CN105111453A - Synthetic method of fluorinated polyacrylate oligomer with optimized mole ratio - Google Patents
Synthetic method of fluorinated polyacrylate oligomer with optimized mole ratio Download PDFInfo
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- CN105111453A CN105111453A CN201510557519.4A CN201510557519A CN105111453A CN 105111453 A CN105111453 A CN 105111453A CN 201510557519 A CN201510557519 A CN 201510557519A CN 105111453 A CN105111453 A CN 105111453A
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Abstract
The invention discloses a synthetic method of a fluorinated polyacrylate oligomer with an optimized mole ratio. The method is characterized by synthesizing hyperbranched polyester through ring-opening polymerization reaction between phthalic anhydride and epoxy butanol, synthesizing fluorinated epoxy acrylate through polymerization reaction between fluorinated acrylate and epoxy acrylate and carrying out graft modification on synthesized hyperbranched polyester with fluorinated epoxy acrylate, thus preparing a cationic light-cured hyperbranched fluorinated polyacrylate oligomer. The synthetic method has the advantages of high curing speed, low film shrinkage ratio and capability of improving the waterproofness and adhesiveness of light curing coatings and is mainly applied to the field of light curing.
Description
Technical field
The present invention relates to curing field, particularly relate to a kind of synthetic method optimizing the fluorine-contaninig polyacrylate oligopolymer of mol ratio.
Background technology
Photo-cured coating refers to irradiate at high energy UV and issues biochemical reaction, in the polymerization of coating Quick cross-linking, and then solidify to form solid-state coating.From the sixties in last century, photo-cured coating achieves the development of advancing by leaps and bounds because of low VOA (volatile organic matter) discharge.
The oligopolymer of tradition photo-cured coating has the following disadvantages: the oligopolymer of (1) traditional photo-cured coating in use, need to add a large amount of polyfunctional monomer as thinner, the use of Macrodilution agent, not only can reduce curing speed, and can cause the significant shrinkage of film; (2) there is the shortcomings such as volatile, toxicity is large in thinner itself; (3) water-repellancy of traditional photo-cured coating, adhesion are all to be improved.
Summary of the invention
The present invention is directed to the defect of prior art, be intended to openly a kind of synthetic method optimizing the fluorine-contaninig polyacrylate oligopolymer of mol ratio.
The present invention solves the problems of the technologies described above by the following technical solutions: a kind of synthetic method optimizing the fluorine-contaninig polyacrylate oligopolymer of mol ratio, described synthetic method comprises the steps:
(1) Tetra hydro Phthalic anhydride taking 0.01 ~ 0.03mol is added in the DMF of 50ml, be warming up to 70 ~ 90 DEG C, after being dissolved into homogeneous phase, the epoxy butanols taking 0.005 ~ 0.015mol slowly drops in system, and adjust ph is 5, after having reacted, after precipitate and separate purification process, dry at 50 ~ 70 DEG C in vacuum drying oven, obtained hyper-branched polyester;
(2) take the pungent fat of vinylformic acid ten trifluoro of 0.015 ~ 0.02mol respectively, the methyl propenoic acid glycidyl fat of 0.05 ~ 0.1mol is added in the 1.4-dioxane solution of 100ml, using butyronitrile as initiator, be warming up to 80 ~ 90 DEG C, after having reacted, after precipitate and separate purification process, dry at 50 ~ 70 DEG C in vacuum drying oven, obtained fluorine-containing epoxy acrylate, the mol ratio of the pungent fat of described vinylformic acid ten trifluoro and described methyl propenoic acid glycidyl fat is 1:3;
(3) take the described hyper-branched polyester of 0.01 ~ 0.02mol respectively, the described fluorine-containing epoxy acrylate of 0.002 ~ 0.01mol is added in the DMF solution of 100ml, take MEHQ as stopper, be 5 in pH value, stirring reaction 30 ~ 60min under the condition of 60 ~ 80 DEG C, obtained product.
The present invention passes through with Tetra hydro Phthalic anhydride and epoxy butanols ring-opening polymerization synthesis of super branched polyester, fluorine-containing epoxy acrylate is synthesized with fluorinated acrylate and epoxy acrylate polyreaction, at the hyper-branched polyester that will synthesize by fluorine-containing epoxy acrylic ester grafted modification, the solid hyperbranched fluorine-contaninig polyacrylate oligopolymer of obtained a kind of cationic photopolymerization.
The invention has the advantages that: curing speed is fast, film forming shrinking percentage is low, can improve the water-repellancy of photo-cured coating, adhesion, mainly apply to curing field.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of hyper-branched polyester in the present invention.
Fig. 2 is the chemical reaction schematic diagram of fluorine-contaninig polyacrylate in the present invention.
Fig. 3 is the schematic diagram of hyper-branched polyester grafted fluoropolymer polyacrylic ester in the present invention.
Fig. 4 is the photocuring film shrinking percentage change curve that the present invention measures for variable with hyper-branched polyester consumption.
Fig. 5 is the photocuring film contact angle change curve that the present invention measures for variable with fluorine-contaninig polyacrylate consumption.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
Embodiment 1
The experiment that different hyper-branched polyester consumption affects photocuring film shrinking percentage:
(1) Tetra hydro Phthalic anhydride (PA) taking 0.02mol is added in the DMF of 50ml, be warming up to 80 DEG C, after being dissolved into homogeneous phase, the epoxy butanols taking 0.01mol respectively slowly drops in system, and adjust ph is 5, after having reacted, after precipitate and separate purification process, dry at 55 DEG C in vacuum drying oven, obtained hyper-branched polyester;
(2) take the pungent fat of vinylformic acid ten trifluoro (PFOA) of 0.016mol respectively, the methyl propenoic acid glycidyl fat (GMA) of 0.032mol is added in the 1.4-dioxane solution of 100ml, using butyronitrile as initiator, be warming up to 80 DEG C, after having reacted, after precipitate and separate purification process, dry at 55 DEG C in vacuum drying oven, obtained fluorine-containing epoxy acrylate;
(3) the fluorine-containing epoxy acrylate taking 0.009mol is added in the DMF solution of 100ml, take 0 respectively, the hyper-branched polyester of 0.012mol, 0.014mol, 0.015mol, 0.018mol, 0.02mol is added in system, take MEHQ as stopper, be 5 in pH value, stirring reaction 50min under the condition of 70 DEG C, obtained product;
(4) product, epoxycyclohexyl manthanoate and light trigger PI are mixed than the ratio for 10:4:1 in massfraction, ultrasonic disperse, stirs, obtained coating;
(5) paint is carried out film on the spreader of 50um, in UV photocuring case, solidify 7min, make its film-forming;
(6) adopt volumetric shrinkage method to calculate photocuring film shrinking percentage, calculation formula is as follows:
As Figure 1-3, in hyperbranched poly Lipase absobed, first there is ring-opening reaction with Tetra hydro Phthalic anhydride (PA) and generate intermediate A in the hydroxyl of epoxy butanols, carboxyl newly-generated in intermediate A reacts the hydroxyl of generation two hearts with another epoxy butanols again, the epoxy group(ing) of intermediate A and the carboxyl reaction of another intermediate obtain the oligomer containing carboxyl and hydroxyl simultaneously, so alternately finally form spherical hyper-branched polyester.Under the initiation of butyronitrile, there is building-up reactions, generate fluorine-containing epoxy acrylate in the pungent fat of vinylformic acid ten trifluoro and methyl propenoic acid glycidyl fat.Utilize the carboxyl reaction of epoxy group(ing) in fluorine-containing epoxy acrylate and hyperbranched poly ester molecule periphery, obtain product.
As shown in Figure 4, when after fluorine-containing epoxy acrylic ester grafted hyper-branched polyester, oligomer structure is spherical, and on global molecular, C=C is less, cure shrinkage step-down.Along with the increase of hyper-branched polyester consumption, cure shrinkage reduces gradually, and when hyper-branched polyester consumption is more than 0.015mol, graft reaction reaches running balance.
Embodiment 2
Different from fluorine-containing epoxy acrylate consumption is to the sex experiment of photocuring film waterproof:
(1) Tetra hydro Phthalic anhydride (PA) taking 0.02mol is added in the DMF of 50ml, be warming up to 80 DEG C, after being dissolved into homogeneous phase, the epoxy butanols taking 0.01mol respectively slowly drops in system, and adjust ph is 5, after having reacted, after precipitate and separate purification process, dry at 55 DEG C in vacuum drying oven, obtained hyper-branched polyester;
(2) take the pungent fat of vinylformic acid ten trifluoro (PFOA) of 0.016mol respectively, the methyl propenoic acid glycidyl fat (GMA) of 0.032mol is added in the 1.4-dioxane solution of 100ml, using butyronitrile as initiator, be warming up to 80 DEG C, after having reacted, after precipitate and separate purification process, dry at 55 DEG C in vacuum drying oven, obtained fluorine-containing epoxy acrylate;
(3) taking the fluorine-containing epoxy acrylate of 0.002mol, 0.005mol, 0.007mol, 0.009mol, 0.01mol is added in the DMF solution of 100ml, the hyper-branched polyester taking 0.015mol is respectively added in system, take MEHQ as stopper, be 5 in pH value, stirring reaction 50min under the condition of 70 DEG C, obtained product;
(4) product, epoxycyclohexyl manthanoate and light trigger PI are mixed than the ratio for 10:4:1 in massfraction, ultrasonic disperse, stirs, obtained coating;
(5) paint is carried out film on the spreader of 50um, in UV photocuring case, solidify 7min, make its film-forming;
(6) contact angle (CA) test light cured film water resistance is adopted.Calculate according to FOWKES theory during the free energy of fluoropolymer surface.
As shown in Figure 5, along with the increase of fluorine-containing epoxy acrylate consumption, the water resistance of product is better, and when the consumption of fluorine-containing epoxy acrylate is more than 0.009mol, continue the consumption increasing fluorine-containing epoxy acrylate, water-repellancy change is not obvious.This is because contact angle is larger, surface tension is less, and hydrophobicity is stronger.
The foregoing is only the preferred embodiment of the invention; not in order to limit the invention; the any amendment done within all spirit in the invention and principle, equivalently to replace and improvement etc., within the protection domain that all should be included in the invention.
Claims (1)
1. optimize a synthetic method for the fluorine-contaninig polyacrylate oligopolymer of mol ratio, it is characterized in that, described synthetic method comprises the steps:
(1) Tetra hydro Phthalic anhydride taking 0.01 ~ 0.03mol is added in the DMF of 50ml, be warming up to 70 ~ 90 DEG C, after being dissolved into homogeneous phase, the epoxy butanols taking 0.005 ~ 0.015mol slowly drops in system, adjust ph is 5, after having reacted, after precipitate and separate purification process, dry at 50 ~ 70 DEG C in vacuum drying oven, obtained hyper-branched polyester;
(2) take the pungent fat of vinylformic acid ten trifluoro of 0.015 ~ 0.02mol respectively, the methyl propenoic acid glycidyl fat of 0.05 ~ 0.1mol is added in the 1.4-dioxane solution of 100ml, using butyronitrile as initiator, be warming up to 80 ~ 90 DEG C, after having reacted, after precipitate and separate purification process, dry at 50 ~ 70 DEG C in vacuum drying oven, obtained fluorine-containing epoxy acrylate, the mol ratio of the pungent fat of described vinylformic acid ten trifluoro and described methyl propenoic acid glycidyl fat is 1:3;
(3) take the described hyper-branched polyester of 0.01 ~ 0.02mol respectively, the described fluorine-containing epoxy acrylate of 0.002 ~ 0.01mol is added in the DMF solution of 100ml, take MEHQ as stopper, be 5 in pH value, stirring reaction 30 ~ 60min under the condition of 60 ~ 80 DEG C, obtained product.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012660A (en) * | 2012-12-05 | 2013-04-03 | 北京化工大学 | Fluorine-containing epoxy acrylate oligomer for photo-curing and synthetic method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012660A (en) * | 2012-12-05 | 2013-04-03 | 北京化工大学 | Fluorine-containing epoxy acrylate oligomer for photo-curing and synthetic method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 孙丽婷等: "多元酸酐型超支化聚合物合成及改性应用研究进展", 《化工新型材料》 * |
| 廖峰等: "超支化聚合物在涂料中应用的研究进展", 《材料导报：综述篇》 * |
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Application publication date: 20151202 |