CN110790715A - Fluoroether acrylate monomer linked with 1,2, 3-triazole group and preparation method and application thereof - Google Patents

Fluoroether acrylate monomer linked with 1,2, 3-triazole group and preparation method and application thereof Download PDF

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CN110790715A
CN110790715A CN201911034479.XA CN201911034479A CN110790715A CN 110790715 A CN110790715 A CN 110790715A CN 201911034479 A CN201911034479 A CN 201911034479A CN 110790715 A CN110790715 A CN 110790715A
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reaction
fluoroether
acrylate
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fluorine
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史大阔
冯威
张永明
荣跃
许烨林
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/22—Esters containing nitrogen

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Abstract

The invention belongs to the technical field of fine chemicals, and particularly relates to a fluoroether acrylate monomer with a 1,2, 3-triazole group as a link, and a preparation method and application thereof. The monomer has a structural formula as follows:
Figure DDA0002251076140000011
wherein: rfIs a hexafluoropropylene oxide oligomer structure: CF (compact flash)3CF2CF2O(CFCF3CF2O)nOCFCF3‑，n＝0～40；R1And R1'Is H or an acrylate structure, R1And R1'The structural formula of the acrylate structure is as follows:R3is one of H, methyl, fluorine or chlorine; r4Is one of H, methyl, fluorine or chlorine; m is 1 to 10. According to the invention, the structure of triazole hydroxyl is directly esterified with acrylic acid, the obtained ester group has strong stability, and the preparation method is scientific, reasonable, simple and feasible; the crosslinking agent is used for fluorine-containing polyacrylate, UV (ultraviolet) photo-curing polyacrylate or photo-curing bridging crosslinking agent.

Description

Fluoroether acrylate monomer linked with 1,2, 3-triazole group and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fine chemicals, and particularly relates to a fluoroether acrylate monomer with a 1,2, 3-triazole group as a link, and a preparation method and application thereof.
Background
Fluorine is the element known to date as the most electronegative, and its atomic covalent radius (0.064nm) is only slightly larger than that of a hydrogen atom, so that when hydrogen on a carbon-hydrogen bond (C-H) is replaced by fluorine, the bond energy of the carbon-fluorine bond (C-F) formed by the fluorine atom and the carbon atom is increased by 63 kJ/mol. Meanwhile, the fluorine atom core has stronger constraint effect on the electron outside the nucleus and the electron cloud forming the bond, the polarity of the C-F bond is small, and the intermolecular force of the polymer containing the C-F bond is lower. The perfluoro-acrylate polymer is prepared by introducing perfluoro groups into the side chains of the original polymer, wherein the perfluoro side chains are oriented outwards to form shielding protection on the main chains and internal molecules, and the electron cloud of fluorine atoms well shields carbon-carbon main bonds, so that the stability of carbon-carbon bonds is ensured, and the perfluoro-acrylate polymer has good physical property stability, durability and chemical resistance. The perfluoroacrylate polymer material thus has many excellent in-use properties. The research on the synthesis of the fluorine-containing (methyl) acrylate monomer is more significant.
At present, there have been reported methods for producing fluorine-containing (meth) acrylates, and the production methods can be classified into two methods according to the difference in starting materials. A fluorine-containing (methyl) acrylate is prepared by taking fluorine-containing alcohol as a starting material and (methyl) acrylic acid and the fluorine-containing alcohol as raw materials; fluorine-containing (meth) acrylates can also be prepared starting from fluorine-containing alkyl halides.
The acyl fluoride group of the hexafluoro epoxy oligomer and the alcoholic hydroxyl group derived from the acrylate are directly esterified to obtain the fluorine-containing acrylate monomer, and the ester group has poor stability and is easy to hydrolyze due to the strong electron-pulling effect of the fluorine ether chain; by the same token, the direct reduction of the acyl fluoride groups of the hexafluoroepoxy oligomer to hydroxyl groups and the esterification of acrylic acid are also poor in stability.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the fluoroether acrylate monomer taking the 1,2, 3-triazole group as the connection is provided, the triazole hydroxyl structure is adopted to be directly esterified with the acrylic acid, and the obtained ester group has strong stability.
The invention relates to a fluoroether acrylate monomer taking a 1,2, 3-triazole group as a link, which has the structural formula:
Figure BDA0002251076120000011
wherein:
Rfis a hexafluoropropylene oxide oligomer structure: CF (compact flash)3CF2CF2O(CFCF3CF2O)nOCFCF3-，n＝0～40；
R1And R1'Is H or an acrylate structure, R1And R1'The structural formula of the acrylate structure is as follows:
R3is one of H, methyl, fluorine or chlorine;
R4is one of H, methyl, fluorine or chlorine;
m＝1～10。
the preparation method of the fluoroether acrylate monomer with the 1,2, 3-triazole group as the link comprises the following steps:
(1) placing a solvent and lithium aluminum hydride in a container, stirring and dropwise adding a hexafluoroepoxy oligomer for reaction under the protection of nitrogen, dropwise adding ethyl acetate for quenching reaction after the reaction is finished, and acidifying to obtain fluoroether alcohol;
(2) placing the fluoroether alcohol prepared in the step (1), alkali and a solvent into a container, and dropwise adding trifluoromethanesulfonic anhydride under stirring to perform coupling reaction to obtain hexafluoroepoxy oligomer trifluoromethanesulfonate; adding hexafluoro epoxy oligomer triflate into a solvent, and adding sodium azide for an azide reaction to prepare an azide product;
(3) and (3) carrying out click reaction on the azide product prepared in the step (2) and alkyne with the end group of acrylate to obtain the fluoroether acrylate monomer with the 1,2, 3-triazole group as the link.
The chemical reaction formula of the above reaction is as follows:
Figure BDA0002251076120000022
reagents and conditions in formula (la):
a) lithium aluminum hydride; b) trifluoromethanesulfonic anhydride, base, sodium azide; c) cu (I), and a solvent.
In the step (1), the solvent is an ether solvent, preferably one or more of tetrahydrofuran, diethyl ether or MTBE, the amount of the lithium aluminum hydride is 1.1-1.5 times of the amount of the hexafluoropropylene oxide oligomer, and the reaction temperature is-30-80 ℃.
In the step (2), the solvent is one or two of dichloromethane or dichloroethane, and the base is one or more of triethylamine, DIPEA or pyridine.
In the step (2), the amount of the trifluoromethanesulfonic anhydride is 1.1-1.8 times of the amount of the fluoroether alcohol prepared in the step (1), and the reaction temperature of the coupling reaction is-10-60 ℃.
In the step (2), the amount of the sodium azide is 1.5-10 times of the amount of a hexafluoroepoxy oligomer trifluoromethanesulfonate substance.
In the step (2), the solvent of the azidation reaction is one or two of DMF or acetone, and the reaction temperature of the azidation reaction is 0-160 ℃.
The step (3) can be carried out in two ways, with and without a catalyst.
When the catalyst is adopted, alkyne with the end group of acrylate and the catalyst are sequentially added into a mixed solvent of DMF (dimethyl formamide) and water, and then an azide product is added for reaction, wherein the catalyst is the combination of cuprous halide or copper sulfate pentahydrate and sodium ascorbate, the dosage of the cuprous halide or copper sulfate pentahydrate is 0.1-2 times of that of an alkynyl raw material substance, the dosage of the sodium ascorbate is 0.1-2 times of that of the alkynyl raw material substance, and the reaction temperature is between room temperature and 160 ℃.
When no catalyst is adopted, the azide product directly reacts with alkyne with the end group of acrylate at 50-180 ℃.
The invention relates to the application of a fluoroether acrylate monomer which takes a 1,2, 3-triazole group as a link and is used for fluorine-containing polyacrylate, UV (ultraviolet) photocuring polyacrylate or photocuring bridging cross-linking agent.
The invention has the following beneficial effects:
the invention adopts the structure of triazole hydroxyl to be directly esterified with acrylic acid, the stability of the obtained ester group is enhanced, and the advantage of the invention is obviously higher than that of common fluoroether acrylate.
Drawings
FIG. 1 shows fluoroether triazole methyl acrylate prepared in example 3 of the invention1Characterization by H NMR.
Detailed Description
The invention is further described with reference to specific examples.
The starting materials used in the examples are all commercially available except where otherwise indicated.
Example 1
Figure BDA0002251076120000031
1000mL of anhydrous diethyl ether and lithium aluminum hydride (22.8g, 0.6mol) were placed in a 5L dry three-necked flask under N2Under protection, hexafluoropropylene oxide trimer (250g, 0.5mol) is added dropwise with stirring, reaction exothermicity is realized, the adding speed is preferably kept to keep ether reflux, stirring is continued for 2 hours at room temperature after the addition is finished, then 5mL of ethyl acetate is added dropwise to quench the reaction, 500g of ice water is added until no obvious exothermicity appears, then 6N sulfuric acid is used for acidification, and 50mL of water phase is used for water phase after liquid separationx3, extracting with diethyl ether, mixing the extract with organic phase, drying with anhydrous magnesium sulfate, filtering, concentrating, and distilling to obtain 220g of fluoroether alcohol with yield of 90% and GC purity of 98.3%.1H NMR shows that a chemical shift of 4.15 has multiple peaks, which are CH2Characteristic peak of O.
Example 2
The fluoroether alcohol of example 1 (153g, 0.32mol), pyridine (37mL, 0.46mol), dry treated dichloromethane 500mL was added to a dry three-necked flask while maintaining 0 deg.C in an ice water bath, trifluoromethanesulfonic anhydride (74mL, 0.46mmol) was slowly added dropwise with constant stirring, the reaction was maintained at 0 deg.C for 2 hours, and the mixture was allowed to warm to room temperature and stirred overnight. After the reaction is completed, filtering and washing with water, drying the organic phase with anhydrous magnesium sulfate, filtering and concentrating, and obtaining a crude product for later use.
The crude product was added to 500mL of DMF followed by 52g of NaN3The reaction mixture was heated to 50 ℃ for 2 days, 80% DMF was evaporated by rotary evaporation, and then 500mL of diethyl ether was added, washed with water, dried over anhydrous magnesium sulfate, and concentrated to give 127g of a pale yellow oil with a yield of 78%.1H NMR shows that a chemical shift of 4.32 has multiple peaks, which are CH2Characteristic peak of O, showing CH2The characteristic peak of O shifts to low field.
Example 3
Figure BDA0002251076120000041
Propargyl acrylate (11g, 0.1mol), CuSO4·5H2O (9mg, 36mmol) and sodium ascorbate (7.12g, 36mmol) were added sequentially to a mixed solvent of DMF (500mL) and water (500mL), stirring was turned on, then the azide of example 2 (50.7g, 0.1mol) was added to the above solution, reacted at room temperature for 12 hours, after completion of the reaction, extracted with ethyl acetate (200mL x3), then washed with saturated brine (50mLx3), dried over anhydrous sodium sulfate, concentrated and flash column chromatographed to give 52.5g of a pale yellow oil with a yield of 85%,HPLC purity 97.8%.
Modified examples
Figure BDA0002251076120000042
65g of crude triflate obtained in the first step of example 2, NaN3Stirring 36g of the mixture in DMF (500mL), reacting at 50 ℃ for 2 days, adding 11g of propargyl acrylate, heating to 130 ℃ under the protection of nitrogen and keeping out of the light, continuing to react for 12 hours, cooling after the reaction is finished, extracting with ethyl acetate (200mL x3), washing with saturated salt water (50mL x3), drying with anhydrous sodium sulfate, concentrating, and performing flash column chromatography to obtain 45g of light yellow oily matter, wherein the yield is 72%, the HPLC purity is 99.2%, and the nuclear magnetic characterization is shown in figure 1.
Example 4
2-acetylenedibutylene diacrylate (20g, 0.1mol), CuSO4·5H2O (9mg, 36mmol) and SodiumL-ascorbate (7.12g, 36mmol) were sequentially added to a mixed solvent of DMF (500mL) and water (500mL), stirring was turned on, then azide (50.7g, 0.1mol) in example 2 was added to the above solution, reacted at room temperature for 12 hours, after completion of the reaction, extracted with ethyl acetate (200mL x3), then washed with saturated brine (50mL x3), dried over anhydrous sodium sulfate, concentrated and flash column chromatographed to give 45.3g of a pale yellow oil in 63% yield and 96.5% HPLC purity.

Claims (10)

1. A fluoroether acrylate monomer linked by a 1,2, 3-triazole group is characterized in that: the structural formula is as follows:
Figure FDA0002251076110000011
wherein:
Rfis a hexafluoropropylene oxide oligomer structure: CF (compact flash)3CF2CF2O(CFCF3CF2O)nOCFCF3-，n＝0～40；
R1And R1'Is H or an acrylate structure, R1And R1'The structural formula of the acrylate structure is as follows:
Figure FDA0002251076110000012
R3is one of H, methyl, fluorine or chlorine;
R4is one of H, methyl, fluorine or chlorine;
m＝1～10。
2. a method for preparing a fluoroether acrylate monomer linked with a 1,2, 3-triazole group according to claim 1, wherein: the method comprises the following steps:
(1) placing a solvent and lithium aluminum hydride in a container, stirring and dropwise adding a hexafluoroepoxy oligomer for reaction under the protection of nitrogen, dropwise adding ethyl acetate for quenching reaction after the reaction is finished, and acidifying to obtain fluoroether alcohol;
(2) placing the fluoroether alcohol prepared in the step (1), alkali and a solvent into a container, and dropwise adding trifluoromethanesulfonic anhydride under stirring to perform coupling reaction to obtain hexafluoroepoxy oligomer trifluoromethanesulfonate; adding hexafluoro epoxy oligomer triflate into a solvent, and adding sodium azide for an azide reaction to prepare an azide product;
(3) and (3) carrying out click reaction on the azide product prepared in the step (2) and alkyne with the end group of acrylate to obtain the fluoroether acrylate monomer with the 1,2, 3-triazole group as the link.
3. The method of claim 2, wherein: in the step (1), the solvent is one or more of tetrahydrofuran, diethyl ether or MTBE, the dosage of the lithium aluminum hydride is 1.1-1.5 times of that of the hexafluoropropylene oxide oligomer, and the reaction temperature is-30-80 ℃.
4. The method of claim 2, wherein: in the step (2), the solvent is one or two of dichloromethane or dichloroethane, and the base is one or more of triethylamine, DIPEA or pyridine.
5. The method of claim 2, wherein: in the step (2), the amount of the trifluoromethanesulfonic anhydride is 1.1-1.8 times of the amount of the fluoroether alcohol prepared in the step (1), and the reaction temperature of the coupling reaction is-10-60 ℃.
6. The method of claim 2, wherein: in the step (2), the amount of the sodium azide is 1.5-10 times of the amount of a hexafluoroepoxy oligomer trifluoromethanesulfonate substance.
7. The method of claim 2, wherein: in the step (2), the solvent of the azidation reaction is one or two of DMF or acetone, and the reaction temperature of the azidation reaction is 0-160 ℃.
8. The method of claim 2, wherein: in the step (3), alkyne with an end group of acrylate and a catalyst are sequentially added into a mixed solvent of DMF (dimethyl formamide) and water, and then azide products are added for reaction, wherein the catalyst is a combination of cuprous halide or copper sulfate pentahydrate and sodium ascorbate, the dosage of the cuprous halide or copper sulfate pentahydrate is 0.1-2 times of that of an alkynyl raw material substance, the dosage of the sodium ascorbate is 0.1-2 times of that of the alkynyl raw material substance, and the reaction temperature is between room temperature and 160 ℃.
9. The method of claim 2, wherein: in the step (3), the azide product directly reacts with alkyne with the end group of acrylate at 50-180 ℃.
10. The use of a fluoroether acrylate monomer linked to a 1,2, 3-triazole group as claimed in claim 1, wherein: the crosslinking agent is used for fluorine-containing polyacrylate, UV (ultraviolet) photo-curing polyacrylate or photo-curing bridging crosslinking agent.
CN201911034479.XA 2019-10-29 2019-10-29 Fluoroether acrylate monomer linked with 1,2, 3-triazole group and preparation method and application thereof Withdrawn CN110790715A (en)

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