CN109810247A - Furyl copolyesters and preparation method thereof - Google Patents
Furyl copolyesters and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of furyl copolyesters and preparation method thereof, it is 1:(1.1~2.0 that the preparation method, which includes: by molar ratio): the first component, the second component and the third component of (0.0001~0.02) are mixed with esterification catalyst, reaction obtains the first intermediate product, wherein, first component includes at least one of furandicarboxylic acid, furandicarboxylic acid carboxylate, second component includes at least one of aromatic diol, aliphatic dihydroxy alcohol, and third component includes the acid anhydrides that carbonyl quantity is more than or equal to 3；The first intermediate product is subjected to prepolymerization reaction again and polycondensation reaction obtains furyl copolyesters.In preparation method, acid anhydrides of the carbonyl quantity more than or equal to 3 is as segment tie point, expanding the segmented structure of furyl copolyesters is network-like structure, to obtain the furyl copolyesters of high molecular weight colourless or light and with excellent mechanical performance and barrier properties for gases, and then it can preferably meet it in the application demand in the fields such as packaging material, film, fiber, engineering plastics.
Description
Technical field
The present invention relates to field of material technology, more particularly to furyl copolyesters and preparation method thereof.
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 furyl copolyesters and preparation method thereof；The preparation side
In method, acid anhydrides of the carbonyl quantity more than or equal to 3 makes the segmented structure of furyl copolyesters from linear structure as segment tie point
Expanding is network-like structure, to obtain high molecular weight colourless or light and with excellent mechanical performance and barrier properties for gases
Furyl copolyesters, and then can preferably meet its fields such as packaging material, film, fiber, engineering plastics apply need
It asks.
A kind of preparation method of furyl copolyesters, comprising the following steps:
(1) the first component, the second component and third component are provided, wherein first component includes furandicarboxylic acid, furan
Mutter at least one of dicarboxylic acid esters compound, second component include aromatic diol, in aliphatic dihydroxy alcohol at least
One kind, the third component include the acid anhydrides that carbonyl quantity is more than or equal to 3；
(2) first component, second component, the third component and esterification catalyst are mixed, in inertia
It is reacted under atmosphere or nitrogen atmosphere, obtains the first intermediate product, wherein first component, second component and institute
The molar ratio for stating third component is 1:(1.1~2.0): (0.0001~0.02)；
(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 furyl copolyesters, the furan
Mutter base copolyesters segmented structure be 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.A reality wherein
It applies in example, furandicarboxylic acid carboxylate described in step (1) includes furandicarboxylic acid dimethyl ester, furandicarboxylic acid diethylester, furan
It mutters at least one of dibutyl carboxylic acid.
In one of the embodiments, aliphatic dihydroxy alcohol described in step (1) include ethylene glycol, propylene glycol, butanediol,
Pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, cyclohexanedimethanol, 2,2,4,4- tetramethyl -1,3- ring
At least one of butanediol, neopentyl glycol；
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.
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, carbonyl quantity is more than or equal to 3 acid anhydrides, furandicarboxylic acid or its carboxylate and dihydric alcohol
After mixing, in addition to esterification or ester that furandicarboxylic acid or its carboxylate and dihydric alcohol occurs are handed in the reaction process of step (2)
It changes outside reaction, acid anhydrides of the carbonyl quantity more than or equal to 3 is as segment tie point, it also occur that carbonyl quantity is more than or equal to 3 acid
The open loop of acid anhydride and with dihydric alcohol or be copolymerized ester oligomer esterification or ester exchange reaction, in the enough situations of reaction condition, carbonyl
Acid anhydrides of the radix amount more than or equal to 3 is in the segment that Esterification Stage will sufficiently be reacted to copolymerization ester oligomer, to promote
The molecule segment structure that first intermediate product is copolymerized ester oligomer is expanded from linear structure becomes network-like structure, is subsequent copolymerization
The rapid growth of ester molecule amount provides precondition.So above-mentioned preparation method can polymerize in polycondensation within the shorter time
To the higher furyl copolyesters of molecular weight, so that the mechanical property such as the stretch modulus of furyl copolyesters, tensile strength can be improved
Energy and gas barrier property.Meanwhile shorter polymerization time, not only it can effectively inhibit the high temperature secondaries such as furandicarboxylic acid decarboxylation anti-
The generation answered, and can be to avoid furyl copolyesters because being present in the high temperature degradation occurred in hot environment, oxidation for a long time
Phenomena such as discoloration and the problem of lead to color burn, to obtain colourless or light furyl copolyesters.
A kind of furyl copolyesters, such as above-mentioned preparation method obtain, and the segmented structure of the furyl copolyesters is network
Shape structure.
The segmented structure of above-mentioned furyl copolyesters is network-like structure, and molecular weight is high, has excellent stretch modulus, draws
Stretch the mechanical properties such as intensity and gas barrier property.Meanwhile furyl copolyesters be it is colourless or light, can be used for manufacturing packing timber
Material, film, fiber, engineering plastics etc..
Detailed description of the invention
Fig. 1 is the sample photo of furyl copolyesters made from embodiment 1；
Fig. 2 is furyl copolyesters made from embodiment 11H-NMR map；
Fig. 3 is the DSC map of furyl copolyesters made from embodiment 1；
Fig. 4 is the TGA map of furyl copolyesters made from embodiment 1；
Fig. 5 is the FTIR map of furyl copolyesters 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
Furyl copolyesters provided by the invention and preparation method thereof will be described further below.
The preparation method of furyl copolyesters provided by the invention the following steps are included:
(1) the first component, the second component and third component are provided, wherein first component includes furandicarboxylic acid, furan
Mutter at least one of dicarboxylic acid esters compound, second component include aromatic diol, in aliphatic dihydroxy alcohol at least
One kind, the third component include the acid anhydrides that carbonyl quantity is more than or equal to 3；
(2) first component, second component, the third component and esterification catalyst are mixed, in inertia
It is reacted under atmosphere or nitrogen atmosphere, obtains the first intermediate product, wherein first component, second component and institute
The molar ratio for stating third component is 1:(1.1~2.0): (0.0001~0.02)；
(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 furyl copolyesters, the furan
Mutter base copolyesters segmented structure be 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.
In step (2), if the additive amount of the third component is too low, only extremely least a portion of segmented structure can be by linear
It is network state that state, which is expanded, when obtained the first intermediate product copolymerization ester oligomer carries out subsequent polycondensation reaction again, Wu Fati
The purpose that molecular weight of polyesters is improved in the short time is realized for enough network structures；And if third component content is excessively high, again
Crosslinking, excessive entanglement between strand can be quickly formed in subsequent polycondensation process, so that the melt strength of copolyesters is excessively high, melt
It is too low to melt index, mobility is deteriorated, and is unfavorable for the processed and applied of copolyester product.Therefore, first component and the third
The molar ratio of component is preferably 1:(0.0003~0.01), further preferably 1:(0.0005~0.005).
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, acid anhydrides of the carbonyl quantity of third component more than or equal to 3 is as segment tie point, it also occur that carbonyl quantity is more than or equal to 3
Acid anhydrides open loop and with dihydric alcohol or be copolymerized ester oligomer esterification or ester exchange reaction, in the situation that reaction condition is enough
Under, acid anhydrides of the carbonyl quantity more than or equal to 3 will be sufficiently reacted in the segment for being copolymerized ester oligomer in Esterification Stage, from
And promoting the segmented structure of the first intermediate product to expand from linear structure is network-like structure, is subsequent copolyesters molecular weight
Rapid growth provides precondition.
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 furyl copolyesters.
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 result result in destructive impacts.
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 furyl copolyesters of molecular weight, so that the mechanics such as furyl copolyesters stretch modulus, tensile strength can be improved
Performance 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 furyl copolyesters because of phenomena such as being present in the high temperature degradation occurred in hot environment, oxidation stain for a long time
And the problem of leading to color burn, to obtain colourless or light furyl copolyesters.
The present invention also provides a kind of furyl copolyesters, such as above-mentioned preparation method is obtained, the chain of the furyl copolyesters
Segment structure is network-like structure.
It is appreciated that ratio and third component that the network-like structure segment of furyl copolyesters is shared in all segments
Additive amount it is related, under actual conditions, may still have in furyl copolyesters small part segment structure be linear structure.
Specifically, third component, by taking pyromellitic dianhydride as an example, the segmented structure of the furyl copolyesters includes:
Wherein, R1、R2、R3And R4For the structural unit of aromatic diol, the structural unit of aliphatic dihydroxy alcohol or equal benzene
One of structural unit of tetracarboxylic acid anhydride.
Specifically, third component, by taking 1,2,4-tricarboxylic anhydride as an example, the segmented structure of the furyl copolyesters includes:
Wherein, R5、R6And R7It is the structural unit of aromatic diol, the structural unit of aliphatic dihydroxy alcohol or 1,2,
One of the structural unit of 4- benzenetricarboxylic anhydride.
So the segmented structure of furyl copolyesters of the invention 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 furyl copolyesters, tensile strength.Meanwhile furyl is total
Polyester be it is colourless or light, can preferably meet it in the application demand in the fields such as packaging material, film, fiber, engineering plastics,
The manufacture level for being conducive to be promoted high performance engineering plastics, so that biology base Polymer Material Industry be promoted to get rid of to petroleum resources
Height rely on.
Hereinafter, will be done further by following specific embodiments to described furyl copolyesters and preparation method thereof
It is bright.
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 and anhydrous zinc acetate according to molar ratio 1:
1.6:0.003:0.002 is added in reaction kettle, vacuumize, filling with inert gas displacement three times, be then gradually heated to 185 DEG C,
React 4h.Then in a kettle be added 2,5- furandicarboxylic acid dimethyl ester mole 0.12% antimony oxide, 0.2%
Triphenyl phosphate, 0.15% antioxidant -168, be slowly evacuated to 200Pa~2000Pa, pre-polymerization at a temperature of 220 DEG C
1h.Then it is gradually warming up to 250 DEG C again, continues to be evacuated to 200Pa or less and reacts 2.5h, obtains furyl copolyesters.
From fig. 1, it can be seen that the furyl copolyesters 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 furyl copolyesters which obtains is
Poly- furandicarboxylic acid glycol ester.
As can be seen from Figure 3, the glass transition temperature for the furyl copolyesters which obtains is 88.9 DEG C.
As can be seen from Figure 4, the thermal decomposition temperature (T for the furyl copolyesters which obtainsD, 5%) it is 365 DEG C.
Through detecting, the inherent viscosity for the furyl copolyesters which obtains is 0.89dL/g, and tensile strength is
74.3MPa, stretch modulus 2.2GPa, carbon dioxide gas barrier property are 1.0 × 10-12cm3·cm/cm2ScmHg,
Oxygen gas barrier property is 1.0 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 2:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pyromellitic dianhydride and anhydrous zinc acetate according to molar ratio 1:
1.6:0.0015:0.002 is added in reaction kettle, vacuumize, inflated with nitrogen displacement three times, start to stir and be gradually heated to 195
DEG C, react 2h.Then in a kettle be added 2,5- furandicarboxylic acid dimethyl ester mole 0.3% antimony oxide,
0.12% trimethyl phosphate, 0.15% antioxidant -1010, be slowly evacuated to 200Pa~1500Pa, temperature be 220
Pre-polymerization 0.5h under conditions of DEG C.Then 240 DEG C are gradually warming up to, continues suction to 200Pa reaction 4h below, obtains furan
It mutters base copolyesters.
The furyl copolyesters that the embodiment obtains is very shallow yellow, and through detecting, inherent viscosity 0.97dL/g is drawn
Stretching intensity is 76.5MPa, and stretch modulus 2.4GPa, carbon dioxide gas barrier property is 0.8 × 10-12cm3·cm/cm2·
ScmHg, oxygen gas barrier property are 1.0 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 3:
By 2,5- furandicarboxylic acid diethylester, ethylene glycol, 1,2,4- benzenetricarboxylic anhydride and anhydrous zinc acetate according to molar ratio 1:
1.6:0.0005:0.001 is added in reaction kettle, under an inert atmosphere, is started to stir and be gradually heated to 170 DEG C, is reacted 5h.
Then 0.1% antimony oxide of 2,5- furandicarboxylic acid diethylester mole, 0.1% tricresyl phosphate are added in a kettle
Phenyl ester, 0.1% antioxidant -1076, be slowly evacuated to 600Pa~2000Pa, pre-polymerization 0.5h at a temperature of 225 DEG C.Again by
Step temperature to 240 DEG C, continue to be evacuated to 200Pa reaction 4h below, obtain furyl copolyesters.
The furyl copolyesters that the embodiment obtains is very shallow yellow, and through detecting, inherent viscosity 0.79dL/g is drawn
Stretching intensity is 70.9MPa, and stretch modulus 2.2GPa, carbon dioxide gas barrier property is 1.2 × 10-12cm3·cm/cm2·
ScmHg, oxygen gas barrier property are 1.2 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 4:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, 1,2,4- benzenetricarboxylic anhydride and anhydrous cobalt acetate according to molar ratio 1:
1.5:0.00075:0.0005 being added in reaction kettle, vacuumize, inflated with nitrogen displacement three times, start to stir and be gradually heated to
180 DEG C, react 4.5h.Then 0.15% three oxidations two of 2,5- furandicarboxylic acid dimethyl ester mole are added in a kettle
Antimony, 0.1% phosphorous acid, 0.05% antioxidant -1010, are slowly evacuated to 200Pa~2000Pa, at a temperature of 200 DEG C
Pre-polymerization 1.5h.Gradually temperature continues to vacuumize to 235 DEG C again, by vacuum degree control in 200Pa hereinafter, reaction 4h, obtains furans
Base copolyesters.
The very shallow yellow of the furyl copolyesters that the embodiment obtains, through detecting, inherent viscosity 0.85dL/g is stretched
Intensity is 72.9MPa, and stretch modulus 2.4GPa, carbon dioxide gas barrier property is 1.1 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 1.2 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 5:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, 1,2,4- benzenetricarboxylic anhydride and anhydrous zinc acetate according to molar ratio 1:
1.8:0.001:0.0015 is added in reaction kettle, vacuumize, inflated with nitrogen displacement three times, be then gradually heated to 190 DEG C, reaction
5h.Then be added 2,5- furandicarboxylic acid dimethyl ester mole 0.2% antimony oxide, 0.05% triphenyl phosphate,
0.15% antioxidant -1076, is slowly evacuated to 200Pa~1000Pa, pre-polymerization 1h at a temperature of 215 DEG C.It then again will be warm
Degree rises to 260 DEG C, continues suction to 200Pa hereinafter, reaction 2.5h, obtains furyl copolyesters.
The very shallow yellow of the furyl copolyesters that the embodiment obtains, through detecting, inherent viscosity 0.85dL/g is stretched
Intensity is 72.5MPa, and stretch modulus 2.3GPa, carbon dioxide gas barrier property is 1.0 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 1.2 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 6:
By 2,5- furandicarboxylic acid dibutyl ester, ethylene glycol, pyromellitic dianhydride and anhydrous cobalt acetate according to molar ratio 1:
1.4:0.0003:0.0025 is added in reaction kettle, vacuumize, inflated with nitrogen displacement three times, be then gradually heated to 150 DEG C, instead
Answer 5h.Then 0.2% antimony oxide of 2,5- furandicarboxylic acid dimethyl ester mole, 0.14% phosphoric acid triphen is added
Ester, 0.1% antioxidant -168, be slowly evacuated to 200Pa~2000Pa hereinafter, at a temperature of 180 DEG C pre-polymerization 4h.Then again
Temperature is risen to 240 DEG C, continues suction to 200Pa hereinafter, reaction 1h, obtains furyl copolyesters.
The embodiment obtain furyl copolyesters be it is colourless, through detecting, inherent viscosity 0.89dL/g, tensile strength
For 73.5MPa, stretch modulus 2.4GPa, carbon dioxide gas barrier property is 0.9 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 1.0 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 7:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, pyromellitic dianhydride and anhydrous zinc acetate according to molar ratio 1:
2.0:0.002:0.002 is added in reaction kettle, vacuumize, filling with inert gas displacement three times, be then gradually heated to 190 DEG C,
React 3h.Then 0.15% antimony oxide of 2,5- furandicarboxylic acid dimethyl ester mole, 0.15% tricresyl phosphate is added
Phenyl ester, 0.15% antioxidant -1010, be slowly evacuated to 300Pa~1500Pa, pre-polymerization 0.5h at a temperature of 260 DEG C.Then
Vacuum degree 200Pa is controlled hereinafter, continuing to obtain furyl copolyesters in 260 DEG C of reaction 2h.
The embodiment obtain furyl copolyesters be it is light yellow, through detecting, inherent viscosity 0.90dL/g, stretch by force
Degree is 75.6MPa, and stretch modulus 2.4GPa, carbon dioxide gas barrier property is 0.9 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 0.9 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 8:
By 2,5- furandicarboxylic acid dimethyl ester, ethylene glycol, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides and anhydrous manganese acetate are pressed
Be added in reaction kettle according to molar ratio 1:1.5:0.0001:0.005, vacuumize, filling with inert gas displacement three times, then gradually rise
Temperature reacts 4.5h to 180 DEG C.Then 0.15% antimony oxide of 2,5-furandicarboxylic acid dimethyl ester mole is added, delays
Slowly it is evacuated to 300Pa~2000Pa, pre-polymerization 0.5h at a temperature of 225 DEG C.250 DEG C are then heated to, vacuum degree 150Pa is controlled
Hereinafter, reaction 2.5h, obtains furyl copolyesters.
The embodiment obtain furyl copolyesters be it is light yellow, through detecting, inherent viscosity 0.95dL/g, stretch by force
Degree is 77.2MPa, and stretch modulus 2.5GPa, carbon dioxide gas barrier property is 0.7 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 0.9 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 9:
By 2,5- furandicarboxylic acid dimethyl ester, butanediol, pyromellitic dianhydride and Dibutyltin oxide according to molar ratio 1:
1.7:0.01:0.01 is added in reaction kettle, vacuumize, filling with inert gas displacement three times, be then gradually heated to 190 DEG C, instead
Answer 2h.Then 0.2% triphenyl phosphate of 2,5- furandicarboxylic acid dimethyl ester mole, 0.2% antioxidant-is added
1076, it is slowly evacuated to 300Pa~1500Pa, pre-polymerization 1h at a temperature of 205 DEG C.225 DEG C are then heated to, vacuum degree is controlled
150Pa obtains furyl copolyesters hereinafter, reaction 1.5h.
The furyl copolyesters that the embodiment obtains is very shallow yellow, and through detecting, inherent viscosity 1.02dL/g is drawn
Stretching intensity is 57.7MPa, and stretch modulus 1.3GPa, carbon dioxide gas barrier property is 4.3 × 10-12cm3·cm/cm2·
ScmHg, oxygen gas barrier property are 1.1 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 10:
By 2,5- furandicarboxylic acid dimethyl ester, butanediol, pyromellitic dianhydride and butyl titanate according to molar ratio 1:
1.5:0.02:0.001 is added in reaction kettle, vacuumize, filling with inert gas displacement three times, be then gradually heated to 150 DEG C, instead
Answer 3h.Then 0.05% butyl titanate of 2,5- furandicarboxylic acid dimethyl ester mole, 0.5% phosphoric acid triphen is added
Ester, 0.2% antioxidant -168, be slowly evacuated to 300Pa~2000Pa, pre-polymerization 2h at a temperature of 200 DEG C.It then heats to
225 DEG C, control vacuum degree 150Pa obtains furyl copolyesters hereinafter, reaction 0.5h.
The embodiment obtain furyl copolyesters be it is colourless, through detecting, inherent viscosity 1.13dL/g, tensile strength
For 62.6MPa, stretch modulus 1.2GPa, carbon dioxide gas barrier property is 4.5 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 0.9 × 10-12cm3·cm/cm2·s·cmHg。
Embodiment 11:
By 2,5- furandicarboxylic acid dimethyl ester, bisphenol S, 1,2,4- benzenetricarboxylic anhydride and Dibutyltin oxide according to molar ratio 1:
1.3:0.015:0.006 is added in reaction kettle, vacuumize, filling with inert gas displacement three times, be then gradually heated to 180 DEG C,
React 3.5h.Then 0.5% Dibutyltin oxide of 2,5- furandicarboxylic acid dimethyl ester mole, 0.5% antioxygen is added
Agent -168, is slowly evacuated to 200Pa~2000Pa, pre-polymerization 1h at a temperature of 210 DEG C.230 DEG C are then heated to, vacuum is controlled
150Pa is spent hereinafter, reaction 1h, obtains furyl copolyesters.
The embodiment obtain furyl copolyesters be it is colourless, through detecting, inherent viscosity 1.25dL/g, tensile strength
For 67.3MPa, stretch modulus 1.4GPa, carbon dioxide gas barrier property is 3.8 × 10-12cm3·cm/cm2·s·
CmHg, oxygen gas barrier property are 0.8 × 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, pre-polymerization 1.5h at a temperature of 220 DEG C.Then heat to 240 DEG C, control vacuum degree 150Pa with
Under, 7h is reacted, poly- 2,5-furandicarboxylic acid glycol ester is obtained.
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, pyromellitic dianhydride, anhydrous zinc acetate 1:1.5 in molar ratio:
0.00005:0.0015 is added in reaction kettle, vacuumize, inflated with nitrogen displacement three times, be then gradually warming up to 180 DEG C, reaction
5h.Then be added 2,5- furandicarboxylic acid dimethyl ester mole 0.1% antimony oxide, 0.2% triphenyl phosphate,
0.5% antioxidant -1010, is slowly evacuated to 200Pa~2000Pa, pre-polymerization 1h at a temperature of 220 DEG C.It then heats to
240 DEG C, control vacuum degree 150Pa obtains furyl copolyesters hereinafter, reaction 8h.
Since the additive amount of the comparative example pyromellitic dianhydride is too low, only extremely least a portion of segmented structure can be by linear shape
It is network state that state, which is expanded, so the time of polycondensation is still longer, the furyl copolyesters of acquisition is buff.
Through detecting, inherent viscosity 0.78dL/g, tensile strength 71.0MPa, stretch modulus 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 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 furyl copolyesters 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.
Comparative example 4:
1,4- dimethyl terephthalate (DMT), ethylene glycol and anhydrous zinc acetate are added to according to molar ratio 1:1.6:0.002
In reaction kettle, vacuumize, inflated with nitrogen displacement three times, be then gradually heated to 200 DEG C, react 4.5h.Then 1,4- is added to benzene
0.12% antimony oxide of dicarboxylic acid dimethyl ester mole, 0.1% triphenyl phosphate, 0.1% antioxidant -1010,
It slowly is evacuated to 200Pa~1000Pa, pre-polymerization 0.5h at a temperature of 240 DEG C.280 DEG C are then heated to, vacuum degree is controlled
200Pa obtains polyethylene terephthalate hereinafter, reaction 5h.
The white for the polyethylene terephthalate that the comparative example obtains, through detecting, inherent viscosity 0.85dL/g,
Carbon dioxide gas barrier property is 1.2 × 10-11cm3·cm/cm2ScmHg, oxygen gas barrier property are 5.2 × 10-12cm3·cm/cm2·s·cmHg。
It follows that furandicarboxylic acid copolyesters of the invention can replace polyethylene terephthalate use, because
This, can reduce the dependence to petroleum base high molecular material.
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 furyl copolyesters, which comprises the following steps:
(1) the first component, the second component and third component are provided, wherein first component includes furandicarboxylic acid, furans two
At least one of formic acid esters compound, second component include at least one of aromatic diol, aliphatic dihydroxy alcohol,
The third component includes the acid anhydrides that carbonyl quantity is more than or equal to 3；
(2) first component, second component, the third component and esterification catalyst are mixed, in inert atmosphere
Or reacted under nitrogen atmosphere, obtain the first intermediate product, wherein first component, second component and described the
The molar ratio of three components is 1:(1.1~2.0): (0.0001~0.02)；
(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 furyl copolyesters, the furyl
The segmented structure of copolyesters is network-like structure.
2. the preparation method of furyl copolyesters according to claim 1, which is characterized in that carbonyl described in step (1)
Acid anhydrides of the quantity more than or equal to 3 includes 1,2,4- benzenetricarboxylic anhydride, pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids two
Acid anhydride, 4,4 '-biphenyl ether dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 4,4 '-(hexafluoro isopropyl alkene) two titanic anhydrides, chlorination are inclined
At least one of benzenetricarboxylic anhydride.
3. the preparation method of furyl copolyesters according to claim 1, which is characterized in that furans described in step (1)
Dicarboxylic acid esters compound includes furandicarboxylic acid dimethyl ester, furandicarboxylic acid diethylester, at least one in furandicarboxylic acid dibutyl ester
Kind.
4. the preparation method of furyl copolyesters according to claim 1, which is characterized in that fat described in step (1)
Race's dihydric alcohol includes ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, ring
At least one of hexane dimethanol, 2,2,4,4- tetramethyl -1,3- cyclobutanediol, neopentyl glycol；
The aromatic diol includes 2- [4- (2- ethoxy) phenoxy group] ethyl alcohol, 1,3- bis- (2- hydroxy ethoxy) benzene, bis-phenol
A, at least one of bisphenol S.
5. the preparation method of furyl copolyesters according to claim 1, which is characterized in that reacted described in step (2)
Temperature be 150 DEG C~220 DEG C, time of reaction is 0.5h~5.0h.
6. the preparation method of furyl copolyesters according to claim 1, which is characterized in that be esterified described in step (2)
The mole of catalyst is the 0.05%~1% of the mole of first component.
7. the preparation method of furyl copolyesters according to claim 1, which is characterized in that pre-polymerization described in step (3)
The reaction temperature of reaction is 180 DEG C~260 DEG C, and the reaction time is 0.5h~4.0h.
8. the preparation method of furyl copolyesters according to claim 1, which is characterized in that further include in step (3) to
Polycondensation catalyst is added in first intermediate product, the mole of the polycondensation catalyst is the mole of first component
0.05%~0.5%；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 furyl copolyesters according to claim 1, which is characterized in that polycondensation described in step (4)
The reaction temperature of reaction is 200 DEG C~260 DEG C, and the reaction time is 0.5h~4h.
10. a kind of furyl copolyesters, which is characterized in that the preparation method as described in any one of claim 1~9 obtains, described
The segmented structure of furyl copolyesters is network-like structure.
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| CN110229480B (en) * | 2019-07-10 | 2021-09-10 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polybutylene furan dicarboxylate and polybutylene terephthalate blend |
| CN113736349A (en) * | 2021-09-14 | 2021-12-03 | 安徽华辉塑业科技股份有限公司 | Corrosion-resistant epoxy resin coating and preparation method thereof |
| CN114466880A (en) * | 2021-10-20 | 2022-05-10 | 擎天材料科技有限公司 | Saturated polyester copolymer and preparation method and application thereof |
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| 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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| CN113736349A (en) * | 2021-09-14 | 2021-12-03 | 安徽华辉塑业科技股份有限公司 | Corrosion-resistant epoxy resin coating and preparation method thereof |
| CN113736349B (en) * | 2021-09-14 | 2022-05-17 | 安徽华辉塑业科技股份有限公司 | Corrosion-resistant epoxy resin coating and preparation method thereof |
| CN114466880A (en) * | 2021-10-20 | 2022-05-10 | 擎天材料科技有限公司 | Saturated polyester copolymer and preparation method and application thereof |
| WO2023065131A1 (en) * | 2021-10-20 | 2023-04-27 | 擎天材料科技有限公司 | Saturated polyester copolymer, and preparation method therefor and use thereof |
| CN114466880B (en) * | 2021-10-20 | 2023-07-07 | 擎天材料科技有限公司 | Saturated polyester copolymer and preparation method and application thereof |
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Application publication date: 20190528 Assignee: SUZHOU YACOO SCIENCE Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980041223 Denomination of invention: Furan based copolyester and its preparation method Granted publication date: 20210824 License type: Exclusive License Record date: 20230905 |