CN108623794A - A kind of preparation method of furans biological poly copolyether ester polymer, novel furan biological poly copolyether ester polymer - Google Patents

A kind of preparation method of furans biological poly copolyether ester polymer, novel furan biological poly copolyether ester polymer Download PDF

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CN108623794A
CN108623794A CN201810443257.2A CN201810443257A CN108623794A CN 108623794 A CN108623794 A CN 108623794A CN 201810443257 A CN201810443257 A CN 201810443257A CN 108623794 A CN108623794 A CN 108623794A
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glycol
esterification
ppegf
present
reaction
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CN108623794B (en
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周光远
王瑞
姜敏
王国强
张强
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Wuhu Wanlong New Material Co Ltd
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Changchun Institute of Applied Chemistry of CAS
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Priority to PCT/CN2019/085664 priority patent/WO2019214575A1/en
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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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

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

Abstract

The present invention provides a kind of preparation methods of polyetherester copolymer, include the following steps, under the conditions of protective atmosphere and metal complex catalysts; by 2; 5 furandicarboxylic acids and ethylene glycol after prepolymerization reaction and polycondensation reaction, obtain polyetherester copolymer after esterification.The present invention can be under the catalytic action of metal complex catalysts; using simple synthesizing mean; polycondensation reaction is directly carried out using FDCA and biological ethyl glycol, in lower temperature and shorter time, is efficiently prepared highly viscous with the full biological poly copolyether ester polymer of new structural furans; contain the oligomeric glycol segment that content is controllable in its molecule; reaction process is steady, easily controllable, mild condition; it is a kind of economic and environment-friendly, is suitble to the preparation method of scale industrial production.There is high-content glycol segment in furans biological poly copolyether ester polymer product structure provided by the invention, there is preferable thermodynamic property, and product color is preferable.

Description

A kind of preparation method of furans biological poly copolyether ester polymer, novel furan biology base Polyetherester copolymer
Technical field
The invention belongs to furyl polyether ester synthesis technical field, it is related to a kind of preparation method of polyetherester copolymer, poly- Copolyether ester polymer more particularly to a kind of preparation method of furans biological poly copolyether ester polymer, novel furan biological poly ether-ether Copolymer.
Background technology
2,5-furandicarboxylic acid (FDCA), chemical formula C6H4O5, structural formula isAs The important derivatives of furans, the biological based high molecular aromatic ring monomer with " rigidity " planar structure can be single with glycol, diamines etc. Body is polymerize, and the new bio based high molecular synthetic material haveing excellent performance is prepared, and is a kind of important industrial chemicals and organic Chemical intermediate.
Currently, as polyester product is widely applied, the high speed development of polyester raw material industry has been driven.Wherein, exploitation is used One of the hot spot of current polyester art research is had become in the biological poly ester monomer of substitution petroleum-based feedstock.Aromatic polyester, Polyethylene terephthalate (PET) has excellent heat resistance, chemical-resistant resistance as a kind of important thermoplastic polyester The advantages that property and the rate of recovery are high, is widely used for packaging field.Currently, the monoethylene glycol of the raw material of production PET can be with It is prepared using biomass material, successfully having been prepared as raw material using biological ethyl glycol such as the prior art can be complete The biology base PET beverage bottle of recycling.But another raw material terephthalic acid (TPA) (PTA) for producing PET is from petroleum base industry What the catalysis oxidation of raw material paraxylene (PX) was prepared, cause in obtained PET plastic product only containing 30% plant Object based component.Although the biology base polyester starting monomer succinic acid studied energetically in recent years has partial alternative petroleum base two The potential of acid, but since it cannot provide the rigidity as terephthalic acid (TPA) fragrant benzene ring structure, dramatically limit The performance of corresponding polyester product.Therefore, it is poly- that the polyester raw material binary acid with rigid ring structure how is obtained from biomass Ester raw material researches and develops an important development direction in field.
In recent years the study found that 2,5-furandicarboxylic acid (FDCA) as a kind of for substituting the ideal polyester of PTA Raw material researches and develops the important source material of full biology base polyester, not only has similar rigid aromatic ring structure, but also contain carbon number, virtue Fragrance is weaker than phenyl ring, it is easier to degrade, it is often more important that 2,5-furandicarboxylic acid is a kind of can be prepared by biomass Bio-based monomer.Thus, the corresponding polyester material of 2,5-furandicarboxylic acid, poly- 2,5 furandicarboxylic acid glycol esters (PEF) are more next The concern of scientific research personnel and Corporation R ＆ D department are received more.Such as CN102453242A, CN104072954A, WO2015137804 etc. reports the preparation method of the equal polyester of PEF and the thermodynamic property of corresponding macromolecule product.Currently, removing It prepares outside the equal polyester of PEF, is copolymerized with FDCA and ethylene glycol by introducing other monomers, and exploitation, expansion furans life A kind of important method of the type of object base polyester is mainly copolymerized by introducing other monomers with FDCA and ethylene glycol, Such as CN102432847 reports the copolyesters of FDCA, ethylene glycol and terephthalic acid monomers.
But the comonomer of these new introducings often has that cost is higher or abiotic base monomer, such as terephthaldehyde Acid, this allows for the attribute that full biology base polyester product loses 100% bio-based materials, and environment protection significance substantially reduces.
Therefore, a kind of novel full biology base furans biological poly ether-ether high molecular material how is obtained, is not only had There is the attribute of 100% bio-based materials, and can avoid due to the problems such as operation caused by monomer and fringe cost is added, Have become in field many forward-looking researchers widely one of focus of attention.
Invention content
In view of this, the technical problem to be solved in the present invention be to provide a kind of polyetherester copolymer preparation method and Polyetherester copolymer, especially a kind of preparation method with the full biological poly copolyether ester polymer of new structural furans, this hair The preparation process reaction process of bright offer is steady, easily controllable, is a kind of economic and environment-friendly, is suitble to the preparation of scale industrial production Method；And there is high-content glycol segment in the furans biological poly copolyether ester polymer product structure prepared, have preferable Thermodynamic property, and product color is preferable.
The present invention provides a kind of preparation methods of polyetherester copolymer, include the following steps：
1) under the conditions of protective atmosphere and metal complex catalysts, 2,5-furandicarboxylic acid and ethylene glycol are passed through into ester After changing reaction, after prepolymerization reaction and polycondensation reaction, polyetherester copolymer is obtained.
Preferably, in the polyetherester copolymer, the molal quantity of glycol segment accounts for the molal quantity of the polyetherester copolymer Degree be 30%~70%；
The general formula of the metal complex is LnX3；
The ligand of the metal complex includes trifluoromethanesulfonic acid base, five fluorine ethanesulfonic acid bases, seven fluorine isopropyl alkane sulfonic groups, nine It is one or more in fluorine butane sulfonic group and trifluoromethanesulfonimide base.
Preferably, the metallic element of the metal complex includes rare earth element, tin, bismuth, zinc, copper, alkali metal and alkaline earth It is one or more in metal；
The molar ratio of the 2,5- furandicarboxylic acids and ethylene glycol is 1:(2~8)；
The ratio that the molal quantity of the metal complex catalysts accounts for the molal quantity of the 2,5- furandicarboxylic acids is 0.5 ‰ ~4 ‰.
Preferably, the temperature of the esterification is at 170~210 DEG C；The time of the esterification is 1~4h；It is described The pressure of esterification is 1~3atm；
The prepolymerization reaction is Depressor response；The time of the prepolymerization reaction is 10~60min；The precondensation is anti- The temperature answered is 170~210 DEG C；
The pressure of the polycondensation reaction is 20~50Pa；The temperature of the polycondensation reaction is 180~250 DEG C；The polycondensation The time of reaction is 2~12h.
The present invention also provides a kind of polyetherester copolymers, have structure shown in formula (I)；
Wherein, n is 10~200；M is 0~200；
P is selected from one or more of 1,2,3 and 4.
Preferably, in the polyetherester copolymer, n/ (n+m) is 0.3~0.7；
The number-average molecular weight of the polyetherester copolymer is 20000~70000.
Preferably, the polyetherester copolymer after 2,5-furandicarboxylic acid and glycol monomer polymerization by obtaining；
The glycol monomer includes the mixture of glycol or glycol and ethylene glycol；
The glycol includes one or more in diethylene glycol (DEG), triethylene glycol, tetraethylene glycol and five glycol；
In the polyetherester copolymer, n/ (n+m) is less than or equal to 1.
Preferably, the polyetherester copolymer is prepared by following methods：
1`) under conditions of protective atmosphere and esterification catalyst, by 2,5-furandicarboxylic acid, ethylene glycol and through over-churning After reaction, after prepolymerization reaction, polycondensation reaction is carried out, metal complex catalysts are added in polycondensation process Afterwards, polyetherester copolymer is obtained.
Preferably, in the polyetherester copolymer, n/ (n+m) is 0.1~0.4；
The esterification catalyst includes stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, acetic acid Asia It is one or more in tin, stannous oxalate, stannous sulfate and stannous hydroxide；
The ratio that the molal quantity of the esterification catalyst accounts for the molal quantity of the 2,5- furandicarboxylic acids is 0.5 ‰~4 ‰.
Preferably, the temperature of the esterification is at 170~210 DEG C；The time of the esterification is 1~4h；It is described The pressure of esterification is 1~3atm；
The pressure of the prepolymerization reaction process be the esterification pressure to the polycondensation reaction pressure；
The time of the prepolymerization reaction is 10~60min；The temperature of the prepolymerization reaction is 170~210 DEG C；
The pressure of the polycondensation reaction is 20~50Pa；The temperature of the polycondensation reaction is 180~250 DEG C；The polycondensation The time of reaction is 2~12h；
The time that is added of the metal complex catalysts is between 0~3 hour of polycondensation reaction starting.
The present invention provides a kind of preparation methods of polyetherester copolymer, include the following steps, in protective atmosphere and gold Under metal complex catalysts conditions, by 2,5-furandicarboxylic acid and ethylene glycol after esterification, using prepolymerization reaction After polycondensation reaction, polyetherester copolymer is obtained.Compared with prior art, the present invention is directed to existing poly- 2,5 furandicarboxylic acids Glycol ester, especially copolyesters need to be copolymerized with FDCA and ethylene glycol by introducing other monomers, and these newly draw The comonomer entered often has that cost is higher or abiotic base monomer, and then allows for full biology base polyester product and lose The attributes of 100% bio-based materials, the defect that environment protection significance substantially reduces.
The invention provides a kind of preparation with the full biological poly copolyether ester polymer of new structural furans Method, the present invention under the catalytic action of metal complex catalysts, using the metallic catalyst containing strong electrophilic ligand compared with Under high-temperature can catalyst etherifying reaction the characteristics of, it is direct using FDCA and biology ethyl glycol using simple synthesizing mean Polycondensation reaction is carried out, at a lower temperature, in the shorter time, is efficiently prepared highly viscous with new structural furans Full biological poly copolyether ester polymer, containing the controllable oligomeric glycol segment of content in molecule, and reaction process is steady, is easy to Control, mild condition are a kind of economic and environment-friendly, are suitble to the preparation method of scale industrial production.Furans life provided by the invention There is high-content glycol segment in object base polyetherester copolymer product structure, there is preferable thermodynamic property, and product color It is damp preferable；The furyl polyetherester copolymer can also be copolymerized by common oligomeric glycol, FDCA and ethylene glycol simultaneously, Only oligomeric glycol (diethylene glycol (DEG), triethylene glycol etc.) is abiotic base monomer so that is carried out by oligomeric glycol and FDCA and ethylene glycol The prepared product of copolymerization loses the attribute of 100% bio-based materials.
Preparation method provided by the invention with the full biological poly copolyether ester polymer of new structural furans, can both obtain To a kind of novel full biology base high molecular material, and can solve to grasp caused by oligomeric glycol due to being added in preparation process The problems such as work and fringe cost.The new structural furans biological poly ether-ether product is pushed and is realized to the renewable money of furans The development and utilization in source and the preparation of environment amenable new bio base polyester, gradually break away from the dependence to petroleum resources, To solving the problems such as shortage of resources and environmental pollution that China's polymer industry faces, that realizes China's Polymer Material Industry can Sustainable development has important impetus and application value.
The experimental results showed that the glass transition temperature of new bio base polyether ester prepared by the present invention can be controlled 30 ~85 DEG C, 5% thermal degradation temperature is 280~400, and tensile strength is in 10MPa~85MPa, and elongation at break is 4%~400%.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the furyl polyether ester copolyesters provided prepared by the embodiment of the present invention 1.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still It should be appreciated that these descriptions are intended merely to the feature and advantage further illustrated the present invention, rather than to invention claim Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art It is prepared by conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or furyl polyethers The conventional purity of Lipase absobed technical field.
All noun expression of the present invention and noun expression and the abbreviation for referred to as belonging to this field routine, each noun expression It is explicit in its related application field with abbreviation, those skilled in the art express and referred to as according to the noun, energy It is enough clear accurately uniquely to be understood.
The present invention provides a kind of preparation methods of polyetherester copolymer, include the following steps：
1) under the conditions of protective atmosphere and metal complex catalysts, 2,5-furandicarboxylic acid and ethylene glycol are passed through into ester After changing reaction, after prepolymerization reaction and polycondensation reaction, polyetherester copolymer is obtained.
The structure of the polyetherester copolymer is not particularly limited in the present invention, with polyethers well known to those skilled in the art The structure of ester copolymer, those skilled in the art can according to practical condition, quality control and product requirement into Row selects and adjustment, and in polyetherester copolymer of the present invention, the molal quantity of glycol segment accounts for rubbing for the polyetherester copolymer Your degree of number is preferably 30%~70%, i.e. more preferably 35%~65%, more preferably 40%~60% are more excellent It is selected as 45%~55%.2,5- furandicarboxylic acids of the present invention preferably include biology base 2,5- furandicarboxylic acids.
The protective atmosphere is not particularly limited in the present invention, is with protective atmosphere well known to those skilled in the art Can, those skilled in the art can select and adjust, this hair according to practical condition, quality control and product requirement The bright protective atmosphere preferably includes nitrogen and/or inert gas, more preferably nitrogen or argon gas.
The specific choice of the metal complex catalysts is not particularly limited in the present invention, ripe with those skilled in the art The conventional metal complex catalysts known, those skilled in the art can according to practical condition, quality control with And product requirement is selected and is adjusted, the general formula of metal complex of the present invention can be LnX3.Metal of the present invention The ligand of composition catalyst preferably includes trifluoromethanesulfonic acid base, five fluorine ethanesulfonic acid bases, seven fluorine isopropyl alkane sulfonic groups, nine fluorine butane It is one or more in sulfonic group and trifluoromethanesulfonimide base, more preferably trifluoromethanesulfonic acid base, five fluorine ethanesulfonic acid bases, seven Fluorine isopropyl alkane sulfonic group, nine fluorine butane sulfonic groups or trifluoromethanesulfonimide base.The metal of metal complex of the present invention Element preferably includes one or more in rare earth element, tin, bismuth, zinc, copper, alkali and alkaline earth metal ions, more preferably rare earth Element, tin, bismuth, zinc, copper, alkali or alkaline earth metal.
The specific choice of the rare earth element is not particularly limited in the present invention, with well known to those skilled in the art common Rare earth element, those skilled in the art can select according to practical condition, quality control and product requirement It selects and adjusts, rare earth element of the present invention is preferably radiationless rare earth element, is specifically as follows lanthanum La, cerium Ce, praseodymium Pr, europium It is one or more in Eu, neodymium Nd, samarium Sm, gadolinium Ga, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, yttrium Y and scandium Sc.
The dosage of the metal complex catalysts is not particularly limited in the present invention, and those skilled in the art can basis Practical condition, quality control and product requirement are selected and are adjusted, metal complex catalysts of the present invention The ratio that molal quantity accounts for the molal quantity of the 2,5-furandicarboxylic acid is preferably 0.5 ‰~4 ‰, more preferably 1 ‰~3.5 ‰, More preferably 1.5 ‰~3 ‰, more preferably 2 ‰~2.5 ‰.
The dosage of the ethylene glycol is not particularly limited in the present invention, with well known to those skilled in the art for such anti- The conventional amount used answered, those skilled in the art can carry out according to practical condition, quality control and product requirement The molar ratio of selection and adjustment, 2,5-furandicarboxylic acid of the present invention and ethylene glycol is preferably 1:(2~8), more preferably 1: (3~7), more preferably 1:(4~6).
The condition of the esterification is not particularly limited in the present invention, with esterification well known to those skilled in the art The condition of reaction, those skilled in the art can select according to practical condition, quality control and product requirement It selects and adjusts, the temperature of esterification of the present invention is preferably 170~210 DEG C, more preferably 175~205 DEG C, more preferably 180~200 DEG C, more preferably 185~195 DEG C.The time of esterification of the present invention is preferably 1~4h, and more preferably 1.5 ~3.5h, more preferably 2~3h.The pressure of esterification of the present invention can be normal pressure or micro-positive pressure, it is particularly preferred as 1~ 3atm (atmospheric pressure can be 0.1MPa), more preferably 1.2~2.8atm, more preferably 1.5~2.5atm.
After the present invention carries out esterification, esterification products directly carry out prepolymerization reaction without separation.The present invention is to described The condition and step of prepolymerization reaction are not particularly limited, with the condition of conventional prepolymerization reaction well known to those skilled in the art With step, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the temperature of prepolymerization reaction of the present invention is preferably 170~210 DEG C, more preferably 175~205 DEG C, more preferably 180~200 DEG C, more preferably 185~195 DEG C.The time of prepolymerization reaction of the present invention is preferably 10~60min, more excellent It is selected as 20~50min, more preferably 30~40min.
Prepolymerization reaction of the present invention, preferably Depressor response, specific reactive mode can be vacuum distillation reaction, together When can also excessive dihydric alcohol in removing system.The pressure of prepolymerization reaction of the present invention is preferably a changing value, is become Change range and is specifically as follows the pressure of the esterification to the pressure of the polycondensation reaction.
The present invention finally carries out polycondensation reaction after above-mentioned prepolymerization reaction under the conditions of low vacuum.The present invention is to institute The condition and step for stating polycondensation reaction are not particularly limited, with conventional polycondensation well known to those skilled in the art reaction condition and Step, those skilled in the art can select and adjust according to practical condition, quality control and product requirement Whole, the pressure of polycondensation reaction of the present invention is preferably 20~50Pa, more preferably 25~45Pa, more preferably 30~40Pa. The temperature of the polycondensation reaction is preferably 180~250 DEG C, more preferably 190~240 DEG C, more preferably 200~230 DEG C, more excellent It is selected as 210~220 DEG C.The time of polycondensation reaction of the present invention is preferably 2~12h, more preferably 4~10h, and more preferably 6 ~8h.
The present invention is to be further ensured that the performance of final products, and complete and refinement preparation process, above-mentioned preparation method are specific Can be：
Using melt-polycondensation, 2,5-furandicarboxylic acid is made through over-churning, prepolymerization and to polymerize with dihydric alcohol (ethylene glycol) It is total in 30%~70% controllable full biological poly ether-ether of novel furan with etherificate structure proportion directly to prepare esterification for three step process Polymers.Under metal complex catalysts effect, 2,5-furandicarboxylic acid first generates 2,5- with biology base dihydric alcohol direct esterification Furandimethyl glycol ester；Then, esterification products continue with vacuum distillation and carry out preshrunk coalescence removing reactant without separation Excessive dihydric alcohol in system；Finally, polycondensation reaction is carried out under the conditions of low vacuum prepare high-molecular-weight poly ether-ether product.
The above-mentioned preparation process of the present invention specifically can be as shown in reaction equation (1)：
Above-mentioned steps of the present invention provide a kind of preparation method of the full biological poly copolyether ester polymer of novel furan, according to this Include mainly the poly- furandicarboxylic acid glycol ester unit in part in the structure segment of novel full biological poly ether-ether prepared by method (PEF) and part glycol ester segment, wherein glycol segment includes diethylene glycol (DEG) and triethylene glycol, can also also have part tetraethylene glycol and/ Or five glycol.It is 30%~70% that glycol segment in prepared polyethers ester structure, which accounts for polymer totality molar content, That is n/ (n+m) is 0.3~0.7, and n of the present invention is preferably 10~200, more preferably 30~180, more preferably 50~150, More preferably 80~120.M of the present invention is preferably 10~200, more preferably 30~180, more preferably 50~150, more excellent It is selected as 80~120.In the present invention, the m and n are both preferably molal quantity.
The present invention is polymerize using metal complex catalysts catalytic diol with furandicarboxylic acid direct esterification, in lower temperature Under degree, in the shorter time, highly viscous 100% novel biology base furans polyether ester is efficiently prepared, reaction process is steady, Easily controllable, product color is preferable, has high-content glycol segment in prepared product structure.And the present invention can also pass through Adjust the ingredient proportion and the esterification time in reaction process, temperature of dihydric alcohol and furandicarboxylic acid, polycondensation time, temperature Etc. conditions can effectively regulate and control the ratio of glycol segment in polyether ester product.Further, specifically preferred according to the invention dilute Earth metal complex catalyst, it is low or nontoxic so that prepared novel high polymer material is more in line with environmentally protective Theory is suitble to the preparation method of scale industrial production.
The present invention provides a kind of polyetherester copolymers, have structure shown in formula (I)；
Wherein, n is 10~200；M is 0~200；
P is selected from one or more of 1,2,3 and 4.
The present invention is preferably copolymerized selection, combination and the preferred scope in the polyetherester copolymer with aforementioned polyether ester It can be corresponded in selection, combination and preferred scope in the preparation method of object, this is no longer going to repeat them.
The present invention especially limits the polyetherester copolymer with structure shown in formula (I) without other, this field skill Art personnel it is understood that the polyetherester copolymer can be the structural formula, can not also be done containing the segment of the structure, the present invention Especially limitation.Polyetherester copolymer of the present invention with structure shown in formula (I), the core of structure is, is that one kind contains There is the copolymer of poly- 2,5-furandicarboxylic acid glycol ester and poly- furandicarboxylic acid and polyol esters combined polymerization, contain 2 in segment, 5- furandicarboxylic acid glycol ester segments also contain 2,5-furandicarboxylic acid multiethylene-glycol ester segment；Its abbreviation can be to be written as： PPEGF, title can be poly- (2,5-furandicarboxylic acid glycol ester-co-2,5- furandicarboxylic acid multiethylene-glycol ester)
In structure shown in formula (I) of the present invention, the part corresponding to n is 2,5-furandicarboxylic acid multiethylene-glycol ester segment, thus The range of choice of the n is not particularly limited, with normal ranges well known to those skilled in the art, people in the art Member can be selected and adjusted according to practical situations, quality control and product requirement, and n of the present invention is preferably 10 ~200, more preferably 30~180, more preferably 50~150, more preferably 80~120.In structure shown in formula (I) of the present invention, m Corresponding part is 2,5-furandicarboxylic acid binary alcohol esters segment, thus the range of choice of the m is not particularly limited, With normal ranges well known to those skilled in the art, those skilled in the art can be according to practical situations, quality control System and product requirement are selected and are adjusted, and m of the present invention is preferably 0~200, and more preferably 10~200, more preferably 30~180, more preferably 50~150, more preferably 80~120.In the present invention, the m and n are both preferably molal quantity.
In structure shown in formula (I) of the present invention, the part corresponding to p is specific first number of multiethylene-glycol, those skilled in the art It can be selected and adjusted according to practical situations, quality control and product requirement, multiethylene-glycol of the present invention can be with Include to be one or more in diethylene glycol (DEG), triethylene glycol, tetraethylene glycol and five glycol, i.e. p preferably be selected from one in 1,2,3 and 4 or It is multiple, more preferably 1,2,3 or 4, more preferably 1,1 and 2,1 and 2 and 3,1 and 2 and 3 and 4, alternatively, 1 and 2 and 3 and 4 and 5.
The specific ratio of the n and m is not particularly limited in the present invention, with conventional mole well known to those skilled in the art Than, those skilled in the art can select and adjust according to practical situations, quality control and product requirement, In polyetherester copolymer of the present invention, n/ (n+m) is preferably smaller than equal to 1, can be equal to 1, i.e. m is 0, might be less that and is equal to 0.8, it might be less that equal to 0.6, might be less that equal to 0.4, or be less than or equal to 0.2.Polyether ester copolymerization of the present invention In object, according to the difference of preparation method, n/ (n+m) can be 0.3~0.7, or 0.35~0.65, or 0.4 ~0.6, or 0.45~0.55.In polyetherester copolymer of the present invention, according to the difference of preparation method, n/ (n+m) Can be 0.1~0.4, or 0.15~0.35, or 0.2~0.3.
The other parameters of the polyetherester copolymer are not particularly limited in the present invention, with well known to those skilled in the art The conventional parameter of polyetherester copolymer, those skilled in the art can be according to practical situations, quality control and productions Product require to be selected and adjusted, and the number-average molecular weight of polyetherester copolymer of the present invention is preferably 20000~70000, more Preferably 30000~60000, more preferably 40000~50000.
The preparation method of the polyetherester copolymer is not particularly limited in the present invention, with well known to those skilled in the art The preparation method of this conventional analog copolymer, those skilled in the art can according to practical condition, quality control and Product requirement is selected and is adjusted, and polyetherester copolymer of the present invention is preferably polymerize by 2,5-furandicarboxylic acid and alcohol monomer After obtain.
The mixture of alcohol monomer of the present invention particularly including glycol or glycol and ethylene glycol.
The specific choice of the glycol is not particularly limited in the present invention, and those skilled in the art can be according to practical application Situation, quality control and product requirement are selected and are adjusted, glycol of the present invention preferably include diethylene glycol (DEG), triethylene glycol, It is one or more in tetraethylene glycol and five glycol, more preferably diethylene glycol (DEG), triethylene glycol, tetraethylene glycol or five glycol.
The concrete mode and step of the polymerization is not particularly limited in the present invention, with well known to those skilled in the art normal The polymerization of rule and mode, those skilled in the art can according to practical condition, quality control and product requirement into Row selection and adjustment.
The present invention is to further increase the controllability of polyetherester copolymer product, the full biological poly ether-ether copolymerization of exploitation furans Object, improves and refines preparation process, improves more complete technical solution for industrial applications, solely the present invention provides other two kinds The preparation method of vertical furyl polyetherester copolymer.
The present invention also provides the preparation methods of another polyetherester copolymer, include the following steps：
1`) under conditions of protective atmosphere and esterification catalyst, by 2,5-furandicarboxylic acid and ethylene glycol through over-churning After reaction, after prepolymerization reaction, polycondensation reaction is carried out, metal complex catalysts are added in polycondensation process Afterwards, polyetherester copolymer is obtained；
In the polyetherester copolymer, the molal quantity of glycol segment accounts for the percentage of the molal quantity of the polyetherester copolymer Content is 10%~40%.
Selection, combination and preferred model of the present invention to the polyetherester copolymer in the preparation method of the polyetherester copolymer It encloses, preferably can be corresponding with selection, combination and the preferred scope in aforementioned polyetherester copolymer, this is no longer going to repeat them.
The structure of the polyetherester copolymer is not particularly limited in the present invention, with polyethers well known to those skilled in the art The structure of ester copolymer, those skilled in the art can according to practical condition, quality control and product requirement into Row selects and adjustment, and in polyetherester copolymer of the present invention, the molal quantity of glycol segment accounts for rubbing for the polyetherester copolymer Your degree of number is preferably 10%~40%, more preferably 15%~35%, more preferably 20%~30%.The present invention The 2,5- furandicarboxylic acids preferably include biology base 2,5- furandicarboxylic acids.
The protective atmosphere is not particularly limited in the present invention, is with protective atmosphere well known to those skilled in the art Can, those skilled in the art can select and adjust, this hair according to practical condition, quality control and product requirement The bright protective atmosphere preferably includes nitrogen and/or inert gas, more preferably nitrogen or argon gas.
The esterification catalyst is not particularly limited in the present invention, and such chemical combination is used for well known to those skilled in the art The esterification catalyst of object routine, those skilled in the art can want according to practical condition, quality control and product It asks and is selected and adjusted, esterification catalyst of the present invention preferably includes stannous oxide, stannous octoate, stannous chloride, bromination It is one or more in stannous, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate and stannous hydroxide, more preferably oxygen Change stannous, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate or hydroxide Stannous.The dosage of the esterification catalyst is not particularly limited in the present invention, and those skilled in the art can be according to actual production Situation, quality control and product requirement are selected and are adjusted, and the molal quantity of esterification catalyst of the present invention accounts for described 2, The ratio of the molal quantity of 5- furandicarboxylic acids is preferably 0.5 ‰~4 ‰, more preferably 1 ‰~3.5 ‰, more preferably 1.5 ‰~ 3 ‰, more preferably 2 ‰~2 ‰.
The dosage of the ethylene glycol is not particularly limited in the present invention, with well known to those skilled in the art for such anti- The conventional amount used answered, those skilled in the art can carry out according to practical condition, quality control and product requirement The molar ratio of selection and adjustment, 2,5-furandicarboxylic acid of the present invention and ethylene glycol is preferably 1:(2~8), more preferably 1: (3~7), more preferably 1:(4~6).
The condition of the esterification is not particularly limited in the present invention, with esterification well known to those skilled in the art The condition of reaction, those skilled in the art can select according to practical condition, quality control and product requirement It selects and adjusts, the temperature of esterification of the present invention is preferably 170~210 DEG C, more preferably 175~205 DEG C, more preferably 180~200 DEG C, more preferably 185~195 DEG C.The time of esterification of the present invention is preferably 1~4h, and more preferably 1.5 ~3.5h, more preferably 2~3h.The pressure of esterification of the present invention can be normal pressure or micro-positive pressure, it is particularly preferred as 1~ 3atm (atmospheric pressure can be 0.1MPa), more preferably 1.2~2.8atm, more preferably 1.5~2.5atm.
After the present invention carries out esterification, esterification products directly carry out prepolymerization reaction without separation.The present invention is to described The condition and step of prepolymerization reaction are not particularly limited, with the condition of conventional prepolymerization reaction well known to those skilled in the art With step, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the temperature of prepolymerization reaction of the present invention is preferably 170~210 DEG C, more preferably 175~205 DEG C, more preferably 180~200 DEG C, more preferably 185~195 DEG C.The time of prepolymerization reaction of the present invention is preferably 10~60min, more excellent It is selected as 20~50min, more preferably 30~40min.
Prepolymerization reaction of the present invention, preferably Depressor response, specific reactive mode can be vacuum distillation reaction, together When can also excessive dihydric alcohol in removing system.The pressure of prepolymerization reaction of the present invention is preferably a changing value, is become Change range and is specifically as follows the pressure of the esterification to the pressure of the polycondensation reaction.
The present invention finally carries out polycondensation reaction after above-mentioned prepolymerization reaction under the conditions of low vacuum.The present invention is to institute The condition and step for stating polycondensation reaction are not particularly limited, with conventional polycondensation well known to those skilled in the art reaction condition and Step, those skilled in the art can select and adjust according to practical condition, quality control and product requirement Whole, the pressure of polycondensation reaction of the present invention is preferably 20~50Pa, more preferably 25~45Pa, more preferably 30~40Pa. The temperature of the polycondensation reaction is preferably 180~250 DEG C, more preferably 190~240 DEG C, more preferably 200~230 DEG C, more excellent It is selected as 210~220 DEG C.The time of polycondensation reaction of the present invention is preferably 2~12h, more preferably 4~10h, and more preferably 6 ~8h.
Metal complex catalysts are especially added in the present invention in polycondensation reaction, wherein can be contracting in the polycondensation reaction In poly- reaction beginning or polycondensation process.The specific time of the addition is not particularly limited in the present invention, art technology Personnel can select and adjust according to practical condition, quality control and product requirement, and metal of the present invention is matched The addition time of mixture catalyst is preferably between 0~3 hour when polycondensation reaction starts, i.e. 0~3 hour of polycondensation reaction, It may be 0.5~2.5 hour, or 1~2 hour.
The specific choice of the metal complex catalysts is not particularly limited in the present invention, ripe with those skilled in the art The conventional metal complex catalysts known, those skilled in the art can according to practical condition, quality control with And product requirement is selected and is adjusted, the general formula of metal complex of the present invention can be LnX3.Metal of the present invention The ligand of composition catalyst preferably includes trifluoromethanesulfonic acid base, five fluorine ethanesulfonic acid bases, seven fluorine isopropyl alkane sulfonic groups, nine fluorine butane It is one or more in sulfonic group and trifluoromethanesulfonimide base, more preferably trifluoromethanesulfonic acid base, five fluorine ethanesulfonic acid bases, seven Fluorine isopropyl alkane sulfonic group, nine fluorine butane sulfonic groups or trifluoromethanesulfonimide base.The metal of metal complex of the present invention Element preferably includes one or more in rare earth element, tin, bismuth, zinc, copper, alkali and alkaline earth metal ions, more preferably rare earth Element, tin, bismuth, zinc, copper, alkali or alkaline earth metal.
The specific choice of the rare earth element is not particularly limited in the present invention, with well known to those skilled in the art common Rare earth element, those skilled in the art can select according to practical condition, quality control and product requirement It selects and adjusts, rare earth element of the present invention is preferably radiationless rare earth element, is specifically as follows lanthanum La, cerium Ce, praseodymium Pr, europium It is one or more in Eu, neodymium Nd, samarium Sm, gadolinium Ga, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, yttrium Y and scandium Sc.
The dosage of the metal complex catalysts is not particularly limited in the present invention, and those skilled in the art can basis Practical condition, quality control and product requirement are selected and are adjusted, metal complex catalysts of the present invention The ratio that molal quantity accounts for the molal quantity of the 2,5-furandicarboxylic acid is preferably 0.5 ‰~4 ‰, more preferably 1 ‰~3.5 ‰, More preferably 1.5 ‰~3 ‰, more preferably 2 ‰~2 ‰.
The present invention is to be further ensured that the performance of final products, and complete and refinement preparation process, above-mentioned preparation method are specific Can be：
Using melt-polycondensation, 2,5-furandicarboxylic acid is made through over-churning, prepolymerization and to polymerize with dihydric alcohol (ethylene glycol) Three step process directly prepares controllable novel furan full biological poly ether-ether of the esterification with etherificate structure proportion 10%~40% Copolymer.Elder generation is under the action of conventional esterification catalyst (PEF esterification catalysts), 2,5-furandicarboxylic acid elder generation and biology base binary Alcohol direct esterification generates 2,5- furandimethyl glycol esters；Then, esterification products continue with vacuum distillation and carry out without separation Preshrunk coalescence removes excessive dihydric alcohol in reaction system；Then, catalyst LnX can be added in different time3, and Polycondensation reaction is carried out under the conditions of low vacuum prepares high-molecular-weight poly ether-ether product.
The above-mentioned preparation process of the present invention specifically can be as shown in reaction equation (2)：
Above-mentioned steps of the present invention provide a kind of preparation method of the full biological poly copolyether ester polymer of novel furan, according to this Include mainly the poly- furandicarboxylic acid glycol ester unit in part in the structure segment of novel full biological poly ether-ether prepared by method (PEF) and part glycol ester segment, wherein glycol segment includes diethylene glycol (DEG) and triethylene glycol, can also also have part tetraethylene glycol and/ Or five glycol.It is 10%~40% that glycol segment in prepared polyethers ester structure, which accounts for polymer totality molar content, That is n/ (n+m) is 0.1~0.4, and n of the present invention is preferably 10~200, more preferably 30~180, more preferably 50~150, More preferably 80~120.M of the present invention is preferably 10~200, more preferably 30~180, more preferably 50~150, more excellent It is selected as 80~120.In the present invention, the m and n are both preferably molal quantity.
The present invention is polymerize using metal complex catalysts catalytic diol with furandicarboxylic acid direct esterification, in lower temperature Under degree, in the shorter time, highly viscous 100% novel biology base furans polyether ester is efficiently prepared, reaction process is steady, Easily controllable, product color is preferable, the glycol segment with higher controllable content in prepared product structure.And it is of the invention It can also be by adjusting the esterification time in the ingredient proportion and reaction process of dihydric alcohol and furandicarboxylic acid, temperature, polycondensation The conditions such as time, temperature can effectively regulate and control the ratio of glycol segment in polyether ester product.Further, the present invention is special It is preferred that rare earth metal complex catalyst, low or nontoxic so that prepared novel high polymer material is more in line with green The theory that colour circle is protected is suitble to the preparation method of scale industrial production.
The present invention also provides a kind of preparation methods of usual polyetherester copolymer, include the following steps：
1``) under conditions of protective atmosphere and esterification catalyst, by 2,5-furandicarboxylic acid, alcohol monomer through over-churning After reaction, using prepolymerization reaction and polycondensation reaction, polyetherester copolymer is obtained.
Selection, combination and preferred model of the present invention to the polyetherester copolymer in the preparation method of the polyetherester copolymer It encloses, preferably can be corresponding with selection, combination and the preferred scope in aforementioned polyetherester copolymer, this is no longer going to repeat them.
The structure of the polyetherester copolymer is not particularly limited in the present invention, with polyethers well known to those skilled in the art The structure of ester copolymer, those skilled in the art can according to practical condition, quality control and product requirement into Row selects and adjustment, and in polyetherester copolymer of the present invention, the molal quantity of glycol segment accounts for rubbing for the polyetherester copolymer Your degree of number is preferably 0.1%~100%, and more preferably 10%~90%, more preferably 20%~80% are more excellent It is selected as 30%~70%, more preferably 40%~60%.2,5- furandicarboxylic acids of the present invention preferably include biology base 2,5- Furandicarboxylic acid.
The protective atmosphere is not particularly limited in the present invention, is with protective atmosphere well known to those skilled in the art Can, those skilled in the art can select and adjust, this hair according to practical condition, quality control and product requirement The bright protective atmosphere preferably includes nitrogen and/or inert gas, more preferably nitrogen or argon gas.
The esterification catalyst is not particularly limited in the present invention, and such chemical combination is used for well known to those skilled in the art The esterification catalyst of object routine, those skilled in the art can want according to practical condition, quality control and product It asks and is selected and adjusted, esterification catalyst of the present invention preferably includes stannous oxide, stannous octoate, stannous chloride, bromination It is one or more in stannous, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate and stannous hydroxide, more preferably oxygen Change stannous, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate or hydroxide Stannous.The dosage of the esterification catalyst is not particularly limited in the present invention, and those skilled in the art can be according to actual production Situation, quality control and product requirement are selected and are adjusted, and the molal quantity of esterification catalyst of the present invention accounts for described 2, The ratio of the molal quantity of 5- furandicarboxylic acids is preferably 0.5 ‰~4 ‰, more preferably 1 ‰~3.5 ‰, more preferably 1.5 ‰~ 3 ‰, more preferably 2 ‰~2 ‰.
The selection of the alcohol monomer is not particularly limited in the present invention, with conventional alcohol monomer well known to those skilled in the art , those skilled in the art can select and adjust according to practical condition, quality control and product requirement, this Invent the mixture that the alcohol monomer preferably includes glycol or glycol and ethylene glycol.It is sweet that glycol of the present invention preferably includes two It is one or more in alcohol, triethylene glycol, tetraethylene glycol and five glycol, more preferably diethylene glycol (DEG) or triethylene glycol.
In the present invention, when alcohol monomer is glycol, in formula (I) structure of the polyetherester copolymer, n=1；The alcohol When monomer is the mixture of glycol and ethylene glycol, in formula (I) structure of the polyetherester copolymer, n/ (n+m) is less than 1.At this In invention, when using above-mentioned preparation method, due to the use of glycol, it is (complete by biological raw material to be unable to biology base in glycol It is complete to prepare) before, it is non-full biological poly copolyether ester polymer that final products, which can consider,.
The dosage of the alcohol monomer is not particularly limited in the present invention, with well known to those skilled in the art for such anti- The conventional amount used answered, those skilled in the art can carry out according to practical condition, quality control and product requirement The molar ratio of selection and adjustment, 2,5-furandicarboxylic acid of the present invention and alcohol monomer is preferably 1:(2~8), more preferably 1: (3~7), more preferably 1:(4~6).
The condition of the esterification is not particularly limited in the present invention, with esterification well known to those skilled in the art The condition of reaction, those skilled in the art can select according to practical condition, quality control and product requirement It selects and adjusts, the temperature of esterification of the present invention is preferably 170~210 DEG C, more preferably 175~205 DEG C, more preferably 180~200 DEG C, more preferably 185~195 DEG C.The time of esterification of the present invention is preferably 1~4h, and more preferably 1.5 ~3.5h, more preferably 2~3h.The pressure of esterification of the present invention can be normal pressure or micro-positive pressure, it is particularly preferred as 1~ 3atm (atmospheric pressure can be 0.1MPa), more preferably 1.2~2.8atm, more preferably 1.5~2.5atm.
After the present invention carries out esterification, esterification products directly carry out prepolymerization reaction without separation.The present invention is to described The condition and step of prepolymerization reaction are not particularly limited, with the condition of conventional prepolymerization reaction well known to those skilled in the art With step, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the temperature of prepolymerization reaction of the present invention is preferably 170~210 DEG C, more preferably 175~205 DEG C, more preferably 180~200 DEG C, more preferably 185~195 DEG C.The time of prepolymerization reaction of the present invention is preferably 10~60min, more excellent It is selected as 20~50min, more preferably 30~40min.
Prepolymerization reaction of the present invention, preferably Depressor response, specific reactive mode can be vacuum distillation reaction, together When can also excessive dihydric alcohol in removing system.The pressure of prepolymerization reaction of the present invention is preferably a changing value, is become Change range and is specifically as follows the pressure of the esterification to the pressure of the polycondensation reaction.
The present invention finally carries out polycondensation reaction after above-mentioned prepolymerization reaction under the conditions of low vacuum.The present invention is to institute The condition and step for stating polycondensation reaction are not particularly limited, with conventional polycondensation well known to those skilled in the art reaction condition and Step, those skilled in the art can select and adjust according to practical condition, quality control and product requirement Whole, the pressure of polycondensation reaction of the present invention is preferably 20~50Pa, more preferably 25~45Pa, more preferably 30~40Pa. The temperature of the polycondensation reaction is preferably 180~250 DEG C, more preferably 190~240 DEG C, more preferably 200~230 DEG C, more excellent It is selected as 210~220 DEG C.The time of polycondensation reaction of the present invention is preferably 2~12h, more preferably 4~10h, and more preferably 6 ~8h.
The present invention is to be further ensured that the performance of final products, and complete and refinement preparation process, above-mentioned preparation method are specific Can be：
Using melt-polycondensation, 2,5-furandicarboxylic acid is made through over-churning, prepolymerization and to polymerize three step process with alcohol monomer, Directly prepare controllable novel furan polyetherester copolymer of the esterification with etherificate structure proportion 0.1%~100%.In conventional ester Under the action of changing catalyst (PEF esterification catalysts), 2,5-furandicarboxylic acid first generates 2,5- furans with alcohol monomer direct esterification Dioctyl phthalate diol ester and 2,5- furandicarboxylic acid diethylene glycol (DEG) esters；Then, esterification products without separation, continue be evaporated under reduced pressure into Row preshrunk coalescence removes excessive alcohol monomer in reaction system；Then, polycondensation reaction is carried out under the conditions of low vacuum prepare high score Son amount polyether ester product.
Above-mentioned steps of the present invention provide a kind of preparation method of novel furan polyetherester copolymer, prepare in the method Novel full biological poly ether-ether structure segment in, mainly include the poly- furandicarboxylic acid glycol ester unit (PEF) in part, and Part or all of glycol ester segment, wherein glycol segment includes diethylene glycol (DEG) and triethylene glycol, can also also have part tetraethylene glycol and/ Or five glycol.Glycol segment in prepared polyethers ester structure account for polymer totality molar content be 0.1%~ 100%, i.e. n/ (n+m) can be less than or equal to 1, and n of the present invention is preferably 10~200, and more preferably 30~180, more preferably It is 50~150, more preferably 80~120.M of the present invention is preferably 0~200, more preferably 10~200, more preferably 30 ~180, more preferably 50~150, more preferably 80~120.In the present invention, the m and n are both preferably molal quantity.
The present invention is polymerize using esterification catalyst catalysis alcohol monomer with furandicarboxylic acid direct esterification, in lower temperature Under, in the shorter time, highly viscous novel furans polyetherester copolymer is efficiently prepared, reaction process is steady, is easy to control System, product color is preferable, the glycol segment with higher controllable content in prepared product structure.And the present invention can also By adjusting the esterification time in the ingredient proportion and reaction process of alcohol monomer and furandicarboxylic acid, temperature, the polycondensation time, The conditions such as temperature can effectively regulate and control the ratio of glycol segment in polyether ester product.
Above-mentioned steps of the present invention provide a kind of polyetherester copolymer and its a variety of preparation methods, which is One kind having the full biological poly copolyether ester polymer of new structural furans, furans biological poly copolyether ester polymer provided by the invention There is high-content glycol segment in product structure, there is preferable thermodynamic property, and product color is preferable.And the present invention The furyl polyetherester copolymer of offer can not only be copolymerized by common oligomeric glycol, FDCA and ethylene glycol, more be examined It is abiotic base monomer to consider oligomeric glycol (diethylene glycol (DEG), triethylene glycol etc.) so that is carried out by oligomeric glycol and FDCA and ethylene glycol The prepared product of copolymerization loses the attribute of 100% bio-based materials.The present invention more in metal complex catalysts, using containing The metallic catalyst of strong electrophilic ligand at relatively high temperatures can catalyst etherifying reaction the characteristics of, especially rare earth metal complex Under the catalytic action of object catalyst, using simple synthesizing mean, it is anti-with biological ethyl glycol directly to carry out polycondensation using FDCA It answers, at a lower temperature, in the shorter time, efficiently prepares highly viscous with the full biological poly of new structural furans Copolyether ester polymer, containing the oligomeric glycol segment that content is controllable in molecule, and reaction process is steady, easily controllable, condition Mildly, it is a kind of economic and environment-friendly, is suitble to the preparation method of scale industrial production.
It is provided by the invention that there is the full biological poly copolyether ester polymer preparation method of new structural furans and new structure The full biological poly copolyether ester polymer of furans, can not only obtain a kind of novel full biology base high molecular material, but also can solve Due to the problems such as operation caused by oligomeric glycol and fringe cost is added in preparation process.The new structural furans biology base Polyether ester product pushes development and utilization and the environment amenable new bio base realized to furans renewable resource The dependence to petroleum resources is gradually broken away from the preparation of polyester, to solving the shortage of resources and environment that China's polymer industry faces The problems such as pollution, realizes that the sustainable development of China's Polymer Material Industry has important impetus and application value.
The experimental results showed that the glass transition temperature of new bio base polyether ester prepared by the present invention can be controlled 30 ~85 DEG C, 5% thermal degradation temperature is 280~400, and tensile strength is in 10MPa~85MPa, and elongation at break is 4%~400%.
For a further understanding of the present invention, with reference to embodiment to a kind of system of polyetherester copolymer provided by the invention Preparation Method, polyetherester copolymer illustrate, but it is to be understood that these embodiments are based on the technical solution of the present invention Under implemented, give detailed embodiment and specific operating process, only the feature to further illustrate the present invention And advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethanesulfonic acid samarium 87 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%), under nitrogen atmosphere, ester under the conditions of 180 DEG C is added Change 105 minutes, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, Poly- (2,5-furandicarboxylic acid glycol ester-co-2,5- the furandicarboxylic acid diethylene glycol (DEG) of yellow is made in melt polycondensation reaction 4 hours Ester-co-2,5- furandicarboxylic acid triethyleneglycol ester), it is denoted as PPEGF.
The furyl polyetherester copolymer prepared to the embodiment of the present invention 1 characterizes, using deuterated trifluoracetic acid as solvent Nuclear magnetic resonance spectroscopy is carried out to the PPEGF copolyesters.
Referring to Fig. 1, Fig. 1 is the hydrogen nuclear magnetic resonance of the furyl polyether ester copolyesters provided prepared by the embodiment of the present invention 1 Spectrogram.As shown in Figure 1, which has structure, the wherein ratio of ethylene glycol segment and glycol segment shown in formula (II) Example is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
By the PPEGF copolyesters of above-mentioned preparation, it is 1 to be dissolved in 25 DEG C of mass ratioes:1 phenol and tetrachloroethanes mixed solvent Middle its inherent viscosity of measurement, inherent viscosity 0.91dL/g.
Performance detection is carried out to furyl polyetherester copolymer prepared by the embodiment of the present invention.
Referring to table 1, table 1 is the performance of typical structure furyl polyether ester prepared by the embodiment of the present invention.
Table 1
Embodiment 2
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethanesulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%), under nitrogen atmosphere, ester under the conditions of 180 DEG C is added Change 105 minutes, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, The PPEGF copolymers of yellow are made in melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 1.01dL/g.
Embodiment 3
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethanesulfonic acid neodymium 85 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%), under nitrogen atmosphere, ester under the conditions of 180 DEG C is added Change 105 minutes, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, The PPEGF copolymers of yellow are made in melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.83dL/g.
Embodiment 4
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethanesulfonic acid lanthanum 85 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%), under nitrogen atmosphere, ester under the conditions of 180 DEG C is added Change 105 minutes, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, The PPEGF copolymers of yellow are made in melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.96dL/g.
Embodiment 5
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethanesulfonic acid cerium 85 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%), under nitrogen atmosphere, ester under the conditions of 180 DEG C is added Change 105 minutes, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, The PPEGF copolymers of yellow are made in melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.69dL/g.
Embodiment 6
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethanesulfonic acid thulium 85 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%), under nitrogen atmosphere, ester under the conditions of 180 DEG C is added Change 105 minutes, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, The PPEGF copolymers of yellow are made in melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.94dL/g.
Embodiment 7
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Five fluorine ethanesulfonic acid base scandiums 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) are added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ Dark-brown PPEGF copolymers are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 1.00dL/g.
Embodiment 8
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Hepta-fluoroiso-propyl scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%), under nitrogen atmosphere, ester under the conditions of 180 DEG C is added Change 105 minutes, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, Dark-brown PPEGF copolymers are made in melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.95dL/g.
Embodiment 9
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethanesulfonimide base scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, at 180 DEG C Under the conditions of be esterified 105 minutes, obtain esterification products；After esterification, it is warming up in 210 DEG C, 25 minutes that pressure is near Dark-brown PPEGF copolymers are made in 20~50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 1.01dL/g.
Embodiment 10
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid bismuth 92 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ Dark-brown PPEGF copolymers are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 1.05dL/g.
Embodiment 11
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 58 milligrams (account for dibasic carboxylic acid monomers' total amount 0.12%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 1：1, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.96dL/g.
Embodiment 12
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 12.0 grams (0.2mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 2 hours, obtains esterification products；After esterification, it is warming up to the near 20~50Pa of pressure in 210 DEG C, 25 minutes, The PPEGF copolymers of yellow are made in melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 65：35, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.92dL/g.
Embodiment 13
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (1mol), ethylene glycol 15.0 grams (0.25mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 60：40, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.82dL/g.
Embodiment 14
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 24.0 grams (0.4mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 45：55, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.98dL/g.
Embodiment 15
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 30.0 grams (0.5mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 43：57, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.71dL/g.
Embodiment 16
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 170 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 60：40, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.90dL/g.
Embodiment 17
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 190 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 44：56, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.98dL/g.
Embodiment 18
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 200 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 37：63, the glycol segment in structure include diethylene glycol (DEG) with triethylene glycol, Tetraethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.81dL/g.
Embodiment 19
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 210 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 30：70, the glycol segment in structure include diethylene glycol (DEG), triethylene glycol, Tetraethylene glycol, five glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.65dL/g.
Embodiment 20
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 60 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 68：32, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.81dL/g.
Embodiment 21
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 90 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 55：45, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.86dL/g.
Embodiment 22
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 150 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 45：55, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.75dL/g.
Embodiment 23
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 210 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 42：58, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.57dL/g.
Embodiment 24
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 180 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 42：58, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.45dL/g.
Embodiment 25
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 190 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 44：56, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.50dL/g.
Embodiment 26
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 200 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 47：53, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.85dL/g.
Embodiment 27
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 220 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 4 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 56：44, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 1.08dL/g.
Embodiment 28
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 1 hour.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 46：54, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.65dL/g.
Embodiment 29
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 2 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 46：54, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.70dL/g.
Embodiment 30
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 2.5 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 49：51, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.80dL/g.
Embodiment 31
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), Trifluoromethayl sulfonic acid scandium 72 milligrams (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, under the conditions of 180 DEG C Esterification 105 minutes, obtains esterification products；After esterification, be warming up in 210 DEG C, 25 minutes by pressure near 20~ The PPEGF copolymers of yellow are made in 50Pa, melt polycondensation reaction 3 hours.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 50：50, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,:1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.87dL/g.
Embodiment 32
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), 24 milligrams of stannous oxalate (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, is esterified under the conditions of 210 DEG C 105 minutes, obtain esterification products；After esterification, by the near 20~50Pa of pressure, melting contracting in 210 DEG C, 25 minutes Poly- reaction 0.5 hour, is added 72 milligrams of trifluoromethanesulfonic acid scandium, continues polycondensation 3.5 hours, and the PPEGF copolymers of yellow are made.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 78：22, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,：1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.70dL/g.
Embodiment 33
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 18.0 grams (0.3mol), 24 milligrams of stannous oxalate (account for dibasic carboxylic acid monomers' total amount 0.15%) is added, under nitrogen atmosphere, is esterified under the conditions of 210 DEG C 105 minutes, obtain esterification products；After esterification, by the near 20~50Pa of pressure, melting contracting in 210 DEG C, 25 minutes Poly- reaction 3 hours, is added 72 milligrams of trifluoromethanesulfonic acid scandium, continues polycondensation 1 hour, and the PPEGF copolymers of yellow are made.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and glycol segment in structure is 90：10, the glycol segment in structure includes diethylene glycol (DEG) and triethylene glycol.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,：1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.78dL/g.
Embodiment 34
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 6.0 grams (0.1mol), 24 milligrams of stannous oxalate (account for dibasic carboxylic acid monomers' total amount 0.15%), nitrogen atmosphere is added in diethylene glycol (DEG) 10.6 grams (0.1mol) Under, it is esterified 105 minutes under the conditions of 210 DEG C, obtains esterification products；It, will pressure in 230 DEG C, 25 minutes after esterification Near 20~the 50Pa of power, melt polycondensation reaction 4 hours.Obtained structure contains the PPEGF of the yellow of diethylene glycol (DEG) and ethylene glycol segment Copolymer.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and diethylene glycol (DEG) segment in structure is 1：1.4.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,：1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.63dL/g.
Embodiment 35
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), ethylene glycol 6.0 grams (0.1mol), 24 milligrams of stannous oxalate (account for dibasic carboxylic acid monomers' total amount 0.15%) is added in triethylene glycol 15 grams (0.1mol), under nitrogen atmosphere, It is esterified 105 minutes under the conditions of 210 DEG C, obtains esterification products；It, will by pressure in 230 DEG C, 25 minutes after esterification To 20~50Pa, melt polycondensation reaction 4 hours.Obtained structure contains the PPEGF copolymerization of the yellow of triethylene glycol and ethylene glycol segment Object.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and triethylene glycol segment in structure is 1：3.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,：1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.65dL/g.
Embodiment 36
In reactor, it is separately added into 2,5-furandicarboxylic acid 15.6 grams (0.1mol), diethylene glycol (DEG) 10.6 grams (0.1mol), 24 milligrams of stannous oxalate (account for dibasic carboxylic acid monomers' total amount 0.15%) is added in triethylene glycol 15 grams (0.1mol), under nitrogen atmosphere, It is esterified 105 minutes under the conditions of 210 DEG C, obtains esterification products；It, will by pressure in 230 DEG C, 25 minutes after esterification To 20~50Pa, melt polycondensation reaction 4 hours.Obtained structure contains the PPEGF copolymerization of the yellow of triethylene glycol and diethylene glycol (DEG) segment Object.
Nuclear magnetic resonance spectroscopy, the PPEGF copolyesters are carried out to the PPEGF copolyesters using deuterated trifluoracetic acid as solvent The ratio of ethylene glycol segment and triethylene glycol segment in structure is 1：2.
It is 1 that the PPEGF copolyesters, which is dissolved in 25 DEG C of mass ratioes,：1 phenol and tetrachloroethanes in the mixed solvent measures Its inherent viscosity, inherent viscosity 0.60dL/g.
Above to a kind of preparation method of furans biological poly copolyether ester polymer provided by the invention, novel furan biology base Polyetherester copolymer is described in detail, and specific case used herein carries out the principle of the present invention and embodiment It illustrates, the explanation of above example is only intended to facilitating the understanding of the method and its core concept of the invention, including best mode, And but also any person skilled in the art can put into practice the present invention, including manufacture and use any device or system, With the method for implementing any combination.It should be pointed out that for those skilled in the art, not departing from the present invention , can be with several improvements and modifications are made to the present invention under the premise of principle, these improvement and modification also fall into right of the present invention It is required that protection domain in.The range of patent protection of the present invention is defined by the claims, and may include people in the art Member it is conceivable that other embodiment.If these other embodiments have the structure for being not different from claim character express Element, or if they include with equivalent structural elements of the character express of claim without essence difference, these its He should also be included in the scope of the claims embodiment.

Claims (10)

1. a kind of preparation method of polyetherester copolymer, which is characterized in that include the following steps：
1) under the conditions of protective atmosphere and metal complex catalysts, 2,5-furandicarboxylic acid and ethylene glycol is anti-through over-churning Ying Hou obtains polyetherester copolymer after prepolymerization reaction and polycondensation reaction.
2. preparation method according to claim 1, which is characterized in that in the polyetherester copolymer, glycol segment rubs The degree that your number accounts for the molal quantity of the polyetherester copolymer is 30%~70%；
The general formula of the metal complex is LnX3；
The ligand of the metal complex includes trifluoromethanesulfonic acid base, five fluorine ethanesulfonic acid bases, seven fluorine isopropyl alkane sulfonic groups, nine fluorine fourths It is one or more in alkyl sulfonic acid base and trifluoromethanesulfonimide base.
3. preparation method according to claim 1 or 2, which is characterized in that the metallic element of the metal complex includes It is one or more in rare earth element, tin, bismuth, zinc, copper, alkali and alkaline earth metal ions；
The molar ratio of the 2,5- furandicarboxylic acids and ethylene glycol is 1:(2~8)；
The molal quantity of the metal complex catalysts account for the molal quantity of the 2,5- furandicarboxylic acids ratio be 0.5 ‰~ 4‰。
4. preparation method according to claim 1 or 2, which is characterized in that the temperature of the esterification is 170~210 ℃；The time of the esterification is 1~4h；The pressure of the esterification is 1~3atm；
The prepolymerization reaction is Depressor response；The time of the prepolymerization reaction is 10~60min；The prepolymerization reaction Temperature is 170~210 DEG C；
The pressure of the polycondensation reaction is 20~50Pa；The temperature of the polycondensation reaction is 180~250 DEG C；The polycondensation reaction Time be 2~12h.
5. a kind of polyetherester copolymer, which is characterized in that have structure shown in formula (I)；
Wherein, n is 10~200；M is 0~200；
P is selected from one or more of 1,2,3 and 4.
6. copolymer according to claim 5, which is characterized in that in the polyetherester copolymer, n/ (n+m) be 0.3~ 0.7；
The number-average molecular weight of the polyetherester copolymer is 20000~70000.
7. copolymer according to claim 5, which is characterized in that the polyetherester copolymer by 2,5-furandicarboxylic acid and It is obtained after glycol monomer polymerization；
The glycol monomer includes the mixture of glycol or glycol and ethylene glycol；
The glycol includes one or more in diethylene glycol (DEG), triethylene glycol, tetraethylene glycol and five glycol；
In the polyetherester copolymer, n/ (n+m) is less than or equal to 1.
8. copolymer according to claim 5, which is characterized in that the polyetherester copolymer is prepared by following methods It arrives：
1`) under conditions of protective atmosphere and esterification catalyst, by 2,5-furandicarboxylic acid, ethylene glycol and pass through esterification Afterwards, after using prepolymerization reaction, polycondensation reaction is carried out, after metal complex catalysts are added in polycondensation process, is obtained To polyetherester copolymer.
9. preparation method according to claim 8, which is characterized in that in the polyetherester copolymer, n/ (n+m) is 0.1 ~0.4；
The esterification catalyst include stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, It is one or more in stannous oxalate, stannous sulfate and stannous hydroxide；
The ratio that the molal quantity of the esterification catalyst accounts for the molal quantity of the 2,5- furandicarboxylic acids is 0.5 ‰~4 ‰.
10. preparation method according to claim 8, which is characterized in that the temperature of the esterification is at 170~210 DEG C； The time of the esterification is 1~4h；The pressure of the esterification is 1~3atm；
The pressure of the prepolymerization reaction process be the esterification pressure to the polycondensation reaction pressure；
The time of the prepolymerization reaction is 10~60min；The temperature of the prepolymerization reaction is 170~210 DEG C；
The pressure of the polycondensation reaction is 20~50Pa；The temperature of the polycondensation reaction is 180~250 DEG C；The polycondensation reaction Time be 2~12h；
The time that is added of the metal complex catalysts is between 0~3 hour of polycondensation reaction starting.
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