CN109851531A - A kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester - Google Patents
A kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester, it includes the following steps: S1. using perfluoroalkyl sulfonyl fluoride and methylamine as raw material, inorganic salt solution is solvent, it is reacted at a temperature of being maintained at lower than 4 DEG C, obtains N- methyl perfluoro alkyl sulfonamide；S2. under basic catalyst effect, N- methyl perfluoro alkyl sulfonamide made from S1 is reacted with ethylene carbonate, obtains N- ethoxy-N- methyl perfluoro alkyl sulfonamide；S3. in the presence of hydroquinone, ester exchange reaction occurs for N- ethoxy-N- methyl perfluoro alkyl sulfonamide made from S2 and methyl acrylate, obtains acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester.Advantage are as follows: using saline solution as the solvent for preparing N- methyl perfluoro alkyl sulfonamide, overcome the technology prejudice for thinking that nonaqueous solvents can only be used in the prior art, COD content substantially reduces in final waste water, environmental-friendly；Yield and purity is high.
Description
Technical field
The present invention relates to the preparation fields of the fabric three proofings main raw material(s) alkyl chain length ester of perfluor containing unsaturated group, specifically
It is related to a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester.
Background technique
It is also higher and higher using the requirement of object to clothing etc., it is desirable that clothes with the continuous improvement of the standard of living of the people
It is light, it breathes freely, waterproof is grease proofing, and dust-proof, this just needs to coat a thin layer of coating on the surface of fabric, and imparting fabric is light,
Ventilative, grease proofing, waterproof, the characteristics such as dust-proof, the clothes made of this fabric, the daily necessities such as umbrella just have ventilative, prevent
Oil, waterproof is dust-proof, the characteristic of fabric three proofings, and doing the most important raw material of this fabric coating is exactly fluorine ester, not all
Fluorine ester can be used, the most commonly used is acrylic acid (N- methyl perfluoro octyl or hexyl or butyl sulfonamide base) ethyl ester, and acrylic acid (N-
N-dimethylpropyl) ethyl ester because in degradation or production generate PFOS due to it is disabled, be allowed for fabric in the world now
The fluorinated ester of three proofings is acrylic acid (N- methyl-perfluoro hexyl or butyl sulfonamide base) ethyl ester, is not allowed with acrylic acid (N- first
Base-perfluorinated octyl sulfuryl amine base) ethyl ester.
Acrylic acid (N- methyl perfluoro alkylsulfonamido) ester be primarily referred to as acrylic acid (N- methyl perfluoro octyl or hexyl or
Butyl sulfonamide base) ethyl ester.It has the copolymerizable of excellent homopolymerization and other monomers, is that a kind of surface property is unique fluorine-containing
Polymerisable monomer is widely used in leather, fabric hates oily hydrophober, antifouling paint, levelling agent, dispersing agent, antiblocking agent, doctor
With material and with the material of photoelectric properties.The spy that acrylic ester high molecular type has good film-forming property, network structure more loose
Point, treated, and product is ventilative good with penetrability, and soft, and high resilience has good feel, keeps processed material original
Style.
The synthetic method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ester divides three steps in the prior art: 1, by triethylamine
It is added in reaction kettle with organic solvent (nonaqueous solvents) and is passed through methylamine gas at 5 DEG C or less, then per-fluoroalkyl sulfonyl is slowly added dropwise
Per-fluoroalkyl sulfonyl methylamine is made in fluorine, then washes the triethylamine salt for removing hydrofluoric acid, and dry；2 and ethylene carbonate in alkali
Property under the conditions of, reaction generate N- methyl perfluoro alkyl amine group ethyl alcohol；3 and acrylic acid occur in the presence of hydroquinone of polymerization retarder
Esterification generates acrylic acid (N- methyl perfluoro sulfoamido) ethyl ester, in order to obtain high yield and the acrylic acid (N- without polymerization
Methyl perfluoro sulfoamido) ethyl ester, acrylic acid is large excess of in step 3, and joined hydroquinone of polymerization retarder.The system
The shortcomings that Preparation Method is to have used organic solvent in step 1, and waste water COD is high when water-washing desalting, and the acrylic acid in step 3 is excessive
, acrylic acid and hydroquinone are not easily recycled in waste water when washing, and waste water COD content is high, not environmentally, in national environmental protection high pressure political affairs
Under plan, it is necessary to find new feature of environmental protection synthetic method, which just has living space.
Summary of the invention
The present invention provides a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester, it is intended to effective gram
It takes and is needed existing for existing preparation method using solvent, waste water COD is high, the deficiency of feature of environmental protection difference.
The technical scheme to solve the above technical problems is that a kind of acrylic acid (N- methyl perfluoro alkyl sulfonamide
Base) ethyl ester preparation method comprising following steps:
S1. using perfluoroalkyl sulfonyl fluoride and methylamine as raw material, inorganic salt solution is solvent, is maintained at the temperature lower than 4 DEG C
The lower reaction of degree, obtains N- methyl perfluoro alkyl sulfonamide；
S2. under basic catalyst effect, N- methyl perfluoro alkyl sulfonamide made from S1 is reacted with ethylene carbonate, is obtained
N- ethoxy-N- methyl perfluoro alkyl sulfonamide；
S3. in the presence of hydroquinone, N- ethoxy-N- methyl perfluoro alkyl sulfonamide and methyl acrylate made from S2
Ester exchange reaction occurs, obtains acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester.
Based on the above technical solution, the present invention can also have following further specific choice.
Further, the specific steps of S1 are as follows: in -8 DEG C of low temperature environments below, the aqueous solution of methylamine is added to reaction kettle
And inorganic salt solution, after mixing evenly, -8 to -4 DEG C at a temperature of, start slowly to drip to reaction solution bottom by bottom insert canal
Add perfluoroalkyl sulfonyl fluoride, kept during being added dropwise the temperature of reaction solution 0 DEG C hereinafter, being added dropwise after, maintain the temperature at 0 DEG C
Sufficiently reaction below, product floats on liquid level, is centrifuged, washing, vacuum drying to get.
Preferably, the concentration of methylamine water solution is 40wt%, and the concentration of inorganic salt solution is 5-22wt%.
Specifically, the perfluoroalkyl sulfonyl fluoride in S1 is any in perfluoro butyl sulfonic acid fluoride and perfluoro hexyl sulfuryl fluoride
Kind.
Further, the specific steps of S2 are as follows: the N- methyl perfluoro alkyl sulfonamide for obtaining basic catalyst, heptane and S1
It is added in reaction vessel, heat preservation flows back at 105 DEG C, is removed water with water segregator, when water is not further added by water segregator, is warming up to 110
DEG C reflux, when water segregator is steamed without heptane again, be cooled to 98 DEG C and ethylene carbonate be slowly added dropwise, after being added dropwise, heat preservation
Sufficiently reaction to get.
Further, the specific steps of S3 are as follows: S2 sufficiently after the reaction was completed, into reaction vessel be added hydroquinone, third
E pioic acid methyl ester and sodium methoxide under inert gas shielding, are warming up to 74 to 76 DEG C, stir and insulation reaction, with dividing water during reaction
Device receives the methanol that reaction generates, and stops reaction when sufficiently reaction methanol quality into water segregator is not further added by, is adjusted with acetic acid
Reaction solution to neutrality, decompression steams extra methyl acrylate to get acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester.
Preferably, the molar ratio of perfluoroalkyl sulfonyl fluoride and methylamine is 1:2-2.5 in S1.
Specifically, the amount ratio of perfluoroalkyl sulfonyl fluoride and inorganic salt solution is 1mol:350-450g in S1；Inorganic salts
The solute of aqueous solution is sodium chloride, potassium chloride, sodium sulphate and any one or more of mixing of potassium sulfate.
It is optimal, it is reacted at a temperature of being maintained in S1 lower than 0 DEG C.
Preferably, S2 neutral and alkali catalyst is sodium carbonate or potassium carbonate, N- methyl perfluoro alkyl sulfonamide and carbonic acid in S2
The molar ratio of vinyl acetate is 1:1.05；N- ethoxy-N- methyl perfluoro alkyl sulfonamide and methyl acrylate 1:1.15- in S3
1.25。
Compared with prior art, the beneficial effects of the present invention are:
(1) N- methyl perfluoro alkyl sulfonamide is prepared using saline solution as reacting with per-fluoroalkyl sulfonyl chlorine with methylamine
Solvent overcomes and thinks the technology prejudice that can only use nonaqueous solvents (because of perfluor alkane in the presence of water in the prior art
Base sulfuryl fluoride facile hydrolysis cannot get N- methyl perfluoro alkyl sulfonamide at perfluoro alkyl sulfonic acid), it has been found that it is higher than in temperature
It is implicitly present in larger amount of perfluoroalkyl sulfonyl fluoride hydrolysis at 4 DEG C, has a small amount of perfluoro butyl sulfonic acid fluoride to hydrolyze between 0-4 DEG C of degree
And perfluoro hexyl sulfuryl fluoride does not hydrolyze, but does not hydrolyze nearly all after temperature is lower than 0 DEG C, and only generate perfluorinated alkyl sulfonamide production
Product, therefore the present invention can be used and be reacted at low temperature with water as solvent, COD content substantially reduces in final waste water, environment
It is more friendly.
(2) if only with water as solvent under low temperature, perfluorinated alkyl sulfonamide in methylamine water solution easily with perfluoroalkyl sulphur
The reaction of acyl fluorides further occurrence generates N- methyl-and enjoys a double blessing fluoroalkyl sulfonamides, and what is finally obtained is N- methyl perfluoro alkyl sulfonyl
Amine and N- methyl-are enjoyed a double blessing the mixtures of fluoroalkyl sulfonamides, and N- methyl-enjoy a double blessing fluoroalkyl sulfonamides can not be with ethylene carbonate
Reaction generates the sulfonamide of hydroxyl, so that esterification, which cannot occur, generates acrylic acid (N- methyl perfluoro alkylsulfonamido)
The purity of ethyl ester, such final products is not high, therefore the present invention makes the N- methyl perfluoro alkyl sulphur generated using saline solution as solvent
Amide floats on reaction liquid level, to reduce the chance with perfluoroalkyl sulfonyl fluoride secondary response again, reduces the generation of by-product, instead
Should completely after only need to centrifugal drying material go out solid (N- perfluorinated alkyl sulfonamide, not soluble in water) be washed with deionized water it is secondary just
, and wash in rear water phase and contain only water and sodium chloride, water is deviate from redistillation, is centrifuged out sodium chloride, can cover in for reacting, no
Pollute environment.
(3) perfluoroalkyl sulfonyl fluoride and generation can also be reduced using bottom dropwise addition is inserted when perfluoroalkyl sulfonyl fluoride is added dropwise
N- methyl perfluoro alkyl sulfonamide further reacts.
(4) fluorine ester is synthesized using ester exchange reaction, lower reaction is protected using argon gas, distillate is monitored with gas-chromatography, arrives
When methanol quality (distillate quality in gas-chromatography content and phase-splitter) is not further added by stop reaction, change decompressor steam it is more
Remaining methyl acrylate is not required to washing to get a small amount of hydroquinone of addition can prevent the acrylic acid generated as polymerization inhibitor
The autohemagglutination that (N- methyl perfluoro alkylsulfonamido) ethyl ester may then occur, yield is higher and product purity is higher, while can
Effectively extend the shelf-life of product；After the reaction was completed, it does not need to isolate hydroquinone, is adjusted with acid pH, then keep the temperature in 50-
Filter desalination between 55 degree, the salt filtered out be collected into it is a certain amount of after be washed with water and refilter acrylic acid (the N- first that is mingled in recycling salt
Base perfluorinated alkyl sulfonamide base) ethyl ester, water phase, which directly covers, to be used in the production of N- methyl perfluoro alkyl sulfonamide, and no three wastes produces
It is raw.
Specific embodiment
Principles and features of the present invention are described below in conjunction with specific embodiment, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
To exempt to repeat, the method used in following embodiment or operation are then unless otherwise noted ordinary skill people
Conventional method or operation known to member, the drug used then are commercial product unless otherwise noted.
Embodiment 1
A kind of preparation method of acrylic acid (N- methyl perfluoro butyl sulfonamide base) ethyl ester, includes the following steps:
S1. a 1000mL four-hole boiling flask reaction kettle with electric stirring and thermometer is immersed in brine temp is -8 DEG C
In water-bath, it is accurately weighed into the methylamine water solution (1.4mol) that 108.5 grams of concentration are 40%, adds 340 grams of water, after mixing evenly
40.5 grams of sodium chloride are added, continues stirring and is all dissolved to sodium chloride, start to be added dropwise 211.4 grams when kettle temperature drops to -8 to -4 DEG C
(0.7mol) perfluorinated butane base sulfuryl fluoride, slotting bottom, which is slowly added dropwise, keeps kettle temperature at 0 DEG C hereinafter, after adding perfluorinated butane base sulfuryl fluoride
Insulation reaction 4 hours, after the reaction was completed, with hydrochloric acid conditioning solution pH 6 or so, generates product and float on liquid level, then centrifugal drying material
Perfluoro butyl sulphonyl methylamine is obtained, 200 grams of water are added in 242.2 grams of wet solids, are warming up to 50 DEG C, stir 4 hours, cool to room temperature
Get rid of material again, wash in this way it is secondary after be centrifuged to obtain 223.5 grams of wet feeds, be dried in vacuo at 50 DEG C 214.7 grams (about 0.686mol) at
Product, yield 98.0%.
S2. one is soaked in oil bath with the 500mL four-hole boiling flask reaction kettle of electric stirring and thermometer, institute in S1 is added
214.7 grams of solid N- methyl perfluoro butyl sulfonamide is obtained, 2.8 grams of natrium carbonicum calcinatum, 150 grams of heptane, heat preservation flows back at 105 DEG C,
It is removed water with water segregator, when water is not further added by water segregator, takes off heptane, be raised to 110 DEG C in kettle temperature, steamed again without heptane in water segregator
It when out, cools to 98 degree and is slowly added dropwise 63.8 grams of ethylene carbonate (0.72mol) and drip off rear insulation reaction 11 hours, obtain N- hydroxyl second
Base-N- methyl perfluoro butyl sulfonamide.
S3. 0.76 gram of hydroquinone is added in the reaction kettle of S2, adds 70 grams of methyl acrylates, and 1 gram of first is added
Sodium alkoxide solid, three times with argon gas displacement, the then insulated and stirred between 74-76 DEG C, and the methanol generated with water segregator reception reaction,
Insulation reaction 10 hours, 27.1 grams of liquid are received in water segregator, account for 81.2% gram with gas chromatographic analysis methanol, acrylic acid first
Ester accounts for 18.8%, adjusts PH to 7 or so with acetic acid, decompression steams extra methyl acrylate, obtains 280.2 grams of acrylic acid (N- first
Base perfluorinated butane base sulfoamido) ethyl ester, yield 99.4%
Embodiment 2
A kind of preparation method of acrylic acid (N- methyl perfluoro butyl sulfonamide base) ethyl ester, includes the following steps:
S1. a 3000mL four-hole boiling flask reaction kettle with electric stirring and thermometer is immersed in brine temp is -8 DEG C
In water-bath, it is accurately weighed into the methylamine water solution (4.2mol) that 325.5 grams of concentration are 40%, 1120 grams of water is added, stirs evenly
131.5 grams of sodium chloride are added afterwards, continues stirring and is all dissolved to sodium chloride, start to be added dropwise when kettle temperature drops to -8 to -4 DEG C
634.2 grams of (2.1mol) perfluoro butyl sulfonic acid fluorides, slotting bottom, which is slowly added dropwise, keeps kettle temperature at 0 DEG C hereinafter, adding perfluoro butyl sulphonyl
Insulation reaction 4 hours after fluorine with hydrochloric acid conditioning solution pH 6 or so, generate product and float on liquid level, then be centrifuged after the reaction was completed
It gets rid of and expects to obtain perfluoro butyl sulphonyl methylamine, 600 grams of water are added in 726.6 grams of wet solids, are warming up to 50 DEG C, stir 4 hours, cool to
Room temperature gets rid of material again, washes in total be centrifuged to obtain 666.5 grams of wet feeds twice in this way, be dried in vacuo at 50 DEG C 655.2 grams (about
2.093mol) finished product, yield 99.68%.
S2. one is soaked in oil bath with the 2000mL four-hole boiling flask reaction kettle of electric stirring and thermometer, is added in S1
8.8 grams of natrium carbonicum calcinatum, 300 grams of heptane are added in 655.2 grams of butyl sulfonamide of obtained solid N- methyl perfluoro (2.093mL), rise
Temperature is to 105 DEG C, heat preservation reflux, when being dewatered to that water is not further added by phase-splitter with water segregator, take off heptane to 110 DEG C of kettle temperature again without
After heptane abjection, cools to 98 degree and is slowly added dropwise 196.8 grams of ethylene carbonate (2.236mol) and drip off rear insulation reaction 11 hours,
Obtain N- ethoxy-N- methyl perfluoro butyl sulfonamide.
S3 adds 2.3 grams of hydroquinones in the reaction kettle of S2, adds 215.0 grams of methyl acrylates, is added 3.0 grams
Sodium methoxide solid, after argon gas conversion three times, the insulated and stirred between 74-76 DEG C, and the methanol that reaction generates is received with water segregator,
Insulation reaction 10 hours, 81.5 grams of liquid are received in water segregator, account for 81.2% gram with gas chromatographic analysis methanol, acrylic acid first
Ester accounts for 18.8%, and decompression steams extra methyl acrylate, and with salt acid for adjusting pH to 7 or so, heat preservation is filtered between 50-55 DEG C
Desalination obtains 858.7 grams of acrylic acid (N- methyl perfluoro butane group sulfoamido) ethyl ester, yield 99.8%.
Embodiment 3
A kind of preparation method of acrylic acid (N- methyl perfluoro hexyl sulfoamido) ethyl ester, includes the following steps:
S1. a 1000ml four-hole boiling flask reaction kettle with electric stirring and thermometer is immersed in brine temp is -8 DEG C
In water-bath, it is accurately weighed into the methylamine water solution (1.4mol) that 108.5 grams of concentration are 40%, adds 340 grams of water, after mixing evenly
34 grams of sodium chloride are added, continues stirring and is all dissolved to sodium chloride, start to be added dropwise 281.4 grams when kettle temperature drops to-8-- 4 DEG C
(0.7mol) perfluoro hexyl sulfuryl fluoride, is slowly added dropwise using slotting bottom, keeps kettle temperature at 4 DEG C hereinafter, adding perfluor hexyl sulphonyl
Insulation reaction 4 hours after fluorine generate product and float on liquid level with hydrochloric acid conditioning solution pH 6 or so, then centrifugal drying material obtain perfluor oneself
200 grams of water are added in base sulphonyl methylamine, 343.2 grams of wet solids, are warming up to 50 DEG C, stir 4 hours, cool to room temperature and get rid of again and expect
306.6 grams of wet feeds add 200 grams of water, are warming up to 50 DEG C, stir 4 hours, cool to room temperature and get rid of again and expect to obtain 303.6 grams of wet feeds,
For chlorine ion concentration in 100PPM hereinafter, being dried in vacuo to obtain 284.7 grams of (about 0.69mol) finished products at 50 DEG C, yield is 98.5% molten
Point is 68-72 DEG C.
S2. one is soaked in oil bath with the 500ml four-hole boiling flask reaction kettle of electric stirring and thermometer, institute in S1 is added
Must be 284.7 grams of sulfonamide of solid N- methyl perfluoro hexyl, 2.8 grams of natrium carbonicum calcinatum, 150 grams of heptane, using water segregator at 105 DEG C
It flows back discrete, when the water wait separate is not further added by, pours out the liquid in water segregator, and steam heptane, in 110 DEG C of water segregators
Liquid cools to 98-100 DEG C of 63.8 grams of dropwise addition ethylene carbonate (0.72mol) and drips off rear insulation reaction 11 not until increase
Hour, obtain N- ethoxy-N- methyl perfluoro hexyl sulfonamide.
S3. 0.76 gram of hydroquinone is added in the reaction kettle of S2, adds 70 grams of methyl acrylates, and 1 gram of first is added
Sodium alkoxide solid, three times with argon gas displacement, the insulated and stirred between 74-76 DEG C, and the methanol that reaction generates, heat preservation are received with water segregator
Reaction 10 hours, 27.1 grams of liquid are received in water segregator, account for 81.2% gram with gas chromatographic analysis methanol, methyl acrylate accounts for
18.8%, decompression steams extra methyl acrylate, adjusts PH to 7 or so with salt acetic acid, heat preservation is obtained in 50-55 DEG C of filtering desalination
347.4 grams of ethyl ester of acrylic acid (N- methyl perfluoro hexyl sulfoamido), yield 98.6%.
Embodiment 4
A kind of preparation method of acrylic acid (N- methyl perfluoro hexyl sulfoamido) ethyl ester, includes the following steps:
S1. a 3000ml four-hole boiling flask reaction kettle with electric stirring and thermometer is immersed in brine temp is -8 DEG C
In water-bath, it is accurately weighed into the methylamine water solution (4.2mol) that 325.5 grams of concentration are 40%, 1120 grams of water is added, stirs evenly
112 grams of sodium chloride are added afterwards, continues stirring and is all dissolved to sodium chloride, start dropwise addition 844.2 when kettle temperature drops to -8 to -4 DEG C
Gram (2.1mol) perfluoro hexyl sulfuryl fluoride is slowly added dropwise using slotting bottom and keeps kettle temperature at 4 DEG C hereinafter, adding perfluoro hexyl sulfuryl fluoride
Insulation reaction 4 hours afterwards generate product and float on liquid level, then centrifugal drying material obtains perfluoro hexyl sulphonyl with dilute hydrochloric acid tune pH 6 or so
600 grams of water are added in methylamine, 1029.6 grams of wet solids, are warming up to 50 DEG C, stir 4 hours, cool to room temperature get rid of again expect 919.8
Gram wet feed, adds 600 grams of water, is warming up to 50 DEG C, stirs 4 hours, cools to room temperature and get rid of again and expect to obtain 910.8 grams of wet feeds, chlorine from
Sub- concentration is in 100PPM hereinafter, being dried in vacuo to obtain 864.5 grams of (about 2.093mol) finished products, yield 99.65%, fusing point at 50 DEG C
It is 68-72 DEG C.
S2. one is soaked in oil bath with the 2000ml four-hole boiling flask reaction kettle of electric stirring and thermometer, is added in S1
864.5 grams of sulfonamide of N- methyl perfluoro hexyl of obtained solid (2.093ml) 8.8 grams of natrium carbonicum calcinatum, is added 300 grams of heptane, rises
Temperature with water segregator reflux water-dividing, until the quality of water is not further added by into water segregator, recycles heptane, is raised in kettle temperature to 105 DEG C
When being steamed again without heptane in 110 DEG C of water segregators, cools to 98 DEG C and be slowly added dropwise 196.8 grams of ethylene carbonate (2.236mol) and drip off
Insulation reaction 11 hours afterwards obtain N- ethoxy-N- methyl perfluoro hexyl sulfonamide.
S3. 2.3 grams of hydroquinones are added in the reaction kettle of S2, add 215.0 grams of methyl acrylates, are added 3.0
Gram sodium methoxide solid, three times with argon gas displacement, the insulated and stirred between 74-76 DEG C, and the methanol that reaction generates is received with water segregator,
Insulation reaction 10 hours, 81.5 grams of liquid are received in water segregator, account for 81.2% gram with gas chromatographic analysis methanol, acrylic acid first
Ester accounts for 18.8%, and decompression steams extra methyl acrylate, adjusts PH to 7 or so with hydrochloric acid, desalination is filtered between 50-55 DEG C
It obtains 1064.3 grams of ethyl ester of acrylic acid (N- methyl perfluoro hexyl sulfoamido), yield 99.5%, loss salt in finally filter salt
Entrainment is washed again after collecting filter salt, is centrifuged acrylic acid (N- methyl perfluoro hexyl sulfoamido) ethyl ester, water phase set is for the
In the production of one step, achieve the purpose that environmental protection.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester, which is characterized in that including walking as follows
It is rapid:
S1. using perfluoroalkyl sulfonyl fluoride and methylamine as raw material, inorganic salt solution is solvent, at a temperature of being maintained at lower than 4 DEG C
Reaction, obtains N- methyl perfluoro alkyl sulfonamide；
S2. under basic catalyst effect, N- methyl perfluoro alkyl sulfonamide made from S1 is reacted with ethylene carbonate, obtains N- hydroxyl
Ethyl-N-methyl perfluorinated alkyl sulfonamide；
S3. in the presence of hydroquinone, N- ethoxy-N- methyl perfluoro alkyl sulfonamide made from S2 and methyl acrylate occur
Ester exchange reaction obtains acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester.
2. a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to claim 1,
It is characterized in that, the specific steps of S1 are as follows: in -8 DEG C of low temperature environments below, methylamine water solution and inorganic salts is added to reaction kettle
Aqueous solution, after mixing evenly, -8 to -4 DEG C at a temperature of, start that perfluor alkane is slowly added dropwise to reaction solution bottom by bottom insert canal
Base sulfuryl fluoride, kept during being added dropwise the temperature of reaction solution 0 DEG C hereinafter, being added dropwise after, maintain the temperature at 0 DEG C or less it is abundant
Reaction, product floats on liquid level, is centrifuged, washing, vacuum drying to get.
3. a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to claim 2,
It is characterized in that, the concentration of methylamine water solution is 40wt%, and the concentration of inorganic salt solution is 5-22wt%.
4. a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to claim 1,
It is characterized in that, the perfluoroalkyl sulfonyl fluoride in S1 is any one of perfluoro butyl sulfonic acid fluoride and perfluoro hexyl sulfuryl fluoride.
5. a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to claim 1,
It is characterized in that, the specific steps of S2 are as follows: the N- methyl perfluoro alkyl sulfonamide for obtaining basic catalyst, heptane and S1 is added anti-
It answers in container, heat preservation flows back at 105 DEG C, and it is removed water with water segregator, when water is not further added by water segregator, is warming up to 110 DEG C of reflux,
It when water segregator is steamed without heptane again, is cooled to 98 DEG C and ethylene carbonate is slowly added dropwise, after being added dropwise, heat preservation is sufficiently anti-
It should be to get.
6. a kind of preparation method of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to claim 5,
Be characterized in that, the specific steps of S3 are as follows: S2 sufficiently after the reaction was completed, into reaction vessel be added hydroquinone, acrylic acid first
Ester and sodium methoxide under inert gas shielding, are warming up to 74 to 76 DEG C, stir simultaneously insulation reaction, are received during reaction with water segregator
The methanol generated is reacted, stops reaction when sufficiently reaction methanol quality into water segregator is not further added by, adjusts reaction solution with acetic acid
To neutrality, decompression steams extra methyl acrylate to get acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester.
7. a kind of system of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to any one of claims 1 to 6
Preparation Method, which is characterized in that the molar ratio of perfluoroalkyl sulfonyl fluoride and methylamine is 1:2.0-2.5 in S1.
8. a kind of system of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to any one of claims 1 to 6
Preparation Method, which is characterized in that the amount ratio of perfluoroalkyl sulfonyl fluoride and inorganic salt solution is 1mol:350-450g in S1；Nothing
The solute of machine saline solution is sodium chloride, potassium chloride, sodium sulphate and any one or more of mixing of potassium sulfate.
9. a kind of system of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to any one of claims 1 to 6
Preparation Method, which is characterized in that reacted at a temperature of being maintained in S1 lower than 0 DEG C.
10. a kind of system of acrylic acid (N- methyl perfluoro alkylsulfonamido) ethyl ester according to any one of claims 1 to 6
Preparation Method, which is characterized in that S2 neutral and alkali catalyst is sodium carbonate or potassium carbonate, N- methyl perfluoro alkyl sulfonamide and carbon in S2
The molar ratio of vinyl acetate is 1:1.05；N- ethoxy-N- methyl perfluoro alkyl sulfonamide and methyl acrylate 1:1.15- in S3
1.25。
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| CN (1) | CN109851531B (en) |
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| CN115181040A (en) * | 2022-07-25 | 2022-10-14 | 武汉松石科技股份有限公司 | Refining and purifying method of (N-methyl perfluoroalkyl sulfonamide) ethyl acrylate |
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| CN109851531B (en) | 2021-06-08 |
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