CN101074277A - Esterified acrylie-ester high-polymer, its synthesis and use - Google Patents
Esterified acrylie-ester high-polymer, its synthesis and use Download PDFInfo
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- CN101074277A CN101074277A CN 200710023350 CN200710023350A CN101074277A CN 101074277 A CN101074277 A CN 101074277A CN 200710023350 CN200710023350 CN 200710023350 CN 200710023350 A CN200710023350 A CN 200710023350A CN 101074277 A CN101074277 A CN 101074277A
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- acrylic ester
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Abstract
An acrylic ester polymer and its synthesis are disclosed. The process is carried out by heat polymerizing for mixture of thermal initiator benzoyl peroxide and acrylic ester under agitation and nitrogen protection to obtain acrylic ester polymer, adding into acrylic acid, taking tosylate as catalyst and hydroquinone as inhibitor, reacting at 100-110 degree, removing water, decompressing, and removing solvent and inactive raw material to obtain final product. It can be used to machine building material cyanamide paper, and improve coating and substrate performances and adhesion.
Description
Technical field
The invention belongs to the environmental friendliness field of light-sensitive high molecular materials, particularly relate to free radical, the prescription of cationic photopolymerization aggressiveness system and synthesizing of special additive.
Background technology
Photopolymerization is to utilize light as reaction power, on photosensitive compound, makes it that a series of optical physics take place by light action, photochemical reaction, generate active substance, thus the initiating activity monomer polymerization, and Ye Tai resin is converted into solid-state macromolecular material the most at last.Its polymerization characteristics are to save the energy, environmental friendliness, economical and efficient, photopolymerization device compactness, production efficiency height.In addition, photopolymerization compares to traditional polymerization technique outstanding advantage, and for example polymerized at room temperature helps the processing of heat-sensitive substrate material; Polymerization formula can be regulated by demand, guarantees product performance (as hardness, flexibility, gloss, weathering resistance etc.); Be easy to realize streamline operration, the level of automation height.Therefore photopolymerization is the advanced manufacturing technology of a kind of being described as " green technology ".
According to the biologically active fragment difference that produces, light trigger can be divided into radical polymerization light trigger and cationoid polymerisation light trigger.What use now is radical photopolymerization the most widely, and it is fast that it has speed, and the surface properties height is to advantages such as humidity are insensitive.Free radical photo-initiation can be divided into crack type photoinitiator and hydrogen-capture-type light initiator according to the mechanism difference that produces the free radical fragment.Hydrogen-capture-type light initiator absorbs luminous energy, in excited state and the effect of aided initiating generation bimolecular, produces living radical.Tertiary amine is to be commonly used to and hydrogen-capture-type light initiator paired aided initiating.Cation light initiator is to produce strong acid and cause epoxy under illumination, and resin polymerizations such as vinyl ether are characterized in there is not oxygen inhibition, and volumetric shrinkage is little during polymerization.
Melamine paper is because its surperficial special construction makes that its surperficial application is very difficult.General coating does not have sticking power on its surface, and for application is carried out on the melamine paper surface, special formulation for coating material is necessary.
Summary of the invention
First purpose of the present invention is to invent a kind of additive of carrying coating at the melamine paper surface adhesion force---the acrylic ester high molecular type of acroleic acid esterification.
Its structure is as follows:
Wherein: n, m, k, p, q are respectively 1～500 integer;
R
1Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R
2Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R
3Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R is CH
2CH
2CH
2, or CH
25CH
2CH
2And CH
2CH
2, or CH
2CH
2CH
2And CHOHCH
2
Special additive of the present invention is the acrylic ester high molecular type of acroleic acid esterification, except that containing capable acrylic double bond, also contain other functional group such as carboxyl, hydroxyl, ester groups etc. are used for the processing of building decoration melamine paper, are used to improve the material of coating property, improve material to base material, particularly the sticking power of coating and melamine paper.
Second purpose of the present invention is to be that above-mentioned additive---the acrylic ester high molecular type of acroleic acid esterification provides a kind of synthetic method.
Synthetic method is: stir and the condition of nitrogen protection under, will to be 0.1～3% thermal initiator benzoyl peroxide and acrylate mixture carry out heat polymerization in concentration is 30～70% toluene solution make acrylic ester high molecular type to monomeric content; Wherein, polymerization temperature is 65～100 ℃, and polymerization time is 3～10 hours.In the synthetic acrylic ester high molecular type, add vinylformic acid again, with the tosic acid is catalyzer, and Resorcinol is a stopper, after 100～110 ℃ of reactions and dewatering, reduce pressure, remove and desolvate and unreacted raw material, obtain the acrylic ester high molecular type of acroleic acid esterification.
The aforesaid propylene acid esters is an ethyl propenoate, or butyl acrylate, or glycidyl methacrylate, or Octyl acrylate, or vinylformic acid, or dodecyl acrylate, or octadecyl acrylate, or Hydroxyethyl acrylate, or Propylene glycol monoacrylate, or propyl acrylate, or in the methyl acrylate at least any one.
The molecular weight of polymkeric substance is by polymerization time, polymerization temperature, initiator amount, toluene level control.The kind control of the character of polymkeric substance acrylate during by polymerization.
Synthetic method of the present invention is simple, easy handling makes things convenient for industrial production to use, and the synthetic special additive is the acrylic ester high molecular type of acroleic acid esterification, it has good solvability at general (methyl) vinylformic acid reactive monomer in Resins, epoxy and (methyl) acrylic resin.
The 3rd purpose of the present invention provides the purposes of the acrylic ester high molecular type of described acroleic acid esterification.
The acrylic ester high molecular type of acroleic acid esterification is used to make ultraviolet-curing paint.
The method of making ultraviolet-curing paint is: in the container of whipping device is housed, add and account for acrylic ester high molecular type, 1%～5% auxiliary agent, 3%～10% free radical and the cation light initiator that total weight percent is 10%～50% reactive thinner, 5%～30% acroleic acid esterification, after the stirring and dissolving, add 20%～50% light reactive resin again, 10～30% Resins, epoxy, under 20～50 ℃ of temperature, stirring makes it to mix and promptly obtains ultraviolet-curing paint.
Described light reactive resin is any in epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of acroleic acid esterification.
Described reactive thinner is any in simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer; Or the combination of any and polyfunctionality in the simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer; Or any and single functionality epoxy in the simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer.
Described auxiliary agent comprises flow agent, defoamer, oxidation inhibitor, uv-absorbing agent.
Described Resins, epoxy is any in bisphenol type epoxy, aliphatic category epoxy, the alicyclic ring same clan epoxy.
When using UV-light of the present invention (UV) coating and carrying out polymerization, can adopt light sources such as mercuryarc lamp, electrodeless lamp source, xenon lamp, metal halide lamp, LED lamp.The UV coating that contains the acrylic ester high molecular type of acroleic acid esterification can carry out quick photocuring as melamine paper decoration lighting solidified coating material.
Embodiment
One, the preparation method of acrylic ester high molecular type:
Stir and the condition of nitrogen protection under, will to be 0.1～3% thermal initiator benzoyl peroxide and acrylate mixture carry out heat polymerization in concentration is 30～70% toluene solution make acrylic ester high molecular type to monomeric content; Wherein, polymerization temperature is 65～100 ℃, and polymerization time is 3～10 hours.
The aforesaid propylene acid esters is an ethyl propenoate, or butyl acrylate, or glycidyl methacrylate, or Octyl acrylate, or vinylformic acid, or dodecyl acrylate, or octadecyl acrylate, or Hydroxyethyl acrylate, or Propylene glycol monoacrylate, or propyl acrylate, or in the methyl acrylate at least any one.
Synthetic example 1
Ethyl propenoate (accounting for weight percent 25%), butyl acrylate (20%), glycidyl methacrylate (5%), octadecyl acrylate (5%), Hydroxyethyl acrylate (20%), methyl acrylate (25%) totally 100 grams join in the 100 gram toluene, add 0.1 gram benzoyl peroxide, be warming up to 80 ℃, react and wait product to be used for further reaction after 10 hours.
Synthetic example 2
Octyl acrylate (30%), butyl acrylate (20%), glycidyl methacrylate (10%), dodecyl acrylate (5%), Propylene glycol monoacrylate (20%), propyl acrylate (15%) totally 100 grams join in the 50 gram toluene, add 0.5 gram benzoyl peroxide, be warming up to 65 ℃, react and wait product to be used for further reaction after 6 hours.
Synthetic example 3
Octyl acrylate (30%), ethyl propenoate (20%), dodecyl acrylate (5%), Propylene glycol monoacrylate (20%), methyl acrylate (25%) totally 100 grams joins in the 150 gram toluene, add 0.2 gram benzoyl peroxide, be warming up to 100 ℃, react and wait product to be used for further reaction after 4 hours.
Synthetic example 4
Butyl acrylate (15%), ethyl propenoate (25%), glycidyl methacrylate (2%), dodecyl acrylate (23%), Propylene glycol monoacrylate (15%), Hydroxyethyl acrylate (20%) totally 100 grams join in the 200 gram toluene, add 3 gram benzoyl peroxides, be warming up to 90 ℃, react and wait product to be used for further reaction after 9 hours.
Synthetic example 5
Butyl acrylate (35%), glycidyl methacrylate (5%), Propylene glycol monoacrylate (25%), ethyl propenoate (35%) totally 100 grams joins in the 80 gram toluene, add 1 gram benzoyl peroxide, be warming up to 70 ℃, react and wait product to be used for further reaction after 5 hours.
Synthetic example 6
Ethyl propenoate (25%), glycidyl methacrylate (8%), Hydroxyethyl acrylate (35%), methyl acrylate (32%) totally 100 grams joins in the 40 gram toluene, add 2 gram benzoyl peroxides, be warming up to 95 ℃, react and wait product to be used for further reaction after 2 hours.
Synthetic example 7
Octyl acrylate (35%), ethyl propenoate (15%), dodecyl acrylate (15%), Propylene glycol monoacrylate (35%), totally 100 grams join in the 200 gram toluene, add 0.7 gram benzoyl peroxide, be warming up to 100 degree, react and wait product to be used for further reaction after 5 hours.
Two, the preparation method of the acrylic ester high molecular type of acroleic acid esterification:
In above-mentioned synthetic acrylic ester high molecular type, add vinylformic acid, with the tosic acid is catalyzer, Resorcinol is a stopper, react and dewater at 100～110 ℃, when water content after a certain amount of, removal of solvent under reduced pressure and unreacted raw material obtain product---the acrylic ester high molecular type of acroleic acid esterification.
Synthetic example 8
In 50 gram acrylic ester high molecular types of above-mentioned synthetic example 1, add 10 gram vinylformic acid, with 0.3 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 110 ℃, when minute water yield be higher than the theoretical branch water yield 80% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 9
In 70 gram acrylic ester high molecular types of above-mentioned synthetic example 1, add 15 gram vinylformic acid, with 0.2 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 100 ℃, when minute water yield be higher than the theoretical branch water yield 85% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 10
In 80 gram acrylic ester high molecular types of above-mentioned synthetic example 2, add 20 gram vinylformic acid, with 0.2 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 100 ℃, when minute water yield be higher than the theoretical branch water yield 85% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 11
In 100 gram acrylic ester high molecular types of above-mentioned synthetic example 2, add 10 gram vinylformic acid, with 0.1 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 105 ℃, when minute water yield be higher than the theoretical branch water yield 87% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 12
In 50 gram acrylic ester high molecular types of above-mentioned synthetic example 3, add 18 gram vinylformic acid, with 0.3 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 100 ℃, when minute water yield be higher than the theoretical branch water yield 85% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 13
In 70 gram acrylic ester high molecular types of above-mentioned synthetic example 3, add 20 gram vinylformic acid, with 0.4 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 100 ℃, when minute water yield be higher than the theoretical branch water yield 83% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 14
In 70 gram acrylic ester high molecular types of above-mentioned synthetic example 4, add 25 gram vinylformic acid, with 0.4 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 110 ℃, when minute water yield be higher than the theoretical branch water yield 85% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 15
In 90 gram acrylic ester high molecular types of above-mentioned synthetic example 5, add 8 gram vinylformic acid, with 0.1 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 100 ℃, when minute water yield be higher than the theoretical branch water yield 86% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 16
In 100 gram acrylic ester high molecular types of above-mentioned synthetic example 6, add 25 gram vinylformic acid, with 0.3 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 100 ℃, when minute water yield be higher than the theoretical branch water yield 85% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 17
In 70 gram acrylic ester high molecular types of above-mentioned synthetic example 6, add 15 gram vinylformic acid, with 0.2 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 100 ℃, when minute water yield be higher than the theoretical branch water yield 88% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
Synthetic example 18
In 65 gram acrylic ester high molecular types of above-mentioned synthetic example 7, add 11 gram vinylformic acid, with 0.2 gram tosic acid is catalyzer, 0.1 the gram Resorcinol is a stopper, react and dewater at 110 ℃, when minute water yield be higher than the theoretical branch water yield 89% after, removal of solvent under reduced pressure and unreacted raw material obtain product.
More than the product molecular structural formula that obtains of each synthetic example as follows:
Wherein: n, m, k, p, q are respectively 1～500 integer;
R
1Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R
2Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R
3Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R is CH
2CH
2CH
2, or CH
2CH
2CH
2And CH
2CH
2, or CH
2CH
2CH
2And CHOHCH
2
Three, UV solidifies prescription and the production method of trimeric cyanamide with coating:
Compound method when the acrylic ester high molecular type of acroleic acid esterification is used for the photo-cured coating prescription: (weight percentage)
Light reactive resin 20%-50%
Resins, epoxy 10-30%
The acrylic ester high molecular type 5-30% of acroleic acid esterification
Reactive thinner 10%-50%
Free radical and cation light initiator 3%-10%
Auxiliary agent 1%-5%
In the container of whipping device is housed, add 10%-50% reactive thinner, 5%-30% special additive (acrylic ester high molecular type of acroleic acid esterification), the 1%-5% auxiliary agent, the 3%-10% initiator, after the stirring and dissolving, add the light reactive resin of 20%-50% again, 10-30% Resins, epoxy, under 20-50 ℃ of temperature, stirring makes it to mix and promptly obtains radical polymerization light solidifying coating material.
Described light reactive resin is epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of acroleic acid esterification etc.
Described reactive thinner is a simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer.Or/and be polyfunctionality, the single functionality epoxy.
Described auxiliary agent is a flow agent, defoamer, oxidation inhibitor, uv-absorbing agent etc.
Described Resins, epoxy is bisphenol type epoxy, aliphatic category epoxy, alicyclic ring same clan epoxy etc.
When using UV-light of the present invention (UV) coating and carrying out polymerization, can adopt light sources such as mercuryarc lamp, electrodeless lamp source, xenon lamp, metal halide lamp, LED lamp.The UV coating that contains the acrylic ester high molecular type of acroleic acid esterification can carry out quick photocuring as melamine paper decoration lighting solidified coating material.
Embodiment 1
Under the lucifuge condition, in being housed, the container of agitator adds 2% benzophenone, 1% mesitylenic acid ethyl ester, 1173 (2-hydroxy-2-methyls-1-phenyl-acetone-1) 5%, 2% phosphofluoric acid diphenyl iodnium, 618 epoxy resin (bisphenol-A epoxy) 29%, TPGDA (tripropylene glycol double methacrylate) 15%, TMPTA (Viscoat 295) 10%, auxiliary agent (flow agent BYK-UV3500, defoamer Dow Corning163, moistened surface agent BYK2700) 1%, 20 ℃ of following stirring and dissolving, add 25% bisphenol A epoxy acrylate again, the product of 10% synthetic example 8 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 2
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 184 (1-hydroxyls-cyclohexyl benzophenone) 1%, auxiliary agent (flow agent Tego flow 300, defoamer Deuchem 2700, moistened surface agent BYK2700) 2%, 1% hexafluoroarsenate diphenyl iodnium, epoxy 828 resins (bisphenol-A epoxy) 10%, HDDA (1,6-hexylene glycol double methacrylate) 14%, TMPTA (Viscoat 295) 20%, 40 ℃ of following stirring and dissolving, add 20% bisphenol A epoxy acrylate again, the product of 30% synthetic example 9 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the electrodeless mercury lamp of 500W illumination 1 minute, photocuring is filmed.
Embodiment 3
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 184 (1-hydroxyls-cyclohexyl benzophenone) 5%, 4% phosphofluoric acid diphenyl iodnium, 618 epoxy resin (bisphenol-A epoxy) 10%, HDDA (1,6-hexylene glycol double methacrylate) 11%, TMPTA (Viscoat 295) 5%, auxiliary agent (flow agent Tego 2100, defoamer SolutiaPC-1344, moistened surface agent BYK2700) 3%, 114 (aliphatic epoxies) 20% are 30 ℃ of following stirring and dissolving, add 20% urethane acrylate again, the product of 20% synthetic example 10 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 4
Under the lucifuge condition, in being housed, the container of agitator adds 184 (1-hydroxyls-cyclohexyl benzophenone) 3%, 2% hexafluoroarsenate diphenyl iodnium, epoxy 828 resins (bisphenol-A epoxy) 10%, auxiliary agent (flow agent BKY361, defoamer Airex 900, moistened surface agent BYK-200) 1%, DPGDA (two contract propylene glycol double methacrylate) 10%, TMPTA (Viscoat 295) 19% 40 ℃ of following stirring and dissolving, adds 50% polyester (methyl) acrylic resin again, the product of 5% synthetic example 11 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 5
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 5%, 3% phosphofluoric acid diphenyl iodnium, 618 epoxy resin (bisphenol-A epoxy) 10%, HDDA (1,6-hexylene glycol double methacrylate) 10%, auxiliary agent (flow agent Tego 2250, defoamer Dow Corning 163) 5%, TMPTA (Viscoat 295) 5%, 114 (aliphatic epoxy) 20% adds 20% polyoxyalkylene acrylate resin again 35 ℃ of following stirring and dissolving, the product of 20% synthetic example 12 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the electrodeless mercury lamp of 500W illumination 1 minute, photocuring is filmed.
Embodiment 6
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 3%, 2% hexafluoroarsenate diphenyl iodnium, epoxy 828 resins (bisphenol-A epoxy) 10%, DPGDA (two contract propylene glycol double methacrylate) 12%, auxiliary agent (flow agent BYK3510, defoamer Deuchem 2700, moistened surface agent BYK2700) 3%, TMPTA (Viscoat 295) 20% 40 ℃ of following stirring and dissolving, adds 40% polyester (methyl) acrylic resin again, the product of 10% synthetic example 13 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 7
Under the lucifuge condition, in being housed, the container of agitator adds 184 (1-hydroxyls-cyclohexyl benzophenone) 3%, 2% phosphofluoric acid diphenyl iodnium, 618 epoxy resin (bisphenol-A epoxy) 10%, DPGDA (two contract propylene glycol double methacrylate) 14%, auxiliary agent (flow agent Wacker Addid 130, defoamer SolutiaPC-1344) 1%, TMPTA (Viscoat 295) 20%, 50 ℃ of following stirring and dissolving, add 45% polyethers (methyl) acrylic resin again, the product of 5% synthetic example 14 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 8
Under the lucifuge condition, in being housed, the container of agitator adds 2% benzophenone, 1% mesitylenic acid ethyl ester, 184 (1-hydroxyls-cyclohexyl benzophenone) 5%, auxiliary agent (flow agent BYK345, defoamer Airex900, moistened surface agent BYK2700) 4%, 2% phosphofluoric acid diphenyl iodnium, 618 epoxy resin (bisphenol-A epoxy) 20%, TPGDA (tripropylene glycol double methacrylate) 11%, TMPTA (Viscoat 295) 10% 20 ℃ of following stirring and dissolving, adds 25% bisphenol A epoxy acrylate again, the product of 20% synthetic example 15 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 9
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 184 (1-hydroxyls-cyclohexyl benzophenone) 5%, auxiliary agent (flow agent BYK361, defoamer Deuchem 3600) 1%, 3% phosphofluoric acid diphenyl iodnium, epoxy 828 resins (bisphenol-A epoxy) 10%, HDDA (1,6-hexylene glycol double methacrylate) 10%, TMPTA (Viscoat 295) 10%, 114 (aliphatic epoxy) 19% adds 20% polyester (methyl) acrylic resin again 45 ℃ of following stirring and dissolving, the product of 20% synthetic example 16 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 10
Under the lucifuge condition, in being housed, the container of agitator adds 184 (1-hydroxyls-cyclohexyl benzophenone) 5%, 4% phosphofluoric acid diphenyl iodnium, 618 epoxy resin (bisphenol-A epoxy) 20%, HDDA (1,6-hexylene glycol double methacrylate) 10%, auxiliary agent (flow agent BYK-UV-3510, defoamer Dow Coming163, moistened surface agent BYK2700) 1%, TMPTA (Viscoat 295) 10%, 114 (aliphatic epoxies) 20% are 40 ℃ of following stirring and dissolving, add 20% polyester (methyl) acrylic resin again, the product of 10% synthetic example 17 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 11
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 184 (1-hydroxyls-cyclohexyl benzophenone) 3%, 5% phosphofluoric acid diphenyl iodnium, epoxy 828 resins (bisphenol-A epoxy) 20%, HDDA (1,6-hexylene glycol double methacrylate) 10%, auxiliary agent (flow agent Tego Flow 300, defoamer Solutia PC-1344, moistened surface agent BKY2700) 2%, 114 (aliphatic epoxy) 10% adds 20% polyester (methyl) acrylic resin again 20 ℃ of following stirring and dissolving, the product of 28% synthetic example 18 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 12
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 3%, 2% hexafluoroarsenate diphenyl iodnium, auxiliary agent (flow agent BYK 361, defoamer Airex 900) 3%, epoxy 828 resins (bisphenol-A epoxy) 10%, DPGDA (two contract propylene glycol double methacrylate) 15%, TMPTA (Viscoat 295) 17%, 450 ℃ of following stirring and dissolving, add 30% polyester (methyl) acrylic resin again, the product of 20% synthetic example 13 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 13
Under the lucifuge condition, in being housed, the container of agitator adds 184 (1-hydroxyls-cyclohexyl benzophenone) 3%, 2% hexafluoroarsenate diphenyl iodnium, auxiliary agent (flow agent BYK361, defoamer Deuchem 3600) 1%, 618 epoxy resin (bisphenol-A epoxy) 10%, DPGDA (two contract propylene glycol double methacrylate) 5%, TMPTA (Viscoat 295) 20%, 40 ℃ of following stirring and dissolving, add 20% polyethers (methyl) acrylic resin again, the product of 29% synthetic example 9 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 14
Under the lucifuge condition, in being housed, the container of agitator adds 1173 (2-hydroxy-2-methyls-1-phenyl-acetone-1) 3%, 2% hexafluoroarsenate diphenyl iodnium, epoxy 828 resins (bisphenol-A epoxy) 10%, auxiliary agent (flow agent Tego 2250, defoamer Solutia PC-1344, moistened surface agent BYK2700) 2%, DPGDA (two contract propylene glycol double methacrylate) 18%, TMPTA (Viscoat 295) 5% 30 ℃ of following stirring and dissolving, adds 30% polyester (methyl) acrylic resin again, the product of 30% synthetic example 10 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 15
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 3%, 2% phosphofluoric acid diphenyl iodnium, 618 epoxy resin (bisphenol-A epoxy) 10%, DPGDA (two contract propylene glycol double methacrylate) 10%, auxiliary agent (flow agent Wacker Addid 200, defoamer BYK380, moistened surface agent BYK200) 1%, TMPTA (Viscoat 295) 9% 40 ℃ of following stirring and dissolving, adds 45% polyester (methyl) acrylic resin again, the product of 20% synthetic example 14 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the electrodeless mercury lamp of 500W illumination 1 minute, photocuring is filmed.
Claims (9)
1, a kind of acrylic ester high molecular type of acroleic acid esterification, its molecular structural formula is as follows:
Wherein: n, m, k, p, q are respectively 1～500 integer;
R
1Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R
2Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R
3Be hydrogen, or alkyl, or hydroxyalkyl, or contain the epoxy group(ing) alkyl;
R is CH
2CH
2CH
2, or CH
2CH
2CH
2And CH
2CH
2, or CH
2CH
2CH
2And CHOHCH
2
2, the synthetic method of the acrylic ester high molecular type of the described acroleic acid esterification of a kind of claim 1, it is characterized in that stir and the condition of nitrogen protection under, will to be 0.1～3% thermal initiator benzoyl peroxide and acrylate mixture carry out heat polymerization in concentration is 30～70% toluene solution make acrylic ester high molecular type to monomeric content; Wherein, polymerization temperature is 65～100 ℃, and polymerization time is 3～10 hours; In the synthetic acrylic ester high molecular type, add vinylformic acid again, with the tosic acid is catalyzer, and Resorcinol is a stopper, after 100～110 ℃ of reactions and dewatering, reduce pressure, remove and desolvate and unreacted raw material, obtain the acrylic ester high molecular type of acroleic acid esterification.
3, according to the synthetic method of the acrylic ester high molecular type of the described acroleic acid esterification of claim 2, it is characterized in that described acrylate is an ethyl propenoate, or butyl acrylate, or glycidyl methacrylate, or Octyl acrylate, or vinylformic acid, or dodecyl acrylate, or octadecyl acrylate, or Hydroxyethyl acrylate, or Propylene glycol monoacrylate, or propyl acrylate, or in the methyl acrylate at least any one.
4, the acrylic ester high molecular type of acroleic acid esterification is used to make ultraviolet-curing paint according to claim 1.
5, purposes according to the acrylic ester high molecular type of the described acroleic acid esterification of claim 4, it is characterized in that the method for making ultraviolet-curing paint is: in the container of whipping device is housed, it is 10%～50% reactive thinner that adding accounts for total weight percent, the acrylic ester high molecular type of 5%～30% acroleic acid esterification, 1%～5% auxiliary agent, 3%～10% free radical and cation light initiator, after the stirring and dissolving, add 20%～50% light reactive resin again, 10～30% Resins, epoxy, under 20～50 ℃ of temperature, stirring makes it to mix and promptly obtains ultraviolet-curing paint.
6,, it is characterized in that described light reactive resin is any in epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of acroleic acid esterification according to the purposes of the acrylic ester high molecular type of the described acroleic acid esterification of claim 5.
7, according to the purposes of the acrylic ester high molecular type of the described acroleic acid esterification of claim 5, it is characterized in that described reactive thinner is any in simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer; Or the combination of any and polyfunctionality in the simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer; Or any and single functionality epoxy in the simple function group, bifunctional, polyfunctional group (methyl) acrylate monomer.
8, according to the purposes of the acrylic ester high molecular type of the described acroleic acid esterification of claim 5, it is characterized in that described auxiliary agent comprises flow agent, defoamer, oxidation inhibitor, uv-absorbing agent.
9, according to the purposes of the acrylic ester high molecular type of the described acroleic acid esterification of claim 5, it is characterized in that described Resins, epoxy is any in bisphenol type epoxy, aliphatic category epoxy, the alicyclic ring same clan epoxy.
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| CN 200710023350 CN101074277A (en) | 2007-06-11 | 2007-06-11 | Esterified acrylie-ester high-polymer, its synthesis and use |
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| CN 200710023350 CN101074277A (en) | 2007-06-11 | 2007-06-11 | Esterified acrylie-ester high-polymer, its synthesis and use |
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| CNA2008101740898A Division CN101418148A (en) | 2007-06-11 | 2007-06-11 | Method for producing ultraviolet curing coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500416A (en) * | 2011-10-13 | 2012-06-20 | 北京化工大学 | Synthesis and preparation methods of polymer particle type esterification catalyst containing sulfonic acid groups |
| CN105225769A (en) * | 2015-10-14 | 2016-01-06 | 南昌航空大学 | A kind of preparation method of basic soil ground network physics resistance reducing agent |
| CN105440169A (en) * | 2015-12-25 | 2016-03-30 | 何明辉 | Acrylic acid acidized polyacrylate capable of realizing ultraviolet curing as well as preparation method and application of acrylic acid acidized polyacrylate |
| CN107746444A (en) * | 2017-10-10 | 2018-03-02 | 华南理工大学 | A kind of ultraviolet light solidification electrophoretic coating of acrylate containing long alkyl side chain and its preparation method and application |
| CN107955433A (en) * | 2017-11-09 | 2018-04-24 | 成都迪泰化工有限公司 | A kind of UV photocurings product |
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2007
- 2007-06-11 CN CN 200710023350 patent/CN101074277A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500416A (en) * | 2011-10-13 | 2012-06-20 | 北京化工大学 | Synthesis and preparation methods of polymer particle type esterification catalyst containing sulfonic acid groups |
| CN105225769A (en) * | 2015-10-14 | 2016-01-06 | 南昌航空大学 | A kind of preparation method of basic soil ground network physics resistance reducing agent |
| CN105225769B (en) * | 2015-10-14 | 2017-03-08 | 南昌航空大学 | A kind of basic soil preparation method of grounded screen physics friction reducer |
| CN105440169A (en) * | 2015-12-25 | 2016-03-30 | 何明辉 | Acrylic acid acidized polyacrylate capable of realizing ultraviolet curing as well as preparation method and application of acrylic acid acidized polyacrylate |
| CN107746444A (en) * | 2017-10-10 | 2018-03-02 | 华南理工大学 | A kind of ultraviolet light solidification electrophoretic coating of acrylate containing long alkyl side chain and its preparation method and application |
| CN107955433A (en) * | 2017-11-09 | 2018-04-24 | 成都迪泰化工有限公司 | A kind of UV photocurings product |
| CN107955433B (en) * | 2017-11-09 | 2020-02-11 | 成都迪泰化工有限公司 | UV light-cured product |
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