CN109912647A - A kind of synthetic method of dimethylphosphite - Google Patents
A kind of synthetic method of dimethylphosphite Download PDFInfo
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- CN109912647A CN109912647A CN201910211568.0A CN201910211568A CN109912647A CN 109912647 A CN109912647 A CN 109912647A CN 201910211568 A CN201910211568 A CN 201910211568A CN 109912647 A CN109912647 A CN 109912647A
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- dimethylphosphite
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Abstract
The invention discloses a kind of using phosphorous acid and methanol be catalytic material lactate synthesis dimethylphosphite synthetic method, concrete operations include: (1) by reaction mass crystal phosphorous acid, anhydrous methanol and catalyst autoclave；(2) it is higher than under condition of normal pressure, opens and stir and lift temperature to reaction temperature reaction a period of time；(3) after the reaction was completed, it steams outside negative pressure and is handled through two-stage rectification and obtain dimethylphosphite and high purity methanol respectively.The catalyst is the concentrated sulfuric acid or p-methyl benzenesulfonic acid, and the method for the present invention uses under condition of high voltage, is catalyzed phosphorous acid and methanol is that raw material reacts synthesizing phosphorous acid dimethyl ester, this method simple process without process such as depicklings, shortens reaction time；Stable product quality, yield is up to 85% or more；Realize the recycling of material, nontoxic byproduct generates, three-waste free discharge, safety and environmental protection, it is easy to accomplish industrialized production.
Description
Technical field
The invention belongs to catalyst preparation fields, and in particular to a kind of to be esterified using phosphorous acid, methanol as catalytic material
The synthetic method of synthesizing phosphorous acid dimethyl ester.
Background technique
Dimethylphosphite is widely used in fine chemicals industry, currently, industrialization product dimethylphosphite is big absolutely
It is the dimethylphosphite crude product that generates through condensation reaction of raw material after distillation removes solvent that majority, which is using phosphorus trichloride and methanol,
Smart ester generates low value by-product hydrogen chloride and chloropropane gas in condensation reaction simultaneously.Chinese patent CN
107082786 A disclose a kind of production method of dimethylphosphite, phosphorus trichloride and methanol through ferric trichloride catalytic 20 ~
10 ~ 20h is reacted at 30 DEG C, and dimethylphosphite is made, the by-product hydrogen chloride that cannot be removed in time in reaction process meeting and phosphorous again
Side reaction generation phosphorous acid occurs for dimethyl phthalate and chloromethanes, main side effect are exothermic reaction, spontaneous can carry out, and raw material turns
Rate and product yield reduce, and this method production cycle length, low output, frequent operation, large labor intensity, and production tail gas increases
Environmental pressure and processing cost.Solventless method, continuous production mode preferably resolve the above problem, and by-product is easy
Separation, product yield and quality are higher.The patent of 107488193 A of publication No. CN discloses a kind of from yellow phosphorus, chlorine, methanol
The method of continuous production dimethylphosphite, but due to production equipment cannot reach fast reaction, the requirement of quick separating and
The method of manual control flow cannot accurately control raw material proportioning, and country's solventless method production technology is in serialization, automatic at present
And there is still a need for be further improved and optimize for optimal control.
Phosphitylated method is to produce the another method of phosphite ester, is raw material in catalyst action using phosphorous acid and alcohol
Lower direct esterification, product are phosphite ester and water.But less, United States Patent (USP) is reported in the document of the preparation method at home and abroad
US3725515A discloses a kind of using the straight chain of phosphorous acid and excessive carbon atom quantity >=4 or with the fatty alcohol of branch
Direct reaction prepares the alkyl phosphite of long-chain, and this method carries out under inert gas shielding or condition of negative pressure, by-product
(alkene, ether) is more.Li Lei etc. is reported using methanol and phosphorous acid as raw material, and toluene is azeotropic aqua, SO4 2-/ TiO2Solid
Super acids are catalyst preparation dimethylphosphite, and product yield is 80% or so, and yield is relatively low, while this method uses
The organic water entrainer of benzene series that is more toxic, environmental protection and post processing cost are big, are unfavorable for industrialized production.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of synthesis side of simply and easily dimethylphosphite
Method.
A kind of synthetic method of dimethylphosphite, specifically includes the following steps: under (1) normal temperature and pressure, by phosphorous acid, nothing
Autoclave is added in water methanol and catalyst；(2) it is higher than under normal pressure, opens stirring and all dissolve and lift temperature to anti-to phosphorous acid
Answer thermotonus 1h or more；(3) after the reaction was completed, it steams outside negative pressure and is separated through rectifying and dimethylphosphite is made, it is isolated
First alcohol and water can recycle respectively.
Wherein, the step (1) phosphorous acid, anhydrous methanol mass fraction be respectively 5 ~ 20 parts and 80 ~ 95 parts.
Wherein, which is characterized in that the dosage of catalyst accounts for the quality hundred of crystal phosphorous acid inventory in the step (1)
Divide than being 1 ~ 15%.
Wherein, the catalyst can choose any one of the concentrated sulfuric acid or p-methyl benzenesulfonic acid.
Wherein, the step (2) mesohigh reaction pressure range is 0.1MPa ~ 0.5MPa.
Wherein, range of reaction temperature is 80 ~ 120 DEG C in the step (2).
Wherein, the step (3) specifically: ester -ol-three component gas of water that (S1) steams negative pressure simultaneously enters cold
Condenser, condensation obtain dimethylphosphite crude product；(S2) obtained dimethylphosphite crude product and methanol are boiled again, largely
Methanol water a small amount of in dimethylphosphite is taken out of, obtain dimethylphosphite sterling.
Further, (S1) and (S2) obtains methanol-water gas and is passed through methanol rectifying tower in the step (3), obtains
Purity is greater than 99% methanol, and the reboiler for being passed through S2 in the reaction kettle of the esterification and step 3 of step 1 again recycles.
Further, in the step S2, the crude product quality ratio of the methanol and dimethylphosphite that are passed through is 1-5:1.
Wherein, the condenser is aerial condenser, and top export temperature is 60-100 DEG C.
Now in the art, one of dimethylphosphite synthetic route is reacted to obtain phosphorous using methanol and phosphorous acid
Dimethyl phthalate, specific reaction are as follows:.The reaction presently, there are the problem of be the selection of catalyst and the selection of water entrainer.This hair
It is bright that using a large amount of methanol, (molar ratio of methanol and phosphorous acid is 10 ~ 25:1), is not only used as reaction raw materials, but also as organic molten
Agent.A large amount of methanol ensure that the fully reacting of phosphorous acid.Simultaneous selection water imbibition is strong, highly acid, the higher boiling that can be dissolved in alcohol
Bronsted acid p-methyl benzenesulfonic acid or the concentrated sulfuric acid cooperate a large amount of methanol, ensure that the phosphorous of height ratio in product as catalyst
Dimethyl phthalate, one methyl esters of phosphorous acid almost without.
The prior art generally uses the organic water entrainer of benzene series, is more toxic, it is known in the art that first alcohol and water not azeotropic.But
It is it is a discovery of the invention that when using a large amount of methanol water entrainer can not used, dimethylphosphite, first alcohol and water can be same
When gasify (being not azeotropic), band water outlet, allow esterification to continue.Obtained ester-water-alcohol ternary gas enters condensation
Device, the higher dimethylphosphite of boiling point condense to obtain dimethylphosphite crude product, and then crude product enters reboiler, continues to be passed through
A large amount of methanol boil again, take remaining water out of, obtain dimethylphosphite sterling.The methanol-water gas of discharge enters methanol rectification
Tower obtains the methanol of high-purity, can return reaction kettle and reboiler is recycled.Whole process only generates water, does not have to environment
Any influence.
Beneficial effect of the invention:
(1) using phosphorous acid and methanol as catalytic material lactate synthesis dimethylphosphite, without process, nontoxic pair such as depicklings
Product generation, simple process, easy-to-operate；
(2) it is reacted under condition of high voltage, shortens reaction time of esterification, improve product yield；
(3) on the one hand the use of excessive methanol can serve as esterification solvent, while also providing azeotropic band water for post-processing
Agent；
(4) this method byproduct water and excessive methanol recyclable recycling, no three wastes after rectifying separates generate.
Specific embodiment
In order to further illustrate essentiality content of the invention, it is illustrated in connection with specific embodiments, needs to explain
, the content of present invention includes but are not limited to following embodiment.
Embodiment 1
(1) successively by 400g phosphorous acid, 2267g anhydrous methanol, (phosphorous acid and anhydrous methanol mass percent are respectively 15% He
85%) high pressure stainless steel cauldron is added to 24g catalyst p-methyl benzenesulfonic acid；
(2) system is forced into 0.1MPa, opens stirring and all dissolves to phosphorous acid and lift temperature to 116 ± 2 DEG C, heat preservation back flow reaction
2 hours；
(3) reaction terminates, and decrease temperature and pressure, and outer steaming obtains colourless through rectifying separating treatment under 0.02 ~ 0.03MPa condition of negative pressure
Prescribed liquid dimethylphosphite 456.38g feeds intake meter product yield with phosphorous acid as 85.05%；Recycle methanol 1866.05g
(rate of recovery 95.45%) is circularly used for the synthetic reaction of dimethylphosphite；The reaction product water rate of recovery is 93.06%.
Through testing and analyzing: the chromatographic purity of dimethylphosphite is 97.18%, acidity (in terms of HCl) 0.37%；Recycle methanol
Chromatographic purity 99.57%.
Embodiment 2
(1) successively by 400g phosphorous acid, 3600g anhydrous methanol, (phosphorous acid and anhydrous methanol mass percent are respectively 10% He
90%) high pressure stainless steel cauldron is added to the 16g catalyst concentrated sulfuric acid；
(2) system is forced into 0.2MPa, opens stirring and all dissolves to phosphorous acid and lift temperature to 108 ± 2 DEG C, heat preservation back flow reaction
1.5 hour；
(3) reaction terminates, and decrease temperature and pressure, and outer steaming obtains colourless through rectifying separating treatment under 0.02 ~ 0.03MPa condition of negative pressure
Prescribed liquid dimethylphosphite 484.25g feeds intake meter product yield with phosphorous acid as 87.82%；Recycle methanol 3186.67g
(rate of recovery 96.23%) is circularly used for the synthetic reaction of dimethylphosphite；The reaction product water rate of recovery is 92.07%.
Through testing and analyzing: the chromatographic purity of dimethylphosphite is 97.31%, acidity (in terms of HCl) 0.45%；Recycle methanol
Chromatographic purity 99.29%.
Embodiment 3
(1) successively by 400g phosphorous acid, 2900g anhydrous methanol, (phosphorous acid and anhydrous methanol mass percent are respectively 12.5% He
87.5%) high pressure stainless steel cauldron is added to 32g catalyst p-methyl benzenesulfonic acid；
(2) system is forced into 0.3MPa, opens stirring and all dissolves to phosphorous acid and lift temperature to 95 ± 2 DEG C, heat preservation back flow reaction 2
Hour；
(3) reaction terminates, and decrease temperature and pressure, and outer steaming obtains colourless through rectifying separating treatment under 0.02 ~ 0.03MPa condition of negative pressure
Prescribed liquid dimethylphosphite 480.75g feeds intake meter product yield with phosphorous acid as 87.49%；Recycle methanol 2545.51g
(rate of recovery 97.66%) is circularly used for the synthetic reaction of dimethylphosphite；The reaction product water rate of recovery is 91.09%.
Through testing and analyzing: the chromatographic purity of dimethylphosphite is 97.65%, acidity (in terms of HCl) 0.36%；Recycle methanol
Chromatographic purity 99.29%.
Embodiment 4
(1) successively by 400g phosphorous acid, 1600g anhydrous methanol, (phosphorous acid and anhydrous methanol mass percent are respectively 20% He
80%) high pressure stainless steel cauldron is added to the 24g catalyst concentrated sulfuric acid；
(2) system is forced into 0.3MPa, opens stirring and all dissolves to phosphorous acid and lift temperature to 118 ± 2 DEG C, heat preservation back flow reaction
0.75 hour；
(3) reaction terminates, and decrease temperature and pressure, and outer steaming obtains colourless through rectifying separating treatment under 0.02 ~ 0.03MPa condition of negative pressure
Prescribed liquid dimethylphosphite 449.39g feeds intake meter product yield with phosphorous acid as 80.71%；Recycle methanol 1233.34g
(rate of recovery 95.23%) is circularly used for the synthetic reaction of dimethylphosphite；The reaction product water rate of recovery is 92.07%.
Through testing and analyzing: the chromatographic purity of dimethylphosphite is 96.37%, acidity (in terms of HCl) 0.58%；Recycle methanol
Chromatographic purity 99.45%.
Embodiment 5
Successively by 100g phosphorous acid, 1900g anhydrous methanol (phosphorous acid and anhydrous methanol mass percent be respectively 5% and 95%) with
The 10g catalyst concentrated sulfuric acid is added to high pressure stainless steel cauldron, other operating conditions are the same as embodiment 3.
Colourless transparent liquid dimethylphosphite 94.40g is handled to obtain, is with the phosphorous acid meter product yield that feeds intake
70.37%；The recycling methanol 1766.95g(rate of recovery 96.38%) it is circularly used for the synthetic reaction of dimethylphosphite；Reaction produces
The object water rate of recovery is 90.29%.
Through testing and analyzing: the chromatographic purity of dimethylphosphite is 96.21%, acidity (in terms of HCl) 0.47%；Recycle methanol
Chromatographic purity 99.38%.
Embodiment 6
(1) successively by 200g phosphorous acid, 1800g anhydrous methanol, (phosphorous acid and anhydrous methanol mass percent are respectively 10% He
90%) high pressure stainless steel cauldron is added to 26g catalyst p-methyl benzenesulfonic acid；
(2) system is forced into 0.2MPa, opens stirring and all dissolves to phosphorous acid and lift temperature to 110 ± 2 DEG C, heat preservation back flow reaction
3 hours；
(3) reaction terminates, and decrease temperature and pressure, and outer steaming obtains colourless through rectifying separating treatment under 0.02 ~ 0.03MPa condition of negative pressure
Prescribed liquid dimethylphosphite 239.60g feeds intake meter product yield with phosphorous acid as 87.33%；Recycle methanol 1585.66g
(rate of recovery 95.84%) is circularly used for the synthetic reaction of dimethylphosphite；The reaction product water rate of recovery is 90.98%.
Through testing and analyzing: the chromatographic purity of dimethylphosphite is 97.79%, acidity (in terms of HCl) 0.44%；Recycle methanol
Chromatographic purity 99.36%.
Comparative example 1
In the prior art, methanol and phosphorous acid molar ratio are 3 to 1, repeat embodiment 1.
Through testing and analyzing: dimethylphosphite yield is 48.12%, product acidity (in terms of HCl) 18.55%.
Comparative example 2
Using the p-methyl benzenesulfonic acid in high strong acid alternative embodiment 1, embodiment 1 is repeated
Through testing and analyzing: dimethylphosphite yield is 95%, product acidity (in terms of HCl) 0.9%.
Claims (10)
1. a kind of synthetic method of dimethylphosphite, which is characterized in that specifically includes the following steps:
Under normal temperature and pressure, autoclave is added in phosphorous acid, anhydrous methanol and catalyst；
1h or more is reacted higher than under normal pressure, opening stirring and all dissolving to phosphorous acid and lift temperature to reaction temperature；
After the reaction was completed, it steams outside negative pressure and is separated through rectifying and dimethylphosphite is made, isolated first alcohol and water can be distinguished
It recycles.
2. a kind of synthetic method of dimethylphosphite according to claim 1, which is characterized in that the step (1)
Phosphorous acid, anhydrous methanol mass fraction be respectively 5 ~ 20 parts and 80 ~ 95 parts.
3. a kind of synthetic method of dimethylphosphite according to claim 1, which is characterized in that the step (1)
The mass percent that the dosage of middle catalyst accounts for crystal phosphorous acid inventory is 1 ~ 15%.
4. according to claim 3, which is characterized in that the catalyst can choose in the concentrated sulfuric acid or p-methyl benzenesulfonic acid
It is any.
5. a kind of synthetic method of dimethylphosphite according to claim 1, which is characterized in that the step (2)
Mesohigh reaction pressure range is 0.1MPa ~ 0.5MPa.
6. a kind of synthetic method of dimethylphosphite according to claim 1, which is characterized in that the step (2)
Middle range of reaction temperature is 80 ~ 120 DEG C.
7. a kind of synthetic method of dimethylphosphite according to claim 1, which is characterized in that the step (3)
Specifically: ester -ol-three component gas of water that negative pressure steams simultaneously is entered condenser by (S1), and condensation obtains dimethylphosphite
Crude product；(S2) obtained dimethylphosphite crude product and methanol are boiled again, a large amount of methanol will be few in dimethylphosphite
The water of amount is taken out of, and dimethylphosphite sterling is obtained.
8. a kind of synthetic method of dimethylphosphite according to claim 7, which is characterized in that the step (3)
In (S1) and (S2) obtain methanol-water gas and be passed through methanol rectifying tower, obtain the methanol that purity is greater than 99%, be passed through step 1 again
Reaction kettle of the esterification and step 3 in the reboiler of S2 recycle.
9. a kind of synthetic method of dimethylphosphite according to claim 7, which is characterized in that the step S2
In, the crude product quality ratio of the methanol and dimethylphosphite that are passed through is 1-5:1.
10. a kind of synthetic method of dimethylphosphite according to claim 7, which is characterized in that the condenser
For aerial condenser, top export temperature is 60-100 DEG C.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2570512A (en) * | 1949-03-26 | 1951-10-09 | Universal Oil Prod Co | Manufacture of dialkyl hydrogen phosphites |
| US3725515A (en) * | 1967-10-13 | 1973-04-03 | Hoechst Ag | Process for the preparation of dialkyl phosphites from alcohols and phosphorous acid |
| DE4121696A1 (en) * | 1991-06-29 | 1993-01-07 | Wittenberg Stickstoff Ag | Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol |
| CN1445232A (en) * | 2002-10-10 | 2003-10-01 | 浙江新安化工集团股份有限公司 | New technique for synthesizing dialkyl ester phosphorous acid |
| WO2004096287A2 (en) * | 2003-04-25 | 2004-11-11 | Gilead Sciences, Inc. | Inosine monophosphate dehydrogenase inhibitory phosphonate compounds |
| CN101214940A (en) * | 2008-01-11 | 2008-07-09 | 山东潍坊润丰化工有限公司 | Method for producing phosphorous acid from dimethyl phosphite high boiling by-product |
| CN105713037A (en) * | 2016-03-19 | 2016-06-29 | 安徽东至广信农化有限公司 | Production technology of dimethyl phosphite |
| CN107501318A (en) * | 2017-07-13 | 2017-12-22 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate intermediate dimethylphosphite |
-
2019
- 2019-03-20 CN CN201910211568.0A patent/CN109912647A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2570512A (en) * | 1949-03-26 | 1951-10-09 | Universal Oil Prod Co | Manufacture of dialkyl hydrogen phosphites |
| US3725515A (en) * | 1967-10-13 | 1973-04-03 | Hoechst Ag | Process for the preparation of dialkyl phosphites from alcohols and phosphorous acid |
| DE4121696A1 (en) * | 1991-06-29 | 1993-01-07 | Wittenberg Stickstoff Ag | Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol |
| CN1445232A (en) * | 2002-10-10 | 2003-10-01 | 浙江新安化工集团股份有限公司 | New technique for synthesizing dialkyl ester phosphorous acid |
| WO2004096287A2 (en) * | 2003-04-25 | 2004-11-11 | Gilead Sciences, Inc. | Inosine monophosphate dehydrogenase inhibitory phosphonate compounds |
| CN101214940A (en) * | 2008-01-11 | 2008-07-09 | 山东潍坊润丰化工有限公司 | Method for producing phosphorous acid from dimethyl phosphite high boiling by-product |
| CN105713037A (en) * | 2016-03-19 | 2016-06-29 | 安徽东至广信农化有限公司 | Production technology of dimethyl phosphite |
| CN107501318A (en) * | 2017-07-13 | 2017-12-22 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate intermediate dimethylphosphite |
Non-Patent Citations (1)
| Title |
|---|
| 李蕾等: "固体超强酸催化合成亚磷酸二甲酯", 《华中师范大学学报》 * |
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Application publication date: 20190621 |