CN1245413C - Improved cyanoethyl saccharide manufacturing method - Google Patents
Improved cyanoethyl saccharide manufacturing method Download PDFInfo
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- CN1245413C CN1245413C CN 03135081 CN03135081A CN1245413C CN 1245413 C CN1245413 C CN 1245413C CN 03135081 CN03135081 CN 03135081 CN 03135081 A CN03135081 A CN 03135081A CN 1245413 C CN1245413 C CN 1245413C
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Abstract
The present invention relates to an improved method for manufacturing cyanoethyl saccharide. The cyanoethyl saccharide can be manufactured by that cane sugar and acrylonitrile make the synthesis reaction under the function of a strong alkalescence catalyst and are purified and processed with crude products, the synthesis reaction is composed of two sections, a reaction temperature of the first second is from 60 to 75 DEG C, the reaction time is from 70 to 120 minutes, a reaction temperature of the second section is 3 to 15 DEG C lower than that of the first section, and the reaction time is from 20 to 40 minutes. Because the two-step method synthesis reaction is adopted, the manufactured cyanoethyl saccharide has the advantages of large substitution degree, and high purity and yield.
Description
Technical field
The present invention relates to a kind of method of in the presence of strong alkali catalyst, making the cyanoethyl candy by sucrose and vinyl cyanide.
Technical background
The cyanoethyl candy has high-k, be applied in the information display spare as organic medium insulating material displaced loop epoxy resins, improved the electroluminescent panel brightness that information shows, strengthened work reliability, possessed high water-repellancy, self-extinguishing, reduced volume weight reduction and make advantages such as device miniaturization.United States Patent (USP) 3068220 " the insoluble cyanoethyl sucrose ether of water " has been narrated sucrose in the presence of strong alkali catalyst, method with acrylonitrile reactor generation cyanoethyl candy, reactant is mixed together at 30-70 ℃, in sucrose molecules, have at least 5 hydroxyls to be replaced by cyanoethyl, alkali catalyst is an alkali metal hydroxide, the sour catalyst neutralisation in back reacts completely, under reduced pressure from reaction mixture, remove volatile matter with distillation, to desalt and other impurity in order removing, this sticky product to be dissolved in the organic solvent of ketone or chlorinated hydrocarbons.The deficiency that exists during this method industrialization is to adopt the single step reaction method, and the cyanoethyl candy purity of acquisition is not high, and substitution value is low, and the electrical property of product does not reach index.
Summary of the invention
The present invention is just in order to overcome above-mentioned deficiency, provide that a kind of suitability for industrialized production is used, on the aforesaid method basis improved manufacturing cyanoethyl candy method, by the product purity height that this method obtains, substitution value is big, and electrical performance indexes is qualified, main innovate point is that building-up reactions divides two stages, promptly adopt two step reaction methods, first section temperature of reaction is controlled at 55-75 ℃, reacts 70-120 minute, second section temperature of reaction is lower than first section 3-15 ℃, reacts 20-40 minute.Specifically be achieved like this, improved cyanoethyl candy manufacture method, building-up reactions under the strong alkali catalyst effect makes with thick purification of product by sucrose and vinyl cyanide, it is characterized in that building-up reactions forms by two sections, first section temperature of reaction is 55-75 ℃, reaction times is 70-120 minute, and second section temperature of reaction is lower than first section 3-15 ℃, and the reaction times is 20-40 minute.For the sucrose cyanoethylation reaction, the product substitution value has a significant impact wetting ability, insulativity and specific inductivity, when substitution value is low, product can be water-soluble, the cyanoethyl candy substitution value that present method adopts two step reaction methods to obtain is big, oxygen base ionic bonding force strengthens in the glycan molecule structure, and resistance increases, and insulating property and specific inductivity improve.The cyanoethylation reaction of sucrose is the process of a more complicated, under reaction conditions, except generating the cyanoethyl candy, also has a series of side reaction, the cyanoethylation reaction of sucrose is a thermopositive reaction, when reaction was in the low degree of substitution process, positive reaction speed was very fast, and side reaction is then slow, but along with increasing gradually of substitution value, positive reaction speed is slack-off, and side reaction speed speeds, so that hinders carrying out smoothly of positive reaction.In order effectively to guarantee carrying out smoothly of positive reaction, resist side reaction to bottom line, the present invention adopts two step reaction methods, and beginning is carried out under comparatively high temps, then suitably reduces temperature of reaction, and not only substitution value is big and purity is high for the product of producing like this.In the synthetic method of the present invention, the optimum temps of first section reaction is 65-70 ℃, and optimum reacting time is 80-110 minute, and second section optimum temps is 55-62 ℃, and optimum reacting time is 20-30 minute.
In the building-up reactions of the present invention, what catalyzer was selected for use is alkali metal hydroxide, in the industrialization from cost consideration, especially be best with sodium hydroxide, the height of naoh concentration is also influential to reaction, excessive concentration or mistake are low all can to impact product color and yield, and the naoh concentration that the present invention adopts is controlled at about 1-2% (weight).
In order not only to guarantee product yield but also do not increase vinyl cyanide and the recovery of oxygen sodium oxide and neutralizing treatment amount, the proportion relation of raw material is in the two step reaction methods of the present invention: vinyl cyanide: sucrose=3.5-2.5: 1, sodium hydroxide: sucrose=0.16-0.28: 1, wherein especially with vinyl cyanide: sucrose=3.0-2.6: 1, sodium hydroxide: sucrose=0.19-0.24: 1 is best.
After second period reaction times arrives, with in the acid and system in the alkaline catalysts termination reaction, reclaim excessive vinyl cyanide, the recovery of vinyl cyanide is to add deionized water, reclaim with distillating method, separate out the thick product of cyanoethyl candy simultaneously, at this moment, this thick product is white or slight yellowy sticking shape liquid.
In reaction process, be difficult in the product removing owing to exist side reaction, the by product of generation to be mingled in, for the good cyanoethyl candy product of obtained performance, also must carry out purification process to the thick product of cyanoethyl candy.The purification process that the present invention adopts is the method for washing the cyanoethyl candy in conjunction with deionized water system alcohol with alcohol, benzene class organic solvent, and promptly purification process was made up of three steps, is followed successively by that deionized water is washed, pure, benzene class organic solvent alcohol/benzene is washed and vacuum-drying.The water temperature that deionized water is washed is controlled at 20-40 ℃, in order to remove a large amount of side reaction products and excessive acid and sodium salt; In the product after washing, still leave a spot of by product, practice shows, being used for the organic solvent that alcohol/benzene washes can be benzene, toluene, ethanol, methyl alcohol etc., wherein be best especially with methyl alcohol, methyl alcohol is having abundant dispersion cyanoethyl candy and don't dissolved characteristic below 10 ℃, and good compatibility is arranged with by product, and when temperature surpasses 15 ℃, methyl alcohol begins to present solvability to the cyanoethyl candy, and increases along with the rising of temperature, is to carry out repetitive scrubbing with methyl alcohol so alcohol of the present invention is washed, wash temperature is controlled at about 10 ℃ ± 2 ℃, when treating pure washing lotion now milkiness not being clear then alcohol wash complete; Product after the purification process carries out vacuum-drying at last, removes retention methyl alcohol and small amount of moisture wherein, more than the control vacuum tightness 750mmHg, temperature 25-100 ℃, no longer presents to the product till the bubble.
The present invention is owing to adopt the two step method building-up reactions, the cyanoethyl candy substitution value that makes is big, purity and productive rate height, adopting deionized water and alcohol, benzene class organic solvents in particular is the purification process that methyl alcohol alcohol is washed, it is light to colourless that product color is subtracted greatly, and a spot of low degree of substitution product in the by product of the overwhelming majority and the reaction can be dissolved by methyl alcohol-deionized water system, almost can all remove, guarantee the quality of product.
Embodiment
Embodiment 1, in stainless steel cauldron, successively add 1 portion of sucrose, 0.2 the catalyzer oxygen aqueous solution of sodium oxide of part 1.35%, under agitation be heated to 55-60 ℃, make sucrose all be added 2.7 parts of fine propylene nitriles by the moistening activation of alkali aqueous solution back, building-up reactions is finished by two sections, and the fs keeps about 66 ℃ and carries out cyanoethylation reaction, 90 minutes time length, be cooled to rapidly and carry out second section reaction about 59 ℃, reaction times is 30 minutes, and the alkaline catalysts that adds in the acetic acid neutralization reaction system stops building-up reactions, then adds appropriate amount of deionized water, excessive vinyl cyanide is reclaimed in distillation, and the thick product of cyanoethyl candy is then come out by precipitating.
The purification process process of thick product cyanoethyl candy is:
(1) deionized water washing.Thick product under agitation carries out repetitive scrubbing with 20-40 ℃ deionized water, and washing lotion is extracted discharging out by vacuum system, treats that the resistance of washing lotion can maintain 100K Ω cm/cm
2Below promptly washing finishes;
(2) alcohol is washed.Product after the washing carries out repetitive scrubbing with about 10 ℃ methyl alcohol again, when treating pure washing lotion now milkiness not being clear then alcohol wash complete.
(3) vacuum-drying.Is about 760mmHg with the product after purified in vacuum tightness, and temperature is for carrying out vacuum-drying under 25-100 ℃, no longer present to the product steam bubble then drying finish.
Embodiment 2, in stainless steel cauldron, successively add 1 portion of sucrose, 0.25 the catalyzer oxygen potassium oxide aqueous solution of part 1.5%, under agitation be heated to 55-60 ℃, make sucrose all be added 3 parts of fine propylene nitriles by the moistening activation of alkali aqueous solution back, building-up reactions is finished by two sections, and the fs keeps about 69 ℃ and carries out cyanoethylation reaction, 80 minutes time length, be cooled to rapidly and carry out second section reaction about 60 ℃, reaction times is 25 minutes, and the alkaline catalysts that adds in the acetic acid neutralization reaction system stops building-up reactions, then adds appropriate amount of deionized water, excessive vinyl cyanide is reclaimed in distillation, and the thick product of cyanoethyl candy is then come out by precipitating.
The purification process process of thick product cyanoethyl candy is with embodiment 1.
Embodiment 3, in stainless steel cauldron, successively add 1 portion of sucrose, 0.18 the catalyzer oxygen aqueous solution of sodium oxide of part 1.8%, under agitation be heated to 55-60 ℃, make sucrose all be added 3.2 parts of fine propylene nitriles by the moistening activation of alkali aqueous solution back, building-up reactions is finished by two sections, and the fs keeps about 63 ℃ and carries out cyanoethylation reaction, 120 minutes time length, be cooled to rapidly and carry out second section reaction about 58 ℃, reaction times is 35 minutes, and the alkaline catalysts that adds in the acetic acid neutralization reaction system stops building-up reactions, then adds appropriate amount of deionized water, excessive vinyl cyanide is reclaimed in distillation, and the thick product of cyanoethyl candy is then come out by precipitating.
Second step adopted benzene to wash in the purification process process of thick product cyanoethyl candy, and all the other are with embodiment 1.
Claims (13)
1. cyanoethyl candy manufacture method, make by sucrose and vinyl cyanide building-up reactions and thick purifying products handled under the strong alkali catalyst effect, it is characterized in that building-up reactions forms by two sections, first section temperature of reaction is 60-75 ℃, reaction times is 70-120 minute, second section temperature of reaction is lower than first section 3-15 ℃, and the reaction times is 20-40 minute.
2. manufacture method according to claim 1, the temperature that it is characterized in that first section reaction in the building-up reactions is 65-70 ℃, and the reaction times is 80-110 minute, and the temperature of second section reaction is 55-62 ℃, and the reaction times is 20-30 minute.
3. manufacture method according to claim 1 and 2 is characterized in that strong alkali catalyst is an alkali metal hydroxide.
4. manufacture method according to claim 3 is characterized in that alkali metal hydroxide is a sodium hydroxide.
5. manufacture method according to claim 4, the weight percent concentration that it is characterized in that sodium hydroxide is 1-2%.
6. manufacture method according to claim 5 is characterized in that the proportion relation of raw material in the building-up reactions is: vinyl cyanide: sucrose=3.5-2.5: 1, and sodium hydroxide: sucrose=0.16-0.28: 1.
7. manufacture method according to claim 6 is characterized in that the proportioning raw materials pass is: vinyl cyanide: sucrose=3.0-2.6: 1, and sodium hydroxide: sucrose=0.19-0.24: 1.
8. according to manufacture method according to claim 1 and 2, it is characterized in that building-up reactions is with in the acid and the alkaline catalysts termination reaction in the system, add deionized water again, excessive vinyl cyanide is reclaimed in distillation, separate out the thick product of cyanoethyl candy simultaneously.
9. manufacture method according to claim 1 and 2 is characterized in that thick purification of product is made up of three steps, is followed successively by deionized water washing, pure, benzene class organic solvent alcohol/benzene is washed and vacuum-drying.
10. manufacture method according to claim 9 is characterized in that the water temperature that deionized water is washed is controlled at 20-40 ℃.
11. manufacture method according to claim 9 is characterized in that the organic solvent that alcohol/benzene is washed is benzene or toluene or ethanol or methyl alcohol.
12. manufacture method according to claim 9 is characterized in that the organic solvent that alcohol/benzene is washed is a methyl alcohol, wash temperature is controlled at 10 ℃ ± 2 ℃.
13. manufacture method according to claim 9 is characterized in that vacuum drying vacuum degree control more than 750mmHg, temperature is 25-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03135081 CN1245413C (en) | 2003-09-27 | 2003-09-27 | Improved cyanoethyl saccharide manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03135081 CN1245413C (en) | 2003-09-27 | 2003-09-27 | Improved cyanoethyl saccharide manufacturing method |
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| CN1528771A CN1528771A (en) | 2004-09-15 |
| CN1245413C true CN1245413C (en) | 2006-03-15 |
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| CN 03135081 Expired - Fee Related CN1245413C (en) | 2003-09-27 | 2003-09-27 | Improved cyanoethyl saccharide manufacturing method |
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| CN105963160A (en) * | 2016-05-06 | 2016-09-28 | 韩山师范学院 | Pure natural plant essential oil mosquito repellent ointment and preparation method thereof |
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