CN109912438A - A kind of synthetic method of N- vinyl formamide - Google Patents
A kind of synthetic method of N- vinyl formamide Download PDFInfo
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- CN109912438A CN109912438A CN201910247270.5A CN201910247270A CN109912438A CN 109912438 A CN109912438 A CN 109912438A CN 201910247270 A CN201910247270 A CN 201910247270A CN 109912438 A CN109912438 A CN 109912438A
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- formamide
- synthetic method
- vinyl formamide
- acetaldehyde
- vinyl
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- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 67
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- -1 alkenyl succinic anhydride Chemical compound 0.000 claims abstract description 31
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000009835 boiling Methods 0.000 claims description 21
- 239000000543 intermediate Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- BAMUPQJDKBGDPU-UHFFFAOYSA-N n-(2-hydroxyethyl)formamide Chemical compound OCCNC=O BAMUPQJDKBGDPU-UHFFFAOYSA-N 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 230000002459 sustained effect Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- MAHHMTSPHIZKCD-UHFFFAOYSA-N acetaldehyde formamide Chemical compound C(C)=O.C(=O)N MAHHMTSPHIZKCD-UHFFFAOYSA-N 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- PMRJLMRZYXKGAT-UHFFFAOYSA-N aziridine-1-carbaldehyde Chemical compound O=CN1CC1 PMRJLMRZYXKGAT-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- HTHVSMTZYMMWKO-UHFFFAOYSA-N formamide Chemical compound NC=O.NC=O HTHVSMTZYMMWKO-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic methods of N- vinyl formamide, using alkenyl succinic anhydride, acetaldehyde and formamide as raw material, synthetic intermediate under the action of basic catalyst, by the intermediate of synthesis, cracking reaction obtains N- vinyl formamide under conditions of 45~150 DEG C.Synthetic method of the invention has many advantages, such as that yield is high, reaction condition is mild, and raw material are easy to get, it is simple to separate, and synthesis cost is lower, has good prospects for commercial application.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of N- vinyl formamide.
Background technique
N- vinyl formamide (NVF) is a kind of nontoxic water-soluble monomer (its structural formula is as shown in Figure 1), is acryloyl
The isomers of amine (AAM), AAM is a kind of solid, and NVF is liquid under normal operation, and two kinds of isomers are in copolyreaction
Aspect is different, i.e., NVF is more reactive.The molecular weight M=71g/mol (N- ethylene amine equivalent 43g/mol) of NVF.Boiling point is higher
Lower 80 DEG C of 80mbar pressure.NVF is a kind of transparent, colourless liquid, can store under suitable condition some months without
It decomposes.
NVF usually in the presence of a free-radical initiator may be used as a kind of vinyl monomer (Q value is that 0.29, e value is -0.52)
It is polymerize, using azo-initiator, produces PNVF with solution polymerization process；It is poly- that precipitating can be carried out in other organic solvents
It closes, suspension polymerisation, emulsion polymerization is carried out in undissolved alkane solvents.PNVF is water-soluble polymer, is white under room temperature
Color solid, high temperature resistant (≤250 DEG C), PNVF can be used as the intermediate of synthesis PVAM.Furthermore NVF can be with various of monomer such as acrylic acid
The copolymerization such as ester, acrylonitrile, amides, vinyl acetate, the polymer of generation are widely used as cation polymeric flocculant, paper grade (stock)
Additive and ion exchange resin etc..Since the monomer ethylene amine of synthesizing polyethylene amine is unstable, cannot industrially pass through always
The polymerization of vinylamine obtains, and the realization of industrialization of NVF in 1993 is using PNVF as intermediate by under alkali or acid condition
The method for obtaining PVAM is hydrolyzed, reaction equation is as shown in Figure 2.
NVF and the copolymerization of acrylonitrile equimolar generate amidine, obtain a kind of macromolecule haveing excellent performance with acid processing again after hydrolysis
Flocculant is widely used in field of waste water treatment.There is solvability, can be used as ultraviolet light solidification or electron beam curing type coating
Response type diluent.N-vinyl pyrrolidone is mainly used currently as response type diluent, NVF is as a kind of excellent
Solvent has the advantages that strength of coating is big after viscosity easily adjusts, solidifies, may replace n-vinyl pyrrolidone.
Since vinylamine is unstable, NVF cannot be prepared by the acylation of vinylamine, synthesize the synthesis of NVF at present
Method has following several:
A) substitution reaction of lactic acid cyanogen and formamide is then in Pintsch process substitution product.Reaction process is as shown in Figure 3.
B) production technology of Mitsubishi, acetaldehyde and formamide react first generates N-a hydroxyethyl formamide, is then etherified
Ethyl alcohol is eliminated by pyrolysis at N- (a methoxyethyl) formamide (NMEF) and generates NVF, reaction process is as shown in Figure 4.
C) a kind of method that University of Pittsburgh discloses synthesis NVF generates N-a ethoxy using acetaldehyde and formamide
Formamide, N-a hydroxyethyl formamide and formamide simultaneously slough molecular water generation ethylene formamide, then by adding
It thermally decomposes ethylene formamide and generates N- vinyl formamide (NVF) and a molecule formamide, formamide can be with during this
Recycling.Reaction process is as shown in Figure 5.
Extremely toxic substance HCN is generated in above method a；The formamide to be removed in c and product NVF boiling point are close, are not easy point
From: b scheme is applied for a patent by Mitsubishi, is the main method of current production NVF, but this method that there are acidic and alkaline waste water amounts is more,
The problems such as reaction step is relatively complicated, yield is not high.In short, there are reaction steps for the synthesis of NVF in current production technology
More, side reaction is seriously, separation is difficult, synthesis cost is higher.A kind of yield is high at present, reaction step is few, raw material are easy to get, separate
Simple NVF synthetic method is urgently developed.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is by providing a kind of synthetic method of N- vinyl formamide, the synthesis
Method has many advantages, such as yield height, and reaction step is few, raw material are easy to get, it is simple to separate, and synthesis cost is lower.
To achieve the above object, the technical solution of the present invention is as follows:
A kind of synthetic method of N- vinyl formamide, using alkenyl succinic anhydride, acetaldehyde and formamide as raw material, in alkali
Synthetic intermediate under the action of property catalyst, by the intermediate of synthesis, cracking reaction obtains N- second under conditions of 45~150 DEG C
Alkenyl formamide.
Preferably, in reaction system, the dosage of the acetaldehyde is relative to formamide excess.
Preferably, the acetaldehyde, formamide, alkenyl succinic anhydride mass ratio be 1.2 ﹕, 1 ﹕ 2.3~3.8.
Preferably, the carbon chain lengths of the alkenyl succinic anhydride are C8~C18；The alkenyl succinic anhydride includes maleic acid
Acid anhydride, phthalic anhydride, cyclic anhydride one of polymer or a variety of.
Preferably, the basic catalyst is inoganic solids alkali；The basic catalyst be alkali metal hydroxide or
Subcarbonate.
Preferably, the subcarbonate is Anhydrous potassium carbonate and/or natrium carbonicum calcinatum.
Preferably, the basic catalyst proportion is the 0.87%-2.14% of formamide mole.
Further, the synthetic method the following steps are included:
(1) N-a hydroxyethyl formamide is synthesized:
It takes distilled acetaldehyde to be put into constant pressure funnel, takes formamide to be added in four-hole boiling flask, will be added on four-hole boiling flask
Reflux condensing tube, thermometer and constant pressure funnel, and basic catalyst is added, temperature maintain 45 DEG C into formamide in batches
Acetaldehyde sustained response 70min is added dropwise, obtains N-a hydroxyethyl formamide；
(2) synthetic reaction object intermediate:
Alkenyl succinic anhydride is added in four-hole boiling flask in the N-a hydroxyethyl formamide for taking step (1) to prepare at room temperature, after
It is continuous to be warming up to 2.0~3.0h of reaction at 70 DEG C；
(3) high-temperature cracking furnace cracking reaction intermediate is used:
The reactant intermediate that step (2) obtain is put into magnetic cup, and is put into tube furnace, tubular type furnace temperature is adjusted and arrives
150 DEG C, and react 2.0h, when tube furnace greenhouse cooling is to room temperature, gained liquid in tube furnace is collected, then through separating-purifying
Obtain N- vinyl formamide.
Preferably, in step (1), the distillating method of acetaldehyde are as follows: it takes acetaldehyde in a round bottom flask, instills a few drop concentrated sulfuric acids,
3 hours are distilled at 60 DEG C.
Preferably, in step (3), using Rotary Evaporators or thin film evaporator, separating-purifying is produced under the conditions of 120 DEG C
N- vinyl formamide.
Compared with prior art, advantages of the present invention:
(1) alkenyl succinic anhydride (ASA, structural formula are as shown in Figure 6) is fixedness clear amber liquid, relatively close
Spend (25 DEG C) 0.784；Viscosity (24 DEG C) 0.16Pas；210 DEG C of flash-point (COC)；It is soluble in acetone, benzene, petroleum ether, is not dissolved in
Water；It is stable in dry conditions.The present invention uses alkenyl succinic anhydride as synthesis material and acetaldehyde and formamide, in alkalinity
Under the action of catalyst, reacted by heating, and evaporate to obtain N- vinyl formamide by thin film evaporator.React remaining
Alkenyl succinic acid can be re-used by dehydrating condensation, can both continue the raw material as production NVF, technology meets green
The production requirement of colour chemistry.
(2) synthetic reaction step of the invention is simple, and reaction process is easily controllable.
(3) raw material is common needed for the present invention is easy to get, lower production costs.
(4) product separating-purifying of the invention is simple, and product is 54% or more, and product purity is 92% or more.
In conclusion synthetic method of the invention has, yield is high, reaction condition is mild, and raw material are easy to get, separate simply
The advantages that, and synthesis cost is lower, has good prospects for commercial application.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the structural formula of N- vinylformamide monomer；
Fig. 2 is using PNVF as intermediate by obtaining the reaction equation of PVAM in alkali or hydrolyzed under acidic conditions；
Fig. 3 is the substitution reaction of lactic acid cyanogen and formamide and then generates the reaction equation of NVF in Pintsch process substitution product；
Fig. 4 is the NVF production process of Mitsubishi；
Fig. 5 is the method that University of Pittsburgh synthesizes NVF；
Fig. 6 is the structural formula of alkenyl succinic anhydride；
Fig. 7 is the reaction equation of NVF preparation process in the present invention；
Fig. 8 is the IR Characterization image for the N-a hydroxyethyl formamide that example 1 of the invention synthesizes；
Fig. 9 is the IR Characterization image for the NVF that example 1 of the invention synthesizes.
Specific embodiment
A kind of synthetic method of N- vinyl formamide, as shown in fig. 7, with alkenyl succinic anhydride, acetaldehyde and formamide
For raw material, synthetic intermediate under the action of basic catalyst, by the intermediate under conditions of 45~150 DEG C cracking reaction
N- vinyl formamide is obtained, reaction process is as shown in Figure 7.It is produced using Rotary Evaporators or thin film evaporator separating-purifying
N- vinyl formamide.
Wherein, in reaction system, the dosage of the acetaldehyde is relative to formamide excess.To guarantee to make another raw material first
Completely, this post-processes the more important boiling point very phase due to formamide and N- vinyl formamide to reaction system for amide conversion
Closely, it is difficult to separate the two by simply distilling, therefore excessive acetaldehyde can be during the reaction as far as possible by formyl
Amine fully reacting.Specifically, the ratio of the acetaldehyde, formamide, alkenyl succinic anhydride is 1.1~4.0 ﹕, 1.0 ﹕ 0.9~2.0.
The alkenyl succinic anhydride includes one of polymer of maleic anhydride, phthalic anhydride, cyclic anhydride or a variety of.
The basic catalyst is inoganic solids alkali；The preferably hydroxide or subcarbonate of alkali metal；More preferably
For Anhydrous potassium carbonate and/or natrium carbonicum calcinatum；And the basic catalyst proportion be formamide mole 0.3~
6.0%；It is more excellent for the basic catalyst be the 0.5%~4.0% of formamide mole.Basic catalyst dosage is excessively few then
Keep the catalytic effect of reaction unobvious, and dosage excessively can then aggravate the generation of side reaction, keep product separating-purifying more difficult.
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
(1) acetaldehyde is distilled
It takes 100 milliliters of acetaldehyde in a round bottom flask, instills a few drop concentrated sulfuric acids, 3 h are distilled at 60 DEG C.
(2) N-a hydroxyethyl formamide is synthesized
It takes distilled acetaldehyde 26.4g (0.6mol) to be put into constant pressure funnel, formamide 22.5g (0.5mol) is taken to be added four
In mouth flask, reflux condensing tube, thermometer and constant pressure funnel will be added on four-hole boiling flask, and it is anhydrous that 0.6g catalyst is added
Potassium carbonate reacts 70min at 45 DEG C, N-a hydroxyethyl formamide is obtained, and carry out infrared analysis to it, as a result such as Fig. 8 institute
Show.
(3) synthetic reaction object intermediate
The N-a ethyl-formamide 20g and 85.5g alkenyl succinic anhydride (R=16) for taking step (2) to obtain are in four-hole boiling flask
2.0h is reacted at 70 DEG C.
(4) high-temperature cracking furnace cracking reaction intermediate is used
Resulting high polymer intermediate is put into magnetic cup, and is put into tube furnace, adjust tubular type furnace temperature to 150 DEG C,
And 2.0h is reacted, when tube furnace greenhouse cooling is to room temperature, collect gained liquid in tube furnace.And it is carried out using thin film evaporator
Purification, obtains colourless transparent liquid.Product NVF yield 63.6%, purity 92.8%.
Gained liquid is subjected to infrared detection, as shown in figure 9, the infrared image of gained IR Characterization image and standard NVF
Main peak is essentially identical.
Embodiment 2
Blender, reflux condensing tube, thermometer and constant pressure funnel are housed, in four-hole boiling flask on the four-hole boiling flask of 250ml
It is added in 22.5g formamide (0.5mol) and 0.6g Anhydrous potassium carbonate, constant pressure funnel and 26.4g (0.6mol) distilled second is added
Aldehyde (purity > 95%), temperature maintain 45 DEG C and acetaldehyde 70min are slowly added dropwise.It is warmed to room temperature and 52.5g (0.25mol) then is added
Octenyl succinic acid anhydride continues to be warming up to 70 DEG C of reaction 3.0h.The reactant intermediate of acquisition is put into magnetic cup, and is put into tubular type
In furnace, tubular type furnace temperature is adjusted to 150 DEG C, and reacts 2.0h, when tube furnace greenhouse cooling arrives room temperature, institute in collection tube furnace
Liquid, products therefrom be added Rotary Evaporators in rotated at 120 DEG C, liquid be N- vinyl formamide.Product
NVF yield 58.6%, purity 92.3%.
Embodiment 3
Blender, reflux condensing tube, thermometer and constant pressure funnel are housed, in four-hole boiling flask on the four-hole boiling flask of 250ml
It is added in 22.5g formamide (0.5mol) and 0.6g Anhydrous potassium carbonate, constant pressure funnel and 26.4g (0.6mol) distilled second is added
Aldehyde (purity > 95%), temperature maintain 45 DEG C and acetaldehyde 70min are added dropwise in batches.Then the alkenyl succinic anhydride of R=16 is added
85.5g (0.25mol) continues to be warming up to 70 DEG C of reaction 3.0h.The reactant intermediate of acquisition is put into magnetic cup, and is put into tubular type
In furnace, tubular type furnace temperature is adjusted to 150 DEG C, and reacts 2.0h, when tube furnace greenhouse cooling arrives room temperature, institute in collection tube furnace
Liquid, products therefrom be added thin film evaporator in rotated at 120 DEG C, liquid be N- vinyl formamide.Product
NVF yield 63.0%, purity 94.1%.
Embodiment 4
Blender, reflux condensing tube, thermometer and constant pressure funnel are housed, in four-hole boiling flask on the four-hole boiling flask of 250ml
It is added in 22.5g formamide (0.5mol) and 0.6g potassium hydroxide, constant pressure funnel and 26.4g (0.6mol) distilled acetaldehyde is added
(purity > 95%), temperature maintain 45 DEG C and acetaldehyde sustained response 70min are added dropwise in batches.It is warmed to room temperature then plus such as R=16
Alkenyl succinic anhydride 85.5g (0.25mol) continues to be warming up to 70 DEG C of reaction 2h.The reactant intermediate of acquisition is put into magnetic cup,
And be put into tube furnace, tubular type furnace temperature is adjusted to 150 DEG C, and reacts 2.0h, when tube furnace greenhouse cooling arrives room temperature, collection
In tube furnace gained liquid, products therefrom be added thin film evaporator in rotated at 120 DEG C, liquid be N- vinyl first
Amide, product NVF yield 54.0%, purity 90.1%.
Embodiment 5
Blender, reflux condensing tube, thermometer and constant pressure funnel are housed, in four-hole boiling flask on the four-hole boiling flask of 250ml
It is added in 22.5g formamide (0.5mol) and 0.6g Anhydrous potassium carbonate, constant pressure funnel and 26.4g (0.6mol) distilled second is added
Aldehyde (purity > 95%), temperature maintain 45 DEG C and acetaldehyde are added dropwise in batches and reacts 70min.Then 85.5g alkenyl succinic anhydride is added
(R=16), continue to be warming up to 70 DEG C of reaction 3h.The reactant intermediate of acquisition is put into magnetic cup, and is put into tube furnace, is adjusted
Tubular type furnace temperature reacts 2.0h to 150 DEG C, when tube furnace greenhouse cooling is to room temperature, collects gained liquid, institute in tube furnace
Product be added thin film evaporator in rotated at 120 DEG C, liquid be N- vinyl formamide.Product NVF yield
55%, purity 92.2%.
Embodiment 6
Blender, reflux condensing tube, thermometer and constant pressure funnel are housed, in four-hole boiling flask on the four-hole boiling flask of 250ml
It is added in 22.5g formamide (0.5mol) and 0.6g Anhydrous potassium carbonate, constant pressure funnel and 26.4g (0.6mol) distilled second is added
Aldehyde (purity > 95%), temperature maintain 45 DEG C and acetaldehyde 70min are added dropwise in batches.Then 64.5g alkenyl succinic anhydride (R=is added
12), continue to be warming up to 70 DEG C of reaction 3.0h.The reactant intermediate of acquisition is put into magnetic cup, and is put into tube furnace, regulation pipe
Formula furnace temperature reacts 2.0h to 150 DEG C, when tube furnace greenhouse cooling is to room temperature, collects gained liquid, gained in tube furnace
Product be added thin film evaporator in rotated at 120 DEG C, liquid be N- vinyl formamide.Product NVF yield 54%,
Purity 93.6%.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (10)
1. a kind of synthetic method of N- vinyl formamide, it is characterised in that: be with alkenyl succinic anhydride, acetaldehyde and formamide
Raw material, synthetic intermediate under the action of basic catalyst, by the intermediate of synthesis under conditions of 45~150 DEG C cracking reaction
Obtain N- vinyl formamide.
2. the synthetic method of N- vinyl formamide according to claim 1, it is characterised in that: described in reaction system
The dosage of acetaldehyde is relative to formamide excess.
3. the synthetic method of N- vinyl formamide according to claim 1, it is characterised in that: the acetaldehyde, formamide,
The mass ratio of alkenyl succinic anhydride is 1.2 ﹕, 1 ﹕ 2.3~3.8.
4. the synthetic method of N- vinyl formamide according to claim 1, it is characterised in that: the alkenyl succinic anhydride
Carbon chain lengths be C8~C18；The alkenyl succinic anhydride includes in the polymer of maleic anhydride, phthalic anhydride, cyclic anhydride
It is one or more.
5. the synthetic method of N- vinyl formamide according to claim 1, it is characterised in that: the basic catalyst is
Inoganic solids alkali；The basic catalyst is the hydroxide or subcarbonate of alkali metal.
6. the synthetic method of N- vinyl formamide according to claim 5, it is characterised in that: the subcarbonate is
Anhydrous potassium carbonate and/or natrium carbonicum calcinatum.
7. the synthetic method of N- vinyl formamide according to claim 1, it is characterised in that: the basic catalyst institute
Accounting example is the 0.87%-2.14% of formamide mole.
8. the synthetic method of N- vinyl formamide according to claim 1-7, which is characterized in that including following
Step:
(1) N-a hydroxyethyl formamide is synthesized:
It takes distilled acetaldehyde to be put into constant pressure funnel, formamide is taken to be added in four-hole boiling flask, reflux will be added on four-hole boiling flask
Condenser pipe, thermometer and constant pressure funnel, and basic catalyst is added, temperature maintains 45 DEG C and is added dropwise in batches into formamide
Acetaldehyde sustained response 70min obtains N-a hydroxyethyl formamide；
(2) synthetic reaction object intermediate:
Alkenyl succinic anhydride is added in four-hole boiling flask in the N-a hydroxyethyl formamide for taking step (1) to prepare at room temperature, after of continuing rising
Temperature is to reacting 2.0~3.0h at 70 DEG C；
(3) high-temperature cracking furnace cracking reaction intermediate is used:
The reactant intermediate that step (2) obtain is put into magnetic cup, and is put into tube furnace, adjusts tubular type furnace temperature to 150
DEG C, and 2.0h is reacted, when tube furnace greenhouse cooling is to room temperature, collects gained liquid in tube furnace, then obtained through separating-purifying
Obtain N- vinyl formamide.
9. the synthetic method of N- vinyl formamide according to claim 8, it is characterised in that: in step (1), acetaldehyde
Distillating method are as follows: take acetaldehyde in a round bottom flask, instill a few drop concentrated sulfuric acids, 3 hours are distilled at 60 DEG C.
10. the synthetic method of N- vinyl formamide according to claim 9, it is characterised in that: in step (3), use
Rotary Evaporators or thin film evaporator, the N- vinyl formamide that separating-purifying produces under the conditions of 120 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112047854A (en) * | 2020-10-20 | 2020-12-08 | 中国科学院长春应用化学研究所 | Preparation method of N-vinyl alkyl amide |
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Application publication date: 20190621 |