CN105037149A - Methacrylate fluorine-containing monomer, and synthesis method and application thereof - Google Patents
Methacrylate fluorine-containing monomer, and synthesis method and application thereof Download PDFInfo
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- CN105037149A CN105037149A CN201510323001.4A CN201510323001A CN105037149A CN 105037149 A CN105037149 A CN 105037149A CN 201510323001 A CN201510323001 A CN 201510323001A CN 105037149 A CN105037149 A CN 105037149A
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- Prior art keywords
- methacryloxy
- reaction
- phenylformic acid
- propyl ester
- organic bases
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- 239000000178 monomer Substances 0.000 title claims abstract description 22
- URFLCXSTNZSALZ-UHFFFAOYSA-N [F].C(C(=C)C)(=O)O Chemical compound [F].C(C(=C)C)(=O)O URFLCXSTNZSALZ-UHFFFAOYSA-N 0.000 title abstract 4
- 238000001308 synthesis method Methods 0.000 title abstract 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000675 fabric finishing Substances 0.000 claims abstract description 7
- 238000009962 finishing (textile) Methods 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- -1 methyl acrylic ester Chemical class 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000013638 trimer Substances 0.000 claims description 15
- 150000007530 organic bases Chemical class 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 4
- 239000003513 alkali Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000009988 textile finishing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of a methacrylate fluorine-containing monomer propyl (2-perfluorononenyloxy-3-(methylacryloyloxy))benzoate. The method comprises the following steps: mixing a hexafluoropropylene tripolymer, propyl (2-hydroxy-3-(methylacryloyloxy)) benzoate and a catalyst, heating while stirring, dropwisely adding organic alkali, sufficiently reacting, and carrying out separation and purification after-treatment on the reaction solution to obtain the methacrylate fluorine-containing monomer propyl (2-perfluorononenyloxy-3-(methylacryloyloxy))benzoate. The methacrylate fluorine-containing monomer propyl (2-perfluorononenyloxy-3-(methylacryloyloxy))benzoate can be used in a fabric finishing agent.
Description
Technical field
The invention belongs to organic chemistry filed, particularly relate to a kind of methyl acrylic ester fluorochemical monomer and synthetic method thereof and application.
Background technology
Fabric finishing agent can reduce the surface of fabric thus make fabric have special performance, as hydrophobic and oil repellent, fire-retardant etc.Fluorine-containing textile finishing agent is the outstanding fabric finishing agent of generally acknowledging in the world, and it has excellent performance and unique purposes.With fluorine-containing textile finishing agent process fabric, thin film can be formed on the surface of fabric, thus show and refuse water, oil repellent energy; And be conducive to fabric and keep original color and luster, good feel and ventilation property.Chinese patent CN200580009651.6 discloses fluorine monomer, and the fluorine-containing structural unit in fluorochemical monomer is mainly containing fluoroalkyl, and the fluoropolymer obtained with these fluorochemical monomers, has good water-repellancy, grease proofness and didirtresistance.Chinese patent CN200710067280 discloses a kind of fluorine-containing hydrophobic and oil repellent fabric finishing agent and preparation method thereof, and wherein fluorochemical monomer is as main raw material, and gained fabric finishing agent has good hydrophobic and oil repellent effect.
Oligomerization of hexafluoropropene can generate dimer and trimerical mixture quantitatively.E.I.Du Pont Company has patent report nineteen fifty-nine, and Japanese Neos company have developed the explained hereafter route of liquid hexafluoropropene oligomers afterwards, by effectively controlling reaction conditions, makes oligomerisation reaction mainly generate tripolymer.
Compared with the fluorochemical surfactant of general straight-chain perfluorocarbon, the fluorochemical surfactant that hexafluoropropene oligomers is derivative, the perfluor carbochain of its hydrophobic group has height collateralization, has more how exposed CF outside
3group, pickup thing and film coated surface expose, closely heap CF
3the Chemical bond that the surface of the perfluoroalkyl of base is formed is the most weak, and therefore the perfluoroalkyl antifouling property of branched is better.
Compared with the fluorochemical surfactant of straight-chain perfluorocarbon, the fluorochemical surfactant that hexafluoropropene oligomers derives has following principal feature: (1), under the condition that concentration is extremely low, can reduce the surface tension of the aqueous solution; (2) thermotolerance is extremely strong; (3) there is stable chemical property, in strong acid, highly basic, also can show extremely strong interfacial activity; (4) there is water and oil repellence; (5) in organic solvent also can display interface active, and its surface tension that declines; (6) solubleness is at room temperature higher than the tensio-active agent of straight chain perfluor carbochain, and the temperature range of application is larger.
But, there is not yet that hexafluoropropylene trimer derives and have the synthesis of the fluorochemical monomer of methyl acrylic ester and benzoates structure fragment and the bibliographical information of application thereof.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of hexafluoropropylene trimer derives and the methyl acrylic ester fluorochemical monomer having methyl acrylic ester and benzoates structure fragment, i.e. phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester and synthetic method thereof and application.
Methyl acrylic ester fluorochemical monomer of the present invention and phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester, have following structure:
Phenylformic acid of the present invention (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester, be prepared as follows: hexafluoropropylene trimer, phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester and catalyst mix heated and stirred, drip organic bases, abundant reaction, reaction solution obtains product through separation and purification aftertreatment.
In above-mentioned reaction, described organic bases can be triethylamine, tripropyl amine, diisopropylethylamine, pyridine, N-methylmorpholine etc., preferred triethylamine.
Described catalyzer can be benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride etc., preferred Tetrabutyl amonium bromide.
Described hexafluoropropylene trimer: the mol ratio of the material that feeds intake of phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester is 1:1.0 ~ 1.5, is preferably 1:1.1 ~ 1.2.
Described hexafluoropropylene trimer: the mol ratio of the material that feeds intake of organic bases is 1:0.8 ~ 1.1.
The quality consumption of described catalyzer is 0.005 ~ 0.02 times of hexafluoropropylene trimer quality, is preferably 0.01 ~ 0.015 times.
Described temperature of reaction is 30 ~ 70 DEG C, is preferably 40 ~ 50 DEG C.
The described reaction times is 4 ~ 20 hours, is preferably 8 ~ 12 hours.
Described separation and purification can adopt following steps: be transferred in separating funnel by reaction solution after reaction terminates, add methylene dichloride, static layering after shake well, separatory, after lower floor's dichloromethane layer washes three times, anhydrous sodium sulfate drying, filter, remove solvent under reduced pressure, carry out column chromatography for separation again, with the mixed solution of ethyl acetate/petroleum ether volume ratio 1:50 for eluent, collect the elutriant containing target compound, after steaming desolventizes, obtain product methyl acrylic ester fluorochemical monomer phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester.
Concrete recommendation synthetic method of the present invention is: hexafluoropropylene trimer, phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester and Tetrabutyl amonium bromide Hybrid Heating are stirred, drip triethylamine, at 40 ~ 50 DEG C 8 ~ 12 hours, reaction solution obtained fluorochemical monomer phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester through separation and purification aftertreatment.
Described hexafluoropropylene trimer: the mol ratio of the material that feeds intake of phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester is 1:1.1 ~ 1.2; Described hexafluoropropylene trimer: the mol ratio of the material that feeds intake of organic bases is 1:0.8 ~ 1.1; The quality consumption of described catalyzer is 0.01 ~ 0.015 times of hexafluoropropylene trimer quality.
Described methyl acrylic ester fluorochemical monomer phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester can be used for fabric finishing agent.Use it for emulsion copolymerization legal system for fluorine-containing textile finishing agent emulsion, test result shows, obtained fluorine-containing textile finishing agent has good water and oil repellant performance.
Embodiment
Below by embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
10mmol hexafluoropropylene trimer (4.5g) is added in the reactor having magneton, phenylformic acid (2-hydroxyl-3-(the methacryloxy)) propyl ester of 11mmol and the Tetrabutyl amonium bromide of 0.045g, 40 DEG C are heated under stirring, drip the triethylamine of 11mmol, drip off follow-up continuous insulation reaction, the reaction times amounts to 10 hours.Reaction solution is transferred in separating funnel, add methylene dichloride, static layering after shake well, separatory, after lower floor's dichloromethane layer washes three times, anhydrous sodium sulfate drying, filter, remove solvent under reduced pressure, cross silicagel column, with the mixed solution of ethyl acetate/petroleum ether volume ratio 1:50 for eluent, the separation yield of methyl acrylic ester fluorochemical monomer phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 81%.
1hNMR, MS and IR data are as described below:
1HNMR（CDCl
3）δppm；1.94（s，3H），4.35-4.63（m，5H），5.63（s，1H），6.13（s，1H），7.42-7.46（m，2H），7.56-7.60（m，1H），7.99-8.03（m，2H）
MS（EI）m/z；694（M
+）
IRν
max（KBr）cm
-1；3443，3068，2968，1725，1661，1604，1454，1235，1071，1028，978，946，893，813，711，692。
Embodiment 2
The consumption 10mmol of phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester, catalyzer changes the benzyltriethylammoinium chloride of 0.09g into, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 78%.
Embodiment 3
Organic bases changes the diisopropylethylamine of 11mmol into, temperature of reaction 70 DEG C, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 78%.
Embodiment 4
Temperature of reaction 30 DEG C, in 20 hours reaction times, other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 73%.
Embodiment 5
The consumption 15mmol of phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester, in 4 hours reaction times, other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 80%.
Embodiment 6
The consumption 12mmol of phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester, catalyzer changes the tetrabutylammonium chloride of 0.045g into, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 78%.
Embodiment 7
The consumption 12mmol of phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester, catalyzer changes the tetradecyl trimethyl ammonium chloride of 0.68g into, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 79%.
Embodiment 8
Catalyzer changes the Dodecyl trimethyl ammonium chloride of 0.045g into, 10 hours reaction times, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 78%.
Embodiment 9
Triethylamine consumption changes 8mmol into, 8 hours reaction times, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 70%.
Embodiment 10
Organic bases changes the pyridine of 10mmol into, temperature of reaction 50 DEG C, 12 hours reaction times, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 77%.
Embodiment 11
Organic bases changes the N-methylmorpholine of 12mmol into, and catalyzer changes the tri-n-octyl methyl ammonium chloride of 0.05g into, and other operation is with embodiment 1.The separation yield of phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester is 79%.
The application of embodiment 12 methyl acrylic ester fluorochemical monomer
By 12.0g methyl acrylic ester fluorochemical monomer phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester, 8.2g stearyl acrylate acid esters, 2.0g methacrylic acid, 1.7g glycidyl methacrylate, 2.0g cats product 1231,8.0g nonionogenic tenside Arlacel-80 and tween-80 mixture (mass ratio 1:2), 0.2g n-dodecyl mereaptan, 0.5g SODIUM PHOSPHATE, MONOBASIC, 120g deionized water is placed in the emulsification cup of mulser, at room temperature carry out pre-emulsification 0.5h, form stable white pre-emulsion.
The pre-emulsion of above-mentioned gained is transferred in the four-hole bottle that the device such as stirring, logical nitrogen, condensation, thermometric is housed.Under nitrogen protection, stir, heat up, and at 70 DEG C, add ammonium persulphate 0.30g, after reaction 6min, have obvious blue fluorescence to occur, namely lower the temperature after insulation 1.0h, obtain the white emulsion with blue-fluorescence.This emulsion presses AATCC22-2001 standard and AATCC118-2007 standard test water and oil repellant performance, and measurement result shows that its waterproof effect is 90 points, and grease proofing have 4 grades.
Claims (10)
1. a methyl acrylic ester fluorochemical monomer, i.e. phenylformic acid (2-perfluorinated nonene oxygen base-3-(methacryloxy)) propyl ester, have following structure:
。
2. the synthetic method of methyl acrylic ester fluorochemical monomer as claimed in claim 1, comprise the following steps: hexafluoropropylene trimer, phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester and catalyst mix post-heating are stirred to 30 ~ 70 DEG C, drip organic bases, reaction 4-20 hour, reaction solution obtains product through separation and purification aftertreatment; Described catalyzer is selected from benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, and it is triethylamine, tripropyl amine, diisopropylethylamine, pyridine, N-methylmorpholine that described organic bases is selected from.
3. method as claimed in claim 2, is characterized in that: the preferred triethylamine of organic bases.
4. method as claimed in claim 2, is characterized in that: the preferred Tetrabutyl amonium bromide of catalyzer.
5. method as claimed in claim 2, it is characterized in that: described hexafluoropropylene trimer: the mol ratio of the material that feeds intake of phenylformic acid (2-hydroxyl-3-(methacryloxy)) propyl ester is 1:1.0 ~ 1.5, be preferably 1:1.1 ~ 1.2.
6. method as claimed in claim 2, is characterized in that: described hexafluoropropylene trimer: the mol ratio of the material that feeds intake of organic bases is 1:0.8 ~ 1.1.
7. method as claimed in claim 2, is characterized in that: the quality consumption of described catalyzer is 0.005 ~ 0.02 times of hexafluoropropylene trimer quality, is preferably 0.01 ~ 0.015 times.
8. method as claimed in claim 2, it is characterized in that: temperature of reaction is 40 ~ 50 DEG C, the reaction times is 8 ~ 12 hours.
9. method as claimed in claim 2, it is characterized in that: described separation and purification can adopt following steps: after reaction terminates, reaction solution is transferred in separating funnel, add methylene dichloride, static layering after shake well, separatory, after lower floor's dichloromethane layer washes three times, anhydrous sodium sulfate drying, filter, remove solvent under reduced pressure, then carry out column chromatography for separation, with the mixed solution of ethyl acetate/petroleum ether volume ratio 1:50 for eluent, collect the elutriant containing target compound, steam after desolventizing, obtain product.
10. the application of methyl acrylic ester fluorochemical monomer in fabric finishing agent as claimed in claim 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140338A (en) * | 1991-11-18 | 1993-06-08 | Hitachi Ltd | Circuit board produced by using fluororesin composition |
| CN101691342A (en) * | 2009-09-30 | 2010-04-07 | 浙江工业大学 | Fluorine-containing acrylate monomer and preparation method and application thereof |
| CN104496814A (en) * | 2014-11-26 | 2015-04-08 | 巨化集团技术中心 | Method for preparing high-stability perfluorononenyloxyethyl methacrylate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140338A (en) * | 1991-11-18 | 1993-06-08 | Hitachi Ltd | Circuit board produced by using fluororesin composition |
| CN101691342A (en) * | 2009-09-30 | 2010-04-07 | 浙江工业大学 | Fluorine-containing acrylate monomer and preparation method and application thereof |
| CN104496814A (en) * | 2014-11-26 | 2015-04-08 | 巨化集团技术中心 | Method for preparing high-stability perfluorononenyloxyethyl methacrylate |
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