CN102432847B - 2,5-furandicarboxylic-terephthalic-aliphatic copolyester and preparation method thereof - Google Patents
2,5-furandicarboxylic-terephthalic-aliphatic copolyester and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of 2,5-furandicarboxylic acid-terephthalic acid (TPA)-aliphatic dihydroxy alcohol copolyesters, with the second repetitive unit shown in the first repetitive unit shown in formula (I) and formula (II), wherein x=2~8; The molar ratio of first repetitive unit and second repetitive unit is 1: 1000~1000: 1. Provided by the invention 2,5- furandicarboxylic-terephthalic-aliphatic copolyester is similar to poly terephthalic acid glycol ester structure, with more superperformance similar with its, it can be used for the materials such as preparation engineering plastics and film, moreover, the 2,5-furandicarboxylic acid as one of raw material can be based on renewable resource, it is from a wealth of sources, it is not influenced by petroleum resources are increasingly depleted. The present invention also provides a kind of preparation methods of 2,5- furandicarboxylic-terephthalic-aliphatic copolyester.
Description
Technical field
The present invention relates to the polyester technical field, relate in particular to a kind of FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters and preparation method thereof.
Background technology
The poly terephthalic acid diol ester is the important polyester of a class, it is widely used in various fields,, and be widely used in the processing of the materials such as engineering plastics and mechanical component owing to having good fibre-forming performance, good mechanical property, wear resistance, creep resistance and electrical insulating property such as polyethylene terephthalate.
At present, prior art discloses the multiple preparation method of poly terephthalic acid diol ester, as utilizes the synthetic poly terephthalic acid diol ester of reaction of terephthalic acid and dibasic alcohol.Wherein, the molecular formula as the terephthalic acid of one of raw material is C
8H
6O
4, molecular weight is 166.13, although it is the di-carboxylic acid of output maximum, also is a kind of Chemicals that rely on petroleum resources, and is not only expensive, and day by day exhausted along with petroleum resources, the output of terephthalic acid also can be restricted.The industrial chemicals that adopts the whole replacements of renewable resources or Partial Replacement to rely on petroleum resources has become the in recent years focus of research, and seek all to replace or the Partial Replacement terephthalic acid based on the di-carboxylic acid of renewable resources, the polyester that preparation has a superperformance similar to the poly terephthalic acid diol ester is wherein one of study hotspot just.
2, the 5-furandicarboxylic acid is a kind of di-carboxylic acid of wide material sources, can renewable resources be the initial feed preparation, if any following two kinds of methods: the fructose that (1) extensively is present in the food such as honey, fruit, roots vegetable forms 5 hydroxymethyl furfural through dehydration, 5 hydroxymethyl furfural obtains FDCA after oxidation; (2) semi-lactosi, melampyrum or the galacturonic that extensively are present in the materials such as milk-product, beet, natural resin generate tetrahydroxyadipic acid through nitric acid oxidation, and tetrahydroxyadipic acid and reaction of hydrogen bromide obtain FDCA.Simultaneously, the molecular formula of FDCA is C
6H
4O
5, molecular weight is that 156.09, CAS accession number is 3238-40-2, and has the FDCA of formula (III) structure and the terephthalic acid structural similitude shown in the formula (IV).Therefore, can replace the part terephthalic acid by FDCA, preparation and poly terephthalic acid diol ester structural similitude, the polyester that performance is suitable.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of 2,5-furandicarboxylic-terephthalic-aliphatic copolyester and preparation method thereof, the present invention is with can be based on 2 of renewable resources, the 5-furandicarboxylic acid is one of raw material, preparation FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters, it has the superperformance similar to the poly terephthalic acid diol ester.
The invention provides a kind of FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters, have the second repeating unit shown in the first repeating unit shown in the formula (I) and the formula (II):
Wherein, x=2～8;
The mol ratio of described the first repeating unit and described the second repeating unit is 1: 1000～1000: 1.
The present invention also provides the preparation method of a kind of FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters, may further comprise the steps:
Under the effect of catalyzer, FDCA, terephthalic acid and aliphatic dihydroxy alcohol generation esterification obtain the first intermediate product;
Described the first intermediate product is carried out polycondensation, obtain FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters.
Preferably, the mol ratio of described terephthalic acid and FDCA is 1: 1000～1000: 1.
Preferably, described aliphatic dihydroxy alcohol is ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol or 1,8-ethohexadiol.
Preferably, the mol ratio of the summation of described FDCA and terephthalic acid and aliphatic dihydroxy alcohol is 1: 1.0～1: 3.0.
Preferably, described catalyzer is tin class catalyzer or titanium class catalyzer.
Preferably, the quality of described catalyzer be FDCA, terephthalic acid and aliphatic dihydroxy alcohol total mass 0.018%～0.30%.
Preferably, the temperature of described esterification is 170 ℃～230 ℃, and the time of described esterification is 120min～300min, and the pressure of described esterification is 0.1MPa～0.4MPa.
Preferably, polycondensation occurs in described the first intermediate product in the presence of Phosphorus compound.
Preferably, the temperature of described polycondensation is 200 ℃～280 ℃, and the time of described polycondensation is 120min～480min, and the pressure of described polycondensation is 0.1Pa～100Pa
Compared with prior art, the present invention carries out esterification with FDCA, terephthalic acid and aliphatic dihydroxy alcohol under the effect of catalyzer, obtain the first intermediate product; Described the first intermediate product is carried out polycondensation, obtain FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters.Provided by the invention described 2, the 5-furandicarboxylic-terephthalic-aliphatic copolyester, have the second repeating unit shown in the first repeating unit shown in the formula (I) and the formula (II), the mol ratio of described the first repeating unit and described the second repeating unit is 1: 1000～1000: 1.Carboxylic acid raw material of the present invention comprises 2, the 5-furandicarboxylic acid, because 2,5-furandicarboxylic acid and terephthalic acid structural similitude, performance is close, therefore, 2, the 5-furandicarboxylic acid can react with aliphatic dihydroxy alcohol, the polyester of preparation and poly terephthalic acid diol ester structural similitude, simultaneously, carboxylic acid raw material of the present invention also comprises terephthalic acid, 2, common and the aliphatic dihydroxy alcohol of two kinds of carboxylic acid raw materials of 5-furandicarboxylic acid and terephthalic acid reacts, the FDCA-terephthalic acid of the second repeating unit shown in the first repeating unit shown in (I) and the formula (II) that obtains having formula-aliphatic dihydroxy alcohol copolyesters.In the present invention, the mol ratio that satisfies described the first repeating unit and described the second repeating unit be 1: 1000～1000: 12, the 5-furandicarboxylic-terephthalic-aliphatic copolyester, not only with poly terephthalic acid diol ester structural similitude, and have and its more similar superperformance, can be widely used in the processing of the materials such as engineering plastics and mechanical component.In addition, can be based on renewable resources as the FDCA of one of raw material, wide material sources can not be subjected to the impact of petroleum resources exhaustion.
Description of drawings
The infrared spectrogram of FDCA-terephthalic acid that Fig. 1 provides for the embodiment of the invention 1-glycol copolyester;
The carbon-13 nmr spectra figure of FDCA-terephthalic acid that Fig. 2 provides for the embodiment of the invention 1-glycol copolyester.
Embodiment
The invention provides a kind of FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters, have the second repeating unit shown in the first repeating unit shown in the formula (I) and the formula (II):
Wherein, x=2～8;
The mol ratio of described the first repeating unit and described the second repeating unit is 1: 1000～1000: 1.
In the present invention, infrared spectrogram and carbon-13 nmr spectra figure all prove, described 2, the 5-furandicarboxylic-terephthalic-aliphatic copolyester has the second repeating unit shown in the first repeating unit shown in the formula (I) and the formula (II), wherein, x=2～8, preferred x=2～5, more preferably x=2～4.
The present invention does not have particular restriction to the polymerization degree of described the first repeating unit and described the second repeating unit, and the polymerization degree of described the first repeating unit is preferably 1～200, and the polymerization degree of described the second repeating unit is preferably 1～200.
Along with the mol ratio of FDCA and terephthalic acid is different, described the first repeating unit is different from the mol ratio of described the second repeating unit, and then the performance of FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters is just different.In the present invention, the mol ratio of described the first repeating unit and described the second repeating unit is 1: 1000～1000: 1, be preferably 1: 100～100: 1, more preferably 1: 50～50: 1, most preferably be 1: 1.0, experiment shows, the mol ratio that satisfies described the first repeating unit and described the second repeating unit be 1: 1000～1000: 12, the 5-furandicarboxylic-terephthalic-aliphatic copolyester, its performance is more similar to the performance of poly terephthalic acid diol ester, can be by extruding, extrude, injection, the complete processing such as fibroblast or film forming is used for the material preparations such as engineering plastics and film.
In the present invention, the limiting viscosity 〉=0.2dL/g of described FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters;
The second-order transition temperature of described FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters is 20 ℃～85 ℃;
The color of described FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters is shallow brown.
The present invention also provides the preparation method of a kind of FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters, may further comprise the steps:
Under the effect of catalyzer, FDCA, terephthalic acid and aliphatic dihydroxy alcohol generation esterification obtain the first intermediate product;
Described the first intermediate product is carried out polycondensation, obtain FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters.
The present invention at first mixes FDCA, terephthalic acid and aliphatic dihydroxy alcohol, adds catalyzer and carries out esterification, obtains the first intermediate product.
FDCA is as raw material widely to originate in the present invention, and the present invention does not have particular restriction to the source of described FDCA, can be for non-full bio-based, also can be for full bio-based.The structure of described FDCA and performance and terephthalic acid are close, can react with aliphatic dihydroxy alcohol the polyester of preparation and poly terephthalic acid diol ester structural similitude.
Although 2,5-furandicarboxylic acid and terephthalic acid structural similitude, but still variant, when especially adopting the direct esterification reaction method to prepare polyester, the difference that produces is comparatively obvious: because the aromaticity of furan nucleus is less than phenyl ring, so, 2, the close power of the carboxyl carbon of 5-furandicarboxylic acid is weaker than the close power of the carboxyl carbon of terephthalic acid, cause 2, the activation energy of 5-furandicarboxylic acid and aliphatic dihydroxy alcohol generation esterification improves, thus the transfer reaction when affect polycondensation of polyester, and then affect the viscosity of the polyester that finally obtains, second-order transition temperature and stretching thereof, the physicalies such as yield strength.
The present invention is take terephthalic acid as raw material, described terephthalic acid and 2, the 5-furandicarboxylic acid can be jointly and aliphatic dihydroxy alcohol react, 2 of the second repeating unit shown in the first repeating unit shown in (I) and the formula (II) that obtains having formula, the 5-furandicarboxylic-terephthalic-aliphatic copolyester, its structure is similar to the poly terephthalic acid diol ester with performance.
The present invention does not have particular restriction to described aliphatic dihydroxy alcohol, and described aliphatic dihydroxy alcohol is preferably ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol or 1,8-ethohexadiol.
The present invention does not have particular restriction to described catalyzer, be preferably the higher tin class catalyzer of catalytic activity or titanium class catalyzer, described tin class catalyzer is tin protoxide, stannous octoate, tin protochloride, tin protobromide, tin protoiodide, stannous acetate, stannous oxalate, stannous sulfate or tindihydroxide etc. more preferably, most preferably is tin protoxide, stannous acetate or stannous oxalate; Described titanium class catalyzer is tetraethyl titanate, tetrabutyl titanate, titanium isopropylate or titanium dioxide etc. more preferably, most preferably is tetrabutyl titanate.
In the presence of catalyzer, FDCA, terephthalic acid and aliphatic dihydroxy alcohol generation esterification generate the first intermediate product, described the first intermediate product comprises that FDCA mixes diol ester, the mixed diol ester of terephthalic acid and part oligopolymer etc.
Owing to regulating terephthalic acid and 2, the mol ratio of 5-furandicarboxylic acid, can synthesize the different copolyesters of performance, in the present invention, the mol ratio of described terephthalic acid and FDCA be preferably 1: 1000～1000: 1, more preferably 1: 100～100: 1, most preferably be 1: 1.0, the FDCA-terephthalic acid that obtains-aliphatic dihydroxy alcohol copolyesters has the superperformance more similar to the poly terephthalic acid diol ester.
The summation of described FDCA and terephthalic acid and the mol ratio of aliphatic dihydroxy alcohol be preferably 1: 1.0～and 1: 3.0, more preferably 1: 1.3～1: 2.5, most preferably be 1: 1.5～1: 2.0.The quality optimization of described catalyzer be described FDCA, terephthalic acid and aliphatic dihydroxy alcohol total mass 0.018%～0.30%, more preferably 0.02%～0.20%, most preferably be 0.04%～0.10%.
In the present invention, the temperature of described esterification is preferably 170 ℃～230 ℃, more preferably 180 ℃～220 ℃, most preferably is 190 ℃～210 ℃; The pressure of described esterification is preferably 0.1MPa～0.4MPa, more preferably 0.2MPa～0.3MPa; The time of described esterification is preferably 120min～300min, and more preferably 150min～250min most preferably is 180min～230min.
After esterification finishes, the first intermediate product that generates is carried out polycondensation, obtain shallow tan FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters.The pressure of described polycondensation is preferably 0.1Pa～100Pa, and more preferably 10Pa～80Pa most preferably is 20Pa～60Pa; The present invention preferably in 20min～30min with Pressure Drop to 0.1Pa～100Pa.The temperature of described polycondensation is preferably 200 ℃～280 ℃, more preferably 210 ℃～270 ℃, most preferably is 220 ℃～250 ℃; The time of described polycondensation is preferably 120min～480min, and more preferably 180min～460min most preferably is 240min～450min.
In the present invention, polycondensation preferably occurs in described the first intermediate product in the presence of Phosphorus compound.Described Phosphorus compound can improve catalytic activity and the thermostability of described catalyzer, not only can reduce side reaction, and can Reaction time shorten, improves reaction yield.Described Phosphorus compound is preferably trialkylphosphate, Triphenyl phosphate or phosphoric acid, more preferably trimethyl phosphite 99.The quality optimization of described Phosphorus compound be described FDCA, terephthalic acid and aliphatic dihydroxy alcohol total mass 0.001%～0.007%, more preferably 0.002%～0.006%, most preferably be 0.003%～0.005%.
After obtaining FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters, it is carried out Infrared spectroscopy and nuclear magnetic resonance spectroscopy.Gained infrared spectrogram and carbon-13 nmr spectra figure all prove, described FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters has the second repeating unit shown in the first repeating unit shown in the formula (I) and the formula (II).
Described FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters is dissolved in the mixed solvent that mass ratio is 1: 1 phenol and tetrachloroethane at 25 ℃, measures its limiting viscosity.Measurement result shows, the limiting viscosity 〉=0.2dL/g of described FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters.
Utilize METTLER TOLEDO DSC1 differential scanning calorimeter to measure described 2; the second-order transition temperature of 5-furandicarboxylic-terephthalic-aliphatic copolyester; condition determination is as follows: under nitrogen protection; heat-up rate is 10 ℃/min, and the temperature range of mensuration is 0 ℃～280 ℃.Measurement result shows, the second-order transition temperature of described FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters is 20 ℃～85 ℃.
Experiment shows, provided by the invention 2, the 5-furandicarboxylic-terephthalic-aliphatic copolyester has the structure similar to the poly terephthalic acid diol ester, have more the superperformance suitable with it, can by push, extrude, the complete processings such as injection, fibroblast or film forming are used for the material preparations such as engineering plastics and film.In addition, the FDCA that the present invention adopts can renewable resources be the initial feed preparation, and wide material sources can not be subjected to the day by day exhausted impact of petroleum resources.
In order to further specify the present invention, below in conjunction with embodiment FDCA-terephthalic acid provided by the invention-aliphatic dihydroxy alcohol copolyesters and preparation method thereof is described in detail.
Embodiment 1
With 3mol2,5-furandicarboxylic acid, 3mol terephthalic acid and 7.2mol ethylene glycol mix, adding quality is 2,0.018% tetrabutyl titanate of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, under nitrogen protection, be that 190 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 200min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,0.004% trimethyl phosphite 99 of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, be warming up to 220 ℃, in 20min, Pressure Drop is reacted to 20Pa, behind the reaction 260min, obtain shallow tan FDCA-terephthalic acid-glycol copolyester.
Described FDCA-terephthalic acid-glycol copolyester is carried out Infrared spectroscopy, and analytical results is referring to Fig. 1, and Fig. 1 is the infrared spectrogram of FDCA-terephthalic acid of obtaining of the embodiment of the invention 1-glycol copolyester.As shown in Figure 1, be 727cm in wave number
-1～729cm
-1The zone has occurred on phenyl ring and the furan nucleus-the C-H stretching vibration peak; Be 830cm in wave number
-1And 873cm
-1The place is phenyl ring para-orientation functional group characteristic peak; Be 1018cm in wave number
-1What the place occurred is the breathing vibration peak of furan nucleus; Be 1093cm in wave number
-1The place occurs on the furan nucleus-the C-O-C-stretching vibration peak; Be 1220cm in wave number
-1To be connected with furan nucleus appear in the place-the C-O stretching vibration peak of COOC-; Be 1253cm in wave number
-1To be connected with phenyl ring appear in the place-the C-O stretching vibration peak of COOC-; Be 1418cm in wave number
-1And 1514cm
-1The framework characteristic peak of furan nucleus has appearred in the place; Be 1489cm in wave number
-1And 1583cm
-1The framework characteristic peak of phenyl ring has appearred in the place; Be 1718cm in wave number
-1C=O key stretching vibration peak has appearred in the place; Be 2964cm in wave number
-1-2968cm
-1The zone has occurred-the C-H stretching vibration peak.In sum, described FDCA-terephthalic acid-glycol copolyester has the second repeating unit shown in the first repeating unit shown in the formula (V) and the formula (VI).
Take deuterium for trifluoracetic acid as solvent to described 2,5-furandicarboxylic acid-terephthalic acid-glycol copolyester carries out nuclear magnetic resonance spectroscopy, analytical results is referring to Fig. 2, and Fig. 2 is the carbon-13 nmr spectra figure of FDCA-terephthalic acid of obtaining of the embodiment of the invention 1-glycol copolyester.As shown in Figure 2, the peak of 64.13ppm and 64.21ppm chemical shift place belongs to the carbon atom on the methylene radical; 120.40ppm and the peak of 120.45ppm chemical shift place belongs to the carbon atom that does not have substituted radical on the furan nucleus; 130.11ppm the peak of chemical shift place belongs to the carbon atom that does not have substituted radical on the phenyl ring; 133.57ppm and the peak of 133.60ppm chemical shift place belongs to the carbon atom that substituted radical is arranged on the phenyl ring; 146.57ppm and the peak of 146.61ppm chemical shift place belongs to the carbon atom that substituted radical is arranged on the furan nucleus; 160.56ppm the peak of chemical shift place belongs to the carbonylic carbon atom that links to each other with furan nucleus; 168.76ppm belong to the carbonylic carbon atom that links to each other with phenyl ring with the peak of 168.80ppm chemical shift place.In sum, described FDCA-terephthalic acid-glycol copolyester has the second repeating unit shown in the first repeating unit shown in the formula (V) and the formula (VI):
Measure the limiting viscosity of described FDCA-terephthalic acid-glycol copolyester, its limiting viscosity is 0.30dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-glycol copolyester, its second-order transition temperature is 70.60 ℃.
Embodiment 2
With 3mol2,5-furandicarboxylic acid, 3mol terephthalic acid and 9.6mol ethylene glycol mix, adding quality is 2,0.018% tetrabutyl titanate of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, under nitrogen protection, be that 190 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 200min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,0.004% trimethyl phosphite 99 of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, be warming up to 220 ℃, in 20min, Pressure Drop is reacted to 50Pa, behind the reaction 360min, obtain shallow tan FDCA-terephthalic acid-glycol copolyester.
Measure the limiting viscosity of described FDCA-terephthalic acid-glycol copolyester, its limiting viscosity is 0.42dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-glycol copolyester, its second-order transition temperature is 69.80 ℃.
Embodiment 3
With 3mol2,5-furandicarboxylic acid, 3mol terephthalic acid and 9.6mol ethylene glycol mix, adding quality is 2,0.03% tetrabutyl titanate of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, under nitrogen protection, be that 190 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 200min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,0.004% trimethyl phosphite 99 of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, be warming up to 220 ℃, in 20min, Pressure Drop is reacted to 50Pa, behind the reaction 360min, obtain shallow tan FDCA-terephthalic acid-glycol copolyester.
Measure the limiting viscosity of described FDCA-terephthalic acid-glycol copolyester, its limiting viscosity is 0.35dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-glycol copolyester, its second-order transition temperature is 65.77 ℃.
Embodiment 4
With 3mol2,5-furandicarboxylic acid, 3mol terephthalic acid and 9.6mol ethylene glycol mix, adding quality is 2,0.03% tetrabutyl titanate of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, under nitrogen protection, be that 190 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 200min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,0.004% trimethyl phosphite 99 of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, be warming up to 220 ℃, in 20min, Pressure Drop is reacted to 50Pa, behind the reaction 480min, obtain shallow tan FDCA-terephthalic acid-glycol copolyester.
Measure the limiting viscosity of described FDCA-terephthalic acid-glycol copolyester, its limiting viscosity is 0.32dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-glycol copolyester, its second-order transition temperature is 72.60 ℃.
Embodiment 5
With 3mol2,5-furandicarboxylic acid, 3mol terephthalic acid and 6mol ethylene glycol mix, adding quality is 2,0.03% tetrabutyl titanate of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, under nitrogen protection, be that 190 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 200min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,0.007% trimethyl phosphite 99 of the total mass of 5-furandicarboxylic acid, terephthalic acid and ethylene glycol, be warming up to 250 ℃, in 20min, Pressure Drop is reacted to 50Pa, behind the reaction 480min, obtain shallow tan FDCA-terephthalic acid-glycol copolyester.
Measure the limiting viscosity of described FDCA-terephthalic acid-glycol copolyester, its limiting viscosity is 0.31dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-glycol copolyester, its second-order transition temperature is 80.40 ℃.
Embodiment 6
With 3mol2,5-furandicarboxylic acid, 3mol terephthalic acid and 9.6mol1, ammediol mixes, the adding quality is 0.03% tetrabutyl titanate of the total mass of FDCA, terephthalic acid and 1,3-PD, under nitrogen protection, be that 190 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 200min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,5-furandicarboxylic acid, terephthalic acid and 1,0.007% trimethyl phosphite 99 of the total mass of ammediol, be warming up to 250 ℃, in 20min, Pressure Drop reacted to 50Pa, behind the reaction 480min, obtain shallow tan FDCA-terephthalic acid-propanediol copolyester.
Measure the limiting viscosity of described FDCA-terephthalic acid-propanediol copolyester, its limiting viscosity is 0.53dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-propanediol copolyester, its second-order transition temperature is 50.91 ℃.
Embodiment 7
With 0.001mol2,5-furandicarboxylic acid, 1mol terephthalic acid and 3.003mol1, ammediol mixes, the adding quality is 0.05% tetrabutyl titanate of the total mass of FDCA, terephthalic acid and 1,3-PD, under nitrogen protection, be that 200 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 200min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,5-furandicarboxylic acid, terephthalic acid and 1,0.007% trimethyl phosphite 99 of the total mass of ammediol, be warming up to 240 ℃, in 20min, Pressure Drop reacted to 50Pa, behind the reaction 480min, obtain shallow tan FDCA-terephthalic acid-propanediol copolyester.
Measure the limiting viscosity of described FDCA-terephthalic acid-propanediol copolyester, its limiting viscosity is 0.75dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-propanediol copolyester, its second-order transition temperature is 75.00 ℃
Embodiment 8
With 1mol2,5-furandicarboxylic acid, 0.001mol terephthalic acid and 3.003mol1, the 8-ethohexadiol mixes, the adding quality is 0.04% tetrabutyl titanate of the total mass of FDCA, terephthalic acid and 1,8-ethohexadiol, under nitrogen protection, be that 210 ℃, pressure are to carry out esterification under the condition of 0.25MPa in temperature, behind the reaction 180min, obtain the first intermediate product;
After esterification finishes, continuing to add quality is 2,5-furandicarboxylic acid, terephthalic acid and 1,0.007% trimethyl phosphite 99 of the total mass of 8-ethohexadiol, be warming up to 230 ℃, in 25min, Pressure Drop reacted to 50Pa, behind the reaction 400min, obtain shallow tan FDCA-terephthalic acid-ethohexadiol copolyesters.
Measure the limiting viscosity of described FDCA-terephthalic acid-ethohexadiol copolyesters, its limiting viscosity is 0.64dL/g.
Measure the second-order transition temperature of described FDCA-terephthalic acid-ethohexadiol copolyesters, its second-order transition temperature is 22.00 ℃
Comparative example 1
6mol terephthalic acid and 6mol ethylene glycol are mixed, react according to the preparation method of embodiment 5, obtain polyethylene terephthalate.
Measure the second-order transition temperature of described polyethylene terephthalate, its second-order transition temperature is 79.00 ℃
Comparative example 2
With 6mol2,5-furandicarboxylic acid and 6mol ethylene glycol mix, and react according to the preparation method of embodiment 5, obtain poly-FDCA glycol ester.
Measure the second-order transition temperature of described poly-FDCA glycol ester, its second-order transition temperature is 89.97 ℃
Comparative example 3
With 6mol terephthalic acid and 9.6mol1, ammediol mixes, and reacts according to the preparation method of embodiment 6, obtains Poly(Trimethylene Terephthalate).
Measure the second-order transition temperature of described Poly(Trimethylene Terephthalate), its second-order transition temperature is 54.00 ℃
Comparative example 4
With 6mol2,5-furandicarboxylic acid and 9.6mol1, ammediol mixes, and reacts according to the preparation method of embodiment 6, obtains poly-FDCA propylene glycol ester.
Measure the second-order transition temperature of described poly-FDCA propylene glycol ester, its second-order transition temperature is 57.90 ℃
With embodiment 5,6 and comparative example 1～4 in the measurement result of second-order transition temperature of products therefrom correspondingly compare, comparative result sees Table 1, table 1 is embodiment 5,6 and the measurement result of the second-order transition temperature of comparative example 1～4 products therefrom.
Table 1 embodiment 5,6 and the measurement result of the second-order transition temperature of comparative example 1～4 products therefrom
As shown in Table 1, provided by the invention 2, the second-order transition temperature of 5-furandicarboxylic-terephthalic-aliphatic copolyester and poly terephthalic acid diol ester are more close, show provided by the invention 2, the 5-furandicarboxylic-terephthalic-aliphatic copolyester has the more similar superperformance to the poly terephthalic acid diol ester, can be used for the material preparations such as engineering plastics and film.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1.2 the 5-furandicarboxylic-terephthalic-aliphatic copolyester has the second repeating unit shown in the first repeating unit shown in the formula (I) and the formula (II):
Wherein, x=3,5,6,7 or 8;
The mol ratio of described the first repeating unit and described the second repeating unit is 1:1000～1000:1.
2. the preparation method of FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters may further comprise the steps:
Under the effect of catalyzer, FDCA, terephthalic acid and aliphatic dihydroxy alcohol generation esterification obtain the first intermediate product;
Described the first intermediate product is carried out polycondensation, obtain FDCA-terephthalic acid-aliphatic dihydroxy alcohol copolyesters.
3. preparation method according to claim 2 is characterized in that, the mol ratio of described terephthalic acid and FDCA is 1:1000～1000:1.
4. preparation method according to claim 2 is characterized in that, described aliphatic dihydroxy alcohol is ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol or 1,8-ethohexadiol.
5. preparation method according to claim 2 is characterized in that, the summation of described FDCA and terephthalic acid and the mol ratio of aliphatic dihydroxy alcohol are 1:1.0～1:3.0.
6. preparation method according to claim 2 is characterized in that, described catalyzer is tin class catalyzer or titanium class catalyzer.
7. preparation method according to claim 2 is characterized in that, the quality of described catalyzer be FDCA, terephthalic acid and aliphatic dihydroxy alcohol total mass 0.018%～0.30%.
8. preparation method according to claim 2 is characterized in that, the temperature of described esterification is 170 ℃～230 ℃, and the time of described esterification is 120min～300min, and the pressure of described esterification is 0.1MPa～0.4MPa.
9. preparation method according to claim 2 is characterized in that, described the first intermediate product in the presence of Phosphorus compound polycondensation occurs.
10. preparation method according to claim 2 is characterized in that, the temperature of described polycondensation is 200 ℃～280 ℃, and the time of described polycondensation is 120min～480min, and the pressure of described polycondensation is 0.1Pa～100Pa.
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| IN2014MN01416A (en) * | 2012-01-04 | 2015-04-03 | Pepsico Inc | |
| WO2013149157A1 (en) * | 2012-03-30 | 2013-10-03 | E. I. Du Pont De Nemours And Company | Polyesters and fibers made therefrom |
| CN102757552B (en) * | 2012-07-19 | 2014-01-08 | 苏州瀚海化学有限公司 | Water-soluble copolyester and preparation method thereof |
| CN103570925A (en) * | 2012-07-31 | 2014-02-12 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polyester and preparation method thereof |
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| CN108129644A (en) * | 2017-12-22 | 2018-06-08 | 中国科学院宁波材料技术与工程研究所 | A kind of furandicarboxylic acid copolyesters and preparation method thereof and application |
| CN108409949B (en) * | 2018-02-10 | 2019-07-26 | 中国科学院长春应用化学研究所 | A kind of 2,5- furandicarboxylic acid base copolyester material and preparation method thereof |
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| CN114133542B (en) * | 2021-12-15 | 2023-03-31 | 吉林建筑大学 | Bio-based copolyester and preparation method thereof |
| CN115232294A (en) * | 2022-07-15 | 2022-10-25 | 华润化学材料科技股份有限公司 | Copolyester material and preparation method and application thereof |
| CN115260505A (en) * | 2022-08-11 | 2022-11-01 | 中国科学院成都有机化学有限公司 | Tough furan dicarboxylic acid polyester and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298418A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Polyester film and methods for making same |
| WO2009135921A1 (en) * | 2008-05-08 | 2009-11-12 | Novamont S.P.A. | Aliphatic-aromatic biodegradable polyester |
| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
-
2011
- 2011-08-25 CN CN 201110246585 patent/CN102432847B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298418A (en) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | Polyester film and methods for making same |
| WO2009135921A1 (en) * | 2008-05-08 | 2009-11-12 | Novamont S.P.A. | Aliphatic-aromatic biodegradable polyester |
| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
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