CN1903822A - Method of synthesizing glutaric acid by environment friendly phase transfer catalyst catalyzing and oxidizing cyclopentene - Google Patents
Method of synthesizing glutaric acid by environment friendly phase transfer catalyst catalyzing and oxidizing cyclopentene Download PDFInfo
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- CN1903822A CN1903822A CN 200610029712 CN200610029712A CN1903822A CN 1903822 A CN1903822 A CN 1903822A CN 200610029712 CN200610029712 CN 200610029712 CN 200610029712 A CN200610029712 A CN 200610029712A CN 1903822 A CN1903822 A CN 1903822A
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Abstract
The present invention relates to a method for synthesizing pentandioic acid by using phase transfer catalyst friendly to environment to catalytically oxidate cyclopentene. It is characterized by that said invention uses a phase transfer compound [Pi-C5H5NC16H33]m{PO4[WO3]n} as catalyst, under the condition of 46-100deg.C uses hydrogen peroxide aqueous solution as oxidant to catalytically oxidate cyclopentene so as to synthesize pentandioic acid. Its yield can be up to 95% and its purity is greater than or equal to 99.0%.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of eco-friendly method of utilizing the aqueous hydrogen peroxide solution catalytically oxidizing cyclopentene to prepare pentanedioic acid.
Background technology
Pentanedioic acid is extremely important industrial chemicals, has at aspects such as chemistry, building, medicine, agriculturals widely to use.In plastics industry, pentanedioic acid and alkyl esters thereof also can be used as the composition of the polyester plasticizer of polyvinyl chloride as the intermediate of softening agent such as polyvinyl chloride, polyester, polymeric amide.Polyester glutarate has the weather resistance plastification as softening agent, is used for the manufacturing of polyvinyl chloride.Aspect medical,, be used to prepare each sterilization and disinfection washing lotion and medicine because it has broad-spectrum bactericidal capacity.Pentanedioic acid not only has killing action to the bacterium on the zooparasite bodily tissue, to planting disease and pest also is agent for killing preferably, as being raw material with the pentanedioic acid, kill the virus washing lotion and sterilization foam and other killing agents that are mixed with, can kill the bacterium that parasitizes on animal, the plant, insect etc., also can be used for insect protected.In addition, pentanedioic acid also can be used for the synthesizing liquid polyester, the molecular structure of improvement PET fiber, thus the dyeability of improvement ET fiber improves dye uptake.Utilize tackiness agent that pentanedioic acid makes can extensive bonding textiles, metal etc.In addition, pentanedioic acid or its ester also can be used for the washing of stack gases such as the preparation of synthetic, scale remover of polyester polyol and sulfur-bearing etc.Recently, Pyroglutaric acid is as important organic synthesis intermediate, and its consumption is greatly improved, and Pyroglutaric acid almost 100% is made by pentanedioic acid dehydration.So, press for a large amount of highly purified industrial pentanedioic acids.
Pentanedioic acid generally obtains by separating among the byproduct dicarboxylic acid mixture in the hexanodioic acid production process.Because the improvement of adipic acid, the pentanedioic acid of its by-product is fewer and feweri.Therefore, press for the route of synthesis of development of new pentanedioic acid.Traditional cyclopentanol or cyclopentanone nitric acid oxidation method generally are not used further to large-scale commercial production because environmental pollution is serious.Consider that from the angle of protection environment the method for research and development novel environmental close friend's catalytic selective oxidation synthesizing glutaric acid seems necessary.
Recently, people such as K.Sato report (Science 1998,281 (5383), 1646) is at consisting of phase-transferring agent tricaprylmethylammonium hydrosulfate [(n-C
8H
17)
3N (CH
3)] HSO
4When existing, with Na
2WO
42H
2O is a catalyzer, and under the condition of organic solvent-free, the yield of the hydrogen peroxide oxidation cyclopentenes with 30% reaches about 90%.Can directly obtain the highly purified pentanedioic acid of 80% yield after the reaction mixture cooling.Yet tricaprylmethylammonium hydrosulfate price is very expensive, and suitability for industrialized production both at home and abroad all is unrealized.The more important thing is that this catalyzer generally can only use once, can't reuse, increased the cost of this technology greatly, limited it and applied.
Behind the seventies, along with developing rapidly of petrochemical complex, the amount of by-product C 5 fraction significantly increases in the ethylene cracker, and the cyclopentadiene resource is abundant day by day.With the cyclopentadiene in the C 5 fraction is raw material, and partial hydrogenation is made cyclopentenes, carries out oxicracking with hydrogen peroxide then and makes the good approach that pentanedioic acid is a synthesizing glutaric acid.Cyclopentadiene is a byproduct in the petrochemical industry, for example C of ethylene project by-product
5Contain 15～25% cyclopentadiene (300,000 tons of ethylene project is produced 2500～3500 tons of cyclopentadiene per year) in the fraction, 4% cyclopentenes.Also mainly contain cyclopentadiene in the foreshot (benzene head part) in coke-oven plant's system benzene process.At present, cyclopentadiene as fuel, wastes except that being used for synthetic ferrocene, epoxy monomer and pyrethrin on a small quantity mostly, and is very unfortunate.The research work of external this respect is carried out early, existing several companies have solved the problem of utilizing of number of C 5 fractions preferably, but most of C5 do not utilized yet preferably, are resolved far away about the problem of its comprehensive utilization, so, also become very urgent about the problem of comprehensive utilization of C 5.Therefore, be that the technology of raw material production pentanedioic acid will have superiority manyly than additive method on the utilization of resources and production cost with the cyclopentadiene, have very strong competitive power.
The technology that with the cyclopentadiene is the raw material production pentanedioic acid mainly is made up of following a few step reactions steps, and promptly dicyclopentadiene depolymerizes to cyclopentadiene monomers earlier, and cyclopentadiene monomers generates cyclopentenes through selective catalytic hydrogenation then.The first step depolymerization yield is more than 95%, and the second step hydrogenation yield can reach 97%, and cyclopentenes generates pentanedioic acid through catalyzed oxidation again, and the whole process raw material availability is higher.Wherein, the depolymerization of double focusing cyclopentadiene has maturation process, the technology of cyclopentadiene selective hydrogenation preparing cyclopentene also after deliberation extremely successful, this two the step all need not to add research.Problem is after the cyclopentadiene selective hydrogenation is cyclopentenes, how to select suitable oxidizing condition, and the energy highly selective is with the carbon-carbon double bond oxidation scission of cyclopentenes, and the generation pentanedioic acid, just becomes this technology key of industrialization smoothly.The present invention discloses a kind of method with cyclopentenes selective oxidation synthesizing glutaric acid of remarkable industrial prospect at this committed step just.
Summary of the invention
The object of the present invention is to provide the method for a kind of more environmental friendliness, efficient and practical catalytically oxidizing cyclopentene synthesizing glutaric acid.
The method of the catalytically oxidizing cyclopentene synthesizing glutaric acid that the present invention proposes is to use the phase transition compound [π-C with reaction control characteristic
5H
5NC
16H
33]
m{ PO
4[WO
3]
n(m=3～7; N=4～12) being catalyzer, is oxygenant with the aqueous hydrogen peroxide solution of 27-50%, at 46～100 ℃ of catalytically oxidizing cyclopentenes, reacts 8～24 hours, obtains the pentanedioic acid product; Wherein the mol ratio of hydrogen peroxide and cyclopentenes is 4～5, and catalyst consumption is 0.2～5% of a raw material cyclopentenes mole number.
Concrete steps of the present invention are as follows: described catalyzer and oxygenant are mixed, stir and drip cyclopentenes down; The oil bath heating, 46～100 ℃ of temperature are bathed in control; Kept the reactant back flow reaction then 8～24 hours; Leach the catalyzer of separating out, in order to secondary response use down; Separate out crystal from reacted filtered liquid, be required pentanedioic acid product, be white, total recovery can reach 90-95%, and fusing point is 97-99 ℃.In the above-mentioned steps, separate out crystal from filtered liquid, crystal is separated out in cooling below can earlier reaction solution being placed ℃; Leach crystal then, washing, drying gets the pentanedioic acid product; Through further evaporation, can obtain part pentanedioic acid product to residual filtrate.
The maximum characteristics of phase-transfer catalyst involved in the present invention are that this catalyzer is a homogeneous phase when reaction, in case hydrogen peroxide is exhausted, reaction finishes, and can separate out from reaction system, thereby can separate with reaction mixture very easily.It is equal phase character in reaction that this characteristic makes catalyzer, active high, stable reaction; Reaction becomes heterogeneous catalyst again after finishing, and is easy to and reactants separate, can significantly reduce production process, reduces labour intensity and production cost.And, because this catalyzer has quaternary ammonium salt functional group, therefore make the oxidation and the hydrolysis reaction that occur in the two-phase system in the water be easy to carry out, and no longer need to add in addition expensive other quaternary ammonium salts, quaternary alkylphosphonium salt is made consisting of phase-transferring agent, the acquisition pentanedioic acid that the while can high yield.
Catalyzer generally be prepared beforehand good standby or when beginning reaction original position synthetic.Catalyzer synthetic main raw material is yellow wolframic acid H
2WO
4NH
2O, hydrogen peroxide, phosphoric acid, cetylpyridinium chloride.The also available sodium wolframate of yellow wolframic acid replaces, but with yellow wolframic acid for well.The amount ranges of reaction control phase transfer catalyst is 0.2～5% (calculating to convert the mol ratio that is equivalent to wolframic acid) of benchmark with raw material cyclopentenes mole number.
Among the present invention, this catalyzer is repeatedly reusable, and the amount that only needs to supply filter loss when at every turn feeding intake gets final product.
The present invention's concentration is that the aqueous hydrogen peroxide solution of 27-50% is an oxygenant, does not re-use any organic solvent and makes reaction medium.The mol ratio of hydrogen peroxide and cyclopentenes is 4～5.
The preparation method of above-mentioned phase transition compound as catalyzer is as follows: phosphoric acid is added the coordination of peroxide wolframic acid solution form phospho-wolframic acid, the organic solution that adds the quaternary ammonium salt cetylpyridinium chloride, make the phospho-wolframic acid root be transferred to organic phase, combine formation salt with quaternary ammonium salt cationic, through separatory, evaporating solvent, drying, granulation, promptly get required catalyzer.Wherein, the mol ratio 4～12 of phosphoric acid and wolframic acid, the mol ratio 2～8 of phosphoric acid and cetylpyridinium chloride.Its preparation process is: add the tungstic acid catalyst of calculated amount earlier, add aqueous hydrogen peroxide solution again, stir under the room temperature, make the wolframic acid dissolving; Add phosphoric acid and cetylpyridinium chloride then, restir added a certain amount of methylene dichloride about 30 minutes under the room temperature, got organic phase after the extraction, and resulting solid is catalyzer behind the evaporating solvent, and yield is greater than 80%.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1:
In 250 milliliter of three neck round-bottomed flask of stirring, reflux condensation mode and thermometer is housed, add 3.63 gram (7.5 mmole) [π-C respectively
5H
5NC
16H
33]
m{ PO
4[WO
3]
n(m=3; N=4) (be designated as A1), concentration is that stirring velocity rises to about 1000R.P.M. behind 27.5% the hydrogen peroxide 146ml (1.32 moles).Drip cyclopentenes 20.4g (0.3 mole) again.By the oil bath heating, control is bathed temperature from 46 ℃～50 ℃, keeps reactant and refluxes, and reacts sampling analysis after 24 hours.
Analytical results: pentanedioic acid, 93.8%; 1,2-encircles pentanediol, 0.4%; Glutaraldehyde, 1.1%; Other 2.7% (see attached list 1 1#).The reaction mixture cooling, 0 ℃ of placement is spent the night, and filters.A small amount of cold wash once gets pentanedioic acid 31.4g (yield 79%).M.p.=97～99 ℃, purity (pressing GC analyzes) 〉=99.0%.Further evaporate residual filtrate, recyclable pentanedioic acid 4.8 grams.
Embodiment 2～4:
Catalyst levels changes 0.2%, 1% into, and 5%.Control is bathed temperature and is respectively 60 ℃, 70 ℃, 100 ℃, and other feeding quantity, operating process are all with embodiment 1.Reaction times and reaction finish post analysis the results are shown in subordinate list 1 (1 the 2# of seeing attached list, 3#, 4#).
Embodiment 5～6:
Hydrogen peroxide concentration changes 35%, 50% into, and other feeding quantity, operating process are all with embodiment 1.Reaction finish post analysis the results are shown in subordinate list 1 (1 the 5# of seeing attached list, 6#).
Embodiment 7～8:
Catalyzer changes [π-C into
5H
5NC
16H
33]
m{ PO
4[WO
3]
n(m=3; N=12) (be designated as A2) and [π-C
5H
5NC
16H
33]
m{ PO
4[WO
3]
n(m=7; N=11) (be designated as A3), same in the mole number and the embodiment 1 of wolframic acid.Other feeding quantity, operating process and time are all with embodiment 1.Reaction finish post analysis the results are shown in subordinate list 1 (1 the 7# of seeing attached list, 8#).
Table 1: reaction control phase transfer catalyst catalytically oxidizing cyclopentene system pentanedioic acid performance relatively
*
| Embodiment | Catalyzer/hydrogen peroxide concentration | Catalyst levels ** (mol％) | Reaction times (h) | Product is formed (%) | ||||
| Cyclopentanone | 1,2-encircles pentanediol | Glutaraldehyde | Other *** | Pentanedioic acid | ||||
| 1 | A1/27.5％ | 2.5 | 24 | 1.0 | 1.4 | 1.1 | 2.7 | 93.8 |
| 2 | A1/27.5％ | 0.2 | 24 | 0.1 | 0.7 | 1.9 | 2.8 | 94.5 |
| 3 | A1/27.5％ | 1 | 12 | 0.1 | 2.6 | 3.3 | 2.0 | 92.0 |
| 4 | A1/27.5％ | 5 | 8 | 0.2 | 1.7 | 0.1 | 3.0 | 95.0 |
| 5 | A1/35％ | 2.5 | 8 | 0.7 | 1.2 | 0.5 | 2.2 | 95.4 |
| 6 | A1/50％ | 2.5 | 8 | 0.9 | 0.7 | 0.2 | 1.4 | 96.8 |
| 7 | A2/27.5％ | 2.5 | 16 | 3.8 | 0.3 | 2.0 | 9.2 | 84.7 |
| 8 | A3/27.5％ | 2.5 | 24 | 2.0 | 0.7 | 3.3 | 8.4 | 85.6 |
*Cyclopentenes 20.4g (300 mmole), 1.32 moles of 27.5%, 35% or 50% aqueous hydrogen peroxide solutions (in pure hydrogen peroxide), 46 ℃～100 ℃ reflux temperature reactions.
*Catalyst levels (to convert the mole number of wolframic acid) is by the cyclopentenes molecular fraction.
* *Other products comprise cyclopentenone, oxalic acid, cyclopentanol etc.
Claims (3)
1, a kind of environmental friendliness catalytically oxidizing cyclopentene prepares the method for pentanedioic acid, it is characterized in that with phase transition compound [π-C
5H
5NC
16H
33]
m{ PO
4[WO
3]
nBe catalyzer, m=3～7; N=4～12 are that the aqueous hydrogen peroxide solution of 27%-50% is an oxygenant with the weight concentration, at 46～100 ℃ of catalytically oxidizing cyclopentenes, react 8～24 hours, promptly obtain the pentanedioic acid product; Wherein the mol ratio of hydrogen peroxide and cyclopentenes is 4～5, and catalyst consumption is 0.2～5% of a raw material cyclopentenes mole number.
2, method according to claim 1 is characterized in that concrete steps are as follows: described catalyzer and oxygenant are mixed, stir down, drip cyclopentenes; The oil bath heating, 46～100 ℃ of temperature are bathed in control; Kept the reactant back flow reaction then 8～24 hours; Leach the catalyzer of separating out, in order to secondary response use down; From reacted filtered liquid, separate out crystal, be required pentanedioic acid product.
3, method according to claim 1 is characterized in that described catalyzer prepared beforehand before reaction, and perhaps original position is synthetic when the reaction beginning.
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| CN100427450C CN100427450C (en) | 2008-10-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631996A (en) * | 2016-12-20 | 2017-05-10 | 新疆大学 | Preparation method of organic-inorganic hybrid polyoxometallate nanorod |
| CN107824219A (en) * | 2017-11-22 | 2018-03-23 | 山东玉皇化工有限公司 | A kind of phase transfer catalyst and preparation method thereof and a kind of method that glutaric acid is prepared using cyclopentene |
| CN108147993A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of method of synthesis in water phospho heteropoly tungstate |
| CN113231102A (en) * | 2021-05-26 | 2021-08-10 | 济宁学院 | Glutaric acid selective polyacid catalyst based on micro-mesoporous Zr-MOF material and preparation method and application thereof |
-
2006
- 2006-08-03 CN CNB2006100297121A patent/CN100427450C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147993A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of method of synthesis in water phospho heteropoly tungstate |
| CN106631996A (en) * | 2016-12-20 | 2017-05-10 | 新疆大学 | Preparation method of organic-inorganic hybrid polyoxometallate nanorod |
| CN107824219A (en) * | 2017-11-22 | 2018-03-23 | 山东玉皇化工有限公司 | A kind of phase transfer catalyst and preparation method thereof and a kind of method that glutaric acid is prepared using cyclopentene |
| CN113231102A (en) * | 2021-05-26 | 2021-08-10 | 济宁学院 | Glutaric acid selective polyacid catalyst based on micro-mesoporous Zr-MOF material and preparation method and application thereof |
| CN113231102B (en) * | 2021-05-26 | 2022-04-26 | 济宁学院 | Glutaric acid selective polyacid catalyst based on micro-mesoporous Zr-MOF material and preparation method and application thereof |
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