CN116332738B - Preparation method of polymethoxy dialkyl ether based on amine binary catalyst - Google Patents
Preparation method of polymethoxy dialkyl ether based on amine binary catalyst Download PDFInfo
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- CN116332738B CN116332738B CN202211552418.4A CN202211552418A CN116332738B CN 116332738 B CN116332738 B CN 116332738B CN 202211552418 A CN202211552418 A CN 202211552418A CN 116332738 B CN116332738 B CN 116332738B
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- 150000001983 dialkylethers Chemical class 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001412 amines Chemical class 0.000 title claims description 8
- 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 67
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002608 ionic liquid Substances 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical group OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 11
- 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 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 23
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 11
- 150000002373 hemiacetals Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 methoxy dialkyl ether Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- 150000001241 acetals Chemical class 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-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
- 238000006471 dimerization reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000007862 dimeric product Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 239000013638 trimer Substances 0.000 description 1
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
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The applicationThe application discloses a catalyst and a preparation method of polymethoxy dialkyl ether based on the catalyst, wherein the preparation method adopts a binary system catalyst of p-toluenesulfonic acid and triethylene diamine ionic liquid 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 single-pass selectivity of the compound with the polymerization degree of n=1 of the polymethoxy dialkyl ether reaches more than 95 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 and a preparation method of polymethoxy dialkyl ether based on the catalyst.
Background
The polymethoxy dialkyl ether is an oxygen-containing fuel with excellent performance, the existing polymethoxy dialkyl ether oxygen-containing fuel preparation technology can only obtain polymethoxy dialkyl ether mixtures with multiple polymerization degrees, in the actual use process, the 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, so that 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 not facilitated.
The synthesis of polymethoxy dialkyl ethers is essentiallyIn particular to an acetal forming process, sulfuric acid or hydrochloric acid is used as a catalyst in the prior art to catalyze the reaction of methanol and formaldehyde, paraformaldehyde or dioxolane to synthesize polymethoxy dialkyl ether. BASF corporation uses H 2 SO 4 Or CF (compact flash) 3 SO 3 H is a catalyst, the strong acid catalyst is severely corroded, and the raw material conversion rate and the selectivity of the methoxy dialkyl ether polymer (n) are low. The BP company adopts molecular sieve or acid resin as catalyst, and realizes the conversion of dimethyl ether and formaldehyde into polymethoxy dialkyl ether through complex process, but the polymethoxy dialkyl ether polymer in the product is lower than 10%. The research on synthesizing the methoxy dialkyl ether polymer by catalyzing the reaction of methanol and trioxymethylene by using ionic liquid is carried out by the Lanzhou compound of the Chinese academy of sciences, the single-pass yield of the product reaches 50%, and the selectivity of the methoxy dialkyl ether polymer is more than 70%.
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 catalyst and a preparation method of polymethoxy dialkyl ether based on the catalyst, which adopts triethylene diamine ionic liquid and liquid acid to form the catalyst, and aims to obtain a polymethoxy dialkyl ether oligomerization product with single polymerization degree, improve the conversion rate of the product and reduce the separation difficulty of the product.
In order to achieve the above object, in one aspect, the present application provides a catalyst for synthesizing polymethoxy dialkyl ether, the catalyst comprising p-toluenesulfonic acid and a triethylene diamine ionic liquid, wherein the triethylene diamine 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 second aspect of the present application provides a catalyst. The catalyst comprises p-toluenesulfonic acid and triethylene diamine ionic liquid, wherein the structural formula of the triethylene diamine 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.
The third aspect of the application provides a preparation method of a catalyst of a binary system of p-toluenesulfonic acid and triethylene diamine ionic liquid, which comprises the following steps: uniformly mixing triethylene diamine and acid in an organic solvent to obtain ionic liquid, then adding p-toluenesulfonic acid, uniformly mixing, and then adding reactants into n-hexane to obtain the binary catalyst system catalyst.
Through the technical scheme, the application has the following beneficial effects:
according to the application, a binary system catalyst of p-toluenesulfonic acid and triethylene diamine ionic liquid is adopted, the acidity of the catalyst system is regulated through the selection of ionic liquid and protonic acid (namely p-toluenesulfonic 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 single-pass selectivity of the compound with the polymethoxy dialkyl ether polymerization degree of n=1 is up to more than 96%, 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 nuclear magnetic resonance hydrogen spectrum of sample No. 4 of example.
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 chemical formula of the polymethoxy dialkyl ether is:
the polymethoxy dialkyl ether oligomer such as polymethoxy dialkyl ether mono-polymer and dimer has better physical and chemical properties, especially low temperature properties, and lower freezing point and cold filtration point than polymethoxy dialkyl ether polymer such as polymethoxy dialkyl ether trimer and tetramer. In order to improve the performance and product stability of the oxygenate, it is desirable to obtain a high selectivity oxygenate with a polymethoxy dialkyl ether oligomer.
For this reason, the present application has been found through extensive studies that the specific reaction mechanism for preparing polymethoxy dialkyl ether oligomer is shown in fig. 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; condensing the protonated hemiacetal (C) with the hemiacetal (D) to obtain a protonated acetal (E2), and deprotonating the (E2) to obtain 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 ╳k 4
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 catalyst, i.e. the hydrogen ion concentration, or H+ is, the more the amount of the monomeric product F is, the smaller the reaction conditions are.
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:
through the research, the preparation method of the low-polymerization-degree polymethoxy dialkyl ether comprises the following steps:
dissolving 0.1mol of triethylenediamine in table 1 in 500-1000mL of chloroform, adding 0.1mol of a first acid, namely hydrochloric acid, into the solution under ice bath, stirring the solution for 1-4h, adding 0.1mol of a second sulfuric acid into the solution, stirring the solution for 1-4h to obtain an ionic liquid, adding 0.105mol of p-toluenesulfonic acid into the solution, and 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 a composite catalyst containing ionic liquid and p-toluenesulfonic acid, 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 ℃. The n-butanol conversion and the selectivity of the polymerization degree n=1 product were measured and calculated, and the results are shown in table 1.
Table 1 results of ionic liquids and p-Benzenesulfonic acid experiments in different molar ratios
From table 1, it can be seen that, at a molar ratio of 1:1, the isooctanol conversion rate and the molar ratio of the ionic liquid to the p-toluenesulfonic acid are in a certain negative correlation, and the polymerization degree n=1 selectively and the molar ratio of the ionic liquid to the p-toluenesulfonic acid are in a certain correlation. When the molar ratio of p-toluenesulfonic acid to ionic liquid is above 0.6, the isooctanol conversion rate and the polymerization degree n=1 selectivity are both higher (above 90%), when the molar ratio of ionic liquid to p-toluenesulfonic acid is 0.9, compared with 0.85, the polymerization degree n=1 selectivity is basically consistent, the isooctanol conversion rate is obviously lower, when the molar ratio is below 0.6, the polymerization degree n=1 selectivity is only 87%, so that the molar ratio of ionic liquid to p-toluenesulfonic acid is 0.6-0.8, which is a preferable range of the application, and when the molar ratio of ionic liquid to p-toluenesulfonic acid is 0.76, the isooctanol conversion rate 78% and the polymerization degree n=1 selectivity is 90%.
Fig. 2 is a nuclear magnetic resonance hydrogen spectrum of sample No. 4, in which only a polymerization product was observed, wherein the main product, namely, polymethoxy dialkyl ether polymerization product data is: 1 H NMR(400MHz,CDCl 3 ):δ＝4.63(s,2H,CH 2 ),3.39-3.40(m,4H,CH 2 ),1.26-1.48(m,20H,CH 2 ),0.85-0.87(m,12H,CH 3 )。
embodiment two:
the preparation method of the low-polymerization-degree polymethoxy dialkyl ether comprises the following steps:
dissolving 0.1mol of triethylenediamine in table 1 in 500-1000mL of chloroform, adding 0.1mol of first acid, namely trifluoromethanesulfonic acid, into the solution under ice bath, stirring the solution for 1-4h, adding 0.1mol of second trifluoroacetic acid into the solution, stirring the solution for 1-4h to obtain an ionic liquid, adding 0.12mol of p-toluenesulfonic acid into the solution in proportion, and 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 isooctanol and paraformaldehyde into a high-temperature high-pressure reaction kettle according to a molar ratio of 1:1, then adding 2wt% of a composite catalyst containing ionic liquid and p-toluenesulfonic acid, 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 ℃. The isooctanol conversion and the selectivity of the polymerization degree n=1 product were measured and calculated, and the results are shown in table 2.
TABLE 2 test results of ionic liquids and p-toluenesulfonic acid at different molar ratios
From table 2, it can be seen that, at a molar ratio of 1:1, the isooctyl alcohol conversion rate and the molar ratio of p-toluenesulfonic acid to ionic liquid are in a certain negative correlation, and the polymerization degree n=1 selectivity and the molar ratio of p-toluenesulfonic acid to ionic liquid are in a certain correlation. The molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.6-0.8, and when the molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.75, the isooctanol conversion rate is 73% and the polymerization degree n=1 selectivity is 94%.
Embodiment III:
the preparation method of the low-polymerization-degree polymethoxy dialkyl ether comprises the following steps:
dissolving 0.1mol of triethylenediamine in table 1 in 500-1000mL of chloroform, adding 0.1mol of first acid, namely methanesulfonic acid, into the solution under ice bath, stirring the solution for 1-4h, adding 0.1mol of second hydrochloric acid into the solution, stirring the solution for 1-4h to obtain an ionic liquid, adding 0.13mol of p-toluenesulfonic acid into the solution, and 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 isooctanol and paraformaldehyde into a high-temperature high-pressure reaction kettle according to a molar ratio of 1:1, then adding 2wt% of a composite catalyst containing ionic liquid and p-toluenesulfonic acid, 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 ℃. The isooctanol conversion and the selectivity of the polymerization degree n=1 product were measured and calculated, and the results are shown in table 3.
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 to 0.8, and when the molar ratio of the ionic liquid to the p-toluenesulfonic acid is 0.75, the isooctanol conversion rate is 73% and the polymerization degree n=1 selectivity is 95%.
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 (8)
1. The preparation method of the polymethoxy dialkyl ether based on the amine binary catalyst is characterized in that a binary system catalyst of p-toluenesulfonic acid and triethylene diamine ionic liquid is adopted to catalyze alcohol and aldehyde to carry out polymerization reaction, and the mole ratio of the triethylene diamine ionic liquid to the p-toluenesulfonic acid is 0.5-0.9:1, the structural formula of the triethylene diamine 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 amine binary catalyst according to claim 1, wherein the preparation of the para-toluenesulfonic acid and triethylene diamine ionic liquid binary system catalyst comprises the following steps: uniformly mixing triethylene diamine and acid in an organic solvent to obtain an ionic liquid, then adding p-toluenesulfonic acid, uniformly mixing, and then adding reactants into n-hexane to obtain the amine binary catalyst.
3. The preparation method of the polymethoxy dialkyl ether based on the amine binary catalyst according to claim 2, wherein the preparation method of the triethylene diamine ionic liquid is as follows: firstly uniformly mixing triethylene diamine and a first acid in a molar ratio of 1:1 in an organic solvent, then adding an equimolar second acid, uniformly mixing,
wherein the first acid is one of HX or HY, and the second acid is the other of HX or HY.
4. The method for preparing polymethoxy dialkyl ether based on amine binary catalyst according to claim 2, wherein the organic solvent is chloroform.
5. The process for preparing polymethoxy dialkyl ethers based on amine binary catalysts according to claim 2, wherein the temperature of n-hexane is from 0 to 10 ℃.
6. The catalyst for synthesizing the polymethoxy dialkyl ether comprises p-toluenesulfonic acid and triethylene diamine ionic liquid, wherein the mole ratio of the triethylene diamine ionic liquid to the p-toluenesulfonic acid is 0.5-0.9:1, the structural formula of the triethylene diamine 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.
7. A method of preparing the catalyst of claim 6, comprising: uniformly mixing triethylene diamine and acid in an organic solvent to obtain an ionic liquid, then adding p-toluenesulfonic acid, uniformly mixing, adding reactants into n-hexane, filtering and drying.
8. The method for preparing the catalyst according to claim 7, wherein uniformly mixing the triethylenediamine and the acid in the organic solvent to obtain the ionic liquid comprises:
firstly uniformly mixing triethylene diamine and a first acid in a molar ratio of 1:1 in an organic solvent, then adding an equimolar second acid, uniformly mixing,
wherein the first acid is one of HX or HY, and the second acid is the other of HX or HY.
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| CN102531915A (en) * | 2011-12-16 | 2012-07-04 | 淮北科达化工有限责任公司 | Method for preparing ethylene diamine through condensation and ammoniation by using bronsted acid ion liquid to catalyze ethanolamine |
| CN103709019A (en) * | 2013-12-09 | 2014-04-09 | 中国科学院兰州化学物理研究所 | Acidic ionic liquid catalyzed synthesis method of low carbon polyether compound |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
| CN109225337A (en) * | 2018-09-10 | 2019-01-18 | 太原理工大学 | A kind of MOFs encapsulation ionic-liquid catalyst and its preparation and application |
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| CN102531915A (en) * | 2011-12-16 | 2012-07-04 | 淮北科达化工有限责任公司 | Method for preparing ethylene diamine through condensation and ammoniation by using bronsted acid ion liquid to catalyze ethanolamine |
| CN103709019A (en) * | 2013-12-09 | 2014-04-09 | 中国科学院兰州化学物理研究所 | Acidic ionic liquid catalyzed synthesis method of low carbon polyether compound |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
| CN109225337A (en) * | 2018-09-10 | 2019-01-18 | 太原理工大学 | A kind of MOFs encapsulation ionic-liquid catalyst and its preparation and application |
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