CN102351981B - Fluorine-containing polyacrylate for photocuring and synthesis method thereof - Google Patents
Fluorine-containing polyacrylate for photocuring and synthesis method thereof Download PDFInfo
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Abstract
The invention provides fluorine-containing polyacrylate for photocuring, belonging to the field of photocuring oligomers. The oligomer has good solubility, low viscosity, small dispersibility and a uniform structure; after curing, the oligomer has good property especially low surface energy, and can be used as photocuring main resins. The oligomer is synthesized by two steps namely radical copolymerization and esterification, wherein a radical comonomer mainly comprises three parts namely (methyl) alkyl acrylate, fluorine-containing (methyl) alkyl acrylate, hydroxyl-containing acrylate or acrylic acid, and polyacrylate with a pure carbon-carbon bond as a main chain is obtained by radical copolymerization; and in the esterification reaction, a double bond having photoreaction activity is introduced through reacting acrylic acid, or acryloyl chloride or hydroxyl acrylate with hydroxyl or carboxyl in the first step, so as to endow the oligomer with the photocuring characteristic. According to the invention, the preparation of the oligomer having good solubility and low surface energy is achieved by adopting a method in which a comonomer ratio is controlled and the use methods of a chain transfer agent and an initiator are added, thus the method is simple and convenient, and industrial production is easy to perform.
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.It meets " 5E principle " fully: efficient, and wide adaptability, economy, energy-conservation, environmental friendliness.
Photocuring system mainly is comprised of oligopolymer, reactive thinner and light trigger, and the character of oligopolymer has decisive role to the character of filming after solidifying.The polyacrylic ester acrylate as the novel esters of acrylic acid photocuring oligopolymer of a class because its structure is various, excellent performance and at coating, printing ink, the fields such as sizing agent have wide practical use.And 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, and viscosity is lower, surface energy is lower, the fluorine-contaninig polyacrylate acrylate 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-contaninig polyacrylate acrylate that has, and its structure represents with (I):
Wherein, x, y, z are respectively 1～400 integer;
R1 is hydrogen atom or methyl;
R2 is that carbonatoms is 1～18 alkyl;
R3 is CH
2CF
2CHFCF
3, or
N=1～2 wherein, m=0～8;
R4 is CH
2CH
2Or
Two of purpose of the present invention provides a kind of preparation method who prepares the fluorine-contaninig polyacrylate acrylate.Copolymerization units is respectively A, B, C unit, the A unit cell comprises n-butyl acrylate, the vinylformic acid n-octyl, Isooctyl acrylate monomer, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, (methyl) methyl acrylate, ethyl propenoate, methacrylic dodecyl gallate, tridecyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems or isodecyl acrylate; The B unit cell comprises vinylformic acid hexafluoro butyl ester specifically, Hexafluorobutyl mathacrylate, vinylformic acid ten trifluoro monooctyl esters or methacrylic acid ten trifluoro monooctyl esters; The C unit cell comprises (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or vinylformic acid.
Building-up process was divided into for two steps: the first step adopts free-radical polymerized, and comonomer mixes according to following two kinds of different ratioss: fixing B unit cell 10mol%, and A: C unit cell molar ratio changed from 1: 8 to 8: 1; Perhaps fixation of C unit cell 10mol%, A: B unit cell molar ratio changed from 1: 8 to 8: 1.The radical initiator that adds monomer total amount 0.5wt%～2wt%, radical initiator comprises benzoyl peroxide or Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile), the chain-transfer agent that adds monomer total amount 0wt%～4wt%, chain-transfer agent comprises positive Dodecyl Mercaptan or octyl mercaptan, with monomer, initiator, chain-transfer agent mixes, and is added drop-wise to the solution system that forms monomer concentration 10mol/L in the solvent; Solvent is organic solvent, for aromatic hydrocarbon based, and 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 product precipitates with non-polar solvent, and drying namely can be used for the second step reaction.
Second step adopts esterification, by vinylformic acid, and crylic acid hydroxy ester, the acrylate chloride monomer is introduced the two keys with light reaction in the first step reaction product; Concrete synthesizing is divided into following two schemes: the first step product is dissolved in ethyl acetate or the organic solvents such as pimelinketone or Isosorbide-5-Nitrae-dioxane; (1) when with vinylformic acid or crylic acid hydroxy ester, adds vinylformic acid or the crylic acid hydroxy ester of 1.2 times of moles of C unit cell; Catalyzer is tosic acid, and add-on is the 0.25wt%～5wt% of vinylformic acid or crylic acid hydroxy ester; Stopper is MEHQ or Resorcinol, and add-on is the 0.3wt%～6wt% of vinylformic acid or crylic acid hydroxy ester; Solvent adopts pimelinketone, and add-on is the every mole of monomer total amount of 100ml/; 110 ℃～155 ℃ lower reactions 1.5～5 hours; (2) when participating in the second step reaction with acrylate chloride, add triethylamine as absorption agent, the mole numbers such as add-on and acrylate chloride; Stopper is MEHQ or Resorcinol, and add-on is the 0.3wt%～6wt% of acrylate chloride; Solvent adopts ethyl acetate or 1.4-dioxane; Solvent adding amount is the every mole of monomer total amount of 100ml/; The acrylate chloride of 1.2 times of moles of C unit cell is added drop-wise in the reactor, under 30～60 ℃ of conditions, reacted 2～8 hours; Through obtaining the fluorine-contaninig polyacrylate acrylate after purification, the drying.
It is good that the prepared fluorine-contaninig polyacrylate origoester acrylate of the present invention has solvability, and viscosity is low, dispersed little, even structure, and solidifying the rear surface can be low, the characteristics of excellent combination property.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 nuclear magnetic spectrogram of Fig. 2 fluorine-contaninig polyacrylate acrylate.
The miscible electromicroscopic photograph of Fig. 3 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 contact angle shows that more greatly surface energy is lower.
Embodiment 1
(1) condensing works is being housed, whipping appts, add 1 in the reactor of temperature regulating device, 4-dioxane 100ml is heated to 75 ℃, with 0.08mol n-butyl acrylate, 0.01mol vinylformic acid hexafluoro butyl ester, 0.01mol Hydroxyethyl acrylate, benzoyl peroxide 0.066g (being 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, stirs while dripping, remove at last sherwood oil, namely get " n-butyl acrylate-vinylformic acid hexafluoro butyl ester-Hydroxyethyl acrylate " random copolymers, outward appearance is transparent thick liquid.
(2) the first step product is carried out esterification, the first step product is dissolved in the 100ml ethyl acetate, add the 0.012mol triethylamine, add 0.003g (being acrylate chloride 0.3wt%) MEHQ, mix, then the acrylate chloride with 0.012mol is added drop-wise in the reactor, and dropping is warming up to 60 ℃ after finishing gradually.Stopped reaction behind the reaction 2h.Through filtering 1mol/L hydrochloric acid separatory, saturated sodium bicarbonate separatory, moisture liquid, anhydrous sodium sulphate dewaters, after rotary evaporation is removed ethyl acetate, namely get product fluorine-contaninig polyacrylate acrylate behind 40 ℃ of lower dry 24h again in vacuum drying oven, outward appearance is faint yellow transparent thick liquid.The first step and second step product are carried out examination of infrared spectrum, can see that the front resin of reaction is at 1660cm
-1There is not the C=C double bond absorption peak, at 3100cm
-1-3400cm
-1Have-OH group absorption peak, the two key peaks of C=C occurred after reaction finished, simultaneously-the OH peak significantly reduces, and this explanation esterification has been taken C=C on the polyacrylic ester side chain to, and conversion rate of esterification reaches 95%.
GPC test number-average molecular weight Mn=39588, Polydispersity PDI=1.9.
Get the polyacrylic ester origoester acrylate that makes, add the light trigger 1173 of reactive thinner TPGDA, 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.
(1) condensing works is being housed, whipping appts, add butylacetate 100ml in the reactor of temperature regulating device, be heated to 75 ℃, with 0.08mol methacrylic dodecyl gallate, 0.01mol methacrylic acid ten trifluoro monooctyl esters, 0.01mol hydroxyethyl methylacrylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.13g (being monomer 0.5wt%), 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.System after the reaction is added drop-wise in the sherwood oil of 500ml, stirs while dripping, remove at last sherwood oil, namely get " methacrylic dodecyl gallate-methacrylic acid ten trifluoro monooctyl ester-hydroxyethyl methylacrylates " random copolymers, outward appearance is white translucent crystal.
(2) to obtain product with embodiment 1. be the translucent crystal of little yellow to second step, and conversion rate of esterification is 90%.GPC test number-average molecular weight Mn=37468, Polydispersity PDI=2.0.The contact angle of test cured film on slide glass, contact angle reach 116 degree, belong to hydrophobic surface.
(1) condensing works is being housed, whipping appts, add butanone 100ml in the reactor of temperature regulating device, be heated to 60 ℃, with 0.01mol n-butyl acrylate, 0.01mol vinylformic acid hexafluoro butyl ester, 0.08mol Hydroxyethyl acrylate, Diisopropyl azodicarboxylate 0.3g (being 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, stirs while dripping, remove at last sherwood oil, namely get " n-butyl acrylate-vinylformic acid hexafluoro butyl ester-Hydroxyethyl acrylate " random copolymers, outward appearance is transparent thick liquid.
(2) the first step product is carried out esterification, the first step product is dissolved in the 100ml ethyl acetate, add the 0.096mol triethylamine, add 0.52g (being acrylate chloride 6wt%) Resorcinol, mix, then the acrylate chloride with 0.096mol is added drop-wise in the reactor, and dropping is warming up to 60 ℃ after finishing gradually.Stopped reaction behind the reaction 8h.Aftertreatment is with embodiment 1.Obtaining product is little yellow transparent liquid, and conversion rate of esterification is 90%.
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.
(1) condensing works is being housed, whipping appts, add methyl ethyl ketone 100ml in the reactor of temperature regulating device, be heated to 75 ℃, with 0.01mol n-butyl acrylate, 0.08mol vinylformic acid hexafluoro butyl ester, 0.01mol Hydroxyethyl acrylate, Diisopropyl azodicarboxylate 0.426g (being monomer 2wt%), be added drop-wise in the reactor after mixing, after dropping finishes, temperature of reaction is elevated to 85 ℃, stopped reaction behind the reaction 3h.Aftertreatment is with embodiment 1, and the product outward appearance is transparent thick liquid.
(2) second step is with embodiment 1, and obtaining product is light yellow transparent liquid, and conversion rate of esterification is 98%.
GPC test number-average molecular weight Mn=26731, Polydispersity PDI=1.8.The contact angle of test cured film on slide glass, contact angle reach 132 degree, belong to hydrophobic surface.
(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 ℃, with 0.08mol n-butyl acrylate, 0.01mol vinylformic acid hexafluoro butyl ester, 0.01mol Hydroxyethyl acrylate, benzoyl peroxide 0.066g (being monomer 0.5wt%), positive Dodecyl Mercaptan 0.528g (being monomer 4wt%) is 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.
(2) second step esterification adopts vinylformic acid to carry out.The first step product is dissolved in the 100ml pimelinketone, adds 0.012mol vinylformic acid, adding initiator is tosic acid 0.002g (being vinylformic acid 0.25wt%); Add MEHQ 0.003g (being vinylformic acid 0.3wt%), stirring fully mixes it, is warming up to gradually 110 ℃, reacts to stop in 5 hours.Cooling after reaction finishes, in 60 ℃ of lower underpressure distillation, the desolventizing pimelinketone obtains final product fluorine-contaninig polyacrylate acrylate, and outward appearance is yellow transparent liquid.Transformation efficiency reaches 75%.
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.
(1) the first step is with embodiment 5.
(2) the first step product is dissolved in the 100ml pimelinketone, adds 0.012mol vinylformic acid, adding initiator is tosic acid 0.04g (being vinylformic acid 5wt%); Add MEHQ 0.003g (being vinylformic acid 0.3wt%), stirring fully mixes it, is warming up to gradually 155 ℃, reacts to stop in 1.5 hours.Cooling after reaction finishes, in 60 ℃ of lower underpressure distillation, the desolventizing pimelinketone obtains final product fluorine-contaninig polyacrylate acrylate, and outward appearance is yellow transparent liquid.Transformation efficiency reaches 85%.
GPC test number-average molecular weight Mn=9927, Polydispersity PDI=2.3.The contact angle of test cured film on slide glass, contact angle reach 100 degree, belong to hydrophobic surface.
(1) condensing works is being housed, whipping appts, add dimethyl formamide 100ml in the reactor of temperature regulating device, be heated to 75 ℃, with 0.08mol n-butyl acrylate, 0.01mol vinylformic acid hexafluoro butyl ester, 0.01mol vinylformic acid, Diisopropyl azodicarboxylate 0.266g (being monomer 2wt%), octyl mercaptan 0.266g (being monomer 4wt%), 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, stirs while dripping, remove at last sherwood oil, namely get " n-butyl acrylate-vinylformic acid hexafluoro butyl ester-vinylformic acid " random copolymers, outward appearance is transparent thick liquid.
(2) the first step product is dissolved in the 100ml pimelinketone, adds the 0.012mol Hydroxyethyl acrylate, adding initiator is tosic acid 0.07g (being vinylformic acid 5wt%); Add MEHQ 0.004g (being vinylformic acid 0.3wt%), stirring fully mixes it, is warming up to gradually 155 ℃, reacts to stop in 1.5 hours.Cooling after reaction finishes, in 60 ℃ of lower underpressure distillation, the desolventizing pimelinketone obtains final product fluorine-contaninig polyacrylate acrylate, and outward appearance is yellow transparent liquid.Transformation efficiency reaches 88%.
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. one kind has photoactive fluorine-contaninig polyacrylate acrylate, and its structure represents with (I):
Wherein, x, y, z are respectively 1 ~ 400 integer;
R1 is hydrogen atom or methyl;
R2 is that carbonatoms is 1 ~ 18 alkyl;
R3 is-CH
2CF
2CHFCF
3, or
, n=1 ~ 2 wherein, m=0 ~ 8;
R4 is-CH
2CH
2-or
2. fluorine-contaninig polyacrylate acrylate according to claim 1; Copolymerization units is respectively A, B, C unit, the A unit cell comprises n-butyl acrylate, the vinylformic acid n-octyl, Isooctyl acrylate monomer, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, (methyl) methyl acrylate, ethyl propenoate, methacrylic dodecyl gallate, tridecyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems or isodecyl acrylate; The B unit cell comprises vinylformic acid hexafluoro butyl ester specifically, Hexafluorobutyl mathacrylate, vinylformic acid ten trifluoro monooctyl esters or methacrylic acid ten trifluoro monooctyl esters; The C unit cell comprises (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or vinylformic acid;
Building-up process was divided into for two steps:
It is free-radical polymerized that the first step adopts, and comonomer mixes according to following two kinds of different ratioss: fixing B unit cell 10mol%, and A:C unit cell molar ratio changes from 1:8 to 8:1; Perhaps fixation of C unit cell 10mol%, A:B unit cell molar ratio changes from 1:8 to 8:1; The radical initiator that adds monomer total amount 0.5wt% ~ 2wt%, radical initiator comprises benzoyl peroxide or Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile), the chain-transfer agent that adds monomer total amount 0wt% ~ 4wt%, chain-transfer agent comprises positive Dodecyl Mercaptan or octyl mercaptan, with monomer, initiator, chain-transfer agent mixes, and is added drop-wise to the solution system that forms monomer concentration 10mol/L in the solvent; Solvent is organic solvent, for aromatic hydrocarbon based, and 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 product precipitates with non-polar solvent, and drying namely can be used for the second step reaction;
Second step adopts esterification, by vinylformic acid, and crylic acid hydroxy ester, the acrylate chloride monomer is introduced the two keys with light reaction in the first step reaction product; Concrete synthesizing is divided into following two schemes: the first step product is dissolved in ethyl acetate or pimelinketone or the Isosorbide-5-Nitrae-dioxane; (1) when with vinylformic acid or crylic acid hydroxy ester, adds vinylformic acid or the crylic acid hydroxy ester of 1.2 times of moles of C unit cell; Catalyzer is tosic acid, and add-on is the 0.25wt% ~ 5wt% of vinylformic acid or crylic acid hydroxy ester; Stopper is MEHQ or Resorcinol, and add-on is the 0.3wt% ~ 6wt% of vinylformic acid or crylic acid hydroxy ester; Solvent adopts pimelinketone, and add-on is the every mole of monomer total amount of 100mL/; 110 ℃ ~ 155 ℃ lower reactions 1.5 ~ 5 hours; (2) when participating in the second step reaction with acrylate chloride, add triethylamine as absorption agent, the mole numbers such as add-on and acrylate chloride; Stopper is MEHQ or Resorcinol, and add-on is the 0.3wt% ~ 6wt% of acrylate chloride; Solvent adopts ethyl acetate or 1.4-dioxane; Solvent adding amount is the every mole of monomer total amount of 100mL/; The acrylate chloride of 1.2 times of moles of C unit cell is added drop-wise in the reactor, under 30 ~ 60 ℃ of conditions, reacted 2 ~ 8 hours; Through obtaining the fluorine-contaninig polyacrylate acrylate after purification, the drying.
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| CN102627721A (en) * | 2012-04-13 | 2012-08-08 | 东南大学 | High-solid hydroxyl fluorine-containing acrylic resin and preparation method thereof |
| CN103951784B (en) * | 2014-04-24 | 2017-02-08 | 北京化工大学 | Reversible CO2 response photo-cured oligomer and synthetic method thereof |
| CN105622834B (en) * | 2016-01-30 | 2018-09-21 | 北京化工大学 | A kind of preparation method of photocuring low dielectric constant fluorine polyacrylate acrylate |
| CN109553715B (en) * | 2018-10-30 | 2020-11-13 | 三明学院 | Fluorine-containing acrylate random copolymer, preparation method and application thereof |
| CN111574656B (en) * | 2020-06-01 | 2022-04-22 | 江苏博砚电子科技有限公司 | Fluorine-containing photosensitive resin for black matrix photoresist and resin composition thereof |
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