CN115745755B - Preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst - Google Patents
Preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst Download PDFInfo
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- CN115745755B CN115745755B CN202211551957.6A CN202211551957A CN115745755B CN 115745755 B CN115745755 B CN 115745755B CN 202211551957 A CN202211551957 A CN 202211551957A CN 115745755 B CN115745755 B CN 115745755B
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- 150000001983 dialkylethers Chemical class 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002608 ionic liquid Substances 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 14
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims abstract description 13
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical group OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 22
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 15
- 150000002373 hemiacetals Chemical class 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- -1 poly-methoxy dialkyl ether Chemical class 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- 150000001241 acetals Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000007862 dimeric product Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst, which is characterized in that p-toluenesulfonic acid and 1, 8-diaminonaphthalene ionic liquid binary system catalyst are adopted to catalyze alcohol and aldehyde to carry out polymerization reaction, and the ionic liquid has the structural formula:wherein X is Cl, trifluoro methane sulfonate, trifluoro acetate or methane sulfonate, and Y is hydrogen sulfate, trifluoro acetate, cl or methane sulfonate. The application reduces the occurrence of high polymerization degree products in the polymerization reaction process of the polymethoxy dialkyl ether, reduces the generation amount of the polymethoxy dialkyl ether with high polymerization degree, ensures that the polymerization degree n=1 of the polymethoxy dialkyl ether is selectively 95 percent, ensures that the conversion rate of the n-butanol reaches 70 percent, and greatly reduces the difficulty of the subsequent separation process.
Description
Technical Field
The application relates to the field of preparation of polymethoxy dialkyl ether, in particular to a catalyst based on 1, 8-diaminonaphthalene ionic liquid and liquid acid, a preparation method and application thereof.
Background
The present state of energy sources in China shows the characteristics of rich coal, lean oil and less gas, and faces the problems of insufficient petroleum resources, continuously increasing the demand of industry on petroleum and derived products thereof, serious environmental pollution and the like. In recent years, the application of an oxygen-containing fuel as a diesel blending component or a separate component to a diesel engine has shown excellent effects in that it is possible to reduce emission of soot particulates during use and improve combustion efficiency of the diesel engine, thereby reducing excessive dependence on petroleum and reducing environmental pollution.
Polymethoxy dialkyl ether (PODE) n ) Is prepared by using methyleneoxy (-CH) 2 O-) is a main chain, and both ends are capped by alkyl groups (C n H 2n+1 ) Is of the formula R 1 -O-(CH 2 O) n -R 2 Wherein R is 1 And R is 2 The groups may be the same or different. According to the study, PODE n The cetane number of the flame retardant is high, and the ignition performance is good; the oxygen content is high, the combustion characteristic can be improved, and the pollutant emission is reduced; the flash point is high, and the safety performance is good; similar to the performance of diesel oil, the two have good intersolubility under the conditions of high temperature and low temperature, and can be applied without any modification to an engine.
The common synthetic route for polymethoxy dialkyl ethers is: takes one of low-carbon alkyl alcohol and paraformaldehyde, trioxymethylene or formaldehyde aqueous solution as raw materials, and generates PODE through condensation reaction under the catalysis of a catalyst n The product is obtained. The whole condensation reaction is a reversible reaction, the existing catalyst is not only favorable for the generation of products, but also favorable for the decomposition of the products, so that the existing preparation technology of the polymethoxy dialkyl ether oxygen-containing fuel only can obtain polymethoxy dialkyl ether mixtures with multiple polymerization degrees, in the actual use process, the polymethoxy dialkyl ether components with different polymerization degrees have obvious difference in performance, particularly the components with larger polymerization degrees have great influence on the low-temperature performance of the polymethoxy dialkyl ether oxygen-containing fuel, the difference among the oxygen-containing fuels with different polymerization degrees is larger, the stability of the oxygen-containing fuel products with different batches is poor, and the popularization and the application of the polymethoxy dialkyl ether oxygen-containing fuel are unfavorable. None of the prior art methods can effectively solve the problem of poly-methoxy dialkyl ether products with multiple degrees of polymerization in oxygen-containing fuels, and it is highly desirable to provide a preparation method for obtaining poly-methoxy dialkyl ether products with single degrees of polymerization so as to improve the performance of oxygen-containing fuels.
Disclosure of Invention
Aiming at the problems, the application provides a preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst, which adopts naphthalene binary system catalyst, aims at improving the conversion rate of the product and simultaneously effectively avoiding the decomposition of the product in the reaction process.
In order to achieve the above purpose, the application provides a preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst, which adopts p-toluenesulfonic acid and 1, 8-diaminonaphthalene ionic liquid binary system catalyst to catalyze alcohol and aldehyde to carry out polymerization reaction, wherein the ionic liquid has the structural formula:
wherein X is Cl, trifluoro methane sulfonate, trifluoro acetate or methane sulfonate, and Y is hydrogen sulfate, trifluoro acetate, cl or methane sulfonate.
Preferably, the molar ratio of the p-toluenesulfonic acid to the ionic liquid is 0.5-0.9:1.
preferably, the preparation method of the catalyst of the 1, 8-diaminonaphthalene ionic liquid and the liquid acid comprises the following steps: uniformly mixing 1, 8-diaminonaphthalene and acid in an organic solvent to obtain ionic liquid, then adding p-toluenesulfonic acid, uniformly mixing, adding reactants into n-hexane, filtering, drying to obtain the product,
the structural formula of the ionic liquid is as follows:
wherein X is Cl, trifluoro methane sulfonate, trifluoro acetate or methane sulfonate, and Y is hydrogen sulfate, trifluoro acetate, cl or methane sulfonate.
Specifically, the preparation method of the ionic liquid comprises the following steps: 1, 8-diaminonaphthalene and a first acid in a molar ratio of 1:1 are uniformly mixed in an organic solvent, and then an equimolar second acid is added to uniformly mix.
Preferably, the organic solvent is chloroform.
Preferably, the molar ratio of the p-toluenesulfonic acid to the ionic liquid is 0.5-0.9:1.
preferably, the temperature of the n-hexane is 0-5 ℃.
In a second aspect the present application provides a catalyst obtainable by the above process.
Through the technical scheme, the application has the following beneficial effects:
according to the application, a binary system of the naphthalene ionic liquid and the liquid acid is used as a catalyst, the acidity of the catalyst system is regulated through the selection of the ionic liquid and the liquid acid, the occurrence of high-polymerization-degree products in the polymerization reaction process of the polymethoxy dialkyl ether is reduced, the generation amount of the polymethoxy dialkyl ether with high polymerization degree is reduced, the polymerization degree n=1 selectivity of the polymethoxy dialkyl ether is 95%, the n-butanol conversion rate reaches 70%, and the difficulty of the subsequent separation process is greatly reduced.
Drawings
FIG. 1 is a diagram showing a mechanism of preparation of a polymethoxy dialkyl ether.
FIG. 2 is a chart of the nuclear magnetic resonance hydrogen spectrum of the monomethoxy dibutyl ether.
FIG. 3 is a gas chromatograph of a monomethoxy dibutyl ether.
Detailed Description
The following describes specific embodiments of the present application in detail with reference to examples. It should be understood that the detailed description and specific examples, while indicating and illustrating the application, are not intended to limit the application.
The application has been found through a great deal of research that the specific reaction mechanism of the preparation of the polymethoxy dialkyl ether oligomer is shown in figure 1.
The intermediate (B) is formed by the addition of formaldehyde (A) to protons, and the protonated hemiacetal (C) is formed by the reaction of (B) with alcohol, and is formed by (C) and hemiacetal (D) +H in the system due to the low chemical stability of the protonated hemiacetal (C) + In the form of an equilibrium mixture of (a) and (b). Further condensing the protonated hemiacetal (C) with alkyl alcohol to obtain protonated acetal (E1), and deprotonating the protonated acetal (E1) to obtain monomethoxy dialkyl ether; the protonated hemiacetal (C) is condensed with the hemiacetal (D) to give the protonated acetal (E2), (E2) deprotonationObtaining the monomethoxy dialkyl ether (F2); the protonated hemiacetal (C) reacts with formaldehyde (A) to obtain protonated monoalkyl dimethoxy ether hemiacetal (C1), and then is condensed with hemiacetal (D) to obtain protonated acetal (E2), the (E2) is deprotonated to obtain trimethoxy dialkyl ether (F3), and similarly, the dialkyl ether of methoxy groups with different polymerization degrees can be obtained. In this mechanism, an increase in the number of polyalkoxy groups is achieved by condensation (D) of the protonated hemiacetal (C, C1, C2 to Cn) with the hemiacetal.
Through researches, D is an important raw material for chain growth, and the control of the effective concentration of the species D is of great significance for regulating the polymerization degree of a product. The higher acidity of the protonic acid accelerates the conversion between C and D, resulting in a lower effective concentration of D; but lower acidity can slow the conversion rate of D to C and can increase the effective concentration of D. If the proton acid is used alone, the concentration of the species D can be kept at a lower level, so that (C, C1, C2 to Cn) has certain opportunity to participate in the reaction to generate the polymethoxy alkyl ether with certain polymerization degree distribution; if a weak protonic acid or Lewis acid is used, the highest concentration of C among C, C1, C2 to Cn will react preferentially with D, which increases the proportion of oligomeric or even monomethoxyalkyl ethers in the final product.
From the reaction kinetics, it is known that:
the equilibrium constant is k 1
The equilibrium constant is k 2
The equilibrium constant is k 3
The equilibrium constant is k 4
The equilibrium constant is k 3
The equilibrium reaction was deduced from the above:
[B]＝[A]╳[H + ]╳k 1
[C]＝[A]╳[H + ]╳[R-OH]╳k 1 ╳k 2
[D]＝[A]╳[R-OH]╳k 1 ╳k 2 ╳k 3
[E]＝[A]╳[R-OH] 2 ╳k 1 ╳k 2 ╳k 3 ╳k4
from this, the concentration of the product of the polymerization [ F1] was determined as
From this formula, it is clear that the more acidic the reaction conditions are, i.e. the higher the hydrogen ion concentration, or H+, the smaller the amount of the monomeric product F1.
In the calculation of dimerization products
The equilibrium constant is k 3 ’
The equilibrium constant is k 4 ’
We compared the amounts of the mono-and dimeric products in the ratio of
From the formula, when the reaction condition is fixed, the acid enhancement contributes to the formation of dimerization products and is unfavorable for the formation of a polymerization product, so that the control of the acid of the catalyst has guiding significance for obtaining the polymerization product.
Embodiment one:
based on the above study, the test method is: dissolving 0.1mol of 1, 8-diaminonaphthalene in 500-1000mL of chloroform, adding 0.1mol of hydrochloric acid into the solution under ice bath, stirring for 1-4h, adding 0.1mol of sulfuric acid into the solution, stirring for 1-4h to obtain ionic liquid, adding p-toluenesulfonic acid into the solution in proportion, and stirring for 1-4h. Pouring the reactant into 2000-4000mL of normal hexane at 4 ℃, precipitating overnight, filtering and collecting solid, vacuum drying at room temperature, and sealing and preserving to obtain the target catalyst.
N-butanol and paraformaldehyde are added into a high-temperature high-pressure reaction kettle according to a molar ratio of 1:1, and then 2wt% of p-toluenesulfonic acid and an ionic liquid are added to prepare a catalyst, and N is used 2 After the air in the reaction kettle is replaced, the pressure is increased to 1.5MPa, and the reaction is carried out for 5 hours at the reaction temperature of 100 ℃. N-butanol conversion and selectivity to the polymerization degree n=1 product were measured and calculated, and the results are shown in the following table:
table 1 results of ionic liquids and p-toluenesulfonic acid tests at different molar ratios
As can be seen from table 1, the n-butanol conversion rate and the molar ratio of the ionic liquid to the p-toluenesulfonic acid are in a certain negative correlation with each other, and the polymerization degree n=1 and the selectivity and the molar ratio of the ionic liquid to the p-toluenesulfonic acid are in a certain positive correlation with each other, respectively, at a molar ratio of 1:1. When the molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.6 or more, the selectivity of n-butanol conversion and the polymerization degree n=1 is high, but when the molar ratio is 0.9, the polymerization degree n=1 selectivity is substantially uniform compared with 0.85, whereas the n-butanol conversion is significantly lower, and when the molar ratio is less than 0.6, the polymerization degree n=1 selectivity is only 86%, so that the ionic liquid and the p-toluenesulfonic acid are in a preferable range of the present application. When the molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.85, the conversion rate of n-butanol reaches 69%, and the polymerization degree n=1 and the selectivity is 94%.
Embodiment two:
the test method comprises the following steps: dissolving 0.1mol of 1, 8-diaminonaphthalene in 500-1000mL of chloroform, adding 0.1mol of trifluoromethanesulfonic acid into the solution under ice bath, stirring the solution for 1-4h, adding 0.1mol of trifluoroacetic acid into the solution, stirring the solution for 1-4h to obtain an ionic liquid, adding p-toluenesulfonic acid into the ionic liquid according to a proportion, and continuously stirring the solution for 1-4h. Pouring the reactant into 2000-4000mL of normal hexane at 4 ℃, precipitating overnight, filtering and collecting solid, vacuum drying at room temperature, and sealing and preserving to obtain the target catalyst.
Adding N-butanol and paraformaldehyde into a high-temperature high-pressure reaction kettle according to a molar ratio of 1:1, then adding 2wt% of p-toluenesulfonic acid, the catalyst and ionic liquid prepared by the method, and using N 2 After the air in the reaction kettle is replaced, the pressure is increased to 1.5MPa, and the reaction is carried out for 5 hours at the reaction temperature of 100 ℃. N-butanol conversion and selectivity to the polymerization degree n=1 product were measured and calculated, and the results are shown in the following table:
TABLE 2 test results of ionic liquids and p-toluenesulfonic acid at different molar ratios
As can be seen from Table 2, the molar ratio of the ionic liquid to the p-toluenesulfonic acid is in the range of 0.6-0.85, and when the molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.85, the conversion of n-butanol reaches 70%, and the polymerization degree n=1 and the selectivity 95%.
Embodiment III:
the test method comprises the following steps: dissolving 0.1mol of 1, 8-diaminonaphthalene in 500-1000mL of chloroform, adding 0.1mol of methanesulfonic acid into the solution under ice bath, stirring the solution for 1-4 hours, adding 0.1mol of hydrochloric acid into the solution, stirring the solution for 1-4 hours to obtain an ionic liquid, adding p-toluenesulfonic acid into the solution in proportion, and continuously stirring the solution for 1-4 hours. Pouring the reactant into 2000-4000mL of normal hexane at 4 ℃, precipitating overnight, filtering and collecting solid, vacuum drying at room temperature, and sealing and preserving to obtain the target catalyst.
N-butanol and paraformaldehyde are added into a high-temperature high-pressure reaction kettle according to a molar ratio of 1:1, 2wt% of the catalyst prepared from p-toluenesulfonic acid and ionic liquid is added, and N is used 2 After the air in the reaction kettle is replaced, the pressure is increased to 1.5MPa, and the reaction is carried out for 5 hours at the reaction temperature of 100 ℃. N-butanol conversion and selectivity to the polymerization degree n=1 product were measured and calculated, and the results are shown in the following table:
TABLE 3 test results of ionic liquids and p-toluenesulfonic acid at different molar ratios
As can be seen from Table 3, the molar ratio of the ionic liquid to the p-toluenesulfonic acid is in the range of 0.6-0.86, and when the molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.86, the n-butanol conversion rate reaches 66% and the polymerization degree n=1 selectivity is 93%.
FIG. 2 is a chart showing nuclear magnetic resonance hydrogen spectrum of methoxydibutyl ether No. 2 of a third sample of the embodiment, wherein the main components are as follows:
1 H NMR(400MHz,CDCl 3 ):δ＝4.58(s,2H,CH 2 ),3.44-3.46(m,4H,CH 2 ),1.35-1.51(m,4H,CH 2 ),1.32-1.35(m,4H,CH 2 ),0.87-0.90(m,6H,CH 3 ).
the spectrogram proves that the product structure obtained by the application is methoxy dibutyl ether; and from the nuclear magnetic resonance hydrogen spectrum, no other impurity peak exists, and the purity is not lower than 95%.
FIG. 3 is a gas chromatograph of example three samples No. 2 methoxy dibutyl ether, wherein the nuclear magnetic resonance apparatus was Bruker AMX-400 and the scanning frequency was 400MHz, using deuterated chloroform (CDCl) without internal standard 3 ) As a solventThe detection temperature was room temperature. The gas chromatograph uses Shimadzu-GC-2000 Plus, chromatographic column number SCLON-5, bonded stationary phase is phenyl dimethyl polysiloxane, the specification is 30.25.0.25, the carrier gas flow rate is 150mL/min, the column temperature (initial temperature 50 ℃,5min,15 ℃/min,10min,260 ℃ and 29 min), the sample injection rate is 1uL, the split ratio is 1:100, the sample injection temperature is 320 ℃, the detector is FID, the temperature of the gasification chamber is 280 ℃, and the detector temperature is 280 ℃. In fig. 3, the signal of the methoxy dibutyl ether monomer is too strong (i.e. the content in the sample is very high) to be effectively observed on the spectrogram. The gas chromatography data for methoxydibutyl ether are shown in table 4. From the raw data in gas chromatography, i.e. the data in table 4, it can be seen that the content of methoxydibutyl ether monomer exceeds 99%, i.e. its purity exceeds 99%.
TABLE 4 gas chromatography data for monomethoxy dibutyl ether
| Retention time | Integral area | Height | Product(s) | Percent% | Degree of separation |
| 4.707 | 57552 | 18616 | 0.036 | -- | |
| 5.146 | 21702 | 6999 | 0.014 | 5.407 | |
| 7.519 | 5700 | 2498 | 0.004 | 33.66 | |
| 8.901 | 71002 | 32547 | 0.045 | 23.705 | |
| 9.09 | 7280 | 3394 | 0.005 | 3.345 | |
| 9.173 | 38778 | 16179 | 0.024 | 1.487 | |
| 10.177 | 483816 | 242333 | 0.305 | 18.781 | |
| 10.954 | 279181 | 146778 | 0.176 | 15.253 | |
| 11.702 | 5961 | 3011 | 0.004 | 14.834 | |
| 12.988 | 23559 | 12218 | 0.015 | 25.71 | |
| 14.519 | 6561 | 3406 | 0.004 | 31.131 | |
| 15.17 | 112174 | 60379 | 0.071 | 13.229 | |
| 17.01 | 257432 | 57360 | 0.162 | 18.526 | |
| 17.652 | 157397095 | 16525610 | n＝1 | 99.108 | 3.193 |
| 18.076 | 27710 | 7971 | 0.017 | 2.553 | |
| 18.159 | 6575 | 3041 | 0.004 | 1.203 | |
| 18.897 | 11815 | 4138 | 0.007 | 11.328 |
The preferred embodiments of the present application have been described in detail above with reference to the examples, but the present application is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present application within the scope of the technical concept of the present application, and all the simple modifications belong to the protection scope of the present application.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the application can be made without departing from the spirit of the application, which should also be considered as disclosed herein.
Claims (6)
1. A preparation method of polymethoxy dialkyl ether based on naphthalene binary catalyst is characterized in that p-toluenesulfonic acid and 1, 8-diaminonaphthalene ionic liquid binary system catalyst are adopted to catalyze alcohol and aldehyde to carry out polymerization reaction, and the molar ratio of ionic liquid to p-toluenesulfonic acid is 0.5-0.9:1, the structural formula of the ionic liquid is as follows:
，
wherein X is Cl, trifluoro methane sulfonate, trifluoro acetate or methane sulfonate, and Y is hydrogen sulfate, trifluoro acetate, cl or methane sulfonate.
2. The method for preparing the polymethoxy dialkyl ether based on the naphthalene binary catalyst according to claim 1, wherein the preparation of the naphthalene binary catalyst comprises the following steps: uniformly mixing 1, 8-diaminonaphthalene and acid in an organic solvent to obtain ionic liquid, then adding p-toluenesulfonic acid, uniformly mixing, adding reactants into n-hexane, filtering, drying to obtain the product,
the structural formula of the ionic liquid is as follows:
wherein X is Cl, trifluoro methane sulfonate, trifluoro acetate or methane sulfonate, and Y is hydrogen sulfate, trifluoro acetate, cl or methane sulfonate.
3. The method for preparing the polymethoxy dialkyl ether based on the naphthalene binary catalyst according to claim 2, wherein the preparation method of the ionic liquid is as follows: 1, 8-diaminonaphthalene and a first acid in a molar ratio of 1:1 are uniformly mixed in an organic solvent, and then an equimolar second acid is added to uniformly mix.
4. The method for preparing polymethoxy dialkyl ether based on naphthalene binary catalyst according to claim 2, wherein the organic solvent is chloroform.
5. The method for preparing the polymethoxy dialkyl ether based on the naphthalene binary catalyst according to claim 2, wherein the temperature of the n-hexane is 0-10 ℃.
6. The naphthalene binary catalyst is characterized by comprising p-toluenesulfonic acid and 1, 8-diaminonaphthalene ionic liquid, wherein the molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.5-0.9:1, the structural formula of the ionic liquid is as follows:
，
wherein X is Cl, trifluoro methane sulfonate, trifluoro acetate or methane sulfonate, and Y is hydrogen sulfate, trifluoro acetate, cl or methane sulfonate.
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| CN106928036A (en) * | 2017-04-19 | 2017-07-07 | 四川达兴能源股份有限公司 | The method that polymethoxy butyl ether is prepared using butyral |
| CN112374971A (en) * | 2020-11-12 | 2021-02-19 | 四川达兴能源有限责任公司 | Production method of polymethoxy dialkyl ether |
| CN113200826A (en) * | 2021-04-29 | 2021-08-03 | 军事科学院系统工程研究院军事新能源技术研究所 | Synthesis method of polymethoxy dialkyl ether |
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| CN106928036A (en) * | 2017-04-19 | 2017-07-07 | 四川达兴能源股份有限公司 | The method that polymethoxy butyl ether is prepared using butyral |
| CN112374971A (en) * | 2020-11-12 | 2021-02-19 | 四川达兴能源有限责任公司 | Production method of polymethoxy dialkyl ether |
| CN113200826A (en) * | 2021-04-29 | 2021-08-03 | 军事科学院系统工程研究院军事新能源技术研究所 | Synthesis method of polymethoxy dialkyl ether |
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