CN115417795B - Fluorine-containing acrylate monomer containing rigid unit and preparation method thereof - Google Patents
Fluorine-containing acrylate monomer containing rigid unit and preparation method thereof Download PDFInfo
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- CN115417795B CN115417795B CN202211198073.7A CN202211198073A CN115417795B CN 115417795 B CN115417795 B CN 115417795B CN 202211198073 A CN202211198073 A CN 202211198073A CN 115417795 B CN115417795 B CN 115417795B
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- 239000000178 monomer Substances 0.000 title claims abstract description 59
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011737 fluorine Substances 0.000 title claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 13
- GPAMBYNRXCUNML-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-ol Chemical compound FC(F)(F)C(F)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GPAMBYNRXCUNML-UHFFFAOYSA-N 0.000 claims abstract description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 abstract 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 abstract 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 13
- 235000010290 biphenyl Nutrition 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- -1 perfluoroalkyl acrylate Chemical compound 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001151024 Giulia Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a fluorine-containing acrylate monomer containing a rigid unit and a preparation method thereof. The structural formula of the fluorine-containing acrylate monomer containing the rigid unit is as follows: The fluoroacrylate monomer containing rigid monomer in molecular structure is prepared by using diisocyanate such as isophorone diisocyanate or 2, 4-toluene diisocyanate and perfluorohexyl ethanol and hydroxyl-containing acrylate monomer such as hydroxyethyl acrylate or hydroxyethyl methacrylate to react stepwise, and by using the activity difference of two isocyanate groups in diisocyanate and controlling the conditions such as raw material adding mode, reaction temperature, reaction time and the like, the fluoroacrylate monomer containing rigid monomer in molecular structure is expected to be applied to liquid crystal polymers and stable hydrophobic coatings. The preparation reaction condition of the monomer is simple, the steps are few, and the yield is high.
Description
Technical Field
The invention relates to the technical field of polyacrylate coatings, in particular to a fluorine-containing acrylate monomer containing a rigid unit and a preparation method thereof.
Background
The fluorine-containing polymer has good heat resistance, chemical resistance, water repellency and oleophobicity due to low fluorine atom polarizability, small atom radius and large C-F bond energy.
Along with the improvement of environmental protection concepts and life quality, the limitation on the content of organic volatile matters is increasingly strict, and the pollution problem of the solvent-based paint is overcome on the basis of keeping the advantages of the solvent-based paint. The water-based fluorine-containing polyacrylate paint has good hydrophobic antifouling property, adhesive force and chemical stability. However, when the hydrophobic coating is in contact with the polar medium, a huge surface energy difference exists between the hydrophobic coating and the polar medium, so that the surface energy difference is reduced, the radicals on the surface of the coating are rearranged, hydrophilic radicals migrate to the surface, and the hydrophobic fluorine-containing radicals turn over to the inner side of the matrix, so that the water resistance of the coating is poor, and the service performance is poor. Researches show that after fluorocarbon chains are grafted on a polymer main chain through rigid structural units such as biphenyl, aromatic rings and the like in fluorinated polyacrylate, a fluorine-containing acrylate monomer with liquid crystal behavior can be obtained, and the fluorine-containing acrylate monomer can be used in a plurality of fields such as stable surface hydrophobicity and the like by utilizing polymerization of the fluorine-containing acrylate monomer and other monomers.
At present, the introduction of rigid structural units into fluorine-containing acrylate monomers is more studied, and the rigid units mainly comprise two groups, namely, mono-benzene rings and biphenyl rings. For example Fornasieri, p-hydroxybenzoic acid is used as raw material, and through esterification reaction with perfluoroalkyl mercapto alcohol step by step, etherification reaction with hydroxyl-containing halohydrocarbon, and finally esterification reaction with acryloyl chloride, the perfluoroalkyl acrylate monomer containing single benzene ring [ Liquid Crystals,2003,30,663-669] is synthesized. Giulia et al link the perfluoro chain and the terminal double bond hydrocarbon chain through thioester bonds using monophenyl, biphenyl and benzoate groups as rigid cores, thereby obtaining the monomers thereof and characterizing the crystallization behavior thereof, the molecular structure thereof is as follows: [ Liquid Crystals,2003,30,251-257]. Although the authors did not conduct hydrophobic stability related studies, it is expected that there is a better application prospect in this respect.
Regarding the related documents which take biphenyl rings as rigid units, such as Patrice and the like, 4' -biphenol is taken as a raw material, and is subjected to etherification reaction with halogenated hydrocarbon containing unsaturated bonds and halogenated hydrocarbon containing hydroxyl groups step by step, then the products are added with perfluorooctyl iodide to generate iodides, and the products after reduction are subjected to esterification reaction with acryloyl chloride to synthesize the perfluoroalkyl acrylate monomer containing biphenyl cores and hydrocarbon spacers with different lengths, wherein the structure is as follows: [ Journal of Fluoride Chemistry,2004,125,1909-1918]. Hartmann et al studied the surface properties of a series of random copolymers of the above-described perfluoroalkyl biphenyl acrylate and Stearyl Methacrylate (SMA) containing rigid units. The structure is as follows: /(I) The hydrophobic stability of the polymer surface is enhanced by the presence of the rigid unit biphenyl in the SMA copolymer [ Macromolecules 2006,39,6975-6982]. Givenhy and the like take 4,4' -biphenol as raw materials, generate allyl monomers containing biphenyl rings and hydroxyl groups through etherification reaction with hydroxyl-containing halohydrocarbon, and then prepare fluorine-containing allyl monomers containing biphenyl rigid units in molecular structures through esterification reaction with perfluoroalkyl carboxylic acid, wherein the structure is shown as follows:
[Mol.Cryst.Liq.Cryst.,2005,436,.237–246]。
In the two modification modes, when the fluorine-containing monomer with a rigid unit is prepared, the experimental conditions are harsh, side reactions are involved, the protection of groups is needed, the operation steps are complicated, and the total reaction yield is low.
Disclosure of Invention
In view of the above, the invention provides a fluorine-containing acrylate monomer containing a rigid unit and a preparation method thereof, which are used for solving the problems of complicated operation steps and low total yield in the existing preparation process.
In order to solve the problems existing in the prior art, the technical scheme of the invention is as follows: a preparation method of a fluorine-containing acrylate monomer containing a rigid unit is characterized by comprising the following steps: the method comprises the following steps:
1) Synthesis of intermediate a:
adding diisocyanate into a three-neck flask with a stirring device at the temperature of 0-40 ℃, uniformly stirring, slowly dropwise adding perfluorohexyl ethanol and a catalyst, wherein the molar ratio of the diisocyanate to the perfluorohexyl ethanol is 1:1, and carrying out heat preservation reaction to obtain an intermediate A;
2) Synthesis of the fluoroacrylate monomer containing rigid units:
Adding the intermediate A obtained in the step 1) into a three-neck flask with the temperature of 80 ℃, and adding the functional monomer and the p-methoxyphenol into the three-neck flask, wherein the molar ratio of the intermediate A to the functional monomer to the p-methoxyphenol in the step 2) is 1:1:0.002, and simultaneously dropwise adding a catalyst, and reacting for 3-5 hours at a constant temperature to obtain the fluorine-containing acrylate monomer containing the rigid unit.
Further, the diisocyanate in the step 1) is one of isophorone diisocyanate or 2, 4-toluene diisocyanate.
Further, the reaction time in the step 1) is 3 to 7 hours.
Further, the functional monomer in the step 2) is one of hydroxyethyl acrylate or hydroxyethyl methacrylate.
Further, the catalyst in steps 1) and 2) is dibutyltin dilaurate.
The fluorine-containing acrylate monomer containing the rigid unit is prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
1. The method utilizes the activity difference of two isocyanate groups in diisocyanate, and has the advantages of high reaction selectivity, almost no side reaction, simple experimental steps and high total reaction yield by controlling the addition mode of raw materials, the reaction temperature, the reaction time and other conditions.
2. After self-polymerization or copolymerization with other proper monomers, the invention is easy to form a crystallization structure due to the existence of a rigid unit, can ensure the structural stability of a fluorine-containing chain segment at a two-phase interface, is not easy to generate structural rearrangement phenomenon, and has excellent hydrophobic stability.
Drawings
FIG. 1 is an infrared spectrum of a fluoroacrylate monomer having a rigid unit in example I.
FIG. 2 is a DSC of a fluoroacrylate monomer containing a rigid unit in example one.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a preparation method of a fluorine-containing acrylate monomer containing a rigid unit, which comprises the following steps:
(1) Synthesis of intermediate a:
Adding a certain amount of diisocyanate into a three-neck flask with a stirring device, stirring and controlling the temperature to be a certain temperature, slowly dripping perfluorohexyl ethanol into the flask, reacting for a certain time, dripping dibutyltin dilaurate into the flask during the reaction, and fully reacting to obtain an intermediate A;
The diisocyanate is one of isophorone diisocyanate or 2, 4-toluene diisocyanate; the molar ratio of diisocyanate to perfluorohexyl ethanol is 1:1; the reaction temperature is 0-40 ℃ and the reaction time is 3-7 h.
(2) Synthesis of the fluoroacrylate monomer containing rigid units:
Taking an intermediate A, hydroxyethyl acrylate or hydroxyethyl methacrylate as a raw material, taking p-methoxyphenol as a polymerization inhibitor and dibutyltin dilaurate as a catalyst, and reacting for 4 hours after the temperature is raised to 80 ℃ to obtain a fluorine-containing acrylate monomer containing a rigid unit;
The molar ratio of the intermediate A to the hydroxyethyl acrylate or the hydroxyethyl methacrylate in the step (2) is 1:1.
Embodiment one:
A method for preparing a fluorine-containing acrylate monomer containing a rigid unit, which comprises the following steps:
Step 1) synthesis of intermediate A:
Accurately weighing 24.00g (108 mmol) of isophorone diisocyanate (IPDI) at 30 ℃ and adding into a three-mouth beaker with a stirring device, uniformly stirring at 300r/min, slowly dropwise adding 39.32g (108 mmol) of perfluorohexyl ethanol (S104) and 2 drops of dibutyltin dilaurate into the system, and reacting at constant temperature for 5h after dropwise adding is completed for about 1 h;
Step 2) synthesis of fluorine-containing acrylate monomer:
The temperature was raised to 80℃and 14.06g (108 mmol) of hydroxyethyl methacrylate (HEMA), 0.0268g (0.216 mmol) of 4-methoxyphenol and 2 drops of dibutyltin dilaurate were slowly added dropwise to the reaction system, and after the completion of the dropwise addition, the reaction was carried out at constant temperature for 4 hours to prepare a fluorine-containing acrylic monomer containing a rigid unit. The overall yield of the reaction was about 94.6%.
As shown in FIG. 1, the infrared spectra of the fluorine-containing acrylic monomer containing a rigid unit obtained in this example revealed that the absorption peak at 3340cm -1 was an N-H stretching vibration absorption peak on the urethane group, the absorption peaks at 2956 and 2885cm -1 were methyl and methylene stretching vibration absorption peaks, the absorption peak at 1714cm -1 was an C=O stretching vibration absorption peak on the ester bond, i.e., a carbonyl stretching vibration absorption peak, the absorption peak at 1635cm -1 was an C=C stretching vibration absorption peak, the absorption peaks at 1234, 1144 and 706cm -1 were C-F stretching vibration absorption peak and bending vibration absorption peak, and the absence of the absorption peak at 2267cm -1 indicated that-NCO groups were all involved in the reaction. The DSC chart, as shown in FIG. 2, shows a distinct endothermic peak at 81.8deg.C, indicating that the fluoroacrylic monomer is a melting peak at about 81℃, i.e., crystals are present in its structure, which may result from the more rigid six-membered alicyclic groups in the molecular structure and the hydrogen bonding associated therewith.
Embodiment two:
a preparation method of a fluorine-containing acrylate monomer containing a rigid unit comprises the following steps:
Step 1) synthesis of intermediate A:
Under the ice water bath condition of 0 ℃, accurately weighing 18.81g (108 mmol) of 2, 4-toluene diisocyanate (2, 4-TDI), adding into a three-port beaker with a stirring device, uniformly stirring at 300r/min, slowly dropwise adding 39.32g (108 mmol) of perfluorohexyl ethanol (S1104) and 2 drops of dibutyltin dilaurate into the system, and reacting at constant temperature for 7h after dropwise adding is completed for about 1 h;
Step 2) synthesis of fluorine-containing acrylate monomer:
The temperature was raised to 80℃and 12.54g (108 mmol) of hydroxyethyl acrylate (HEA), 0.0268g (0.216 mmol) of 4-methoxyphenol and 2 drops of dibutyltin dilaurate were slowly added dropwise to the reaction system, and after the completion of the dropwise addition, the reaction was carried out at constant temperature for 4 hours to prepare a fluorine-containing acrylic monomer containing a rigid unit. The overall yield of the reaction was about 95.8%.
Embodiment III:
a preparation method of a fluorine-containing acrylate monomer containing a rigid unit comprises the following steps:
Step 1) synthesis of intermediate A:
accurately weighing 24.00g (108 mmol) of isophorone diisocyanate (IPDI) at 20 ℃ and adding into a three-mouth beaker with a stirring device, uniformly stirring at 300r/min, slowly dropwise adding 39.32g (108 mmol) of perfluorohexyl ethanol (S104) and 2 drops of dibutyltin dilaurate into the system, and reacting at constant temperature for 6h after dropwise adding is completed for about 1 h;
Step 2) synthesis of fluorine-containing acrylate monomer:
The temperature was raised to 80℃and 14.06g (108 mmol) of hydroxyethyl methacrylate (HEMA), 0.0268g (0.216 mmol) of 4-methoxyphenol and 2 drops of dibutyltin dilaurate were slowly added dropwise to the reaction system, and after the completion of the dropwise addition, the reaction was carried out at constant temperature for 4 hours to prepare a fluorine-containing acrylic monomer containing a rigid unit. The overall yield of the reaction was about 94.3%.
Embodiment four:
A preparation method of a fluorine-containing acrylate monomer containing a rigid unit comprises the following steps: :
Step 1) synthesis of intermediate A:
accurately weighing 18.81g (108 mmol) of 2, 4-toluene diisocyanate (2, 4-TDI) at 10 ℃ and adding into a three-port beaker with a stirring device, uniformly stirring at 300r/min, slowly dropwise adding 39.32g (108 mmol) of perfluorohexyl ethanol (S104) and 2 drops of dibutyltin dilaurate into the system, and reacting at constant temperature for 6 hours after dropwise addition is completed for about 1 hour;
Step 2) synthesis of fluorine-containing acrylate monomer:
The temperature was raised to 80℃and 14.06g (108 mmol) of hydroxyethyl methacrylate (HEMA), 0.0268g (0.216 mmol) of 4-methoxyphenol and 2 drops of dibutyltin dilaurate were slowly added dropwise to the reaction system, and after the completion of the dropwise addition, the reaction was carried out at constant temperature for 4 hours to prepare a fluorine-containing acrylic monomer containing a rigid unit. The overall yield of the reaction was about 95.2%.
Fifth embodiment:
a preparation method of a fluorine-containing acrylate monomer containing a rigid unit comprises the following steps:
Step 1) synthesis of intermediate A:
Accurately weighing 24.00g (108 mmol) of isophorone diisocyanate (IPDI) at 40 ℃ and adding into a three-mouth beaker with a stirring device, uniformly stirring at 300r/min, slowly dropwise adding 39.32g (108 mmol) of perfluorohexyl ethanol (S104) and 2 drops of dibutyltin dilaurate into the system, and reacting at constant temperature for 3h after dropwise adding is completed, wherein the time of dropwise adding is about 1 h;
Step 2) synthesis of fluorine-containing acrylate monomer:
The temperature was raised to 80℃and 14.06g (108 mmol) of hydroxyethyl methacrylate (HEMA), 0.0268g (0.216 mmol) of 4-methoxyphenol and 2 drops of dibutyltin dilaurate were slowly added dropwise to the reaction system, and after the completion of the dropwise addition, the reaction was carried out at constant temperature for 4 hours to prepare a fluorine-containing acrylic monomer containing a rigid unit. The overall yield of the reaction was about 94.1%.
The reagents in the above examples all need to be dried before use.
The foregoing description is only illustrative of the preferred embodiments of the invention, and is not intended to limit the scope of the invention, since it should be appreciated that modifications and variations could be made by those skilled in the art without departing from the principles of the invention.
Claims (1)
1. A preparation method of a fluorine-containing acrylate monomer containing a rigid unit is characterized by comprising the following steps: the method comprises the following steps:
1) Synthesis of intermediate a:
adding diisocyanate into a three-neck flask with a stirring device at the temperature of 0-40 ℃, uniformly stirring, slowly dropwise adding perfluorohexyl ethanol and a catalyst, wherein the molar ratio of the diisocyanate to the perfluorohexyl ethanol is 1:1, and carrying out heat preservation reaction to obtain an intermediate A;
2) Synthesis of the fluoroacrylate monomer containing rigid units:
Adding the intermediate A obtained in the step 1) into a three-neck flask with the temperature of 80 ℃, and adding the functional monomer and the p-methoxyphenol into the three-neck flask, wherein the molar ratio of the intermediate A to the functional monomer to the p-methoxyphenol in the step 2) is 1:1:0.002, at the same time, dropwise adding a catalyst, and reacting for 3-5 hours at a constant temperature to obtain a fluorine-containing acrylate monomer containing a rigid unit;
the diisocyanate in the step 1) is one of isophorone diisocyanate or 2, 4-toluene diisocyanate;
the reaction time in the step 1) is 3-7 hours;
the functional monomer in the step 2) is one of hydroxyethyl acrylate or hydroxyethyl methacrylate;
the catalyst in the steps 1) and 2) is dibutyl tin dilaurate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61162559A (en) * | 1985-01-09 | 1986-07-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Coating composition for application to metal |
| CN101691342A (en) * | 2009-09-30 | 2010-04-07 | 浙江工业大学 | Fluorine-containing acrylate monomer and preparation method and application thereof |
| CN114687210A (en) * | 2021-12-22 | 2022-07-01 | 浙江科峰新材料有限公司 | Environment-friendly washable waterproof and oil-proof agent and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61162559A (en) * | 1985-01-09 | 1986-07-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Coating composition for application to metal |
| CN101691342A (en) * | 2009-09-30 | 2010-04-07 | 浙江工业大学 | Fluorine-containing acrylate monomer and preparation method and application thereof |
| CN114687210A (en) * | 2021-12-22 | 2022-07-01 | 浙江科峰新材料有限公司 | Environment-friendly washable waterproof and oil-proof agent and preparation method thereof |
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