CN103232366A - Preparation method of alpha-cyano propenoic acid-2-methoxy ethyl ester - Google Patents
Preparation method of alpha-cyano propenoic acid-2-methoxy ethyl ester Download PDFInfo
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- CN103232366A CN103232366A CN2013101481767A CN201310148176A CN103232366A CN 103232366 A CN103232366 A CN 103232366A CN 2013101481767 A CN2013101481767 A CN 2013101481767A CN 201310148176 A CN201310148176 A CN 201310148176A CN 103232366 A CN103232366 A CN 103232366A
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Abstract
The invention discloses a preparation method of alpha-cyano propenoic acid-2-methoxy ethyl ester, which comprises the following steps: (1) mixing and stirring polyformaldehyde and methanol, adding piperidine, and performing heating reflux until the polyformaldehyde is completely dissolved; (2) performing condensation reaction on cyano acetic acid-2-methoxy ethyl ester and the polyformaldehyde methanol solution in the presence of an alkali catalyst, thus obtaining a prepolymer; (3) adding petroleum ether into the prepolymer, performing heating reflux and dehydration, recovering the petroleum ether when the water content is no longer increased in the reaction, adding phosphorus pentoxide and free radical polymerization inhibitor into the reaction solution, and performing high-temperature cracking and distillation; and (4) mixing the obtained distillation product with phosphorus pentoxide and free radical polymerization inhibitor, and rectifying the mixed components to obtain the alpha-cyano propenoic acid-2-methoxy ethyl ester. According to the invention, the synthesis method has the advantages of short reaction time, cheap and accessible catalyst, simple technological operation and high operability; and the product has the advantages of high yield and purity.
Description
Technical field
The invention belongs to preparation α-Qing Jibingxisuanzhi field, in particular, relate to the preparation method of the alpha-cyanoacrylate that can be used as tackiness agent or the sealing agent-2-methoxyl group ethyl ester of a kind of low albefaction, low irritant, high tenacity.
Background technology
No matter in daily life still was industrial production, α-Qing Jibingxisuanzhi class tackiness agent had a lot of application.This tackiness agent is in research and development success and introducing to the market in 1958 the earliest by U.S. Eastman Kodark company, advantage with a series of uniquenesses, for example solvent-free, do not need heating and pressurizing, bonding scope is wide, intensity is high, instantaneous solidification, nontoxic substantially, and biological tissues such as skin is also had very strong adhesive effect.Nowadays, along with continuous progress in science and technology, the over-all properties of α-Qing Jibingxisuanzhinianheji is also improving constantly, and is widely used in industry, agricultural, field such as civilian.Simultaneously, be developed to and be widely used in clinical for adhesive of medical.
As everyone knows, obtain the purity height, the α-Qing Jibingxisuanzhidanti of quality better, its synthesis technique has great importance.As the synthetic method of raw material cyanoacetate or technology the performance of product also there is significant effects.Mostly the synthetic method of the cyanoacetic acid-2-methoxyl group ethyl ester of report is sulfuric acid catalysis esterification process or ester-interchange method at present.Although it is higher to carry out cyanoacetic acid-2-methoxyl group ethyl ester purity that esterification obtains with sulfuric acid as catalyzer, sulfuric acid can etching apparatus, and not easy to operate, and yield is low, and this technology is not used in suitability for industrialized production substantially at present; Ester-interchange method synthesizes cyanoacetic acid-2-methoxyl group ethyl ester and is mostly that with ethyl cyanoacetate and ethylene glycol monomethyl ether be raw material, carry out under as the condition of transesterification catalyst at tetrabutyl titanate, the limitation of this method is that ethyl cyanoacetate and cyanoacetic acid-2-methoxyl group ethyl ester boiling point difference are little, is difficult to by underpressure distillation the two be separated fully obtain the high cyanoacetic acid-2-methoxyl group ethyl ester of purity.
United States Patent (USP) 3639361,3254111,3577394 and Chinese patent CN101497767, CN102101833 all discloses synthesis technique or the method for preparation α-Qing Jibingxisuanzhi.The described main technique of these patents or method are the cyanoacetic acid alkyl ester to be mixed the back carry out condensation reaction in formalin or with Paraformaldehyde 96 in the presence of basic catalyst, resulting prepolymer is shifted out, after organic solvent extraction or oven dry dewater, add stopper again and carry out the cracking distillation, obtain the α-Qing Jibingxisuanzhi crude monomer, can obtain corresponding product after the rectifying.
The shortcoming of above-mentioned known technology is: when carrying out condensation reaction, selected formaldehyde raw material mostly is formalin or Paraformaldehyde 96.When being raw material with the Paraformaldehyde 96, Paraformaldehyde 96 dissolves in organic solvent and causes long reaction time slowly; When being raw material with the aqueous solution of formaldehyde, owing to there is a large amount of water, need after polycondensation is finished prepolymer is filtered to isolate, dry naturally then or hot-air seasoning, not only complicated operation, and dry the length that expends time in naturally, drying time is wayward, and moisture content is wayward, and during depolymerization the moisture of trace will make α-Qing Jibingxisuanzhidanti again polymerization cause the failure of an experiment, this operation bigger human cost, synthetic cost height of expending consuming time.
Summary of the invention
It is a kind of simple to operate that one of purpose of the present invention is to provide, and catalyzer is cheap and easy to get, the method for preparing cyanoacetic acid-2-methoxyl group ethyl ester that the yield high purity is good.
Two of the object of the invention is to provide the cyanoacetic acid-2-methoxyl group ethyl ester of method for preparing.
For achieving the above object, technical scheme of the present invention is as follows:
The preparation method of a kind of alpha-cyanoacrylate-2-methoxyl group ethyl ester comprises the steps:
(1) Paraformaldehyde 96 and methanol mixed are stirred, add piperidines, reflux is dissolved in fully to Paraformaldehyde 96 and forms homogeneous phase solution in the methyl alcohol;
(2) condensation reaction takes place in the methanol solution with cyanoacetic acid-2-methoxyl group ethyl ester and Paraformaldehyde 96 under the condition of basic catalyst, obtains alpha-cyanoacrylate-2-methoxyl group ethyl ester prepolymer; Its reaction equation is:
(3) add sherwood oil in above-mentioned prepolymer, the reflux dehydration when moisture no longer increases in the reaction, is reclaimed sherwood oil, adds negatively charged ion stopper Vanadium Pentoxide in FLAKES and free radical polymerization inhibitor in reaction solution, carries out the cracking distillation under the temperature more than 150 ℃;
(4) product of distillation with gained mixes with Vanadium Pentoxide in FLAKES, free radical polymerization inhibitor, then above-mentioned blending ingredients is carried out rectifying, obtains alpha-cyanoacrylate-2-methoxyl group-ethyl ester (purity is more than 98%).
Preferably, by weight percentage, the consumption of Paraformaldehyde 96 is 50% of methyl alcohol, and the consumption of piperidines is 0.05%～0.20% of Paraformaldehyde 96.
Preferably, in the formaldehyde in the Paraformaldehyde 96 methanol solution, the mol ratio of described cyanoacetic acid-2-methoxyl group ethyl ester and formaldehyde is 1.00～1.10:1.00; In molar percentage, the consumption of described basic catalyst is 0.1%～0.6% of formaldehyde; 70～80 ℃ of setting-up point, mechanical stirring backflow 5～20min reclaims methyl alcohol.
Preferably, in the formaldehyde in the Paraformaldehyde 96 methanol solution, step (3) PetroChina Company Limited. ether consumption is 100～200mL/mol formaldehyde, and the add-on of Vanadium Pentoxide in FLAKES is 5～8g/mol formaldehyde in the distillation, and free radical polymerization inhibitor is 1～3g/mol formaldehyde; The condition of described distillation: vacuum tightness is 150～300Pa, and temperature is 160～230 ℃.
Preferably, the consumption of Vanadium Pentoxide in FLAKES is every mole of product of distillation 0.05g～0.1g in step (4) rectifying, and the free radical polymerization inhibitor consumption is every mole of product of distillation 0.01g～0.05g; The condition of described rectifying: vacuum tightness is in the 230Pa, and temperature is 98～102 ℃.
Preferably, described basic catalyst is one or more mixtures in sodium hydroxide, potassium hydroxide, pyridine, piperidines, thanomin and the triethylamine; Described free radical polymerization inhibitor is the one or more kinds of mixtures in Resorcinol, pyrocatechol and the tert.-butyl phenol.
Preferably, the preparation method of described cyanoacetic acid-2-methoxyl group ethyl ester is as follows:
(1) cyanoacetic acid and ethylene glycol monomethyl ether are in organic solvent, and tosic acid is catalyzer, in magnetic agitation, carry out esterification under the condition of reflux, stop the heating (reaction times about 3～6h) when moisture no longer increases in the reaction; Its reaction equation is:
(2) remove by filter white solid, filtrate is used saturated NaHCO
3Solution washing is washed to neutrality with saturated common salt again, remove moisture after, steam again except organic solvent, obtain weak yellow liquid;
(3) with above-mentioned weak yellow liquid underpressure distillation, obtain cyanoacetic acid-2-methoxyl group ethyl ester (purity is more than 98%).
Preferably, the mol ratio of described ethylene glycol monomethyl ether and cyanoacetic acid is 1.2～1.7:1.0; In molar percentage, described Catalyzed by p-Toluenesulfonic Acid agent consumption is 0.5%～3.5% of cyanoacetic acid.
Preferably, described organic solvent is again as the band aqua, a kind of in preferred ethylene dichloride, propylene dichloride, the hexanaphthene; Every mole of used volume of organic solvent of cyanoacetic acid is 150～300mL.
Preferably, the condition of described underpressure distillation: vacuum tightness 200Pa, 90～92 ℃ of temperature.
The preparation method of alpha-cyanoacrylate involved in the present invention-2-methoxyl group ethyl ester is to be starting raw material with cyanoacetic acid and ethylene glycol monomethyl ether, obtains cyanoacetic acid-2-methoxyl group ethyl ester through esterification; Under basic catalyst, obtain alpha-cyanoacrylate-2-methoxyl group ethyl ester prepolymer with formaldehyde solution generation polycondensation then, obtain alpha-cyanoacrylate-2-methoxyl group ethyl ester monomer through Pintsch process again.Compared with prior art, the inventive method has following advantage:
(1) the present invention is that catalyzer has made the cyanoacetic acid-2-methoxyl group ethyl ester raw material of purity more than 98% with the tosic acid, and technology is simple, and the reaction times is short, and catalyzer is cheap and easy to get.
(2) condensation reaction of the present invention is carried out in the alcoholic solution of Paraformaldehyde 96, is dewatering agent with the less sherwood oil of toxicity, and the dewatering agent consumption is little, and the reaction times is short.
(3) preparation method of cyanoacetic acid-2-methoxyl group ethyl ester is simple to operate, and the yield high purity is good, and purity reaches more than 98%.
(4) preparation method of alpha-cyanoacrylate-2-methoxyl group ethyl ester, its catalyzer and raw material are cheap and easy to get, and be simple to operate, and the reaction times is short, and yield and purity are higher.
Description of drawings
Fig. 1 is cyanoacetic acid-2-methoxyl group ethyl ester
1H-NMR figure.
Fig. 2 is alpha-cyanoacrylate-2-methoxyl group ethyl ester
1H-NMR figure.
Fig. 3 is tensile shear strength test synoptic diagram.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiments of the present invention are not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
The nmr analysis condition: the Avance III400MHz of Switzerland Bruker company nuclear magnetic resonance analyser, deuterochloroform is made solvent.
GC conditions: adopt Agilent7890 type gas chromatograph, HP-5 type quartz capillary chromatographic column, specification is 30m*0.32mm*0.25mm.Initial temperature is 100 ℃, keeps 2min, is warming up to 180 ℃ with the speed of 15 ℃/min, keeps 2min, and the speed with 25 ℃/min is warming up to 280 ℃ again, keeps 1min.Be carrier gas with high-purity helium, flow is 1.0mL/min.Injector temperature is 250 ℃, and sample size is 1.0 μ L.
The mass spectrum condition: adopt Agilent5975 type mass spectrograph, EI ion source, ion source temperature are 230 ℃, electron energy 70eV, and voltage 1.976kV, interface temperature is 250 ℃.
In the there-necked flask that thermometer, water trap and reflux condensing tube are housed, add the hexanaphthene of 85g cyanoacetic acid, 106g ethylene glycol monomethyl ether, 4.0g tosic acid and 200mL, load onto water trap and reflux condensing tube, reflux is opened magnetic agitation.Recording reacting time when beginning the backflow of branch water, the control temperature makes reaction be in reflux state.When treating that the volume of water no longer increases in the water trap, divide the water yield about 16mL, stop heating, have white solid in the reaction solution at this moment and separate out, naturally cool to room temperature.Remove by filter white solid, filtrate is used saturated NaHCO
3Solution washing is washed to neutrality with saturated common salt again, through separating funnel except after anhydrating, with an amount of anhydrous MgSO
4Dried overnight.Remove by filter MgSO
4, filtrate is removed hexanaphthene with the Rotary Evaporators steaming, obtain weak yellow liquid.This liquid through underpressure distillation, under 200Pa vacuum tightness, is collected 90～92 ℃ cut, obtain 115.8g cyanoacetic acid-2-methoxyl group ethyl ester, yield 81%, purity 99.1%.
1H-NMR(CDCl
3,400MHz,δppm):4.37(t,2H),3.64(t,2H),3.53(s,2H),3.41(s,3H);EI-MS:m/z45,m/z58,m/z68,m/z112;GC:99.1%。Nuclear magnetic spectrogram is seen accompanying drawing 1.
In the there-necked flask that thermometer, water trap and reflux condensing tube are housed, add the hexanaphthene of 85g cyanoacetic acid, 91.6g ethylene glycol monomethyl ether, 4.0g tosic acid and 200mL, load onto water trap and reflux condensing tube, reflux is opened magnetic agitation.Recording reacting time when beginning the backflow of branch water, the control temperature makes reaction be in reflux state.When treating that the volume of water no longer increases in the water trap, divide the water yield about 15mL, stop heating, have white solid in the reaction solution at this moment and separate out, naturally cool to room temperature.Aftertreatment is with embodiment 1.Obtain 107.3g cyanoacetic acid-2-methoxyl group ethyl ester, yield 75%, purity 98.9%.
Embodiment 3
In the there-necked flask that thermometer, water trap and reflux condensing tube are housed, add the hexanaphthene of 85g cyanoacetic acid, 106g ethylene glycol monomethyl ether, 4.8g tosic acid and 200mL, load onto water trap and reflux condensing tube, reflux is opened magnetic agitation.Recording reacting time when beginning the backflow of branch water, the control temperature makes reaction be in reflux state.When treating that the volume of water no longer increases in the water trap, divide the water yield about 17mL, stop heating, have white solid in the reaction solution at this moment and separate out, naturally cool to room temperature.Aftertreatment is with embodiment 1.Obtain 125.8g cyanoacetic acid-2-methoxyl group ethyl ester, yield 88%, purity 98.6%.
Embodiment 4
Take by weighing 100g Paraformaldehyde 96 and 200g methanol mixed, place three mouthfuls of round-bottomed flasks of 1L, add the piperidines of 0.2ml, reflux, behind the mechanical stirring 3h, Paraformaldehyde 96 is dissolved in fully and obtains the water white transparency homogeneous phase solution in the methyl alcohol, namely is that massfraction is the methanol solution of 33% Paraformaldehyde 96.
The methanol solution (containing 0.5mol formaldehyde), the 0.2mL piperidines that in the three neck round-bottomed flasks of the 500mL that reflux water-dividing device, condenser, whipping appts, thermometer and dropping funnel are housed, add the 45g Paraformaldehyde 96, stirring also is warming up to 40 ℃, drip 75.0g (0.52mol) cyanoacetic acid-2-methoxyl group ethyl ester, add in about 10min, at 75～80 ℃ of following backflow 15min.Reclaim methyl alcohol, reclaiming top temperature is 97 ℃, obtains alpha-cyanoacrylate-2-methoxyl group ethyl ester prepolymer.In above-mentioned prepolymer, then drip the 90mL sherwood oil, at 65～75 ℃ of scope internal reflux no droplet drippage to the water trap that dewaters, reclaim sherwood oil to 115 ℃ of temperature.In reaction solution, add 3.5g Vanadium Pentoxide in FLAKES and 0.5g Resorcinol rapidly, fully stir.Underpressure distillation removes remaining sherwood oil, collects product of distillation (alpha-cyanoacrylate-2-methoxyl group ethyl ester crude monomer) with the two neck flasks that 0.05g Vanadium Pentoxide in FLAKES and 0.01g Resorcinol are housed, and the condition of distillation is vacuum tightness 230Pa, 160～230 ℃ of temperature.The blending ingredients 60.5g of above-mentioned gained is carried out rectifying, and collection vacuum tightness is 230Pa, and temperature is 95～110 ℃ cut, obtains rectifying product 48.8g, productive rate 63.0%, and purity is 98.5.
1H-NMR(CDCl
3,400MHz,δppm):7.06(s,1H),6.65(s,1H),4.43(s,2H),3.67(t,2H),3.40(s,3H);EI-MS:m/z45,m/z58,m/z80,m/z124;GC:98.5%。Nuclear magnetic spectrogram is seen accompanying drawing 2.
Embodiment 5
(massfraction is 33% to the methanol solution of adding 180g Paraformaldehyde 96 in the three neck round-bottomed flasks of the 2L that reflux water-dividing device, condenser, whipping appts, thermometer and dropping funnel are housed, contain 2mol formaldehyde), the 0.8mL piperidines, stirring also is warming up to 40 ℃, drip 300.3g (2.1mol) cyanoacetic acid-2-methoxyl group-ethyl ester, add in about 30min, at 75～80 ℃ of following backflow 20min.Reclaim methyl alcohol, reclaiming top temperature is 97 ℃, obtains alpha-cyanoacrylate-2-methoxyl group ethyl ester prepolymer.In above-mentioned prepolymer, then drip the 300mL sherwood oil, at 65～75 ℃ of scope internal reflux no droplet drippage to the water trap that dewaters, reclaim sherwood oil to 115 ℃ of temperature.Add 14g Vanadium Pentoxide in FLAKES and 2g Resorcinol rapidly, fully stir.Underpressure distillation removes remaining sherwood oil, collect product of distillation (alpha-cyanoacrylate-2-methoxyl group ethyl ester crude monomer) with the two neck flasks that 0.04g Resorcinol and 0.2g Vanadium Pentoxide in FLAKES are housed, the condition of distillation is that vacuum tightness is 230Pa, and temperature is 160～230 ℃.The 240.4g blending ingredients of gained is carried out rectifying, and when vacuum tightness was 230Pa, the cut when the collection temperature is 95～105 ℃ obtained rectifying product 210.5g, productive rate 67.9%, purity 98.3%.
Embodiment 6
(1) test of tensile shear strength:
The size of standard test piece is: 100mm * 25mm * 2mm, and the lap length of test piece is 12.5 ± 0.5mm, and the material of test piece is respectively aluminium, iron, steel, and test piece overlap joint specification requires as shown in Figure 3.The quantity of sample is no less than 5.
In acetone solvent, steep 30min in advance before use at the bonded position of tinsel, with the gauze wiping that speckles with acetone solvent, dry then.Alpha-cyanoacrylate-2-methoxyl group ethyl ester is evenly spread upon in one of them test piece, then with the another one test piece by the overlapping overlap joint of bonding portion (wherein 1-cemented side seam, 2-is coated with sizing agent) as shown in Figure 3.The test piece good overlap joint is placed on the horizontal plate, and with the tinsel pad of same thickness at unsettled tinsel one end, guarantee to be parallel to each other by two bonding tinsels, and the adjustment tinsel makes its overlap fully overlapping, two edges keep point-blank.After finishing, the test piece overlap joint leaves standstill 24h.
With length and the width of vernier caliper measurement sample, and lap length; Start tension testing machine, load with the 100mm/min steady speed, the maximum load of record sample shear fracture.Calculate tensile shear strength, ask its arithmetical av, the result is as shown in table 1.
Table 1 product is to the adhesiveproperties of various materials
(2) viscosity test: get 18mL alpha-cyanoacrylate-2-methoxyl group ethyl ester and place SHP NDJ-5S type viscometer, with the 0# rotor, 21.2 ℃ of temperature, its viscosity of test is repeatedly measured and is averaged under the condition of humidity 69.4%, and the result is 5.36mPa.s.
(3) water surface film-forming properties test: the alpha-cyanoacrylate-2-methoxyl group ethyl ester sizing agent of at every turn measuring 50 μ L drips in the clear water diffusion film forming rapidly, with manual time-keeping, set time 5～6S, the about 5～8cm of film forming diameter, cured film water white transparency and bending are constantly.
The above is preferred embodiment of the present invention only, is not that the present invention is done any pro forma restriction.Every those skilled in the art utilizes technical scheme of the present invention that above-described embodiment is made any becoming, modify or differentiation etc. of being equal to, and all belongs in the scope of technical solution of the present invention.
Claims (10)
1. the preparation method of alpha-cyanoacrylate-2-methoxyl group ethyl ester is characterized in that, comprises the steps:
(1) Paraformaldehyde 96 and methanol mixed are stirred, add piperidines, reflux is dissolved in fully to Paraformaldehyde 96 and forms homogeneous phase solution in the methyl alcohol;
(2) condensation reaction takes place in the methanol solution with cyanoacetic acid-2-methoxyl group ethyl ester and Paraformaldehyde 96 under the condition of basic catalyst, obtains alpha-cyanoacrylate-2-methoxyl group ethyl ester prepolymer;
(3) add sherwood oil in above-mentioned prepolymer, the reflux dehydration when moisture no longer increases in the reaction, is reclaimed sherwood oil, adds negatively charged ion stopper Vanadium Pentoxide in FLAKES and free radical polymerization inhibitor in reaction solution, carries out the cracking distillation under the temperature more than 150 ℃;
(4) product of distillation with gained mixes with Vanadium Pentoxide in FLAKES, free radical polymerization inhibitor, then above-mentioned blending ingredients is carried out rectifying, obtains alpha-cyanoacrylate-2-methoxyl group-ethyl ester.
2. preparation method according to claim 1 is characterized in that, by weight percentage, the consumption of Paraformaldehyde 96 is 50% of methyl alcohol, and the consumption of piperidines is 0.05%～0.20% of Paraformaldehyde 96.
3. preparation method according to claim 1 is characterized in that, in the formaldehyde in the Paraformaldehyde 96 methanol solution, the mol ratio of described cyanoacetic acid-2-methoxyl group ethyl ester and formaldehyde is 1.00～1.10:1.00; In molar percentage, the consumption of described basic catalyst is 0.1%～0.6% of formaldehyde; 70～80 ℃ of setting-up point, mechanical stirring backflow 5～20min reclaims methyl alcohol.
4. preparation method according to claim 1, it is characterized in that, in the formaldehyde in the Paraformaldehyde 96 methanol solution, step (3) PetroChina Company Limited. ether consumption is 100～200mL/mol formaldehyde, the add-on of Vanadium Pentoxide in FLAKES is 5～8g/mol formaldehyde in the distillation, and free radical polymerization inhibitor is 1～3g/mol formaldehyde; The condition of described distillation: vacuum tightness is 150～300Pa, and temperature is 160～230 ℃.
5. preparation method according to claim 1 is characterized in that, the consumption of Vanadium Pentoxide in FLAKES is every mole of product of distillation 0.05g～0.1g in step (4) rectifying, and the free radical polymerization inhibitor consumption is every mole of product of distillation 0.01g～0.05g; The condition of described rectifying: vacuum tightness is in the 230Pa, and temperature is 98～102 ℃.
6. preparation method according to claim 1 is characterized in that, described basic catalyst is one or more mixtures in sodium hydroxide, potassium hydroxide, pyridine, piperidines, thanomin and the triethylamine; Described free radical polymerization inhibitor is the one or more kinds of mixtures in Resorcinol, pyrocatechol and the tert.-butyl phenol.
7. according to any described preparation method of claim 1～6, it is characterized in that the preparation method of described cyanoacetic acid-2-methoxyl group ethyl ester is as follows:
(1) cyanoacetic acid and ethylene glycol monomethyl ether are in organic solvent, and tosic acid is catalyzer, in magnetic agitation, carry out esterification under the condition of reflux, stop heating when moisture no longer increases in the reaction;
(2) remove by filter white solid, filtrate is used saturated NaHCO
3Solution washing is washed to neutrality with saturated common salt again, remove moisture after, steam again except organic solvent, obtain weak yellow liquid;
(3) with above-mentioned weak yellow liquid underpressure distillation, obtain cyanoacetic acid-2-methoxyl group ethyl ester.
8. preparation method according to claim 7 is characterized in that, the mol ratio of described ethylene glycol monomethyl ether and cyanoacetic acid is 1.2～1.7:1.0; In molar percentage, described Catalyzed by p-Toluenesulfonic Acid agent consumption is 0.5%～3.5% of cyanoacetic acid.
9. preparation method according to claim 7 is characterized in that, described organic solvent is a kind of in ethylene dichloride, propylene dichloride, the hexanaphthene; Every mole of used volume of organic solvent of cyanoacetic acid is 150～300mL.
10. preparation method according to claim 7 is characterized in that, the condition of described underpressure distillation: vacuum tightness 200Pa, 90～92 ℃ of temperature.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108689881A (en) * | 2018-07-12 | 2018-10-23 | 广州白云医用胶有限公司 | The synthetic method of α-n-octylcyanoacrylate |
| CN115260059A (en) * | 2022-07-26 | 2022-11-01 | 万华化学集团股份有限公司 | Method for preparing 2-cyano-3,3-ethyl diphenylacrylate |
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| 葛增蓓等: "α—氰基丙烯酸乙酯合成的研究(甲醛水溶液——二氯乙烷法)", 《粘接》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108689881A (en) * | 2018-07-12 | 2018-10-23 | 广州白云医用胶有限公司 | The synthetic method of α-n-octylcyanoacrylate |
| CN108689881B (en) * | 2018-07-12 | 2021-09-17 | 广州白云医用胶有限公司 | Synthesis method of alpha-n-octyl cyanoacrylate |
| CN115260059A (en) * | 2022-07-26 | 2022-11-01 | 万华化学集团股份有限公司 | Method for preparing 2-cyano-3,3-ethyl diphenylacrylate |
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