CN112745283A - Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction - Google Patents
Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction Download PDFInfo
- Publication number
- CN112745283A CN112745283A CN201911042118.XA CN201911042118A CN112745283A CN 112745283 A CN112745283 A CN 112745283A CN 201911042118 A CN201911042118 A CN 201911042118A CN 112745283 A CN112745283 A CN 112745283A
- Authority
- CN
- China
- Prior art keywords
- furandicarboxylic acid
- fdca
- esterification reaction
- solubility
- solvent
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in an esterification reaction. The method comprises the following steps: crystallizing the 2, 5-furandicarboxylic acid and the amide compound by an addition crystallization method to generate a 2, 5-furandicarboxylic acid adduct crystal; mixing the 2, 5-furandicarboxylic acid adduct crystals with an esterification reaction solvent to rapidly dissolve the 2, 5-furandicarboxylic acid adduct crystals. In the method for rapidly improving the solubility of the 2, 5-furandicarboxylic acid in the esterification reaction, the solubility of the 2, 5-furandicarboxylic acid adduct crystal is higher than that of the 2, 5-furandicarboxylic acid, and the adduct crystal is easy to release the 2, 5-furandicarboxylic acid again and rapidly reacts with the solvent, so that the dissolution of the 2, 5-furandicarboxylic acid can be accelerated, and the method has the advantages of simple and convenient operation, safety, reliability, remarkable improvement of the dissolution effect and the like.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in an esterification reaction.
Background
During the esterification reaction, the rate of esterification reaction increases with the rate of dissolution of the reaction substrate, and although increasing the reaction temperature may accelerate the dissolution of the reaction substrate, side reactions may be initiated that affect product purity, yield, and further polycondensation reactions. Common polyester raw materials such as terephthalic acid, isophthalic acid and 2, 5-furandicarboxylic acid (FDCA) have low solubility in reaction solvents such as octanol, ethylene glycol, 1, 3-butanediol, hexamethylene diamine and the like, and a substrate monomer is easy to decarboxylate, open loop and the like under a high temperature condition, so that a long chain cannot be formed in the next step of polycondensation reaction, a polymer is difficult to form, or an obtained product contains colored impurities which are difficult to remove.
Dendromo, etc. (plastics industry, 2018, 46(1):119-123) react at 90 ℃ for 1.5h to prepare 2, 5-furandicarboxylic acid isooctyl ester by a direct esterification method, wherein the chroma is more than 500APAH, and when the 2, 5-furandicarboxylic acid isooctyl ester prepared by an acyl chloride method is changed, the chroma is only 30-40 APAH. When the direct esterification method is used, the solubility of the 2, 5-furandicarboxylic acid in isooctanol is low, and thermal decomposition and other side reactions in the dissolving process can be reasons for the high chroma of the product. When the isooctyl 2, 5-furandicarboxylate is prepared by the acyl chloride method, the substrate is changed into 2, 5-furandiformyl chloride, the chemical activity is greatly improved, the dissolution is also improved, the reaction activity and the yield are both greatly improved, and the chroma is also obviously reduced.
The patent publication No. CN102453242A provides a method for preparing a polyfuranic dicarboxylic acid ester by direct esterification polymerization of 2, 5-furandicarboxylic acid with 1, 2-ethanediol, 1, 3-propanediol or 1, 4-butanediol2O3、Zn(OAc)2、ZnCl2、Ca(OAc)2、PbO、Ti(n-OC4H9)4、Ti(i-OC4H9)4、SnCl2And (3) the esterification temperature (130-180 ℃) and the reaction time (1-8 h) are changed by different bifunctional catalysts, so that the molar yield of the polyester can be improved (86-98%).
Therefore, the solubility of the 2, 5-furandicarboxylic acid is improved, the 2, 5-furandicarboxylic acid is rapidly dissolved, the esterification reaction of the 2, 5-furandicarboxylic acid is accelerated, a more stable product is generated, and the product purity is improved.
In view of the problems of low solubility and slow dissolution of 2, 5-furandicarboxylic acid in a reaction solvent, which affect the reaction rate and easily cause side reactions in the current esterification reaction, how to rapidly and effectively improve the solubility of 2, 5-furandicarboxylic acid in the esterification reaction has been the direction of efforts of researchers in the industry for a long time.
Disclosure of Invention
The invention mainly aims to provide a method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in esterification reaction, so that the 2, 5-furandicarboxylic acid is rapidly dissolved and reacts to generate a stable compound, thereby overcoming the defects of slow dissolution, long reaction time and side reaction of raw materials at high temperature in the prior art of the 2, 5-furandicarboxylic acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in esterification reaction, which comprises the following steps:
(1) crystallization yields adduct crystals. Crystallizing 2, 5-furandicarboxylic acid and an amide compound to generate 2, 5-furandicarboxylic acid adduct crystals, wherein the molar ratio of the 2, 5-furandicarboxylic acid to the amide compound in the 2, 5-furandicarboxylic acid adduct crystals is 1: 1-3.5;
(2) and mixing the 2, 5-furandicarboxylic acid adduct crystals instead of the 2, 5-furandicarboxylic acid with an esterification reaction solvent to rapidly dissolve the 2, 5-furandicarboxylic acid adduct crystals.
In some embodiments, the specific steps of the method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in an esterification reaction include:
(1) preparing an adduct crystal from 2, 5-furandicarboxylic acid and an amide compound by an adduct crystallization method, wherein the molar ratio of the 2, 5-furandicarboxylic acid to the amide compound in the obtained adduct crystal is 1: 1-3.5. To further illustrate, the theoretical molar ratio of the adduct crystal formed by FDCA and the amide compound is 1:2, when the molar ratio of FDCA to the amide compound is less than 1:1, hydrogen bonds formed between molecules of FDCA and the amide compound are too little, and the solubility is improved too little; when the molar ratio of the amide-based compound is too large, the crystals are unstable due to the adhesion of more solvent, and the subsequent treatment is difficult due to the presence of more solvent.
(2) And mixing the 2, 5-furandicarboxylic acid adduct crystals with an esterification solvent to quickly dissolve the 2, 5-furandicarboxylic acid adduct crystals, wherein the molar ratio of the 2, 5-furandicarboxylic acid in the 2, 5-furandicarboxylic acid adduct crystals to the esterification solvent is 1: 2-150. When the proportion of the esterification reaction solvent is small, the 2, 5-furandicarboxylic acid adduct crystal is slowly dissolved, and the esterification reaction rate is also slow; with the increase of the proportion of the esterification reaction solvent, the dissolution rate of the 2, 5-furandicarboxylic acid adduct crystal is increased, the corresponding esterification reaction rate is also increased, but the excessive solvent affects the concentration of a reaction substrate and the concentration of a catalyst, the yield is possibly reduced, and the recovery of a product is not facilitated, so that the molar ratio of the 2, 5-furandicarboxylic acid to the esterification reaction solvent is controlled to be 1: 2-150.
In some embodiments, the amide-based compound includes any one or a combination of two or more of N, N-dimethylformamide, N-Dimethylacetamide (DMAC), N-methyl-pyrrolidone (NMP), N-ethyl-pyrrolidone (npd), and the like, but is not limited thereto.
In some embodiments, the esterification reaction solvent includes, but is not limited to, linear and/or branched chain-containing monohydric alcohols, dihydric alcohols, and the like.
Further, the monohydric alcohol includes monohydric alcohols of C2 to C16, and for example, any one or a combination of two or more of butanol, hexanol, octanol, decanol, and the like may be preferable, but not limited thereto.
The diol includes a diol having a carbon number of 2 to 16, and may preferably be any one or a combination of two or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and the like, but is not limited thereto.
In some embodiments, the esterification reaction temperature is 20 to 320 ℃, preferably 160 to 280 ℃. Some milder and efficient catalysts can enable the esterification reaction to be carried out at a lower temperature, but when the temperature is too low, the viscosity of some alcohols is larger, and mass transfer and reaction rate are influenced in the reaction process, so that the temperature is not easy to be too low, when the temperature is too high, a reaction solvent is easy to vaporize after reaching a boiling point, the product yield is influenced, FDCA is easy to decompose, and side reaction is easy to occur, so that the esterification reaction temperature is 20-320 ℃.
In some embodiments, the optimal conditions for the esterification reaction are to first add the esterification solvent to the reaction vessel, heat to a temperature of T-80 ℃ to T, where T is the reaction temperature for the esterification reaction, and then add the 2, 5-furandicarboxylic acid adduct crystals to the esterification reaction solvent, preferably T-50 ℃ to T, which facilitates rapid dissolution and reaction of FDCA without the tendency to form by-products at high temperatures.
In some embodiments, the esterification reaction may be performed under reduced pressure or under vapor pressure generated by the solvent.
Further, the esterification reaction pressure is 20 Pa-0.3 MPa, after the 2, 5-furandicarboxylic acid and the alcohol react, the residual adduct crystal solvent in the adduct crystal can be removed by reduced pressure distillation in the reduced pressure esterification process or after the reaction is finished, the normal pressure reaction of the esterification reaction is not influenced, and the adduct crystal solvent is kept in the reaction solution.
The above technical scheme of the invention is based on the principle that: taking 2, 5-furandicarboxylic acid-N, N-dimethylacetamide adduct crystals (FDCA-DMAC) as an example, the adduct crystal formation process is:
at a certain temperature, FDCA is dissolved in an addition crystallization solvent, and spontaneous and synchronous addition crystallization occurs, FDCA molecules and the addition crystallization solvent molecules are connected by strong hydrogen bond O-H.O (see figure 1) to form an addition crystal FDCA-DMAC, and the molecular structure of 2, 5-furandicarboxylic acid is unchanged, usually the molar ratio of the 2, 5-furandicarboxylic acid molecules in the addition crystal to the addition crystal solvent molecules is 1:2, and is expressed by FDCA.2DMAC. The adduct crystals can also be obtained by cooling the crystals and thermostatting the crystals. After the adduct crystal is heated or when the adduct crystal is added into a solvent, the FDCA exists in a single compound form, the esterification reaction is not influenced, and the thermal gravimetric analysis (see figure 2) of the FDCA-2DMAC adduct crystal shows that the hydrogen bond is easy to break after heating, DMAC is volatilized or decomposed firstly, and can be completely volatilized at about 116 ℃, the temperature for initiating the decomposition of the FDCA is more than 210 ℃, and the maximum decomposition rate temperature is 335.45 ℃, so that the FDCA is more stable in the temperature range of 116-210 ℃, and is less decomposed in the temperature range of 210-270 ℃. After being formed, the FDCA & 2DMAC has the solubility far higher than that of FDCA, can be quickly dissolved into an alcohol solvent of an esterification reaction to quickly generate ester, and has stronger chemical stability than that of FDCA, so that the FDCA is protected, side reactions such as ring opening and the like are not easy to occur, the reaction rate and the conversion rate of the FDCA are effectively improved, and meanwhile, the additive crystallization solvent can be removed through reduced pressure distillation.
In the method, because the solubility of the FDCA adduct crystal is higher than that of the FDCA, the FDCA adduct crystal is easy to release FDCA and quickly reacts with the solvent, the dissolution of the FDCA can be accelerated, and the method has simple operation and remarkable improvement on the solubility.
Compared with the prior art, the method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in the esterification reaction has the advantages of simple and convenient operation, safety, reliability, obvious solubility improvement effect, capability of improving the solubility by more than 5.67 times and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic representation of the crystal molecular structure of 2, 5-furandicarboxylic acid (FDCA) -N, N-Dimethylacetamide (DMAC) adduct in example 1 of the present invention.
FIG. 2 is a thermogram of crystal of 2, 5-furandicarboxylic acid (FDCA) -N, N-Dimethylacetamide (DMAC) adduct in example 1 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. In the method, because the solubility of the FDCA adduct crystal is higher than that of the FDCA, the FDCA adduct crystal is easy to release FDCA and quickly reacts with the solvent, the dissolution of the FDCA can be accelerated, and the method has simple operation and remarkable improvement on the solubility. However, the solubility of FDCA is only measured in the examples of the present invention, and the solubility of the adduct crystals is not accurately measured, but the solubility of FDCA is significantly improved after the FDCA adduct crystals are prepared.
For further understanding of the present invention, the following description will specifically describe a method for rapidly increasing solubility of FDCA in esterification reaction according to the present invention with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all of them. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
35g of N, N-Dimethylacetamide (DMAC) and 10g of 2, 5-furandicarboxylic acid (FDCA) solid powder are mixed (mass ratio is 2:1), stirred in a water bath at 50 ℃ for 10min, after the FDCA is dissolved, the temperature is reduced to 20 ℃ for crystallization, and after filtration, 10.52g of FDCA-DMAC adduct crystals are obtained (the molecular structure schematic diagram is shown in figure 1). Weighing 0.1g of FDCA-DMAC adduct crystal, dissolving in methanol to prepare 0.1g/LFDCA-DMAC adduct methanol solution, measuring the concentration of FDCA by using a high-pressure liquid chromatograph, and dividing by the concentration (0.1g/L) of the prepared sample to obtain the specific gravity of FDCA in the FDCA-DMAC adduct crystal. The high pressure liquid chromatography determination conditions are as follows: c18 reverse phase chromatography column, mobile phase 95:5 in 0.05% aqueous trifluoroacetic acid: and (3) performing gradient elution by using methanol until the mobile phase is methanol, the flow rate is 1mL/min, the column temperature is 35 ℃, and the ultraviolet detection wavelength is 278 nm. FDCA was found to have a mass specific gravity of 46.80% in the adduct crystals and a molar ratio of FDCA to DMAC of 1: 2.04.
Example 2
In this example, the preparation of crystals of FDCA adduct was carried out in a similar manner to example 1 except that N-methyl-pyrrolidone (NMP) was used as the adduct solvent in this example, the mass ratio of FDCA to NMP was 1:2.2, the dissolution temperature was 80 ℃, crystallization was carried out by cooling to 4 ℃, and 10.61g of crystals of FDCA-NMP adduct were obtained after filtration. The mass specific gravity of FDCA in the FDCA-NMP adduct crystals was 45.09% and the molar ratio of FDCA to DMAC was 1:1.92, as determined by liquid chromatography.
Example 3
In this example the preparation of crystals of an adduct of FDCA was carried out in a similar manner to example 1 except that the crystals of the adduct of FDCA-DMAC in this example were partially volatilized after drying in vacuo to give 7.67g of crystals with FDCA representing 64.18% of the mass of the adduct crystals and a molar ratio of FDCA to DMAC of 1:1.
Example 4
In this example the preparation of crystals of an FDCA adduct was carried out in a similar manner to example 1, except that in this example 30g of N, N-Dimethylacetamide (DMAC) and a crystallization temperature of 4 ℃ were used, and after filtration of the crystals 15.60g of crystals of an FDCA-DMAC adduct containing 33.86% of FDCA, were obtained with a molar ratio of FDCA to DMAC of 1: 3.5.
Example 5
Adding 0.8g of FDCA into 100g of n-butanol, stirring at the constant temperature of 30 ℃ for 20h, filtering the turbid solution by using a 0.22 mu m filter, weighing a certain mass of filtrate, and measuring the concentration of the FDCA on a high pressure liquid chromatograph, wherein the solubility of the FDCA in the n-butanol is 0.49g/100g under the condition of 30 ℃. Adding 4.02g of FDCA-DMAC adduct crystal with FDCA content of about 1.88g and FDCA-DMAC adduct crystal mass specific gravity of 46.80% into 100g of n-butanol at 30 ℃ (esterification temperature of 50 ℃), wherein the mol ratio of FDCA to n-butanol is 1:112, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously improved by at least 2.84 times. Multiple of increase
Multiple of increase
C1At a certain temperature, after addition of the crystals of the FDCA adduct, dissolution of FDCA in hectogram's solventAmount, unit g/100 g;
c- -solubility of FDCA in a solvent at a certain temperature, in g/100 g.
Example 6
In this example, FDCA was dissolved in a similar manner to example 5 except that the solvent was changed to n-octanol and the temperature was changed to 20 deg.C (esterification temperature 20 deg.C), and the solubility of FDCA in n-octanol was measured to be 0.12g/100g at 20 deg.C. Adding 1.70g of FDCA-DMAC adduct crystal with the mass proportion of FDCA being 46.80 percent and the content of FDCA being about 0.80g, wherein the mol ratio of FDCA to n-octanol is 1:150, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously improved by at least 5.67 times.
Example 7
In this example, FDCA was dissolved in a similar manner to example 5 except that the solvent was changed to n-decanol, and it was found that FDCA had a solubility of 0.18g/100g in n-decanol at 30 ℃. Adding 2.0g of FDCA-DMAC adduct crystal with the mass proportion of FDCA being 46.80 percent and the content of FDCA being 0.936g, wherein the mol ratio of FDCA to n-decanol is about 1:105, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously improved by at least 4.2 times.
Example 8
In this example, FDCA was dissolved in a manner similar to that of example 7 except that the adduct crystals were changed to FDCA having a mass specific gravity of 45.09%, FDCA content of about 0.99g of FDCA-NMP adduct crystals of 2.2g, and a molar ratio of FDCA to n-decanol of about 1:100, the crystals were rapidly dissolved, the liquid was clear, and the amount of FDCA dissolved in hectogram solvent was significantly increased by at least 4.5 times.
Example 9
In this example, FDCA was dissolved in a similar manner to example 5 except that the solvent was changed to ethylene glycol, and it was found that the solubility of FDCA in ethylene glycol was 0.7g/100g at 30 ℃. Adding 6g of FDCA-DMAC adduct crystal with the FDCA content of 2.808g and the FDCA mass specific gravity of 46.80 percent, wherein the mol ratio of the FDCA to the glycol is about 1:90, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of the FDCA in hectogram solvent is obviously improved by at least 3.01 times.
Example 10
In this example, FDCA was dissolved in a similar manner to example 5 except that the solvent was changed to butanediol, and the solubility of FDCA in butanediol at 30 ℃ was found to be 0.72g/100 g. Adding 8.2g of FDCA-DMAC adduct crystal with the mass proportion of FDCA being 46.80 percent and the content of FDCA being about 3.84g, wherein the mol ratio of FDCA to butanediol is about 1:45, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously improved by at least 4.33 times.
Example 11
In this example, FDCA was dissolved in a manner similar to that of example 10 except that the adduct crystals were changed to FDCA-NMP adduct crystals having a mass specific gravity of 45.09% of FDCA, 6.5g of FDCA-NMP adduct crystals having an FDCA content of about 2.93g were added, the molar ratio of FDCA to butanediol was about 1:59, the crystals were rapidly dissolved, the liquid was clear, and the amount of FDCA dissolved in a hectogram solvent was significantly increased by at least 3.07 times.
Example 12
In this example FDCA was dissolved in a similar manner to example 10 except that the temperature was changed to 120 deg.C (esterification temperature 160 deg.C) and the solubility of FDCA in butanediol at 120 deg.C was determined to be 7.12g/100 g. Adding 46.09g of FDCA-DMAC adduct crystal with the FDCA content of about 21.57g and the FDCA-DMAC adduct crystal mass proportion of about 46.80 percent, wherein the mol ratio of the FDCA to butanediol is about 1:8, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of the FDCA in hectogram solvent is obviously improved by at least 2.03 times.
Example 13
In this example FDCA was dissolved in a similar manner to example 9 except that the temperature was changed to 170 deg.C (esterification temperature 170 deg.C), and the solubility of FDCA in ethylene glycol was measured to be 12.31g/100g at 170 deg.C. The adduct crystal is changed into 58.88g of FDCA-NMP adduct crystal with the mass specific gravity of the FDCA of 45.09 percent, the mol ratio of the FDCA to the ethylene glycol is about 1:9.5, the crystal is quickly dissolved, the liquid is clear, the content of the dissolved FDCA is about 26.55g, and the dissolving amount of the FDCA in hectogram solvent is obviously improved by at least 1.16 times.
Example 14
In this example FDCA was dissolved in a similar manner to example 6 except that the temperature was changed to 170 deg.C (esterification temperature 250 deg.C), and the solubility of FDCA in n-octanol was measured to be 2.3g/100g at 170 deg.C. Adding 14g of FDCA-DMAC adduct crystal with the FDCA content of 6.552g and the FDCA-DMAC adduct crystal with the mass proportion of 46.80 percent of FDCA, wherein the mol ratio of FDCA to n-octanol is about 1:18, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously improved by at least 1.85 times.
Example 15
In this example, FDCA was dissolved in a similar manner to example 7 except that the temperature was changed to 170 ℃ and the solubility of FDCA in n-decanol was measured to be 1.17g/100g at 170 ℃. Adding 12g of FDCA-DMAC adduct crystal with the FDCA content of 5.616g and the FDCA-DMAC adduct crystal with the mass proportion of 46.80 percent of FDCA, wherein the mol ratio of FDCA to n-decanol is about 1:18, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously improved by at least 3.8 times.
Example 16
In this example FDCA was dissolved in a similar manner to example 7 except that the temperature was changed to 250 deg.C (esterification temperature 250 deg.C), and the solubility of FDCA in n-decanol was measured to be 1.72g/100g at 250 deg.C. Adding 18.34g of FDCA-DMAC adduct crystal with the FDCA mass proportion of 33.86 percent and the FDCA content of 6.21g, wherein the mol ratio of the FDCA to the n-decanol is about 1:16, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of the FDCA in hectogram solvent is obviously improved by at least 2.61 times.
Example 17
In this example FDCA was dissolved in a similar manner to example 9 except that the temperature was changed to 170 deg.C (esterification temperature 190 deg.C), the mass ratio of FDCA in the crystals of the addition FDCA-DMAC adduct was 64.18%, and the solubility of FDCA in ethylene glycol at 170 deg.C was determined to be 12.31g/100 g. The mass proportion of added FDCA is 64.18%, the FDCA content is 41.15g of FDCA-DMAC adduct crystal with FDCA content being 26.41g, the mole ratio of FDCA to glycol is about 1:9.5, the crystal is quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously increased by at least 1.15 times.
Example 18
In this example FDCA was dissolved in a similar manner to example 11 except that the temperature was changed to 270 deg.C (esterification temperature 320 deg.C) and the solubility of FDCA in butanediol at 270 deg.C was determined to be 14.45g/100 g. The mass proportion of added FDCA is 45.09%, the FDCA content is about 30.65g of 67.98g of FDCA-NMP adduct crystals, the mol ratio of FDCA to butanediol is about 1:5.7, the crystals are quickly dissolved, the liquid is clear, and the dissolving amount of FDCA in hectogram solvent is obviously improved by at least 1.12 times.
Example 19
In this example FDCA was dissolved in a similar manner to example 18 except that the mass of butanediol was changed to 34g and the temperature was changed to 250 ℃ and the solubility of FDCA in butanediol was measured to be 13.55g/100g at 250 ℃. Adding 64.25g of FDCA-NMP adduct crystals, wherein the mol ratio of the FDCA to butanediol is 1:2, the FDCA in the adduct crystals is dissolved by 10.88g, and the dissolving amount of the FDCA in hectogram solvent is 1.36 times higher than that of single FDCA.
In summary, according to the above technical solution of the present invention, in the method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in esterification reaction provided by the present invention, since the solubility of the 2, 5-furandicarboxylic acid adduct crystal is higher than that of 2, 5-furandicarboxylic acid, the adduct crystal is easy to release 2, 5-furandicarboxylic acid, and can rapidly react with a solvent, the dissolution of aromatic ring dicarboxylic acid can be accelerated, and the method has the advantages of simple operation, safety, reliability, significant solubility improvement effect, and the like.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in an esterification reaction, comprising:
(1) crystallizing 2, 5-furandicarboxylic acid and an amide solvent by an addition crystallization method to generate 2, 5-furandicarboxylic acid adduct crystals, wherein the molar ratio of the 2, 5-furandicarboxylic acid to the amide compound in the 2, 5-furandicarboxylic acid adduct crystals is 1: 1-3.5;
(2) mixing the 2, 5-furandicarboxylic acid adduct crystals with an esterification reaction solvent to rapidly dissolve the 2, 5-furandicarboxylic acid adduct crystals.
2. The method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 1, wherein: the molar ratio of the 2, 5-furandicarboxylic acid to the esterification solvent in the 2, 5-furandicarboxylic acid adduct crystal is 1: 2-150.
3. The method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 1, wherein: the amide compound comprises any one or the combination of more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methyl-pyrrolidone and N-ethyl-pyrrolidone.
4. The method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 1, wherein: the esterification reaction solvent comprises monohydric alcohol and/or dihydric alcohol containing straight chain and/or branched chain.
5. The method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 4, wherein: the monohydric alcohol comprises C2-C16 monohydric alcohol, preferably any one or the combination of more than two of butanol, hexanol, octanol and decanol.
6. The method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 4, wherein: the dihydric alcohol comprises C2-C16 dihydric alcohol, preferably one or the combination of more than two of ethylene glycol, propylene glycol, butanediol and hexanediol.
7. The method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 1, wherein: the temperature of the esterification reaction is 20-320 ℃.
8. The method for rapidly increasing the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 7, wherein: the temperature of the esterification reaction is 160-280 ℃.
9. The method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 1, comprising: firstly adding an esterification reaction solvent into a reaction vessel, heating to T-80-T, and then adding 2, 5-furandicarboxylic acid adduct crystals into the reaction vessel, wherein T is the reaction temperature of the esterification reaction.
10. The method for rapidly improving the solubility of 2, 5-furandicarboxylic acid in esterification reaction according to claim 9, comprising: firstly, adding an esterification reaction solvent into a reaction vessel, heating to T-50-T, and then adding 2, 5-furandicarboxylic acid adduct crystals into the reaction vessel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911042118.XA CN112745283B (en) | 2019-10-30 | 2019-10-30 | Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911042118.XA CN112745283B (en) | 2019-10-30 | 2019-10-30 | Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112745283A true CN112745283A (en) | 2021-05-04 |
| CN112745283B CN112745283B (en) | 2023-01-03 |
Family
ID=75640358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911042118.XA Active CN112745283B (en) | 2019-10-30 | 2019-10-30 | Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112745283B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070442A (en) * | 2010-12-28 | 2011-05-25 | 浙江大学 | Method for producing high-purity naphthalic acid |
| CN103380120A (en) * | 2011-02-24 | 2013-10-30 | 赢创奥克森诺有限责任公司 | Pentyl esters of furandicarboxylic acid as softeners |
| WO2017019447A1 (en) * | 2015-07-24 | 2017-02-02 | E I Du Pont De Nemours And Company | Reactive distillation process for the esterification of furandicarboxylic acid |
| CN109232489A (en) * | 2017-07-10 | 2019-01-18 | 沈阳开拓利思科技有限公司 | A kind of preparation method of furans biology base dibutyl ester |
| CN109721577A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | A kind of purification process of furans dicarboxylic acids |
-
2019
- 2019-10-30 CN CN201911042118.XA patent/CN112745283B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070442A (en) * | 2010-12-28 | 2011-05-25 | 浙江大学 | Method for producing high-purity naphthalic acid |
| CN103380120A (en) * | 2011-02-24 | 2013-10-30 | 赢创奥克森诺有限责任公司 | Pentyl esters of furandicarboxylic acid as softeners |
| WO2017019447A1 (en) * | 2015-07-24 | 2017-02-02 | E I Du Pont De Nemours And Company | Reactive distillation process for the esterification of furandicarboxylic acid |
| CN109232489A (en) * | 2017-07-10 | 2019-01-18 | 沈阳开拓利思科技有限公司 | A kind of preparation method of furans biology base dibutyl ester |
| CN109721577A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | A kind of purification process of furans dicarboxylic acids |
Non-Patent Citations (1)
| Title |
|---|
| 刘茜 等: ""直接酯化法合成聚2,5-呋喃二甲酸乙二酯"", 《应用化学》, vol. 29, no. 7, 31 July 2012 (2012-07-31), pages 751 - 756 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112745283B (en) | 2023-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021004069A1 (en) | Method for recycling waste polyester material | |
| ITBO950017A1 (en) | PROCESS FOR THE PREPARATION OF BIS (2-HYDROXYETHYL) TERAPHTHALATE | |
| US11174269B2 (en) | Method for producing 1,2,4,5-cyclohexanetetracarboxylic dianhydride | |
| CN110105191A (en) | A method of high-purity naphthalic acid is prepared by raw material of beta-methylnaphthalene | |
| CN104945627A (en) | Method for preparing ultra-high heat resistant polyimide polymer | |
| CN108503613A (en) | A method of preparing 2,5- furandicarboxylic acids | |
| EP1746081B1 (en) | Production method of highly pure pyromellitic dianhydride | |
| CN112645814A (en) | Method for purifying glycolic acid, glycolic acid crystal and use thereof | |
| CN112745283B (en) | Method for rapidly improving solubility of 2, 5-furandicarboxylic acid in esterification reaction | |
| CN102070442B (en) | Method for producing high-purity naphthalic acid | |
| CN102952143B (en) | A kind of preparation method of tetraphenylporphines | |
| CN101016275B (en) | 5-Amide-6-hydroxy-2-(4-carboxylphenyl)benzoxazole salt synthesis method | |
| CN110862520A (en) | Method for preparing PET (polyethylene terephthalate) by using terephthalic acid in alkali-minimization wastewater | |
| CN102414148A (en) | Diaryl iodonium salt mixture and process for production thereof, and process for production of diaryl iodonium compound | |
| JP2002097168A (en) | Method for producing aromatic tetracarboxylic acid | |
| JPH01216955A (en) | Purification of 2-hydroxynaphthalene-6- carboxylic acid | |
| CN101333167A (en) | Separating and purifying method for catabolite of polyethylene terephthalate | |
| RU2047595C1 (en) | Process for preparing phthalic acid isomers having high purification degree | |
| CN108003013A (en) | A kind of recoverying and utilizing method of nylon acid | |
| JP4439964B2 (en) | Method for producing 2,6-naphthalenedicarboxylic acid | |
| JPH049352A (en) | Production of naphthalenedicarboxylic acid | |
| JPH05331096A (en) | Production of bismuth acetate | |
| WO2023242150A1 (en) | Producing 2,5-furandicarboxylic acid in the presence of modifying acid | |
| CN115057767A (en) | Preparation method of phthalic acid | |
| TW202311400A (en) | Method for improving the hue of recycled bhet |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |