CN108299356A - A kind of preparation method of furan dicarboxylic acid compound - Google Patents
A kind of preparation method of furan dicarboxylic acid compound Download PDFInfo
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- CN108299356A CN108299356A CN201710021928.1A CN201710021928A CN108299356A CN 108299356 A CN108299356 A CN 108299356A CN 201710021928 A CN201710021928 A CN 201710021928A CN 108299356 A CN108299356 A CN 108299356A
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- 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
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- Polyesters Or Polycarbonates (AREA)
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Abstract
This application provides a kind of preparation methods of furan dicarboxylic acid compound, and using furancarboxylic acid or its carboxylate as raw material, furan dicarboxylic acid compound is prepared by simply chemically reacting, and the furan compound of single functionality is made to realize bifunctionality.This method raw material sources are abundant, cheap and easy to get, preparation method is simple and efficient, flow is short, by-product is few, the furan dicarboxylic acid compound purity prepared using this method is high, can meet the raw material as polymer such as high-performance polyester, epoxy resin, polyamide, polyurethane and the requirement as industrial chemicals and medicine intermediate raw material.
Description
Technical field
The application belongs to the preparation of the polymer monomers such as high-performance polyester, epoxy resin, polyamide and polyurethane and chemical industry, doctor
The technical field of medicine intermediate, specifically, this application involves a kind of preparation methods of furandicarboxylic acid.
Background technology
Furan dicarboxylic acid (furandicarboxylic acid) compound, can because of the diformyl structure of furan nucleus and contraposition containing rigidity
It is directly used in the preparation of the high performance polymer such as polyester, epoxy resin, polyamide, polyurethane.It is prepared using furans diacid poly-
Close object intensity, modulus, creep resistant etc. have excellent mechanical property, while have higher glass transition temperature and
Heat distortion temperature.In addition, furan dicarboxylic acid compound itself can also be used as industrial chemicals and medicine intermediate uses.
Furandicarboxylic acid is mainly raw material by 5 hydroxymethyl furfural (HMF) at present, oxidation obtains, but raw material HMF is prepared and is stranded
Difficulty, it is of high cost, it is difficult to realize the shortcomings that heavy industrialization is applied.Even if HMF preparation process ameliorations, yield improves, but prepares
The starting material of HMF is fructose and glucose, is main raw-food material, if being used for large-scale industrial production, certainly will break food
Product supply chain balances.
In conclusion this field still lacks a kind of high efficiency, inexpensively difunctionality is prepared by biological-based chemicals
The method of the furan compound of degree.
Invention content
The object of the present invention is to provide a kind of high efficiency, inexpensively prepare bifunctionality by biological-based chemicals
The method of furan compound.
The first aspect of the present invention provides a kind of preparation method of furan dicarboxylic acid compound, includes the following steps：
(1) haptoreaction is carried out with halogenated hydrocarbons, fatty alcohol and catalyst with furancarboxylic acid or its carboxylate, it is mixed obtains the first reaction
Close object；
(2) cool down to first reaction mixture, be then evaporated under reduced pressure, obtain the second reaction mixing
Object；
(3) second reaction mixture is mixed with alkaline aqueous solution and is reacted, after the completion of reaction, adjust reaction
Mixture pH ＜ 3, point isolated solid, obtain furan dicarboxylic acid compound.
In another preferred example, the alkaline aqueous solution is the aqueous solution of substance selected from the group below：Alkali metal or alkaline earth
The oxide of metal, the hydroxide of alkali or alkaline earth metal, the carbonate of alkali or alkaline earth metal, ammonium hydroxide；Preferably,
The alkaline aqueous solution is the aqueous solution of substance selected from the group below：Sodium hydroxide, potassium hydroxide, hydrogen-oxygen lithium, rubidium hydroxide, hydrogen
Cesium oxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide, or combinations thereof.
In another preferred example, the adjusting pH is carried out using acidic materials selected from the group below：Inorganic acidic materials,
And/or organic acidic substances；Preferably, the acidic materials are selected from the group：Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, methanesulfonic acid, trifluoro
Change diethyl etherate, benzene methanesulfonic acid, or combinations thereof.
In another preferred example, in the reaction, the fatty alcohol and furancarboxylic acid or the molar ratio of its carboxylate
For 1-30:1, preferably 5-20:1, further preferably 6-15:1.
In another preferred example, when using furancarboxylic acid as reactant, fatty alcohol and furancarboxylic acid feeds intake in the reaction
Molar ratio is 1-30:1, preferably 5-20:1, further preferably 6-15:1.
In another preferred example, when using furancarboxylic acid carboxylate as reactant, fatty alcohol and furancarboxylic acid in the reaction
Molar ratio be 1-15:1, preferably 2-10:1, further preferably 3-8:1.
In another preferred example, the catalyst is the compound of metal selected from the group below：Fe、Co、Ni、Cu、Zn、Mg、
Cr, Zr, Al, V, or combinations thereof.
In another preferred example, the catalyst is the compound of metal selected from the group below：Fe, Co, Ni, Cr or its group
It closes.
In another preferred example, the catalyst is selected from the group：Iron chloride, ferric bromide, ferric iodide, diethyl iron, acetyl
Acetone iron, cobalt chloride, cobaltous bromide, cobaltous iodide, diethyl cobalt, acetylacetone cobalt, nickel chloride, nickelous bromide, nickel iodide, diethyl
Nickel, nickel acetylacetonate, or combinations thereof.
In another preferred example, in the step (1), the catalyst and the molar ratio of furancarboxylic acid or its carboxylate are
0.001~0.2:1.
In another preferred example, the halogenated hydrocarbons and the molar ratio of furancarboxylic acid or its carboxylate are 1~20:1, preferably
For 2-10:1.
In another preferred example, the catalyst and the molar ratio of furancarboxylic acid or its carboxylate are 0.005-0.1:1.
In another preferred example, the furancarboxylic acid or its carboxylate are selected from the group：Furancarboxylic acid, methylfuroate, ethyl furoate, chaff
The own ester of propyl propionate, butyl pyromucate, amyl furoate, furancarboxylic acid, furancarboxylic acid heptyl ester, furancarboxylic acid monooctyl ester, furancarboxylic acid nonyl ester, furancarboxylic acid last of the ten Heavenly stems ester or its group
It closes.
In another preferred example, the furancarboxylic acid or its carboxylate are selected from the group：Furancarboxylic acid, methylfuroate, ethyl furoate, chaff
The own ester of propyl propionate, butyl pyromucate, amyl furoate, furancarboxylic acid, or combinations thereof.
In another preferred example, the furancarboxylic acid or its carboxylate are selected from the group：Furancarboxylic acid, methylfuroate, ethyl furoate, chaff
Propyl propionate, or combinations thereof.
In another preferred example, the halogenated hydrocarbons is selected from the group：1- chloromethanes, dichloromethane, chloroform, four chlorinations
Carbon, dichloroethanes, tetrachloroethanes, 1- bromomethanes, methylene bromide, bromoform, carbon tetrabromide, Bromofume, tetrabromoethane,
Or combinations thereof.
In another preferred example, the halogenated hydrocarbons is selected from the group：1- chloromethanes, dichloromethane, chloroform, four chlorinations
Carbon, dichloroethanes, tetrachloroethanes, or combinations thereof.
In another preferred example, the fatty alcohol is selected from the group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutyl
Alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, or combinations thereof.
In another preferred example, the fatty alcohol is the linear chain or branched chain alcohol of C1-C10.
In another preferred example, the fatty alcohol is selected from the group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutyl
Alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol；It is more preferably selected from the following group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, or combinations thereof.
In another preferred example, the catalytic reaction temperature is 60-250 DEG C；Preferably 120-200 DEG C.
In another preferred example, the catalytic reaction kettle is acid resistance reaction kettle.
The second aspect of the present invention provides a kind of method preparing the polymer with furan structure unit, including step
Suddenly：
Furan dicarboxylic acid compound is prepared with method as described in the first aspect of the invention；With
The furan dicarboxylic acid compound is used to carry out polymerisation as monomer, to obtain the polymer.
In another preferred example, the polymerisation is homopolymerization or copolyreaction.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Specific implementation mode
The present inventor's in-depth study by long-term, it has unexpectedly been found that, use furfural as raw material, with halogenated hydrocarbons, catalysis
Agent and fatty alcohol react successively, furan dicarboxylic acid compound can be obtained with very high yield, and then for containing furan structure
In the preparation of unit polymer.Based on above-mentioned discovery, inventor completes the present invention.
The preparation of furan dicarboxylic acid compound
The present invention provides a kind of preparation method of furan dicarboxylic acid compound, the method is with furancarboxylic acid or its carboxylate
Raw material, a step high yield prepare furan dicarboxylic acid.It the described method comprises the following steps：
(1) haptoreaction is carried out with halogenated hydrocarbons, fatty alcohol and catalyst with furancarboxylic acid or its carboxylate, it is mixed obtains the first reaction
Close object；
(2) cool down to first reaction mixture, be then evaporated under reduced pressure, obtain the second reaction mixing
Object；
(3) second reaction mixture is mixed with alkaline aqueous solution and is reacted, after the completion of reaction, adjust reaction
Mixture pH ＜ 3, point isolated solid, obtain furan dicarboxylic acid compound.
In another preferred example, the alkaline aqueous solution is the aqueous solution of substance selected from the group below：Alkali metal or alkaline earth
The oxide of metal, the hydroxide of alkali or alkaline earth metal, the carbonate of alkali or alkaline earth metal, ammonium hydroxide；Preferably,
The alkaline aqueous solution is the aqueous solution of substance selected from the group below：Sodium hydroxide, potassium hydroxide, hydrogen-oxygen lithium, rubidium hydroxide, hydrogen
Cesium oxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide, or combinations thereof.
In another preferred example, the adjusting pH is carried out using acidic materials selected from the group below：Inorganic acidic materials,
And/or organic acidic substances；Preferably, the acidic materials are selected from the group：Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, methanesulfonic acid, trifluoro
Change diethyl etherate, benzene methanesulfonic acid, or combinations thereof.
In a preferred embodiment of the invention, the fatty alcohol and the molar ratio of furancarboxylic acid or its carboxylate are 1-
30:1, preferably 5-20:1, further preferably 6-15:1.Specific molar ratio can be true according to used raw material
Fixed, for example, when raw material is furancarboxylic acid carboxylate, the inventory of alcohol can be reduced suitably.
The method of the present invention carries out under the conditions of catalyst is added, it is preferable that the catalyst is metal selected from the group below
Compound：Fe, Co, Ni, Cu, Zn, Mg, Cr, Zr, Al, V, or combinations thereof；It is highly preferred that the catalyst is to be selected from the group
Metal compound：Fe, Co, Ni, Cr, or combinations thereof；For example, iron chloride, ferric bromide, ferric iodide, diethyl iron, levulinic
Ketone iron, cobalt chloride, cobaltous bromide, cobaltous iodide, diethyl cobalt, acetylacetone cobalt, nickel chloride, nickelous bromide, nickel iodide, diethyl nickel,
Nickel acetylacetonate, or combinations thereof.
The dosage of the catalyst is not particularly limited, can according to reaction system, the actual conditions of reaction unit and
It determines.Preferably, in the step (1), the catalyst and the molar ratio of furancarboxylic acid or its carboxylate are 0.001~0.2:
1。
In the present invention, the rate of charge of halogenated hydrocarbons and furancarboxylic acid or its carboxylate is not particularly limited, preferred at one
In embodiment, the halogenated hydrocarbons is 1~20 with the molar ratio of furancarboxylic acid or its carboxylate:1, preferably 2~10:1.
In another preferred example, the molar ratio of the catalyst and 2- substituted furan compounds be 0.005~
0.1:1。
Arbitrary furancarboxylic acid carboxylate may be used in the preparation method of the present invention, and the preferably furancarboxylic acid carboxylate is selected from down
Group：Methylfuroate, ethyl furoate, furancarboxylic acid propyl ester, butyl pyromucate, amyl furoate, the own ester of furancarboxylic acid, furancarboxylic acid heptyl ester, furancarboxylic acid monooctyl ester, chaff
Sour nonyl ester, furancarboxylic acid last of the ten Heavenly stems ester, or combinations thereof；More preferably it is selected from the group：Methylfuroate, ethyl furoate, furancarboxylic acid propyl ester, furancarboxylic acid fourth
The own ester of ester, amyl furoate, furancarboxylic acid, or combinations thereof.
The type of the substituted furan compound is not particularly limited, in the present invention, it is preferred to the substitution
Furan compound is selected from the group：The halogenated hydrocarbons is selected from the group：1- chloromethanes, dichloromethane, chloroform, carbon tetrachloride, two
Chloroethanes, tetrachloroethanes, 1- bromomethanes, methylene bromide, bromoform, carbon tetrabromide, Bromofume, tetrabromoethane or its
Combination.
In another preferred example, the halogenated hydrocarbons is selected from the group：1- chloromethanes, dichloromethane, chloroform, four chlorinations
Carbon, dichloroethanes, tetrachloroethanes, or combinations thereof.
The fatty alcohol is not particularly limited, and can be the straight chain alcohol of C1-C10.Preferably, fatty alcohol choosing
From the following group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol,
Or combinations thereof.
The haptoreaction can carry out under arbitrary suitable reaction condition, the condition can according to reaction system,
Situations such as reaction unit, specifically considers.For example, in a preferred embodiment, the catalytic reaction temperature is 60-
250℃；Preferably 120-200 DEG C.
In another preferred example, the catalytic reaction kettle is acid resistance reaction kettle.
One step of the advantages of this method directly prepares furandicarboxylic acid, and yield is up to 99%, it is most important that obtains
Product be mainly 2,5-furandicarboxylic acid, the purity of 2,5-furandicarboxylic acid in the product can reach 98%, it is entirely avoided
Furancarboxylic acid prepares 2,5-furandicarboxylic acid in carbonate high temperature at present, and disproportionated reaction occurs, contains 2,4- furans diformazans in product
Acid isomer is difficult to detach, cause to prepare the problem of 2,5-furandicarboxylic acid yield is low and poor selectivity.Prepared by the present invention
Furan dicarboxylic acid can meet as the raw material of the polymer such as high-performance polyester, epoxy resin, polyamide, polyurethane and as change
The requirement of work raw material and medicine intermediate raw material.
The advantageous effect that the application can generate includes at least：
(1) herein described method develops new route prepared by the compound of a furan dicarboxylic acid.With furancarboxylic acid or its
Carboxylate is raw material, and it is catalyst, the furans dicarboxyl for preparing high-purity of high yield that cheap iron, cobalt, nickel metallization, which close object,
Acid compound, to got through the furancarboxylic acid by raw material single functionality to bifunctionality furan dicarboxylic acid compound again to high-performance
The technology path of engineering material.
(2) due to raw material furancarboxylic acid or its carboxylate can with bio-based source, the application can drive biological based high molecular
The development of material industry reduces current high molecular material to being depended on unduly to petroleum resources, entire high molecular material is promoted to produce
The sustainable development of industry, and reduce pollution of the existing fossil resources to environment.(3) herein described method be simple and efficient, flow
It is short, by-product is few, product total recovery 70%-99%, be suitble to large-scale industrial production.
(4) the furan dicarboxylic acid compound purity that prepared by herein described method is high, can meet as high-performance polyester, ring
The raw material of the polymer such as oxygen resin, polyamide, polyurethane and requirement as industrial chemicals and medicine intermediate raw material.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.Implementing
Density is not specified in example, the reagent of the parameters such as concentration is commercially available pure reagent.
Embodiment 1
In 250ml reaction kettles, furancarboxylic acid 11.5g is dissolved in 15ml isopropanols and 30g carbon tetrachloride, chlorination is added
Cobalt 1mmol, 60 DEG C of back flow reaction 2h, cooling, vacuum distillation removal isopropanol and carbon tetrachloride, are added NaOH aqueous solutions, reflux
0.5h is down to room temperature, and pH value is adjusted with hydrochloric acid<1, solid is precipitated, obtains furandicarboxylic acid, yield 78%.Through1H-NMR
(400MHz, DMSO) test obtains, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ (13.60), liquid chromatography mass spectrometric combined instrument
(LC-MS) molecular weight 156.1 is measured, purity is more than 99.4%.
Embodiment 2
In 250ml reaction kettles, methylfuroate 14.0g is dissolved in 8ml ethyl alcohol and 60g tetrachloroethanes, iodate is added
Nickel 5mmol, 80 DEG C of back flow reaction 1h, cooling, vacuum distillation removal ethyl alcohol and tetrachloroethanes, are added KOH aqueous solutions, reflux
1.0h is down to room temperature, uses phosphoric acid regulating ph value<1, solid is precipitated, obtains furandicarboxylic acid, yield 89%.Through1H-NMR
(400MHz, DMSO) test obtains, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ (13.60), liquid chromatography mass spectrometric combined instrument
(LC-MS) molecular weight 156.1 is measured, purity is more than 99.1%.
Embodiment 3
In 250ml reaction kettles, furancarboxylic acid 11.5g is dissolved in 38ml methanol and 20g tetrabromoethanes, zinc iodide is added
5mmol, 70 DEG C of back flow reaction 10h, cooling, vacuum distillation removal methanol and tetrabromoethane, are added KOH aqueous solutions, and flow back 1.0h,
It is down to room temperature, pH value is adjusted with nitric acid<1, solid is precipitated, obtains furandicarboxylic acid, yield 99%.Through1H-NMR (400MHz,
DMSO) test obtains, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ (13.60), liquid chromatography mass spectrometric combined instrument (LC-MS)
Molecular weight 156.1 is measured, purity is more than 99.9%.
Embodiment 4
In 250ml reaction kettles, furancarboxylic acid 11.5g is dissolved in 60ml butanol and 30g tetraiodo ethane, diethyl is added
Iron 50mmol, 180 DEG C of back flow reaction 0.2h, cooling, vacuum distillation removal butanol and tetraiodo ethane, are added LiOH aqueous solutions, return
1.0h is flowed, room temperature is down to, uses phosphoric acid regulating ph value<1, solid is precipitated, obtains furandicarboxylic acid, yield 94%.Through1H-NMR
(400MHz, DMSO) test obtains, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ (13.60), liquid chromatography mass spectrometric combined instrument
(LC-MS) molecular weight 156.1 is measured, purity is more than 99.0%.
Embodiment 5 (comparative example)
In 250ml reaction kettles, furancarboxylic acid 11.5g is dissolved in 10ml butanol and 60g tetraiodo ethane, diethyl is added
Iron 50mmol, 140 DEG C of back flow reaction 0.5h, cooling, vacuum distillation removal butanol and tetraiodo ethane, are added LiOH aqueous solutions, return
1.0h is flowed, room temperature is down to, uses phosphoric acid regulating ph value<1, solid is precipitated, obtains furandicarboxylic acid, yield 71%.Through1H-NMR
(400MHz, DMSO) test obtains, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ (13.60), liquid chromatography mass spectrometric combined instrument
(LC-MS) molecular weight 156.1 is measured, purity is more than 98.5%.
In the preparation method of the application, the inventory by reducing alcohol avoids product from being esterified, but when alcohol inventory is too low,
Being easy to cause the yield of product reduces.Therefore, the inventory of alcohol should control in reasonable range.
Embodiment 6
In 250ml reaction kettles, butyl pyromucate 17.1g is dissolved in 30ml propyl alcohol alcohol and 60g chloroforms, diethyl is added
Base iron 80mmol, 130 DEG C of back flow reaction 5h, cooling, vacuum distillation removal butanol and tetraiodo ethane, are added NaOH aqueous solutions, return
1.0h is flowed, room temperature is down to, uses phosphoric acid regulating ph value<1, solid is precipitated, obtains furandicarboxylic acid, yield 94%.Through1H-NMR
(400MHz, DMSO) test obtains, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ (13.60), liquid chromatography mass spectrometric combined instrument
(LC-MS) molecular weight 156.1 is measured, purity is more than 99.5%.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of preparation method of furan dicarboxylic acid compound, which is characterized in that include the following steps：
(1) haptoreaction is carried out with halogenated hydrocarbons, fatty alcohol and catalyst with furancarboxylic acid or its carboxylate, obtains the first reaction mixing
Object；
(2) cool down to first reaction mixture, be then evaporated under reduced pressure, obtain the second reaction mixture；
(3) second reaction mixture is mixed with alkaline aqueous solution and is reacted, after the completion of reaction, adjust reaction mixing
Object pH ＜ 3, point isolated solid, obtain furan dicarboxylic acid compound.
2. the method as described in claim 1, which is characterized in that in the reaction, the fatty alcohol and furancarboxylic acid or its ester
The molar ratio of compound is 1-30:1, preferably 5-20:1, further preferably 6-15:1.
3. the method as described in claim 1, which is characterized in that the catalyst is the compound of metal selected from the group below：Fe、
Co, Ni, Cu, Zn, Mg, Cr, Zr, Al, V, or combinations thereof.
4. the method as described in claim 1, which is characterized in that the catalyst is the compound of metal selected from the group below：Fe、
Co, Ni, Cr, or combinations thereof.
5. the method as described in claim 1, which is characterized in that in the step (1), the catalyst and furancarboxylic acid or its
The molar ratio of carboxylate is 0.001~0.2:1.
6. the method as described in claim 1, which is characterized in that the halogenated hydrocarbons and furancarboxylic acid or its carboxylate feed intake mole
Than being 1~20:1, preferably 2-10:1.
7. the method as described in claim 1, which is characterized in that the furancarboxylic acid or its carboxylate are selected from the group：Furancarboxylic acid, furancarboxylic acid
Methyl esters, ethyl furoate, furancarboxylic acid propyl ester, butyl pyromucate, amyl furoate, the own ester of furancarboxylic acid, furancarboxylic acid heptyl ester, furancarboxylic acid monooctyl ester, furancarboxylic acid nonyl ester,
Furancarboxylic acid last of the ten Heavenly stems ester, or combinations thereof.
8. the method as described in claim 1, which is characterized in that the halogenated hydrocarbons is selected from the group：1- chloromethanes, dichloromethane
Alkane, chloroform, carbon tetrachloride, dichloroethanes, tetrachloroethanes, 1- bromomethanes, methylene bromide, bromoform, carbon tetrabromide, dibromo
Ethane, tetrabromoethane, or combinations thereof.
9. the method as described in claim 1, which is characterized in that the fatty alcohol is selected from the group：It is methanol, ethyl alcohol, propyl alcohol, different
Propyl alcohol, butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, or combinations thereof.
10. a kind of method preparing the polymer with furan structure unit, which is characterized in that including step：
Furan dicarboxylic acid compound is prepared with the method as described in claim 1-9 is any；With
The furan dicarboxylic acid compound is used to carry out polymerisation as monomer, to obtain the polymer.
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