CN113200826A - Synthesis method of polymethoxy dialkyl ether - Google Patents

Synthesis method of polymethoxy dialkyl ether Download PDF

Info

Publication number
CN113200826A
CN113200826A CN202110489090.5A CN202110489090A CN113200826A CN 113200826 A CN113200826 A CN 113200826A CN 202110489090 A CN202110489090 A CN 202110489090A CN 113200826 A CN113200826 A CN 113200826A
Authority
CN
China
Prior art keywords
reaction
fragment ion
och
ion peak
dialkyl ether
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.)
Granted
Application number
CN202110489090.5A
Other languages
Chinese (zh)
Other versions
CN113200826B (en
Inventor
安高军
范娜
商红岩
鲁长波
林旭锋
郑哲
徐曦萌
薛真真
崔赛楠
王晴茹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute Of Military New Energy Technology Institute Of Systems Engineering Academy Of Military Sciences
Original Assignee
Institute Of Military New Energy Technology Institute Of Systems Engineering Academy Of Military Sciences
China University of Petroleum East China
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute Of Military New Energy Technology Institute Of Systems Engineering Academy Of Military Sciences, China University of Petroleum East China filed Critical Institute Of Military New Energy Technology Institute Of Systems Engineering Academy Of Military Sciences
Priority to CN202110489090.5A priority Critical patent/CN113200826B/en
Publication of CN113200826A publication Critical patent/CN113200826A/en
Application granted granted Critical
Publication of CN113200826B publication Critical patent/CN113200826B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for synthesizing polymethoxy dialkyl ether. The synthesis method comprises the following steps: methylal and alkyl alcohol are used as raw materials, and the reaction is carried out under the action of an acid catalyst to obtain the polymethoxy dialkyl ether, wherein the structural general formula of the polymethoxy dialkyl ether is as follows: R-O- (CH)2O)‑CH3And/or R-O- (CH)2O) -R. The product synthesized by the method has less by-products, no generation of formaldehyde and water, easy separation and capability of synthesizing the product with different alkyl groups at two ends (wherein one end is CH)3) And polymethoxy dialkyl ether having the same alkyl group at both ends. The method is used for synthesizing the target product, the synthesis process is simple, the depolymerization process of paraformaldehyde or trioxymethylene is not needed, the process cost can be greatly reduced in the further refining and separating process, the operation difficulty is reduced, and the higher separation efficiency is realized.

Description

Synthesis method of polymethoxy dialkyl ether
Technical Field
The invention relates to the technical field of clean energy, in particular to a synthetic method of polymethoxy dialkyl ether.
Background
The current energy situation of China shows the characteristics of rich coal, poor oil and less gas, and faces the problems of insufficient petroleum resources, continuous increase of industrial demand for petroleum and derived products, serious environmental pollution and the like. In recent years, the oxygen-containing fuel is applied to diesel engines as a diesel blending component or a single component, and has excellent effects of reducing the emission of soot particles and improving the combustion efficiency of the diesel engines during the use process, thereby reducing the excessive dependence on petroleum and reducing the environmental pollution.
Polymethoxydialkyl ethers (PODE)n) Is methoxy (-CH)2O-) is a main chain, and two ends are alkyl end capping (C)nH2n+1) Of the acetal polymer of formula R1-O-(CH2O)n-R2Wherein R is1And R2The groups may be the same or different. According to the study, PODEnThe cetane number of the fuel is high, and the ignition performance of the fuel is good; the oxygen content is high, so that the combustion characteristic can be improved, and the pollutant emission is reduced; the flash point is high, and the safety performance is good; the performance of the diesel oil is similar to that of diesel oil, the diesel oil and the diesel oil have good intersolubility under high-temperature and low-temperature conditions, and the diesel oil can be applied without changing an engine.
The common synthetic route for polymethoxy dialkyl ethers is: using low-carbon alkyl alcohol and one of paraformaldehyde, trioxymethylene or formaldehyde aqueous solution as raw materials, and generating PODE (peroxidase) through condensation reaction under the catalysis condition of acid catalystnAnd (3) obtaining the product. But utilizing such synthetic PODEnThe method of (2) can generate a depolymerization process of trioxymethylene or paraformaldehyde in the reaction process, the reaction time is too long, and a certain influence is generated on the separation and refining processes of the product, so that a purer target product and a higher yield thereof are difficult to obtain. Mainly because: 1) paraformaldehyde, trioxymethylene or formaldehyde aqueous solution can generate formaldehyde molecules in the reaction process, the reaction is a reversible reaction, raw materials cannot be completely converted into target products according to the thermodynamic equilibrium principle of the reaction, formaldehyde inevitably exists in the products, and formaldehyde gas is polymerized into paraformaldehyde solid in a rectifying device when meeting cold, so that a pipeline is blocked, and the separation is influenced; 2) water is also produced by the aldolization of alcohols with aldehydes, but the production of a large amount of water causes the product to form two phases, water and oil, and water must be removed to obtain a purer product. And industrially for PODEnThe synthesis and refining, the removal of formaldehyde and water, increase the process production cost.
Therefore, a new PODE was explorednThe synthesis method reduces the adverse conditions of product separation and refining, and needs to carry out related research.
Disclosure of Invention
The invention aims to provide a synthetic method of polymethoxy dialkyl ether, which is free from formaldehyde and water, has no by-product which is difficult to separate, greatly reduces the operation difficulty of the process in the product refining process, and realizes the advantages of high separation efficiency, low cost and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing polymethoxy dialkyl ether comprises the following steps: methylal and alkyl alcohol are used as raw materials, and the reaction is carried out under the action of an acid catalyst to obtain the polymethoxy dialkyl ether, wherein the structural general formula of the polymethoxy dialkyl ether is as follows:
R-O-(CH2O)-CH3and/or R-O- (CH)2O)-R；
Wherein R is alkyl in alkyl alcohol.
The reaction equation of the synthesis method is as follows:
Figure BDA0003047057400000021
preferred alkyl alcohols of the present invention are selected from C2-C10Corresponding to R in the above reaction equation being C2-C10Alkyl group of (1).
From the above reaction equation, the reaction of the present invention is a substitution reaction process of alcohol and methylal, and the possible mechanism is: under the action of acid catalyst, methylal is protonated to generate oxonium ions, then alcohol attacks the carbon atom of a middle methylene group, and deprotonation is carried out to generate methanol and polymethoxy dialkyl ether with different alkyl groups at two ends (one end is methyl); under the action of an acid catalyst, the generated polymethoxy dialkyl ether is protonated to generate oxonium ions, alcohol attacks the carbon atom of the middle methylene group, and deprotonation is carried out to generate polymethoxy dialkyl ether and methanol with the same alkyl at two ends. The possible reaction mechanism is as follows:
Figure BDA0003047057400000022
Figure BDA0003047057400000031
in the prior art, methylal is also used as a raw material, but the methylal is used as a terminal blocking raw material and reacts with trioxymethylene or paraformaldehyde, the trioxymethylene or paraformaldehyde is firstly depolymerized into formaldehyde single molecules, and the formaldehyde molecules are subjected to carbonyl protonation under an acidic condition; under the action of an acid catalyst, methylal generates reaction central body hemiacetal; finally, the activated formaldehyde reacts with hemiacetal to generate polymethoxy dimethyl ether. The prior art uses methylal as a terminal methyl provider, while the method of the invention uses methylal as an intermediate methylene provider and alcohol as a terminal alkoxy provider, and does not require the depolymerization of paraformaldehyde or trioxane to form formaldehyde molecules.
The synthesis method can obtain two polymethoxy dialkyl ethers which are respectively as follows: polymethoxy dialkyl ether having the same alkyl group at both ends and different alkyl groups at both ends (wherein one end is CH)3) The polymethoxydialkyl ether of (1).
According to the synthesis method of the present invention, preferably, after the reaction is finished, the reaction mixture is rectified to obtain two polymethoxy dialkyl ethers. The two polymethoxy dialkyl ether products can obtain respective pure products or the mixture of the two products by adjusting rectification conditions according to different specific structures.
The synthetic method of the invention does not generate formaldehyde and water, thereby greatly reducing the difficulty of the rectification process.
According to the synthesis method of the present invention, preferably, the molar ratio of the methylal to the alkyl alcohol is (0.4-2): 1; more preferably (0.5-1.5): 1.
according to the synthesis method of the present invention, preferably, the alkyl alcohol is selected from one or a combination of two or more of n-butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutanol, n-heptanol, n-octanol, and 2-ethylhexanol.
According to the synthesis method of the present invention, preferably, the acidic catalyst is a strongly acidic cation exchange resin. More preferably, the strong acid cation exchange resin is a macroporous cation exchange resin with a pore radius of 20nm to 40 nm.
According to the synthesis method of the present invention, the amount of the catalyst is preferably 1% to 6%, more preferably 2% to 4%, for example 4% of the total mass of the raw materials.
According to the synthesis method of the present invention, preferably, the reaction temperature is 50 ℃ to 150 ℃, the reaction pressure is 0.1MPa to 4.0MPa, more preferably, the reaction temperature is 80 ℃ to 120 ℃, such as 110 ℃; the pressure of the reaction is 0.1MPa to 2MPa, for example 0.1 MPa.
According to the synthesis method of the present invention, the reaction time is preferably 0.5h to 12h, more preferably 4h to 10h, for example 10 h.
According to the synthesis method of the present invention, preferably, the reaction is performed in a nitrogen atmosphere. The reaction of the present invention is preferably carried out in a reaction vessel, and after the raw materials and the catalyst are added, nitrogen gas is introduced to displace the air in the reaction vessel and to achieve a prescribed reaction pressure.
The beneficial effects of the invention include:
the invention utilizes alkyl alcohol and methylal as raw materials to synthesize PODEnThe product synthesized by the method has less by-products, no generation of formaldehyde and water, easy separation and capability of synthesizing the product with different alkyl groups at two ends (wherein one end is CH)3) And polymethoxy dialkyl ether having the same alkyl group at both ends. The synthetic method of the invention avoids using paraformaldehyde or trioxymethylene, and correspondingly does not have the depolymerization process of the paraformaldehyde or the trioxymethylene, and can greatly reduce the process cost, reduce the operation difficulty and realize higher separation efficiency in the further refining and separating process. The synthetic process is simple to operate, high in safety and suitable for general popularization and industrial production.
Drawings
FIG. 1 is a gas chromatogram of the synthesized product in example 1.
FIG. 2 is a mass spectrum corresponding to peak # 1 in the gas chromatogram of FIG. 1.
FIG. 3 is a mass spectrum corresponding to peak # 2 in the gas chromatogram of FIG. 1.
FIG. 4 is a gas chromatogram of the synthesized product in example 2.
FIG. 5 is a mass spectrum corresponding to peak # 1 in the gas chromatogram of FIG. 4.
FIG. 6 is a mass spectrum corresponding to peak # 2 in the gas chromatogram of FIG. 4.
FIG. 7 is a gas chromatogram of the synthesized product in example 3.
FIG. 8 is a mass spectrum corresponding to peak # 1 in the gas chromatogram of FIG. 7.
FIG. 9 is a mass spectrum corresponding to peak # 2 in the gas chromatogram of FIG. 7.
FIG. 10 is a gas chromatogram of the synthesized product in example 4.
FIG. 11 is a mass spectrum corresponding to peak # 1 in the gas chromatogram of FIG. 10.
FIG. 12 is a mass spectrum corresponding to peak # 2 in the gas chromatogram of FIG. 10.
FIG. 13 is a gas chromatogram of the synthesized product in example 5.
FIG. 14 is a mass spectrum corresponding to peak # 1 in the gas chromatogram of FIG. 13.
FIG. 15 is a mass spectrum corresponding to peak # 2 in the gas chromatogram of FIG. 13.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, and the like, including ranges for each) may generally be approximations that vary (+) or (-) in increments of 0.1 or 1.0 as appropriate. All numerical designations should be understood as preceded by the term "about".
The strong acid cation exchange resin used in the examples of the present invention was a macroporous cation exchange resin purchased from Nanjing Koucao catalyst factory.
Example 1
78.14g of n-octanol, 36.52g of methylal and 4.59g of strong acid cation exchange resin are added into a kettle type continuous reactor, nitrogen is filled for protection, the pressure is increased to 2MPa, the rotating speed is kept at 250r/min, and the temperature is kept at 100 ℃ for 10 hours. After the reaction is finished, cooling to room temperature, taking out the synthesized mixture to be clear and transparent liquid, carrying out oil-water separation, taking supernatant, and carrying out qualitative and quantitative analysis on the product by utilizing a gas chromatography-mass spectrometry technology and a gas chromatography respectively to obtain the distribution and the content of different components of the product, wherein the results are shown in table 1 and figures 1-3. The reaction equation is as follows:
Figure BDA0003047057400000051
the mass spectrum of the peak # 1 in the gas chromatogram 1 is shown in FIG. 2. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 45.13OCH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 61.13OCH2Fragment ion peak of O-, CH at 71.13CH2CH2CH2CH2Fragment ion peak of-CH at 75.13OCH2OCH2Fragment ion peak of-CH at 85.13CH2CH2CH2CH2CH2Fragment ion peak of-CH at 99.13CH2CH2CH2CH2CH2CH2Fragment ion peak of-CH at 113.13CH2CH2CH2CH2CH2CH2CH2Fragment ion peak of-C at 129.18H17Fragment ion peak of O-, therefore the molecular structure of the 1# peak is CH3CH2CH2CH2CH2CH2CH2CH2OCH2OCH3。
The mass spectrum of peak # 2 in the gas chromatogram of FIG. 1 is shown in FIG. 3. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 71.13CH2CH2CH2CH2Fragment ion peak of-CH at 85.13CH2CH2CH2CH2CH2Fragment ion peak of-CH at 99.13CH2CH2CH2CH2CH2CH2Fragment ion peak of-CH at 113.13CH2CH2CH2CH2CH2CH2CH2Fragment ion peak of-C at 129.18H17Fragment ion peak of O-, C at 143.18H17OCH2Fragment ion peak of-C at 159.18H17OCH2Fragment ion peak of O-, 271.2 is CH3CH2CH2CH2CH2CH2CH2CH2OCH2OCH2CH2CH2CH2CH2CH2CH2CH3Fragment ion peak of n-1, so that the molecular structure of peak # 2 is CH3CH2CH2CH2CH2CH2CH2CH2OCH2OCH2CH2CH2CH2CH2CH2CH2CH3。
Example 2
44.47g of n-butanol, 45.65g of methylal and 3.61g of strong acid cation exchange resin are added into a kettle type continuous reactor, nitrogen is filled into the kettle type continuous reactor, the pressure is increased to 2MPa, the rotating speed is kept at 250r/min, and the kettle type continuous reactor is heated to a constant temperature of 100 ℃ for continuous reaction for 10 hours. After the reaction is finished, cooling to room temperature, taking out the synthesized mixture to be clear and transparent liquid, carrying out oil-water separation, taking the supernatant, and carrying out qualitative and quantitative analysis on the product by using a GC-MS (gas chromatography-Mass spectrometer) combined technology and a GC technology to obtain the distribution and the content of different components of the product, wherein the results are shown in table 1 and figures 4-6. The reaction equation is as follows:
Figure BDA0003047057400000061
the mass spectrum of the peak # 1 in the gas chromatogram of FIG. 4 is shown in FIG. 5. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 45.13OCH2Fragments of (A) to (B)Ion Peak, 57.1 CH3CH2CH2CH2Fragment ion peak of-CH at 613OCH2Fragment ion peak of O-, CH at 75.13OCH2OCH2Fragment ion peak of-CH at 87.13CH2CH2CH2OCH2Fragment ion peak of-CH at 117.13CH2CH2CH2OCH2OCH3N-1 fragment ion peak of (E), so that the molecular structure of the 1# peak is CH3CH2CH2CH2OCH2OCH3。
The mass spectrum of peak # 2 in the gas chromatogram of FIG. 4 is shown in FIG. 6. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 73.13CH2CH2CH2Fragment ion peak of O-CH at 87.13CH2CH2CH2OCH2Fragment ion peak of-C at 103.14H9OCH2Fragment ion peak of O-CH at 117.13CH2CH2CH2OCH2OCH2Fragment ion peak of-CH at 159.13CH2CH2CH2OCH2OCH2CH2CH2CH3Fragment ion peak of n-1, so that the molecular structure of peak # 2 is CH3CH2CH2CH2OCH2OCH2CH2CH2CH3。
Example 3
Adding 61.30g of n-hexanol, 54.78g of methylal and 4.64g of strong acid cation exchange resin into a high-pressure reaction kettle, filling nitrogen, pressurizing to 2MPa, keeping the rotation speed at 250r/min, heating to constant temperature of 100 ℃, and continuously reacting for 10 hours. After the reaction is finished, cooling to room temperature, taking out the synthesized mixture to be clear and transparent liquid, carrying out oil-water separation, taking the supernatant, and carrying out qualitative and quantitative analysis on the product by using a GC-MS (gas chromatography-Mass spectrometer) combined technology and a GC technology to obtain the distribution and the content of different components of the product, wherein the results are shown in table 1 and figures 7-9. The reaction equation is as follows:
Figure BDA0003047057400000071
the mass spectrum of the peak # 1 in the gas chromatogram 7 is shown in FIG. 8. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 45.13OCH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 61.13OCH2Fragment ion peak of O-, CH at 71.13CH2CH2CH2CH2Fragment ion peak of-CH at 75.13OCH2OCH2Fragment ion peak of-CH at 85.13CH2CH2CH2CH2CH2Fragment ion peak of-CH at 101.13CH2CH2CH2CH2CH2Fragment ion peak of O-CH at 145.13CH2CH2CH2CH2CH2OCH2OCH3N-1 fragment ion peak of (E), so that the molecular structure of the 1# peak is CH3CH2CH2CH2CH2CH2OCH2OCH3。
The mass spectrum of peak # 2 in the gas chromatogram 7 is shown in FIG. 9. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 71.13CH2CH2CH2CH2Fragment ion peak of-CH at 85.13CH2CH2CH2CH2CH2Fragment ion peak of-CH at 101.13CH2CH2CH2CH2CH2Fragment ion peak of O-, CH at 115.13CH2CH2CH2CH2CH2OCH2Fragment ion peak of-CH at 131.13CH2CH2CH2CH2CH2OCH2Fragment ion peak of O-CH at 145.13CH2CH2CH2CH2CH2OCH2OCH2Fragment ion peak of-CH at 215.13CH2CH2CH2CH2CH2OCH2OCH2CH2CH2CH2CH2CH3Fragment ion peak of n-1, so that the molecular structure of peak # 2 is CH3CH2CH2CH2CH2CH2OCH2OCH2CH2CH2CH2CH2CH3。
Example 4
Adding 69.72g of n-heptanol, 45.65g of methylal and 4.61g of strong acid cation exchange resin into a high-pressure reaction kettle, introducing nitrogen, pressurizing to 2MPa, keeping the rotation speed at 250r/min, heating to constant temperature of 100 ℃, and continuously reacting for 10 hours. After the reaction is finished, cooling to room temperature, taking out the synthesized mixture to be clear and transparent liquid, carrying out oil-water separation, taking the supernatant, and carrying out qualitative and quantitative analysis on the product by using a GC-MS (gas chromatography-Mass spectrometer) combined technology and a GC technology to obtain the distribution and the content of different components of the product, wherein the results are shown in table 1 and figures 10-12. The reaction equation is as follows:
Figure BDA0003047057400000081
the mass spectrum of the peak # 1 in the gas chromatogram 10 is shown in FIG. 11. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 45.13OCH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 61.13OCH2Fragment ion peak of O-, CH at 71.13CH2CH2CH2CH2Fragment ion peak of-CH at 75.13OCH2OCH2Fragment ion peak of-CH at 85.13CH2CH2CH2CH2CH2Fragment ion peak of-CH at 99.13CH2CH2CH2CH2CH2CH2Fragment ion peak of-CH at 115.13CH2CH2CH2CH2CH2CH2Fragment ion peak of O-, therefore the molecular structure of the 1# peak is CH3CH2CH2CH2CH2CH2CH2OCH2OCH3。
The mass spectrum of peak # 2 in the gas chromatogram of FIG. 10 is shown in FIG. 12. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 71.13CH2CH2CH2CH2Fragment ion peak of-CH at 85.13CH2CH2CH2CH2CH2Fragment ion peak of-CH at 99.13CH2CH2CH2CH2CH2CH2Fragment ion peak of-CH at 115.13CH2CH2CH2CH2CH2CH2Fragment ion peak of O-, C at 129.17H15OCH2Fragment ion peak of-C at 145.17H15OCH2Fragment ion peak of O-, C at 159.17H15OCH2OCH2Fragment ion peak of-CH at 243.23CH2CH2CH2CH2CH2CH2OCH2OCH2CH2CH2CH2CH2CH2CH3Fragment ion peak of n-1, so that the molecular structure of peak # 2 is CH3CH2CH2CH2CH2CH2CH2OCH2OCH2CH2CH2CH2CH2CH2CH3。
Example 5
Adding 78.14g of isooctanol, 45.65g of methylal and 4.95g of strong-acid cation exchange resin into a high-pressure reaction kettle, filling nitrogen, pressurizing to 2MPa, keeping the rotation speed at 250r/min, heating to constant temperature of 100 ℃, and continuously reacting for 10 hours. After the reaction is finished, cooling to room temperature, taking out the synthesized mixture to be clear and transparent liquid, carrying out oil-water separation, taking supernatant, and carrying out qualitative and quantitative analysis on the product by using a GC-MS (gas chromatography-Mass spectrometer) combined technology and a GC technology to obtain the distribution and the content of different components of the product, wherein the results are shown in Table 1. The reaction equation is as follows:
Figure BDA0003047057400000091
the mass spectrum of the peak # 1 in the gas chromatogram 13 is shown in FIG. 14. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 45.13OCH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 61.13OCH2Fragment ion peak of O-, CH at 75.13OCH2OCH2Fragment ion peak of-CH at 99.13CH2CH2CH2(C2H5) Fragment ion peak of CH-is CH at 113.13CH2CH2CH2(C2H5)CHCH2Fragment ion peak of-CH at 129.13CH2CH2CH2(C2H5)CHCH2Fragment ion peak of O-, therefore the molecular structure of the 1# peak is CH3CH2CH2CH2CH(C2H5)CH2OCH2OCH3。
The mass spectrum of peak # 2 in the gas chromatogram of FIG. 13 is shown in FIG. 15. Wherein, the 43.1 position is CH3CH2CH2Fragment ion peak of-CH at 57.13CH2CH2CH2Fragment ion peak of-CH at 99.13CH2CH2CH2(C2H5) Fragment ion peak of CH-is CH at 113.13CH2CH2CH2(C2H5)CHCH2Fragment ion peak of-CH at 129.13CH2CH2CH2(C2H5)CHCH2Fragment ion peak of O-, CH at 143.13CH2CH2CH2(C2H5)CHCH2OCH2-, 159.1 is CH3CH2CH2CH2(C2H5)CHCH2OCH2Fragment ion peak of O-, therefore the molecular structure of the 2# peak is CH3CH2CH2CH2CH(C2H5)CH2OCH2OCH2CH(C2H5)CH2CH2CH2CH3。
Table 1 contents of different components in reaction solutions of examples 1 to 5
Figure BDA0003047057400000092
Example 6
This example explores the experimental mechanism, and the exploration experimental process includes the following experiments 1-4:
experiment 1: adding methylal and sec-butyl alcohol in a molar ratio of 10:1 into a reaction kettle, adding strong acid cation exchange resin accounting for 3% of the total mass of the raw materials, filling nitrogen into the reaction kettle to exhaust the gas so that the initial pressure is atmospheric pressure, keeping the rotating speed at 250r/min, heating the reaction kettle to a constant temperature of 110 ℃ for continuous reaction for two hours, and cooling the reaction kettle to room temperature after the reaction is finished.
Experiment 2: adding methylal and sec-butyl alcohol in a molar ratio of 10:1 into a reaction kettle, adding strong acid cation exchange resin accounting for 3% of the total mass of the raw materials, introducing nitrogen into the reaction kettle, pressurizing the reaction kettle to 1MPa, keeping the rotating speed at 250r/min, heating the reaction kettle to a constant temperature of 110 ℃ for continuous reaction for two hours, and cooling the reaction kettle to room temperature after the reaction is finished.
Experiment 3: methylal and sec-butyl alcohol with a molar ratio of 1:10 are added into a reaction kettle, strong acid cation exchange resin with the total mass of 3 percent of the raw materials is added, the reaction conditions are the same as those of experiment 1, and after the reaction is finished, the mixture is cooled to room temperature.
Experiment 4: methylal and sec-butyl alcohol with a molar ratio of 1:10 are added into a reaction kettle, strong acid cation exchange resin with the total mass of 3 percent of the raw materials is added, the reaction conditions are the same as those of experiment 2, and after the reaction is finished, the mixture is cooled to room temperature.
The supernatants of the mixtures obtained in experiments 1-4 were chromatographed, normalized to the content of the two different products, to obtain the respective contents of products with a double sec-butyl end group and a mono sec-butyl end group, the results being shown in table 2.
TABLE 2 results of experiments 1-4
Figure BDA0003047057400000101
Comparing experiments 1 and 2 with experiments 3 and 4, when methylal and sec-butyl alcohol are added into the raw materials at a molar ratio of 10:1, most of the products are monomes-sec-butyl polymethoxy dialkyl ether, and trace amount of di-sec-butyl polymethoxy dialkyl ether is contained; when methylal and sec-butyl alcohol with the molar ratio of 1:10 are added into the raw materials, the content of the generated di-sec-butyl product is obviously increased, and the content of the mono-sec-butyl product is obviously reduced. Therefore, methylal and sec-butyl alcohol are used as raw materials, under the action of an acid catalyst, firstly, a product is generated to be the monomecondary butyl polymethoxy dialkyl ether, and then, under the action of an acid catalyst, the monomecondary butyl product is taken as a base to be regenerated to be the di-sec-butyl polymethoxy dialkyl ether. The reaction mechanism of the route according to the invention can thus be derived, for example, as follows:
Figure BDA0003047057400000111
it should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. A synthetic method of polymethoxy dialkyl ether is characterized by comprising the following steps: methylal and alkyl alcohol are used as raw materials, and the reaction is carried out under the action of an acid catalyst to obtain the polymethoxy dialkyl ether, wherein the structural general formula of the polymethoxy dialkyl ether is as follows:
R-O-(CH2O)-CH3and/or R-O- (CH)2O)-R；
Wherein R is alkyl in alkyl alcohol.
2. The synthesis method according to claim 1, wherein after the reaction is finished, the reaction mixture is rectified to obtain two polymethoxy dialkyl ethers with different structures.
3. The synthesis process according to claim 1, wherein the molar ratio of methylal to alkyl alcohol is (0.4-2): 1.
4. the method of claim 1, wherein the alkyl alcohol is selected from the group consisting of C2-C10The alcohol of (1).
5. The method of claim 1, wherein the alkyl alcohol is selected from the group consisting of n-butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutanol, n-heptanol, n-octanol, and 2-ethylhexanol, and combinations thereof.
6. The method of synthesis of claim 1, wherein the acidic catalyst is a strongly acidic cation exchange resin.
7. The synthesis method according to claim 1 or 6, characterized in that the amount of the catalyst is 1-6% of the total mass of the raw materials.
8. The synthesis method according to claim 1, wherein the reaction temperature is 50 ℃ to 150 ℃ and the reaction pressure is 0.1MPa to 4.0 MPa.
9. The synthesis method according to claim 8, wherein the reaction time is 0.5-12 h.
10. The method of synthesis according to claim 1, wherein the reaction is carried out in a nitrogen atmosphere.
CN202110489090.5A 2021-04-29 2021-04-29 Synthesis method of polymethoxy dialkyl ether Active CN113200826B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110489090.5A CN113200826B (en) 2021-04-29 2021-04-29 Synthesis method of polymethoxy dialkyl ether

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110489090.5A CN113200826B (en) 2021-04-29 2021-04-29 Synthesis method of polymethoxy dialkyl ether

Publications (2)

Publication Number Publication Date
CN113200826A true CN113200826A (en) 2021-08-03
CN113200826B CN113200826B (en) 2022-07-19

Family

ID=77030291

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110489090.5A Active CN113200826B (en) 2021-04-29 2021-04-29 Synthesis method of polymethoxy dialkyl ether

Country Status (1)

Country Link
CN (1) CN113200826B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115745755A (en) * 2022-12-05 2023-03-07 中国人民解放军军事科学院系统工程研究院 Preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101048357A (en) * 2004-10-25 2007-10-03 巴斯福股份公司 Method for producing polyoxymethylene dimethyl ethers
EP1902009A1 (en) * 2005-06-15 2008-03-26 Basf Se Method for the production of polyoxymethylene dialkyl ethers from trioxan and dialkylethers
FR2906815A1 (en) * 2006-10-10 2008-04-11 Total France Sa Mixtures of symmetrical and unsymmetrical polyoxymethylene dialkyl ethers, used in fuel compositions based on hydrocarbon distillates, especially diesel fuel
CN102775284A (en) * 2011-05-13 2012-11-14 南京大学 Synthesis method of polyoxymethylene dimethyl ethers
CN103420817A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde
CN103772164A (en) * 2012-10-18 2014-05-07 中国科学院兰州化学物理研究所 Reaction system for continuously preparing polyoxymethylene dialkyl ether, and process thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101048357A (en) * 2004-10-25 2007-10-03 巴斯福股份公司 Method for producing polyoxymethylene dimethyl ethers
EP1902009A1 (en) * 2005-06-15 2008-03-26 Basf Se Method for the production of polyoxymethylene dialkyl ethers from trioxan and dialkylethers
DK1902009T3 (en) * 2005-06-15 2010-11-08 Basf Se Process for preparing polyoxymethylene dialkyl ethers from trioxane and dialkyl ether
FR2906815A1 (en) * 2006-10-10 2008-04-11 Total France Sa Mixtures of symmetrical and unsymmetrical polyoxymethylene dialkyl ethers, used in fuel compositions based on hydrocarbon distillates, especially diesel fuel
CN102775284A (en) * 2011-05-13 2012-11-14 南京大学 Synthesis method of polyoxymethylene dimethyl ethers
CN103420817A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde
CN103772164A (en) * 2012-10-18 2014-05-07 中国科学院兰州化学物理研究所 Reaction system for continuously preparing polyoxymethylene dialkyl ether, and process thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115745755A (en) * 2022-12-05 2023-03-07 中国人民解放军军事科学院系统工程研究院 Preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst
CN115745755B (en) * 2022-12-05 2023-12-08 中国人民解放军军事科学院系统工程研究院 Preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst

Also Published As

Publication number Publication date
CN113200826B (en) 2022-07-19

Similar Documents

Publication Publication Date Title
US9266990B2 (en) Method for producing polyoxymethylene dimethyl ethers
CN104447237B (en) Process with methanol polyoxymethylene dimethyl ether
EP2810930B1 (en) A method for refining polyoxymethylene dialkyl ethers by catalytic hydrogenation using a fixed bed
CN105152882B (en) Method for preparing DMM3-5 from hypercoagulable polyoxymethylene dimethyl ether component DMM6+ and dimethoxymethane DMM
CN104230685B (en) With the process that methyl alcohol and paraformaldehyde produce polyoxymethylene dimethyl ether
CN104230684B (en) Process by methanol-fueled CLC polyoxymethylene dimethyl ether
CN103360224A (en) Combined process for preparing poly methoxy-dimethyl ether
CN102180778A (en) Method for preparing low-polymerization-degree polyformaldehyde dialkyl ether from mixture of lower alcohols and application thereof
CN104276931B (en) By methyl alcohol and the process of paraformaldehyde synthesizing polyoxymethylene dimethyl ether
CN113200826B (en) Synthesis method of polymethoxy dialkyl ether
CN104276933B (en) By methanol and the process of paraformaldehyde synthesizing polyoxymethylene dimethyl ether
CN112225650A (en) Refining method for obtaining high-purity methylal by purifying industrial-grade methylal
US20100263265A1 (en) Method for converting biomass into products containing acetal groups and use thereof as biofuels
CN102173984B (en) Method for preparing low-polymerization-degree polyformaldehyde dialkyl ether from petroleum fractions and application
CN104498114B (en) A kind of automobile-used ethers mixes fuel burning and its preparation method and application
CN107652169A (en) A kind of preparation technology of polymethoxy dimethyl ether production formaldehyde alcoholic solution
EP2810929B1 (en) A method for refining polyoxymethylene dialkyl ethers by catalytic hydrogenation using a slurry bed
CN102627985B (en) Gasoline and diesel oil additive composition and preparation method and application thereof
CN104449896A (en) Ether blending-combustion fuel for automobile as well as preparation method and application of ether blending-combustion fuel
CN102775284A (en) Synthesis method of polyoxymethylene dimethyl ethers
CN101121645A (en) Production method for vinyl ethers
CN106495996A (en) A kind of method with lewis acid as catalyst preparation polymethoxy dimethyl ether
CN108794310B (en) Method for separating and purifying two acetals and raw material alcohol by pressure swing distillation
CN115745755B (en) Preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst
CN104449897A (en) Ether-mixed burning fuel for vehicle and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information

Inventor after: An Gaojun

Inventor after: Fan Na

Inventor after: Lu Changbo

Inventor after: Zheng Zhe

Inventor after: Xu Ximeng

Inventor after: Xue Zhenzhen

Inventor after: Cui Sainan

Inventor after: Wang Qingru

Inventor before: An Gaojun

Inventor before: Wang Qingru

Inventor before: Fan Na

Inventor before: Shang Hongyan

Inventor before: Lu Changbo

Inventor before: Lin Xufeng

Inventor before: Zheng Zhe

Inventor before: Xu Ximeng

Inventor before: Xue Zhenzhen

Inventor before: Cui Sainan

CB03 Change of inventor or designer information
TA01 Transfer of patent application right

Effective date of registration: 20220629

Address after: 102300 Beijing city Mentougou District Street No. three

Applicant after: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences

Address before: 102300 Beijing city Mentougou District Street No. three

Applicant before: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences

Applicant before: China University of Petroleum (East China)

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant
CP02 Change in the address of a patent holder

Address after: 102300 Beijing city Mentougou District Three Street No. 1

Patentee after: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences

Address before: 102300 Beijing city Mentougou District Street No. three

Patentee before: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences

CP02 Change in the address of a patent holder