CN109734886A - Copolyesters and preparation method thereof containing furan nucleus - Google Patents
Copolyesters and preparation method thereof containing furan nucleus Download PDFInfo
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Abstract
The present invention relates to a kind of furandicarboxylic acid copolyesters and preparation method thereof, the segmented structure of the copolyesters containing furan nucleus is network-like structure, it is 1:(1.1~2.0 by molar ratio): (0.0001~0.02): first component of (0.0001~0.02), second component, third component and the 4th component are polymerized, wherein, first component includes furandicarboxylic acid, at least one of furandicarboxylic acid carboxylate, second component includes aromatic diol, at least one of aliphatic dihydroxy alcohol, third component includes the polyalcohol that hydroxyl quantity is more than or equal to 3, 4th component includes the acid anhydrides that carbonyl quantity is more than or equal to 3.In preparation method, the acid anhydrides of polyalcohol of the hydroxyl quantity more than or equal to 3 and carbonyl quantity more than or equal to 3 is as segment tie point, expanding the segmented structure of the copolyesters containing furan nucleus is network-like structure, to obtain the copolyesters containing furan nucleus of high molecular weight colourless or light and with excellent mechanical performance and barrier properties for gases.
Description
Technical field
The present invention relates to field of material technology, more particularly to the copolyesters and preparation method thereof containing furan nucleus.
Background technique
Currently, widely used biology base high molecular material mainly has polylactic acid (PLA), poly-hydroxy fatty acid (PHA), gathers
Hydroxyacetic acid (PGA), polybutylene glycol succinate (PBS) etc..But they belong to fatty quasi polymer, due to molecule knot
Lack rigid aromatic ring structure, mechanical property (such as intensity, modulus, creep resistant) and heat resistance (such as hot mechanicalness in structure
Energy, heat distortion temperature etc.) it is significantly lower than polyethylene terephthalate (PET), polycarbonate (PC), aramid fiber
(PA), the petroleum bases high molecular material such as bisphenol A type epoxy resin (Epoxy), seriously limits their application range.
Contain aromatic rings in the molecular structure of 2,5-furandicarboxylic acid (2,5-FDCA), is used for synthesising biological based high molecular material
Material can effectively improve its heat resistance and mechanical performance.Meanwhile the opposite use of oxygen-barrier property of the polyester material containing furan nucleus
It can be improved 2~10 times in the PET of packaging material, it is sufficient to effectively improve the shelf-life of agricultural product, fish, meat products etc..
However, using polyester material made from 2,5-furandicarboxylic acid, often there is also some disadvantages at present, and such as: due to the reaction time
Color is deeper caused by the reasons such as too long, and stretch modulus is low caused by molecular weight is relatively low, tensile strength is low etc..
Summary of the invention
Based on this, it is necessary in view of the above-mentioned problems, providing a kind of copolyesters and preparation method thereof containing furan nucleus；The system
In Preparation Method, acid anhydrides of polyalcohol of the hydroxyl quantity more than or equal to 3 with carbonyl quantity more than or equal to 3 is connected collectively as segment
Point, make the segmented structure of the copolyesters containing furan nucleus from linear structure expand be network-like structure, thus obtain it is colourless or light,
And the copolyesters containing furan nucleus of the high molecular weight with excellent mechanical performance and barrier properties for gases, and then can preferably meet it
Application demand in fields such as packaging material, film, fiber, engineering plastics.
A kind of preparation method of the copolyesters containing furan nucleus, comprising the following steps:
(1) the first component, the second component, third component and the 4th component are provided, wherein first component includes furans
At least one of dioctyl phthalate, furandicarboxylic acid carboxylate, second component include aromatic diol, aliphatic dihydroxy alcohol
At least one of, the third component includes the polyalcohol that hydroxyl quantity is more than or equal to 3, and the 4th component includes carbonyl number
Amount is more than or equal to 3 acid anhydrides；
(2) by first component, second component, the third component, the 4th component and catalyzing esterification
Agent mixing, is reacted under inert atmosphere or nitrogen atmosphere, obtains the first intermediate product, wherein is first component, described
The molar ratio of second component, the third component and the 4th component is 1:(1.1~2.0): (0.0001~0.025):
(0.0001~0.025)；
(3) under vacuum conditions, first intermediate product carries out prepolymerization reaction, obtains the second intermediate product；
(4) under vacuum conditions, second intermediate product carries out polycondensation reaction, obtains the copolyesters containing furan nucleus, institute
The segmented structure for stating the copolyesters containing furan nucleus is network-like structure.
Acid anhydrides of the carbonyl quantity described in step (1) more than or equal to 3 includes 1,2,4- benzene three in one of the embodiments,
Acid anhydrides, pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 4,4 '-biphenyl ether dianhydrides, 3,3 ', 4,4 '-biphenyl
At least one of tetracarboxylic acid dianhydride, 4,4 '-(hexafluoro isopropyl alkene) two titanic anhydrides, chlorination trimellitic anhydride.
In one of the embodiments, hydroxyl quantity described in step (1) more than or equal to 3 polyalcohol include glycerine,
Butantriol, 2- methylol -2- methyl-1,3-propanediol, erythrol, pentaerythrite, dipentaerythritol, pentitol, hexitol, sugar
At least one of alcohol.
The sum of the mole of third component described in step (2) and the 4th component is in one of the embodiments,
The 0.05%~3% of the mole of first component.
The temperature of reaction described in step (2) is 150 DEG C~220 DEG C in one of the embodiments, and the time of reaction is
0.5h~5.0h.
The mole of esterification catalyst described in step (2) is rubbing for first component in one of the embodiments,
The 0.05%~1% of that amount.
The reaction temperature of prepolymerization reaction described in step (3) is 180 DEG C~260 DEG C in one of the embodiments, reaction
Time is 0.5h~4.0h.
It in one of the embodiments, further include adding polycondensation catalyst into first intermediate product in step (3),
The mole of the polycondensation catalyst is the 0.05%~0.5% of the mole of first component；And/or
Stabilizer is added into first intermediate product, the mole of the stabilizer is mole of first component
The 0.05%~0.5% of amount；And/or
Antioxidant is added into first intermediate product, the mole of the antioxidant is mole of first component
The 0.05%~0.5% of amount.
The reaction temperature of polycondensation reaction described in step (4) is 200 DEG C~260 DEG C in one of the embodiments, reaction
Time is 0.5h~4h.
In above-mentioned preparation method, polyalcohol of the hydroxyl quantity more than or equal to 3, acid anhydrides of the carbonyl quantity more than or equal to 3, furans
Dioctyl phthalate or its carboxylate and dihydric alcohol mixing after, in the reaction process of step (2) in addition to occur furandicarboxylic acid or its
Outside the esterification or ester exchange reaction of carboxylate and dihydric alcohol, hydroxyl quantity more than or equal to 3 polyalcohol and carbonyl quantity be greater than etc.
In 3 acid anhydrides as segment tie point, it also occur that the open loop of acid anhydrides of the carbonyl quantity more than or equal to 3 and with dihydric alcohol or copolymerization
The esterification or ester exchange reaction of ester oligomer, in the enough situations of reaction condition, acid anhydrides of the carbonyl quantity more than or equal to 3 is in ester
The change stage will sufficiently be reacted in the segment of copolymerization ester oligomer and hydroxyl quantity is more than or equal to 3 polyalcohol and furan
It mutters the esterification or ester exchange reaction of dioctyl phthalate or its carboxylate or polyester oligomer, to promote the first intermediate product copolyesters low
The molecule segment structure of polymers is expanded from linear structure becomes network-like structure, mentions for the rapid growth of subsequent copolyesters molecular weight
For precondition.So above-mentioned preparation method can to polymerize to obtain molecular weight higher containing furans for polycondensation within the shorter time
The copolyesters of ring, so that the mechanical properties such as the stretch modulus of the copolyesters containing furan nucleus, tensile strength and gas barrier can be improved
Performance.Meanwhile shorter polymerization time, it not only can effectively inhibit the generation of the high temperature side reaction such as furandicarboxylic acid decarboxylation, and
And it can be existing because being present in the high temperature degradation occurred in hot environment, oxidation stain etc. for a long time to avoid the copolyesters containing furan nucleus
As and the problem of lead to color burn, to obtain the colourless or light copolyesters containing furan nucleus.
In addition, individually polyalcohol of the addition hydroxyl quantity more than or equal to 3 or carbonyl quantity are more than or equal to 3 acid anhydrides, when it
Additive amount reaches after certain value, it may occur that gel or crosslinking phenomena, the serious processed and applied for limiting polyester material lose it
Practical application value.And after adding the acid anhydrides of polyalcohol of the hydroxyl quantity more than or equal to 3 and carbonyl quantity more than or equal to 3 simultaneously,
In copolyesters polymerization process, acid anhydrides of the carbonyl quantity more than or equal to 3 can open loop and the ester with dihydric alcohol or copolymerization ester oligomer
Change or ester exchange reaction obtains intermediate material, it, can be certain after which contacts with polyalcohol of the amount of hydroxyl groups more than or equal to 3
By alcoholysis in degree, the generation of excessive acid anhydrides bring gel or crosslinking phenomena is prevented.Meanwhile copolyesters strand can be kept
Network-like structure, achieve the purpose that improve copolyesters molecular weight.
A kind of copolyesters containing furan nucleus, such as above-mentioned preparation method obtain, the segment knot of the copolyesters containing furan nucleus
Structure is network-like structure.
The segmented structure of the above-mentioned copolyesters containing furan nucleus is network-like structure, and molecular weight is high, has excellent stretching die
The mechanical properties such as amount, tensile strength and gas barrier property.Meanwhile the copolyesters containing furan nucleus be it is colourless or light, can be used for
Manufacture packaging material, film, fiber, engineering plastics etc..
Detailed description of the invention
Fig. 1 is the sample photo of the copolyesters containing furan nucleus made from embodiment 1；
Fig. 2 is the copolyesters containing furan nucleus made from embodiment 11H-NMR map；
Fig. 3 is the DSC map of the copolyesters containing furan nucleus made from embodiment 1；
Fig. 4 is the TGA map of the copolyesters containing furan nucleus made from embodiment 1；
Fig. 5 is the FTIR map of the copolyesters containing furan nucleus made from embodiment 1；
Fig. 6 is the sample photo of poly- 2,5- furandicarboxylic acid glycol ester made from comparative example 1.
Specific embodiment
The copolyesters and preparation method thereof provided by the invention containing furan nucleus will be described further below.
The preparation method of copolyesters provided by the invention containing furan nucleus the following steps are included:
(1) the first component, the second component, third component and the 4th component are provided, wherein first component includes furans
At least one of dioctyl phthalate, furandicarboxylic acid carboxylate, second component include aromatic diol, aliphatic dihydroxy alcohol
At least one of, the third component includes the polyalcohol that hydroxyl quantity is more than or equal to 3, and the 4th component includes carbonyl number
Amount is more than or equal to 3 acid anhydrides；
(2) by first component, second component, the third component, the 4th component and catalyzing esterification
Agent mixing, is reacted under inert atmosphere or nitrogen atmosphere, obtains the first intermediate product, wherein is first component, described
The molar ratio of second component, the third component and the 4th component is 1:(1.1~2.0): (0.0001~0.025):
(0.0001~0.025)；
(3) under vacuum conditions, first intermediate product carries out prepolymerization reaction, obtains the second intermediate product；
(4) under vacuum conditions, second intermediate product carries out polycondensation reaction, obtains the copolyesters containing furan nucleus, institute
The segmented structure for stating the copolyesters containing furan nucleus is network-like structure.
In step (1), the furandicarboxylic acid carboxylate include furandicarboxylic acid dimethyl ester, furandicarboxylic acid diethylester,
At least one of furandicarboxylic acid dibutyl ester.Wherein, the furan nucleus in furandicarboxylic acid or furandicarboxylic acid carboxylate comes from
Biomass material, the biomass material include at least one of cellulose, fructose, glucose sugar, furancarboxylic acid.
In view of the reactivity of 2,5-furandicarboxylic acid dimethyl ester is preferable, it is preferred that first component is 2,5- furan
It mutters dicarboxylic acid dimethyl ester.
The aliphatic dihydroxy alcohol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol,
Nonanediol, decanediol, cyclohexanedimethanol, 2,2,4,4- tetramethyl -1,3- cyclobutanediol, at least one in neopentyl glycol
Kind.
The aromatic diol include 2- [4- (2- ethoxy) phenoxy group] ethyl alcohol, bis- (2- hydroxy ethoxy) benzene of 1,3-,
At least one of bisphenol-A, bisphenol S.
Acid anhydrides of the carbonyl quantity more than or equal to 3 includes 1,2,4- benzenetricarboxylic anhydride, pyromellitic dianhydride, 3,3 ', and 4,4 '-
Benzophenone tetracarboxylic dianhydride, 4,4 '-biphenyl ether dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 4,4 '-(hexafluoro isopropyl alkene)
At least one of two titanic anhydrides, chlorination trimellitic anhydride.
Polyalcohol of the hydroxyl quantity more than or equal to 3 includes glycerine, butantriol, 2- methylol -2- methyl-1,3- third
At least one of glycol, erythrol, pentaerythrite, dipentaerythritol, pentitol, hexitol, sugar alcohol.
In step (2), if the sum of additive amount of the third component and the 4th component is too low, only few part
Segmented structure can by linear condition expand be network state, obtain the first intermediate product copolymerization ester oligomer carry out again it is subsequent
When polycondensation reaction, enough network structures can not be provided to realize the purpose for improving molecular weight of polyesters in the short time；And if third
The sum of the additive amount of component and the 4th component is excessively high, then can quickly form crosslinking in subsequent polycondensation process again, between strand
Excessive entanglement, so that the melt strength of copolyesters is excessively high, melt index is too low, and mobility is deteriorated, and is unfavorable for copolyester product
Processed and applied.Preferably, the sum of mole of the third component and the 4th component is the mole of first component
0.05%~3%.
Equally, it is contemplated that real reaction can be gone on smoothly, and reduce cost of material, it is preferred that first component and institute
The molar ratio for stating the second component is 1:(1.3~1.8), further preferably 1:(1.4~1.7).
The esterification catalyst include anhydrous zinc acetate, anhydrous cobalt acetate, anhydrous manganese acetate, in Dibutyltin oxide extremely
Few one kind, and the mole of the esterification catalyst is the 0.05%~1% of the mole of first component.In view of guaranteeing
The dosage of catalyst should not be excessive while sufficient catalytic efficiency, it is preferred that the mole of the esterification catalyst is described
The 0.1%~0.5% of the mole of first component.
Specifically, the reaction includes esterification or ester exchange reaction, the temperature of the reaction is 150 DEG C~220 DEG C,
The time of reaction is 0.5h~5.0h.In view of the boiling point of the pure and mild aromatic diol of used binary aliphatic, it is preferred that
The temperature of the reaction is 150 DEG C~200 DEG C, and the time of reaction is 2.0h~5.0h.
Esterification or ester exchange reaction in esterification or ester-exchange reaction, in addition to the first component and the second component occurs
Outside, the carbonyl quantity of polyalcohol of the hydroxyl quantity of third component more than or equal to 3 and the 4th component is more than or equal to 3 acid anhydrides conduct
Segment tie point, it also occur that the open loop of acid anhydrides of the carbonyl quantity more than or equal to 3 and the ester with dihydric alcohol or copolymerization ester oligomer
Change or ester exchange reaction, in the enough situations of reaction condition, acid anhydrides of the carbonyl quantity more than or equal to 3 will be filled in Esterification Stage
Point be reacted in the segment of copolymerization ester oligomer and polyalcohol of the hydroxyl quantity more than or equal to 3 and furandicarboxylic acid or its
The esterification or ester exchange reaction of carboxylate or polyester oligomer.To promote the molecule segment structure of copolymerization ester oligomer from line
Property structure expand and become network-like structure, the rapid growth for subsequent copolyesters molecular weight provides precondition.
In addition, individually polyalcohol of the addition hydroxyl quantity more than or equal to 3 or carbonyl quantity are more than or equal to 3 acid anhydrides, when it
Additive amount reaches after certain value, it may occur that gel or crosslinking phenomena, the serious processed and applied for limiting polyester material lose it
Practical application value.And after adding the acid anhydrides of polyalcohol of the hydroxyl quantity more than or equal to 3 and carbonyl quantity more than or equal to 3 simultaneously,
In copolyesters polymerization process, acid anhydrides of the carbonyl quantity more than or equal to 3 can open loop and the ester with dihydric alcohol or copolymerization ester oligomer
Change or ester exchange reaction obtains intermediate material, it, can be certain after which contacts with polyalcohol of the amount of hydroxyl groups more than or equal to 3
By alcoholysis in degree, the generation of excessive acid anhydrides bring gel or crosslinking phenomena is prevented.
In step (3), the vacuum degree of the prepolymerization reaction is 2000Pa and hereinafter, reaction temperature is 180 DEG C~260 DEG C,
Reaction time is 0.5h~4.0h.To remove excessive second component, keep the first intermediate product copolymerization ester oligomer further
Polymerization, obtains the second intermediate product.
Specifically, further including adding polycondensation catalyst, the polycondensation reaction into first intermediate product in step (3)
The mole of catalyst is the 0.05%~0.5% of the mole of first component.
Wherein, the polycondensation catalyst includes at least one of antimony-based catalyst, germanium series catalysts, tin series catalysts,
Preferably at least one of antimony oxide, antimony glycol, antimony acetate, Dibutyltin oxide.
It is appreciated that esterification catalyst and polycondensation catalyst can be identical, e.g., it is all made of Dibutyltin oxide.Therefore, may be used
First intermediate product is directly carried out to the prepolymerization reaction of step (2).But after esterification or ester exchange reaction, catalyzing esterification
Agent can partial failure.Therefore, under esterification catalyst and the identical situation of polycondensation catalyst, can step (3) precondensation it is anti-
Part polycondensation catalyst should be added in the process.
Specifically, further including adding stabilizer or antioxidant into first intermediate product, or stablize in step (3)
The mole of the mixture of agent and antioxidant, the stabilizer or the antioxidant is the mole of first component
0.05%~0.5%.
Wherein, stabilizer can reduce ester bond, aliphatic chain and carbon-carbon bond etc. and generate oxidation scission under oxygen, prevent heat point
The generation of solution.The stabilizer includes phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, phosphoric acid diformazan
Ester, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, ammonium dihydrogen phosphate are at least
It is a kind of.
Antioxidant can capture oxygen radical, eliminate micro oxygen, to reduce pyrolysis and oxidation side reaction
Generation.The antioxidant includes phenolic antioxidant, preferably antioxidant -1010, antioxidant -1076, in antioxidant -168
It is at least one.
In step (4), the vacuum degree of the polycondensation reaction is 200Pa and hereinafter, preferably 1.5Pa~200Pa, reaction temperature
Degree is 200 DEG C~260 DEG C, and the reaction time is 0.5h~4h.To make the second intermediate product carry out under the appropriate reaction conditions
Polycondensation reaction, molecular weight gradually increase, and obtain the copolyesters containing furan nucleus.
It is appreciated that the vacuum degree during final polycondensation reaction is preferably shorter than the vacuum degree during prepolymerization reaction.But
It is, it, can't be to anti-when vacuum degree during the vacuum degree during prepolymerization reaction is equal to or less than final polycondensation reaction
Should causing damage property of result influence.
So the first intermediate product that segmented structure of the present invention is network-like structure can gather in polycondensation within the shorter time
Conjunction obtains the higher copolyesters containing furan nucleus of molecular weight, so that the stretch modulus of the copolyesters containing furan nucleus can be improved, stretch
The mechanical properties such as intensity and gas barrier property.
Meanwhile shorter polymerization time, it not only can effectively inhibit the generation of the high temperature side reaction such as furandicarboxylic acid decarboxylation,
And it can be to avoid the copolyesters containing furan nucleus because being present in the high temperature degradation occurred in hot environment, oxidation stain etc. for a long time
Phenomenon and the problem of lead to color burn, to obtain the colourless or light copolyesters containing furan nucleus.
The present invention also provides a kind of copolyesters containing furan nucleus, such as above-mentioned preparation method is obtained, being total to containing furan nucleus
The segmented structure of polyester is network-like structure.
It is appreciated that ratio and third that the network-like structure segment of the copolyesters containing furan nucleus is shared in all segments
Component, the additive amount of the 4th component are related, and under actual conditions, small part segment may be still remained in the copolyesters containing furan nucleus
Structure be linear structure.
Specifically, third component is by taking pentaerythrite as an example, the 4th component is by taking pyromellitic dianhydride as an example, it is described to contain furan nucleus
The segmented structure of copolyesters includes:
Wherein, R1、R2、R3、R4、R5、R6And R7For the structural unit of aromatic diol, the structure list of aliphatic dihydroxy alcohol
One of member, the structural unit of pentaerythrite or structural unit of pyromellitic dianhydride.
Specifically, third component by taking glycerine as an example, the 4th component by taking pyromellitic dianhydride as an example, it is described total containing furan nucleus
The segmented structure of polyester includes:
Wherein, wherein R8、R9、R10、R11、R12And R13For the structural unit of aromatic diol, aliphatic dihydroxy alcohol
One of structural unit, the structural unit of glycerine or structural unit of pyromellitic dianhydride.
So the segmented structure of the copolyesters of the invention containing furan nucleus is network-like structure, molecular weight is high, so as to
Assign mechanical properties and the gas barrier properties such as the superior stretch modulus of copolyesters, the tensile strength containing furan nucleus.Meanwhile
Copolyesters containing furan nucleus be it is colourless or light, can preferably meet its packaging material, film, fiber, engineering plastics etc. lead
The application demand in domain is conducive to the manufacture level for promoting high performance engineering plastics, to promote biology base Polymer Material Industry
Get rid of the height dependence to petroleum resources.
Hereinafter, by being done further by following specific embodiments to the copolyesters and preparation method thereof containing furan nucleus
Explanation.
In the examples below, conventional method and conventional equipment can be used to carry out furandicarboxylic acid copolyesters of the invention
Performance measurement is measured referring to national standard GB or other standards.
Specifically, nuclear magnetic resonance spectroscopy (1H-NMR) in Bruker 400AVANCE III Spectrometer type instrument
Upper measurement, 400MHz, CF3COOD。
The measurement of inherent viscosity with phenol/tetrachloroethanes (m:m=1:1) be solvent, at 30 ± 0.05 DEG C, with Ubbelohde viscosity
Meter is tested, and the inherent viscosity [η] of copolyesters is calculated according to formula (1), (2).
ηsp=(t1-t0)/t0 (1)
[η]=[(1+1.4 ηsp)1/2-1]/0.7c (2)
Wherein: t0For the flow time (s) of solvent；t1For the flow time (s) for being copolymerized ester solution；C is copolymerization ester solution
Concentration is 5g/L.
Heat analysis (DSC) carries out on differential scanning calorimeter, N2Atmosphere, 25 DEG C~300 DEG C of temperature of test scanning.
Thermogravimetic analysis (TGA) (TGA) carries out on Perkin-Elmer Diamond TG/DTA, 10 DEG C/min of the rate of heat addition,
50 DEG C~800 DEG C of Range of measuring temp.
The barrier property of oxygen and carbon dioxide carries out permeability test using LabthinkVAC-V2, respectively with CO2And O2
For gas source, under conditions of temperature and humidity is respectively 23 DEG C and 50%RH, sample size Ф=97mm, the transmission area of selection
For 38.5cm2。
Embodiment 1:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pyromellitic dianhydride, pentaerythrite and anhydrous zinc acetate according to rubbing
You are added in reaction kettle than 1:1.6:0.003:0.0005:0.001, under an inert atmosphere, are gradually heated to 185 DEG C, reaction
4.5h.Then be added in a kettle 2,5- furandicarboxylic acid dimethyl ester mole 0.12% antimony oxide, 0.2%
Triphenyl phosphate, 0.1% antioxidant -1010, be slowly evacuated to 600Pa~2000Pa, pre-polymerization at a temperature of 220 DEG C
0.5h.Then it is gradually warming up to 240 DEG C again, continues to be evacuated to 200Pa or less and reacts 3h, obtains the copolyesters containing furan nucleus.
From fig. 1, it can be seen that the copolyesters containing furan nucleus that the embodiment obtains is very shallow yellow.
It is solvent C F at 11.31ppm in Fig. 23The peak of COOD is the peak (2H) of hydrogen on furan nucleus at 7.17ppm,
It is the peak (4H) of hydrogen on ethylene glycol segment at 4.59ppm, so, as can be seen from Figure 2, the copolymerization containing furan nucleus which obtains
Ester is poly- furandicarboxylic acid glycol ester.
As can be seen from Figure 3, the glass transition temperature for the copolyesters containing furan nucleus which obtains is 87.5 DEG C.
As can be seen from Figure 4, the thermal decomposition temperature (T for the copolyesters containing furan nucleus which obtainsD, 5%) it is 368 DEG C.
Through detecting, the inherent viscosity for the copolyesters containing furan nucleus which obtains is 1.12dL/g, and tensile strength is
79.3MPa, stretch modulus 2.7GPa, carbon dioxide gas barrier property are 0.7 × 10-12cm3·cm/cm2ScmHg,
Oxygen gas barrier property is 0.8 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 2:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pyromellitic dianhydride, pentaerythrite and anhydrous cobalt acetate according to rubbing
You are added in reaction kettle than 1:1.5:0.003:0.001:0.0012, vacuumize, inflated with nitrogen displacement three times, start stirring and by
180 DEG C are gradually warming up to, 4.5h is reacted.Then the 0.15% of 2,5- furandicarboxylic acid dimethyl ester mole is added in a kettle
Antimony oxide, 0.2% diphenyl phosphate, 0.1% antioxidant -168, are slowly evacuated to 300Pa~2000Pa, in temperature
Degree is pre-polymerization 0.5h under conditions of 225 DEG C.Then 240 DEG C are gradually warming up to, continues suction to 200Pa reaction below
2.5h obtains the copolyesters containing furan nucleus.
The copolyesters containing furan nucleus that the embodiment obtains is very shallow yellow, through detecting, inherent viscosity 0.98dL/
G, tensile strength 76.8MPa, stretch modulus 2.5GPa, carbon dioxide gas barrier property are 0.8 × 10-12cm3·cm/
cm2ScmHg, oxygen gas barrier property are 1.0 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 3:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pyromellitic dianhydride, pentaerythrite and anhydrous cobalt acetate according to rubbing
You are added in reaction kettle than 1:1.8:0.001:0.001:0.0015, vacuumize, inflated with nitrogen displacement three times, start stirring and by
190 DEG C are gradually warming up to, 4h is reacted.Then the three of the 0.2% of 2,5- furandicarboxylic acid dimethyl ester mole are added in a kettle
Two antimony, 0.05% diphenyl phosphate, 0.1% antioxidant -1010 are aoxidized, 200Pa~2000Pa is slowly evacuated to,
Pre-polymerization 1h at a temperature of 200 DEG C.Again gradually temperature to 245 DEG C, continue to be evacuated to 200Pa reaction 4h below, obtain containing furans
The copolyesters of ring.
The copolyesters containing furan nucleus that the embodiment obtains is very shallow yellow, through detecting, inherent viscosity 0.93dL/
G, tensile strength 76.6MPa, stretch modulus 2.5GPa, carbon dioxide gas barrier property are 0.8 × 10-12cm3·cm/
cm2ScmHg, oxygen gas barrier property are 1.0 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 4:
By 2,5- furandicarboxylic acid diethylester, ethylene glycol, pyromellitic dianhydride, pentaerythrite and anhydrous zinc acetate according to rubbing
You are added in reaction kettle than 1:1.6:0.001:0.002:0.0015, vacuumize, inflated with nitrogen displacement three times, start stirring and by
195 DEG C are gradually warming up to, 2h is reacted.Then the three of the 0.3% of 2,5- furandicarboxylic acid diethylester mole are added in a kettle
Two antimony, 0.2% ammonium phosphate, 0.05% antioxidant -1010 are aoxidized, 200Pa~1800Pa is slowly evacuated to, at 215 DEG C
At a temperature of pre-polymerization 1h.Gradually temperature continues to vacuumize to 250 DEG C again, by vacuum degree control in 200Pa hereinafter, reaction 2h, obtains
Copolyesters containing furan nucleus.
The very shallow yellow of the copolyesters containing furan nucleus that the embodiment obtains, through detecting, inherent viscosity 0.90dL/g,
Tensile strength is 75.8MPa, and stretch modulus 2.5GPa, carbon dioxide gas barrier property is 0.9 × 10-12cm3·cm/
cm2ScmHg, oxygen gas barrier property are 0.9 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 5:
By 2,5- furandicarboxylic acid diethylester, ethylene glycol, pyromellitic dianhydride, glycerine and anhydrous zinc acetate according to mole
Be added in reaction kettle than 1:1.4:0.002:0.0005:0.001, vacuumize, inflated with nitrogen displacement three times, be then gradually heated to
180 DEG C, react 3.5h.Then be added 2,5- furandicarboxylic acid diethylester mole 0.2% antimony oxide, 0.2%
Triphenyl phosphate, 0.1% antioxidant -1010, be slowly evacuated to 2000Pa hereinafter, at a temperature of 220 DEG C pre-polymerization 0.5h.So
Temperature is risen to 240 DEG C again afterwards, continues suction to 200Pa hereinafter, reaction 3.5h, obtains the copolyesters containing furan nucleus.
The very shallow yellow of the copolyesters containing furan nucleus that the embodiment obtains, through detecting, inherent viscosity 0.89dL/g,
Tensile strength is 76.1MPa, and stretch modulus 2.4GPa, carbon dioxide gas barrier property is 0.8 × 10-12cm3·cm/
cm2ScmHg, oxygen gas barrier property are 0.9 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 6:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pyromellitic dianhydride, glycerine and anhydrous manganese acetate according to mole
Be added in reaction kettle than 1:2.0:0.0001:0.002:0.0015, vacuumize, inflated with nitrogen displacement three times, be then gradually warmed up
To 190 DEG C, 3h is reacted.Then be added 2,5- furandicarboxylic acid dimethyl ester mole 0.15% antimony oxide, 0.5%
Triphenyl phosphate, 0.1% antioxidant -168, be slowly evacuated to 2000Pa hereinafter, at a temperature of 210 DEG C pre-polymerization 1.5h.So
Temperature is risen to 245 DEG C again afterwards, continues suction to 200Pa hereinafter, reaction 3h, obtains the copolyesters containing furan nucleus.
The very shallow yellow of the copolyesters containing furan nucleus that the embodiment obtains, through detecting, inherent viscosity 1.05dL/g,
Tensile strength is 78.2MPa, and stretch modulus 2.6GPa, carbon dioxide gas barrier property is 1.1 × 10-12cm3·cm/
cm2ScmHg, oxygen gas barrier property are 1.0 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 7:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, 1,2,4- benzenetricarboxylic anhydride, pentaerythrite and anhydrous zinc acetate according to
Molar ratio 1:1.6:0.015:0.015:0.002 is added in reaction kettle, vacuumize, filling with inert gas displacement three times, then by
180 DEG C are gradually warming up to, 4h is reacted.Then 0.12% antimony oxide of 2,5-furandicarboxylic acid dimethyl ester mole is added,
It slowly is evacuated to 200Pa~1300Pa, pre-polymerization 0.5h at a temperature of 220 DEG C.240 DEG C are then heated to, vacuum degree is controlled
200Pa obtains the copolyesters containing furan nucleus hereinafter, reaction 2h.
The very shallow yellow of the copolyesters containing furan nucleus that the embodiment obtains, through detecting, inherent viscosity 0.99dL/g,
Tensile strength is 74.7MPa, and stretch modulus 2.6GPa, carbon dioxide gas barrier property is 0.7 × 10-12cm3·cm/
cm2ScmHg, oxygen gas barrier property are 0.9 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 8:
By 2,5- furandicarboxylic acid dibutyl ester, ethylene glycol, 1,2,4- benzenetricarboxylic anhydride, pentaerythrite and anhydrous zinc acetate according to
Molar ratio 1:1.5:0.003:0.0001:0.0018 is added in reaction kettle, is vacuumized, three times, then filling with inert gas is replaced
180 DEG C are gradually heated to, 4.5h is reacted.Then three oxidations two of the 0.15% of 2,5- furandicarboxylic acid dibutyl ester mole are added
Antimony, 0.2% phosphoric acid, 0.5% antioxidant -1076, are slowly evacuated to 500Pa~1500Pa, pre-polymerization at a temperature of 225 DEG C
0.5h.250 DEG C are then heated to, control vacuum degree 150Pa obtains the copolyesters containing furan nucleus hereinafter, reaction 3h.
The embodiment obtain the copolyesters containing furan nucleus be it is light yellow, through detecting, inherent viscosity 1.09dL/g, drawing
Stretching intensity is 79.0MPa, and stretch modulus 2.7GPa, carbon dioxide gas barrier property is 0.7 × 10-12cm3·cm/cm2·
ScmHg, oxygen gas barrier property are 0.7 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 9:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, 1,2,4- benzenetricarboxylic anhydride, glycerine and anhydrous zinc acetate according to rubbing
You are added in reaction kettle than 1:1.7:0.002:0.002:0.0013, vacuumize, three times, then gradually filling with inert gas is replaced
180 DEG C are warming up to, 4.5h is reacted.Then be added 2,5- furandicarboxylic acid dimethyl ester mole 0.5% antimony oxide,
0.2% trimethyl phosphate, 0.1% antioxidant -1010,300Pa~1600Pa is slowly evacuated to, at a temperature of 200 DEG C
Pre-polymerization 0.5h.255 DEG C are then heated to, control vacuum degree 150Pa obtains the copolyesters containing furan nucleus hereinafter, reaction 2.5h.
The embodiment obtain the copolyesters containing furan nucleus be it is light yellow, through detecting, inherent viscosity 0.95dL/g, drawing
Stretching intensity is 75.9MPa, and stretch modulus 2.6GPa, carbon dioxide gas barrier property is 0.9 × 10-12cm3·cm/cm2·
ScmHg, oxygen gas barrier property are 0.8 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 10:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, 1,2,4- benzenetricarboxylic anhydride, glycerine and anhydrous zinc acetate according to rubbing
You are added in reaction kettle than 1:1.5:0.02:0.01:0.0015, vacuumize, filling with inert gas displacement three times, then gradually rise
Temperature reacts 5h to 180 DEG C.Then be added 2,5- furandicarboxylic acid dimethyl ester mole 0.15% antimony oxide, slowly
It is evacuated to 400Pa~2000Pa, pre-polymerization 0.5h at a temperature of 260 DEG C.Then control vacuum degree 150Pa is hereinafter, at 260 DEG C
The reaction was continued 0.5h, obtains the copolyesters containing furan nucleus.
The embodiment obtain the copolyesters containing furan nucleus be it is light yellow, through detecting, inherent viscosity 0.95dL/g, drawing
Stretching intensity is 74.9MPa, and stretch modulus 2.4GPa, carbon dioxide gas barrier property is 1.0 × 10-12cm3·cm/cm2·
ScmHg, oxygen gas barrier property are 1.1 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 11:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pentaerythrite, pyromellitic dianhydride, anhydrous manganese acetate according to rubbing
You are added in reaction kettle than 1:1.5:0.025:0.025:0.001, vacuumize, three times, then gradually filling with inert gas is replaced
180 DEG C are warming up to, 4h is reacted.Then be added 2,5- furandicarboxylic acid dimethyl ester mole 0.1% antimony oxide,
0.2% triphenyl phosphate, 0.2% antioxidant -1010,200Pa~2000Pa is slowly evacuated to, at a temperature of 210 DEG C
Pre-polymerization 1h.240 DEG C are then heated to, controls vacuum degree in 150Pa hereinafter, reaction 0.5h, obtains the copolyesters containing furan nucleus.
The embodiment obtain the copolyesters containing furan nucleus be it is colourless, through detecting, inherent viscosity 1.2dL/g, stretching
Intensity is 80.7MPa, and stretch modulus 2.9GPa, carbon dioxide gas barrier property is 0.5 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 0.6 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 12:
By 2,5- furandicarboxylic acid dimethyl ester, butanediol, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, erythrol and titanium
Sour four butyl esters are added in reaction kettle according to molar ratio 1:1.6:0.005:0.015:0.005, are vacuumized, filling with inert gas displacement
Three times, 170 DEG C are then gradually heated to, 5h is reacted.Then 0.2% phosphorus of 2,5- furandicarboxylic acid dimethyl ester mole is added
Triphenyl phosphate ester, 0.2% antioxidant -1076, be slowly evacuated to, 200Pa~2000Pa, pre-polymerization 4h at a temperature of 180 DEG C.So
After be warming up to 230 DEG C, control vacuum degree 150Pa obtains the copolyesters containing furan nucleus hereinafter, reaction 1.5h.
The copolyesters containing furan nucleus that the embodiment obtains is light yellow, through detecting, inherent viscosity 1.12dL/
G, tensile strength 79.1MPa, stretch modulus 2.6GPa, carbon dioxide gas barrier property are 0.9 × 10-12cm3·cm/
cm2ScmHg, oxygen gas barrier property are 1.0 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 13:
By 2,5- furandicarboxylic acid diethylester, butanediol, 1,2,4- benzenetricarboxylic anhydride, erythrol and Dibutyltin oxide according to
Molar ratio 1:1.6:0.01:0.02:0.01 is added in reaction kettle, vacuumize, filling with inert gas displacement three times, then gradually rise
Temperature reacts 5h to 170 DEG C.Then 0.3% triphenyl phosphate of addition 2,5- furandicarboxylic acid diethylester mole, 0.2%
Antioxidant -1076, be slowly evacuated to, 200Pa~2000Pa, pre-polymerization 0.5h at a temperature of 200 DEG C.Then heat to 230
DEG C, control vacuum degree 150Pa obtains the copolyesters containing furan nucleus hereinafter, reaction 0.5h.
The embodiment obtain the copolyesters containing furan nucleus be it is colourless, through detecting, inherent viscosity 1.18dL/g, stretching
Intensity is 78.5MPa, and stretch modulus 2.5GPa, carbon dioxide gas barrier property is 0.6 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 0.7 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 14:
2,5- furandicarboxylic acid diethylester, bisphenol S, pyromellitic dianhydride, dipentaerythritol and Dibutyltin oxide are pressed
It is added in reaction kettle, vacuumizes, filling with inert gas is replaced three times, so according to molar ratio 1:1.3:0.0002:0.0003:0.006
After be gradually heated to 180 DEG C, react 5h.Then 0.05% dibutyl oxygen of 2,5- furandicarboxylic acid diethylester mole is added
Change tin, 0.2% triphenyl phosphate, 0.1% antioxidant -1010, is slowly evacuated to, 200Pa~2000Pa, at 200 DEG C
At a temperature of pre-polymerization 0.5h.Then vacuum degree 150Pa is controlled hereinafter, the reaction was continued at 200 DEG C 2.5h, obtains being total to containing furan nucleus
Polyester.
The embodiment obtain the copolyesters containing furan nucleus be it is light yellow, through detecting, inherent viscosity 1.1dL/g, drawing
Stretching intensity is 77.7MPa, and stretch modulus 2.5GPa, carbon dioxide gas barrier property is 0.9 × 10-12cm3·cm/cm2·
ScmHg, oxygen gas barrier property are 0.9 × 10-12cm3·cm/cm2·s·cmHg。
Comparative example 1:
2,5- furandicarboxylic acid dimethyl ester, ethylene glycol and anhydrous zinc acetate are added to according to molar ratio 1:1.6:0.001
In reaction kettle, vacuumize, inflated with nitrogen displacement three times, be then gradually heated to 180 DEG C, react 5h.Then 2,5- furans two is added
0.1% antimony oxide of formic acid dimethyl ester mole, 0.1% triphenyl phosphate, 0.1% antioxidant -1010, slowly
It is evacuated to 200Pa~2000Pa, precondensation 1.5h at a temperature of 220 DEG C.240 DEG C are then heated to, vacuum degree 150Pa is controlled
Hereinafter, reaction 7h, obtains poly- 2,5-furandicarboxylic acid glycol ester.
Since the comparative example polycondensation time is longer, poly- 2,5-furandicarboxylic acid glycol ester is present in hot environment for a long time
In, so, as shown in fig. 6, the color for the poly- 2,5-furandicarboxylic acid glycol ester that the comparative example obtains is buff.
Through detecting, inherent viscosity 0.75dL/g, tensile strength 70.2MPa, stretch modulus are 2.2GPa titanium dioxide
Carbon gas barrier property is 1.2 × 10-12cm3·cm/cm2ScmHg, oxygen gas barrier property are 1.3 × 10-12cm3·
cm/cm2·s·cmHg。
Comparative example 2:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pentaerythrite, anhydrous zinc acetate 1:1.5:0.025 in molar ratio:
0.001 is added in reaction kettle, vacuumize, inflated with nitrogen displacement three times, be then gradually warming up to 180 DEG C, react 3h.Then it is added
0.1% antimony oxide, 0.2% triphenyl phosphate, 0.2% antioxygen of 2,5- furandicarboxylic acid dimethyl ester mole
Agent -1010, is slowly evacuated to 200Pa~2000Pa, pre-polymerization 1h at a temperature of 220 DEG C.240 DEG C are then heated to, control is true
Reciprocal of duty cycle 150Pa obtains the copolyesters containing furan nucleus hereinafter, reaction 0.5h.
Since the additive amount of pentaerythrite in the comparative example is excessive, after polycondensation reaction 0.5h, excessive hydroxyl will be sent out
Apparent crosslinking phenomena is given birth to, excessive entanglement between strand, dissolubility is very poor, and the data such as inherent viscosity can not be characterized.
Comparative example 3:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pyromellitic dianhydride, anhydrous zinc acetate 1:1.5 in molar ratio:
0.025:0.001 is added in reaction kettle, vacuumize, inflated with nitrogen displacement three times, be then gradually warming up to 180 DEG C, react 4h.So
0.1% antimony oxide of 2,5- furandicarboxylic acid dimethyl ester mole, 0.1% triphenyl phosphate, 0.1% are added afterwards
Antioxidant -1010, is slowly evacuated to 200Pa~2000Pa, pre-polymerization 1h at a temperature of 220 DEG C.240 DEG C are then heated to, control
Vacuum degree 150Pa processed obtains the copolyesters containing furan nucleus hereinafter, reaction 0.5h.
Since the additive amount of pyromellitic dianhydride in the comparative example is excessive, after polycondensation reaction 0.5h, will occur very bright
Aobvious crosslinking phenomena, excessive entanglement between strand, dissolubility is very poor, and the data such as inherent viscosity can not be characterized.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of the copolyesters containing furan nucleus, which comprises the following steps:
(1) the first component, the second component, third component and the 4th component are provided, wherein first component includes furans diformazan
Acid, at least one of furandicarboxylic acid carboxylate, second component include aromatic diol, in aliphatic dihydroxy alcohol
At least one, the third component include the polyalcohol that hydroxyl quantity is more than or equal to 3, and the 4th component includes that carbonyl quantity is big
In the acid anhydrides for being equal to 3；
(2) first component, second component, the third component, the 4th component and esterification catalyst are mixed
It closes, is reacted under inert atmosphere or nitrogen atmosphere, obtain the first intermediate product, wherein first component, described second
The molar ratio of component, the third component and the 4th component is 1:(1.1~2.0): (0.0001~0.025): (0.0001
~0.025)；
(3) under vacuum conditions, first intermediate product carries out prepolymerization reaction, obtains the second intermediate product；
(4) under vacuum conditions, second intermediate product carries out polycondensation reaction, obtains the copolyesters containing furan nucleus, described to contain
The segmented structure of the copolyesters of furan nucleus is network-like structure.
2. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that described in step (1)
Acid anhydrides of the carbonyl quantity more than or equal to 3 includes 1,2,4- benzenetricarboxylic anhydride, pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acids
Acid dianhydride, 4,4 '-biphenyl ether dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 4,4 '-(hexafluoro isopropyl alkene) two titanic anhydrides, chlorine
Change at least one of trimellitic anhydride.
3. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that described in step (1)
Hydroxyl quantity more than or equal to 3 polyalcohol include glycerine, butantriol, 2- methylol -2- methyl-1,3-propanediol, erythrol,
At least one of pentaerythrite, dipentaerythritol, pentitol, hexitol, sugar alcohol.
4. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that described in step (2)
The sum of mole of third component and the 4th component is the 0.05%~3% of the mole of first component.
5. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that described in step (2)
The temperature of reaction is 150 DEG C~220 DEG C, and the time of reaction is 0.5h~5.0h.
6. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that described in step (2)
The mole of esterification catalyst is the 0.05%~1% of the mole of first component.
7. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that described in step (3)
The reaction temperature of prepolymerization reaction is 180 DEG C~260 DEG C, and the reaction time is 0.5h~4.0h.
8. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that step is also wrapped in (3)
It includes and adds polycondensation catalyst into first intermediate product, the mole of the polycondensation catalyst is rubbing for first component
The 0.05%~0.5% of that amount；And/or
Stabilizer is added into first intermediate product, the mole of the stabilizer is the mole of first component
0.05%~0.5%；And/or
Antioxidant is added into first intermediate product, the mole of the antioxidant is the mole of first component
0.05%~0.5%.
9. the preparation method of the copolyesters according to claim 1 containing furan nucleus, which is characterized in that described in step (4)
The reaction temperature of polycondensation reaction is 200 DEG C~260 DEG C, and the reaction time is 0.5h~4h.
10. a kind of copolyesters containing furan nucleus, which is characterized in that the preparation method as described in any one of claim 1~9 obtains,
The segmented structure of the copolyesters containing furan nucleus is network-like structure.
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| CN105916575A (en) * | 2013-08-30 | 2016-08-31 | 可口可乐公司 | Poly(ethylenefuranoate) copolymers and methods |
| CN108840995A (en) * | 2018-07-17 | 2018-11-20 | 中国科学院长春应用化学研究所 | A kind of preparation method of the poly- 2,5- furandicarboxylic acid glycol ester of high melt viscosity |
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| CN105916575A (en) * | 2013-08-30 | 2016-08-31 | 可口可乐公司 | Poly(ethylenefuranoate) copolymers and methods |
| CN108840995A (en) * | 2018-07-17 | 2018-11-20 | 中国科学院长春应用化学研究所 | A kind of preparation method of the poly- 2,5- furandicarboxylic acid glycol ester of high melt viscosity |
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