CN111234189B - Preparation method of furan ring-containing polyester - Google Patents
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- CN111234189B CN111234189B CN202010116815.1A CN202010116815A CN111234189B CN 111234189 B CN111234189 B CN 111234189B CN 202010116815 A CN202010116815 A CN 202010116815A CN 111234189 B CN111234189 B CN 111234189B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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Abstract
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of furan ring-containing polyester. The polyester containing furan ring is synthesized by polymerizing mono-furan or di-furan compound and aliphatic chain compound under the catalysis of pyridine halogen salt. The catalyst used in the synthesis method is green and nontoxic, the obtained polymer has no metal residue, and the synthesis method is simple, rapid, economic, more extensive in applicability and more suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of furan ring-containing polyester.
Background
Since the first polymer emerged in 1970, the polymer materials have been widely used in the fields of transportation, construction, agriculture, medicine, etc. due to their superior properties and high cost performance comparable to those of conventional materials such as metal and wood, and easy preparation.
With the development of science and technology, high molecular materials are distributed in daily life of people, wherein polyvinyl chloride, polystyrene and the like are difficult to degrade in nature and cause great pollution to the environment, and polyesters such as polylactic acid, poly aliphatic lactone, polycarbonate and the like are biodegradable and bioabsorbable high molecular materials and are widely applied to the biological and medical industries. The synthetic polymers with raw materials derived from biomass resources are collectively called as bio-based polymers, and include bio-based polymers directly synthesized by microorganisms with biomass as raw materials, such as Polyhydroxyalkanoates (PHAs), and bio-based polymers prepared by synthesizing bio-based monomers by biological or chemical conversion with biomass as raw materials and then performing polymerization reaction, such as polylactic acid (PLA) and poly (1, 3-trimethylene terephthalate) (PTT). The polymerized monomer is generally derived from fossil raw materials, consumes a large amount of petroleum resources and causes environmental pollution. With the concept of sustainable development, the conversion and utilization of biomass raw materials have become a new research hotspot.
Most polyester products in the market have a benzene ring structure, and the added benzene ring structure can have certain rigidity and can increase the glass transition temperature, so that the polyester has a wider application range. However, substrates for preparing corresponding polyester such as terephthalic acid, bisphenol A and p-phenylene diphenol substrates are all from petrochemicals at present, and with energy exhaustion and reduction of petrochemicals, the polyester materials prepared by using furan-type diacid, diol and diamine as substrates gradually replace the traditional polyester materials. Because the furan polyester has aromaticity and has some characteristics similar to benzene rings, the product performance is similar to that of the traditional polyester, the furan polyester is easy to be accepted by the market, and the furan polyester has wide application prospect.
2, 5-Furanedicarboxylic acid (FDCA) is a classical bio-based aromatic monomer and can be prepared from biomass such as starch and cellulose through hydrolysis, dehydration, oxidation and other reactions. FDCA has similar structure and physical properties to petroleum-based monomer terephthalic acid (TPA), can be used for synthesizing high-performance polyester and epoxy resin, is determined by the U.S. department of energy as one of the 12 most potential bio-based platform compounds, and is also considered as "sleeping giant".
The traditional methods for preparing FDCA mainly comprise a solution polycondensation method, a melt-solid phase polycondensation method and a ring-opening polymerization method, wherein the melt polycondensation method has the most industrialized value and the most challenging property, and needs to be studied deeply to solve the bottleneck problem of promoting the molecular weight growth and inhibiting the occurrence of side reactions.
Disclosure of Invention
The invention provides a pyridine halogen acid salt as a catalyst, which is used for preparing a polyester polymer compound based on a furan ring-containing compound, and aims to solve the problems of complex process, complex synthesis, metal residue, multiple side reactions and the like in the prior art.
The specific technical scheme of the invention is as follows:
a preparation method of furan ring-containing polyester comprises the following steps of polymerizing a mono-furan type polymerized monomer shown as a formula II or a di-furan type polymerized monomer shown as a formula VI with an aliphatic chain type polymerized monomer shown as a formula III under the catalysis of pyridine hydrohalide shown as a formula I to obtain a polyester product:
x is selected from halogen;
R1、R2、R3are respectively selected from hydrogen, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, N, N-dimethylamino group, and the same or different substituents in substituted or unsubstituted N-pyrrolidyl; the aforementioned alkyl group includes a saturated or unsaturated alkyl group.
R4Selected from carboxyl, acyl chloride, ester group, hydroxyl or alkyl substituted by hydroxyl; the above-mentioned ester group is-COOR, and R generally means a non-hydrogen group such as an alkyl group.
R5Selected from carboxyl, acyl chloride, ester group, hydroxyl or alkyl substituted by hydroxyl;
R6is a hydroxyl group corresponding to formula II or formula IV, an alkyl group substituted by the hydroxyl group, an acyl chloride group, a carboxyl group or an ester group;
R7and R8The same or different substituents selected from hydrogen, alkyl with 1-6 carbon atoms, furyl, phenyl, substituted phenyl and cycloalkyl; the alkyl group having 1 to 6 carbon atoms includes a straight-chain alkyl group (e.g., n-propyl group) and a branched-chain alkyl group (e.g., isopropyl group), and the cycloalkyl group is preferably cyclopentane or cyclohexane.
n is an integer of 2 to 15.
Preferably, X is selected from chlorine, bromine and iodine;
R1、R2、R3the same or different substituents are respectively selected from hydrogen, alkyl with 1-3 carbon atoms, alkoxy with 1-3 carbon atoms, N, N-dimethylamino and unsubstituted N-pyrrolidyl;
R4selected from the group consisting of formyl, formyl chloride, and methyl formate;
R5selected from the group consisting of formyl, formyl chloride, methyl formate, ethyl formate, hydroxymethyl;
R6is a hydroxyl, acid chloride, formate or formate group corresponding to formula II or formula IV;
R7and R8The same or different substituents selected from hydrogen, saturated alkyl with 1-3 carbon atoms, 2-furyl, phenyl, cyclopentyl and cyclohexyl;
n is an integer of 2 to 12.
Preferably, the structure of the pyridine hydrohalide shown in the formula I is selected from the following structures:
preferably, the aliphatic chain-type polymerized monomer represented by formula III is selected from the following structures:
preferably, the mono-furan type polymeric monomer of formula II is selected from the following structures:
(ii) a The bis-furan type polymeric monomer of formula IV is selected from the following structures:
preferably, the pyridine hydrohalide shown in the formula I accounts for 0.1-10% of the total mass of the two feeding materials.
Preferably, the molar ratio of the carboxyl, acid chloride or ester group-containing polymerized monomer to the hydroxyl group-containing alkyl group-containing polymerized monomer is 1: 1.1 to 2. Preferably, the polymerization reaction is carried out under an inert gas atmosphere, such as nitrogen.
Preferably, the specific preparation method comprises the following steps:
(1) prepolymerization reaction: reacting the raw material with a pyridine halogen acid salt catalyst shown as a formula I at the temperature of 120-180 ℃;
(2) post polymerization reaction: reacting the product obtained in the step (1) at the temperature of 200-250 ℃.
Preferably, the reaction time of the prepolymerization reaction is 1.5-3 h; the reaction time of the post-polymerization reaction is 2-5 h.
Has the advantages that:
by adopting the technical scheme of the invention, the method has at least one of the following advantages:
1) the catalyst used in the synthesis method is green and nontoxic, and the obtained polymer has no metal residue;
2) the synthetic method is simple and economical;
3) the scheme can accelerate the prepolymerization reaction speed, promote the forward progress of the polycondensation reaction in the prepolymerization stage, and make up for the problem of reverse reaction interference caused by small molecules in the process;
4) the applicability is wider;
5) is more suitable for large-scale production;
6) the yield of the product is high.
Drawings
FIG. 1 is a DSC representation spectrum of a product obtained by polycondensation of furandicarboxylic acid and ethylene glycol
FIG. 2 is a TGA characterization spectrum of a product obtained by polycondensation of furandicarboxylic acid and ethylene glycol
FIG. 3 is a DMAP & HCl nuclear magnetic hydrogen spectrum diagram
FIG. 4 is a DMAP & HCl nuclear magnetic carbon spectrum.
Detailed Description
In order to facilitate understanding for those skilled in the art, the concept of the present invention will be further described with reference to the following examples. The following specific description of the embodiments is not to be construed as limiting the invention, but merely as a prelude to the more detailed description that is presented for the understanding of the principles of the invention. The raw materials referred to in the specification are purchased from the market or obtained by simple synthesis, and the information of the used chemicals and instrument types is shown in the following table:
TABLE 1 reagent sources and purities
TABLE 2 instruments and apparatus
The catalysts used in the following examples were obtained by simple synthesis, for example, FIG. 3 is a diagram of the nuclear magnetic hydrogen spectrum of DMAP & HCl obtained by synthesis; FIG. 4 shows the nuclear magnetic carbon spectrum of DMAP & HCl obtained by synthesis.
Example 1
Changing N2 in a three-neck flask for three times, slowly heating, continuously stirring, adding 7ml and 10ml (1: 1) of 90ml and 88ml under the condition of filling nitrogen, adding 3 of 2.5g (1% wt), then sealing a reaction system, heating to 180 ℃, reacting for 1.5h, circulating nitrogen into the reaction system to evaporate small molecules along with the nitrogen, sealing the system after evaporating the small molecules, raising the temperature to 230 ℃, continuing to react for 3h, exhausting for 0.5h under the vacuum degree of 0.5mbar, stopping heating and stirring, cooling to room temperature by introducing nitrogen, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying after vacuum drying to obtain 216g of white furan polyester solid with the yield of 88.0%.
Example 2
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 8ml and 166ml of 11 (1: 1.2) in a nitrogen-filled state, adding 1.4g (0.5 wt%) of 5, then sealing a reaction system, heating to 170 ℃, reacting for 1.5h, circulating nitrogen into the reaction system to evaporate small molecules along with the nitrogen, sealing the system again after evaporating the small molecules, raising the temperature to 250 ℃, continuing to react for 2h, exhausting for 0.5h under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying after vacuum drying to obtain 235g of light yellow furan polyester solid, wherein the yield is 82.1%.
Example 3
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 133ml of 9 and 262ml of 12 (1: 1.5) in a nitrogen-filled state, adding 0.4g (0.1% wt) of 6, then closing a reaction system, heating to 180 ℃, reacting for 2 hours, evaporating small molecules, sealing the system again, then raising the temperature to 240 ℃, continuing to react for 2.5 hours, exhausting for 0.5 hour in a vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum, and obtaining 357g of light yellow furan polyester solid with the yield of 84.3%.
Example 4
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 133ml of 9 and 117ml of 10 (1: 1) in a nitrogen-filled state, adding 8.6g (3% wt) of 1, then sealing a reaction system, heating to 120 ℃, reacting for 3 hours, evaporating small molecules, sealing the system again, then raising the temperature to 200 ℃, continuing to react for 5 hours, pumping for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the surface small molecules and oligomer residues with ethanol, drying after vacuum drying to obtain 266g of light yellow furan polyester solid, wherein the yield is 93.0%. (thermodynamic characterization of the product is shown in FIGS. 1 and 2)
Example 5
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 8ml and 92ml of 14 (1: 1) under the condition of filling nitrogen, adding 1.3g (5% wt) of 2, then sealing a reaction system, heating to 130 ℃, reacting for 3 hours, evaporating small molecules, sealing the system again, then raising the temperature to 210 ℃, continuing to react for 4.5 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying after vacuum drying to obtain 223g of light yellow furan polyester solid, wherein the yield is 86.5%.
Example 6
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 200ml of 9 and 164ml of 15 (1.5: 1) in a nitrogen-filled state, adding 36g (8% wt) of 3, then sealing a reaction system, heating to 140 ℃, reacting for 2.5 hours, evaporating small molecules, sealing the system again, then heating up to 220 ℃, continuing to react for 4 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying under vacuum to obtain 400g of light yellow furan polyester solid, wherein the yield is 88.9%.
Example 7
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 8ml and 16 ml (1.2: 1) of 120ml and 238ml under the condition of nitrogen filling, adding 3g (10% wt), then closing a reaction system, heating to 150 ℃, reacting for 2 hours, evaporating small molecules, sealing the system again, then raising the temperature to 230 ℃, continuing to react for 2.5 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying under vacuum to obtain 300g of yellow furan polyester solid, wherein the yield is 84.7%.
Example 8
Changing N2 in a three-neck flask for three times, slowly heating, continuously stirring, adding 190ml of 21 and 88ml of 13 (1: 1) in a nitrogen-filled state, adding 3.7g (1% wt) of 3, then sealing a reaction system, heating to 180 ℃, reacting for 2 hours, evaporating small molecules, then heating, sealing the system again, then continuing to react for 2.5 hours, exhausting air for 0.5 hour under the vacuum degree mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum, and obtaining 333g of milky furan polyester solid with the yield of 89.0%.
Example 9
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 175ml of 18 and 89ml of 14 (1: 1) under the condition of filling nitrogen, adding 2.6g (1% wt) of 6, then sealing a reaction system, heating to 150 ℃, reacting for 2 hours, evaporating small molecules, sealing the system again, then raising the temperature to 250 ℃, continuing to react for 3 hours, pumping for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing away the small molecules and oligomer residues on the surface by using ethanol, drying under vacuum, drying to obtain 198g of light yellow furan polyester solid, wherein the yield is 85.0%.
Example 10
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 195ml of 23 and 167ml of 11 (1: 1.2) in a nitrogen-filled state, adding 3.5g (1% wt) of 3, then closing a reaction system, heating to 180 ℃, reacting for 2 hours, evaporating small molecules, sealing the system again, then heating to 200 ℃, continuing to react for 5 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum, and obtaining 395g of light yellow furan polyester solid, wherein the yield is 87.8%.
Example 11
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 200ml of 22 and 140ml of 13 (1: 1.2) in a nitrogen-filled state, adding 21g (5% wt) of 5, then sealing a reaction system, heating to 170 ℃, reacting for 2 hours, evaporating small molecules, sealing the system again, then heating to 240 ℃, continuing to react for 3 hours, pumping for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing out the surface small molecules and oligomer residues by using ethanol, drying after vacuum drying to obtain 377g of white furan polyester solid, wherein the yield is 89.3%.
Example 12
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 25 ml and 10ml (1: 1.2) of 210ml and 110ml under the condition of nitrogen filling, adding 6 of 4.2g (1% wt), then closing a reaction system, heating to 130 ℃, reacting for 2.5 hours, evaporating small molecules, sealing the system again, then raising the temperature to 210 ℃, continuing to react for 4.5 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying under vacuum, and drying to obtain 391g of light yellow furan polyester solid, wherein the yield is 83.2%.
Example 13
Changing N2 in a three-neck flask for three times, slowly heating, continuously stirring, adding 195ml of 26 and 238ml of 11 (1: 1) in a nitrogen-filled state, adding 16g (3% wt) of 5, then closing a reaction system, heating to 150 ℃, reacting for 2.5 hours, evaporating small molecules, then heating, sealing the system again, then heating to 200 ℃, continuing to react for 5 hours, exhausting for 0.5 hour in a vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the surface small molecules and oligomer residues by using ethanol, drying after vacuum drying to obtain 413g of light yellow furan polyester solid, wherein the yield is 84.1%.
Example 14
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 27 ml of 200ml and 12 ml of 175ml (1: 1.5) in a nitrogen-filled state, adding 3.5g (1% wt) of 6, then closing a reaction system, heating to 120 ℃, reacting for 3 hours, evaporating small molecules, sealing the system again, then heating up to 210 ℃, continuing to react for 5 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum to obtain 411g of white furan polyester solid, wherein the yield is 86.9%.
Example 15
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 200ml of 28 and 174ml of 12 (1: 1) under the condition of filling nitrogen, adding 2.5g (0.5% wt) of 3, then closing a reaction system, heating to 180 ℃, reacting for 2 hours, evaporating small molecules, sealing the system again, then raising the temperature to 220 ℃, continuing to react for 4 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying under vacuum to obtain 428g of light yellow furan polyester solid, wherein the yield is 89.5%.
Example 16
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 190ml of 19 and 174ml of 13 (1: 1) in a nitrogen-filled state, adding 2.5g (0.5% wt) of 3, then sealing a reaction system, heating to 180 ℃, reacting for 3 hours, evaporating small molecules, sealing the system again, then heating to 210 ℃, continuing to react for 3 hours, exhausting for 0.5 hour in a vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum, and obtaining 423g of light yellow furan polyester solid with the yield of 87.6%.
Example 17
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 20ml of 200ml and 15 ml of 174ml (1: 1.1) in a nitrogen-filled state, adding 3.5g (1% wt) of 3, then closing a reaction system, heating to 180 ℃, reacting for 2.5 hours, evaporating small molecules, sealing the system again, then raising the temperature to 230 ℃, continuing to react for 4.5 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum, and obtaining 411g of light yellow furan polyester solid with the yield of 86.7%.
Example 18
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 200ml of 29 and 160ml of 13 (1.2: 1) in a nitrogen-filled state, adding 2.5g (0.5 wt%) of 3, then closing a reaction system, heating to 180 ℃, reacting for 3 hours, evaporating small molecules, sealing the system again, then raising the temperature to 240 ℃, continuing to react for 4 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum, and obtaining 401g of light yellow furan polyester solid with the yield of 83.3%.
Example 19
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 188ml of 30 and 188ml of 11 (1: 1.1) in a nitrogen-filled state, adding 5g (1% wt) of 3, then sealing a reaction system, heating to 180 ℃, reacting for 2.5 hours, evaporating small molecules, sealing the system again, then heating to 220 ℃, continuing to react for 4.5 hours, exhausting for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing off the small molecules and oligomer residues on the surface by using ethanol, drying in vacuum, and obtaining 395g of light yellow furan polyester solid, wherein the yield is 83.2%.
Example 20
Changing N2 in a three-neck flask for three times, slowly heating up, continuously stirring, adding 31 ml of 31 and 190ml of 10 (1: 1) under the condition of filling nitrogen, adding 3 of 25g (5 percent wt), then sealing a reaction system, heating to 180 ℃, reacting for 2 hours, evaporating small molecules, sealing the system again, then raising the temperature to 210 ℃, continuing to react for 5 hours, exhausting air for 0.5 hour under the vacuum degree of 0.5mbar, stopping heating and stirring, ventilating and cooling to room temperature, taking out a product, washing away the small molecules and oligomer residues on the surface by using ethanol, drying under vacuum to obtain 400g of light yellow furan polyester solid, wherein the yield is 80.1%.
Claims (10)
1. A preparation method of furan ring-containing polyester is characterized in that a mono-furan type polymerized monomer shown in formula II or a di-furan type polymerized monomer shown in formula IV and an aliphatic chain type polymerized monomer shown in formula III are polymerized under the catalysis of pyridine halogen acid salt shown in formula I to obtain a polyester product:
x is selected from halogen;
R1、R2、R3the same or different substituents are respectively selected from hydrogen, alkyl with 1-3 carbon atoms, alkoxy with 1-3 carbon atoms, N-dimethylamino and unsubstituted N-pyrrolidyl;
R4selected from carboxyl, acyl chloride, ester group, hydroxyl or alkyl substituted by hydroxyl;
R5selected from carboxyl, acyl chloride, ester group, hydroxyl or alkyl substituted by hydroxyl;
R6is a hydroxyl group corresponding to formula II or formula IV, an alkyl group substituted by the hydroxyl group, an acyl chloride group, a carboxyl group or an ester group;
R7and R8The same or different substituents selected from hydrogen, alkyl with 1-6 carbon atoms, furyl, phenyl, substituted phenyl and cycloalkyl;
n is an integer of 2 to 15.
2. The process according to claim 1, wherein X is selected from the group consisting of chlorine, bromine, and iodine;
R4selected from the group consisting of formyl, formyl chloride, and methyl formate;
R5selected from the group consisting of formyl, formyl chloride, methyl formate, ethyl formate, hydroxymethyl;
R6is hydroxyl, acyl chloride or formic acid radical corresponding to formula II or formula IVOr a methyl formate group;
R7and R8The same or different substituents selected from hydrogen, saturated alkyl with 1-3 carbon atoms, 2-furyl, phenyl, cyclopentyl and cyclohexyl;
n is an integer of 2 to 12.
3. The method according to claim 1, wherein the pyridine hydrohalide of formula I has a structure selected from the group consisting of:
4. the method according to claim 1, wherein the aliphatic chain type polymerized monomer represented by formula III is selected from the following structures:
5. the method according to claim 1, wherein the mono-furan type polymeric monomer represented by formula II is selected from the following structures:
the bis-furan type polymeric monomer of formula IV is selected from the following structures:
6. the method according to claim 1, wherein the pyridine hydrohalide represented by the formula I accounts for 0.1-10% of the total mass of the two feeds.
7. The method according to claim 1, wherein the molar ratio of the carboxyl group-, acid chloride group-or ester group-containing polymerizable monomer to the hydroxyl group-containing polymerizable monomer is 1: 1.1 to 2.
8. The method according to claim 1, wherein the polymerization is carried out under an inert gas atmosphere.
9. The preparation method according to claim 1, wherein the specific preparation method comprises the following steps:
(1) prepolymerization reaction: reacting the raw material with a pyridine halogen acid salt catalyst shown as a formula I at the temperature of 120-180 ℃;
(2) post polymerization reaction: reacting the product obtained in the step (1) at the temperature of 200-250 ℃.
10. The preparation method according to claim 9, wherein the reaction time of the prepolymerization reaction is 1.5-3 h; the reaction time of the post-polymerization reaction is 2-5 h.
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