CN1215074C - New technique for synthesizing dialkyl ester phosphorous acid - Google Patents
New technique for synthesizing dialkyl ester phosphorous acid Download PDFInfo
- Publication number
- CN1215074C CN1215074C CN 02150012 CN02150012A CN1215074C CN 1215074 C CN1215074 C CN 1215074C CN 02150012 CN02150012 CN 02150012 CN 02150012 A CN02150012 A CN 02150012A CN 1215074 C CN1215074 C CN 1215074C
- Authority
- CN
- China
- Prior art keywords
- technology
- phosphite
- boiling point
- phosphorous acid
- high boiling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
The present invention relates to a novel improved technology for phosphorous acid dialkyl ester. In the technology, phosphorus trichloride and alkyl monohydric alcohol are used as raw materials, and the carbon number of the alkyl monohydric alcohol is 1 to 8. The novel improved technology is different from the original technology that generated substances containing phosphorous acid single alkyl ester, phosphorous acid, etc. are converted into phosphorous acid dialkyl ester again by using high boiling point by-products of the substances. The yield of the novel improved technology is much larger than that of the original technology for the preparation of the phosphorous acid dialkyl ester, and the yield can reach to 98 to 99.9%.
Description
Technical field
The present invention relates to the improvement of dialkyl phosphite production technology, more particular words is to utilize the by product that contains phosphorous acid that produces in the dialkyl phosphite production process to come the synthesizing phosphorous acid dialkyl.
Background technology
Contain
Or
(R is an alkyl, as methyl, ethyl, phenyl etc.) material of structure is called inferior phosphide dialkyl, this class material especially dimethylphosphite and diethyl phosphite is a kind of important chemical material and intermediate, and it is widely used in the preparation industry of organophosphorus acid type inhibiter, synthetic plastics auxiliary agent, dye additive, fire retardant and agricultural chemicals.With organophosphorus acid type and organic phospho acid---the water quality corrosion inhibiting and descaling agent of carboxylic acid type that it is produced, be widely used in industry and chemical cycle water treatment; It is auxiliary agent that the multiple phosphite ester compound of producing with it is widely used in the phosphorus of making difference in functionality in the plastics industry, the additive in dyestuffs industries and the oil product; Simultaneously, it still produces the important intermediate of organophosphorus insecticide such as Trichlorphon, SD-1750, Kitazine, omethoate, glyphosate etc.The output of domestic inferior phosphide dialkyl has reached 200,000 tons.
The production method of inferior phosphide dialkyl is a lot, and present industrialized method mainly contains two kinds: the one, and be the solvent method or the solventless method of raw material with phosphorus trichloride and corresponding alcohol (as methyl alcohol, ethanol etc.); The 2nd, be the esterification process of raw material with phosphorous acid with corresponding alcohol (as methyl alcohol, ethanol etc.).To produce dialkyl phosphite be maximum problem of research both at home and abroad and directly reacted with alcohol by phosphorus trichloride, and its industrial production technology integrates and is divided into following two kinds of situations (is example with the dimethylphosphite):
1) is reflected at the industrial production technology that carries out in the organic medium.
This technology is normally lower temperature (general≤10 ℃), do not having or having under the condition that acid binding agent (organic amine or ammonia) exists, in inert or halogenated organic solvent by phosphorus trichloride directly and methyl alcohol react and produce dimethylphosphite.Industrial production has interrupter method and continuous processing.This method reaction conditions gentleness, operational safety are easily controlled, but yield is subjected to all multifactor influences and instability.With the phosphorus trichloride be the yield that calculates of benchmark usually at 65-90%, and the recovery set of solvent is with having increased process cost.
2) solvent-free serialization industrial production technology
In this industrial production technology, have plenty of the gas-phase reaction of carrying out, the dimethylphosphite yield is about 90%; Have plenty of liquid phase reaction, its yield is about 86-93%.The common advantage of solventless method production is that production rate is fast, product yield is high, and the purity of product can reach 98.9% as long as control is proper.Because production process is not used solvent, production cost and process cost are low again.Vapor phase process and liquid phase method are compared, and the former equipment is huge, the production investment is bigger, and the latter's production investment much less.But solventless method is higher to ingredient requirement, especially methyl alcohol.This method is accepted by domestic and international producer now.
The weak point that the above-mentioned phosphorous acid dialkyl production method that generally adopts exists is that the industrialization yield is lower than 93%, and having by product (during product purification remaining the higher thick material of boiling point) to produce, its major ingredient is phosphorous acid mono alkyl ester, phosphorous acid and their polymkeric substance or multipolymer.
For this class by product, application number is the method that 97123386 patent of invention discloses its manufacture phosphorous acid of a kind of usefulness, the by product that this method will be dropped is in the past turned waste into wealth, a kind of extraordinary method of can yet be regarded as, but handle this by product in this way, because low its added value of phosphorous acid value is not high.
Method provided by the present invention has solved the problems referred to above well, has improved existing dialkyl phosphite production technique, makes its yield reach 98-99.9%.
Summary of the invention
For the description of this invention is more clearly reached succinctly, with the dimethylphosphite is that example is explained the present invention, but this technology is equally applicable to the preparation of all dialkyl phosphite, and the present invention includes all is the technology that the monohydroxy-alcohol of 1-8 carries out the prepared in reaction dialkyl phosphite with phosphorus trichloride and carbonatoms.
Phosphorus trichloride is that phosphorus trichloride forms trimethyl phosphite with the methyl alcohol reaction earlier with its reaction mechanism of reaction that methyl alcohol directly contacts the synthesizing phosphorous acid dimethyl ester:
Trimethyl phosphite acidolysis in the presence of hydrogenchloride is a dimethylphosphite:
The side reaction that this process exists is that the further acidolysis of dimethylphosphite is phosphorous acid mono-methyl and phosphorous acid:
In order to reduce side reaction, existing processes is for adopt the method for vacuum and heating that it is removed (being called deacidification process) from system in the hydrogenchloride that generates rapidly in reaction process as far as possible, material when deacidification process finishes is called thick ester, but the acidolysis reaction of tricresyl phosphite (list, two) ester is comparatively rapid, often there are a considerable amount of phosphorous acid mono-methyls and phosphorous acid to generate, be dissolved among the thick ester, cause the main reaction yield not high.(100-170 ℃) generation at high temperature in product purification (employing rectificating method) process of phosphorous acid mono-methyl that generates and phosphorous acid contains P-O-P key polymkeric substance, and these by products are referred to as high boiling point by-products produced in the present invention.In original technology, the amount of its generation is about the 5-20% of product population.
High boiling point by-products produced its of producing in the dimethylphosphite production process consists of: the phosphorous acid mono-methyl is 0.1-70%, phosphorous acid 10-95%, polymkeric substance 0.1-20%, dimethylphosphite 1-10%.
In the synthetic and rectifying of production process of dimethyl, in vacuum tightness is also to isolate under the 10-200mmHg to account for the low-boiling point material that product population is 1-20%, be called low-boiling by-products, wherein contain methyl alcohol, trimethyl phosphite, synthetic system can return deacidification process in existing technology before is with hcl reaction generation dimethylphosphite and by product phosphorous acid mono-methyl and the phosphorous acid in the system.
The present invention has analyzed the composition of each operation generation material in the dimethylphosphite production process, the creationary proposition improved one's methods, make the yield of dimethylphosphite reach unprecedented 98-99.9%, for the entire reaction system, produce tedious high boiling point by-products produced (its weight be not more than target product 5%) hardly.
The method that the present invention adopts is to return in the synthetic system high boiling point by-products produced, with the intermediate trimethyl phosphite following reaction takes place:
In reaction system, phosphorus trichloride contacts with methyl alcohol one and promptly generates inferior phosphorus trimethyl, and the speed of response of trimethyl phosphite and phosphorous acid and phosphorous acid mono-methyl is very fast, in high boiling point by-products produced adding reaction system, the concentration of phosphorous acid and phosphorous acid mono-methyl in can the raising system, make its rapidly with the harsh trimethyl phosphite reaction formation target product that becomes, improved target product yield.The concentration of trimethyl phosphite is the highest in phosphorus trichloride contacts with methyl alcohol moment, and in order to promote high boiling point by-products produced conversion, it is dissolved in the methyl alcohol parallel feeding is method preferably, and high boiling point by-products produced weight concentration is 0.1-20%.Perhaps, generate target product with unconverted trimethyl phosphite reaction with high boiling point by-products produced adding deacidification process.
Also having a kind of this high boiling point by-products produced method of handling is to be that its 0.5-6.0 trimethyl phosphite doubly mixes with itself and weight, control reaction temperature is 0-110 ℃, reaction solution is returned the rectification working process of inferior phosphorus dimethyl ester production again or directly separate to obtain target product.Certainly taking cost into account, it is uneconomic adopting the commodity trimethyl phosphite, can adopt the low-boiling by-products that generates in the dimethylphosphite production process to replace or part replaces trimethyl phosphite, separate or directly make with extra care entering above-mentioned rectification working process after low-boiling by-products and the high boiling point by-products produced mixing.
In actual production, owing to have polymkeric substance in high boiling point by-products produced, color and luster is dark and contain mechanical impurity, therefore before being returned synthesis system, it is hydrolyzed behind water of high boiling point by-products produced weight 1-10% of adding earlier, it is necessary carrying out filtration treatment again, but the water yield that adds is to want strict control, if excessive, then in system, introduced water, will form phosphorous acid with raw material phosphorus trichloride or phosphite reactions.The add-on of considering water depend on high boiling point by-products produced in the amount of polymkeric substance, and the detection of this polymkeric substance is very difficult, excessive for preventing that sealing adds, also can not add entry, like this because polymkeric substance can not be converted into inferior phosphorus dimethyl ester, for whole production system, also generate a spot of high boiling point by-products producedly, the yield that is to say target product will not reach the level near 100% in theory.
Phosphorous acid that produces in the synthetic and deacidification process at dimethylphosphite or phosphorous acid mono-methyl are dissolved with to be separated in thick ester, and another kind of method is that with its all or part of target product that is converted into, this is most economical method before rectifying or distillation.Because the speed of response of trimethyl phosphite and phosphorous acid or phosphorous acid mono-methyl is very fast, under low concentration, also can carry out, the method that can take is to add the compound that contains trimethyl phosphite in thick ester, generate dimethylphosphite with phosphorous acid and the reaction of phosphorous acid mono-methyl, go rectifying or distillation again, isolate wherein low-boiling point material such as methyl alcohol, trimethyl phosphite and a spot of unreacted high boiling point by-products produced.The amount that adds the compound that contains trimethyl phosphite should determine that its content is 5%-20% usually according to the content of phosphorous acid in the thick ester or phosphorous acid mono-methyl, and the amount that then adds the compound that contains trimethyl phosphite is the 0.25-120% of thick ester weight.Certainly from economic angle, it is uneconomic adopting the commodity trimethyl phosphite, can adopt the low-boiling by-products that generates in the dimethylphosphite production process to replace the mixture of trimethyl phosphite or both arbitrary proportions.
Embodiment
Embodiments of the invention are all with the example that synthesizes of dimethylphosphite, but do not represent that this scheme is only applicable to the preparation of dimethylphosphite, this technical scheme are applied among synthetic the present invention of being also included within of other dialkyl phosphite.
Embodiment 1: take by weighing 72g industrial methanol (99%), place be equipped with stir and with chilled brine as heat-eliminating medium and have the four-hole boiling flask of spherical condenser, stir; Take by weighing 100g industry phosphorus trichloride (99%), keep vacuum tightness be-continue to come control reaction temperature below 40 ℃ by adding speed in the above-mentioned flask of adding under the 0.09MPa.Reaction finishes the back and heats up under-the 0.09MPa in vacuum tightness, is collected in fraction (being called low-boiling by-products) below 90 ℃ and 90-140 ℃ fraction (principal product) respectively, last remaining is high boiling point by-products produced, the difference weighing.
Embodiment 2: with embodiment 1, reaction the time add simultaneously 10g by embodiment 1 obtain high boiling point by-products produced.
Embodiment 3: with embodiment 1, raw material is in the high boiling point by-products produced 72g of the being dissolved in methyl alcohol that 18g is obtained by embodiment 1.
Embodiment 4: with embodiment 1,10g obtain by embodiment 1 high boiling point by-products produced in add 1g water, when reaction, add simultaneously behind the thorough mixing.
Embodiment 5: the high boiling point by-products produced and 20g trimethyl phosphite hybrid reaction with 15g is obtained by embodiment 1, again reaction solution is added in the reaction solution that makes by embodiment 1, and carry out underpressure distillation by the condition of embodiment 1 again.
Embodiment 6: with embodiment 5, trimethyl phosphite is replaced by the low-boiling by-products that embodiment 1 makes with 10g.
Embodiment 7: with embodiment 1, but added the 8g trimethyl phosphite before the fraction of 90-140 ℃ of collection, distill.
Embodiment 8: with embodiment 7, but replace trimethyl phosphite with 10g by the low-boiling by-products that embodiment 1 makes.
The experimental result tabulation
| Lot number | Principal product | Principal product content | High boiling point by-products produced | Yield | Remarks |
| g | ％ | g | ％ | ||
| 1 | 69.8 | 96.7 | 10.3 | 85.2 | Comparative Examples |
| 2 | 80.8 | 96.4 | 11.4 | 98.3 | |
| 3 | 81.0 | 96.9 | 13.5 | 99.1 | |
| 4 | 80.2 | 97.2 | 10.1 | 98.4 | |
| 5 | 82.6 | 95.8 | 0.5 | 99.9 | |
| 6 | 81.6 | 96.6 | 2.8 | 99.5 | |
| 7 | 80.8 | 96.7 | 5.4 | 98.6 | |
| 8 | 80.5 | 96.5 | 6.7 | 98.1 |
Claims (16)
1. one kind is the technology of raw material synthesizing phosphorous acid dialkyl with phosphorus trichloride and alkyl alcohol, it is characterized in that utilizing the high boiling point by-products produced dialkyl phosphite that generates that generates in its reaction process; Described high boiling point by-products produced for containing one or more the mixture in phosphorous acid mono alkyl ester, phosphorous acid, poly-phosphorous acid or the poly-phosphorous acid ester.
2. according to the technology of claim 1, described alkyl alcohol is the monohydroxy-alcohol of carbonatoms 1-8.
3. according to the technology of claim 2, described alkyl alcohol is selected from methyl alcohol and ethanol.
4. according to the technology of claim 1, described dialkyl phosphite is meant that structure is
Or
Compound, wherein R is that carbonatoms is the alkyl of 1-8.
5. according to the technology of claim 4, R is selected from methyl and ethyl.
6. according to the technology of claim 1, it is characterized in that the described high boiling point by-products produced preparation process of returning dialkyl phosphite.
7. according to the technology of claim 6, it is characterized in that high boiling point by-products produced being dissolved in the reaction raw materials alkyl alcohol fed intake, wherein high boiling point by-products produced mass percent is 0.1-20%.
8. according to the technology of claim 1, it is characterized in that high boiling point by-products produced the mixing with the material that contains trialkyl phosphite reacted, again reaction mass is returned the preparation process of dialkyl phosphite.
9. technology according to Claim 8, the described material that contains trialkyl phosphite are the low-boiling by-products that produces in trialkyl phosphite or the dialkyl phosphite production process or the mixture of its arbitrary proportion; Described low-boiling by-products is in trialkyl phosphite or the dialkyl phosphite production process, is isolated cut below 90 ℃ under the 10-200mmHg in vacuum tightness.
10. according to Claim 8,9 technology, high boiling point by-products produced and the weight ratio that contains the material of trialkyl phosphite are 1: 0.5-6.
11., it is characterized in that earlier high boiling point by-products produced and water or the solution that contains water are mixed its part or all of hydrolysis according to claim 6,7,8 technology.
12. according to the technology of claim 11, the add-on that it is characterized in that water is the 1-10% of high boiling point by-products produced weight.
13., it is characterized in that not from system, separating and in original system, adding the material that contains trialkyl phosphite and make it be converted into dialkyl phosphite with high boiling point by-products produced according to the technology of claim 1.
14. according to the technology of claim 13, the material that contains trialkyl phosphite is preferably and adds among the thick ester.
15. according to the technology of claim 14, the add-on that contains the material of trialkyl phosphite is the 0.25-120% of thick ester weight.
16. according to claim 13,14 or 15 technology, the described material that contains trialkyl phosphite is the low-boiling by-products that produces in trialkyl phosphite or the dialkyl phosphite production process or the mixture of its arbitrary proportion; Described low-boiling by-products is in trialkyl phosphite or the dialkyl phosphite production process, is isolated cut below 90 ℃ under the 10-200mmHg in vacuum tightness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02150012 CN1215074C (en) | 2002-10-10 | 2002-10-10 | New technique for synthesizing dialkyl ester phosphorous acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02150012 CN1215074C (en) | 2002-10-10 | 2002-10-10 | New technique for synthesizing dialkyl ester phosphorous acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1445232A CN1445232A (en) | 2003-10-01 |
| CN1215074C true CN1215074C (en) | 2005-08-17 |
Family
ID=27811353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02150012 Expired - Lifetime CN1215074C (en) | 2002-10-10 | 2002-10-10 | New technique for synthesizing dialkyl ester phosphorous acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1215074C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003188A (en) * | 2017-12-25 | 2018-05-08 | 长春吉大天元化学技术股份有限公司 | A kind of new purification process of alkyl phosphoric acid esters compound |
| CN109912647A (en) * | 2019-03-20 | 2019-06-21 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of dimethylphosphite |
| CN109824720A (en) * | 2019-03-29 | 2019-05-31 | 山东泰和水处理科技股份有限公司 | A kind of dimethylphosphite is continuously synthesizing to method and device |
-
2002
- 2002-10-10 CN CN 02150012 patent/CN1215074C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1445232A (en) | 2003-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101367833A (en) | Preparation method for organic phosphate nucleating agent | |
| JP5666535B2 (en) | Diarylalkylphosphonates and methods for their preparation | |
| CN1215074C (en) | New technique for synthesizing dialkyl ester phosphorous acid | |
| EP1808437A1 (en) | Method for producing phosphorus compound having phosphate-phosphonate bond | |
| CN112661790B (en) | Preparation method of dialkyl phosphinate | |
| CN1113847C (en) | Process for C-alkylation of malonic esters | |
| CN112010898B (en) | Novel method for preparing diaryl methyl substituted phosphonate | |
| CN1075954A (en) | 3-cyano group-3,5,5-trialkyl cyclohexanone catalyst and preparation method thereof | |
| CN100560593C (en) | The method for preparing alkyl phenyl phosphates | |
| CN101747367A (en) | Preparation method of glufosinate | |
| CN1699318A (en) | Improved process for preparing edible grease antioxidant 2-tert-butyl hydroquinone | |
| CN115141226B (en) | Preparation method of 3- (methyl alkoxy phosphoryl) propionate | |
| Zhang et al. | Intermolecular Carbophosphination of Alkynes with Phosphole Oxides via Ni− Al Bimetal‐Catalyzed C− P Bond Activation | |
| US5639909A (en) | Production of 2-phosphonobutane-1,2,4-tricarboxylic acid and the alkali metal salts thereof | |
| CN1121923A (en) | Process for the preparation of diesters of phosphonocarboxylic acid derivatives | |
| CN102448971A (en) | Method for the manufacture of dialkylphosphites | |
| CN1288074C (en) | Process for producing orthophosphorous acid from high boiling byproducts of dialkyl ester phosphite | |
| WO2023054663A1 (en) | Method for producing vinylphosphonic acid monoester | |
| CN112844488B (en) | Catalyst composition and application thereof in styrene hydroformylation reaction | |
| CN102807582A (en) | Preparation methods of organic phosphate ester and organic phosphate nucleating agent | |
| US20240058723A1 (en) | Method of purifying phosphorus compound and method of reusing the same | |
| WO2006049010A1 (en) | Method for producing phosphonate having alcoholic hydroxy group | |
| CN113292597A (en) | Preparation method of phosphate compound | |
| CN118126088A (en) | Synthesis method of antioxidant 626 with low 2,4 di-tert-butylphenol residue | |
| CN1894198A (en) | Method for producing alpha-fluoromalonic acid dialkyl esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050817 |
|
| CX01 | Expiry of patent term |