CN102030777B - Production method of 2-butane phosphonate-1,2,4-tricarboxylic acid - Google Patents
Production method of 2-butane phosphonate-1,2,4-tricarboxylic acid Download PDFInfo
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Abstract
The invention discloses a production method of green energy-saving 2-butane phosphonate-1,2,4-tricarboxylic acid, comprising the following steps of: adding phosphorous acid and corresponding alcohol used as raw reaction materials into a reaction kettle, reacting at 120-140 DEG C to obtain an ester mixture of phosphite diester and phosphite triester, sequentially adding maleate diester and maleate monoester into the reaction kettle for reaction to obtain phosphonate succinate tetracarbalkoxy, adding acrylic ester into the reaction kettle for reaction to obtain 2-dialkyl ester butane phosphonate-1,2,4-tricarboxylic tricarbalkoxy, and finally hydrolyzing to obtain the 2-butane phosphonate-1,2,4-tricarboxylic acid. In the invention, phosphorous acid, maleic anhydride, acrylic acid and alcohol are used as raw materials, and no other separation process is carried out in the reaction except for solvent evaporation so that the purpose of energy saving is achieved; all the alcohol is recycled and is not discharged so that the purposes of greening and environmental protection are achieved; and hydrogen chloride, chloralkane and other side products are not generated, the energy consumption is low and the product quality is good.
Description
Technical field
The invention belongs to fine chemistry industry auxiliary agent, circulating water treatment agent technical field, be specifically related to a kind of 2-phosphonic acids butane-1,2 of green energy conservation, the tricarboxylic production method of 4-.
Background technology
At present, the 2-phosphonic acids butane-1,2 in fine chemistry industry auxiliary agent, circulating water treatment agent field, the tricarboxylic production of 4-, all take volatile phosphorus trichloride and methyl alcohol (or ethanol) as raw material, also adopt toluene etc. as solvent in many techniques, under 50～70 ℃ of low temperature, react.When methyl alcohol (or ethanol) is excessive, obtain trimethyl phosphite (or ethyl ester) and a large amount of hydrogenchloride and by product alkyl chloride, when methyl alcohol (or ethanol) quantity not sufficient and in the presence of hydrogenchloride trimethyl phosphite (or ethyl ester) can be decomposed into dimethylphosphite (or ethyl ester) and corresponding alkyl chloride.After reaction finishes, steam hydrogenchloride and alkyl chloride that reaction produces, underpressure distillation obtains corresponding phosphorous acid ester again, and this moment is the high boiling product such as residual phosphorous acid in still.
Take the phosphorous acid ester (such as dimethylphosphite or diethyl phosphite) that obtains as raw material and dimethyl maleate (or ethyl ester) carry out addition reaction and obtain phosphonic acids Succinic Acid four alkane esters.Then phosphonic acids Succinic Acid four alkane esters obtain 2-phosphonic acids dialkyl butane-1,2,4-tricarboxylic acid three alkane esters with methyl acrylate (or ethyl ester) reaction again, hydrolysis obtains 2-phosphonic acids butane-1 in the presence of catalyzer at last, 2,4-tricarboxylic acid, and a large amount of methyl alcohol (or ethanol) by product is arranged.
Above-mentioned phosphorus trichloride technological reaction speed is fast, reaction is violent, only needs low temperature to react.Yet selected raw material phosphorus trichloride is volatile, toxicity is large, and operating environment is poor, and more crucial be to select phosphorus trichloride to produce more by product as reaction raw materials.Be to reduce the generation of side reaction, need to add solvent toward contact, even and add solvent and also have the by products such as hydrogenchloride, chloroparaffin, phosphorous acid, so product is difficult for purifying.In addition, the purposes of above-mentioned by product is all limited.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of 2-phosphonic acids butane-1,2 of green energy conservation, the tricarboxylic production method of 4-.
Its technical solution is:
A kind of 2-phosphonic acids butane-1,2 of green energy conservation, the tricarboxylic production method of 4-may further comprise the steps:
A chooses phosphorous acid and correspondent alcohol as reaction raw materials, adds in the reactor, under 120～140 ℃, reacts 2～10 hours, makes the mixed ester of phosphorous acid diester and tris phosphite;
After b step a finishes, add maleic acid ester and maleic acid monoesters successively in reactor, reaction obtains phosphonic acids Succinic Acid four alkane esters;
After c step b finishes, add acrylate in reactor, reaction obtains 2-phosphonic acids dialkyl butane-1,2,4-tricarboxylic acid three alkane esters, and then hydrolysis obtains 2-phosphonic acids butane-1,2,4-tricarboxylic acid.
Among the step a, the consumption of described alcohol is counted with phosphorous acid complete reaction required amount 1～3 times with amount of substance, and described alcohol is ethanol, propyl alcohol, the trimethyl carbinol or propyl carbinol.
Among the step a, when selected alcohol is ethanol, propyl alcohol or the trimethyl carbinol, also need before the reaction to add the band aqua in reactor, component distillation is except anhydrating and being with aqua after the reaction.
Among the step b, comprise step:
After b1 step a finishes, add maleic acid ester and strong alkali catalyst first in reactor, under 90～150 ℃, reacted 1～6 hour, alcohol excess was removed in decompression after reaction finished, and obtained the mixture of tris phosphite and phosphonic acids Succinic Acid four alkane esters;
After b2 step b1 finishes, add maleic acid monoesters and acetic acid again in reactor, under 50～150 ℃, reacted 1～6 hour, acetic acid was removed in decompression after reaction finished, and obtained phosphonic acids Succinic Acid four alkane esters.
Among the step b1, the add-on of described maleic acid ester is 1.01～1.05: 1 with the ratio of the amount of substance of mixed ester Central Asia phosphodiester, and wherein, the amount of substance of mixed ester Central Asia phosphodiester is by the Analysis deterrmination to the phosphorous acid mixed ester.
Among the step b2, the ratio of the amount of tris phosphite is 1: 1 in the add-on of described maleic acid monoesters and the mixed ester, and wherein, the amount of substance of tris phosphite is by the Analysis deterrmination to the phosphorous acid mixed ester in the mixed ester.
Among the step b1, described maleic acid ester is reacted under sodium bisulfate catalysis by cis-butenedioic anhydride and propyl carbinol and obtains, and the consumption of described propyl carbinol is counted and 1.2～2 of the complete esterification required amount of cis-butenedioic anhydride with amount of substance.
Among the step b2, described maleic acid monoesters is reacted under sodium bisulfate catalysis by cis-butenedioic anhydride and propyl carbinol and obtains, and the additional proportion of described cis-butenedioic anhydride and propyl carbinol is counted 1: 1 with amount of substance.
Among the step c, described acrylate is that vinylformic acid and correspondent alcohol make in the presence of stopper and catalyzer, the additional proportion of described vinylformic acid and correspondent alcohol with amount of substance count 1: 2～4.
Among the step c, described hydrolytic process is carried out according to the following steps:
Reaction obtains 2-phosphonic acids dialkyl butane-1,2, behind the 4-tricarboxylic acid three alkane esters, then cooling adds water in the reactor and removes stopper, heat up again and make excessive unsaturated materials polymerization, pass at last water vapour and add acid or alkaline catalysts, steam hydrolysis alcohol, namely obtain 2-phosphonic acids butane-1,2,4-tricarboxylic acid.
Useful technique effect of the present invention is:
The present invention is take phosphorous acid, cis-butenedioic anhydride, vinylformic acid and alcohol as raw material, reaction except steaming solvent without other sepn processes, energy-conservation; All alcohol all recycle, without discharging, environmental protection; Without by products such as hydrogenchloride, alkyl chloride, energy consumption is low, superior product quality.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail: (the raw material consumption is all in weight part)
Embodiment 1
Each intermediate preparation: take by weighing 67 parts of cis-butenedioic anhydrides, 200 parts of propyl carbinols, add in the reactor, then add catalyst sulfuric acid hydrogen sodium, reaction and steam suff water under boiling, remove by filter sodium pyrosulfate, obtain maleic acid n-butyl and propyl carbinol mixture; Take by weighing 36 parts of cis-butenedioic anhydrides, 26 parts of propyl carbinols, add in the reactor, then add catalyst sulfuric acid hydrogen sodium, 120 ℃ of lower reactions, remove moisture and elimination sodium pyrosulfate, obtain the positive butyl ester of maleic acid list; Take by weighing 56 parts of vinylformic acid and 300 parts of propyl carbinols, add in the reactor, then add hydroquinone of polymerization retarder and catalyst sulfuric acid hydrogen sodium, reaction under boiling, elimination catalyst sulfuric acid hydrogen sodium after reaction is finished obtains n-butyl acrylate and propyl carbinol mixture.
2-phosphonic acids butane-1,2, the tricarboxylic preparation of 4-: take by weighing 82 parts in phosphorous acid, 600 parts of propyl carbinols, add in the jacketed type stainless steel cauldron of the band stirring that is accompanied with the dividing wall type rectifying tower, 120 ℃ of lower reactions 6 hours, and in reaction process, constantly dewater, make the mixture that phosphorous acid mixes positive butyl ester (di-n-butyl phosphite and tri-n-butylphosphite) and propyl carbinol; Then add maleic acid n-butyl and the propyl carbinol mixture that makes in the said process in the reactor, and add sodium alkoxide and make catalyzer, 120 ℃ of lower reactions 4 hours, after reaction finishes, reduce pressure and remove propyl carbinol; Add the positive butyl ester of maleic acid list that makes in the said process again in reactor, and add 300 parts of acetic acid, 80 ℃ of lower reactions 6 hours, after reaction finished, acetic acid was removed in decompression; In reactor, add n-butyl acrylate and the propyl carbinol mixture that makes in the said process again, and adding catalyzer Tributylamine, 60 ℃ of lower reactions 6 hours, make 2-phosphonic acids dialkyl butane-1,2, the mixture of 4-tricarboxylic acid tri-n-butyl and solvent, n-butanol, add again a small amount of water in the reactor and remove hydroquinone of polymerization retarder, then heating makes excessive unsaturated materials polymerization, and passes into water vapour, adds the hydrolysis of acidity or basic catalyst, and in hydrolysis, steam the azeotrope of water and propyl carbinol, obtain the finished product 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid aqueous solution.
Embodiment 2
Each intermediate preparation: take by weighing 49 parts of cis-butenedioic anhydrides, 148 parts of the trimethyl carbinols, 70 parts of normal hexanes, add in the reactor, then add catalyst sulfuric acid hydrogen sodium, reaction and steam suff water and normal hexane under boiling, remove by filter sodium pyrosulfate, make maleic acid di tert butyl carbonate and trimethyl carbinol mixture; Take by weighing 49 parts of cis-butenedioic anhydrides, 74 parts of the trimethyl carbinols, add in the reactor, then add catalyst sulfuric acid hydrogen sodium and normal hexane, 120 ℃ of lower reactions, remove corresponding moisture and normal hexane and elimination sodium pyrosulfate, obtain the maleic acid list tert-butyl ester; Take by weighing 72 parts of vinylformic acid, 200 parts of trimethyl carbinols and 50 parts of normal hexanes, add in the reactor, then add hydroquinone of polymerization retarder and catalyst sulfuric acid hydrogen sodium, reaction under boiling, steam corresponding moisture and normal hexane, elimination catalyst sulfuric acid hydrogen sodium after reaction is finished obtains tert-butyl acrylate and trimethyl carbinol mixture.
2-phosphonic acids butane-1,2, the tricarboxylic preparation of 4-: take by weighing 600 parts in 82 parts in phosphorous acid, the trimethyl carbinol and 100 parts of normal hexanes, add in the jacketed type stainless steel cauldron of the band stirring that is accompanied with the dividing wall type rectifying tower, 140 ℃ of lower reactions 8 hours, remove moisture and normal hexane, make the mixture of the phosphorous acid mixing tert-butyl ester (phosphorous acid di tert butyl carbonate and the tricresyl phosphite tert-butyl ester) and the trimethyl carbinol; Then add maleic acid di tert butyl carbonate and the trimethyl carbinol mixture that makes in the said process in the reactor, and add sodium alkoxide and make catalyzer, 90 ℃ of lower reactions 6 hours, after reaction finishes, reduce pressure and remove the trimethyl carbinol; Add the maleic acid list tert-butyl ester that makes in the said process again in reactor, and add 300 parts of acetic acid, 100 ℃ of lower reactions 4 hours, after reaction finished, acetic acid was removed in decompression; In reactor, add tert-butyl acrylate and the trimethyl carbinol mixture that makes in the said process again, and adding catalyzer Tributylamine, 100 ℃ of lower reactions 2 hours, make 2-phosphonic acids dialkyl butane-1,2, the mixture of 4-tricarboxylic acid three tert-butyl esters and solvent tertiary butanol, add again a small amount of water in the reactor and remove hydroquinone of polymerization retarder, then heating makes excessive unsaturated materials polymerization, and passes into water vapour, adds the hydrolysis of normal hexane and acidity or basic catalyst, and in hydrolysis, steam water and normal hexane, the azeotrope of the trimethyl carbinol, obtain the finished product 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid aqueous solution.
Embodiment 3
Each intermediate preparation is with embodiment 1.
2-phosphonic acids butane-1,2, the tricarboxylic preparation of 4-: take by weighing 82 parts in phosphorous acid, 250 parts of propyl carbinols, add in the jacketed type stainless steel cauldron of the band stirring that is accompanied with the dividing wall type rectifying tower, 120 ℃ of lower reactions 8 hours, and in reaction process, constantly dewater, make the mixture that phosphorous acid mixes positive butyl ester (di-n-butyl phosphite and tri-n-butylphosphite) and propyl carbinol; Then add maleic acid n-butyl and the propyl carbinol mixture that makes in the said process in the reactor, and add sodium alkoxide and make catalyzer, 90 ℃ of lower reactions 2 hours, after reaction finishes, reduce pressure and remove propyl carbinol; Add the positive butyl ester of maleic acid list that makes in the said process again in reactor, and add 300 parts of acetic acid, 100 ℃ of lower reactions 4 hours, after reaction finished, acetic acid was removed in decompression; In reactor, add n-butyl acrylate and the propyl carbinol mixture that makes in the said process again, and adding catalyzer Tributylamine, 80 ℃ of reactions 3 hours, make 2-phosphonic acids dialkyl butane-1,2, the mixture of 4-tricarboxylic acid tri-n-butyl and solvent, n-butanol, add again a small amount of water in the reactor and remove hydroquinone of polymerization retarder, then heating makes excessive unsaturated materials polymerization, and passes into water vapour, adds the hydrolysis of acidity or basic catalyst, and in hydrolysis, steam the azeotrope of water and propyl carbinol, obtain the finished product 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid aqueous solution.
Embodiment 4
Each intermediate preparation: take by weighing 49 parts of cis-butenedioic anhydrides, 140 parts of ethanol, 70 parts of normal hexanes, add in the reactor, then add catalyst sulfuric acid hydrogen sodium, reaction and steam suff water and normal hexane under boiling, remove by filter sodium pyrosulfate, make diethyl maleate and alcohol mixture; Take by weighing 49 parts of cis-butenedioic anhydrides, 46 parts of ethanol, add in the reactor, then add catalyst sulfuric acid hydrogen sodium and normal hexane, 120 ℃ of lower reactions, remove corresponding moisture and normal hexane and elimination sodium pyrosulfate, obtain cis-butenedioic acid mono ethyl maleate; Take by weighing 72 parts of vinylformic acid, 200 parts of ethanol and 50 parts of normal hexanes, add in the reactor, then add hydroquinone of polymerization retarder and catalyst sulfuric acid hydrogen sodium, reaction under boiling, steam corresponding moisture and normal hexane, elimination catalyst sulfuric acid hydrogen sodium after reaction is finished obtains ethyl propenoate and alcohol mixture.
2-phosphonic acids butane-1,2, the tricarboxylic preparation of 4-: take by weighing 82 parts in phosphorous acid, 250 parts of ethanol, add in the jacketed type stainless steel cauldron of the band stirring that is accompanied with the dividing wall type rectifying tower, 120 ℃ of lower reactions 8 hours, and in reaction process, constantly dewater, make the mixture of phosphorous acid mixing ethyl ester (diethyl phosphite and triethyl-phosphite) and ethanol; Then add diethyl maleate and the alcohol mixture that makes in the said process in the reactor, and add sodium alkoxide and make catalyzer, 90 ℃ of lower reactions 2 hours, after reaction finished, ethanol was removed in decompression; Add the cis-butenedioic acid mono ethyl maleate that makes in the said process again in reactor, and add 300 parts of acetic acid, 100 ℃ of lower reactions 4 hours, after reaction finished, acetic acid was removed in decompression; In reactor, add ethyl propenoate and the alcohol mixture that makes in the said process again, and adding catalyzer Tributylamine, 80 ℃ of reactions 3 hours, make 2-phosphonic acids dialkyl butane-1,2, the mixture of 4-tricarboxylic acid triethyl and etoh solvent, add again a small amount of water in the reactor and remove hydroquinone of polymerization retarder, then heating makes excessive unsaturated materials polymerization, and passes into water vapour, adds the hydrolysis of acidity or basic catalyst, and in hydrolysis, steam the azeotrope of water and ethanol, obtain the finished product 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid aqueous solution.
Products obtained therefrom or middle sampling analysis all can adopt high-efficient liquid phase chromatogram technique analysis in above-described embodiment.
Claims (10)
1. 2-phosphonic acids butane-1,2, the tricarboxylic production method of 4-is characterized in that may further comprise the steps:
A chooses phosphorous acid and correspondent alcohol as reaction raw materials, adds in the reactor, under 120～140 ℃, reacts 2～10 hours, makes the mixed ester of phosphorous acid diester and tris phosphite;
After b step a finishes, add maleic acid ester and maleic acid monoesters successively in reactor, reaction obtains phosphonic acids Succinic Acid four alkane esters;
After c step b finishes, add acrylate in reactor, reaction obtains 2-phosphonic acids dialkyl butane-1,2,4-tricarboxylic acid three alkane esters, and then hydrolysis obtains 2-phosphonic acids butane-1,2,4-tricarboxylic acid.
2. a kind of 2-phosphonic acids butane-1 according to claim 1, the tricarboxylic production method of 2,4-is characterized in that: among the step a, the consumption of described alcohol is counted with phosphorous acid complete reaction required amount 1～3 times with amount of substance, and described alcohol is ethanol, propyl alcohol, the trimethyl carbinol or propyl carbinol.
3. a kind of 2-phosphonic acids butane-1 according to claim 2, the tricarboxylic production method of 2,4-is characterized in that: when selected alcohol is ethanol, propyl alcohol or the trimethyl carbinol, also need before the reaction to add the band aqua in reactor, component distillation is except anhydrating and being with aqua after the reaction.
4. a kind of 2-phosphonic acids butane-1,2 according to claim 1, the tricarboxylic production method of 4-is characterized in that: among the described step b, comprise step:
After b1 step a finishes, add maleic acid ester and strong alkali catalyst first in reactor, under 90～150 ℃, reacted 1～6 hour, alcohol excess was removed in decompression after reaction finished, and obtained the mixture of tris phosphite and phosphonic acids Succinic Acid four alkane esters;
After b2 step b1 finishes, add maleic acid monoesters and acetic acid again in reactor, under 50～150 ℃, reacted 1～6 hour, acetic acid was removed in decompression after reaction finished, and obtained phosphonic acids Succinic Acid four alkane esters.
5. a kind of 2-phosphonic acids butane-1,2 according to claim 4, the tricarboxylic production method of 4-is characterized in that: among the step b1, the add-on of described maleic acid ester is 1.01～1.05: 1 with the ratio of the amount of substance of mixed ester Central Asia phosphodiester.
6. a kind of 2-phosphonic acids butane-1,2 according to claim 4, the tricarboxylic production method of 4-is characterized in that: among the step b2, the ratio of the amount of tris phosphite is 1: 1 in the add-on of described maleic acid monoesters and the mixed ester.
7. a kind of 2-phosphonic acids butane-1 according to claim 4,2, the tricarboxylic production method of 4-, it is characterized in that: among the step b1, described maleic acid ester is reacted under sodium bisulfate catalysis by cis-butenedioic anhydride and propyl carbinol and obtains, and the consumption of described propyl carbinol is counted with the complete esterification required amount of cis-butenedioic anhydride 1.2～2 times with amount of substance.
8. a kind of 2-phosphonic acids butane-1 according to claim 4,2, the tricarboxylic production method of 4-, it is characterized in that: among the step b2, described maleic acid monoesters is reacted under sodium bisulfate catalysis by cis-butenedioic anhydride and propyl carbinol and obtains, and the additional proportion of described cis-butenedioic anhydride and propyl carbinol is counted 1: 1 with amount of substance.
9. a kind of 2-phosphonic acids butane-1 according to claim 1,2, the tricarboxylic production method of 4-, it is characterized in that: among the step c, described acrylate is that vinylformic acid and correspondent alcohol make in the presence of stopper and catalyzer, the additional proportion of described vinylformic acid and correspondent alcohol with amount of substance count 1: 2～4.
10. a kind of 2-phosphonic acids butane-1,2 according to claim 9, the tricarboxylic production method of 4-is characterized in that: among the step c, described hydrolytic process is carried out according to the following steps:
Reaction obtains 2-phosphonic acids dialkyl butane-1,2, behind the 4-tricarboxylic acid three alkane esters, then cooling adds water in the reactor and removes stopper, heat up again and make excessive unsaturated materials polymerization, pass at last water vapour and add acid or alkaline catalysts, steam hydrolysis alcohol, namely obtain 2-phosphonic acids butane-1,2,4-tricarboxylic acid.
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| CN102675363B (en) * | 2011-05-06 | 2013-01-30 | 江苏大明科技有限公司 | 2-phosphonobutane-1,2,4-tricarboxylic acid production process |
| CN105601668A (en) * | 2015-12-24 | 2016-05-25 | 常州大学 | Preparation method of low-phosphorous corrosion and scale inhibitor PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid) |
| CN107652987B (en) * | 2017-10-17 | 2020-06-23 | 太原理工大学 | Preparation method of maleic acid cholesterol monoester group citric acid triester liquid crystal |
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| US4931586A (en) * | 1988-09-03 | 1990-06-05 | Bayer Aktiengesellschaft | Process for the continuous production of 2-phosphone-butane-1,2,4-tricarboxylic acid and alkali metal salts thereof |
| DE19525966A1 (en) * | 1995-07-17 | 1997-01-23 | Bayer Ag | Prodn. of 2-phosphono-butane-1,2,4-tri:carboxylic acid |
| CN101503426A (en) * | 2009-03-02 | 2009-08-12 | 江苏江海化工集团有限公司 | Novel technique for coproduction of 2-phosphonobutane-1,2,4-tricabroxylic acid and methyl chloride |
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| US4931586A (en) * | 1988-09-03 | 1990-06-05 | Bayer Aktiengesellschaft | Process for the continuous production of 2-phosphone-butane-1,2,4-tricarboxylic acid and alkali metal salts thereof |
| DE19525966A1 (en) * | 1995-07-17 | 1997-01-23 | Bayer Ag | Prodn. of 2-phosphono-butane-1,2,4-tri:carboxylic acid |
| CN101503426A (en) * | 2009-03-02 | 2009-08-12 | 江苏江海化工集团有限公司 | Novel technique for coproduction of 2-phosphonobutane-1,2,4-tricabroxylic acid and methyl chloride |
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