CN105131196A - Method for synthesizing use-quantity-optimized fluorine containing polyacrylate oligomers - Google Patents
Method for synthesizing use-quantity-optimized fluorine containing polyacrylate oligomers Download PDFInfo
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- CN105131196A CN105131196A CN201510558128.4A CN201510558128A CN105131196A CN 105131196 A CN105131196 A CN 105131196A CN 201510558128 A CN201510558128 A CN 201510558128A CN 105131196 A CN105131196 A CN 105131196A
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- Prior art keywords
- fluorine
- fluorine containing
- epoxy acrylate
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 6
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000728 polyester Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 7
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 abstract description 10
- 238000001723 curing Methods 0.000 abstract description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006150 hyperbranched polyester Polymers 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 acrylic ester Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a method for synthesizing use-quantity-optimized fluorine containing polyacrylate oligomers. The method includes the steps that ring-opening polymerization is carried out on phthalic anhydride and epoxy butyl alcohol to synthesize hyperbranched polyester, and a polymerization reaction is carried out on fluorine containing acrylate and epoxy acrylate to synthesize fluorine containing epoxy acrylate; graft modification is carried out on the synthesized hyperbranched polyester through the fluorine containing epoxy acrylate, and the cationic photocuring hyperbranched fluorine containing polyacrylate oligomers are prepared. The method has the advantages that the curing speed is high, the film forming shrinkage rate is low, the waterproof performance and the adhesiveness of photocuring paint can be improved, and the method is mainly applied to the photocuring field.
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 consumption.
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 consumption.
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 consumption, 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 0.016mol respectively, the methyl propenoic acid glycidyl fat of 0.052mol 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;
(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 0.052mol 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 0.052mol 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 consumption, 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 0.016mol respectively, the methyl propenoic acid glycidyl fat of 0.052mol 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;
(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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| CN201510558128.4A CN105131196A (en) | 2015-09-02 | 2015-09-02 | Method for synthesizing use-quantity-optimized fluorine containing polyacrylate oligomers |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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: 20151209 |