CN103012660A - Fluorine-containing epoxy acrylate oligomer for photo-curing and synthetic method thereof - Google Patents
Fluorine-containing epoxy acrylate oligomer for photo-curing and synthetic method thereof Download PDFInfo
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Abstract
A fluorine-containing epoxy acrylate for photo-curing belongs to the field of photo-curing oligomer. The oligomer has higher photoactivity and good solubleness, is not affected by oxygen inhibition, is small in volume reduction, is uniform in structure, can carry out post curing after illuminating, is especially low in interface energy, and can be used as photo-curing matrix resin. The oligomer is synthetized through 'free radical copolymerization'. A free radical comonomer mainly comprises three components, namely, (methyl) crylic acid alkyl ester, fluorine-containing (methyl) crylic acid alkyl ester, and epoxy group-containing (methyl) crylic acid alkyl ester, a main chain obtained through free radical polymerization is polyacrylate of pure carbon-carbon bond, a side chain has an epoxy group with optical reactivity, thus endowing the oligomer with photo-curing characteristic. By adopting controlling of the comonomer proportion and adding of use amount of chain transfer agent and initiator, the preparation of oligomer which has good solubleness and low interface energy is realized, the operation is simple, and the fluorine-containing epoxy acrylate oligomer for photo-curing is beneficial to industrial production and has wide application prospect.
Description
Technical field
The present invention relates to environmental friendliness photo-curing material field, particularly the synthetic field of fluorine-containing photocuring oligopolymer.
Background technology
Photocuring technology is to utilize light or electron beam to be the energy, and causing the fluent meterial fast transition with chemical reactivity is solid-state process.Photocuring technology is an energy-conservation and environment-friendly type new technology.Photocuring technology meets " 5E principle ": Efficient (efficiently) fully, Enabling (wide adaptability), Economical (economy), Energy saving (energy-conservation), Environmental friendly (environmental friendliness).
Photocuring system mainly is comprised of oligopolymer, reactive thinner and light trigger, and wherein oligopolymer accounts for the 50-80% of whole prescription, has determined Main physical and the chemical property of cured film, is of paramount importance integral part.Oxygen inhibition, volumetric shrinkage are not little because it is afraid of as cationic photocuring oligopolymer for epoxy acrylate, excellent performance and at coating, printing ink, the fields such as sizing agent have wide practical use.Fluorine atom has the outer minimum van der Waals radius of strong electronegativity, high C-F bond energy, dehydrogenation and fluorine to the shielding protection effect of carbochain, given the low surface energy of fluoropolymer uniqueness, the characteristics of low-k, superior weathering resistance, thermostability and unreactiveness, and the character such as low-friction coefficient, low-refraction and reduce power consumption factor, and the low surface energy of fluoropolymer and low-friction coefficient make it again to have outstanding hydrophobic and oil repellent and didirtresistance; The molar polarization that fluoro-containing group is lower, larger free volume can reach the purpose of improving the dielectric material performance.
Say in theory, can by selecting comonomer, regulate the consumption of initiator, chain-transfer agent, the control charging capacity, the methods such as control level of response obtain favorable solubility, viscosity is lower, and surface energy is lower, the fluorine-containing epoxy group(ing) polyacrylic ester that specific inductivity is lower, and the advantage such as keep that conventional polypropylene acid esters acrylate cured film glossiness is full, strong adhesion and high resilience, weather ability are strong, because of favorable solubility, viscosity is lower, uses so can be used as the main body oligopolymer.
Summary of the invention
One of purpose of the present invention is synthetic a kind of photoactive fluorine-containing epoxy acrylate that has, the fluorine-containing epoxy acrylate oligomer of photocuring, it is characterized in that, main chain is made of pure C-C, contain fluorine atom and the epoxide group that can carry out photocuring in the side chain, its structure represents with (I):
Wherein, a, b, c are respectively 1 ~ 600 integer;
R1 is hydrogen atom or methyl;
R2 is that carbonatoms is 1 ~ 20 alkyl;
R3 is-CH
2CF
2CHFCF
3, or
, n=1 ~ 3 wherein, m=0 ~ 10;
R4 is methylene radical.
Adopt free-radical polymerized, adopt following three kinds of monomers: the x unit cell is n-butyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, vinylformic acid 20 esters, (methyl) methyl acrylate, ethyl propenoate, the methacrylic dodecyl gallate, tridecyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems or isodecyl acrylate;
The y unit cell is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, vinylformic acid ten trifluoro monooctyl esters or methacrylic acid ten trifluoro monooctyl esters;
The z unit cell is glycidyl methacrylate, isobornyl methacrylate;
Concrete building-up process is that comonomer is mixed according to different ratios, fixing y unit cell 10mol%, and x:z unit cell molar ratio changes from 1:8 to 8:1, fixing z unit cell 10mol%, x:y unit cell molar ratio changes from 1:8 to 8:1; Adding is the radical initiator of the 0.5wt% ~ 2wt% of monomer total amount, initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, adding is the chain-transfer agent of the 0wt% ~ 4wt% of monomer total amount, and chain-transfer agent is positive Dodecyl Mercaptan or octyl mercaptan, with monomer, initiator, chain-transfer agent mixes, and is added drop-wise in the solvent, and solvent is for aromatic hydrocarbon based, the ester class, the mixture of one or more in the ketone; Temperature of reaction is controlled at 60 ℃ ~ 100 ℃, and the reaction times is controlled at 3h ~ 6h, and final product precipitates with non-polar solvent, is drying to obtain the purpose product.
It is characterized in that main chain is made of pure C-C, contain fluorine atom and the epoxide group that can carry out photocuring in the side chain, its structure represents with (I):
Wherein, a, b, c are respectively 1 ~ 600 integer;
R1 is hydrogen atom or methyl.
R2 is that carbonatoms is 1 ~ 20 alkyl; This monomer includes but not limited to n-butyl acrylate specifically, the vinylformic acid n-octyl, Isooctyl acrylate monomer (claiming again 2-EHA) dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, vinylformic acid 20 esters, (methyl) methyl acrylate, ethyl propenoate, the methacrylic dodecyl gallate, tridecyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems, isodecyl acrylate etc.
R3 is-CH
2CF
2CHFCF
3, or
, n=1 ~ 3 wherein, m=0 ~ 10; This unit includes but not limited to vinylformic acid hexafluoro butyl ester specifically, Hexafluorobutyl mathacrylate, vinylformic acid ten trifluoro monooctyl esters, methacrylic acid ten trifluoro monooctyl esters etc.
R4 is methylene radical.
2. fluorine-containing epoxy acrylate according to claim 1, its synthetic method is: adopt free-radical polymerized, copolymerization units is respectively above-mentioned a, b, c unit, the c unit includes but not limited to that (glycidyl methacrylate, isobornyl methacrylate etc. are with the functional monomer of ring texture.Concrete building-up process is that comonomer is mixed according to different ratios, fixing y unit cell 10mol%, and a:c unit cell molar ratio changes from 1:8 to 8:1, fixing c unit cell 10mol%, a:b unit cell molar ratio changes from 1:8 to 8:1.Adding is the radical initiator of the 0.5wt% ~ 2wt% of monomer total amount; include but not limited to benzoyl peroxide or Diisopropyl azodicarboxylate, adding is the chain-transfer agent of the 0wt% ~ 4wt% of monomer total amount, includes but not limited to positive Dodecyl Mercaptan or octyl mercaptan; with monomer; initiator, chain-transfer agent mixes, and is added drop-wise in the solvent; solvent is organic solvent; for aromatic hydrocarbon based, ester class, the mixture of one or more in the ketone.Temperature of reaction is controlled at 60 ℃ ~ 100 ℃, and the reaction times is controlled at 3h ~ 6h, and final product precipitates with non-polar solvent, is drying to obtain the purpose product.
The prepared fluorine-containing epoxy group(ing) polyacrylic acid ester oligomer of the present invention has higher photolytic activity, and solvability is good, not affected by oxygen inhibition, and volumetric shrinkage is little, even structure, the characteristics such as can also after fixing, especially surface energy after the illumination low.And the preparation method is simple, and raw material type is various, can suitably adjust the conditions such as monomer ratio, initiator and chain-transfer agent consumption, level of response, temperature of reaction according to performance need, satisfies the performance requriements under the different condition.
Description of drawings
The infrared spectrum of Fig. 1 fluorine-contaninig polyacrylate acrylate.
The miscible electromicroscopic photograph of Fig. 2 fluorine-contaninig polyacrylate acrylate and photo-curing monomer
Embodiment:
Following embodiment can illustrate further characteristics of the present invention, but not limited by these examples.
Molecular weight and molecular weight distribution are recorded by the GPC that waters company produces, and weight-average molecular weight is measured by the polystyrene standard conversion and obtained.The sample concentration of GPC test is 2mg/mL, and the Sample introduction amount is 50 μ mL, and 30 ℃ of temperature under the condition of flow velocity 1mL/min, are measured by the tetrahydrofuran (THF) dissolving.
During the test of cured film contact angle, adopt line rod spreader will prepare resin and be coated on the slide glass, thickness is about 60 μ m.Under high voltage mercury lamp, shine certain hour, film-forming, the contact angle data are obtained by dataphysics company contact angle test macro, and the larger surface energy that shows of contact angle is lower.
(1) condensing works is being housed, whipping appts, add 1 in the reactor of temperature regulating device, 4-dioxane 100ml is heated to 75 ℃, and 0.08mol n-butyl acrylate, 0.01mol vinylformic acid hexafluoro butyl ester, 0.01mol glycidyl methacrylate, benzoyl peroxide 0.066g(are accounted for monomer 0.5wt%), be added drop-wise in the reactor after mixing, after dripping end, temperature of reaction is elevated to 100 ℃, stopped reaction behind the reaction 3h.System after the reaction is added drop-wise in the sherwood oil of 500ml, stir while dripping, remove at last sherwood oil, namely get " n-butyl acrylate-vinylformic acid hexafluoro butyl ester-glycidyl methacrylate " random copolymers, outward appearance is transparent thick liquid, this oligopolymer has higher photolytic activity, and solvability is good, not affected by oxygen inhibition, volumetric shrinkage is little, even structure, the characteristics such as can also after fixing, especially surface energy after the illumination low.
Product is carried out examination of infrared spectrum, can see 1640cm
-1With 810cm
-1Two key characteristic peaks at place disappear, and polyreaction is complete as can be known.1171cm
-1And 1242cm
-1The place is the stretching vibration peak of C-F key, 1267cm
-1And 910cm
-1The place is the charateristic avsorption band of epoxide group, 2880cm
-1And 2960cm
-1The place is CH
3The stretching vibration absorption peak, can prove that thus three kinds of monomers have all participated in polyreaction, products therefrom is target product.
GPC test number-average molecular weight Mn=19588, Polydispersity PDI=1.9.
Get the polyacrylic acid ester oligomer that makes, add the triaryl phosphofluoric acid sulfonium salt cation light initiator of reactive thinner BDGE, the 2wt% of 15wt%, system is clear, shows that product has excellent compatibility.Under the irradiation of the UV-light of 30mW, double bond conversion rate reaches about 90% about 1 minute, can find out that product has preferably photolytic activity.
The contact angle of test cured film on slide glass, contact angle reach 102 degree, belong to hydrophobic surface.
Embodiment 2
(1) condensing works is being housed, whipping appts, add 1 in the reactor of temperature regulating device, 4-dioxane 100ml is heated to 75 ℃, and 0.08mol methacrylic dodecyl gallate, 0.01mol methacrylic acid ten trifluoro monooctyl esters, 0.01mol glycidyl methacrylate, benzoyl peroxide 0.13g(are accounted for monomer 0.5wt%), be added drop-wise in the reactor after mixing, after dripping end, temperature of reaction is elevated to 100 ℃, stopped reaction behind the reaction 6h.System after the reaction is added drop-wise in the sherwood oil of 500ml, stir while dripping, remove at last sherwood oil, namely get " methacrylic dodecyl gallate-methacrylic acid ten trifluoro monooctyl ester-glycidyl methacrylate " random copolymers, outward appearance is white translucent solid, this oligopolymer has higher photolytic activity, and solvability is good, not affected by oxygen inhibition, volumetric shrinkage is little, even structure, the characteristics such as can also after fixing, especially surface energy after the illumination low.
GPC test number-average molecular weight Mn=17468, Polydispersity PDI=2.0.The contact angle of test cured film on slide glass, contact angle reach 116 degree, belong to hydrophobic surface.
Embodiment 3
(1) condensing works is being housed, whipping appts, add ethyl acetate 100ml in the reactor of temperature regulating device, be heated to 55 ℃, 0.01mol n-butyl acrylate, 0.01mol vinylformic acid hexafluoro butyl ester, 0.08mol isobornyl methacrylate, Diisopropyl azodicarboxylate 0.3g(are accounted for monomer 2wt%), be added drop-wise in the reactor after mixing, after dropping finishes, temperature of reaction is elevated to 75 ℃, stopped reaction behind the reaction 3h.System after the reaction is added drop-wise in the sherwood oil of 500ml, stir while dripping, remove at last sherwood oil, namely get " n-butyl acrylate-vinylformic acid hexafluoro butyl ester-isobornyl methacrylate " random copolymers, outward appearance is transparent thick liquid, this oligopolymer has higher photolytic activity, and solvability is good, not affected by oxygen inhibition, volumetric shrinkage is little, even structure, the characteristics such as can also after fixing, especially surface energy after the illumination low.
GPC test number-average molecular weight Mn=23254, Polydispersity PDI=2.0.The contact angle of test cured film on slide glass, contact angle reach 102 degree, belong to hydrophobic surface.
Embodiment 4
(1) condensing works is being housed, whipping appts, add ethyl acetate 100ml in the reactor of temperature regulating device, be heated to 75 ℃, 0.01mol n-butyl acrylate, 0.08mol vinylformic acid hexafluoro butyl ester, 0.01mol glycidyl methacrylate, Diisopropyl azodicarboxylate 0.426g(are accounted for monomer 2wt%), be added drop-wise in the reactor after mixing, after dropping finishes, temperature of reaction is elevated to 100 ℃, stopped reaction behind the reaction 3h.Aftertreatment is with embodiment 1, and the product outward appearance is transparent thick liquid, and this oligopolymer has higher photolytic activity, and solvability is good, not affected by oxygen inhibition, and volumetric shrinkage is little, even structure, the characteristics such as can also after fixing, especially surface energy after the illumination low.
GPC test number-average molecular weight Mn=9731, Polydispersity PDI=1.8.The contact angle of test cured film on slide glass, contact angle reach 132 degree, belong to hydrophobic surface.
Embodiment 5
(1) condensing works is being housed, whipping appts, add Isosorbide-5-Nitrae-dioxane 100ml in the reactor of temperature regulating device, be heated to 75 ℃, 0.08mol n-butyl acrylate, 0.01mol vinylformic acid hexafluoro butyl ester, 0.01mol glycidyl methacrylate, benzoyl peroxide 0.066g(are accounted for monomer 0.5wt%), positive Dodecyl Mercaptan 0.528g(accounts for monomer 4wt%), be added drop-wise in the reactor after mixing, after dropping finishes, temperature of reaction is elevated to 100 ℃, stopped reaction behind the reaction 6h.Aftertreatment is with embodiment 1, and outward appearance is transparent thick liquid, and this oligopolymer has higher photolytic activity, and solvability is good, not affected by oxygen inhibition, and volumetric shrinkage is little, even structure, the characteristics such as can also after fixing, especially surface energy after the illumination low.
GPC test number-average molecular weight Mn=8836, Polydispersity PDI=2.3.The contact angle of test cured film on slide glass, contact angle reach 95 degree, belong to hydrophobic surface.
Embodiment 6
(1) condensing works is being housed, whipping appts, add Isosorbide-5-Nitrae-dioxane 100ml in the reactor of temperature regulating device, be heated to 75 ℃, 0.08mol vinylformic acid, 0.01mol vinylformic acid hexafluoro butyl ester, 0.01mol glycidyl methacrylate, Diisopropyl azodicarboxylate 0.266g(are accounted for monomer 2wt%), octyl mercaptan 0.266g(accounts for monomer 4wt%), be added drop-wise in the reactor after mixing, after dropping finishes, temperature of reaction is elevated to 100 ℃, stopped reaction behind the reaction 3h.System after the reaction is added drop-wise in the sherwood oil of 500ml, stir while dripping, remove at last sherwood oil, namely get " vinylformic acid-vinylformic acid hexafluoro butyl ester-glycidyl methacrylate " random copolymers, outward appearance is transparent thick liquid, this oligopolymer has higher photolytic activity, and solvability is good, not affected by oxygen inhibition, volumetric shrinkage is little, even structure, the characteristics such as can also after fixing, especially surface energy after the illumination low.
GPC test number-average molecular weight Mn=10567, Polydispersity PDI=2.5.The contact angle of test cured film on slide glass, contact angle reach 105 degree, belong to hydrophobic surface.
Claims (2)
1. the fluorine-containing epoxy acrylate oligomer of photocuring is characterized in that, main chain is made of pure C-C, contains fluorine atom and the epoxide group that can carry out photocuring in the side chain, and its structure represents with (I):
Wherein, a, b, c are respectively 1 ~ 600 integer;
R1 is hydrogen atom or methyl;
R2 is that carbonatoms is 1 ~ 20 alkyl;
R3 is-CH
2CF
2CHFCH
3, or
, n=1 ~ 3 wherein, m=0 ~ 10;
R4 is methylene radical.
2. photocuring according to claim 1 with the synthetic method of fluorine-containing epoxy acrylate oligomer is: adopt free-radical polymerized, adopt following three kinds of monomers: the x unit cell is n-butyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, vinylformic acid 20 esters, (methyl) methyl acrylate, ethyl propenoate, the methacrylic dodecyl gallate, tridecyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems or isodecyl acrylate;
The y unit cell is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, vinylformic acid ten trifluoro monooctyl esters or methacrylic acid ten trifluoro monooctyl esters;
The z unit cell is glycidyl methacrylate, isobornyl methacrylate;
Concrete building-up process is that comonomer is mixed according to different ratios, fixing y unit cell 10mol%, and x:z unit cell molar ratio changes from 1:8 to 8:1, fixing z unit cell 10mol%, x:y unit cell molar ratio changes from 1:8 to 8:1; Adding is the radical initiator of the 0.5wt% ~ 2wt% of monomer total amount, initiator is benzoyl peroxide or Diisopropyl azodicarboxylate, adding is the chain-transfer agent of the 0wt% ~ 4wt% of monomer total amount, and chain-transfer agent is positive Dodecyl Mercaptan or octyl mercaptan, with monomer, initiator, chain-transfer agent mixes, and is added drop-wise in the solvent, and solvent is for aromatic hydrocarbon based, the ester class, the mixture of one or more in the ketone; Temperature of reaction is controlled at 60 ℃ ~ 100 ℃, and the reaction times is controlled at 3h ~ 6h, and final product precipitates with non-polar solvent, is drying to obtain the purpose product.
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