CN109517406A - A kind of preparation method of color-changing polyurethane acrylate dyestuff - Google Patents
A kind of preparation method of color-changing polyurethane acrylate dyestuff Download PDFInfo
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
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- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C08G18/4808—Mixtures of two or more polyetherdiols
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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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/67—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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- 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- 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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- C08G18/00—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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/095—Amino naphthalenes
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Abstract
The present invention relates to a kind of discoloration of urethane acrylate and preparation methods.The acrylamide containing azo group is prepared first；Using macromolecular polyol, multicomponent isocyanate and hydroxy-acrylate monomer by the base polyurethane prepolymer for use as containing double bond sealing end of gradually polymerization system, is emulsified by mixture of ice and water, obtain double bond end capping nonionic polyurethane.Free radical polymerization is carried out with acrylic monomers again, polyurethane acroleic acid discoloration is made.Present invention discoloration is highly stable, has obvious photochromic characteristic；Since dyestuff is accessed in polymer molecular chain in such a way that chemistry is keyed in, it is remarkably improved dyestuff rub resistance, resistance to migration, resistant, gloss retention and uses the advantages that safe.So that the polyurethane acroleic acid of synthesis changes colour while having the excellent properties of both polyurethane and acrylate.
Description
Technical field
The present invention relates to a kind of urethane acrylate dyestuffs more particularly to a kind of color-changing polyurethane acrylate to contaminate
The preparation method of material.
Background technique
In recent years, the development of high molecular dye is very rapid, has become a frontier of dyestuff chemistry.
Polyurethane dyestuff has the advantages that polyurethane easily forms a film, easy processing and wholesomeness are good.However polyurethane contaminates
There is also the defects such as at high cost, poor water resistance and glossiness be low for material.Since polyacrylic acid radical dye has excellent toughness, resistance to molten
The characteristics such as agent, compatibility, sub-dued lustre and low cost have caused people extensively to send out concern.But polyacrylic acid radical dye there is also
The deficiencies of elasticity, ductility, scratch resistance and pliability.
Polyurethane dyestuff and polyacrylic acid ester-based dyes have very big complementarity in performance, and use is waterborne polyurethane modified
Polyene acid esters dyestuff, the two is compound, it can learn from other's strong points to offset one's weaknesses, make and the performance of film is significantly improved.Just because of water
Property polyurethane-modified polyacrylate dyestuff excellent properties, have become develop the important of modified polyacrylate dyestuff at present
Approach, therefore there are wide Research Prospects.
Summary of the invention
The present invention is reacted by contained amino in a kind of photochromic dye molecules structure with acryloyl chloride first is made discoloration third
Acrylamide.Then, aqueous anion is made by polymer diatomic alcohol, diisocyanate, hydrophilic chain extender and salt forming agent to gather
Urethane.Again using anion polyurethane as seed.Toward middle addition initiator, emulsifier, acrylic ester monomer and synthesis discoloration
Acrylamide dye is polymerize, and aqueous anionic color-changing polyurethane acrylate dyestuff is made.
The present invention is achieved through the following technical solutions.
1, a kind of preparation method and preparation method thereof of color-changing polyurethane acrylate dyestuff, which is characterized in that including with
Lower step:
(1) 12~25% polymer polyatomic alcohols are heated to 100~140 DEG C, under the conditions of vacuum degree≤0.1MPa, at dehydration
Manage 0.5~1h；
(2) 60~90 DEG C are cooled to, 6~15% polyisocyanates, 0.01~0.03% catalyst, nitrogen protection is added
Under, react 1~3h；
(4) 4~10% hydrophilic monomers are added, react 1~3h at 50~90 DEG C；
(5) 30~50 DEG C are cooled to, 2~6% salt forming agents are added and react 30~60min；
(6) 50~70% 10~30min of deionized water high speed dispersion is added；
(7) aqueous anion-type water-thinned polyurethane is made in vacuum degree desolventizing；
(8) aqueous anionic polyurethane of above-mentioned 2/3 volume, 0.1~0.5% emulsifier, 0.5-0.8% carbonic acid are taken
Hydrogen sodium is in 40~50 DEG C of 0.5~1h of emulsification.Temperature rises to 70 DEG C, is slowly added to remaining 1/3 volume aqueous anionic polyurethane, 10
~20% acrylic ester monomer, 5~10% azo group acrylamide, 0.1~0.5% initiator, 2~4h adds
It is complete, 2~3h of constant temperature.Naturally room temperature is down to get color-changing polyurethane acrylate dyestuff is arrived.
(9) ammonium hydroxide is added and adjusts pH to 8~10, obtain color-changing polyurethane acrylate dyestuff.
In the step (8), the acrylamide of azo group the preparation method is as follows:
Appropriate diethylene glycol (DEG) is added to completely molten in solvent yellow 5, acryloyl chloride, triethylamine by 1:1~5:1~10 in molar ratio
Solution, 25~35 DEG C of reactions 12 of holding~for 24 hours, it dries after the sediment acetone washing of filtering to constant weight, it is molten to obtain acrylamide
Agent Huang 5, structural formula are as follows:
In the step (8), the acrylamide of azo group the preparation method is as follows: 1:1~5:1~10 in molar ratio
Appropriate diethylene glycol (DEG) is added to being completely dissolved in solvent yellow 5, metering system isoxazolecarboxylic acid, triethylamine, keep 25~35 DEG C of reactions 12~
For 24 hours, it dries after the sediment acetone washing of filtering to constant weight, obtains Methacrylamide solvent yellow 5, structural formula are as follows:
In the step (8), the acrylamide of azo group the preparation method is as follows: 1:1~5:1~10 in molar ratio
Appropriate diethylene glycol (DEG) is added to being completely dissolved in solvent yellow 5,3,3- dimethyl acryloyl chloride, triethylamine, keeps 25~35 DEG C of reactions
12~for 24 hours, it dries after the sediment acetone washing of filtering to constant weight, obtains 3,3- dimethylacrylamide solvent yellow 5, structure
Formula are as follows:
In the step (8), the acrylamide of azo group the preparation method is as follows: 1:1~5:1~10 in molar ratio
Appropriate diethylene glycol (DEG) is added to being completely dissolved in solvent yellow 5, beta-phenyl acryloyl chloride, triethylamine, keep 25~35 DEG C of reactions 12~
For 24 hours, it dries after the sediment acetone washing of filtering to constant weight, obtains beta-phenyl acrylamide solvent yellow 5, structural formula are as follows:
2, the preparation method of a kind of color-changing polyurethane acrylate dyestuff according to claim 1, it is characterised in that:
Polymer polyatomic alcohol is one or two kinds of in polyether polyol, polyester polyol；
3, the preparation method of a kind of color-changing polyurethane acrylate dyestuff according to claim 1, it is characterised in that:
Isocyanate-monomer be selected from one of aromatic polyisocyanate, aliphatic polyisocyante, alicyclic polyisocyanates or
It is a variety of；
4, a kind of color-changing polyurethane acrylate dyestuff according to claim 1 preparation method it is characterized by:
Hydrophilic chain extender is selected from tartaric acid, dihydromethyl propionic acid, diaminobenzoic acid, maleic anhydride, phthalic anhydride, succinic anhydride, penta
One of dicarboxylic anhydride is a variety of；
5, the preparation method of a kind of color-changing polyurethane acrylate dyestuff according to claim 1, it is characterised in that:
It is characterized by: catalyst is one or both of organic tin, tertiary amines.
6, a kind of preparation method of color-changing polyurethane acrylate dyestuff according to claim 1 and its preparation side
Method, it is characterised in that: organic solvent is selected from acetone, butanone, methyl ethyl ketone, dioxane, N, N- dimethylformamide, N- methyl pyrrole
One of pyrrolidone, ethyl acetate are a variety of；
7, the preparation method of a kind of color-changing polyurethane acrylate dyestuff according to claim 1, it is characterised in that:
Salt forming agent is selected from triethylamine, one of ammonium hydroxide, sodium hydroxide or a variety of.
8, the preparation method of a kind of color-changing polyurethane acrylate dyestuff according to claim 1, it is characterised in that:
Acrylic ester monomer is selected from acrylate, methyl methacrylate, styrene, butyl acrylate, butyl methacrylate third
Alkene nitrile, tertiary ethylene carbonate, tricarboxylic trimethacrylate, trimethylol-propane trimethacrylate, acetic acid
One of ethylene, acrylic acid-2-ethyl caproite, methacrylic acid -2- hydroxy methacrylate are a variety of；
9, the preparation method of a kind of color-changing polyurethane acrylate dyestuff according to claim 1, it is characterised in that:
Emulsifier is selected from allyl polysulfide ether sodium sulfate (ammonium), allyl polythiaether sodium sulfosuccinate, sodium vinyl sulfonate, 3- allyl
Oxygroup -2- hydroxyl-propyl sodium sulfonate (COPS-1), 3- allyloxy -2- hydroxyl-propyl sodium ascorbyl phosphate (COPS-3), allyl oxygen
Base fatty alcohol ethylene oxide ether ammonium sulfate (SR-10), allyl polyethenoxy ether, methallyl hydroxide sodium dimercaptosulphanatein, allyloxy hydroxyl
Propanesulfonate is one or more；
10, a kind of preparation method of color-changing polyurethane acrylate dyestuff according to claim 1, feature exist
One of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate or a variety of are selected from: initiator.
Since discoloration acrylamide can partly or entirely substitute other acrylic ester monomers, change can be controlled as needed
Content of the color acrylamide in polyacrylate molecular, simultaneously because discoloration acrylamide dye is keyed in by chemistry
Mode enters in the strand of dyestuff, is remarkably improved the performances such as dyestuff elasticity, ductility, scratch resistance, resistance to migration.And due to
Color-changing polyurethane acrylate dyestuff is made between the two with acrylate chemistry modified aqueous polyurethane with chemical bond form knot
It closes, so that the color-changing polyurethane acrylate dyestuff of synthesis has the excellent properties of both polyurethane and acrylate simultaneously.
The present invention has the advantage that color-changing polyurethane acrylate dyestuff prepared by the present invention has compared with prior art
The performances such as excellent elasticity, ductility, scratch resistance, resistance to migration.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated, it should be understood that following specific embodiments are only used for
It is bright the present invention rather than limit the scope of the invention.
Embodiment 1
0.06mol Polyoxyethylene glycol is taken to be added equipped with thermometer, blender, reflux condenser and dropping funel
It is warming up to 120 DEG C in four-hole boiling flask, is dehydrated, after 1h, is passed through nitrogen and is cooled to 60 DEG C, 0.1mol isophorone diisocyanate is added
Ester (IPDI) and 0.0003mol stannous octoate (T9), are warming up to 90 DEG C, constant temperature 3h, cool to 70 DEG C, and 0.035mol first is added
Base hydroxy-ethyl acrylate, reaction 3h or so are added 20ml acetone and adjust viscosity.30 DEG C or less are cooled to, 150g ice water is added to emulsify,
High-speed stirred 30min or so.At 60 DEG C, non-ionic polyurethane is made in desolventizing under 0.6MPa.
It takes the aqueous anionic polyurethane of above-mentioned 2/3 volume, 0.5g sodium bicarbonate, 0.2g allyl polyethenoxy be added
Ether, 0.2g methallyl hydroxide sodium dimercaptosulphanatein are in 40~50 DEG C of 0.5~1h of emulsification.Temperature rises to 70 DEG C, is slowly added to remaining 1/3 body
Aqueous anion polyurethane, 30g acrylamide solvent yellow 5,30g acrylate, 30g styrene, 3.6g potassium peroxydisulfate, about
3h is added, 2~3h of constant temperature, is down to room temperature naturally to get color-changing polyurethane acrylate dyestuff is arrived.Averaging of income partial size
112nm, pH=8.0, solid content 46%, viscosity 280mPas.
Embodiment 2
Take 0.04mol Polyoxyethylene glycol and 0.2mol polyoxypropyleneglycol be added equipped with thermometer, blender,
It is warming up to 120 DEG C in the four-hole boiling flask of reflux condenser and dropping funel, is dehydrated, after 1h, is passed through nitrogen and is cooled to 60 DEG C, add
Enter 4, the 4- methyl diphenylene diisocyanate (MDI) and 0.0003mol dibutyl tin dilaurate (T12) of 0.1mol, heats up
To 80 DEG C, constant temperature 3h, 70 DEG C are cooled to, is added 0.035mol hydroxypropyl acrylate (HPA), 20ml is added in reaction 3h or so
Acetone adjusts viscosity.30 DEG C or less are cooled to, adds 150g ice water to emulsify, high-speed stirred 30min or so.At 60 DEG C, under 0.6MPa
Non-ionic polyurethane is made in desolventizing.
It takes the aqueous anionic polyurethane of above-mentioned 2/3 volume, 0.5g sodium bicarbonate, 0.2g allyl polythiaether sulfuric acid be added
Sodium (ammonium) and 0.1g sodium vinyl sulfonate are in 40~50 DEG C of 0.5~1h of emulsification.Temperature rises to 70 DEG C, is slowly added to remaining 1/3 body
Aqueous anion polyurethane, 18g methacrylic solvent yellow 5,20g methyl methacrylate, 20g styrene, 3.6g
Potassium peroxydisulfate about 3h is added, 2~3h of constant temperature, is down to room temperature naturally to get color-changing polyurethane acrylate dyestuff is arrived.Gained
Average grain diameter 105nm, pH=8, solid content 46%, viscosity 260mPas.
Embodiment 3
0.03mol Polyoxyethylene glycol and 0.03mol polyoxypropyleneglycol, 0.03mol is taken to be added equipped with temperature
Meter, blender, reflux condenser and dropping funel four-hole boiling flask in be warming up to 120 DEG C, dehydration after 1h, is passed through nitrogen cooling
To 60 DEG C, 2, the 4- toluene di-isocyanate(TDI) (TDI) and 0.0003mol dibutyl tin dilaurate of 0.1mol is added, is warming up to
80 DEG C, constant temperature 3h, 70 DEG C are cooled to, 0.035mol hydroxyethyl methacrylate, reaction 3h or so is added, 20 ml acetone are added
Adjust viscosity.At 60 DEG C, non-ionic polyurethane is made in desolventizing under 0.6MPa.
It takes the aqueous anionic polyurethane of above-mentioned 2/3 volume, 0.5g sodium bicarbonate, 0.2g allyloxy fatty alcohol oxygen be added
Ethylene ether ammonium sulfate, 0.1g allyl polyethenoxy ether, in 40~50 DEG C of 0.5~1h of emulsification.Temperature rises to 70 DEG C, slowly adds
Enter remaining 1/3 volume aqueous anionic polyurethane, 10g acrylamide solvent yellow 85,10g3,3- dimethylacrylamide solvent
5,20g of Huang butyl acrylate, 20g styrene, 2.6g ammonium persulfate, about 3h are added, and 2~3h of constant temperature is down to room temperature naturally,
Obtain color-changing polyurethane acrylate dyestuff.Averaging of income partial size 122nm, pH=8.0, solid content 40%, viscosity
300mPa·s。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method and preparation method thereof of color-changing polyurethane acrylate, which comprises the following steps:
(1) 12~25% polymer polyatomic alcohols are heated to 100~140 DEG C, under the conditions of vacuum degree≤0.1MPa, dehydration
0.5~1h；
(2) it is cooled to 60~90 DEG C, is added 6~15% polyisocyanates, 0.01~0.03% catalyst, under nitrogen protection, instead
Answer 1~3h；
(4) 4~10% hydrophilic monomers are added, react 1~3h at 50~90 DEG C；
(5) 30~50 DEG C are cooled to, 2~6% salt forming agents are added and react 30~60min；
(6) 50~70% 10~30min of deionized water high speed dispersion is added；
(7) aqueous anion-type water-thinned polyurethane is made in vacuum degree desolventizing；
(8) aqueous anionic polyurethane of above-mentioned 2/3 volume, 0.1~0.5% emulsifier, 0.5-0.8% sodium bicarbonate is taken to exist
40~50 DEG C of 0.5~1h of emulsification.Temperature rises to 70 DEG C, is slowly added to remaining 1/3 volume aqueous anionic polyurethane, 10~20%
Acrylic ester monomer, 5~10% azo group acrylamide, 0.1~0.5% initiator, 2~4h adds, permanent
2~3h of temperature.Naturally room temperature is down to get color-changing polyurethane acrylate dyestuff is arrived.
(9) ammonium hydroxide is added and adjusts pH to 8~10, obtain color-changing polyurethane acrylate.
In the step (8), the acrylamide of azo group the preparation method is as follows:
Appropriate diethylene glycol (DEG) is added to being completely dissolved in solvent yellow 5, acryloyl chloride, triethylamine by 1:1~5:1~10 in molar ratio, is protected
25~35 DEG C of reactions 12~for 24 hours are held, dries after the sediment acetone washing of filtering to constant weight, obtains acrylamide solvent yellow 5,
Structural formula are as follows:
In the step (8), the acrylamide of azo group the preparation method is as follows: 1:1~5:1~10 are by solvent in molar ratio
Appropriate diethylene glycol (DEG) is added to being completely dissolved in Huang 5, metering system isoxazolecarboxylic acid, triethylamine, keeps 25~35 DEG C of reactions 12~for 24 hours, mistake
It dries after the sediment acetone washing of filter to constant weight, obtains Methacrylamide solvent yellow 5, structural formula are as follows:
In the step (8), the acrylamide of azo group the preparation method is as follows: 1:1~5:1~10 are by solvent in molar ratio
Appropriate diethylene glycol (DEG) is added to being completely dissolved in Huang 5,3,3- dimethyl acryloyl chloride, triethylamine, keep 25~35 DEG C of reactions 12~
For 24 hours, it dries after the sediment acetone washing of filtering to constant weight, obtains 3,3- dimethylacrylamide solvent yellow 5, structural formula
Are as follows:
In the step (8), the acrylamide of azo group the preparation method is as follows: 1:1~5:1~10 are by solvent in molar ratio
Appropriate diethylene glycol (DEG) is added to being completely dissolved in Huang 5, beta-phenyl acryloyl chloride, triethylamine, keeps 25~35 DEG C of reactions 12~for 24 hours, mistake
It dries after the sediment acetone washing of filter to constant weight, obtains beta-phenyl acrylamide solvent yellow 5, structural formula are as follows:
2. a kind of preparation method of color-changing polyurethane acrylate according to claim 1, it is characterised in that: polymer is more
First alcohol is one or two kinds of in polyether polyol, polyester polyol.
3. a kind of preparation method of color-changing polyurethane acrylate according to claim 1, it is characterised in that: isocyanates
Monomer is selected from one of aromatic polyisocyanate, aliphatic polyisocyante, alicyclic polyisocyanates or a variety of.
4. a kind of preparation method of color-changing polyurethane acrylate according to claim 1 is it is characterized by: hydrophilic chain extension
Agent is in tartaric acid, dihydromethyl propionic acid, diaminobenzoic acid, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride
It is one or more.
5. a kind of preparation method of color-changing polyurethane acrylate according to claim 1, it is characterised in that: its feature exists
In: catalyst is one or both of organic tin, tertiary amines.
6. a kind of preparation method and preparation method thereof of color-changing polyurethane acrylate according to claim 1, feature
Be: organic solvent is selected from acetone, butanone, methyl ethyl ketone, dioxane, N, N- dimethylformamide, N-Methyl pyrrolidone, acetic acid
One of ethyl ester is a variety of.
7. a kind of preparation method of color-changing polyurethane acrylate according to claim 1, it is characterised in that: salt forming agent choosing
From triethylamine, one of ammonium hydroxide, sodium hydroxide or a variety of.
8. a kind of preparation method of color-changing polyurethane acrylate according to claim 1, it is characterised in that: acrylate
Class monomer is selected from acrylate, methyl methacrylate, styrene, butyl acrylate, butyl methacrylate acrylonitrile, tertiary carbon
Vinyl acetate, tricarboxylic trimethacrylate, trimethylol-propane trimethacrylate, vinyl acetate, propylene
One of acid -2- ethylhexyl, methacrylic acid -2- hydroxy methacrylate are a variety of.
9. a kind of preparation method of color-changing polyurethane acrylate according to claim 1, it is characterised in that: emulsifier choosing
From allyl polysulfide ether sodium sulfate (ammonium), allyl polythiaether sodium sulfosuccinate, sodium vinyl sulfonate, 3- allyloxy -2-
Hydroxyl-propyl sodium sulfonate (COPS-1), 3- allyloxy -2- hydroxyl-propyl sodium ascorbyl phosphate (COPS-3), allyloxy fatty alcohol
Ethylene oxide ether ammonium sulfate (SR-10), allyl polyethenoxy ether, methallyl hydroxide sodium dimercaptosulphanatein, allyloxy hydroxide sodium dimercaptosulphanatein
It is one or more.
10. a kind of preparation method of color-changing polyurethane acrylate according to claim 1, it is characterised in that: initiator
Selected from one of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate or a variety of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073408A (en) * | 2019-12-02 | 2020-04-28 | 安徽富瑞雪化工科技股份有限公司 | Color-changing building coating for chemical engineering workshop and preparation and application thereof |
| CN114316151A (en) * | 2021-12-14 | 2022-04-12 | 福建汇得新材料有限公司 | Modified waterborne polyurethane, preparation method thereof and surface treating agent |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035302A (en) * | 1988-02-06 | 1989-09-06 | 浙江大学 | The preparation of water dispersion of network polyurethane |
| CN1729266A (en) * | 2002-11-04 | 2006-02-01 | 澳大利亚聚合物有限公司 | Photochromic compositions and light transmissible articles |
| CN105949425A (en) * | 2016-06-07 | 2016-09-21 | 安徽建筑大学 | Polyurethane-based black polymeric dye, preparing method and application |
| CN106496485A (en) * | 2016-11-09 | 2017-03-15 | 广州慧谷化学有限公司 | A kind of epoxide modified the moon/non-ionic water polyurethane resin and preparation method thereof |
| CN107501511A (en) * | 2017-09-14 | 2017-12-22 | 安徽建筑大学 | A kind of anionic compounding water polyurethane base black dyes and preparation method thereof |
| CN107573477A (en) * | 2017-09-14 | 2018-01-12 | 安徽建筑大学 | A kind of cationic compounding water polyurethane base black dyes and preparation method thereof |
| CN107868204A (en) * | 2017-11-30 | 2018-04-03 | 上海大学 | Anionic water type polyurethane resin, its preparation method and its application |
| CN108530602A (en) * | 2018-03-19 | 2018-09-14 | 安徽建筑大学 | A kind of color-changing polyurethane acrylic colour resin and preparation method |
-
2018
- 2018-11-12 CN CN201811339914.5A patent/CN109517406A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035302A (en) * | 1988-02-06 | 1989-09-06 | 浙江大学 | The preparation of water dispersion of network polyurethane |
| CN1729266A (en) * | 2002-11-04 | 2006-02-01 | 澳大利亚聚合物有限公司 | Photochromic compositions and light transmissible articles |
| CN105949425A (en) * | 2016-06-07 | 2016-09-21 | 安徽建筑大学 | Polyurethane-based black polymeric dye, preparing method and application |
| CN106496485A (en) * | 2016-11-09 | 2017-03-15 | 广州慧谷化学有限公司 | A kind of epoxide modified the moon/non-ionic water polyurethane resin and preparation method thereof |
| CN107501511A (en) * | 2017-09-14 | 2017-12-22 | 安徽建筑大学 | A kind of anionic compounding water polyurethane base black dyes and preparation method thereof |
| CN107573477A (en) * | 2017-09-14 | 2018-01-12 | 安徽建筑大学 | A kind of cationic compounding water polyurethane base black dyes and preparation method thereof |
| CN107868204A (en) * | 2017-11-30 | 2018-04-03 | 上海大学 | Anionic water type polyurethane resin, its preparation method and its application |
| CN108530602A (en) * | 2018-03-19 | 2018-09-14 | 安徽建筑大学 | A kind of color-changing polyurethane acrylic colour resin and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073408A (en) * | 2019-12-02 | 2020-04-28 | 安徽富瑞雪化工科技股份有限公司 | Color-changing building coating for chemical engineering workshop and preparation and application thereof |
| CN114316151A (en) * | 2021-12-14 | 2022-04-12 | 福建汇得新材料有限公司 | Modified waterborne polyurethane, preparation method thereof and surface treating agent |
| CN114316151B (en) * | 2021-12-14 | 2023-09-12 | 福建汇得新材料有限公司 | Modified waterborne polyurethane, preparation method thereof and surface treatment agent |
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