CN116217527A - Furan polyester catalyst and preparation method thereof - Google Patents
Furan polyester catalyst and preparation method thereof Download PDFInfo
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- CN116217527A CN116217527A CN202111460404.5A CN202111460404A CN116217527A CN 116217527 A CN116217527 A CN 116217527A CN 202111460404 A CN202111460404 A CN 202111460404A CN 116217527 A CN116217527 A CN 116217527A
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- 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
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- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/23—Calcium
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Abstract
The invention discloses a furan polyester catalyst and a preparation method thereof. The furan polyester catalyst is a 2, 5-furan dicarboxylic acid metal compound with a general formula of L-M n+ L is furan carboxylic acid ligand, the 2 and 5 positions of furan ring of which are respectively combined with-COO ‑ 、‑COOH、‑COO(CH 2 ) x OH group, -COO (CH) 2 ) x (OH) 2 Any one of the groups being attached to at least one-COO ‑ Are connected; m is M n+ Is one of calcium, zinc, germanium, antimony, tin and titanium metal ions, n is an integer of 2-5, and x is an integer of 2-16. The furan polyester catalyst can be used for the polyester synthesis catalysis of 2, 5-furan dicarboxylic acid and C2-C16 straight-chain and branched-chain diols. The furan polyester catalyst provided by the invention has the advantages of no non-polymeric unit impurity and high catalytic efficiency, and is a novel furan bio-based polyester catalyst.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a furan polyester catalyst and a preparation method thereof.
Background
2, 5-furandicarboxylic acid (FDCA) has received significant attention for the last 20 years as a bio-based platform compound that is more renewable and biosafety than petroleum-based benzene ring carboxylic acid chemicals, being one of the twelve bio-based platform compounds that are listed by the U.S. department of energy as having the most potential to develop. Ester compounds prepared from FDCA and alkyl alcohol are already applied to the aspects of plasticizers (Liu Zhichun and the like, response surface method optimization of n-butyl ester esterification reaction of bio-based plasticizers 2, 5-furandicarboxylic acid 2018), nucleation aids (Yan Zhuoran and the like, research on crystallization behavior of polylactic acid regulated and controlled by 2, 5-furandicarboxylic acid didecyl ester and talcum powder in a synergistic manner, 2021) and the like, and poly (2, 5-furandicarboxylic acid) glycol (PEF) synthesized by FDCA and ethylene glycol is a hot spot of the current bio-based ester polymerization research, and PEF has similar physical and chemical properties to the traditional poly (ethylene terephthalate) (PET), but has more advantages in the aspects of water, carbon dioxide, oxygen and the like, is an excellent bio-based polyester product, and has good application prospect in the fields of packaging materials such as bottles, films and the like.
In addition to the synthetic polyester with ethylene glycol, FDCA can also be synthesized with other alcohols such as butanediol, glycerol, etc. to form polyesters or copolyesters. The current common catalyst for FDCA polyester synthesis is Sb 2 O 3 、Zn(OAc) 2 、ZnCl 2 、Ca(OAc) 2 Organic and inorganic metal catalysts such as PbO, tetrabutyl phthalate, stannous oxalate and the like (CN 102453242B; gu Shuyong and the like, stannous oxalate: a novel catalyst for synthesizing polytrimethylene terephthalate, 2007) and the like, and special catalysts for furan bio-based polyesters have not been reported yet. In the process of synthesizing furan polyester, the catalyst uses three common polyethylene terephthalate (PET) catalysts of titanium (Ti), antimony (Sb) and tin (Sn), and the furan polyester obtained by catalytic polymerization has deep chromaticity and wider molecular weight distribution of the polymer, thereby affecting various performances. Therefore, a new catalyst special for furan polyester needs to be developed to improve the polymerization efficiency and the polymerIs a performance of the (c).
Disclosure of Invention
The invention mainly aims to provide a furan polyester catalyst and a preparation method thereof, which can improve the reaction rate of the catalyst for catalyzing furan reaction substrates to carry out polymerization reaction, improve the polymerization efficiency and reduce the chromaticity of polyester.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps: provides a furan polyester catalyst and a preparation method thereof:
In a first aspect, the invention provides a furan polyester catalyst which is a 2, 5-furan dicarboxylic acid metal compound with a general formula of L-M n+ Wherein L is furan carboxylic acid ligand, and has a structure shown in formula (I), formula (II) and/or formula (III), M n+ Is a metal ion, n is an integer of 2 to 5;
in the formula (I), R 1 Selected from-O (CH) 2 ) x OH、-O(CH 2 ) x (OH) 2 Any one of the groups; x is an integer of 2 to 16.
Still further, the metal ions include ions of metals such as calcium (Ca), zinc (Zn), germanium (Ge), antimony (Sb), tin (Sn), and titanium (Ti).
Further, the molar ratio of M to oxygen (O) in the catalyst is 1:5 to 1:35.
Further, the-O (CH 2 ) x The OH group is derived from an alkyl diol having 2 to 16 carbon atoms, and further from a linear or branched alkyl diol such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, decylene glycol, undecylene glycol, dodecylene glycol, tetradecylene glycol, hexadecylene glycol, or the like.
Further, the-O (CH 2 ) x (OH) 2 The radicals are derived from C3-16 alkyl triols, and further from glycerol, butanetriol and pentanStraight-chain or branched alkyl triols such as triols, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, dodecyl triol and hexadecyl triol.
Still further, the catalyst may be used in the catalysis of polyester synthesis of 2, 5-furandicarboxylic acid with an alkyl diol or an alkyl triol in which the alkyl group of the alkyl diol or alkyl triol is a C2-C16 alkyl group.
Further, the alkyl glycol specifically includes ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, decylene glycol, undecylene glycol, dodecylene glycol, tetradecylene glycol, hexadecylene glycol, and the like.
More specifically, the alkyl triols include glycerol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, dodecyl triol, hexadecyl triol, and the like.
In a second aspect, the invention also provides a preparation method of the furan polyester catalyst, which is used for preparing L-M synthesized by furan carboxylic acid ligand with a structure of formula (I) and M metal ions n+ The catalyst specifically comprises: dissolving 5-carboxyl-2-furancarboxylic acid ester and sodium or potassium alkaline compound to obtain alkali metal salt solution of 5-methyl carboxyl-2-furancarboxylic acid ester, and performing metal ion displacement reaction with M metal compound to obtain L-M n+ The coordination structure is adopted to obtain the furan polyester catalyst with the ligand L structure as formula (I).
Further, the solvent of the alkali metal salt solution is at least one of water or a protic organic solvent.
Further, the solvent for the metal ion substitution reaction includes a protic organic solvent containing 0 to 20wt% of water.
Still further, the protic organic solvents include methanol, ethanol, propanol, n-butanol, ethylene glycol, glycerol, ethyl acetate, ethyl propionate, and the like.
Further, the concentration of the ligand L in the alkali metal salt solution is 0.01 to 2.5mol/L.
Still further, the sodium or potassium alkaline compound is preferably selected from the group consisting of sodium or potassium hydroxides, carbonates, bicarbonates, and the like.
Still further, the M metal compound for metal ion substitution reaction is preferably selected from calcium chloride, zinc chloride, antimony trichloride, germanium tetrachloride, tin tetrachloride, titanium tetrachloride, antimony pentachloride, etc.
Further, the preparation method of the catalyst comprises the following steps:
optionally, when the M metal ion is selected from divalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 4:1-1:1, the reaction temperature of the metal ion replacement reaction is 4-70 ℃, and the reaction time is 0.1-6 h;
optionally, when M metal ions are selected from trivalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 5:1-2:1, the reaction temperature of the metal ion replacement reaction is 10-75 ℃, and the reaction time is 0.1-8 h;
Optionally, when M metal ions are selected from tetravalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 6:1-3:1, the reaction temperature of the metal ion replacement reaction is 15-80 ℃, and the reaction time is 0.1-10 h;
optionally, when the M metal ion is selected from pentavalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 7:1-4:1, the reaction temperature of the metal ion replacement reaction is 20-90 ℃, and the reaction time is 0.1-12 h.
In a third aspect, the present invention also provides a method for preparing the furan polyester catalyst, which is used for preparing L-M synthesized by furan carboxylic acid ligand with a structure of formula (II) and/or formula (III) and M metal ions n+ The catalyst specifically comprises: dissolving 2, 5-furan dicarboxylic acid and alkali metal compound such as alkaline sodium or potassium to obtain alkali metal salt solution of 2, 5-furan dicarboxylic acid, and performing metal ion replacement reaction with M metal compound to obtain L-M n+ And (3) precipitating to obtain the furan polyester catalyst with the L structure shown in the formula (II) and/or the formula (III).
Further, the alkali metal compound is preferably selected from the group consisting of sodium or potassium hydroxide, carbonate, bicarbonate, and the like.
Further, the M metal compound for the substitution reaction is preferably selected from calcium chloride, zinc chloride, antimony trichloride, germanium tetrachloride, tin tetrachloride, titanium tetrachloride, antimony pentachloride, etc.
Further, the solvent of the alkali metal salt solution includes at least one of water or a protic organic solvent.
Further, the solvent for the metal ion substitution reaction is a protic organic solvent containing 0 to 20wt% of water.
Further, the protic organic solvents include methanol, ethanol, propanol, n-butanol, isoamyl alcohol, ethylene glycol, glycerol, and the like.
Further, the concentration of the ligand L in the alkali metal salt solution is 0.01 to 2.5mol/L.
Further, the preparation method of the catalyst comprises the following steps:
optionally, when the M metal ion is selected from divalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 3:1-1:2, the reaction temperature of the metal ion replacement reaction is 10-70 ℃, and the reaction time is 0.1-6 h;
optionally, when M metal ions are selected from trivalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 4:1-1:1, the reaction temperature of the metal ion replacement reaction is 15-75 ℃, and the reaction time is 0.1-8 h;
optionally, when the M metal ion is selected from tetravalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 5:1-2:1, the reaction temperature of the metal ion replacement reaction is 20-80 ℃, and the reaction time is 0.1-20 h;
Optionally, when the M metal ion is selected from pentavalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 6:1-3:1, the reaction temperature of the metal ion replacement reaction is 25-90 ℃, and the reaction time is 0.1-24 h; .
In a fourth aspect, the present invention also provides the furans described aboveProcess for preparing polyester catalysts for preparing L-M by synthesis of furancarboxylic acid ligands of the formula (I) and formula (II) or formula (I) and formula (III) or formula (I), formula (II) and formula (III) with M metal ions n+ The catalyst specifically comprises: dissolving 5-carboxyl-2-furancarboxylate and 2, 5-furandicarboxylic acid in alkaline compound of sodium or potassium to obtain alkali metal salt solution of 5-carboxyl-2-furancarboxylate and 2, 5-furandicarboxylic acid, and performing metal ion replacement reaction with metal ion in M metal compound to obtain L-M n+ Precipitating to obtain the furan polyester catalyst with the ligand L structure shown in the formula (I) and the formula (II) or the formula (I) and the formula (III) or the formula (I), the formula (II) and the formula (III).
Still further, the sodium or potassium alkaline compound is preferably selected from the group consisting of sodium or potassium hydroxides, carbonates, bicarbonates, and the like.
Still further, the M metal compound used for the metal ion substitution reaction is preferably selected from the group consisting of calcium chloride, zinc chloride, antimony trichloride, germanium tetrachloride, tin tetrachloride, titanium tetrachloride, antimony pentachloride, and the like.
Further, the molar ratio of the 5-carboxyl-2-furancarboxylic acid ester to the 2, 5-furandicarboxylic acid is 6:1-1:2;
further, the solvent of the alkali metal salt solution is at least one of water or a protic organic solvent.
Further, the solvent for the metal ion substitution reaction is a protic organic solvent containing 0 to 20wt% of water.
Still further, the protic organic solvents include methanol, ethanol, propanol, n-butanol, isoamyl alcohol, ethylene glycol, glycerol, and the like.
Further, the concentration of the ligand L in the solution is 0.01 to 2.5mol/L.
Further, the preparation method of the catalyst comprises the following steps:
optionally, when the M metal ion is selected from divalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylate and the 2, 5-furandicarboxylic acid to the M metal compound is 3:1-1:2, the reaction temperature of the metal ion replacement reaction is 10-70 ℃, and the reaction time is 0.1-6 h;
optionally, when M metal ions are selected from trivalent ions, the molar ratio of the alkali metal salts of the 5-carboxyl-2-furancarboxylic acid ester and the 2, 5-furandicarboxylic acid to the M metal compound is 4:1-1:1, the reaction temperature of the metal ion replacement reaction is 15-75 ℃, and the reaction time is 0.1-8 h;
Optionally, when M metal ions are selected from tetravalent ions, the molar ratio of the alkali metal salts of the 5-carboxyl-2-furancarboxylic acid ester and the 2, 5-furandicarboxylic acid to the M metal compound is 5:1-2:1, the reaction temperature of the metal ion replacement reaction is 20-80 ℃, and the reaction time is 0.1-20 h;
alternatively, when M metal ions are selected from pentavalent ions, the molar ratio of the alkali metal salts of 5-carboxyl-2-furancarboxylate and 2, 5-furandicarboxylic acid to the M metal compound is 6:1-3:1, the reaction temperature of the metal ion replacement reaction is 25-90 ℃, and the reaction time is 0.1-24 h.
Based on the technical scheme, the invention has the beneficial effects that:
(1) The invention provides a novel special synthesis catalyst for furan carboxylic acid polyester, which is very suitable for catalyzing the synthesis reaction of furan polyester.
(2) The catalyst provided by the invention has no non-polymerized unit impurity, and can effectively avoid the problem of chromaticity rise caused by adding other groups.
(3) The catalyst provided by the invention has the advantages of high catalytic rate and high catalytic efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a Fourier infrared spectrum of a polymer produced in example 36 of the present invention.
Detailed Description
In view of the problems that a special catalyst for furan bio-based polyester is not reported yet, and the color of furan polyester obtained by catalytic polymerization of a common catalyst for polyester is deep and the molecular weight distribution of a polymer is relatively wide, the inventor provides a technical scheme of the invention through long-term research and a great deal of practice, and the furan polyester catalyst and the preparation method thereof are provided, wherein the catalyst is a 2, 5-furan dicarboxylic acid metal compound with a general formula of L-M n+ L is furan carboxylic acid ligand, the 2 and 5 positions of furan ring of which are respectively combined with-COO - 、-COOH、-COO(CH 2 ) x OH group, -COO (CH) 2 ) x (OH) 2 Any one of the groups being attached to at least one-COO - Are connected; m is M n+ Is the ion of metals such as calcium, zinc, germanium, antimony, tin, titanium, etc. The catalyst can be used for the synthesis catalysis of polyesters of 2, 5-furan dicarboxylic acid and C2-C16 straight-chain and branched-chain diols.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further elucidated with reference to the embodiment. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. It should be understood that the specific embodiments described herein are merely illustrative of the present invention, and the experimental conditions and setting parameters thereof should not be construed as limiting the basic technical scheme of the present invention. And the scope of the present invention is not limited to the following examples. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, all starting materials and reagents in the examples herein were purchased commercially.
It is understood that the 5-carboxyl-2-furancarboxylic acid ester used in the present invention may be named as 2-carboxyl-5-furancarboxylic acid ester, and the compounds named in each named mode are the same known compound, and the technical conception and the protection scope of the present invention are not affected by the named modes of each raw material and the compound.
The technical scheme of the invention is further described in detail through a plurality of embodiments. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
0.1mol of 5- ((2-hydroxyethoxy) carbonyl) furan-2-carboxylic acid was reacted with 0.1mol of sodium hydroxide in 100mL of water to complete dissolution, with an L ligand concentration of 1mol/L. 0.025mol of calcium chloride (CaCl) is added 2 ) The reaction is carried out for 2 hours at the reaction temperature of 4 ℃, the reaction product is collected, washed, dried and weighed, the productivity of the prepared catalyst is 96.52 percent, the catalyst is respectively subjected to elemental analysis by a transmission electron microscope (TEM, with EDS function) and an inductively coupled plasma emission spectrometer (ICP-OES) and an elemental analyzer, and the molar ratio of Ca/O is 1:12.03 measured by EDS. The concentration of Ca was measured by ICP-OES, and it was calculated that the mass percentage in the catalyst was 9.13%, the content of carbon (C) was 43.84%, the content of hydrogen (H) was 3.22%, the content of oxygen (O) was 43.81%, and the ratio was 1:12.02 in terms of Ca/O mole ratio.
Example 2
This example operates and tests substantially the same as example 1, except that:
according to the preparation method of the furan polyester catalyst adopted in the embodiment, the addition amount of calcium chloride is changed to 0.05mol, the reaction temperature is changed to 30 ℃, the productivity of the prepared catalyst is 95.67%, the molar ratio of Ca to O measured by EDS is 1:12.01, the contents of calcium (Ca) and oxygen (O) measured by ICP-OES and an elemental analyzer are 9.13% and 43.80%, and the conversion is 1:12.02.
Example 3
This example operates and tests substantially the same as example 2, except that:
the preparation method of the furan polyester catalyst adopted in the embodiment changes sodium hydroxide into 0.05mol of potassium carbonate, the reaction time into 0.1 hour, the productivity of the prepared catalyst is 90.35%, the molar ratio of Ca to O measured by EDS is 1:12.2, the contents of calcium (Ca) and oxygen (O) measured by ICP-OES and an elemental analyzer are 9.14% and 43.80%, respectively, and the conversion is 1:12.00.
Example 4
This example operates and tests substantially the same as example 2, except that:
according to the preparation method of the furan polyester catalyst adopted in the embodiment, 5- ((2-hydroxyethoxy) carbonyl) furan-2-carboxylic acid is changed into 0.25mol, sodium hydroxide is changed into 0.1mol sodium bicarbonate, all reaction solvents are changed into 100mL of 9:1 ethanol-water (v: v) solution, the time is changed into 6 hours, the prepared catalyst yield is 97.21%, the molar ratio of Ca/O measured by EDS is 1:12.04, the contents of calcium (Ca) and oxygen (O) measured by ICP-OES and an elemental analyzer are respectively 9.11% and 43.82%, and the conversion is 1:12.05.
Example 5
0.001mol of 5- ((2-hydroxyethoxy) carbonyl) furan-2-carboxylic acid was reacted with 0.001mol of potassium hydroxide in 100mL of a 8:2 ethanol/water (v: v) solution for 1h at a ligand L concentration of 0.01mol/L. Then 0.001mol of zinc chloride (ZnCl) is added 2 ) The reaction was carried out at a reaction temperature of 70℃for 2 hours, the reaction product was collected, washed, dried and weighed to give a catalyst having a productivity of 97.28% and a Zn/O molar ratio of 1:11.997 as measured by EDS and 14.11% and 41.41% as measured by ICP-OES and elemental analyzer, respectively, converted to a Zn/O molar ratio of 1:11.99.
Example 6
This example operates and tests substantially the same as example 5, except that:
the preparation method of the furan polyester catalyst adopted in the embodiment changes the raw material of the L ligand into 0.1mol of 5- ((8-hydroxyoctyloxy) carbonyl) furan-2-carboxylic acid, changes the reaction solvent into ethylene glycol, changes the reaction temperature into 40 ℃ and changes the reaction time into 4 hours, so that the yield of the prepared catalyst is 98.53%, the Zn/O molar ratio measured by EDS is 1:12.00, the Zn and O contents measured by ICP-OES and an elemental analyzer are respectively 10.33% and 30.39%, and the conversion is 1:12.02.
Example 7
This example operates and tests substantially the same as example 6, except that:
According to the preparation method of the furan polyester catalyst adopted in the embodiment, the raw material of the L ligand is changed into 0.1mol of 5- ((16-hydroxy hexadecyloxy) carbonyl) furan-2-carboxylic acid, zinc chloride is changed into calcium chloride, the initial reaction solvents are changed into 9:1 ethylene glycol water (v: v) solutions, when calcium chloride is added, the water is added to the solvents, the volume ratio of the ethylene glycol to the water is changed into 8:2, the catalyst yield is 99.20%, the molar ratio of Ca to O measured by EDS is 1:12.05, the contents of Ca and O measured by ICP-OES and the contents of O measured by an elemental analyzer are respectively 4.81% and 23.10%, and the conversion is 1:12.03.
TABLE 1 EXAMPLES 1 to 7 Experimental data sheets
Note that: the solvent 1 is a reaction solution of furan compounds and alkaline substances of sodium or potassium; the solvent 2 is a reaction solution when the compound containing the L ligand and the M metal compound undergo metal ion replacement reaction;
wherein, raw material 1:5- ((2-hydroxyethoxy) carbonyl) furan-2-carboxylic acid, starting material 2:5- ((8-hydroxyoctyloxy) carbonyl) furan-2-carboxylic acid, starting material 3:5- ((16-hydroxyhexadecyloxy) carbonyl) furan-2-carboxylic acid.
Example 8
This example operates and tests substantially the same as example 1, except that:
the preparation method of the furan polyester catalyst adopted in the embodiment changes sodium hydroxide into potassium hydroxide, and changes M metal compound into 0.02mol of antimony chloride (SbCl 3 ) The reaction solvent is changed into ethanol when the antimony chloride is added, the reaction temperature is changed into 10 ℃, the yield of the prepared catalyst is 98.33%, the molar ratio of Sb/O measured by EDS is 1:12.01, and the molar ratio of Sb/O measured by ICP-OES and an elemental analyzer is 1:12.02.
Example 9
This example operates and tests substantially the same as example 8, except that:
the preparation method of the furan polyester catalyst adopted in the embodiment changes the raw material of the L ligand into 0.12mol5- ((6-hydroxyhexyloxy) carbonyl) furan-2-carboxylic acid, sbCl 3 Changing the reaction solvent into a solution of 99:1 ethanol and water (v: v) when adding antimony chloride into the reaction solvent, changing the reaction temperature into 30 ℃, obtaining the catalyst with the yield of 98.82 percent, wherein the molar ratio of Sb to O measured by EDS is 1:12.02, and the molar ratio of Sb to O measured by ICP-OES and an elemental analyzer is 1:12.01.
Example 10
This example operates and tests substantially the same as example 8, except that:
the preparation method of the furan polyester catalyst adopted in the embodiment changes the L ligand raw material into 0.1mol 5- ((14-hydroxy tetradecyloxy) carbonyl) furan-2-carboxylic acid, sbCl 3 Changing the reaction solution into ethanol when adding potassium hydroxide for reaction, changing the reaction solvent into ethylene glycol when adding antimony chloride, changing the reaction temperature into 75 ℃, changing the reaction time into 0.1 hour, obtaining the catalyst with 93.12 percent of productivity, 1:12.05 of Sb/O mole ratio measured by EDS, and 1:12.07 of Sb/O mole ratio measured by ICP-OES and an elemental analyzer.
Example 11
0.1mol of 5- ((2, 3-dihydroxypropoxy) carbonyl) furan-2-carboxylic acid was reacted with 0.1mol of sodium bicarbonate in 100mL of 9:1 ethanol: water (v: v) solvent until sodium bicarbonate was completely dissolved, with an L ligand concentration of 1mol/L. 0.05mol SbCl is added 3 The reaction was carried out at a reaction temperature of 30℃for 8 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst was found to have a yield of 98.46%, a sample analysis was carried out according to the method of example 1, an Sb/O molar ratio of 1:21.02 was found by EDS, a mass percent of Sb in the catalyst was found to be 14.99% by ICP-OES, a carbon (C) content of 39.92%, a hydrogen (H) content of 3.72%, an oxygen (O) content of 41.37% and a conversion to an Sb/O molar ratio of 1:21.01 were found by elemental analysis.
Example 12
0.25mol of 5- ((3, 4-dihydroxybutoxy) carbonyl) furan-2-carboxylic acid was reacted with 0.12mol of potassium hydroxide in 100mL of water (v: v) solvent until potassium hydroxide was completely dissolved, with an L ligand concentration of 2.5mol/L. The resulting potassium salt containing L ligand was separated from the solution, and then added to 20mL of water to obtain 0.0357mol of antimony pentachloride (SbCl 5 ) Dissolving in armorAlcohol and adding the catalyst into the potassium salt aqueous solution containing the L ligand, reacting for 2 hours at the reaction temperature of 20 ℃, collecting a reaction product, cleaning, drying and weighing the reaction product, wherein the yield of the prepared catalyst is 94.57 percent, sample analysis is carried out according to the method of the example 1, the molar ratio of Sb/O is 1:34.99 by EDS, and the molar ratio of Sb/O is 1:35.00 by ICP-OES and an elemental analyzer.
Example 13
0.15mol of 5- ((6-hydroxyhexyloxy) carbonyl) furan-2-carboxylic acid was reacted with 0.75mol of sodium carbonate in 70mL of methanol, 0.03mol of antimony pentachloride (SbCl 5 ) Dissolving in 50mL of methanol, mixing the two solutions, reacting for 12 hours at the reaction temperature of 40 ℃, collecting a reaction product, cleaning, drying and weighing, wherein the yield of the prepared catalyst is 96.85%, sample analysis is carried out according to the method of example 1, the molar ratio of Sb/O is 1:35.00 by EDS, and the molar ratio of Sb/O is 1:34.98 by ICP-OES and an elemental analyzer.
Example 14
0.001mol of 5- ((10-hydroxydecyloxy) carbonyl) furan-2-carboxylic acid is reacted with 0.001mol of sodium hydroxide in 100mL of 9:1 methanol-to-water (v: v) solvent to produce a sodium containing compound containing L ligand at a concentration of 0.01mol/L. Separating the resulting sodium compound containing L ligand from the solution, adding to 100mL of n-butanol, adding 0.25mmol of SbCl 5 The reaction was carried out at a reaction temperature of 90℃for 0.1 hour, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 96.38%, and was analyzed by a sample analysis by the method of example 1, the molar ratio of Sb/O was 1:34.98 as measured by EDS, and the molar ratio of Sb/O was 1:35.00 as measured by ICP-OES and an elemental analyzer.
Table 2 Experimental data Table for examples 8-14
Note that: the solvent 1 is a reaction solution of furan compounds and alkaline substances of sodium or potassium; the solvent 2 is a reaction solution when the compound containing the L ligand and the M metal compound undergo metal ion replacement reaction;
wherein, raw material 4:5- ((6-hydroxyhexyloxy) carbonyl) furan-2-carboxylic acid, starting material 5:5- ((14-hydroxytetradecyloxy) carbonyl) furan-2-carboxylic acid, starting material 6:5- ((2, 3-dihydroxypropoxy) carbonyl) furan-2-carboxylic acid, starting material 7:5- ((3, 4-dihydroxybutoxy) carbonyl) furan-2-carboxylic acid, starting material 8:5- ((10-hydroxydecyloxy) carbonyl) furan-2-carboxylic acid, and the compounds corresponding to the remaining raw material numbers are the same as in table 1 above.
Example 15
0.012mol of 5- ((2-hydroxyethoxy) carbonyl) furan-2-carboxylic acid is reacted with 0.012mol of sodium hydroxide in 100mL of water to produce a sodium-containing compound containing L ligand, wherein the concentration of L ligand is 0.12mol/L. The resulting sodium compound containing the L ligand was separated from the solution, and then added to 100mL of ethanol, followed by addition of 0.002mol of titanium tetrachloride (TiCl 4 ) The reaction was carried out at 15℃for 2 hours, the reaction product was collected, washed, dried and weighed, and the catalyst prepared was 98.59% in yield, and was analyzed by sample analysis according to the method of example 1, the molar ratio of Ti to O was 1:24.06 as measured by EDS, and the molar ratio of Ti to O was 1:24.02 as measured by ICP-OES and elemental analyzer.
Example 16
0.12mol of 5- ((3-hydroxypropoxy) carbonyl) furan-2-carboxylic acid is reacted with 0.06mol of potassium carbonate in 100mL of water to produce a potassium-containing compound containing the L ligand. The resulting potassium compound containing the L ligand was separated from the solution and added to 100mL of a 99:1 ethanol/water (v: v) solution, followed by addition of 0.024mol of titanium tetrachloride (TiCl 4 ) The reaction was carried out at a reaction temperature of 50℃for 2 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 98.13%, and was analyzed by a sample according to the method of example 1, the molar ratio of Ti to O was 1:24.03 as measured by EDS, and the molar ratio of Ti to O was 1:24.01 as measured by ICP-OES and an elemental analyzer.
Example 17
Mixing 0.12mol of 5- ((16-hydroxyhexadecyloxy) carbonyl) furan-2-carboxylic acid with 0.12mol of potassium hydroxide at 1The reaction is carried out in 00mL of ethanol to generate the potassium compound containing the L ligand. The resulting potassium compound containing the L ligand was separated from the solution, and then added to 100mL of ethylene glycol, followed by addition of 0.04mol of germanium tetrachloride (GeCl 4 ) The reaction was carried out at a reaction temperature of 80℃for 0.1 hour, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 96.88%, and was analyzed by a sample analysis by the method of example 1, the molar ratio of Ge/O was 1:24.05 by EDS, and the molar ratio of Ge/O was 1:24.02 by ICP-OES and an elemental analyzer.
Example 18
0.1mol of 5- ((2, 3-dihydroxypropoxy) carbonyl) furan-2-carboxylic acid is reacted with 0.12mol of sodium bicarbonate in 100mL of a 4:5:1 methanol-ethanol-water (v: v) solution to form a sodium-containing compound containing L ligand, and 0.02mol of germanium tetrachloride (GeCl) is added 4 ) The reaction was carried out at a reaction temperature of 40℃for 10 hours, the reaction product was collected, washed, dried and weighed, and the catalyst produced was 98.81% in yield, and was analyzed by a sample according to the method of example 1, the molar ratio of Ge/O was 1:28.01 as measured by EDS, and the molar ratio of Ge/O was 1:27.98 as measured by ICP-OES and an elemental analyzer.
Example 19
Reacting 0.1mol of 5- ((3, 4-dihydroxybutoxy) carbonyl) furan-2-carboxylic acid with 0.1mol of potassium hydroxide in 100mL of water to form a potassium compound containing L ligand, separating the potassium compound containing L ligand, adding the potassium compound to 80mL of 8:2 methanol-water (v: v) solution, and adding 0.02mol of titanium tetrachloride (TiCl 4 ) The reaction was carried out at a reaction temperature of 20℃for 4 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 97.54%, and was analyzed by sample analysis according to the method of example 1, the molar ratio of Ti to O was 1:28.05 by EDS, and the molar ratio of Ti to O was 1:28.03 by ICP-OES and elemental analyzer.
Example 20
Reacting 0.1mol of 5- ((6-hydroxyhexyloxy) carbonyl) furan-2-carboxylic acid with 0.05mol of sodium carbonate in 100mL of methanol to form a sodium-containing compound containing L ligand, adding a proper amount of water to a solvent ratio of 8:2 methanol to water (v: v), and adding 0.02mol of tin tetrachloride (SnCl 4 ) Reacting at 40 ℃ for 4 hours, collecting reaction productsThe catalyst was prepared in a yield of 97.98% by weight after washing and drying, and was analyzed by sample analysis according to the method of example 1, with an Sn/O molar ratio of 1:23.97 as measured by EDS and an Sn/O molar ratio of 1:23.98 as measured by ICP-OES and elemental analyzer.
Example 21
0.1mol of 5- ((10-hydroxydecyloxy) carbonyl) furan-2-carboxylic acid and 0.1mol of sodium hydroxide are reacted in 100mL of a solution of 4:1 ethylene glycol in water (v: v) to form a sodium compound containing L ligand, the sodium compound containing L ligand is separated, and then added to 80mL of n-butanol, and 0.02mol of titanium tetrachloride (TiCl 4 ) The reaction was carried out at a reaction temperature of 80℃for 4 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 96.62%, and was analyzed by sample analysis according to the method of example 1, with a molar ratio of Sn/O of 1:23.99 as measured by EDS, and a molar ratio of Sn/O of 1:23.96 as measured by ICP-OES and elemental analyzer.
Table 3 Experimental data Table of examples 15-21
Note that: the solvent 1 is a reaction solution of furan compounds and alkaline substances of sodium or potassium; the solvent 2 is a reaction solution when the compound containing the L ligand and the M metal compound undergo metal ion replacement reaction;
wherein, raw material 9: the 5- ((3-hydroxypropoxy) carbonyl) furan-2-carboxylic acid and the remaining starting material numbers correspond to the same compounds as in tables 1-2 above.
Example 22
0.1mol of 2, 5-furandicarboxylic acid (FDCA) and 0.22mol of sodium hydroxide are reacted in 100mL of water to form a sodium-containing compound containing L ligand, and 0.033mol of calcium chloride (CaCl 2 ) The reaction was carried out at a reaction temperature of 4℃for 2 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst was 99.34% in yield, and was analyzed by a sample according to the method of example 1, the molar ratio of Ca/O was 1:5.02 as measured by EDS, and the molar ratio of Ca/O was 1:5.00 as measured by ICP-OES and an elemental analyzer.
Example 23
0.1mol of 2, 5-furandicarboxylic acid is reacted with 0.1mol of sodium hydroxide in 100mL of water to form a sodium-containing compound containing L ligand, and 0.05mol of calcium chloride (CaCl 2 ) The reaction was carried out at a reaction temperature of 30℃for 0.1 hour, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 91.53%, and was analyzed by a sample analysis by the method of example 1, the molar ratio of Ca to O was 1:10.06 as measured by EDS, and the molar ratio of Ca to O was 1:10.04 as measured by ICP-OES and an elemental analyzer.
Example 24
This example operates and tests substantially the same as example 23, except that:
the preparation method of the furan polyester catalyst adopted in the embodiment changes sodium hydroxide into 0.13mol and M metal compound into ZnCl 2 The reaction time was changed to 6 hours, and the catalyst produced had a productivity of 99.82%, an Sb/O molar ratio of 1:6.27 as measured by EDS, and an Sb/O molar ratio of 1:6.26 as measured by ICP-OES and an elemental analyzer.
Example 25
This example operates and tests substantially the same as example 23, except that:
the preparation method of furan polyester catalyst adopted in the embodiment changes sodium hydride into 0.12 sodium bicarbonate, and changes solvent into 100mL of 9:1 methanol-water (v: v) solution, caCl 2 The reaction time was changed to 6 hours instead of 0.05mol, the productivity of the catalyst was 97.84%, the molar ratio of Sb/O measured by EDS was 1:6.60, and the molar ratio of Sb/O measured by ICP-OES and elemental analyzer was 1:6.56.
Example 26
0.1mol of FDCA and 0.16mol of potassium hydroxide are reacted in 100mL of ethanol to generate a potassium compound containing L ligand, a small amount of water is added to change the solution into 8:2 ethanol-water (v: v) solution, and 0.05mol of SnCl is added 4 The reaction was carried out at a reaction temperature of 70℃for 2 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 98.35%, and was analyzed by a sample according to the method of example 1, with an Sn/O molar ratio of 1:19.26 as measured by EDS, and an Sn/O molar ratio of 1:19.23 as measured by ICP-OES and an elemental analyzer.
Example 27
Reacting 0.12mol FDCA with 0.14mol potassium hydroxide in 100ml8:2 ethanol-water (v: v) solution to produce a potassium-containing compound containing L ligand, adding 0.04mol SbCl 3 The reaction was carried out at a reaction temperature of 40℃for 4 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 99.15%, and was analyzed by a sample according to the method of example 1, the molar ratio of Sb/O was 1:10.99 as measured by EDS, and the molar ratio of Sb/O was 1:10.96 as measured by ICP-OES and an elemental analyzer.
Example 28
0.12mol of FDCA is reacted with 0.12mol of potassium hydroxide in 100ml of 8:2 ethylene glycol/water (v: v) to form a potassium compound containing L ligand, and 0.02mol of SbCl is added 5 The reaction was carried out at a reaction temperature of 40℃for 4 hours, the reaction product was collected, washed, dried and weighed, and the prepared catalyst had a productivity of 97.08%, and was analyzed by sample analysis according to the method of example 1, with a molar ratio of Sb/O of 1:25.01 as measured by EDS, and a molar ratio of Sb/O of 1:24.99 as measured by ICP-OES and an elemental analyzer.
Table 4 Table 22-28 Experimental data
Note that: the solvent 1 is a reaction solution of furan compounds and alkaline substances of sodium or potassium; the solvent 2 is a reaction solution when the compound containing the L ligand and the M metal compound undergo a metal ion substitution reaction.
Examples 29 to 35
0.03mol of FDCA is mixed with different 5-carboxyl-2-furancarboxylic acid esters, the molar ratio of the 5-carboxyl-2-furancarboxylic acid esters to the FDCA is 6:1-1:2, then 0.04mol of different sodium or potassium alkaline compounds are added to react in 100mL of different solutions, the molar ratio of the L ligand-containing compound and the sodium or potassium compound to the M metal compound is 6:1-1:1, the reaction temperature, the reaction time, the yield of the prepared catalyst and the analysis result of the catalyst are shown in Table 5, the analysis operation method is referred to in example 1, and experimental data of examples 29-35 are shown in Table 5. After adding potassium carbonate to produce a compound containing L ligand and potassium in example 33, appropriate water was added to bring the volume ratio of ethanol to water in the solution to 8:2. In example 34, potassium hydroxide was added to form a compound containing an L ligand and potassium, and then water was added to the solution so that the volume ratio of ethylene glycol to water was 9:1.
Table 5 Experimental data Table of examples 29-35
Note that: the solvent 1 is a reaction solution of furan compounds and alkaline substances of sodium or potassium; the solvent 2 is a reaction solution when the compound containing the L ligand and the M metal compound undergo metal ion replacement reaction;
wherein, raw material 10:5- ((4-hydroxybutoxy) carbonyl) furan-2-carboxylic acid, and the compounds corresponding to the remaining starting material numbers are the same as in the foregoing tables 1 to 3.
Comparative example 1
With 10g FDCA and 9.9g ethylene glycol as substrates, 0.1g Sb was added 2 O 3 Reacting for 2h under the protection of nitrogen at 120 ℃ as a catalyst, reacting for 2h under the protection of nitrogen at 180 ℃ as well as decompressing for 2h (150 Pa) to remove redundant glycol, heating to 230 ℃ and decompressing for 1h (100 Pa), cooling to obtain yellow poly (2, 5-furandicarboxylic acid) glycol ester (PEF), performing infrared spectrum test (FTIR) by using a Fourier infrared spectrometer, testing the intrinsic viscosity by using a Ubbelohde viscometer at 30+/-0.05 ℃, dissolving by using a mixed solvent of phenol and tetrachloroethane, and calculating the intrinsic viscosity [ eta ] of the copolyester according to formulas (1) and (2)]。
η sp =(t 1 -t 0 )/t 0 (1)
[η]=[(1+1.4η sp ) 1/2 -1]/0.7c (2)
Wherein: t is t 0 Is the flow-through time(s) of the solvent; t is t 1 Flow time(s) for the polyester solution; c is the concentration of the copolyester solution, which is 5g/L.
Further, in the esterification reaction, the activity of the catalyst was characterized by calculating the esterification rate (DE) of PTA in terms of the amount of water produced, de=v/2.3×100%, where V (mL) is the amount of water produced and 2.3mL is the amount of water produced after the entire FDCA reaction. The test results are:
the intrinsic viscosity of the resulting polymer was 0.82dL/g, and the DE was 72.5% by reacting under reduced pressure at 180℃for 0.1 hour, and 98.3% by reacting under reduced pressure at 180℃for 2 hours. The resulting polymer was subjected to FTIR testing with a major characteristic peak, similar to that reported in the prior literature, being PEF.
Example 36
10g of FDCA and 9.9g of ethylene glycol are taken as substrates, 0.08g of Sb-containing catalyst prepared in example 8 is added, the mixture is reacted for 2 hours under the protection of nitrogen at 120 ℃, then reacted for 2 hours under the protection of nitrogen at 180 ℃, then the mixture is decompressed for 2 hours (150 Pa) to remove excessive ethylene glycol, the mixture is heated to 230 ℃ and decompressed for 1 hour (100 Pa), and then the mixture is cooled to obtain nearly colorless poly (2, 5-ethylene furandicarboxylate) (PEF). The test methods of intrinsic viscosity, DE and the like were the same as those of comparative example 1, the intrinsic viscosity was 1.02dL/g, DE was 89.6% as measured by a decompression reaction at 180℃for 0.1 hour, and DE was 99.8% as measured by a decompression reaction at 180℃for 2 hours. The resulting polymer was subjected to FTIR testing, as shown in fig. 1, with the main characteristic peak being PEF, similar to that reported in the prior literature.
Example 37
10g of FDCA and 9.9g of ethylene glycol are taken as substrates, 0.08g of Sb-containing catalyst prepared in example 34 is added, the mixture is reacted for 2 hours under the protection of nitrogen at 120 ℃, then reacted for 2 hours under the protection of nitrogen at 180 ℃, then decompressed for 2 hours, (150 Pa) excess ethylene glycol is removed, the mixture is heated to 230 ℃ and decompressed for 1 hour, (100 Pa), and nearly colorless poly (2, 5-furandicarboxylic acid) ethylene ester (PEF) is obtained after cooling. The test methods for intrinsic viscosity, DE and the like were the same as those of comparative example 1, and the intrinsic viscosity was 1.07dL/g, and the DE was 90.7% by the reaction under reduced pressure at 180℃for 0.1 hour and 99.9% by the reaction under reduced pressure at 180℃for 2 hours. The resulting polymer was subjected to FTIR testing, and the main characteristic peak was PEF, in accordance with fig. 1.
As is clear from comparison of comparative example 1 with examples 36 and 37, the catalyst provided by the invention effectively avoids the problem of chromaticity rise caused by adding other groups, and has a catalytic efficiency for catalyzing furan carboxylic acid polymerization reaction which is obviously higher than that of the conventional common catalyst.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely 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 present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, 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 the scope thereof. 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. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A furan polyester catalyst is characterized in that the furan polyester catalyst is a 2, 5-furan dicarboxylic acid metal compound with a general formula of L-M n+ Wherein L is furan carboxylic acid ligand, and has a structure shown in at least any one of formula (I), formula (II) and formula (III), M n+ Is a metal ion, n is an integer of 2 to 5;
in the formula (I), R 1 Selected from-O (CH) 2 ) x OH、-O(CH 2 ) x (OH) 2 Any one of the groups, x is an integer from 2 to 16.
2. The furan-based polyester catalyst of claim 1, wherein the metal ion comprises at least any one of calcium ion, zinc ion, germanium ion, antimony ion, tin ion, and titanium ion;
and/or, in the furan polyester catalyst, the molar ratio of the metal element to the oxygen element is 1:5-1:35.
3. The furan-based polyester catalyst of claim 1, characterized in that said-O (CH 2 ) x The OH group is derived from an alkyl diol having 2 to 16 carbon atoms, preferably from at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, decylene glycol, undecylene glycol, dodecylene glycol, tetradecylene glycol and hexadecylene glycol; said-O (CH) 2 ) x (OH) 2 The group is derived from an alkyl triol having 3 to 16 carbon atoms, preferably from at least one of glycerol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, dodecyl triol and hexadecyl triol.
4. A process for producing a furan-based polyester catalyst which is used for producing the furan-based polyester catalyst having the structural ligand represented by the formula (i) as claimed in any one of claims 1 to 3, characterized by comprising:
dissolving 5-carboxyl-2-furancarboxylic acid ester and sodium or potassium alkaline compound to obtain alkali metal salt solution of 5-methyl carboxyl-2-furancarboxylic acid ester, and performing metal ion displacement reaction with M metal compound to obtain L-M n+ The coordination structure is adopted to obtain the furan polyester catalyst with the ligand L structure as formula (I);
wherein n is an integer of 2 to 5;
5. the method according to claim 4, wherein the solvent of the alkali metal salt solution comprises at least one of water or a protic organic solvent;
and/or the solvent for the metal ion displacement reaction comprises a protic organic solvent comprising 0 to 20wt% of water;
preferably, the protic organic solvent comprises one or more of methanol, ethanol, propanol, n-butanol, isoamyl alcohol, ethylene glycol and glycerol;
preferably, the concentration of the ligand L in the alkali metal salt solution is 0.01 to 2.5mol/L.
6. The method of manufacturing according to claim 5, wherein:
When M metal ions are selected from divalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 4:1-1:1, the reaction temperature of the metal ion replacement reaction is 4-70 ℃, and the reaction time is 0.1-6 h;
when M metal ions are selected from trivalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 5:1-2:1, the reaction temperature of the metal ion replacement reaction is 10-75 ℃, and the reaction time is 0.1-8 h;
when M metal ions are selected from tetravalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 6:1-3:1, the reaction temperature of the metal ion replacement reaction is 15-80 ℃, and the reaction time is 0.1-10 h;
when M metal ions are selected from pentavalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 7:1-4:1, the reaction temperature of the metal ion replacement reaction is 20-90 ℃, and the reaction time is 0.1-12 h.
7. A process for preparing a furan-based polyester catalyst having a ligand of the structure of formula (ii) and/or formula (iii) as claimed in any one of claims 1 to 3, characterized by comprising:
Dissolving 2, 5-furan dicarboxylic acid and alkali compound of sodium or potassium to obtain alkali metal salt solution of 2, 5-furan dicarboxylic acid, and performing metal ion replacement reaction with M metal compound to obtain L-M n+ Coordination structure and precipitation to obtain furan polyester catalyst with ligand L structure shown as formula (II) and/or formula (III)
Wherein n is an integer of 2 to 5;
8. the method of manufacturing according to claim 7, wherein: the solvent of the alkali metal salt solution is at least one of water or a proton organic solvent;
and/or the solvent of the metal ion replacement reaction is a protonic organic solvent containing 0-20wt% of water;
preferably, the protic organic solvent comprises one or more of methanol, ethanol, propanol, n-butanol, isoamyl alcohol, ethylene glycol and glycerol;
preferably, the concentration of the ligand L in the alkali metal salt solution is 0.01-2.5 mol/L;
preferably, when the M metal ion is selected from divalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 3:1-1:2, the reaction temperature of the metal ion replacement reaction is 10-70 ℃, and the reaction time is 0.1-6 h;
When M metal ions are selected from trivalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 4:1-1:1, the reaction temperature of the metal ion replacement reaction is 15-75 ℃, and the reaction time is 0.1-8 h;
when M metal ions are selected from tetravalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 5:1-2:1, the reaction temperature of the metal ion replacement reaction is 20-80 ℃, and the reaction time is 0.1-20 h;
when M metal ions are selected from pentavalent ions, the molar ratio of the alkali metal salt of the 5-carboxyl-2-furancarboxylic acid ester to the M metal compound is 6:1-3:1, the reaction temperature of the metal ion replacement reaction is 25-90 ℃, and the reaction time is 0.1-24 h.
9. A process for producing a furan-based polyester catalyst which is used for producing a furan-based polyester catalyst having the structural ligand represented by the formula (i) and the formula (ii) or the formula (i) and the formula (iii) or the formula (i), the formula (ii) and the formula (iii) according to any one of claims 1 to 3, characterized by comprising:
dissolving 5-carboxyl-2-furancarboxylate and 2, 5-furandicarboxylic acid in alkaline compound of sodium or potassium to obtain alkali metal salt solution of 5-carboxyl-2-furancarboxylate and 2, 5-furandicarboxylic acid, and performing metal ion displacement reaction with M metal compound to obtain L-M n+ The ligand L structure is obtained by precipitation, and the furan polyester catalyst shown in the formula (I) and the formula (II) or the formula (I) and the formula (III) or the formula (I), the formula (II) and the formula (III) is obtained;
wherein n is an integer of 2 to 5;
10. the method of manufacturing according to claim 9, wherein:
the molar ratio of the 5-carboxyl-2-furancarboxylic acid ester to the 2, 5-furandicarboxylic acid is 6:1-1:2;
the solvent of the alkali metal salt solution is at least one of water or a proton organic solvent;
and/or the solvent for the metal ion displacement reaction comprises a protic organic solvent comprising 0 to 20wt% of water;
preferably, the protic organic solvent comprises one or more of methanol, ethanol, propanol, n-butanol, isoamyl alcohol, ethylene glycol and glycerol;
preferably, the concentration of the ligand L in the alkali metal salt solution is 0.01-2.5 mol/L;
preferably, when the M metal ion is selected from divalent ions, the molar ratio of the alkali metal salts of the 5-carboxyl-2-furancarboxylic acid ester and the 2, 5-furandicarboxylic acid to the M metal compound is 3:1-1:2, the reaction temperature of the metal ion replacement reaction is 10-70 ℃, and the reaction time is 0.1-6 h;
when M metal ions are selected from trivalent ions, the molar ratio of the alkali metal salts of the 5-carboxyl-2-furancarboxylic acid ester and the 2, 5-furandicarboxylic acid to the M metal compound is 4:1-1:1, the reaction temperature of the metal ion replacement reaction is 15-75 ℃, and the reaction time is 0.1-8 h;
When M metal ions are selected from tetravalent ions, the molar ratio of the alkali metal salts of the 5-carboxyl-2-furancarboxylic acid ester and the 2, 5-furandicarboxylic acid to the M metal compound is 5:1-2:1, the reaction temperature is 20-80 ℃, and the reaction time is 0.1-20 h;
when M metal ions are selected from pentavalent ions, the molar ratio of the alkali metal salts of the 5-carboxyl-2-furancarboxylic acid ester and the 2, 5-furandicarboxylic acid to the M metal compound is 6:1-3:1, the reaction temperature of the metal ion replacement reaction is 25-90 ℃, and the reaction time is 0.1-24 h.
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