CN106867376B - The preparation method and applications of polyfunctionality hydrophily UV-cured resin - Google Patents
The preparation method and applications of polyfunctionality hydrophily UV-cured resin Download PDFInfo
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- CN106867376B CN106867376B CN201710055097.XA CN201710055097A CN106867376B CN 106867376 B CN106867376 B CN 106867376B CN 201710055097 A CN201710055097 A CN 201710055097A CN 106867376 B CN106867376 B CN 106867376B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The present invention provides a kind of preparation method and applications of polyfunctionality hydrophily UV-cured resin, the preparation method uses two step Michael's addition methods, specially obtains double ends secondary amino compound intermediate through Michael addition reaction using the methoxy polyethylene glycol acrylate of binary polyetheramine and twice of equivalent；Then the intermediate carries out Michael addition reaction with the polyfunctional acrylic ester of twice of equivalent again up to light-cured resin.Light-cured resin produced by the present invention is applied in ultraviolet light anti-fog coating formula, and after ultraviolet light solidifies, not only initial hydrophilicity is good for film, and water-tolerant, has lasting anti-fog performance, and hardness of film is high, resistance to wiping is good.It is highly suitable for the demanding field of anti-fog performance, such as car light, windshield, bathroom mirror, optical lens material.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, and in particular to a kind of polyfunctionality hydrophily UV-cured resin
Preparation method and applications.
Background technique
Vapor in air will condense into small drop and mist formation when temperature is lower than dew point.It is this undesirable
Influence frequently occurs in window, bathroom mirror, glasses, swimming and Lunettes, windshield, optical instrument camera lens, solar energy
Battery light-transmitting plate, car light, indicator light, agricultural film etc. these live on the transparent material that is closely related with us.Transparent material surface
Water droplet atomization as a result, not only light transmittance decline influence vision, harm is generated sometimes, such as when droplet is condensed in such as infrared light
When learning on the lens surfaces of sophisticated analytical instruments such as microscope, the accuracy of analysis can be reduced.And when droplet condenses in the sun
When on energy battery light-transmitting plate, causes the reduction of solar absorption efficiency, give full play to and should have to be unfavorable for solar cell device
Effect.
In order to solve these problems, can generally hydrophobic or hydrophilic treated be carried out to material surface.Hydrophobic common perfluorinated resin
Class, one side price is higher, and on the other hand the resinoid is generally softer, wears no resistance, while its hydrophobic property also leads to its table
Face easily adsorbs greasy dirt and dust, the effect not reached requirement instead.And organic hydrophilic coating price itself is inexpensively, it can also
Its wearability is improved by some modifications.Using organic hydrophilic coating compared to hydrophobic coating processing method not only construction party
Just, and it is cheap.
It is concentrated mainly on super hydrophilic research both at home and abroad now, as coating surface introducing can form the group such as carboxylic of hydrogen bond
Base, amino, sulfydryl, hydroxyl or some ionic groups: carboxylate radical, sulfonate radical, ammonium root, phosphate radical etc., when these groups of introducing
Or when ion, the surface of coating reaches super hydrophilic state, sprawls after moisture condensation in substrate surface height, forms one layer
Even moisture film eliminates tiny drops of water and achievees the purpose that antifog to the diffusing reflection of light.Super hydrophilic approach master is prepared at present
If passing through physical blending, Chemical modification, chemical bond connection.Anti-fog coating currently on the market is typically all initial antifog
Better performances, but after a period of use, anti-fog performance just declines obviously, i.e., persistently anti-fog performance is poor.
Chinese patent CN 104053731A discloses a kind of thermosetting property anti-fog coating, which includes polyurethane
Dispersion, modified aziridine hardener, hydrophilic silicon oxides nanoparticle, surfactant.This is a kind of thermosetting aqueous
Coating, need 110 degree or more heat 20 minutes more than can just be cured, formation cross-linked network.Although anti-fog performance is preferable,
But energy consumption is high and to play the ingredient of hydrophilic antifogging performance here be mainly surfactant in fact, and it is not involved at all consolidates
Change reaction, be only crosslinked network physical and fix, in the case where high humility, is easy to be lost and influence to continue anti-fog properties
Energy.In addition, hydrophilic silicon oxides nanoparticle also needs to carry out nanometer using the silane coupling agent with hydrophilic radical
Silica dispersion is surface-treated to obtain, and technics comparing is complicated.And hydrophilic silane coupling agent price is somewhat expensive, and plants
Class is rare.Therefore manufacturing cost can improve.
Chinese patent CN102911582A discloses a kind of ultraviolet light curing anti fogging coating.The main body hydrophilic resin of the coating
Rouge is by polymerizable nonionic surfactant allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether, acrylate and acrylic acid
The polyacrylate that side chain contains carboxyl is obtained through free radical polymerization, then it is sweet to carry out open loop Glycidyl methacrylate for side chain carboxyl group
The epoxy group of grease and obtain side chain photocuring hydrophilic polyacrylic ester containing double bonds.But allyloxy monomer is poly-
It is more much lower than the polymerization activity of acrylic ester monomer to close activity, therefore a large amount of unreacted allyloxy nonyl benzene oxygen can be remained
Base propyl alcohol polyoxyethylene ether.Although light can also occur in coating for remaining allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether
Polymerization reaction, but its polymerization activity is lower, therefore still has part and remain in coating, is not engaged in curing reaction and is formed
Cross-linked network is only crosslinked network physical and fixes, and in the case where high humility, is easy to be lost and influence to continue anti-fog properties
Energy.
It is general to there is persistently anti-fog effect in most of anti-fog coating on the market.It is persistently anti-fog properties to require the resistance to of film well
Mill property is good, but it is again contradictory each other well with initial anti-fog performance that wearability is good.Therefore, to solve this contradiction, it is badly in need of exploitation
Hydrophilic and excellent wearability anti-fog coating just can guarantee the initial antifog and lasting anti-fog performance that coating has had both in this way.And it wants
Meet it is such require, the bulk composition-for developing anti-fog coating is hydrophilic and hydrophilic resin that wearability is good is to be highly desirable
's.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of solidifications of polyfunctionality hydrophily ultraviolet light to set
The preparation method and applications of rouge, prepared resin is used in ultraviolet light anti-fog coating formula, after ultraviolet light solidifies, film
Not only initial hydrophilicity is good, and water-tolerant, has lasting anti-fog performance, and hardness of film is high, resistance to wiping is good, very suitable
It closes and is applied to that there is the demanding field of anti-fog performance, such as car light, windshield, bathroom mirror, optical lens material.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of preparation method of polyfunctionality hydrophily UV-cured resin, the method includes with
Lower step:
Under room temperature, by the methoxy polyethylene glycol acrylate of binary polyetheramine and twice of equivalent in alcohol solvent
It carries out Michael addition reaction 1-2 hours, obtains double ends secondary amino compound intermediate；
Double end secondary amino compound intermediates are again with the polyfunctional acrylic ester of twice of equivalent in 40-45 DEG C of item
Under part, Michael addition reaction 2-3 hours is carried out to get polyfunctionality hydrophily UV-cured resin is arrived.
Preferably, the binary polyetheramine includes D-230, D-400, D-2000, D4000, ED- of Huntsman Corporation's production
600, one of ED-900, ED-2003.
Preferably, the binary polyetheramine is one of D-400, ED-600, ED-900, ED-2003.
Preferably, the molecular weight of the polyethylene glycol unit in the methoxy polyethylene glycol acrylate is not less than 400.If
The molecular weight of polyethylene glycol unit in methoxy polyethylene glycol acrylate then will lead to polyfunctionality hydrophily less than 400
UV-cured resin hydrophily is too poor, and anti-fog performance is poor.
Preferably, the molecular weight of the polyethylene glycol unit in the methoxy polyethylene glycol acrylate is not less than 600.
Preferably, the polyfunctional acrylic ester is the acrylate monomer that degree of functionality is not less than 4.According to degree of functionality
The degree of functionality of acrylate monomer less than 4, the then light-cured resin prepared is low, and water resistance can reduce, and lasting anti-fog performance is poor,
In addition wearability also can be reduced accordingly.
Preferably, ethoxy unit is contained in the polyfunctional acrylic ester, the quantity of the ethoxy unit is not
Less than 20.When the ethoxy unit is less than 20, polyfunctionality hydrophily UV-cured resin hydrophily will lead to too
Difference, anti-fog performance are poor.
Preferably, the quantity of the ethoxy unit is no less than 30.
Preferably, the degree of functionality for the polyfunctionality hydrophily UV-cured resin that the method obtains is not less than 4.
The present invention also provides a kind of polyfunctionality hydrophily UV-cured resins according to the method preparation anti-
Application in mist coating.
It can be by synthesizing original using the hydrophilicrty of the polyfunctionality hydrophily UV-cured resin of above method preparation
Material is to control, such as the molecular weight of binary polyetheramine is big, i.e. ethyoxyl or isopropoxy number is more, and hydrophily is bigger；Methoxyl group
The molecular weight of polyethylene glycol unit is higher in polyethylene glycol acrylate structure, and hydrophily is bigger；In polyfunctional acrylic ester
Ethoxy unit number is more, and hydrophily is bigger.For polyfunctional acrylic ester, in the case where same ethoxy unit number,
Degree of functionality is bigger, and hydrophily is smaller.Therefore, it is used for using the polyfunctionality hydrophily UV-cured resin as matrix resin
In photocuring anti-fog coating system, due to introducing a large amount of hydrophilic parts, film has excellent hydrophilicity, can make sky
Condensation vapor in gas is formed on its surface moisture film rather than water droplet, has good initial anti-fog performance.On the other hand, due to
Polyfunctionality structure can be formed after the solidification of ultraviolet official with the other UV-cured resins or monomer in coating system
Cross-linked network structure, hydrophilic parts are not fixed on cross-linked network not instead of physically, are fixed on crosslinking with chemical bond
On network, water or vapor will not be caused to fall painting film bubble, so film protracted hydrophilicity is good, embodied anti-fog properties with continuing
Energy.
The prior art is compared, the present invention have it is following the utility model has the advantages that
1, the preparation method for the polyfunctionality hydrophily UV-cured resin that the present invention uses is simple, in lower temperature
Under, it can be made, and do not have to post-processing, can be directly used by two step Michael addition reactions in the short time.
2, the hydrophilicrty of more official's photocuring hydrophily UV-cured resins of the invention can be controlled arbitrarily as desired
System.When meeting the Superhydrophilic in some fields and needing, the binary polyetheramine more than ethyoxyl or isopropoxy number can choose
The big methoxy polyethylene glycol acrylate and ethoxy radix is more, degree of functionality is slightly much lower with polyethylene glycol unit molecular weight
Degree of functionality acrylate.Meet with superior abrasion resistance, i.e. guarantee is initial anti-fog properties, also continues anti-fog performance with excellent
When the domain requirement got well, it can be reached by using the high polyfunctional acrylic ester of degree of functionality.
3, using polyfunctionality hydrophily UV-cured resin of the invention for passing through in photocuring anti-fog coating formula
After ultraviolet light solidification, film initial hydrophilicity is good, has excellent wear-resisting property, therefore have good water resistance.It is reflected in
Be exactly on anti-fog performance not only initial stage anti-fog performance it is good, and have lasting anti-fog performance.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The raw material used in the preparation of the present embodiment and the polyfunctionality photocuring hydrophilic resin of comparative example is as follows:
Since commercially available raw material limit, methoxy polyethylene glycol acrylate is only with following four:
Methoxymethoxy polyethylene glycol (400) acrylate, methoxymethoxy polyethylene glycol (600) acrylate,
Methoxy poly (ethylene glycol) (1000) acrylate and methoxy poly (ethylene glycol) (2000) acrylate.
The more official's acrylate of ethyoxyl use following five kinds:
3 officials: ethyoxyl trimethylolpropane trimethacrylate (EO35mol), ethyoxyl quantity therein are 35；
4 officials: ethoxylated pentaerythritol tetraacrylate (EO15mol), ethyoxyl quantity therein are 15；
4 officials: ethoxylated pentaerythritol tetraacrylate (EO35mol), ethyoxyl quantity therein are 35；
4 officials: ethoxylated pentaerythritol tetraacrylate (EO120mol), ethyoxyl quantity therein are 120；
6 officials: ethyoxyl double pentaerythritol methacrylate (EO96mol), ethyoxyl quantity therein are 96.
Embodiment 1
A kind of preparation method of polyfunctionality hydrophily UV-cured resin is present embodiments provided, specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (61 grams), polymerization inhibitor
P-hydroxyanisole (0.18 gram), polyetheramine D-400 (2.30 grams, 5mmol) and methoxy poly (ethylene glycol) (1000) acrylate
(10.54 grams, 10mmol) react at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction
Terminate.Then be added ethyoxyl double pentaerythritol methacrylate (EO96mol) (48.02 grams, 10mmol), be warming up to 45 degree it is anti-
It answers 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, light yellow clear liquid is obtained,
For 10 official's hydrophily UV-cured resins of 50% solid content.
Embodiment 2
A kind of preparation method of polyfunctionality hydrophily UV-cured resin is present embodiments provided, specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (69 grams), polymerization inhibitor
P-hydroxyanisole (0.21 gram), polyetheramine D400 (2.30 grams, 5mmol) and methoxy poly (ethylene glycol) (1000) acrylate
(10.54 grams, 10mmol) react at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction
Terminate.Then be added ethoxylated pentaerythritol tetraacrylate (EO120mol) (56.32 grams, 10mmol), be warming up to 45 degree it is anti-
It answers 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, light yellow clear liquid is obtained,
For 6 official's hydrophily UV-cured resins of 50% solid content.
Embodiment 3
A kind of preparation method of polyfunctionality hydrophily UV-cured resin is present embodiments provided, specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (61 grams), polymerization inhibitor
P-hydroxyanisole (0.18 gram), polyetheramine ED-600 (2.64 grams, 5mmol) and methoxy poly (ethylene glycol) (1000) acrylate
(10.54 grams, 10mmol) react at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction
Terminate.Then be added ethyoxyl double pentaerythritol methacrylate (EO96mol) (48.02 grams, 10mmol), be warming up to 45 degree it is anti-
It answers 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, light yellow clear liquid is obtained,
For 10 official's hydrophily UV-cured resins of 50% solid content.
Embodiment 4
A kind of preparation method of polyfunctionality hydrophily UV-cured resin is present embodiments provided, specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (45 grams), polymerization inhibitor
P-hydroxyanisole (0.14 gram), polyetheramine ED-900 (5.0 grams, 5mmol) and methoxy poly (ethylene glycol) (2000) acrylate
(20.96 grams, 10mmol) react at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction
Terminate.Then ethoxylated pentaerythritol tetraacrylate (EO35mol) (18.92 grams, 10mmol) are added, are warming up to 45 degree of reactions
3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow clear liquid, is
6 official's hydrophily UV-cured resins of 50% solid content.
Embodiment 5
A kind of preparation method of polyfunctionality hydrophily UV-cured resin is present embodiments provided, specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (82 grams), polymerization inhibitor
P-hydroxyanisole (0.25 gram), polyetheramine ED-2003 (23.0 grams, 10mmol) and methoxy poly (ethylene glycol) (1000) acrylic acid
Ester (21.08 grams, 20mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, the first step is anti-
It should terminate.Then be added ethoxylated pentaerythritol tetraacrylate (EO35mol) (37.84 grams, 20mmol), be warming up to 45 degree it is anti-
It answers 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, light yellow clear liquid is obtained,
For 6 official's hydrophily UV-cured resins of 50% solid content.
Embodiment 6
A kind of preparation method of polyfunctionality hydrophily UV-cured resin is present embodiments provided, specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (67 grams), polymerization inhibitor
P-hydroxyanisole (0.14 gram), polyetheramine ED-900 (5.0 grams, 5mmol) and methoxy poly (ethylene glycol) (600) acrylate
(6.16 grams, 10mmol) react at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction
Terminate.Then be added ethoxylated pentaerythritol tetraacrylate (EO120mol) (56.32 grams, 10mmol), be warming up to 45 degree it is anti-
It answers 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, light yellow clear liquid is obtained,
For 6 official's hydrophily UV-cured resins of 50% solid content.
Comparative example 1
This comparative example provides a kind of preparation method of polyfunctionality hydrophily UV-cured resin, and specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (59 grams), polymerization inhibitor
P-hydroxyanisole (0.18 gram), hexamethylene diamine (0.58 gram, 5mmol) and methoxy poly (ethylene glycol) (1000) acrylate (10.54
Gram, 10mmol), it reacts at room temperature 1.5 hours, FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction terminates.
Then ethyoxyl double pentaerythritol methacrylate (EO96mol) (48.02 grams, 10mmol) are added, it is small is warming up to 45 degree of reactions 3
When, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow clear liquid, is 50%
10 official's hydrophily UV-cured resins of solid content.
Comparative example 2
This comparative example provides a kind of preparation method of polyfunctionality hydrophily UV-cured resin, and specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (60 grams), polymerization inhibitor
P-hydroxyanisole (0.18 gram), polyetheramine D400 (2.30 grams, 5mmol) and butyl acrylate (1.28 grams, 10mmol), room temperature
Reaction 1.5 hours, FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction terminates.Then ethyoxyl season is added
Penta tetra-acrylate (EO120mol) (56.32 grams, 10mmol) is warming up to 45 degree and reacts 3 hours, and FT-IR can't detect
3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow clear liquid, is that 6 officials of 50% solid content are hydrophilic
Property UV-cured resin.
Comparative example 3
This comparative example provides a kind of preparation method of polyfunctionality hydrophily UV-cured resin, and specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (72 grams), polymerization inhibitor
P-hydroxyanisole (0.22 gram), polyetheramine ED-900 (10.0 grams, 10mmol) and methoxy poly (ethylene glycol) (2000) acrylic acid
Ester (41.92 grams, 20mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, the first step is anti-
It should terminate.Then be added ethoxylated pentaerythritol tetraacrylate (EO15mol) (20.24 grams, 20mmol), be warming up to 45 degree it is anti-
It answers 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, light yellow clear liquid is obtained,
For 6 official's hydrophily UV-cured resins of 50% solid content.
Comparative example 4
This comparative example provides a kind of preparation method of polyfunctionality hydrophily UV-cured resin, and specific steps are such as
Under: equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (56 grams), polymerization inhibitor
P-hydroxyanisole (0.15 gram), polyetheramine ED-900 (10.0 grams, 10mmol) and methoxy poly (ethylene glycol) (2000) acrylic acid
Ester (9.08 grams, 20mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, the first step is anti-
It should terminate.Then ethyoxyl trimethylolpropane trimethacrylate (EO35mol) (36.72 grams, 20mmol) are added, are warming up to 45
Degree reaction 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow clear liquid
Body is 4 official's hydrophily UV-cured resins of 50% solid content.
Performance test
To polyfunctionality hydrophily UV-cured resin prepared by synthesized example 1~6 and comparison synthesis example 1~4, respectively
After being made into the ultraviolet light curing anti fogging coating of the Application Example 1-6 being listed in Table 1 below and Comparison study example 1-4, using PET as base
Coating (30% contains admittedly) prepared by embodiment and comparative example is coated on its surface with No. 10 line stick, is put into 60 DEG C of baking ovens by material
1min passes through ultra-violet curing, energy 500mJ/cm later2。
It respectively corresponds the coating made from Examples 1 to 6 and Comparison study example 1~4 and carries out performance detection, measure coating
Adhesive force, pencil hardness, wearability, initial stage water contact angle and sustained water contact angle and anti-fog performance.Concrete outcome is listed in table 1
In.
Specific performance detection project and corresponding method are as follows:
One, adhesive force
Using baige method, specimen page adhesive force is tested with 3M Pressure sensitive adhesive tape.
Appraisal procedure:
5B- scribing edge is smooth, falls off the edge and intersection of scribing line are uncoated；
4B- has the coating shedding of small pieces in the intersection of scribing line, and the gross area that falls off is less than 5%；
3B- has the coating shedding of small pieces at the edge and intersection of scribing line, and fall off the gross area 5~15% it
Between；
2B- has sheet of coating shedding at the edge and intersection of scribing line, and fall off the gross area 15~35% it
Between；
1B- has sheet of coating shedding at the edge and intersection of scribing line, and fall off the gross area 35~65% it
Between；
0B- has sheet of coating shedding at the edge and intersection of scribing line, and the gross area that falls off is greater than 65%.
Two, pencil hardness
Referring to standard GB/T/T6739 " hardness of paint film pencil measuring method ".
Three, wear-resisting property
Using 0000# steel wool, 300g power, one is denoted as once back and forth, and the number scratched occurs in recording surface.
Appraisal procedure: after the friction of certain number, whether observation coating has scratch, is resistant to when recording without scratch
Most Rubbing numbers.
Four, initial stage hydrophilic angle
4 μ L deionized waters are dripped in the specimen surface being cured, are measured within the scope of 20~25 DEG C with contact angle tester.
Five, continue hydrophilic angle
The sample being cured is put into deionized water and is impregnated for 24 hours, is measured after drying with contact angle measurement.
Six: anti-fog properties: the test board that surface temperature is 25 degree being horizontally placed above 80 DEG C of the water surface at 10cm, sample is observed
The time that plate hazes.
It hazes in X:1 seconds
Δ: it hazes after 10 seconds
It hazes after zero: 30 second
◎: it does not haze
Table 1
Application Example 1~6 has preferable anti-fog performance it can be seen from the performance test results of table 1.Initial water connects
Feeler is below 10 degree, and the water contact angle after impregnating for 24 hours is below 35 degree, and anti-fog performance is excellent, while wearability might as well.
Comparison study example 1 is compared with Application Example 1, since hydrophily polyfunctionality purple light solidified resin used synthesizes
When, polyetheramine D400 is replaced using hexamethylene diamine, the hydrophily of the final polyfunctionality UV-cured resin of gained is poor, because
This is used in anti-fog coating formula, although coating abrasion performance improves a lot, causes the hydrophily of coating poor, because without having
Standby anti-fog performance.
Comparison study example 2 is compared with Application Example 2, since hydrophily polyfunctionality UV-cured resin used synthesizes
When, when the first step is reacted, replace methoxy poly (ethylene glycol) (1000) acrylate using butyl acrylate, the final more officials of gained
The hydrophily of energy degree UV-cured resin is poor, therefore is used in anti-fog coating formula, although coating abrasion performance slightly mentions
Height, but cause the hydrophily of coating poor, because without having anti-fog performance.
Comparison study example 3 is compared with Application Example 4, since hydrophily polyfunctionality UV-cured resin used synthesizes
When, radix containing ethoxy is replaced using the ethoxylated pentaerythritol tetraacrylate (EO15mol) of the small number containing ethyoxyl
Measure more ethoxylated pentaerythritol tetraacrylate (EO35mol), the parent of the final polyfunctionality UV-cured resin of gained
It is aqueous poor, therefore be used in anti-fog coating formula, although coating abrasion performance slightly improves, lead to the hydrophily of coating
Difference, because without having anti-fog performance.
Comparison study example 4 is compared with Application Example 4, since hydrophily polyfunctionality UV-cured resin used synthesizes
When, ethoxylated pentaerythritol tetraacrylate is replaced using ethyoxyl trimethylolpropane trimethacrylate (EO35mol)
(EO35mol), tetra functional UV-cured resin is obtained.Because final resin degree of functionality is lower, hydrophily is very good, causes final
Coating is detached from hydrophilic segment network from substrate surface, and hydrophobic part in coating is caused to be in the great majority, and makes
Hydrophily substantially reduces.The wear-resisting and hardness of coating is significantly reduced simultaneously.
It should be pointed out that above embodiments are merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.It is right
For those skilled in the art, without departing from the principle of the present invention, several improvement can also be made,
These improvement also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of polyfunctionality hydrophily UV-cured resin, which is characterized in that the method includes following
Step:
Under room temperature, binary polyetheramine and the methoxy polyethylene glycol acrylate of twice of equivalent are carried out in alcohol solvent
Michael addition reaction 1-2 hours, obtain double ends secondary amino compound intermediate；
Double end secondary amino compound intermediates are again with the polyfunctional acrylic ester of twice of equivalent in 40-45 DEG C of condition
Under, Michael addition reaction 2-3 hours is carried out to get polyfunctionality hydrophily UV-cured resin is arrived；
The polyfunctional acrylic ester is the acrylate monomer that degree of functionality is not less than 4；In the polyfunctional acrylic ester
Containing ethoxy unit, the quantity of the ethoxy unit is not less than 20.
2. the preparation method of polyfunctionality hydrophily UV-cured resin according to claim 1, which is characterized in that institute
State D-230, D-400, D-2000, D4000, ED-600, ED-900, ED- that binary polyetheramine includes Huntsman Corporation's production
One of 2003.
3. the preparation method of polyfunctionality hydrophily UV-cured resin according to claim 2, which is characterized in that institute
Stating binary polyetheramine is one of D-400, ED-600, ED-900, ED-2003.
4. the preparation method of polyfunctionality hydrophily UV-cured resin according to claim 1, which is characterized in that institute
The molecular weight of the polyethylene glycol unit in methoxy polyethylene glycol acrylate is stated not less than 400.
5. the preparation method of polyfunctionality hydrophily UV-cured resin according to claim 1, which is characterized in that institute
The molecular weight of the polyethylene glycol unit in methoxy polyethylene glycol acrylate is stated not less than 600.
6. the preparation method of polyfunctionality hydrophily UV-cured resin according to claim 1, which is characterized in that institute
The quantity for stating ethoxy unit is no less than 30.
7. the preparation method of polyfunctionality hydrophily UV-cured resin according to claim 1, which is characterized in that institute
The degree of functionality for the polyfunctionality hydrophily UV-cured resin that the method for stating obtains is not less than 4.
8. the polyfunctionality hydrophily UV-cured resin that one kind is prepared method according to claim 1 is in anti-fog coating
Application.
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| CN115028830B (en) * | 2022-05-10 | 2023-12-22 | 武汉中科先进材料科技有限公司 | Hydrophilic resin for anti-fog coating and preparation method thereof |
| CN116023849B (en) * | 2022-11-21 | 2023-08-01 | 武汉中科先进材料科技有限公司 | Anti-fog coating, preparation method thereof and anti-fog coating |
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| CN101935494B (en) * | 2010-08-18 | 2013-11-13 | 梁鹏飞 | Ultraviolet-cured resin composition and preparation method thereof |
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