CN103613747B - A kind of preparation method of 2,4-Sorbic Acid polyester - Google Patents
A kind of preparation method of 2,4-Sorbic Acid polyester Download PDFInfo
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- CN103613747B CN103613747B CN201310587234.6A CN201310587234A CN103613747B CN 103613747 B CN103613747 B CN 103613747B CN 201310587234 A CN201310587234 A CN 201310587234A CN 103613747 B CN103613747 B CN 103613747B
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- sorbic acid
- acid polyester
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- hexanolactam
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Abstract
The invention provides a kind of 2, the preparation method of 4-Sorbic Acid polyester, comprise the following steps: add 500-650 weight part Beta-methyl propenal and 3-15 parts by weight of titanium dioxide-silicon-dioxide-hexanolactam composite catalyst in a kettle., stirring, is pass into ketene gas under the condition of 35 ~ 50 DEG C to react, after having reacted in temperature, filter, by reaction solution after negative pressure rectifying, obtain 2,4-Sorbic Acid polyester.The condensation catalyst of the method adopts titania-silica-hexanolactam composite catalyst, improves Beta-methyl acrolein conversion rate and improves product 2,4-Sorbic Acid polyester yield simultaneously, and reduces the wastewater flow rate produced and produce; The method makes raw material Beta-methyl propenal per pass conversion reach 95%, 2,4-Sorbic Acid polyester once through yield to reach more than 90%.
Description
Technical field
The invention belongs to chemical production field, be specifically related to a kind of preparation method of 2,4-Sorbic Acid polyester.
Background technology
2,4-Sorbic Acid polyester is the important intermediate of production 2,4-Sorbic Acid.2,4-Sorbic Acid is white needles or Powdered crystal, is slightly soluble in water, can be dissolved in multiple organic solvent.The molecular weight of 2,4-Sorbic Acid: 112.13; Fusing point: 132-135 DEG C; Boiling point: 228 DEG C (decomposition); Density: 1.204(19 DEG C);
Flash-point: 127 DEG C.2,4-Sorbic Acid a kind ofly has the unsaturated fatty acids gripping diene altogether, it can the activity of mould fungus inhibition, yeast and aerobic bacteria effectively, and it suppresses the effect of harmful microorganism development and fecundity stronger than germicidal action, is the sanitas that United Nations's grain tissue is recommended to countries in the world.2,4-Sorbic Acid has been widely used in the anticorrosion and fresh-keeping of the industries such as various food, veterinary antibiotics, medicine, rubber, papermaking, animal-feed, makeup, paint, tobacco, beverage.
The technique of prior art synthesis 2,4-Sorbic Acid polyester: exemplary production method is that Glacial acetic acid Pintsch process generates ketene, gluing shape product polyester in the middle of the condensation under catalyst action of ketene and Beta-methyl propenal generates.The shortcoming of this technique is: in the selection of catalyzer, its catalyzer mainly used has zinc acetate, methylacrylic acid zinc, α-methylpyridine, zinc chloride, aluminum chloride etc., make raw material Beta-methyl acrolein conversion rate low, produce upper raw material Beta-methyl acrolein conversion rate at present and only have 80%; 2,4-Sorbic Acid polyester yield is low, produces upper 2,4-Sorbic Acid polyester yields at present and is only 85%.
Summary of the invention
In order to solve the problem, the object of the invention is the preparation method providing a kind of 2,4-Sorbic Acid polyester, and raw material Beta-methyl acrolein conversion rate is improved, and product 2,4-Sorbic Acid polyester yield improves.
Technical solution of the present invention is as follows: a kind of 2, the preparation method of 4-Sorbic Acid polyester, it is characterized in that, comprise the following steps: add 500-650 weight part Beta-methyl propenal and 3-15 parts by weight of titanium dioxide-silicon-dioxide-hexanolactam composite catalyst in a kettle., stir, be pass into ketene gas under the condition of 35 ~ 50 DEG C to react in temperature, after having reacted, filter, by reaction solution after negative pressure rectifying, obtain 2,4-Sorbic Acid polyester.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, further preferably, 580-620 weight part Beta-methyl propenal and 7-12 parts by weight of titanium dioxide-silicon-dioxide-hexanolactam composite catalyst is added in this preparation method.
According to provided by the invention 2, the preparation method of 4-Sorbic Acid polyester, preferably, the mass percent of described titania-silica-hexanolactam composite catalyst consists of: titanium dioxide: 10 ~ 20%, silicon-dioxide: 30 ~ 60%, hexanolactam: 25 ~ 60%.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, further preferably, in described titania-silica-hexanolactam composite catalyst, the mass percent of hexanolactam is: 35 ~ 50%.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, further preferably, in described titania-silica-hexanolactam composite catalyst, the mass percent of titanium dioxide is: 15 ~ 18%.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, further preferably, in described titania-silica-hexanolactam composite catalyst, the mass percent of silicon-dioxide is: 40 ~ 45%.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, preferably, the intake of described ketene is 300 ~ 390 weight parts.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, further preferably, the intake of described ketene is 345 ~ 372 weight parts.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, preferably, the time that described ketene gas passes into is 2 ~ 4 hours.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, preferably, described ketene gas ventilation is incubated 1 ~ 3 hour after terminating at 35 ~ 50 DEG C.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, preferably, the vacuum tightness of described negative pressure rectifying is 0.095 ~ 0.10MPa.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, further preferably, the vacuum tightness of described negative pressure rectifying is 0.098 ~ 0.099MPa.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, preferably, described reaction solution is reclaimed unreacted raw material Beta-methyl propenal through negative pressure rectifying.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, described titania-silica-hexanolactam composite catalyst is made up of following steps:
Butyl (tetra) titanate is hydrolyzed in 0.1mol/L hydrochloric acid and obtains TiO
2sol A; Again tetraethoxy is hydrolyzed in the mixing solutions of 0.2mol/L hydrochloric acid and ethanol and obtains SiO
2sol B; A and B is mixed, obtains TiO
2/ SiO
2colloidal sol C; By massfraction be 90% aqueous ethanolic solution add in colloidal sol C, washing and drying; Again that hexanolactam is soluble in water, obtain solution D, instilled in solution D by colloidal sol C, washing and drying, obtains titania-silica-hexanolactam composite catalyst.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, in the preparation of wherein said titania-silica-hexanolactam composite catalyst, preferably, described aqueous ethanolic solution massfraction is 80-98%.
According to the preparation method of 2,4-Sorbic Acid polyester provided by the invention, in the preparation of wherein said titania-silica-hexanolactam composite catalyst, further preferably, described aqueous ethanolic solution massfraction is 90%.
Titania-silica of the present invention-hexanolactam composite catalyst filters after completion of the reaction to be applied mechanically to next batch, applies mechanically and criticizes postactivated re-using at the most.
Ketene of the present invention is made up at 700-800 DEG C of Pintsch process of Glacial acetic acid.
Provided by the invention with Beta-methyl propenal and ketene for raw material, condensation is formed in 2,4-Sorbic Acid PET Process, and the selection of catalyzer is the key improving Beta-methyl acrolein conversion rate and improve 2,4-Sorbic Acid polyester yield.The present invention is directed to this condensation gordian technique difficult problem, develop 2,4-Sorbic Acid polyester synthetic process of the present invention.Catalyzer of the present invention is titania-silica-hexanolactam composite catalyst.
The preparation method of titania-silica of the present invention-hexanolactam composite catalyst:
Butyl (tetra) titanate is hydrolyzed in 0.1mol/L hydrochloric acid and obtains TiO
2sol A; Again tetraethoxy is hydrolyzed in the mixing solutions of 0.2mol/L hydrochloric acid and ethanol and obtains SiO
2sol B; A and B is mixed, obtains the TiO that achromaticity and clarification is transparent
2/ SiO
2colloidal sol C; By massfraction be 90% aqueous ethanolic solution add in colloidal sol C, washing and drying, obtains catalyzer TS; Hexanolactam is soluble in water, and obtain solution D, instilled in solution D by colloidal sol C, washing and drying, obtains catalyzer TSN-1.
Wherein, described TS catalyzer also can make Beta-methyl propenal and ketene be condensed into 2,4-Sorbic Acid polyester, but the adding of hexanolactam in TSN-1, better can improve the activity of titanium, improve the yield of polyester.
Catalyzer TSN-1 of the present invention is titania-silica-hexanolactam composite catalyst; Catalyzer TS of the present invention is titania-silica catalyzer.
2,4-Sorbic Acid polyester is production 2, the important intermediate of 4-Sorbic Acid, the finished product 2 in prior art processes, 4-Sorbic Acid wastewater flow rate is that 1 ton of product produces 3-4 ton waste water, and applies 2,4-Sorbic Acid polyester process provided by the invention in production process, produce the waste water that 1 ton of 2,4-Sorbic Acid produces 2 tons.
Advantageous Effects:
Provided by the invention 2, the preparation method of 4-Sorbic Acid polyester, the condensation catalyst of the method adopts titania-silica-hexanolactam composite catalyst, improve Beta-methyl acrolein conversion rate and improve product 2 simultaneously, 4-Sorbic Acid polyester yield, and reduce the wastewater flow rate produced and produce; The method makes raw material Beta-methyl propenal per pass conversion reach 95%, 2,4-Sorbic Acid polyester once through yield to reach more than 90%.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, it will be appreciated by those skilled in the art that described embodiment is only for example, and do not form any restriction to the present invention.
Ketene described in the present invention is by Glacial acetic acid under 700 ~ 800 DEG C of conditions, and in acetic acid cracking stove, Pintsch process makes ketene.
Embodiment 1: the preparation method of titania-silica-caprolactam composite catalyst:
8.8083g butyl (tetra) titanate is hydrolyzed in 103.6ml0.1mol/L hydrochloric acid and obtains TiO2 Sol A; Again 21.5544g tetraethoxy is hydrolyzed in the mixing solutions of 12.8ml0.2mol/L hydrochloric acid and 15.4ml ethanol and obtains SiO2 sol B; A and B is mixed, stirs 0.5 hour, obtain the TiO2/SiO2 colloidal sol C that achromaticity and clarification is transparent; Be dissolved in 780g water by 11.7099g hexanolactam, obtain solution D, instilled in solution D by colloidal sol C, washing and drying, obtains titania-silica-hexanolactam composite catalyst.
The preparation method of embodiment 2:2,4-Sorbic Acid polyester
550Kg Beta-methyl propenal and 5Kg titania-silica-hexanolactam composite catalyst is added in 1500L reactor, start stirring, be warming up to 40 DEG C, and control temperature passes into 330Kg ketene gas between 40 ± 1 DEG C reacts, after having reacted, filtering catalyst, reaction solution is reclaimed Beta-methyl propenal 27Kg(per pass conversion 95.1% through negative pressure rectifying (vacuum tightness 0.098MPa)) apply mechanically to next batch, obtain high viscosity 2,4-Sorbic Acid polyester 757.3Kg, once through yield 90.5%.
The preparation method of embodiment 3:2,4-Sorbic Acid polyester
580Kg Beta-methyl propenal and 7Kg titania-silica-hexanolactam composite catalyst is added in 1500L reactor, start stirring, be warming up to 45 DEG C, and control temperature passes into 345Kg ketene gas between 45 ± 1 DEG C reacts, after having reacted, filtering catalyst, reaction solution is reclaimed Beta-methyl propenal 24.4Kg(per pass conversion 95.8% through negative pressure rectifying (vacuum tightness 0.099MPa)) apply mechanically to next batch, obtain high viscosity 2,4-Sorbic Acid polyester 809.8Kg, once through yield 91.1%.
The preparation method of embodiment 4:2,4-Sorbic Acid polyester
620Kg Beta-methyl propenal and 12Kg titania-silica-hexanolactam composite catalyst is added in 1500L reactor, start stirring, be warming up to 45 DEG C, and control temperature passes into 372Kg ketene gas between 45 ± 1 DEG C reacts, after having reacted, filtering catalyst, reaction solution is reclaimed Beta-methyl propenal 27.3Kg(per pass conversion 95.6% through negative pressure rectifying (vacuum tightness 0.10MPa)) apply mechanically to next batch, obtain high viscosity 2,4-Sorbic Acid polyester 861.1Kg, once through yield 90.8%.
The preparation method of embodiment 5:2,4-Sorbic Acid polyester
650Kg Beta-methyl propenal and 15Kg titania-silica-hexanolactam composite catalyst is added in 1500L reactor, start stirring, be warming up to 48 DEG C, and control temperature passes into 390Kg ketene gas between 48 ± 1 DEG C reacts, after having reacted, filtering catalyst, reaction solution is reclaimed Beta-methyl propenal 25.4Kg(per pass conversion 96.1% through negative pressure rectifying (vacuum tightness 0.10MPa)) apply mechanically to next batch, obtain high viscosity 2,4-Sorbic Acid polyester 906.4Kg, once through yield 90.7%.
Comparative example 1:
In 1500ml condensation reaction still, add 1000g Beta-methyl propenal and 10g methylacrylic acid zinc catalyst, then pass into the ketene gas that cracking obtains, condensation obtains 2,4-Sorbic Acid polyester.Beta-methyl propenal per pass conversion is that 80.3%(can apply mechanically to next batch), obtain high viscosity 2,4-Sorbic Acid polyester 1097 grams, once through yield 85.4%.
Get the hydrochloric acid 5000g that Sorbic Acid polyester 1000g adds 30%, be warmed up to 80 DEG C of insulation depolymerization reactions 3 hours, cold filtration obtains crude product Sorbic Acid.Crude product Sorbic Acid add water 5000ml with 30% aqueous sodium hydroxide solution to carry out alkali molten, adjust after pH value to 7.5 and add 100g activated carbon decolorizing except tar removing, filter, in filtrate hydrochloric acid and acid out, adjust pH value to 2.5, filter, washing, dry, obtain the finished product Sorbic Acid 832g of white, content is greater than 99.5%, is 83.2% to the depolymerization yield of Sorbic Acid polyester, produces 2936g brine waste.
Provided by the invention 2, the preparation method of 4-Sorbic Acid polyester, the condensation catalyst of the method adopts titania-silica-hexanolactam composite catalyst, improve Beta-methyl acrolein conversion rate and improve product 2 simultaneously, 4-Sorbic Acid polyester yield, and reduce the wastewater flow rate produced and produce; The method makes raw material Beta-methyl propenal per pass conversion reach 95%, 2,4-Sorbic Acid polyester once through yield to reach more than 90%.
Below the present invention is disclosed with preferred embodiment; all catalyst combination embodiments are not showed; so it is not intended to limiting the invention, and all employings are equal to replacement or the technical scheme that obtains of equivalent transformation mode, all drop within protection scope of the present invention.
Claims (9)
1. one kind 2, the preparation method of 4-Sorbic Acid polyester, it is characterized in that, comprise the following steps: add 500-650 weight part Beta-methyl propenal and 3-15 parts by weight of titanium dioxide-silicon-dioxide-hexanolactam composite catalyst in a kettle., stir, be pass into ketene gas under the condition of 35 ~ 50 DEG C to react in temperature, after having reacted, filter, by reaction solution after negative pressure rectifying, obtain 2,4-Sorbic Acid polyester;
The mass percent of described titania-silica-hexanolactam composite catalyst consists of: titanium dioxide: 10 ~ 20%, silicon-dioxide: 30 ~ 60%, hexanolactam: 25 ~ 60%.
2. the preparation method of 2,4-Sorbic Acid polyester according to claim 1, is characterized in that: the mass percent of the hexanolactam in described titania-silica-hexanolactam composite catalyst is: 35 ~ 50%.
3. the preparation method of 2,4-Sorbic Acid polyester according to claim 1, is characterized in that: the intake of described ketene is 300 ~ 390 weight parts.
4. the preparation method of 2,4-Sorbic Acid polyester according to claim 1, is characterized in that: the time that described ketene gas passes into is 2 ~ 4 hours.
5. the preparation method of 2,4-Sorbic Acid polyester according to claim 1, is characterized in that: at 35 ~ 50 DEG C, be incubated 1 ~ 3 hour after described ketene gas ventilation terminates.
6. the preparation method of 2,4-Sorbic Acid polyester according to claim 1, is characterized in that: the vacuum tightness of described negative pressure rectifying is 0.095 ~ 0.10MPa.
7. the preparation method of 2,4-Sorbic Acid polyester according to claim 1, is characterized in that: be describedly used for reclaiming unreacted raw material Beta-methyl propenal through negative pressure rectifying by reaction solution.
8. the preparation method of 2,4-Sorbic Acid polyester according to claim 1, is characterized in that: described titania-silica-hexanolactam composite catalyst is made up of following steps:
Butyl (tetra) titanate is hydrolyzed in 0.1mol/L hydrochloric acid and obtains TiO
2sol A; Again tetraethoxy is hydrolyzed in the mixing solutions of 0.2mol/L hydrochloric acid and ethanol and obtains SiO
2sol B; A and B is mixed, obtains TiO
2/ SiO
2colloidal sol C; Aqueous ethanolic solution is added in colloidal sol C, washing and drying; Again that hexanolactam is soluble in water, obtain solution D, instilled in solution D by colloidal sol C, washing and drying, obtains titania-silica-hexanolactam composite catalyst.
9. the preparation method of 2,4-Sorbic Acid polyester according to claim 8, is characterized in that: described aqueous ethanolic solution massfraction is 80-98%.
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| CN105712869B (en) * | 2016-04-29 | 2018-03-27 | 南通大学 | Activated carbon briquetting to be decolourized for sorbic acid and preparation method thereof |
| CN109608629B (en) * | 2018-12-10 | 2020-11-17 | 沈阳化工大学 | Poly-3-hexenedioic acid-1, 2-propylene glycol ester polar flexibilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1850768A (en) * | 2006-05-25 | 2006-10-25 | 宁波王龙集团有限公司 | Process for preparing high purity crystalline sorbic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1850768A (en) * | 2006-05-25 | 2006-10-25 | 宁波王龙集团有限公司 | Process for preparing high purity crystalline sorbic acid |
Non-Patent Citations (2)
| Title |
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| 基于TiO2/SiO2溶胶的新型PET缩聚催化剂的合成;殷明等;《高等学校化学学报》;20100228;第31卷(第2期);第418-420页 * |
| 山梨酸的制备;靳通收等;《河北大学学报（自然科学版）》;19870402(第1期);第24页、第26页 * |
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