CN1048988C - Method for synthetizing 2-phosphonate butane-1,2,4-tricarboxylic acid - Google Patents
Method for synthetizing 2-phosphonate butane-1,2,4-tricarboxylic acid Download PDFInfo
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- CN1048988C CN1048988C CN97108210A CN97108210A CN1048988C CN 1048988 C CN1048988 C CN 1048988C CN 97108210 A CN97108210 A CN 97108210A CN 97108210 A CN97108210 A CN 97108210A CN 1048988 C CN1048988 C CN 1048988C
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Abstract
The present invention discloses a synthetic method of 2-butane phosphate-1, 2 4-tri-carboxylic acid. In the method, fumaric acid dioxane ester (A), dioxane ester phosphite (B) and alkane ester acrylate (C) are taken as raw materials and have the following proportion: the molar ratio of B to A is 1:0.8 to 1.2; the molar ratio of B to C is 1:0.6 to 1.2; reaction products are generated through two-step addition and hydrolyzation. The present invention effectively solves the comprehensive utilization problem of the downstream products of cis-acid with is waste liquid of benzoic anhydride industry and has the advantages of convenient method, low production cost, environment pollution eliminationm, etc.; products can be used for the fields of the corrosion inhibition and the scaling stopping processing of industrial cycle cooling water, the processing of light-sensitive materials of silver halide, etc.
Description
The present invention relates to a kind of 2-phosphonic acids butane-1,2, the synthetic method of 4-tricarboxylic acid (english abbreviation PBTCA), especially the derived product FUMARIC ACID TECH GRADE dialkyl with the industrial effluent of phthalic anhydride production is the synthetic method of raw material.
In the prior art, US3,886,205 to have introduced several employing phosphonic acids Succinic Acid tetramethyl esters and methyl acrylate or vinyl cyanide or methyl methacrylate or dimethyl maleic acid and phosphonic acids Succinic Acid tetra-ethyl ester and ethyl crotonate be the technological line of the synthetic PBTCA of raw material.US4,931,586 have introduced the technological line that a kind of employing dimethyl maleate (being dimethyl maleate), dimethylphosphite and methyl acrylate are the synthetic continuously PBTCA of raw material." Treatment of Industrial Water ", 1993,13 (6): 16 to have introduced a kind of dimethyl maleate, dimethylphosphite and methyl acrylate of adopting be the technological line of the synthetic PBTCA of raw material.Above technology is all made raw material with the maleic acid dialkyl, its production cost height, inconvenient PBTCA applies, in addition, can not provide phthalic anhydride manufacture waste liquid derived product utilize method.
The objective of the invention is to utilize the synthetic PBTCA of derived product FUMARIC ACID TECH GRADE dialkyl of the industrial effluent that phthalic anhydride produces, reduce its production cost, thereby obtain cheap PBTCA, to satisfy the needs of industrial circulating cooling water processing and the processing of photochromics silver halide etc.
In order to achieve the above object, the present invention has adopted following technical scheme: with chemical structural formula be
FUMARIC ACID TECH GRADE dialkyl (A) make raw material, process comprises: (1) one step addition: make raw material with phosphorous acid dialkyl (B) and A, the mol ratio of B: A is 1: 0.8～1.2, add total amount is 10%～30% (weight in batches, in the B consumption) the catalyzer sodium alkoxide, under 60～80 ℃ temperature, begin reaction, and under 140～160 ℃ temperature, reacted 10～60 minutes, (2) two step additions then: be cooled to 4～20 ℃ earlier, in the mol ratio of B and alkyl acrylate (C) is that 1: 0.6～1.2 ratio adds C, adding or drip consumption in batches is 10%～30% (weight, in the B consumption) the catalyzer sodium alkoxide after, under 4～20 ℃ temperature, reacted 6～10 hours, again (3) hydrolysis: with water vapor hydrolysis 5～7 hours under 100～105 ℃ temperature, steam alcohol, add no salt solution resultant is made solution.
Chemical reaction process of the present invention is as follows: the chemical equation of a step addition reaction is:
In this reaction process, must be noted that and control temperature of reaction, reaction times and catalyst levels well.At first, under 60～80 ℃ temperature, begin reaction, because the exothermic effect in the reaction progressively is increased to about 140～160 ℃ temperature of reaction system, under this temperature, react and got final product in 10～60 minutes, when initial reaction temperature is too high, can make dimethyl fumarate cause wastage of material, but cross when low, then react insufficient when temperature because of distillation; Reaction times is also not too long or too short, too short then reaction of time not exclusively, the reaction times is long then not to have great practical significance.Secondly, the consumption of catalyzer sodium alkoxide should be 10%～30% of phosphorous acid dialkyl weight, crosses when low when catalyst levels, and reaction is difficult to fully.
The chemical equation of two step addition reactions is:
R is-CH in the formula
3Or-C
2H
5
Under 4～20 ℃ temperature, phosphonic acids Succinic Acid four alkane esters (D) carry out addition reaction once more with alkyl acrylate under the katalysis of sodium alkoxide, generate 2-phosphonic acids butane-1,2,4-tricarboxylic acid five alkane esters (E), temperature of reaction is too high, pay the reaction aggravation, reaction temperature is spent low, and the load of the cold machine of ammonia increases the weight of, and energy consumption increases; Reaction times is 6～10 hours, is preferably 6～8 hours, and the reaction times is long, has little significance, and the reaction times is too short, and reaction not exclusively; The consumption of catalyzer sodium alkoxide is 10～30% of a phosphorous acid dialkyl weight, the catalyst consumption deficiency, and reaction is difficult to fully, and consumption is crossed at most can cause waste.
The chemical equation of hydrolysis reaction is:
Under the effect of water vapor, 2-phosphonic acids butane-1,2, five alkane ester (E) hydrolysis of 4-tricarboxylic acid generate target product PBTCA, displace corresponding alcohol simultaneously, hydrolysis temperature is 100～105 ℃, and temperature is too high, can cause and dash material, temperature is low excessively, and hydrolysis is incomplete, and the flow in the hydrolysis later stage along with alcohol reduces gradually, progressively be warming up to 135 ℃, until the outflow of not having alcohol, hydrolysis time was controlled at 5～7 hours, and hydrolysis time is long, steam consumption is too big, time is too short, and hydrolysis is incomplete, influences quality product, after hydrolysis is intact, adds an amount of no salt solution and be made into 40～50% the PBTCA aqueous solution.
The present invention's technical scheme preferably can be: a step is during addition, the mol ratio of phosphorous acid dialkyl (B) and FUMARIC ACID TECH GRADE dialkyl (A) is 1: 1.0～1.05, if A use quantity not sufficient, then the inferior phosphorus content of product will increase, otherwise as excessive too many, product yield will descend.
The present invention's technical scheme preferably can also be: in the two step addition processes, phosphorous acid dialkyl (B) is 1: 0.85～0.95 with the mol ratio of alkyl acrylate (C), the consumption of C can be selected for use in B: C is 1: 0.6～1.2 scope because of other the variation of processing condition, but the mol ratio of B and C is 1: 0.85～0.95 o'clock the best generally speaking, and the too much or very few yield of product that all can make of the consumption of C reduces.
Compared with prior art, the present invention has following tangible advantage:
1, the present invention has utilized FUMARIC ACID TECH GRADE dialkyl and maleic acid dialkyl for isomers, the identical characteristics of molecular composition, under the katalysis of catalyzer sodium alkoxide, can carry out nucleophilic addition equally.
2, the FUMARIC ACID TECH GRADE dialkyl is than maleic acid dialkyl low price, and the present invention can be raw material along sour derived product dimethyl fumarate with the waste liquid of phthalic anhydride industry, thus help reducing cost, and eliminated of the pollution of phthalic anhydride production spent acid to environment.Adopt the technology of the present invention can make 2-phosphonic acids butane-1,2, the tricarboxylic products production cost per ton of 4-reduces about 2000 yuan, and economic benefit is very remarkable.
Below the present invention is described in further detail by specific embodiment:
Embodiment 1:
One reflux exchanger is housed, in the 250ml there-necked flask that stirs, add 66.0g (0.6mol) dimethylphosphite and 86.4g (0.6mol) dimethyl fumarate, be warming up to 70 ℃, stir and add the 13.2g sodium methylate down in batches, temperature reaches 150 ℃, react after 30 minutes, be cooled to 5 ℃, add 46.4g (0.54mol) methyl acrylate, drip the 10.0g sodium methylate then, keep temperature of reaction at 5 ℃, be incubated 6 hours again after dripping, be warming up to 60 ℃ then, the feeding water vapor is hydrolyzed, 100～105 ℃ of following hydrolysis 6 hours,, be warming up to 135 ℃ gradually along with progressively reducing of methyl alcohol flow, till no methyl alcohol flows out, the no salt solution of cooling cooling back adding is made into 40～50% the PBTCA aqueous solution, and the inferior phosphorus content of product is 0.25%, and active matter content is 41.7%.
Embodiment 2:
One reflux exchanger is housed, in the 250ml there-necked flask that stirs, add 69.0g (0.5mol) diethyl phosphite and 86.0g (0.5mol) DEF, be warming up to 70 ℃, stir and add the 13.8g sodium ethylate down in batches, temperature reaches 150 ℃, react and be cooled to 5 ℃ after 30 minutes, add 45.0g (0.45mol) ethyl propenoate, drip the 10.4g sodium ethylate then, keep temperature of reaction, be incubated 6 hours again after dripping at 5 ℃, be warming up to 60 ℃ then, the feeding water vapor is hydrolyzed, 100～105 ℃ of following hydrolysis 6 hours, along with reducing gradually of ethanol flow, progressively be warming up to 135 ℃, till no ethanol flowed out, an amount of no salt solution of cooling cooling back adding was made into 40～50% the PBTCA aqueous solution, and the inferior phosphorus content of product is that 0.31% active matter content is 40.6%.
Embodiment 3～20:
Reaction raw materials and operation steps wherein one go on foot addition reaction with embodiment 1:
Reaction times was respectively 10 minutes, 60 minutes.
The mol ratio value of dimethylphosphite and dimethyl fumarate was respectively 1: 0.8,1: 1.0,1: 1.2.
Catalyzer sodium methylate consumption is respectively 10% (wt), 20% (wt), 30% (wt) of dimethylphosphite consumption.
Temperature of reaction is respectively 80 ℃, 70 ℃, 60 ℃.
Two step addition reactions:
The mol ratio value of dimethylphosphite and methyl acrylate was respectively 1: 1.2,1: 0.9,1: 0.6.
Catalyzer sodium methylate consumption is respectively 10% (wt), 20% (wt), 30% (wt) of dimethylphosphite consumption.
Temperature of reaction is respectively 4～6 ℃, 10～12 ℃, 18～20 ℃.
Reaction times was respectively 6 hours, 8 hours, 10 hours.
Process data and quality product are as table-1.
Embodiment 21～38:
Reaction raw materials and operation steps wherein one go on foot addition reaction with embodiment 2:
Reaction times was respectively 10 minutes, 60 minutes.
The mol ratio value of diethyl phosphite and DEF was respectively 1: 0.8,1: 1.0,1: 1.2.
Catalyzer sodium ethylate consumption is respectively 10% (wt), 20% (wt), 30% (wt) of diethyl phosphite consumption.
Temperature of reaction is respectively 80 ℃, 70 ℃, 60 ℃.
Two step addition reactions:
The mol ratio value of diethyl phosphite and ethyl propenoate was respectively 1: 1.2,1: 0.9,1: 0.6.
Catalyzer sodium ethylate consumption is respectively 10% (wt), 20% (wt), 30% (wt) of diethyl phosphite consumption.
Temperature of reaction is respectively 4～6 ℃, 10～12 ℃, 18～20 ℃.
Reaction times was respectively 6 hours, 8 hours, 10 hours.
Process data and quality product are as table-2.
Table-1 embodiment 3～20 process datas and quality product
| Embodiment | Reaction times (minute) | Dimethylphosphite/dimethyl fumarate | Sodium methylate consumption (%) | Temperature of reaction (℃) | Dimethylphosphite/methyl acrylate | Sodium methylate consumption (%) | Temperature of reaction (℃) | Reaction times (hour) | Inferior phosphorus content (%) | Active matter content (%) |
| 3 | 10 | 1∶0.8(66.0/69.1g) | 10(6.6g) | 80 | 1∶1.2(61.9g) | 10(6.6g) | 4～6 | 6 | 3.3 | 40.4 |
| 4 | 10 | 1∶0.8(66.0g/69.1g) | 20(13.2g) | 70 | 1∶0.9(46.4g) | 20(13.2g) | 10～12 | 8 | 2.9 | 41.7 |
| 5 | 10 | 1∶0.8(66.0g/69.1g) | 30(19.8g) | 60 | 1∶0.6(31.0g) | 30(19.8g) | 18～20 | 10 | 3.0 | 40.9 |
| 6 | 10 | 1∶1.0(66.0g/86.4g) | 10(6.6g) | 80 | 1∶0.9(46.4g) | 20(13.2g) | 18～20 | 10 | 1.7 | 43.8 |
| 7 | 10 | 1∶1.0(66.0g/86.4g) | 20(13.2g) | 70 | 1∶0.6(31.0g) | 30(19.8g) | 4～6 | 6 | 0.8 | 40.7 |
| 8 | 10 | 1∶1.0(66.0g/86.4g) | 30(19.8g) | 60 | 1∶1.2(61.9g) | 10(6.6g) | 10～12 | 8 | 0.5 | 42.1 |
| 9 | 10 | 1∶1.2(66.0g/103.7g) | 10(6.6g) | 70 | 1∶1.2(61.9g) | 30(19.8g) | 10～12 | 10 | 1.4 | 41.9 |
| 10 | 10 | 1∶1.2(66.0g/103.7g) | 20(13.2g) | 60 | 1∶0.9(46.4g) | 10(6.6g) | 18～20 | 6 | 0.6 | 42.2 |
| 11 | 10 | 1∶1.2(66.0g/103.7g) | 30(19.8g) | 80 | 1∶0.6(31.0g) | 20(13.2g) | 4～6 | 8 | 0.5 | 41.6 |
| 12 | 60 | 1∶0.8(66.0g/69.1g) | 10(6.6g) | 60 | 1∶0.6(31.0g) | 20(13.2g) | 10～12 | 6 | 3.8 | 40.1 |
| 13 | 60 | 1∶0.8(66.0g/69.1g) | 20(13.2g) | 80 | 1∶1.2(61.9g) | 30(19.8g) | 18～20 | 8 | 3.6 | 40.7 |
| 14 | 60 | 1∶0.8(66.0g/69.1g) | 30(19.8g) | 70 | 1∶0.9(46.4g) | 10(6.6g) | 4～6 | 10 | 2.8 | 41.6 |
| 15 | 60 | 1∶1.0(66.0g/86.4g) | 10(6.6g) | 70 | 1∶0.6(31.0g) | 10(6.6g) | 18～20 | 8 | 2.6 | 40.3 |
| 16 | 60 | 1∶1.0(66.0g/86.4g) | 20(13.2g) | 60 | 1∶1.2(61.9g) | 20(13.2g) | 4～6 | 10 | 0.3 | 41.2 |
| 17 | 60 | 1∶1.0(66.0g/86.4g) | 30(19.8g) | 80 | 1∶0.9(46.4g) | 30(19.8g) | 10～12 | 6 | 0.4 | 43.5 |
| 18 | 60 | 1∶1.2(66.0g/103.7g) | 10(6.6g) | 60 | 1∶0.9(46.4g) | 30(19.8g) | 4～6 | 8 | 2.1 | 40.2 |
| 19 | 60 | 1∶1.2(66.0g/103.7g) | 20(13.2g) | 80 | 1∶0.6(31.0g) | 10(6.6g) | 10～12 | 10 | 0.8 | 42.3 |
| 20 | 60 | 1∶1.2(66.0g/103.7g) | 30(19.8g) | 70 | 1∶1.2(61.9g) | 20(13.2g) | 18～20 | 6 | 1.7 | 41.0 |
Table-2 embodiment 21～38 process datas and quality product
| Embodiment | Reaction times (minute) | Diethyl phosphite/DEF | Sodium ethylate consumption (%) | Temperature of reaction (℃) | Diethyl phosphite/ethyl propenoate | Sodium ethylate consumption (%) | Temperature of reaction (℃) | Reaction times (hour) | Inferior phosphorus content (%) | Active matter content (%) |
| 21 | 10 | 1∶0.8(69.0g/68.8g) | 10(6.9g) | 80 | 1∶1.2(60.0g) | 10(6.9g) | 4～6 | 6 | 2.9 | 40.2 |
| 22 | 10 | 1∶0.8(69.0g/68.8g) | 20(13.8g) | 70 | 1∶0.9(45.0g) | 20(13.8g) | 10～12 | 8 | 2.0 | 40.6 |
| 23 | 10 | 1∶0.8(69.0g/68.8g) | 30(20.7g) | 60 | 1∶0.6(30.0g) | 30(20.7g) | 18～20 | 10 | 2.4 | 40.9 |
| 24 | 10 | 1∶1.0(69.0g/86.0g) | 10(6.9g) | 80 | 1∶0.9(45.0g) | 20(13.8g) | 18～20 | 10 | 1.8 | 41.6 |
| 25 | 10 | 1∶1.0(69.0g/86.0g) | 20(13.8g) | 70 | 1∶0.6(30.0g) | 30(20.7g) | 4～6 | 6 | 0.4 | 41.1 |
| 26 | 10 | 1∶1.0(69.0g/86.0g) | 30(20.7g) | 60 | 1∶1.2(60.0g) | 10(6.9g) | 10～12 | 8 | 0.7 | 40.1 |
| 27 | 10 | 1∶1.2(69.0g/103.2g) | 10(6.9g) | 70 | 1∶1.2(60.0g) | 30(20.7g) | 10～12 | 10 | 1.4 | 40.4 |
| 28 | 10 | 1∶1.2(69.0g/103.2g) | 20(13.8g) | 60 | 1∶0.9(45.0g) | 10(6.9g) | 18～20 | 6 | 1.2 | 41.2 |
| 29 | 10 | 1∶1.2(69.0g/103.2g) | 30(20.7g) | 80 | 1∶0.6(30.0g) | 20(13.8g) | 4～6 | 8 | 1.5 | 41.8 |
| 30 | 60 | 1∶0.8(69.0g/68.8g) | 10(6.9g) | 60 | 1∶0.6(30.0g) | 20(13.8g) | 10～12 | 6 | 3.2 | 40.8 |
| 31 | 60 | 1∶0.8(69.0g/68.8g) | 20(13.8g) | 80 | 1∶1.2(60.0g) | 30(20.7g) | 18～20 | 8 | 2.8 | 41.6 |
| 32 | 60 | 1∶0.8(69.0g/68.8g) | 30(20.7g) | 70 | 1∶0.9(45.0g) | 10(6.9g) | 4～6 | 10 | 2.0 | 40.2 |
| 33 | 60 | 1∶1.0(69.0g/86.0g) | 10(6.9g) | 70 | 1∶0.6(30.0g) | 10(6.9g) | 18～20 | 8 | 2.0 | 40.7 |
| 34 | 60 | 1∶1.0(69.0g/86.0g) | 20(13.8g) | 60 | 1∶1.2(60.0g) | 20(13.8g) | 4～6 | 10 | 0.3 | 43.1 |
| 35 | 60 | 1∶1.0(69.0g/86.0g) | 30(20.7g) | 80 | 1∶0.9(45.0g) | 30(20.7g) | 10～12 | 6 | 0.4 | 40.3 |
| 36 | 60 | 1∶1.2(69.0g/103.2g) | 10(6.9g) | 60 | 1∶0.9(45.0g) | 30(20.7g) | 4～6 | 8 | 1.4 | 40.2 |
| 37 | 60 | 1∶1.2(69.0g/103.2g) | 20(13.8g) | 80 | 1∶0.6(30.0g) | 10(6.9g) | 10～12 | 10 | 0.8 | 41.6 |
| 38 | 60 | 1∶1.2(69.0g/103.2g) | 30(20.7g) | 70 | 1∶1.2(60.0g) | 20(13.8g) | 18～20 | 6 | 1.2 | 40.1 |
Claims (3)
1, a kind of 2-phosphonic acids butane-1,2, the tricarboxylic synthetic method of 4-is a raw material with the dialkyl, sodium alkoxide is a catalyzer, through processes such as synthetic reaction and hydrolysis, the invention is characterized in: adopt chemical structural formula to be
FUMARIC ACID TECH GRADE dialkyl (A) make raw material, process comprises:
(1) one step addition: make raw material, B with phosphorous acid two lower alkyl esters (B) and A: the mol ratio of A is 1: 0.8～1.2, and add total amount is the catalyzer C of 10%～30% (weight is in the B consumption) in batches
1～C
4Sodium alkoxide begins reaction, and reacted under 140～160 ℃ temperature 10～60 minutes, then under 60～80 ℃ temperature
(2) two step additions: being cooled to 4～20 ℃ earlier, is that 1: 0.6～1.2 ratio adds C by the mol ratio of B and vinylformic acid lower alkyl ester (C), and adding or dropping consumption are the catalyzer C of 10%～30% (weight is in the B consumption) in batches
1～C
4Behind the sodium alkoxide, under 4～20 ℃ temperature, reacted 6～10 hours, again
(3) hydrolysis: with water vapor hydrolysis 5～7 hours under 100～105 ℃ temperature, steam alcohol, thick 2-phosphonic acids butane-1,2,4-tricarboxylic acid product adds no salt solution product is made solution.
2, synthetic method according to claim 1 is characterized in that: a step during addition mol ratio of B: A be 1: 1.0～1.05.
3, synthetic method according to claim 1 and 2 is characterized in that: two steps during addition the mol ratio of B: C be 1: 0.85～0.95.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108210A CN1048988C (en) | 1997-09-03 | 1997-09-03 | Method for synthetizing 2-phosphonate butane-1,2,4-tricarboxylic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108210A CN1048988C (en) | 1997-09-03 | 1997-09-03 | Method for synthetizing 2-phosphonate butane-1,2,4-tricarboxylic acid |
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| CN1173499A CN1173499A (en) | 1998-02-18 |
| CN1048988C true CN1048988C (en) | 2000-02-02 |
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| 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) |
| CN111848672B (en) * | 2020-08-26 | 2022-09-09 | 华东理工大学 | Continuous synthesis process of phosphonic acid tetramethyl succinate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3886205A (en) * | 1970-12-16 | 1975-05-27 | Bayer Ag | 2-Phosphono-butane-1,2,4-tricarboxylic acids |
| 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 |
-
1997
- 1997-09-03 CN CN97108210A patent/CN1048988C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3886205A (en) * | 1970-12-16 | 1975-05-27 | Bayer Ag | 2-Phosphono-butane-1,2,4-tricarboxylic acids |
| 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 |
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Effective date of registration: 20030214 Address after: Hunan province Yueyang city Yunxi District of Baling Petrochemical Limited liability company technology development department Patentee after: Baling Petrochemical Co., Ltd., SINOPEC Address before: Yunxi town Yueyang city Hunan Province Patentee before: Yueyang Petrochemical general Plant, Baling Petrochemical Corp. |
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