CN111393473A - Preparation method of ethyl methyl ethyl phosphinate - Google Patents
Preparation method of ethyl methyl ethyl phosphinate Download PDFInfo
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- CN111393473A CN111393473A CN202010359373.3A CN202010359373A CN111393473A CN 111393473 A CN111393473 A CN 111393473A CN 202010359373 A CN202010359373 A CN 202010359373A CN 111393473 A CN111393473 A CN 111393473A
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- -1 ethyl methyl ethyl Chemical group 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 14
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 claims description 41
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 15
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- HCDWPKSCTVCUAM-UHFFFAOYSA-N 1-[ethyl(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)CC HCDWPKSCTVCUAM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- AGWPTXYSXUNKLV-UHFFFAOYSA-N ethoxy-methyl-oxophosphanium Chemical compound CCO[P+](C)=O AGWPTXYSXUNKLV-UHFFFAOYSA-N 0.000 claims 4
- 238000007259 addition reaction Methods 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 abstract description 18
- 238000009776 industrial production Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000000630 rising effect Effects 0.000 abstract description 6
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- BCDIWLCKOCHCIH-UHFFFAOYSA-M methylphosphinate Chemical compound CP([O-])=O BCDIWLCKOCHCIH-UHFFFAOYSA-M 0.000 abstract 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention relates to the technical field of methyl phosphinate, and discloses a preparation method of ethyl methyl ethyl phosphinate. According to the preparation method of the ethyl methyl ethyl phosphinate, the increase of the temperature rising probability along with the rising of the highest temperature is avoided by the preparation method of the dropwise addition method, the safety risk is effectively reduced, the large-scale industrial production is facilitated, the reaction rate does not tend to be reduced while the usage amount of the catalyst is effectively reduced, the advantages of safety, simplicity in operation and the like are achieved, the purpose of large-scale industrial production can be achieved, the potential safety hazard in the one-pot conversion process is solved, and the problems that the one-pot reaction rate and efficiency are relatively slow, the safety risk is high, and the large-scale amplification is difficult are solved.
Description
Technical Field
The invention relates to the technical field of organic phosphinates, in particular to a preparation method of ethyl methyl ethyl phosphinate.
Background
The organic phosphinate has high phosphorus content and good flame retardance, and simultaneously, the molecular structure of the organic phosphinate is introduced with alkyl, so that the hydrophobicity and the thermal decomposition temperature of the organic phosphinate are greatly improved compared with inorganic phosphinate, the organic phosphinate is applied to a high polymer material, cannot migrate and absorb moisture, can tolerate high processing temperature, cannot cause the reduction of the insulating property of the material, has compatibility with matrix resin, and can maintain the mechanical property of the matrix material. Due to the characteristics of the excellent flame retardant, the flame retardant is widely applied to the fields of engineering plastics with high processing temperature, high shear strength, high CTI value and the like, in particular to the fields of glass fiber reinforced nylon, polyester and the like.
Diethyl methylphosphonite is a raw material for preparing flame retardant, which can be rearranged and isomerized into ethyl methylethylphosphinate under the action of catalyst, and the product can be used for preparing alkyl hypophosphite. With the increasing demand for alkyl phosphinate salts, there is a current need for large-scale production of ethyl methyl ethyl phosphinate. However, in the prior art reports, diethyl methylphosphonite is usually subjected to isomerization conversion by a one-pot method, and is mostly in the order of ten grams.
Disclosure of Invention
Technical problem to be solved
When the feeding amount of the one-pot method is increased, the inventor finds that a great deal of heat is suddenly released from a reaction system in the early stage of the isomerization conversion process of diethyl methylphosphonite, so that the temperature of the reaction system is sharply increased, for example, the temperature of the reaction system is rapidly increased from 120 ℃ to 170 ℃ or even higher within a few seconds, so that the temperature is easily flushed, flushed and even exploded in the production process, and huge economic losses and risks of casualties are caused. In order to solve the problems, when a one-pot method is adopted, a large amount of solvent can only be added for dilution, which inevitably causes the reduction of the production efficiency, and meanwhile, a series of post-treatment units are added for separating the product and the introduced solvent, so that the steps are complicated, the production efficiency is not high, and the production cost is further increased.
In order to solve the problems, the invention provides a preparation method of ethyl methyl ethylphosphinate, which has the advantages of safety, simple operation and the like, can be used for large-scale industrial production and solves the problems that diethyl methyl phosphinate is usually subjected to isomerization conversion by a one-pot method, the one-pot conversion process has potential safety hazards, the reaction rate and efficiency are relatively slow, the safety risk is high, and large-scale amplification is difficult in the conventional isomerization preparation method.
(II) technical scheme
In order to realize the advantages of safety, simple operation and the like and realize the purpose of large-scale industrial production, the invention provides the following technical scheme:
in one aspect, the invention provides a preparation method of ethyl methyl ethyl phosphinate, which is characterized by comprising the following steps:
firstly, mixing a substrate and a catalyst, adding diethyl methylphosphonite into a reaction system in a dropwise manner, and reacting to generate ethyl methylethylphosphinate; the substrate is selected from one or more of ethyl methyl ethylphosphinate, diethyl methyl phosphonite or an organic solvent.
Under the dropwise adding mode, with the continuous addition of diethyl methylphosphonite, the reaction rate is not reduced but improved, and the production efficiency is improved. In addition, fresh catalyst does not need to be supplemented in the reaction process, and compared with a one-pot method, the total catalyst consumption can be greatly reduced, thereby being beneficial to the control and reduction of production cost.
Typically, the initial concentration of catalyst in the system after mixing the substrate with the catalyst is from 3 wt% to 10 wt%.
Preferably, the substrate is ethyl methyl ethyl phosphinate. The efficiency varies with different substrates. Compared with the method using ethyl methyl ethylphosphinate as a substrate, when diethyl methyl phosphinate is used as the substrate, diethyl methyl phosphinate and a catalyst react, so that the two are mixed and then need to react for a period of time according to a one-pot method standard, and then the next step is carried out, so that the efficiency is reduced; when an organic solvent is used as a substrate, the subsequent separation steps exist, and the process is relatively complex.
The organic solvent can be selected from inert solvents with the boiling point of more than or equal to 70 ℃, and the inert solvents are selected from one or more of benzene, toluene, xylene, trimethylbenzene, chlorobenzene, 1, 4-dioxane, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide.
Preferably, the catalyst is sodium iodide or ethyl iodide. However, it is understood that one skilled in the art, in light of the present disclosure, can select other suitable catalysts without departing from the scope of the present invention.
The reaction temperature of the reaction is 70-170 ℃, preferably 120-140 ℃. The reaction temperature is too low, and the reaction rate is slow; too high a reaction temperature will increase the safety risk. However, it should be understood that other suitable temperatures can be selected by one skilled in the art in light of the teachings of the present invention without departing from the scope of the present invention.
The dropping is carried out in a continuous or batchwise manner. Diethyl methylphosphonite is a flammable and explosive reaction raw material, has a large safety risk when a traditional kettle type reaction is carried out, and can reduce the safety risk by adopting modes of controlling reaction scale, reaction rate and the like. It is therefore a further advantage of the present invention that the dropwise addition can be carried out with a reduced risk of the accumulation of dangerous reaction raw materials and also with a reduced risk of the violent exothermic reactions.
The batch dropwise adding is to divide the diethyl methylphosphonite into more than one reaction batch, and perform batch dropwise adding, wherein the reaction mixture of each reaction batch is obtained after the diethyl methylphosphonite of each reaction batch is dropwise added, and preferably, after the content of the diethyl methylphosphonite in the reaction mixture of the reaction batch is more than 80%, the diethyl methylphosphonite of the subsequent reaction batch is added, so that the safety risk can be reduced better.
The dripping speed can be adjusted according to the actual production condition and the productivity. However, since the reaction is exothermic, the dropping rate is preferably controlled so that the temperature in the reaction system does not exceed the maximum value of the aforementioned preferred reaction temperature.
In some embodiments of the invention, diethyl methylphosphonite is added dropwise in portions of 5 to 10 parts. However, it should be understood that in actual production, those skilled in the art can select other suitable batch quantities for dripping according to actual situations and needs without departing from the protection scope of the present invention.
Preferably, in the dropwise addition-divided reaction batches, the amount of diethyl methylphosphonite used in each reaction batch is increased in turn, so that the production efficiency can be improved. The successively larger amounts may be adjusted depending on the actual production conditions and productivity, and at the same time, the amount of diethyl methylphosphonite used per batch and the dropping rate of the batch are correlated with each other, and are preferably controlled so that the temperature in the reaction system does not exceed the maximum value of the aforementioned preferred reaction temperature.
In some embodiments of the invention, each batch of dropwise addition takes about 1 hour. However, it should be understood that in actual production, one skilled in the art can select shorter or longer dropping time as required without departing from the scope of the present invention. The choice of the time interval for the dropwise addition is also within the abilities of the person skilled in the art, without departing from the scope of the present invention.
Preferably, the diethyl methylphosphonite is added dropwise at a rate such that the temperature of the system does not exceed the maximum temperature required for the reaction, thereby reducing the safety risk.
The mass concentration of the catalyst in the system is 0.09 wt% -10 wt%, and preferably 0.09 wt% -3 wt%.
Preferably, the reaction apparatus is replaced three times with an inert gas, which may be nitrogen or argon, and kept dry before the reaction. The reaction apparatus may be a four-neck flask or a production reaction apparatus, and any suitable apparatus or vessel is within the scope of the present invention.
Preferably, during the reaction, an inert gas blanket is performed, which may be nitrogen or argon.
In another aspect, the present invention provides ethyl methyl ethylphosphinate prepared by the process of the present invention.
In yet another aspect, the present invention provides a process for the preparation of an alkyl hypophosphite salt, after which the ethyl methyl ethylphosphinate obtained is further used for the preparation of an alkyl hypophosphite salt.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation method of ethyl methyl ethyl phosphinate, which has the following beneficial effects:
the preparation method of the ethyl methyl ethyl phosphinate is a preparation method by a dropping method, so that the temperature rising probability is prevented from increasing along with the rising of the highest temperature, the safety risk is effectively reduced, the large-scale industrial production is facilitated, the reaction rate does not tend to decrease while the usage amount of the catalyst is effectively reduced, the production efficiency is improved, the advantages of safety, simple operation and the like are achieved, and the purpose of large-scale industrial production can be achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
MDEP: methylphosphinic acid diethyl ester
The method comprises the following steps of:
1-0#, replacing a four-neck flask with nitrogen for three times, keeping the interior of the flask dry, adding 80g of diethyl methylphosphonite and 80g of trimethylbenzene into the four-neck flask, taking 2.4g of iodoethane by using an injector, adding the iodoethane into the four-neck flask, wherein the content of the catalyst in the system is 1.48 wt%, performing nitrogen protection in the process, setting the oil bath temperature to be 140 ℃, gradually heating to raise the temperature, starting timing after the temperature of the reaction system in the flask rises to 130 ℃, maintaining the state for about 3 hours, and detecting at 1 hour until the target product is 89%; detecting at 2h, wherein the target product is 95%; and detection is carried out for 3h, the reactant is completely converted, the target product is 97%, obvious temperature flushing does not occur in the reaction process, and the highest temperature is 142 ℃.
1-1#, the catalyst content ratio in the system was changed to 0.99 wt%, and the amounts and conditions of other substrates were kept consistent with those of the test conditions # 1-0, and the results are shown in Table 1.
1-2# and changing the catalyst content ratio in the system to 0.49 wt%, respectively, and reducing the substrate dosage, i.e., using 20g of diethyl methylphosphonite and 20g of trimethylbenzene, the other conditions were kept consistent with the test conditions # 1-0, and the results are shown in Table 1.
1-2 #', the temperature of the reactants was varied on a 1-2# basis, and a timer was started when 115 ℃ was reached, with the other conditions remaining consistent with the test conditions # 1-2, and the results are set forth in Table 1.
1-3# keeping the catalyst content in the system at 1.48% by weight, increasing the substrate dosage, i.e. using 180g of diethyl methylphosphonite and 180g of trimethylbenzene, the other conditions remaining identical to those of the test # 1-0, and the results are given in Table 1.
TABLE 1
Example two:
dropwise addition in portions with trimethylbenzene:
the four-necked flask was replaced with nitrogen three times, and the inside of the flask was kept dry. 1100g of diethyl methylphosphonite is divided into 5 parts (0#, 1#, 2#, 3#, 4#), and each part is 220g on average. Diethyl methylphosphonite 0# and 440g trimethylbenzene were added to a four-necked flask, and 6.6g of iodoethane was taken by a syringe and added to the four-necked flask, with nitrogen protection being taken into account. The oil bath temperature was set at 140 ℃ and gradually heated, and the temperature of the reaction system in the flask was raised to 130 ℃ and then the time was counted to maintain this state for about 2 hours.
Subsequently, the internal temperature of the reaction system is maintained at 130-140 ℃, a syringe pump is adopted to continuously drop diethyl methylphosphonite 1# -4# into the reaction system, the dropping time of each batch is 1h, the dropping time of each batch is timed, and the content of the target product is detected in 1.25h, 1.5h and 2h of each batch respectively, which are listed in table 2.
The data are shown in table 2, wherein the catalyst content in the system is uniformly changed along with the dropwise addition of diethyl methylphosphonite and gradually decreases, and the catalyst content in the listed system is listed as 2 groups of data, namely an initial value and the catalyst content in the system after a single batch of diethyl methylphosphonite is completely added; the mass ratio of the diethyl methylphosphonite to the trimethylbenzene is in a single batch range, and the ratio of the diethyl methylphosphonite to the trimethylbenzene in an actual system needs to be dropwise added.
TABLE 2
Example three:
dropwise adding in batches, wherein trimethyl benzene is absent, and methyl ethyl phosphinate is used as a substrate:
the four-necked flask was replaced with nitrogen three times, and the inside of the flask was kept dry. Dividing 700g of diethyl methylphosphonite into 7 parts (0#, 1#, 2#, 3#, 4#, 5#, 8#), and averaging 100g of each part; in addition, 2 additional portions of diethyl methylphosphonite were prepared, 800g of diethyl methylphosphonite No. 6 and 1500g of diethyl methylphosphonite No. 7, respectively. 100g of ethyl methyl ethyl phosphinate is added into a four-neck flask, 3g of iodoethane is taken by an injector and added into the four-neck flask, and nitrogen protection is taken during the process. Setting the oil bath temperature to be 140 ℃, gradually heating to raise the temperature until the temperature of a reaction system in a bottle rises to 130 ℃, starting timing, maintaining the temperature in the reaction system to be 130-140 ℃, continuously dropwise adding diethyl methylphosphonite 0# into the reaction system by using an injection pump, starting timing, wherein the dropwise adding takes 1h, and detecting at 1.25h to obtain a target product of 92%; detecting for 1.5h, wherein the target product is 95%; the detection is carried out at 2h, and the target product is 97 percent.
Subsequently, the internal temperature of the reaction system is maintained at 130-140 ℃, a syringe pump is adopted to continuously drop diethyl methylphosphonite 1# -8 # into the reaction system, the dropping time of each batch is 1h, the dropping time of each batch is timed, and the content of the target product is detected in 1.25h, 1.5h and 2h of each batch respectively, which are listed in table 3. The catalyst content in the system is uniformly changed along with the dropwise addition of diethyl methylphosphonite and gradually decreases, and the catalyst content in the listed system is listed as 2 groups of data, namely an initial value and the catalyst content in the system after a single batch of diethyl methylphosphonite is completely added.
TABLE 3
And (4) judging the standard: in the early stage of the reaction process, due to the combined action of comprehensive factors such as reaction heat release characteristics, material accumulation, catalyst activity and the like, an obvious temperature runaway phenomenon can occur in a reaction system within a very short time range, the recorded highest temperature is the highest temperature which can be monitored in the temperature runaway process, and the excessive temperature indicates that the heat release is excessive in the reaction process, so that the temperature rush phenomenon occurs due to the fact that the actual reaction temperature is difficult to control. Therefore, in the one-pot method, after the dosage of the diethyl methylphosphonite is increased, the highest temperature is increased, the temperature-flushing probability is increased, the safety risk is increased, the method is not suitable for large-scale industrial production, moreover, in the one-pot method, the catalyst content in the system is not too low, the reaction rate is obviously reduced due to too low reaction rate, comparing the data with the number 2-4# (dropping method) and the number 1-2# (one-pot method), comparing 2-1# (dropping method) and 1-1# (one-pot method), it can be seen that the influence of catalyst content in the system on the reaction rate of one-pot method is large, when the catalyst content of the system is low, the reaction rate of one-pot method is relatively slow, while the reaction rate of the dropping method was not greatly affected, it can be seen from the data in Table 3 that when the catalyst content in the whole reaction system was reduced to 0.09 wt% to 0.10 wt%, no significant reduction tendency was seen in the whole reaction rate. Therefore, the skilled person has reason to consider that there is room for further reduction of the catalyst content in the system, thereby further improving production efficiency and reducing production costs.
The invention has the beneficial effects that: according to the preparation method of the ethyl methyl ethyl phosphinate, the increase of the temperature rising probability along with the rising of the highest temperature is avoided by the preparation method of the dropwise addition method, the safety risk is effectively reduced, the large-scale industrial production is facilitated, the reaction rate does not tend to be reduced while the usage amount of the catalyst is effectively reduced, the production efficiency is improved, the advantages of safety, simplicity in operation and the like are achieved, the purpose of large-scale industrial production can be achieved, and the problems that in the traditional isomerization preparation method, a one-pot method is usually adopted for isomerization conversion of diethyl phosphite, the potential safety hazard exists in the one-pot method conversion process, the one-pot method is relatively slow in reaction rate and efficiency, the safety risk is high, and the large-scale amplification is difficult are solved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of ethyl methyl ethyl phosphinate is characterized by comprising the following steps:
firstly, mixing a substrate and a catalyst, adding diethyl methylphosphonite into a reaction system in a dropwise manner, and reacting to generate ethyl methylethylphosphinate; the substrate is selected from one or more of ethyl methyl ethylphosphinate, diethyl methyl phosphonite or an organic solvent.
2. The method for preparing ethyl methyl ethylphosphinate according to claim 1, wherein the substrate is selected from ethyl methyl ethylphosphinate.
3. The method for preparing ethyl methyl ethylphosphinate according to claim 1, wherein the catalyst is sodium iodide or ethyl iodide.
4. The process for preparing ethyl methyl phosphinate according to claim 1, characterized in that the reaction temperature is between 70 ℃ and 170 ℃, preferably between 120 ℃ and 140 ℃.
5. The process for preparing ethyl methyl phosphinate according to any one of claims 1 to 4, wherein the dropwise addition is carried out continuously or in portions;
the batch dropwise adding is to divide the diethyl methylphosphonite into more than one reaction batch for batch dropwise adding, the reaction mixture of each reaction batch is obtained after the diethyl methylphosphonite of each reaction batch is dropwise added, and the diethyl methylphosphonite of the subsequent reaction batch is added when the content of the diethyl methylphosphonite in the reaction mixture of the reaction batch is more than 80 percent.
6. The method for preparing ethyl methyl phosphinate according to claim 5, wherein the amount of diethyl methylphosphonite used in each reaction batch is increased in turn in the dropwise addition reaction batches.
7. The process according to claim 1, wherein the diethyl methylphosphinate is added dropwise at a rate such that the maximum temperature required for the reaction is not exceeded by the system.
8. The preparation method of ethyl methyl phosphinate according to claim 1, characterized in that the mass concentration of the catalyst in the reaction system is 0.09-10 wt%, preferably 0.09-3 wt%.
9. Ethyl methyl ethylphosphinate prepared by the process of any one of claims 1 to 8.
10. A process for the preparation of an alkyl hypophosphite salt, characterized in that, after the process as claimed in any of claims 1 to 8, the ethyl methyl ethyl phosphinate obtained is further used to prepare an alkyl hypophosphite salt.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693237A (en) * | 2015-03-26 | 2015-06-10 | 洪湖市一泰科技有限公司 | Preparing method for dialkyl phosphinate salt |
| CN104693238A (en) * | 2015-03-26 | 2015-06-10 | 洪湖市一泰科技有限公司 | Preparing method for dialkyl group phosphinic acid alkyl ester and dialkyl phosphinate salt |
| CN104788493A (en) * | 2015-03-26 | 2015-07-22 | 洪湖市一泰科技有限公司 | Preparation method for dialkyl phosphinic acid and salt thereof |
| CN109293694A (en) * | 2018-11-30 | 2019-02-01 | 利尔化学股份有限公司 | One kettle way prepares methyl-phosphinic acid aluminium salt |
| CN109400643A (en) * | 2019-01-02 | 2019-03-01 | 利尔化学股份有限公司 | Methylethyl phosphinicacid ethyl ester and Methylethyl phosphinic acids aluminium salt preparation process |
| CN110229184A (en) * | 2019-07-25 | 2019-09-13 | 利尔化学股份有限公司 | The preparation method of Methylethyl phosphinic acids and its aluminium salt |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693237A (en) * | 2015-03-26 | 2015-06-10 | 洪湖市一泰科技有限公司 | Preparing method for dialkyl phosphinate salt |
| CN104693238A (en) * | 2015-03-26 | 2015-06-10 | 洪湖市一泰科技有限公司 | Preparing method for dialkyl group phosphinic acid alkyl ester and dialkyl phosphinate salt |
| CN104788493A (en) * | 2015-03-26 | 2015-07-22 | 洪湖市一泰科技有限公司 | Preparation method for dialkyl phosphinic acid and salt thereof |
| CN109293694A (en) * | 2018-11-30 | 2019-02-01 | 利尔化学股份有限公司 | One kettle way prepares methyl-phosphinic acid aluminium salt |
| CN109400643A (en) * | 2019-01-02 | 2019-03-01 | 利尔化学股份有限公司 | Methylethyl phosphinicacid ethyl ester and Methylethyl phosphinic acids aluminium salt preparation process |
| CN110229184A (en) * | 2019-07-25 | 2019-09-13 | 利尔化学股份有限公司 | The preparation method of Methylethyl phosphinic acids and its aluminium salt |
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