Cm2Room temperature reaction under ultra violet lamp
After 6h, 160g deionized waters are added, at a high speed after dispersion 40min, it is 1.53Wt% that de- acetone obtains hydroxy radical content, Gu contain for 38%
Hydroxyl polyurethane aqueous dispersion body.
Embodiment 4
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By polyester diol, the polybutadiene two that 5.6g mean molecule quantities are 1000 that 24.5g mean molecule quantities are 1000
Alcohol, 24.6g methyl diphenylene diisocyanates, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g third
Ketone is added in the reaction bulb with stirring, and 0.01g stannous octoates are added dropwise, and 75 DEG C is warming up to, after reaction 2.5h, first by by 6.56g's
3- (acryloxy) -2- hydroxy propyl methacrylates are slowly dropped in reaction bulb with the solution of 10g acetone composition, are kept
To NCO after completion of the reaction, system is cooled to 28 DEG C to temperature continuation reaction 2h, adds 2.17g triethylamine neutralization reactions
35min, obtains the polyurethane prepolymer of carbon-carbon double bonds;
2) preparation of hydroxyl polyurethane aqueous dispersion body
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 2.33g light trigger 2- hydroxyl -2- first
3- sulfydryls-the 1,2-PD of base -1- phenyl -1- acetone and 7.75g, reaction system is placed in 1.8mW/Cm2Under ultra violet lamp
After room temperature reaction 10h, 130g deionized waters are added, at a high speed after dispersion 40min, it is 3.26Wt% that de- acetone 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 polyether Glycols, the polybutadiene two that 2.8g mean molecule quantities are 1000 that 27.6g mean molecule quantities are 1000
Alcohol, 16.5g hexamethylene diisocyanates, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g acetone add band
In the reaction bulb of stirring, 0.02g dibutyl tin laurates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, first will be by 9.13g seasons
Penta tetrol triacrylate is slowly dropped in reaction bulb with the solution of 10g acetone composition, and keeping temperature continues to react 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
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 2.46g light trigger 2- hydroxyl -2- first
The 2 mercapto ethanol of base -1- phenyl -1- acetone and 7.49g, reaction system is placed in 1.8mW/Cm2Room temperature reaction under ultra violet lamp
After 8h, 100g deionized waters are added, at a high speed after dispersion 40min, it is 2.02Wt% that de- acetone obtains hydroxy radical content, Gu contain for 36%
Hydroxyl polyurethane aqueous dispersion body.
Embodiment 6
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By polyether Glycols, the polybutadiene two that 2.8g mean molecule quantities are 1000 that 27.6g mean molecule quantities are 1000
Alcohol, 16.5 hexamethylene diisocyanates, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g acetone add band
In the reaction bulb of stirring, 0.01g stannous octoates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, first will be by 9.13g pentaerythrites three
Acrylate is slowly dropped in reaction bulb with the solution of 10g acetone composition, and it is anti-to NCO that keeping temperature continues reaction 2h
After should finishing, system is cooled to 28 DEG C, adds 2.17g triethylamine neutralization reaction 35min, and the polyurethane for obtaining carbon-carbon double bonds is pre-
Polymers;
2) preparation of hydroxyl polyurethane aqueous dispersion body
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 2.46g light trigger 2- hydroxyl -2- first
The 2 mercapto ethanol of base -1- phenyl -1- acetone and 8.9g, reaction system is placed in 1.8mW/Cm2Room temperature reaction under ultra violet lamp
After 8h, 100g deionized waters are added, at a high speed after dispersion 40min, it is 2.41Wt% that de- acetone obtains hydroxy radical content, Gu contain for 36%
Hydroxyl polyurethane aqueous dispersion body.
Embodiment 7
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By polyester diol, the polybutadiene two that 2.8g mean molecule quantities are 1000 that 27.6g mean molecule quantities are 1000
Alcohol, 17g toluene di-isocyanate(TDI)s, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g acetone add band
In the reaction bulb of stirring, 0.02g dibutyl tin laurates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, first will be by 9.13g seasons
Penta tetrol triacrylate is slowly dropped in reaction bulb with the solution of 10g acetone composition, and keeping temperature continues to react 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
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 2.46g light trigger 2- hydroxyl -2- first
3- sulfydryls-the 1,2-PD of base -1- phenyl -1- acetone and 10.38g, reaction system is placed in 1.8mW/Cm2Under ultra violet lamp
After room temperature reaction 10h, 107g deionized waters are added, at a high speed after dispersion 40min, it is 4.14Wt% that de- acetone 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 polyether Glycols, the polybutadiene two that 2.8g mean molecule quantities are 1000 that 27.6g mean molecule quantities are 1000
Alcohol, 17g toluene di-isocyanate(TDI)s, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g acetone add band
In the reaction bulb of stirring, 0.01g stannous octoates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, will be by 9.13g pentaerythrites 3 third
Olefin(e) acid ester is slowly dropped in reaction bulb with the solution of 10g acetone composition, and keeping temperature continues to react 2h to NCO reaction
After finishing, system is cooled to 28 DEG C, adds 2.17g triethylamine neutralization reaction 35min, obtains the polyurethane prepolymer of carbon-carbon double bonds
Thing;
2) preparation of hydroxyl polyurethane aqueous dispersion body
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 1.65g light trigger dimethoxybenzoins
With the 2 mercapto ethanol of 9.36g, reaction system is placed in 1.8mW/Cm2Under ultra violet lamp after room temperature reaction 7h, add 88g go from
Sub- water, at a high speed after dispersion 40min, it is 2.53Wt% that de- acetone obtains hydroxy radical content, Gu containing the hydroxyl polyurethane aqueous for 38%
A prose style free from parallelism.
Embodiment 9
1) preparation of carbon-carbon double bonds polyurethane prepolymer
By polyether Glycols, the polybutadiene two that 2.8g mean molecule quantities are 1000 that 27.6g mean molecule quantities are 1000
Alcohol, 17g toluene di-isocyanate(TDI)s, 2.49g cis-2-butene -1,4- glycol, 2.40g dihydromethyl propionic acids and 20g acetone add band
In the reaction bulb of stirring, 0.02g dibutyl tin laurates are added dropwise, are warming up to 75 DEG C, after reaction 2.5h, first will be by 9.13g seasons
Penta tetrol triacrylate is slowly dropped in reaction bulb with the solution of 10g acetone composition, and keeping temperature continues to react 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
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 2.46g light trigger 2- hydroxyl -2- first
3- sulfydryls-the 1,2-PD of base -1- phenyl -1- acetone and 12.33g, reaction system is placed in 1.8mW/Cm2Under ultra violet lamp
After room temperature reaction 11h, 140g deionized waters are added, at a high speed after dispersion 40min, it is 4.85Wt% that de- acetone obtains hydroxy radical content, Gu
Containing the hydroxyl polyurethane aqueous dispersion body for 35%.
In following application examples 1~9, defoamer is Akzo Nobel SF-208, and thickener is Tao Shi PUR2020, is soaked
Agent is Tao Shi EH-40, and from bauhinia painting, polyisocyanate curing agent is Bayer Bayhydur XP to aqueous blue mill base
2655。
Application examples 1
Hydroxyl polyurethane aqueous dispersion body prepared by 80g embodiments 1 is taken as components, add 0.1g defoamers,
0.07g thickeners and 4.5g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g is subsequently adding aqueous
Blue mill base, after the two is stirred, adds 0.79g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is abundant
In pouring 486g white sands after stirring into, it is stirred continuously with pallette knife until white sand is dyed to blueness entirely.Dyeing sand is placed in again
15min is dried at 80 DEG C must be dried dyeing sand.
Application examples 2
Hydroxyl polyurethane aqueous dispersion body prepared by 97g embodiments 2 is taken as components, add 0.1g defoamers,
0.08g thickeners and 1g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g aqueous blues are subsequently adding
Color mill base, after the two is stirred, adds 0.50g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is fully stirred
Pour in 486g white sands after mixing uniformly, be stirred continuously with pallette knife until white sand is dyed to blueness entirely.Again dyeing sand is placed in into 80
15min is dried at DEG C must be dried dyeing sand.Application examples 3
The hydroxyl polyurethane aqueous dispersion body prepared by 94.5g embodiments 3 is taken as components, 0.1g froth breakings are added
Agent, 0.2g thickeners and 1.5g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g water is subsequently adding
Property blue mill base, after the two is stirred, add 0.34g polyisocyanate curing agents and 3g wetting agents, above-mentioned material is filled
Divide and poured in 486g white sands after stirring, be stirred continuously with pallette knife until white sand is dyed to blueness entirely.Dyeing sand is put again
15min is dried at 80 DEG C must be dried dyeing sand.
Application examples 4
Hydroxyl polyurethane aqueous dispersion body prepared by 102g embodiments 4 is taken as components, add 0.1g defoamers,
0.06g thickeners and 1g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g aqueous blues are subsequently adding
Color mill base, after the two is stirred, adds 0.746g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is fully stirred
Pour in 486g white sands after mixing uniformly, be stirred continuously with pallette knife until white sand is dyed to blueness entirely.Again dyeing sand is placed in into 80
15min is dried at DEG C must be dried dyeing sand.
Application examples 5
Hydroxyl polyurethane aqueous dispersion body prepared by 103g embodiments 5 is taken as components, add 0.1g defoamers,
0.08g thickeners and 1.2g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g is subsequently adding aqueous
Blue mill base, after the two is stirred, adds 0.45g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is abundant
In pouring 486g white sands after stirring into, it is stirred continuously with pallette knife until white sand is dyed to blueness entirely.Dyeing sand is placed in again
15min is dried at 80 DEG C must be dried dyeing sand.
Application examples 6
The hydroxyl polyurethane aqueous dispersion body prepared by 97.4g embodiments 6 is taken as components, 0.1g froth breakings are added
Agent, 0.06g thickeners and 1g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g is subsequently adding aqueous
Blue mill base, after the two is stirred, adds 0.57g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is abundant
In pouring 486g white sands after stirring into, it is stirred continuously with pallette knife until white sand is dyed to blueness entirely.Dyeing sand is placed in again
15min is dried at 80 DEG C must be dried dyeing sand.
Application examples 7
The hydroxyl polyurethane aqueous dispersion body prepared by 96.5g embodiments 7 is taken as components, 0.1g froth breakings are added
Agent, 0.06g thickeners and 1g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g is subsequently adding aqueous
Blue mill base, after the two is stirred, adds 0.99g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is abundant
In pouring 486g white sands after stirring into, it is stirred continuously with pallette knife until white sand is dyed to blueness entirely.Dyeing sand is placed in again
15min is dried at 80 DEG C must be dried dyeing sand.
Application examples 8
Hydroxyl polyurethane aqueous dispersion body prepared by 73g embodiments 8 is taken as components, add 0.1g defoamers,
0.06g thickeners and 1g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g aqueous blues are subsequently adding
Color mill base, after the two is stirred, adds 0.44g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is fully stirred
Pour in 486g white sands after mixing uniformly, be stirred continuously with pallette knife until white sand is dyed to blueness entirely.Again dyeing sand is placed in into 80
15min is dried at DEG C must be dried dyeing sand.
Application examples 9
The hydroxyl polyurethane aqueous dispersion body prepared by 99.3g embodiments 9 is taken as components, 0.1g froth breakings are added
Agent, 0.06g thickeners and 1g deionized waters, stir and are configured to base paint.8.5g base paints are taken, 0.5g is subsequently adding aqueous
Blue mill base, after the two is stirred, adds 0.59g polyisocyanate curing agents and 3g wetting agents, and above-mentioned material is abundant
In pouring 486g white sands after stirring into, it is stirred continuously with pallette knife until white sand is dyed to blueness entirely.Dyeing sand is placed in again
15min is dried at 80 DEG C must be dried dyeing sand.
The artificial color sand of above-mentioned preparation is carried out into solvent resistance and wearability test, test result is as shown in table 1.
Resistance to water, solvent resistance test operation method:The artificial color sand for taking 3g present invention preparations is immersed in 30ml water, alcohol ester
In 12 and 1.2- propane diols, after placing 7 days, upper solution is poured out into the color sand discoloration of observation.Upper solution color with it is pure
Solvent is identical, is considered as and passes through.
Abrasion resistance test method is as follows:The artificial color sand for taking 40g present invention preparations is put in the there-necked flask with stirring, room temperature
Under with 200r/min stir 30min, pour out pave with the color sand for not carrying out wearability test carry out color comparator paired observation its
Fade situation, to visually observe do 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 obtained in the hydroxyl polyurethane aqueous dispersion body for preparing of the invention,
Resistance to water, resistance to general film forming solvent and wearability preferably, can be used for building coating field.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Any modification, equivalent and improvement for being made within principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of hydroxyl polyurethane aqueous dispersion body, it is characterised in that:It is, by polyaddition, to obtain containing carboxyl and carbon carbon
The polyurethane prepolymer of double bond, is initially charged in nertralizer and carboxyl is to alkalescent, obtains carbon-carbon double bonds polyurethane prepolymer;Again
Addition is further reacted containing mercaptoalcohol with light trigger, obtains hydroxyl base polyurethane prepolymer for use as, and being subsequently adding deionized water is carried out
Moisture dissipates, and obtains hydroxyl polyurethane aqueous dispersion body.
2. a kind of preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 1, it is characterised in that:The method
Comprise the following steps:
1) preparation of carbon-carbon double bonds polyurethane prepolymer:
By the oligomer dihydroxylic alcohols of 25~50 weight portions, the diisocyanate of 10~25 weight portions, 1~10 weight portion carbon containing carbon
The dihydroxylic alcohols of double bond, the hydrophilic chain extender of 2~5 weight portions, the acetone of 26~45 weight portions, 0.01~0.1 weight portion organotin
Class catalyst is added in reactor, and 70~80 DEG C are warming up under agitation, after 1~3h of reaction, adds the carbon containing of 3~10 weight portions
The acetone of carbon double bond monohydric alcohol and 26~45 weight portions continues to react 1~3h, and the polyurethane obtained containing carboxyl and carbon-carbon double bond is pre-
Polymers, the nertralizer for adding 5~10 weight portions is neutralized reaction, obtains the polyurethane prepolymer of carbon-carbon double bonds;
2) preparation of hydroxyl polyurethane aqueous dispersion body:
To step 1) obtained by carbon-carbon double bonds polyurethane prepolymer in add 3~15 weight portions containing mercaptoalcohol, 0.1~3
The light trigger of weight portion, under UV light irradiation further 3~20h of reaction, the base polyurethane prepolymer for use as of hydroxyl is obtained, at a high speed
The deionized water of stirring 200~320 weight portions of lower addition carries out moisture and dissipates, and obtains hydroxyl polyurethane aqueous after removing acetone and dissipates
Body.
3. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 2, it is characterised in that:The oligomer
The mean molecule quantity of dihydroxylic alcohols is 500~3000, and hydroxyl average functionality is 2~2.5, wherein the weight of polybutadiene dihydroxylic alcohols
Part is the 5%~30% of oligomer dihydroxylic alcohols.
4. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 2, it is characterised in that:Two isocyanide
Acid esters is hexamethylene diisocyanate, IPDI, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate
In the mixture of one or more.
5. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 2, it is characterised in that:The carbon containing carbon
The dihydroxylic alcohols of double bond is selected from cis-2-butene -1,4- glycol, 1,5'- hexadiene -3,4- glycol, 5,5'- diallyls -2,2'- connection
Benzenediol or double (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 methacrylates or pentaerythritol triacrylate.
6. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 2, 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 laurate or octanoic acid are sub-
Tin.
7. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 2, it is characterised in that:The nertralizer
For one or more in triethylamine, triethanolamine, ammoniacal liquor, potassium hydroxide, NaOH.
8. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 2, it is characterised in that:It is described containing sulfydryl
Alcohol is selected from 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 3- sulfydryl -1,2- propane diols, 3- sulfydryl -1- hexanols, 6- sulfydryl hexanols, 4-
Any one or a few mixture in sulfydryl-n-butyl alcohol.
9. the preparation method of hydroxyl polyurethane aqueous dispersion body according to claim 2, it is characterised in that:It is described light-initiated
Agent is selected from dimethoxybenzoin or 2- hydroxy-2-methyl -1- phenyl -1- acetone.
10. in the artificial application for contaminating sand, its feature exists a kind of hydroxyl polyurethane aqueous dispersion body according to claim 1
In:Hydroxyl polyurethane aqueous dispersion body is used for into the colouring method of aqueous color sand, is comprised the following steps:
1) add defoamer, thickener and water, mixing and stirring in obtained hydroxyl polyurethane aqueous dispersion body, be used for
Dye sand base paint is prepared, the weight portion of each component is as follows:
2) addition aqueous color paste, polyisocyanate curing agent, wetting agent and white sand in base paint, mixing and stirring, 60~
80 DEG C dry to obtain aqueous color sand, and the weight portion of each component is as follows:
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Cited By (2)
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CN112321176A (en) * | 2020-11-30 | 2021-02-05 | 天长市墨缘玻璃建材有限公司 | Artistic glass color fixing agent and using method thereof |
CN113683944A (en) * | 2021-07-30 | 2021-11-23 | 安徽众雁涂料有限公司 | Production process of water-bubble-resistant corrosion-resistant stone-like paint |
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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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2016
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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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Publication number | Priority date | Publication date | Assignee | Title |
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CN112321176A (en) * | 2020-11-30 | 2021-02-05 | 天长市墨缘玻璃建材有限公司 | Artistic glass color fixing agent and using method thereof |
CN113683944A (en) * | 2021-07-30 | 2021-11-23 | 安徽众雁涂料有限公司 | Production process of water-bubble-resistant corrosion-resistant stone-like paint |
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 |
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