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CN108341925A - High molecular compound for preparing polyester or polyamide based on difuran diol or difuran diacid and application - Google Patents

High molecular compound for preparing polyester or polyamide based on difuran diol or difuran diacid and application Download PDF

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Publication number
CN108341925A
CN108341925A CN201810366861.XA CN201810366861A CN108341925A CN 108341925 A CN108341925 A CN 108341925A CN 201810366861 A CN201810366861 A CN 201810366861A CN 108341925 A CN108341925 A CN 108341925A
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substrate
reaction
mmol
catalyst
diol
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Inventor
朱晨杰
沈涛
应汉杰
李明
唐成伦
陈勇
吴菁岚
牛欢青
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Nanjing Tech University
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/226—General preparatory processes using carbonyl halides and alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a high molecular compound for preparing polyester or polyamide based on difuran diol or difuran diacid, which is prepared by polymerizing diol furan monomers, diacid furan monomers and corresponding substrates. The invention also discloses application of the macromolecular compound in preparing plastic products. Compared with the prior art, the invention firstly provides a structure and a method for preparing the polymer of the dual-furan type polymer based on the catalytic conversion of biomass resources, and the polymer of the dual-furan type polymer mainly comprises products such as dual-furan type polyester, epoxy resin, polycarbonate, polyamide and the like.

Description

High molecular compound for preparing polyester or polyamide based on difuran diol or difuran diacid and application
Technical Field
The invention belongs to the field of bio-based high polymer materials, and particularly relates to a high polymer compound for preparing polyester or polyamide based on difuran diol or difuran diacid.
Background
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. A representative class of monomers is bisphenol A (BPA). Bisphenol a is used industrially to synthesize materials such as Polycarbonate (PC) and epoxy resin. Have been used for the 60 s for the manufacture of plastic bottles, drinking cups for infants, inner coatings for food and beverage cans. Bisphenol a is contained in mineral water bottles, medical instruments, and the interiors of food packages. However, materials made from bisphenol a degrade during use to produce toxic substances, which have a wide range of undesirable effects on living organisms: including affecting the endocrine, reproductive and nervous systems, promoting cancer, etc. With the development of industrialization, the wide application of plastic products and epoxy resins increases the demand for BPA, which leads to the increase of the discharge amount of BPA pollutants in the environment and causes serious environmental pollution.
Diphenolic acid (DPA) is a recyclable polymer monomer, can completely replace bisphenol A, and is used for preparing high polymer materials such as epoxy resin, polycarbonate and the like. The diphenolic acid is mainly used for producing various synthetic resins (epoxy resin, polycarbonate, water-soluble resin and hyperbranched polyester), water-soluble grease resin, electrophoretic paint, bright ink resin, coating, spice, lubricant, adhesive and the like. But the raw material levulinic acid for preparing the diphenolic acid is too expensive, the cost of completely replacing the market is too high, and the furan type bisphenol A monomer has rigidity similar to that of a benzene ring and has similar properties, so that the furan type bisphenol A monomer has great market prospect for preparing polyester and the like by replacing bisphenol A.
In addition, most of polyester and polyamide products in the current market have a benzene ring structure, and the added benzene ring structure can have certain rigidity and improve the glass transition temperature, so that the application range is wider. However, substrates for preparing corresponding polyester and polyamide such as terephthalic acid, bisphenol A and p-phenylenediamine are all from petrochemical products at present, along with energy depletion and reduction of petrochemical products, bio-based material substitute products gradually replace traditional polyester and polyamide materials, and furan type diacid, diol and diamine substrates have the characteristics similar to benzene rings, so that the prepared product has the performance similar to that of the traditional polyester and polyamide, is easy to accept by the market and has wide application prospect.
The furyl platform compound is a platform chemical derived from biomass resources, wherein the furfural is a representative furyl platform compound which is industrially produced at present. A polymerization monomer with a dual-furan ring and a dual-active group can be obtained through a series of catalytic conversion based on furfural, mainly comprises a structure of dual-furan diol, dual-furan diacid and the like, and the polymerization monomer can effectively replace a polymerization monomer extracted from traditional petrochemical resources, such as polymerization material monomers of bisphenol A, terephthalic acid and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high molecular compound for preparing polyester or polyamide based on difuranic diol or difuranic diacid and application thereof, so as to solve the problems of high cost, complex synthesis and the like in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a high molecular compound for preparing polyester or polyamide based on difuran diol or difuran diacid is polymerized by a compound I and a substrate;
wherein,
X1and X2At the same time, hydroxymethyl or carboxyl;
R1and R2Is any one or combination of more of hydrogen, methyl, ethyl, hydroxymethyl, carboxypropyl, furyl, benzene ring and cyclopentane;
the substrate is diacid substrate, diol substrate, carbonate substrate, diamine substrate, phosgene, epichlorohydrin or aromatic phenols.
Wherein, when X1And X2When the substrate is hydroxymethyl, the substrate is epichlorohydrin, phosgene, carbonate substrate or diacid substrate; wherein the carbonate substrate is diethyl carbonate or diphenyl carbonate, and the diacid substrate is succinic acid, adipic acid, pimelic acid, terephthalic acid or furandicarboxylic acid.
In this case, the polymer compound is a difuran-type polyester having a structural formula shown in formula II:
further, the structural formula of a preferred polymer compound is as follows:
when the substrate is epichlorohydrin, the dosage ratio of the compound I, the epichlorohydrin, the catalyst and the solvent in the polymerization reaction is 10 mmol: 20-50 mmol: 2-3 mmol: 60mL, the catalyst is sodium hydroxide or potassium hydroxide, and the solvent is prepared from water and tetrahydrofuran in a ratio of 1: 20-30, the reaction temperature is 70-100 ℃, and the reaction time is 1-4 h; and after the reaction is finished, removing the solvent to obtain the epoxy resin.
When the substrate is phosgene, the ratio of the compound I, the phosgene and the solvent is 10 mmol: 10-15 mmol: 40mL, solvent from pyridine and chloroform in a ratio of 1: 1-2, the reaction temperature is 20-80 ℃, and the reaction time is 1-4 h; after the reaction is finished, adding the obtained organic phase into methanol or water for crystallization to obtain the product.
When the substrate is carbonate, the ratio of the compound I, the carbonate and the catalyst is 10 mmol: 10-15 mmol: 1mmol, diphenyl phosphate, butyl titanate and other catalysts, no solvent is used in the reaction, the reaction temperature is 200-260 ℃, and the reaction time is 2-6 h; in the reaction process, vacuumizing every 1h to remove generated impurities such as water and the like, and cooling to normal temperature after the reaction is finished to obtain the solid carbonate.
When the substrate is diacid substrate, the dosage ratio of the compound I, the diacid substrate and the catalyst in the polymerization reaction is 10 mmol: 10-15 mmol: 2-3 mmol, the catalyst is butyl titanate or antimony oxide, the reaction temperature is 200-280 ℃, and the reaction time is 4-10 hours; in the reaction process, vacuumizing every 2h to remove generated impurities such as water and the like, and cooling to normal temperature after the reaction is finished to obtain solid polyester;
wherein, X1And X2When the carboxyl is adopted, the substrate is a diol substrate, an aromatic phenol substrate or a diamine substrate; wherein the diol substrate is ethylene glycol, propylene glycol, butanediol or pentanediol, the aromatic phenol is hydroquinone or resorcinol, and the diamine substrate is ethylenediamine, pentanediamine, decamethylenediamine or p-phenylenediamine.
In this case, the polymer compound is a difuran-type polyester or difuran-type polyamide, and the structural formula is shown in formula III:
further, the structural formula of a preferred polymer compound is as follows:
when the substrate is a diol substrate, the molar ratio of the compound I, the diol substrate and the catalyst is 10: 10-15: 1-3, taking diphenylphosphoric acid (DPPA), antimony oxide or butyl titanate as a catalyst, carrying out reaction at the temperature of 200-280 ℃ for 4-8 h, vacuumizing every 1h in the reaction process to remove generated impurities such as water and the like, and cooling to normal temperature after the reaction is finished to obtain the novel furan-type polyester.
When the substrate is aromatic phenol, the molar ratio of the compound I, the aromatic phenol substrate and the catalyst is 10: 10-15: 1-3, taking diphenylphosphoric acid (DPPA), antimony oxide or butyl titanate as a catalyst, carrying out reaction at the temperature of 200-280 ℃ for 6-8 h, vacuumizing every 1h in the reaction process to remove generated impurities such as water and the like, and cooling to normal temperature after the reaction is finished to obtain the novel furan-type polyester.
When the substrate is a diamine substrate, the molar ratio of the compound I, the diamine substrate and the catalyst in the polymerization reaction is 10: 10-15: 1-3, using diphenyl phosphoric acid (DPPA), antimony oxide or butyl titanate as a catalyst, wherein the reaction temperature is 200-280 ℃, and the reaction time is 6-10 hours; in the reaction process, vacuumizing every 1h to remove impurities such as generated water and the like, and cooling to normal temperature after the reaction is finished to obtain the novel furan type polyamide.
Wherein, X1And X2At the same time, carboxyl group, diol substrate, aromatic phenol substrateOr in the case of diamine substrates, after the compound I reacts with solid phosgene to prepare acyl chloride, the acyl chloride is polymerized with the substrates;
wherein,
the reaction conditions for preparing acyl chloride by reacting the compound I with solid phosgene are as follows: the dosage ratio of the compound I, the solid phosgene powder and the solvent is 1 mmol: 1-2 mmol: 10mL, solvent from toluene and DMF in a ratio of 1:5, the reaction temperature is 0-5 ℃ (ice bath), and the reaction time is 0.5-1 h; after the reaction is finished, removing the solvent to obtain acyl chloride;
the reaction conditions for the polymerization of the acid chloride and the substrate are as follows: the dosage ratio of acyl chloride, substrate, acid-binding agent and solvent is 1 mmol: 1-1.2 mol: 2-2.5 mmol: 5-8 mL, wherein the reaction solvent is anhydrous N-methylpyrrolidone or anhydrous dimethylacetamide, the reaction acid-binding agent is anhydrous pyridine or anhydrous triethylamine, the reaction temperature is 50-60 ℃, and the reaction time is 12-20 hours; and after the reaction is finished, adding water (the volume ratio of the solvent to the water is 1: 10-20) into the obtained mixed system, separating out solids, and filtering and drying in vacuum to obtain the catalyst.
The application of the macromolecular compound in the preparation of plastic products is also within the protection scope of the invention.
The difuran type polyester can be used for preparing products such as films, plastic plasticizers, cross-linking agents and plastics, and the difuran type polyamide can be used for preparing engineering plastics and applied to the fields of machinery, automobiles, electric appliances, textile equipment, chemical equipment, aviation, metallurgy and the like.
Has the advantages that:
compared with the prior art, the invention has the following advantages:
the scheme firstly provides a structure and a method for preparing a dual-furan type polymer based on catalytic conversion of biomass resources, and the structure and the method mainly comprise products such as dual-furan type polyester, epoxy resin, polycarbonate, polyamide and the like.
The scheme provides a method for preparing a difuran polymer, which comprises a traditional esterification polymerization method, an acyl chloride polymerization method and an ester exchange polymerization method.
Drawings
FIG. 1 is a schematic diagram of the preparation of polyester, epoxy resin from diol furan-type monomers using acetone as a carbonyl substrate in examples 1, 2 and 4;
FIG. 2 is a schematic diagram of the preparation of polyester and polyamide from the diacid furan-type monomer with acetone as the carbonyl substrate in examples 3, 5 and 6;
FIG. 3 shows the hydrogen spectrum of the polymerization of diol furan-type monomers with acetone as carbonyl substrate and terephthalic acid in example 4: 1H NMR (400MHz, CDCl3) δ 6.29(d, J ═ 2.6Hz,2H),6.00-5.86(m,2H),5.15-4.91 (m,3H),2.64(s,4H),1.63(s, 6H).
Detailed Description
The following bis-furan diol and bis-furan diacid are polymerized, and the monomer is the bis-furan diol bis-furan diacid monomer when acetone is used as a carbonyl compound, and the structure is shown as follows:
example 1
Preparation of furan type epoxy resin from diol type bio-based furan type monomer: polymerizing the monomer a and epoxy chloropropane. And (2) putting a 10mmol, 20mmol of epoxy chloropropane and 40mL of tetrahydrofuran in a flask, stirring at 75 ℃ until the two raw materials are mutually mixed, dissolving 3mmol of sodium hydroxide serving as a catalyst in 5mL of water to prepare an alkali solution, dropwise adding the alkali solution into the solution, keeping the temperature of 75 ℃ for reaction for 2 hours, cooling to room temperature after the reaction is finished, adding ethyl acetate and water for extraction, combining organic phases, carrying out reduced pressure concentration to remove the solvent, and carrying out column chromatography on the remaining product, namely 3.12g of furan type epoxy resin, wherein the reaction conversion rate is 97%.
The furan type epoxy resin and the traditional bisphenol A type epoxy resin are blended according to the ratio of 1:5, and the extruded sample has the bending strength of 144MPa, the tensile strength of 70MPa and the impact strength of 24KJ/m2TGA has a glass transition temperature Tg of 124.3 ℃ at 370 ℃. The performance after blending is improved compared with that of the simple bisphenol A type resin, and the blended bisphenol A type resin can be used as a cross-linking agent, a plasticizer and other fields.
Example 2
Preparation of furan-type polycarbonate from diol bio-based furan-type monomer: the product a of example 1 is used as a polymerization monomer to carry out polymerization reaction with solid phosgene. And (2) putting 10mmol of a and 20mL of pyridine in a flask, stirring at room temperature until the two raw materials are mutually miscible, dissolving 12mmol of solid phosgene in 20mL of chloroform, dropwise adding into the reaction solution, reacting at 50 ℃ for 4 hours, cooling to room temperature after the reaction is finished, adding water and chloroform for extraction to remove pyridine, combining organic phases, concentrating, adding water, and separating out 2.66g of brown yellow solid product, namely furan type polycarbonate. The reaction conversion was 96%, the number average molecular weight was 10800, and the dispersity PDI was 1.21.
The polycarbonate was recast to determine a flexural strength of 106MPa, a tensile strength of 56MPa and an impact strength of 50KJ/m2TGA has a glass transition temperature Tg of 54.3 ℃ at 335 ℃. The properties can partially replace the application of the traditional polycarbonate in the plastic industry.
Example 3
Preparation of furan polyamide from diacid bio-based furan monomer: to polymerize the monomer b with pentamethylenediamine. And b 100mmol and 100mmol of pentamethylene diamine are taken to be put in a polymerization kettle, 10mmol of catalyst butyl titanate is added to the polymerization kettle to react for 2 hours at the temperature of 240 ℃, the reaction system is decompressed and dehydrated, and then the temperature is raised to 260 ℃ to react for 4 hours. After the reaction is finished, cooling, dissolving the viscous substance in chloroform, adding methanol or ethanol for crystallization to obtain 34g of furan polyamide, wherein the reaction conversion rate is 94%, the number average molecular weight is 23800, and the dispersity PDI is 1.13.
The above polyamide was recast and tested to have a flexural strength of 86MPa, a tensile strength of 56MPa and an impact strength (unnotched) of 256KJ/m2TGA has a glass transition temperature Tg of 98 ℃ at 320 ℃. The performance reaches the standard of type I nylon, and can be used for partially replacing the traditional polyamide material.
Example 4
Preparation of furan-type polyester from diol bio-based furan-type monomer: so that the polymerization monomer and the terephthalic acid have polymerization reaction. Taking 100mmol of alpha and 100mmol of terephthalic acid to a polymerization kettle, adding 10mmol of catalyst butyl titanate to the polymerization kettle, reacting for 2 hours at 240 ℃, decompressing and dewatering a reaction system, and then heating to 260 ℃ for reacting for 4 hours. After the reaction is finished, cooling, dissolving the viscous substance in chloroform, adding methanol or ethanol for crystallization to respectively obtain 39g of furan type polyester, wherein the reaction conversion rate is 96%; the number average molecular weight was 17400 and the dispersity PDI was 1.05.
The furan-type polyester was recast and tested to have a flexural strength of 56MPa, a tensile strength of 43MPa and an impact strength (unnotched) of 43KJ/m2TGA has a glass transition temperature Tg of 56 ℃ at 348 ℃. The above properties can be used to partially replace conventional polyamide materials.
Examples 5 to 6
Preparing furan type polyester by diacid bio-based furan type monomer: the polymerization reaction of the monomer b, glycol and hydroquinone is carried out. And b, taking 100mmol of ethylene glycol and 100mmol of hydroquinone, adding a catalyst of butyl titanate into a polymerization kettle, reacting for 2 hours at 240 ℃, decompressing and dewatering a reaction system, and heating to 260 ℃ for reaction for 4 hours. After the reaction is finished, cooling, dissolving the viscous substance in chloroform, adding methanol or ethanol for crystallization, and respectively obtaining 31g of furan type polyester and 36g of furan type polyester with the reaction conversion rate of 96% and the reaction conversion rate of 97%; number average molecular weight 23800, 32400 dispersity PDI 1.12, 1.21.

Claims (12)

1. A high molecular compound for preparing polyester or polyamide based on difuran diol or difuran diacid is characterized in that the high molecular compound is polymerized by a compound I and a substrate;
wherein,
X1and X2At the same time, hydroxymethyl or carboxyl;
R1and R2Is any one or combination of more of hydrogen, methyl, ethyl, hydroxymethyl, carboxypropyl, furyl, a benzene ring and cyclopentyl;
the substrate is diacid substrate, diol substrate, carbonate substrate, diamine substrate, phosgene, epichlorohydrin or aromatic phenols.
2. A polymer compound according to claim 1, wherein when X is X1And X2When the substrate is hydroxymethyl, the substrate is epichlorohydrin, phosgene, carbonate substrate or diacid substrate; wherein the carbonate substrate is diethyl carbonate or diphenyl carbonate, and the diacid substrate is succinic acid, adipic acid, pimelic acid, terephthalic acid or furandicarboxylic acid.
3. A polymer compound according to claim 2, wherein when the substrate is epichlorohydrin, the ratio of the amounts of the compound i, epichlorohydrin, catalyst and solvent used in the polymerization reaction is 10 mmol: 20-50 mmol: 2-3 mmol: 60mL, the catalyst is sodium hydroxide or potassium hydroxide, and the solvent is prepared from water and tetrahydrofuran in a ratio of 1: 20-30, the reaction temperature is 70-100 ℃, and the reaction time is 1-4 h; and after the reaction is finished, removing the solvent to obtain the epoxy resin.
4. A polymer compound according to claim 2, wherein when the substrate is phosgene, the ratio of the amount of the compound i, phosgene and solvent used in the polymerization reaction is 10 mmol: 10-15 mmol: 40mL, solvent from pyridine and chloroform in a ratio of 1: 1-2, the reaction temperature is 20-80 ℃, and the reaction time is 1-4 h; after the reaction is finished, adding the obtained organic phase into methanol or water for crystallization to obtain the product.
5. A polymer compound according to claim 2, wherein when the substrate is a carbonate, the ratio of the amount of the compound I, the carbonate and the catalyst used in the polymerization reaction is 10 mmol: 10-15 mmol: 1mmol, diphenyl phosphate or butyl titanate as catalyst, reaction temperature of 200-260 deg.c and reaction time of 2-6 hr; and in the reaction process, vacuumizing every 1h to remove impurities, and cooling to normal temperature after the reaction is finished.
6. A polymer compound according to claim 2, wherein when the substrate is a diacid substrate, the ratio of the amount of compound i, the diacid substrate and the catalyst used in the polymerization reaction is 10 mmol: 10-15 mmol: 2-3 mmol, the catalyst is butyl titanate or antimony oxide, the reaction temperature is 200-280 ℃, and the reaction time is 4-10 hours; and in the reaction process, vacuumizing every 1h to remove impurities, and cooling to normal temperature after the reaction is finished.
7. A polymer compound according to claim 1, wherein X is1And X2When the carboxyl is adopted, the substrate is a diol substrate, an aromatic phenol substrate or a diamine substrate; wherein the diol substrate is ethylene glycol, propylene glycol, butanediol or pentanediol, the aromatic phenol is hydroquinone or resorcinol, and the diamine substrate is ethylenediamine, pentanediamine, decamethylenediamine or p-phenylenediamine.
8. A polymer compound according to claim 7, wherein when the substrate is a diol substrate, the molar ratio of the compound I, the diol substrate and the catalyst in the polymerization reaction is 10: 10-15: 1-3, using diphenyl phosphoric acid, antimony oxide or butyl titanate as a catalyst, wherein the reaction temperature is 200-280 ℃, and the reaction time is 4-8 h; and in the reaction process, vacuumizing every 1h to remove impurities, and cooling to normal temperature after the reaction is finished.
9. A polymer compound according to claim 7, wherein when the substrate is an aromatic phenol, the molar ratio of the compound I, the aromatic phenol substrate and the catalyst in the polymerization reaction is 10: 10-15: 1-3, using diphenyl phosphoric acid, antimony oxide or butyl titanate as a catalyst, wherein the reaction temperature is 200-280 ℃, and the reaction time is 6-8 h; and in the reaction process, vacuumizing every 1h to remove impurities, and cooling to normal temperature after the reaction is finished.
10. A polymer compound according to claim 7, wherein when the substrate is a diamine substrate, the molar ratio of the compound I to the diamine substrate to the catalyst in the polymerization reaction is 10: 10-15: 1-3, the catalyst is diphenyl phosphoric acid, antimony oxide or butyl titanate, the reaction temperature is 200-280 ℃, and the reaction time is 6-10 hours; and in the reaction process, vacuumizing every 1h to remove impurities, and cooling to normal temperature after the reaction is finished.
11. A macromolecular compound according to claim 7, characterized in that compound I is polymerized with a substrate after reacting with solid phosgene to produce acyl chloride;
wherein,
the reaction conditions for preparing acyl chloride by reacting the compound I with solid phosgene are as follows: the dosage ratio of the compound I, the solid phosgene powder and the solvent is 1 mmol: 1-2 mmol: 10mL, solvent from toluene and DMF in a ratio of 1:5, the reaction temperature is 0-5 ℃, and the reaction time is 0.5-1 h; after the reaction is finished, removing the solvent to obtain acyl chloride;
the reaction conditions for the polymerization of the acid chloride and the substrate are as follows: the dosage ratio of acyl chloride, substrate, acid-binding agent and solvent is 1 mmol: 1-1.2 mol: 2-2.5 mmol: 5-8 mL, wherein the reaction solvent is anhydrous N-methylpyrrolidone or anhydrous dimethylacetamide, the reaction acid-binding agent is anhydrous pyridine or anhydrous triethylamine, the reaction temperature is 50-60 ℃, and the reaction time is 12-20 hours; and after the reaction is finished, adding water into the obtained mixed system, and separating out a solid to obtain the catalyst.
12. Use of the polymer compound according to claim 1 for producing a plastic product.
CN201810366861.XA 2018-04-23 2018-04-23 High molecular compound for preparing polyester or polyamide based on difuran diol or difuran diacid and application Pending CN108341925A (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN111196874A (en) * 2018-11-19 2020-05-26 万华化学集团股份有限公司 Polyester block copolycarbonate and preparation method thereof
CN111548480A (en) * 2019-12-08 2020-08-18 南京工业大学 Synthetic method of furan ring-containing polymer
WO2021016731A1 (en) * 2019-07-26 2021-02-04 擎天材料科技有限公司 Polyester resin and preparation method therefor, coating, and workpiece
CN112724392A (en) * 2020-08-26 2021-04-30 杭州师范大学 Preparation method of bio-based modified polypropylene carbonate and fiber
CN115703880A (en) * 2021-08-05 2023-02-17 中国科学院大连化学物理研究所 Polyester material containing difuranic ring diol group and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120220742A1 (en) * 2009-09-08 2012-08-30 Korea Institute Of Industrial Technology Furan-Based Curable Compound Derived from Biomass, Solvent-Free Curable Composition, and Method for Preparing Same
US9527952B1 (en) * 2014-02-17 2016-12-27 The University Of Toledo Amorphous polyester from bio-based bis-furan assembly
CN107001582A (en) * 2015-02-05 2017-08-01 积水化学工业株式会社 Ester type epoxy furane resins and its manufacture method, resin combination and resin cured matter

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120220742A1 (en) * 2009-09-08 2012-08-30 Korea Institute Of Industrial Technology Furan-Based Curable Compound Derived from Biomass, Solvent-Free Curable Composition, and Method for Preparing Same
US9527952B1 (en) * 2014-02-17 2016-12-27 The University Of Toledo Amorphous polyester from bio-based bis-furan assembly
CN107001582A (en) * 2015-02-05 2017-08-01 积水化学工业株式会社 Ester type epoxy furane resins and its manufacture method, resin combination and resin cured matter

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
S. GHARBI ET AL: ""Polyamides incorporating furan moieties. 1. Interfacial polycondensation of 2,2’-bis(5-chloroformyl-2-furyl)propane with 1,6-diaminohexane"", 《ACTA POLYMERICA》 *
WIDED KAMOUN ET AL.: ""Synthesis, characterization and ring-closing depolymerization of furanic polyesters"", 《E-POLYMERS》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111196874A (en) * 2018-11-19 2020-05-26 万华化学集团股份有限公司 Polyester block copolycarbonate and preparation method thereof
CN111196874B (en) * 2018-11-19 2022-04-22 万华化学集团股份有限公司 Polyester block copolycarbonate and preparation method thereof
WO2021016731A1 (en) * 2019-07-26 2021-02-04 擎天材料科技有限公司 Polyester resin and preparation method therefor, coating, and workpiece
CN111548480A (en) * 2019-12-08 2020-08-18 南京工业大学 Synthetic method of furan ring-containing polymer
CN111548480B (en) * 2019-12-08 2022-04-22 南京工业大学 Synthetic method of furan ring-containing polymer
CN112724392A (en) * 2020-08-26 2021-04-30 杭州师范大学 Preparation method of bio-based modified polypropylene carbonate and fiber
CN112724392B (en) * 2020-08-26 2022-05-27 杭州师范大学 Preparation method of bio-based modified polypropylene carbonate and fiber
CN115703880A (en) * 2021-08-05 2023-02-17 中国科学院大连化学物理研究所 Polyester material containing difuranic ring diol group and preparation method thereof

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