CN106905197A - A kind of fluorine-containing propene acid amides and its synthetic method - Google Patents
A kind of fluorine-containing propene acid amides and its synthetic method Download PDFInfo
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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Abstract
The invention discloses a kind of fluorine-containing propene acid amides and its synthetic method, the wherein general structure of fluorine-containing propene acid amides is that shown in Formulas I, Rf is C in Formulas I3‑C20Perfluor chain radicals；R ' is the CO or SO of divalence2Group；R1It is C2‑C6Divalent alkyl group；R2It is H or C1‑C3Monovalent alkyl radical；N is the integer more than or equal to 1.Its synthesis step is as follows：1）Polyhydric amine compounds obtain the double fluorine chain acid amides containing secondary amine with the derivatives reaction of perfluorocarbon substituent group formic acid；2）N2Under protection, acryloyl halide is slowly added dropwise into the double fluorine chain acid amides containing secondary amine, reacted 1 ~ 5 hour, obtain fluorine-containing propene amide compound.Fluorine-containing propene acid amides involved in the present invention is the acrylamide containing fluorocarbon chain of enjoying a double blessing, and can be that single acrylamide structure can also be bisacrylamide or many acrylamide structures, therefore the invention provides a kind of synthetic method of the adjustable fluorine-containing propene acid amides of degree of functionality, its is comparatively safe environmentally friendly, simple, is conducive to industrialized implementation.
Description
Technical field
The invention belongs to the field of acrylamide monomer synthesis, more particularly to a kind of fluorine-containing propene acid amides and its synthesis side
Method.
Background technology
Acrylamide and its derivative are the important chemical products of a class, be widely used in synthetic environment improvement, water process,
The chemicals in the fields such as the oil field displacement of reservoir oil, coating material production.And fluorine-containing propene acid amides is made due to the low-surface-energy characteristic with fluorine material
It shows more remarkable performance in the application.Donghua University Meng Weidong discloses a kind of synthesis of fluorine-containing alkyl acrylamide
Method, its specific steps：By non-fluorine alcohol under condition of ice bath with PCl3Reaction, is subsequently added fluorine-containing alcohol reaction, obtains double fluothane
Epoxide phosphonic acids；Again through chlorination reagent chlorination, double Fluoroalkyloxy phosphonic chlorides are obtained；Finally contained with hydroxyethyl acrylamide reaction
The acrylamide of fluoroalkyl, using the fluorine-containing alkyl acryl amine monomers synthetic copolymer emulsion, is applied to textile finishing, performance
Go out excellent waterproof and oilproof antifouling property.
The content of the invention
It is an object of the invention to provide a kind of acrylamide containing double fluorine chains, and provide this propylene containing double fluorine chains
The synthetic method of acid amides.
The technical scheme is that designing a kind of fluorine-containing propene acid amides, it is characterised in that the general structure of compound is
（I）：
Wherein Rf, R ', R1、R2, n etc. is described below respectively：
1）Rf is C3-20Perfluor carbon-based group, preferably perfluoroalkyl, such as：
-CF2CF(CF3)2、
-CF(CF3)CF2CF3、
-CF2CF2CF2CF3、
-CF2CF2CFCF3CF2CF3、
-CF2CF2CF2CF2CF2CF3、
-CF2CF(CF3)CF2CF2CF3、
-CF2CF(CF3)CF2CF2CF2CF3、
-CF2CF2CF2CF2CF2(CF3)2、
-CF2CF2CF2CF2CF2CF2CF2CF3、
-CF2CF2CF2CF(CF3)CF2CF2CF3、
-CF2CF(CF3)CF2CF2CF2CF2CF3、
-CF2CF2CF(CF3)CF2CF2CF2CF2CF3、
-CF2CF(CF3)CF2CF(CF3)CFCF2CF3、
-CF2CF2CF2CF2CF2CF2CF2CF2CF2CF2CF2CF3Group etc.；It can also be the perfluor that oxygen atom is inserted in main chain
Polyether group, such as：
-CF2CF2OCF(CF3)2、
-CF(CF3)OCF(CF3)2、
-CF(CF3)OCF2CF2CF3、
-CF2OCF2CF2OCF2CF3、
-CF(CF3)OCF2CF(CF3)OCF2CF2CF3、
-CF2CF2OCF2CF(CF3)OCF2CF2CF3、
-CF2CF2CF2OCF2CF2CF2OCF2CF2CF3、
-CF2CF(CF3)OCF2CF2OCF2CF2CF3、
-CF2OCF(CF3)OCF2CF2OCF(CF3)2、
-CF2CF2OCF(CF3)OCF2CF2OCF2CF2CF3、
-CF2CF(CF3)OCF2CF(CF3)OCF(CF3)2、
-CF(CF3)OCF2CF(CF3)OCF(CF3)2、
-CF2CF(CF3)OCF2CF(CF3)OCFCF2CF3、
-CF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)2、
-CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)2Group etc.；
2）R ' is the CO or SO of divalence2Group；
3）R1It is C2-C6Divalent alkyl group, such as-CH2CH2-、-CH2CH2CH2-、-CH2CH(CH3)-、-CH2CH2CH2CH2-、-
CH2CH(CH3)CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2- etc.；
4）R2It is-H or C1-C3Monovalent alkyl radical, such as-H ,-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)CH3Deng；
5）N is the integer more than or equal to 1.
Heretofore described fluorine-containing propene acid amides, its synthetic method is comprised the following steps：
1）Add 1 molar part polyamine, stirring solvent uniform in a kettle..At -30 ~ 50 DEG C, stir and in reactor
It is slowly added dropwise the derivative of 2 molar part perfluorocarbon substituent group formic acid（Or the derivative of perfluorocarbon substituent group sulfonic acid）, it is added dropwise
Completely, continue to react 3 ~ 12h, the double fluorine chain acid amides containing secondary amine are obtained after solvent, vacuum drying is distilled off；
2）Under nitrogen protection, toward step 1）Solvent and acid binding agent are added in the double fluorine chain acid amides containing secondary amine for obtaining, -30
The acryloyl halide of 1.05n molar parts is slowly added dropwise under ~ 50 DEG C of reaction temperatures（Or 2- alkyl carboxylic acid halides）, 1 ~ 5 is reacted after adding
Hour, then obtain fluorine-containing propene amide compound after filtering, washing, dry, concentration.
Step 1）Described in polyamine, its general structure is（）It is shown：
Wherein R1, n etc. above carried out elaboration, therefore described polyamine is：
H2NCH2CH2CH2CH2NHCH2CH2CH2CH2NHCH2CH2CH2CH2NH2
H2NCH2CH2CH2CH2NHCH2CH2CH2CH2NH2
H2NCH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NH2
H2NCH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NH2
H2NCH2CH2CH2NHCH2CH2CH2NH2
H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2
H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2
H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2
H2NCH2CH2NHCH2CH2NHCH2CH2NH2
H2NCH2CH2NHCH2CH2NH2
Step 1）Described in solvent be dichloromethane, chloroform, methyl alcohol, ethanol, isopropanol, tetrahydrofuran, dimethyl ether, second
Ether, ethyl methyl ether, 1,4- dioxane, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, third
2-ethoxyethanol, propylene glycol monobutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, propane diols diethyl ether,
Propane diols butyl oxide, methyl formate, Ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate
Ester, isoamyl acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetate etc. it is therein one or more；
Step 1）Described in perfluorocarbon substituent group formic acid derivative（Or the derivative of perfluorocarbon substituent group sulfonic acid）For complete
Perfluoroalkyl polyether formyl fluoride, PFPE formyl chloride, PFPE formyl bromine and PFPE methyl formate, PFPE formic acid second
Ester, PFPE isopropyl formate, PFPE sulfuryl fluoride, PFPE sulfonic acid chloride, PFPE sulfonic acid bromide and PFPE
Methylmesylate, PFPE sulfonic acid, PFPE sulfonic acid isopropyl ester, perfluoro butyl formyl chloride, perfluoro butyl methyl formate,
Perfluoro butyl Ethyl formate, perfluoro butyl isopropyl formate, perfluoro butyl sulfonic acid chloride, perfluoro butyl methylmesylate, perfluoro butyl
Sulfonic acid, perfluoro butyl sulfonic acid isopropyl ester, perfluoro hexyl formyl chloride, perfluoro hexyl methyl formate, perfluoro hexyl Ethyl formate,
Perfluoro hexyl isopropyl formate, perfluoro hexyl sulfonic acid chloride, perfluoro hexyl methylmesylate, perfluoro hexyl sulfonic acid, perfluoro hexyl
Sulfonic acid isopropyl ester, perfluoro capryl formyl chloride, perfluoro capryl methyl formate, perfluoro capryl Ethyl formate, perfluoro capryl formic acid isopropyl
Ester, perfluoro capryl sulfonic acid chloride, perfluoro octyl sulfonic acid methyl esters, perfluoro octyl sulfonic acid ethyl ester, perfluoro octyl sulfonic acid isopropyl ester, etc. chemical combination
One kind in thing, and perfluor carbon-based group therein be Rf, before carried out elaboration；
Step 2）Described in solvent be dichloromethane, chloroform, tetrahydrofuran, dimethyl ether, ether, ethyl methyl ether, 1,4- bis-
The ring of oxygen six, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, propane diols diethyl ether, propane diols butyl oxide, formic acid
Methyl esters, Ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, isoamyl acetate, the third two
Alcohol methyl ether acetate, propylene-glycol ethyl ether acetate etc. it is therein one or more；
Step 2）Described in acid binding agent be triethylamine, pyridine, N- methyl nafoxidine, N, N- dimethyl propylamines, N, N- diethyl
The one kind therein such as propylamine, N, N- dimethyl amines, N, N- diisopropylethylamine, three n-propyl amine.
Step 2）Described in acryloyl halide or 2- alkyls carboxylic acid halides be acryloyl chloride, methacrylic chloride, second
One kind in the compounds such as base acryloyl chloride, propyl group acryloyl chloride.
It is in place of gain of the invention：1）There is provided the comparatively safe environmental protection of one kind, simply containing double fluorine chain acrylamides
Synthesis technique, be conducive to industrialized implementation；2）Fluorine-containing propene acid amides involved in the present invention is containing fluorocarbon chain of enjoying a double blessing third
Acrylamide, and can be that single acrylamide structure can also be bisacrylamide or many acrylamide structures, therefore this hair
The bright synthetic method there is provided a kind of adjustable fluorine-containing propene acid amides of degree of functionality.
Fluorine-containing propene acid amides is synthesized using method disclosed by the invention, technique is easy, the yield of product and purity all compare
Height, the fluorine-containing propene amide compound for obtaining can be applied to synthesize fluorine resin or be applied to design the photocuring of low-surface-energy
Material.
Specific embodiment
With reference to specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following implementation
Example.
Embodiment 1
The present embodiment will synthesize the Methacrylamide containing double fluorine chains, and its structure is as follows：
Wherein Rf- is 17 fluorine octyl groups：
1）The synthesis of N, the N perfluorinated octyl sulfuryl amine of '-two
10.32g is added in 500ml reaction bulbs（0.1mol）Diethylenetriamine, the tetrahydrofuran of 50ml, 100ml ethyl acetate,
Under ice-water bath, stirring while be slowly added dropwise 102.82g（0.2mol）Perfluoro octyl sulfonic acid methyl esters, is added dropwise to complete, and removes frozen water
Bath, continue react 10h, low boiling component then is distilled off using Rotary Evaporators, obtained after vacuum drying intermediate N, N '-
Two perfluorinated octyl sulfuryl amines.Wherein used diethylenetriamine structure is as follows：
2）The synthesis of the Methacrylamide containing double fluorine chains
Toward above-mentioned equipped with N, 60ml dichloromethane, 90ml second two are added in the reaction bulb of N '-dihydroxy ethyl perfluorinated octyl sulfuryl amine
Diethylene glycol dimethyl ether, 10.62g（0.105mol）Stirred under triethylamine, ice-water bath, the air led in nitrogen displacement system, and
10.46g is slowly added dropwise under nitrogen protection（0.1mol）Methacrylic chloride, is added dropwise to complete recession and goes ice-water bath continuation reaction 5 small
When, solid is filtered to remove, filtrate is washed three times, dried through anhydrous magnesium sulfate, be concentrated to give the methacryl containing double fluorine chains
Amine.
The NMR data of product is as follows：
1H-NMR(400MHz, DMSO_d6)：7.52(s, 2H); 6.62(d, 1H); 6.35(d, 1H);
4.13(m, 4H);3.55(m, 4H); 2.32(m, 3H)。
19F-NMR(400MHz, DMSO_d6)：-80.21(s, 6F); -119.61(s, 4F); -122.19(s,
8F);
-123.32(s, 8F); -127.02(s, 8F)。
Embodiment 2
The present embodiment will synthesize the Methacrylamide containing double fluorine chains, and its structure is as follows：
Wherein Rf- is heptafluoropropyl：
1）The synthesis of N, N the perfluoro propyl sulfonamide of '-two
21.54g is added in 500ml reaction bulbs（0.1mol）The EGME of two hexene triamines and 150ml, under ice-water bath,
55.6g is slowly added dropwise while stirring（0.2mol）Perfluoro propyl sulfonic acid, is added dropwise to complete, and removes ice-water bath, continues to react
10h, is then distilled off low boiling component using Rotary Evaporators, and intermediate N, N '-two perfluoro propyl is obtained after vacuum drying
Sulfonamide.The wherein used amine structure of two hexene three is as follows：
2）The synthesis of the Methacrylamide containing double fluorine chains
Toward above-mentioned equipped with N, 150ml propylene glycol methyl ether acetates, 14.22g are added in the reaction bulb of the perfluoro propyl sulfonamide of N '-two
（0.11mol）Stirred under DIPEA, ice-water bath, the air led in nitrogen displacement system, and protected in nitrogen
13.26g is slowly added dropwise under shield（0.1mol）2- propyl group acryloyl chlorides, are added dropwise to complete recession and go ice-water bath to continue to react 5 hours, mistake
Solid is filtered, filtrate is washed three times, dried through anhydrous magnesium sulfate, be concentrated to give the Methacrylamide containing double fluorine chains.
The NMR data of product is as follows：
1H-NMR(400MHz, DMSO_d6)：8.01(s, 2H); 6.02(d, 1H); 5.56(d, 1H);
3.05(m, 4H); 2.95(m, 4H); 2.38(m, 2H); 1.55(m,8H);
1.43(m, 2H); 1.26(m, 8H); 0.90(m, 3H)。
19F-NMR(400MHz, DMSO_d6)：-80.03(s, 6F); -120.56(s, 4F); -126.93(s,
4F)。
Embodiment 3
The bisacrylamide containing double fluorine chains that the present embodiment will synthesize, its structure is as follows：
Wherein Rf- is：
1）The synthesis of N, N the PFPE formamide of '-two
14.63g is added in 500ml reaction bulbs（0.1mol）The dichloromethane of triethylene tetramine and 50ml, the acetic acid second of 100ml
Ester, under ice-water bath, stirring while be slowly added dropwise 135.2g（0.2mol）PFPE methyl formate, is added dropwise to complete, and removes ice
Water-bath, continues to react 10h, and low boiling component then is distilled off using Rotary Evaporators, and intermediate N is obtained after vacuum drying,
The PFPE formamides of N '-two.Wherein used triethylene tetramine structure is as follows：
2）The synthesis of the bisacrylamide containing double fluorine chains
Added toward above-mentioned equipped with intermediate N, in the reaction bulb of the PFPE formamides of N '-two 150ml Propylene Glycol Dimethyl Ethers,
16.61g（0.21mol）Stirred under pyridine, ice-water bath, the air led in nitrogen displacement system, and delay under nitrogen protection
It is slow that 23.72g is added dropwise（0.2mol）2- ethyl propylene acyl chlorides, is added dropwise to complete recession and goes ice-water bath to continue to react 5 hours, is filtered to remove
Solid, filtrate is washed three times, is dried through anhydrous magnesium sulfate, is concentrated to give the bisacrylamide containing double fluorine chains.
The NMR data of product is as follows：
1H-NMR(400MHz, DMSO_d6)：7.87(s, 2H); 6.48(d, 2H); 5.79(d, 2H);
5.15(m, 2H); 3.31(m, 4H); 3.04(m, 4H); 2.91(m,
4H)。
19F-NMR(400MHz, DMSO_d6)：-80.56(s, 6F); -81.25(s, 6F); -82.67(s, 6F);
-82.98(s, 6F); -129.21(s, 4F); -130.69(m, 4F);
-132.58(m, 8F);
-146.01(m, 6F)。
Embodiment 4
The bisacrylamide containing double fluorine chains that the present embodiment will synthesize, its structure is as follows：
Wherein Rf- is：
1）The synthesis of N, N the PFPE formamide of '-two
27.54g is added in 500ml reaction bulbs（0.1mol）The tetrahydrofuran of the amine of six ethene seven and 50ml, the chloromethanes of 100ml tri-
Alkane, under ice-water bath, stirring while be slowly added dropwise 234.8g（0.2mol）PFPE methyl formate, is added dropwise to complete, and removes ice
Water-bath, continues to react 10h, and low boiling component then is distilled off using Rotary Evaporators, and intermediate N is obtained after vacuum drying,
The PFPE formamides of N '-two.The wherein used amine structure of six ethene seven is as follows：
2）The synthesis of many acrylamides containing double fluorine chains
Toward above-mentioned equipped with intermediate N, 50ml chloroforms, 100ml second are added in the reaction bulb of the PFPE formamides of N '-two
Ether, 44.46g（0.51mol）Stirred under N, N- dimethyl propylamine, ice-water bath, the air led in nitrogen displacement system, and
45.25g is slowly added dropwise under nitrogen protection（0.5mol）Acryloyl chloride, is added dropwise to complete recession and goes ice-water bath to continue to react 5 hours, mistake
Solid is filtered, filtrate is washed three times, dried through anhydrous magnesium sulfate, be concentrated to give many acrylamides containing double fluorine chains.
The NMR data of product is as follows：
1H-NMR(400MHz, DMSO_d6)：7.92(s, 2H); 6.58(d, 5H); 5.89(d, 5H);
5.25(d, 5H); 3.62(m,4H); 3.35(m, 4H); 3.18(s, 16H)。
19F-NMR(400MHz, DMSO_d6)：-80.26(s, 6F); -81.17(m, 12F); -82.35(m,
18F);
-82.78(s, 6F); -129.16(s, 4F); -130.67(m,
4F); -132.48(m,20F);
-145.94(m, 12F)。
Claims (15)
1. a kind of fluorine-containing propene acid amides, it is characterised in that the general structure of compound is Formulas I：
Wherein：Rf is C3-20Perfluor carbon-based group；R ' is the CO or SO of divalence2Group；R1It is C2-C6Divalent alkyl group；R2For-H
Or C1-C3Monovalent alkyl radical；N is the integer more than or equal to 1.
2. a kind of fluorine-containing propene acid amides according to claim 1, it is characterised in that：Described perfluor carbon-based group is perfluoroparaffin
Base.
3. a kind of fluorine-containing propene acid amides according to claim 2, it is characterised in that：Described perfluoroalkyl is following group
In any one：-CF2CF(CF3)2、
-CF(CF3)CF2CF3、
-CF2CF2CF2CF3、
-CF2CF2CFCF3CF2CF3、
-CF2CF2CF2CF2CF2CF3、
-CF2CF(CF3)CF2CF2CF3、
-CF2CF(CF3)CF2CF2CF2CF3、
-CF2CF2CF2CF2CF2(CF3)2、
-CF2CF2CF2CF2CF2CF2CF2CF3、
-CF2CF2CF2CF(CF3)CF2CF2CF3、
-CF2CF(CF3)CF2CF2CF2CF2CF3、
-CF2CF2CF(CF3)CF2CF2CF2CF2CF3、
-CF2CF(CF3)CF2CF(CF3)CFCF2CF3、
-CF2CF2CF2CF2CF2CF2CF2CF2CF2CF2CF2CF3。
4. a kind of fluorine-containing propene acid amides according to claim 1, it is characterised in that：Described perfluor carbon-based group is in main chain
The perfluoropolyether group of middle insertion oxygen atom.
5. a kind of fluorine-containing propene acid amides according to claim 4, it is characterised in that：Described perfluoropolyether group is following
Any one of group,
-CF2CF2OCF(CF3)2、
-CF(CF3)OCF(CF3)2、
-CF(CF3)OCF2CF2CF3、
-CF2OCF2CF2OCF2CF3、
-CF(CF3)OCF2CF(CF3)OCF2CF2CF3、
-CF2CF2OCF2CF(CF3)OCF2CF2CF3、
-CF2CF2CF2OCF2CF2CF2OCF2CF2CF3、
-CF2CF(CF3)OCF2CF2OCF2CF2CF3、
-CF2OCF(CF3)OCF2CF2OCF(CF3)2、
-CF2CF2OCF(CF3)OCF2CF2OCF2CF2CF3、
-CF2CF(CF3)OCF2CF(CF3)OCF(CF3)2、
-CF(CF3)OCF2CF(CF3)OCF(CF3)2、
-CF2CF(CF3)OCF2CF(CF3)OCFCF2CF3、
-CF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)2、
-CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)2。
6. a kind of fluorine-containing propene acid amides according to claim 1, it is characterised in that：Described R1It is any for following group
It is a kind of：-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH(CH3)-、-CH2CH2CH2CH2-、-CH2CH(CH3)CH2-、-
CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-。
7. a kind of fluorine-containing propene acid amides according to claim 1, it is characterised in that：Described R2It is any for following group
It is a kind of：-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)CH3。
8. a kind of fluorine-containing propene acid amides according to claim 1, its synthetic method is as follows：
The first step：Add 1 molar part polyamine, stirring solvent uniform in a kettle., at -30 ~ 50 DEG C, stir and to reaction
The derivative of 2 molar part perfluorocarbon substituent group formic acid or the derivative of perfluorocarbon substituent group sulfonic acid are slowly added dropwise in kettle, are dripped
Complete, continuation 3 ~ 12h of reaction is added, the double fluorine chain acid amides containing secondary amine are obtained after solvent, vacuum drying is distilled off；
Second step：Under nitrogen protection, solvent and acid binding agent are added in the double fluorine chain acid amides containing secondary amine obtained toward the first step,
The acryloyl halide or 2- alkyl carboxylic acid halides of 1.05n molar parts are slowly added dropwise under -30 ~ 50 DEG C of reaction temperatures, 1 is reacted after adding
~ 5 hours, then obtain fluorine-containing propene amide compound after filtering, washing, dry, concentration.
9. a kind of fluorine-containing propene acid amides synthetic method according to claim 8, it is characterised in that：Institute in the described first step
The polyamine stated, its general structure is formulaIt is shown：
。
10. a kind of fluorine-containing propene acid amides synthetic method according to claim 9, it is characterised in that：Described polyamine is：
H2NCH2CH2CH2CH2NHCH2CH2CH2CH2NHCH2CH2CH2CH2NH2,
H2NCH2CH2CH2CH2NHCH2CH2CH2CH2NH2,
H2NCH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NH2,
H2NCH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NH2,
H2NCH2CH2CH2NHCH2CH2CH2NH2,
H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2,
H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2,
H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2,
H2NCH2CH2NHCH2CH2NHCH2CH2NH2,
H2NCH2CH2NHCH2CH2NH2In any one.
A kind of 11. fluorine-containing propene acid amides synthetic methods according to claim 9, it is characterised in that：The solvent of the first step is
Dichloromethane, chloroform, methyl alcohol, ethanol, isopropanol, tetrahydrofuran, dimethyl ether, ether, ethyl methyl ether, 1,4- dioxane,
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propyleneglycol monobutyl
Ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, propane diols diethyl ether, propane diols butyl oxide, methyl formate,
Ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, isoamyl acetate, propylene glycol monomethyl ether
Any one or a few in acetate, propylene-glycol ethyl ether acetate.
A kind of 12. fluorine-containing propene acid amides synthetic methods according to claim 8, it is characterised in that：Perfluor described in the first step
The derivative of carbon-based group substitution formic acid or the derivative of perfluorocarbon substituent group sulfonic acid are PFPE formyl fluoride, PFPE first
It is acyl chlorides, PFPE formyl bromine and PFPE methyl formate, PFPE Ethyl formate, PFPE isopropyl formate, complete
Perfluoroalkyl polyether sulfuryl fluoride, PFPE sulfonic acid chloride, PFPE sulfonic acid bromide and PFPE methylmesylate, PFPE sulfonic acid second
Ester, PFPE sulfonic acid isopropyl ester, perfluoro butyl formyl chloride, perfluoro butyl methyl formate, perfluoro butyl Ethyl formate, perfluor fourth
Base isopropyl formate, perfluoro butyl sulfonic acid chloride, perfluoro butyl methylmesylate, perfluoro butyl sulfonic acid, perfluoro butyl sulfonic acid are different
Propyl ester, perfluoro hexyl formyl chloride, perfluoro hexyl methyl formate, perfluoro hexyl Ethyl formate, perfluoro hexyl isopropyl formate, perfluor
Hexyl sulfonic acid chloride, perfluoro hexyl methylmesylate, perfluoro hexyl sulfonic acid, perfluoro hexyl sulfonic acid isopropyl ester, perfluoro capryl formyl
Chlorine, perfluoro capryl methyl formate, perfluoro capryl Ethyl formate, perfluoro capryl isopropyl formate, perfluoro capryl sulfonic acid chloride, perfluor are pungent
Base methylmesylate, perfluoro octyl sulfonic acid ethyl ester, perfluoro octyl sulfonic acid isopropyl ester, etc. one kind in compound, it is and therein complete
Fluorocarbon group is Rf.
A kind of 13. fluorine-containing propene acid amides synthetic methods according to claim 8, it is characterised in that：Described in second step
Solvent is dichloromethane, chloroform, tetrahydrofuran, dimethyl ether, ether, ethyl methyl ether, 1,4- dioxane, glycol dinitrate
Ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, propane diols diethyl ether, propane diols butyl oxide, methyl formate, Ethyl formate, formic acid
Butyl ester, methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, isoamyl acetate, propylene glycol methyl ether acetate, propane diols
One or more in ethyl ether acetate ester.
A kind of 14. fluorine-containing propene acid amides synthetic methods according to claim 8, it is characterised in that：The acid binding agent is three
Ethamine, pyridine, N- methyl nafoxidine, N, N- dimethyl propylamines, N, N- diethyl propylamine, N, N- dimethyl amines, N, N- bis-
One kind in wopropyl ethyl amine, three n-propyl amine.
A kind of 15. fluorine-containing propene acid amides synthetic methods according to claim 8, it is characterised in that：Described acryloyl halide
Or 2- alkyls carboxylic acid halides is any one in acryloyl chloride, methacrylic chloride, ethyl propylene acyl chlorides, propyl group acryloyl chloride
Kind.
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