CN109734886B - Copolyester containing furan ring and preparation method thereof - Google Patents
Copolyester containing furan ring and preparation method thereof Download PDFInfo
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Abstract
The invention relates to furan dicarboxylic acid copolyester and a preparation method thereof, wherein the chain segment structure of the furan ring-containing copolyester is a network structure and is formed by polymerizing a first component, a second component, a third component and a fourth component in a molar ratio of 1 (1.1-2.0) (0.0001-0.02), wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid esterified matter, the second component comprises at least one of aromatic dihydric alcohol and aliphatic dihydric alcohol, the third component comprises polyhydric alcohol with the hydroxyl number being more than or equal to 3, and the fourth component comprises anhydride with the carbonyl number being more than or equal to 3. In the preparation method, the polyol with the hydroxyl number being more than or equal to 3 and the anhydride with the carbonyl number being more than or equal to 3 are used as chain segment connection points, so that the chain segment structure of the furan ring-containing copolyester is expanded into a network structure, and the high molecular weight furan ring-containing copolyester which is colorless or light-colored and has excellent mechanical properties and gas barrier property is obtained.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a furan ring-containing copolyester and a preparation method thereof.
Background
At present, the bio-based polymer materials widely used mainly include polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), polybutylene succinate (PBS), and the like. However, they all belong to aliphatic polymers, and because of the lack of rigid aromatic ring structure in the molecular structure, their mechanical properties (such as strength, modulus, creep resistance, etc.) and heat resistance (such as thermo-mechanical properties, heat distortion temperature, etc.) are significantly lower than petroleum-based polymer materials such as polyethylene terephthalate (PET), Polycarbonate (PC), aromatic nylon (PA), bisphenol a Epoxy resin (Epoxy), etc., and their application range is severely limited.
The molecular structure of the 2, 5-furandicarboxylic acid (2,5-FDCA) contains aromatic rings, and the heat resistance and the mechanical property of the bio-based polymer material can be effectively improved when the bio-based polymer material is used for synthesizing the bio-based polymer material. Meanwhile, the oxygen barrier property of the furan ring-containing polyester material can be improved by 2-10 times compared with that of PET used for a packaging material, so that the quality guarantee period of agricultural products, fishes, meat products and the like can be effectively prolonged. However, the polyester materials currently produced with 2, 5-furandicarboxylic acid also tend to have some drawbacks, such as: the color is darker due to an excessively long reaction time, and the tensile modulus and the tensile strength are low due to a low molecular weight.
Disclosure of Invention
In view of the above, there is a need to provide a furan ring-containing copolyester and a preparation method thereof; in the preparation method, the polyol with the hydroxyl number being more than or equal to 3 and the anhydride with the carbonyl number being more than or equal to 3 are jointly used as chain segment connection points, so that the chain segment structure of the furan ring-containing copolyester is expanded from a linear structure to a network structure, and the colorless or light-colored high-molecular-weight furan ring-containing copolyester with excellent mechanical properties and gas barrier properties is obtained, and further the application requirements of the furan ring-containing copolyester in the fields of packaging materials, films, fibers, engineering plastics and the like can be better met.
A preparation method of a furan ring-containing copolyester comprises the following steps:
(1) providing a first component, a second component, a third component and a fourth component, wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid ester, the second component comprises at least one of aromatic diol and aliphatic diol, the third component comprises polyhydric alcohol with the number of hydroxyl groups being more than or equal to 3, and the fourth component comprises acid anhydride with the number of carbonyl groups being more than or equal to 3;
(2) mixing the first component, the second component, the third component, the fourth component and an esterification catalyst, and reacting in an inert atmosphere or a nitrogen atmosphere to obtain a first intermediate product, wherein the molar ratio of the first component to the fourth component to the second component to the third component to the fourth component is 1 (1.1-2.0) to 0.0001-0.025;
(3) under the vacuum condition, the first intermediate product is subjected to prepolymerization reaction to obtain a second intermediate product;
(4) and carrying out polycondensation reaction on the second intermediate product under a vacuum condition to obtain the furan ring-containing copolyester, wherein the chain segment structure of the furan ring-containing copolyester is a network structure.
In one embodiment, the acid anhydride having a carbonyl group number of 3 or more in step (1) includes at least one of 1,2, 4-trimellitic anhydride, pyromellitic anhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 4,4 '-diphenyl ether dianhydride, 3', 4,4 '-biphenyltetracarboxylic dianhydride, 4, 4' - (hexafluoroisopropylidene) dititanic anhydride, and chlorinated trimellitic anhydride.
In one embodiment, the polyol having a hydroxyl number of 3 or more in step (1) includes at least one of glycerol, butanetriol, 2-hydroxymethyl-2-methyl-1, 3-propanediol, butanetetraol, pentaerythritol, dipentaerythritol, pentanol, hexitol, and sugar alcohol.
In one embodiment, the sum of the molar amounts of the third component and the fourth component in step (2) is 0.05% to 3% of the molar amount of the first component.
In one embodiment, the reaction temperature in the step (2) is 150-220 ℃, and the reaction time is 0.5-5.0 h.
In one embodiment, the molar amount of the esterification catalyst in step (2) is 0.05 to 1% of the molar amount of the first component.
In one embodiment, the reaction temperature of the prepolymerization reaction in the step (3) is 180-260 ℃, and the reaction time is 0.5-4.0 h.
In one embodiment, step (3) further comprises adding a polycondensation catalyst to the first intermediate product, wherein the molar amount of the polycondensation catalyst is 0.05 to 0.5 percent of the molar amount of the first component; and/or
Adding a stabilizer to the first intermediate product, wherein the molar weight of the stabilizer is 0.05-0.5% of that of the first component; and/or
And adding an antioxidant into the first intermediate product, wherein the molar weight of the antioxidant is 0.05-0.5% of that of the first component.
In one embodiment, the reaction temperature of the polycondensation reaction in the step (4) is 200-260 ℃, and the reaction time is 0.5-4 h.
In the above-mentioned production method, after mixing the polyhydric alcohol having a hydroxyl number of 3 or more, the acid anhydride having a carbonyl number of 3 or more, the furan dicarboxylic acid or its esterified product and the dihydric alcohol, in the reaction process of the step (2), in addition to the esterification or transesterification of the furan dicarboxylic acid or its esterified product with the dihydric alcohol, the polyhydric alcohol having a hydroxyl number of 3 or more and the acid anhydride having a carbonyl number of 3 or more as the segment connecting points, the ring opening of the acid anhydride having a carbonyl number of 3 or more and the esterification or transesterification with the dihydric alcohol or the copolyester oligomer may also occur, and in the case that the reaction conditions are sufficient, the acid anhydride having a carbonyl number of 3 or more may be sufficiently reacted into the segment of the copolyester oligomer in the esterification stage, and the esterification or transesterification of the polyhydric alcohol having a hydroxyl number of 3 or more and the furan dicarboxylic acid or its esterified product or the polyester oligomer, thereby promoting the molecular chain segment structure of the copolyester oligomer of the first intermediate product to expand from a linear structure to a network structure and providing a precondition for the rapid growth of the molecular weight of the subsequent copolyester. Therefore, the preparation method can obtain the furan ring-containing copolyester with higher molecular weight through polycondensation in shorter time, thereby improving the mechanical properties such as tensile modulus, tensile strength and the like and the gas barrier property of the furan ring-containing copolyester. Meanwhile, the short polymerization time can effectively inhibit the occurrence of high-temperature side reactions such as decarboxylation of furan dicarboxylic acid and the like, and can avoid the problem of color deepening of the furan ring-containing copolyester due to the phenomena of high-temperature degradation, oxidation, discoloration and the like caused by the fact that the furan ring-containing copolyester exists in a high-temperature environment for a long time, so that colorless or light-colored furan ring-containing copolyester is obtained.
In addition, when the polyol with the hydroxyl number being more than or equal to 3 or the anhydride with the carbonyl number being more than or equal to 3 is independently added, after the addition amount reaches a certain value, the gel or crosslinking phenomenon can occur, the processing application of the polyester material is seriously limited, and the practical application value of the polyester material is lost. And after the polyol with the hydroxyl number being more than or equal to 3 and the anhydride with the carbonyl number being more than or equal to 3 are added at the same time, in the polymerization process of the copolyester, the anhydride with the carbonyl number being more than or equal to 3 can be subjected to ring opening and esterification or ester exchange reaction with the dihydric alcohol or the copolyester oligomer to obtain an intermediate substance, and after the intermediate substance is contacted with the polyol with the hydroxyl number being more than or equal to 3, the intermediate substance can be subjected to alcoholysis to a certain extent, so that the occurrence of gel or crosslinking phenomena caused by excessive anhydride is prevented. Meanwhile, the network structure of the copolyester molecular chain can be kept, and the purpose of improving the molecular weight of the copolyester is achieved.
The furan ring-containing copolyester is obtained by the preparation method, and the chain segment structure of the furan ring-containing copolyester is a network structure.
The chain segment structure of the furan ring-containing copolyester is a network structure, has high molecular weight, and has excellent mechanical properties such as tensile modulus, tensile strength and the like and gas barrier property. Meanwhile, the copolymer ester containing furan rings is colorless or light-colored, and can be used for manufacturing packaging materials, films, fibers, engineering plastics and the like.
Drawings
FIG. 1 is a photograph of a sample of the furan ring-containing copolyester obtained in example 1;
FIG. 2 is a diagram of the furan ring-containing copolyester obtained in example 11An H-NMR spectrum;
FIG. 3 is a DSC chart of the furan ring-containing copolyester obtained in example 1;
FIG. 4 is a TGA spectrum of a furan ring-containing copolyester prepared in example 1;
FIG. 5 is an FTIR spectrum of a furan ring-containing copolyester prepared in example 1;
FIG. 6 is a photograph of a sample of polyethylene 2, 5-furandicarboxylate obtained in comparative example 1.
Detailed Description
The furan ring-containing copolyester and the preparation method thereof provided by the present invention will be further described below.
The preparation method of the furan ring-containing copolyester comprises the following steps:
(1) providing a first component, a second component, a third component and a fourth component, wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid ester, the second component comprises at least one of aromatic diol and aliphatic diol, the third component comprises polyhydric alcohol with the number of hydroxyl groups being more than or equal to 3, and the fourth component comprises acid anhydride with the number of carbonyl groups being more than or equal to 3;
(2) mixing the first component, the second component, the third component, the fourth component and an esterification catalyst, and reacting in an inert atmosphere or a nitrogen atmosphere to obtain a first intermediate product, wherein the molar ratio of the first component to the fourth component to the second component to the third component to the fourth component is 1 (1.1-2.0) to 0.0001-0.025;
(3) under the vacuum condition, the first intermediate product is subjected to prepolymerization reaction to obtain a second intermediate product;
(4) and carrying out polycondensation reaction on the second intermediate product under a vacuum condition to obtain the furan ring-containing copolyester, wherein the chain segment structure of the furan ring-containing copolyester is a network structure.
In the step (1), the furan dicarboxylate includes at least one of furan dicarboxylic acid dimethyl ester, furan dicarboxylic acid diethyl ester and furan dicarboxylic acid dibutyl ester. Wherein, furan dicarboxylic acid or furan dicarboxylic acid ester is derived from biomass raw material, and the biomass raw material comprises at least one of cellulose, fructose, glucose and furoic acid.
In view of the better reactivity of dimethyl 2, 5-furandicarboxylate, it is preferable that the first component be dimethyl 2, 5-furandicarboxylate.
The aliphatic diol comprises at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol and neopentyl glycol.
The aromatic dihydric alcohol comprises at least one of 2- [4- (2-hydroxyethyl) phenoxy ] ethanol, 1, 3-bis (2-hydroxyethoxy) benzene, bisphenol A and bisphenol S.
The acid anhydride with the carbonyl number being more than or equal to 3 comprises at least one of 1,2, 4-trimellitic anhydride, pyromellitic anhydride, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, 4,4 '-diphenyl ether dianhydride, 3', 4,4 '-biphenyl tetracarboxylic dianhydride, 4, 4' - (hexafluoro-isopropenyl) dititanic anhydride and chlorinated trimellitic anhydride.
The polyhydric alcohol with the hydroxyl number being more than or equal to 3 comprises at least one of glycerol, butanetriol, 2-hydroxymethyl-2-methyl-1, 3-propanediol, butanetetraol, pentaerythritol, dipentaerythritol, pentanol, hexanehexol and sugar alcohol.
In the step (2), if the sum of the addition amounts of the third component and the fourth component is too low, only a few chain segment structures can be expanded from a linear state to a network state, and the obtained first intermediate product copolyester oligomer cannot provide enough network structures to achieve the purpose of improving the molecular weight of the polyester in a short time during the subsequent polycondensation reaction; if the sum of the addition amounts of the third component and the fourth component is too high, crosslinking can be quickly formed in the subsequent polycondensation process, and molecular chains are excessively entangled, so that the melt strength of the copolyester is too high, the melt index is too low, the fluidity is poor, and the processing application of a copolyester product is not facilitated. Preferably, the sum of the molar amounts of the third component and the fourth component is 0.05 to 3% of the molar amount of the first component.
Also, in view of smooth progress of the actual reaction and reduction of the cost of raw materials, it is preferable that the molar ratio of the first component to the second component is 1 (1.3 to 1.8), and more preferably 1 (1.4 to 1.7).
The esterification catalyst comprises at least one of anhydrous zinc acetate, anhydrous cobalt acetate, anhydrous manganese acetate and dibutyl tin oxide, and the molar weight of the esterification catalyst is 0.05-1% of that of the first component. In view of ensuring sufficient catalytic efficiency while the amount of the catalyst used is not excessively large, it is preferable that the molar amount of the esterification catalyst is 0.1 to 0.5% of the molar amount of the first component.
Specifically, the reaction comprises esterification reaction or ester exchange reaction, the reaction temperature is 150-220 ℃, and the reaction time is 0.5-5.0 h. In consideration of the boiling points of the aliphatic diol and the aromatic diol used, it is preferable that the reaction temperature is 150 to 200 ℃ and the reaction time is 2.0 to 5.0 hours.
In the esterification or ester exchange reaction process, in addition to the esterification or ester exchange reaction of the first component and the second component, the polyol with the hydroxyl number of 3 or more of the third component and the anhydride with the carbonyl number of 3 or more of the fourth component are taken as chain segment connection points, the ring opening of the anhydride with the carbonyl number of 3 or more and the esterification or ester exchange reaction of the anhydride with the diol or copolyester oligomer are also taken, under the condition that the reaction conditions are enough, the anhydride with the carbonyl number of 3 or more is fully reacted into the chain segment of the copolyester oligomer in the esterification stage, and the esterification or ester exchange reaction of the polyol with the hydroxyl number of 3 or more and furan dicarboxylic acid or an esterified product thereof or a polyester oligomer is also taken. Therefore, the molecular chain segment structure of the copolyester oligomer is promoted to expand from a linear structure to a network structure, and a precondition is provided for the rapid increase of the molecular weight of the subsequent copolyester.
In addition, when the polyol with the hydroxyl number being more than or equal to 3 or the anhydride with the carbonyl number being more than or equal to 3 is independently added, after the addition amount reaches a certain value, the gel or crosslinking phenomenon can occur, the processing application of the polyester material is seriously limited, and the practical application value of the polyester material is lost. And after the polyol with the hydroxyl number being more than or equal to 3 and the anhydride with the carbonyl number being more than or equal to 3 are added at the same time, in the polymerization process of the copolyester, the anhydride with the carbonyl number being more than or equal to 3 can be subjected to ring opening and esterification or ester exchange reaction with the dihydric alcohol or the copolyester oligomer to obtain an intermediate substance, and after the intermediate substance is contacted with the polyol with the hydroxyl number being more than or equal to 3, the intermediate substance can be subjected to alcoholysis to a certain extent, so that the occurrence of gel or crosslinking phenomena caused by excessive anhydride is prevented.
In the step (3), the vacuum degree of the prepolymerization reaction is 2000Pa or less, the reaction temperature is 180-260 ℃, and the reaction time is 0.5-4.0 h. Thereby, excess second component is removed and the first intermediate copolyester oligomer is further polymerized to obtain a second intermediate.
Specifically, the step (3) further comprises adding a polycondensation catalyst into the first intermediate product, wherein the molar weight of the polycondensation catalyst is 0.05-0.5% of the molar weight of the first component.
Wherein the polycondensation catalyst comprises at least one of antimony catalyst, germanium catalyst and tin catalyst, preferably at least one of antimony trioxide, ethylene glycol antimony, antimony acetate and dibutyl tin oxide.
It is understood that the esterification catalyst and the polycondensation catalyst can be the same, e.g., both dibutyl tin oxide is used. Therefore, the first intermediate product can be directly subjected to the pre-polycondensation reaction of step (2). However, it is considered that the esterification catalyst is partially deactivated after the esterification or transesterification reaction. Therefore, in the case where the esterification catalyst and the polycondensation catalyst are the same, it suffices to supplement a part of the polycondensation catalyst during the pre-polycondensation reaction in step (3).
Specifically, the step (3) further comprises adding a stabilizer or an antioxidant or a mixture of the stabilizer and the antioxidant into the first intermediate product, wherein the molar weight of the stabilizer or the antioxidant is 0.05-0.5% of that of the first component.
Wherein, the stabilizer can reduce the oxidative fracture of ester bonds, fatty chains, carbon-carbon bonds and the like under oxygen and prevent the occurrence of thermal decomposition. The stabilizer comprises at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite and ammonium dihydrogen phosphate.
The antioxidant can capture oxygen free radicals and eliminate trace oxygen, thereby reducing thermal decomposition reaction and oxidation side reaction. The antioxidant comprises a phenolic antioxidant, preferably at least one of antioxidant-1010, antioxidant-1076 and antioxidant-168.
In the step (4), the degree of vacuum of the polycondensation reaction is 200Pa or less, preferably 1.5Pa to 200Pa, the reaction temperature is 200 ℃ to 260 ℃, and the reaction time is 0.5h to 4 h. Thus, the second intermediate product is subjected to polycondensation reaction under suitable reaction conditions, and the molecular weight of the second intermediate product is gradually increased to obtain the furan ring-containing copolyester.
It will be appreciated that the degree of vacuum during the final polycondensation reaction is preferably lower than that during the prepolycondensation reaction. However, when the degree of vacuum in the course of the pre-polycondensation reaction is equal to or lower than that in the course of the final polycondensation reaction, there is no destructive influence on the reaction result.
Therefore, the first intermediate product with the chain segment structure of the network structure can be subjected to polycondensation polymerization in a shorter time to obtain the furan ring-containing copolyester with higher molecular weight, so that the mechanical properties such as tensile modulus, tensile strength and the like and the gas barrier property of the furan ring-containing copolyester can be improved.
Meanwhile, the short polymerization time can effectively inhibit the occurrence of high-temperature side reactions such as decarboxylation of furan dicarboxylic acid and the like, and can avoid the problem of color deepening of the furan ring-containing copolyester due to the phenomena of high-temperature degradation, oxidation, discoloration and the like caused by the fact that the furan ring-containing copolyester exists in a high-temperature environment for a long time, so that colorless or light-colored furan ring-containing copolyester is obtained.
The invention also provides the furan ring-containing copolyester, which is obtained by the preparation method, and the chain segment structure of the furan ring-containing copolyester is a network structure.
It can be understood that the proportion of the network structure chain segments of the furan ring-containing copolyester in all the chain segments is related to the addition amount of the third component and the fourth component, and in practical cases, the structure of a small part of the chain segments in the furan ring-containing copolyester may still be a linear structure.
Specifically, the third component is pentaerythritol, the fourth component is pyromellitic anhydride, and the chain segment structure of the furan ring-containing copolyester comprises:
wherein R is1、R2、R3、R4、R5、R6And R7Is one of a structural unit of aromatic dihydric alcohol, a structural unit of aliphatic dihydric alcohol, a structural unit of pentaerythritol or a structural unit of pyromellitic anhydride.
Specifically, the third component is glycerol as an example, the fourth component is pyromellitic anhydride as an example, and the chain segment structure of the furan ring-containing copolyester comprises:
wherein, R is8、R9、R10、R11、R12And R13Is one of a structural unit of aromatic diol, a structural unit of aliphatic diol, a structural unit of glycerol or a structural unit of pyromellitic anhydride.
Therefore, the segmented structure of the furan ring-containing copolyester is a network structure, and the molecular weight is high, so that the furan ring-containing copolyester can be endowed with more excellent mechanical properties such as tensile modulus, tensile strength and the like and gas barrier property. Meanwhile, the copolymer containing furan rings is colorless or light-colored, so that the application requirements of the copolymer in the fields of packaging materials, films, fibers, engineering plastics and the like can be better met, the manufacturing level of high-performance engineering plastics can be improved, and the high dependence on petroleum resources in the bio-based high polymer material industry can be promoted.
Hereinafter, the furan ring-containing copolyester and the preparation method thereof will be further described by the following specific examples.
In the following examples, the furan dicarboxylic acid copolyester of the present invention may be subjected to performance measurement by conventional methods and conventional equipment, with reference to national standard GB or other standards.
Specifically, nuclear magnetic resonance hydrogen spectrum (1H-NMR) on a Bruker 400AVANCE III Spectrometer type instrument, 400MHz, CF3COOD。
The intrinsic viscosity was measured by using phenol/tetrachloroethane (m: m ═ 1:1) as a solvent, at 30 ± 0.05 ℃ using an uge viscometer, and the intrinsic viscosity [. eta. ] of the copolyester was calculated according to the formulae (1) and (2).
ηsp＝(t1-t0)/t0 (1)
[η]＝[(1+1.4ηsp)1/2-1]/0.7c (2)
Wherein: t is t0The flow time(s) of the solvent; t is t1Is the flow time(s) of the copolyester solution; c is the concentration of the copolyester solutionAnd the concentration is 5 g/L.
Thermal analysis (DSC) was performed on a differential scanning calorimeter, N2Atmosphere, test scanning temperature 25-300 deg.c.
Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer Diamond TG/DTA with a heating rate of 10 ℃/min and a test temperature range of 50 ℃ to 800 ℃.
Oxygen and carbon dioxide barrier properties were measured by permeability testing using LabthinkVAC-V2, respectively, as CO2And O2Is used as an air source, under the conditions of 23 ℃ and 50% RH of temperature and humidity respectively, the selected sample size phi is 97mm, and the transmission area is 38.5cm2。
Example 1:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic anhydride, pentaerythritol and anhydrous zinc acetate into a reaction kettle according to a molar ratio of 1:1.6:0.003:0.0005:0.001, gradually heating to 185 ℃ under an inert atmosphere, and reacting for 4.5 hours. Then antimony trioxide with the molar weight of 0.12 percent of dimethyl 2, 5-furandicarboxylate, triphenyl phosphate with the molar weight of 0.2 percent and antioxidant-1010 with the molar weight of 0.1 percent are added into a reaction kettle, the mixture is slowly vacuumized to 600Pa to 2000Pa, and prepolymerization is carried out for 0.5h at the temperature of 220 ℃. Then gradually heating to 240 ℃, continuously vacuumizing to below 200Pa and reacting for 3h to obtain the furan ring-containing copolyester.
As is clear from FIG. 1, the copolymer ester having a furan ring obtained in this example was very pale yellow.
In FIG. 2, the solvent CF is at 11.31ppm3The peak of COOD was found to be a peak of hydrogen on the furan ring (2H) at 7.17ppm and a peak of hydrogen on the ethylene glycol chain (4H) at 4.59ppm, and thus, as is clear from FIG. 2, the furan ring-containing copolymer obtained in this example was polyethylene furandicarboxylate.
As can be seen from fig. 3, the glass transition temperature of the copolyester containing furan rings obtained in this example was 87.5 ℃.
As can be seen from FIG. 4, the thermal decomposition temperature (T) of the furan ring-containing copolyester obtained in this exampled,5％) At 368 ℃.
The furan ring-containing copolyester obtained in this example was found to have an intrinsic viscosity of 1.12dL/g and a tensile strength79.3MPa, tensile modulus of 2.7GPa, and carbon dioxide gas barrier property of 0.7 x 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.8X 10-12cm3·cm/cm2·s·cmHg。
Example 2:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic anhydride, pentaerythritol and anhydrous cobalt acetate into a reaction kettle according to the molar ratio of 1:1.5:0.003:0.001:0.0012, vacuumizing, filling nitrogen for replacement for three times, starting stirring, gradually heating to 180 ℃, and reacting for 4.5 hours. Then antimony trioxide of 0.15 percent of the molar weight of 2, 5-furandicarboxylic acid dimethyl ester, diphenyl phosphate of 0.2 percent and antioxidant-168 of 0.1 percent are added into a reaction kettle, the reaction kettle is slowly vacuumized to 300Pa to 2000Pa, and prepolymerization is carried out for 0.5h at the temperature of 225 ℃. Then gradually raising the temperature to 240 ℃, and continuing to pump the vacuum degree to be less than 200Pa for reaction for 2.5h to obtain the copolyester containing furan rings.
The copolymer ester containing furan rings obtained in this example was found to be very pale yellow, and it was found that the intrinsic viscosity was 0.98dL/g, the tensile strength was 76.8MPa, the tensile modulus was 2.5GPa, and the carbon dioxide gas barrier property was 0.8X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.0X 10-12cm3·cm/cm2·s·cmHg。
Example 3:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic anhydride, pentaerythritol and anhydrous cobalt acetate into a reaction kettle according to the molar ratio of 1:1.8:0.001:0.001:0.0015, vacuumizing, filling nitrogen for replacement for three times, starting stirring, gradually heating to 190 ℃, and reacting for 4 hours. Then adding antimony trioxide of 0.2 percent of the molar weight of 2, 5-furandicarboxylic acid dimethyl ester, diphenyl phosphate of 0.05 percent and antioxidant-1010 of 0.1 percent into a reaction kettle, slowly vacuumizing to 200 Pa-2000 Pa, and prepolymerizing for 1 hour at the temperature of 200 ℃. Then gradually heating to 245 ℃, continuously vacuumizing to below 200Pa, and reacting for 4h to obtain the furan ring-containing copolyester.
The copolymer ester containing furan rings obtained in this example was found to be very pale yellow in color and was found to be very specificThe viscosity is 0.93dL/g, the tensile strength is 76.6MPa, the tensile modulus is 2.5GPa, and the carbon dioxide gas barrier property is 0.8 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.0X 10-12cm3·cm/cm2·s·cmHg。
Example 4:
adding diethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic anhydride, pentaerythritol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.6:0.001:0.002:0.0015, vacuumizing, filling nitrogen for replacement for three times, starting stirring, gradually heating to 195 ℃, and reacting for 2 hours. Then antimony trioxide with the molar weight of 0.3 percent of diethyl 2, 5-furandicarboxylate, ammonium phosphate with the molar weight of 0.2 percent and antioxidant-1010 with the molar weight of 0.05 percent are added into a reaction kettle, the mixture is slowly vacuumized to 200Pa to 1800Pa, and prepolymerization is carried out for 1h at the temperature of 215 ℃. And gradually heating to 250 ℃, continuously vacuumizing, controlling the vacuum degree below 200Pa, and reacting for 2h to obtain the furan ring-containing copolyester.
The furan ring-containing copolyester obtained in the example is light yellow, and the intrinsic viscosity of the copolyester is 0.90dL/g, the tensile strength of the copolyester is 75.8MPa, the tensile modulus of the copolyester is 2.5GPa, and the carbon dioxide gas barrier property of the copolyester is 0.9 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.9X 10-12cm3·cm/cm2·s·cmHg。
Example 5:
adding 2, 5-furandicarboxylic acid diethyl ester, ethylene glycol, pyromellitic dianhydride, glycerol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.4:0.002:0.0005:0.001, vacuumizing, filling nitrogen for replacement for three times, then gradually heating to 180 ℃, and reacting for 3.5 hours. Then adding antimony trioxide of 0.2 percent of the molar weight of 2, 5-furan dicarboxylic acid diethyl ester, triphenyl phosphate of 0.2 percent and antioxidant-1010 of 0.1 percent, slowly vacuumizing to below 2000Pa, and carrying out prepolymerization for 0.5h at the temperature of 220 ℃. And then, raising the temperature to 240 ℃, continuously vacuumizing to below 200Pa, and reacting for 3.5 hours to obtain the furan ring-containing copolyester.
The furan ring-containing copolyester obtained in this example was very light yellow and, upon examination,the intrinsic viscosity is 0.89dL/g, the tensile strength is 76.1MPa, the tensile modulus is 2.4GPa, and the carbon dioxide gas barrier property is 0.8 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.9X 10-12cm3·cm/cm2·s·cmHg。
Example 6:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic dianhydride, glycerol and anhydrous manganese acetate into a reaction kettle according to the molar ratio of 1:2.0:0.0001:0.002:0.0015, vacuumizing, filling nitrogen for replacement for three times, then gradually heating to 190 ℃ and reacting for 3 hours. Then adding antimony trioxide of 0.15 percent of the molar weight of 2, 5-furandicarboxylic acid dimethyl ester, triphenyl phosphate of 0.5 percent and antioxidant-168 of 0.1 percent, slowly vacuumizing to below 2000Pa, and prepolymerizing for 1.5h at the temperature of 210 ℃. And then, raising the temperature to 245 ℃, continuously vacuumizing to below 200Pa, and reacting for 3 hours to obtain the furan ring-containing copolyester.
The furan ring-containing copolyester obtained in the example is light yellow, and the intrinsic viscosity of the copolyester is 1.05dL/g, the tensile strength of the copolyester is 78.2MPa, the tensile modulus of the copolyester is 2.6GPa, and the carbon dioxide gas barrier property of the copolyester is 1.1 x 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.0X 10-12cm3·cm/cm2·s·cmHg。
Example 7:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, 1,2, 4-trimellitic anhydride, pentaerythritol and anhydrous zinc acetate into a reaction kettle according to a molar ratio of 1:1.6:0.015:0.015:0.002, vacuumizing, filling inert gas for replacement for three times, gradually heating to 180 ℃, and reacting for 4 hours. Then antimony trioxide with the molar weight of 0.12 percent of the dimethyl 2, 5-furandicarboxylate is added, the vacuum pumping is slowly carried out until the pressure reaches 200 Pa-1300 Pa, and the prepolymerization is carried out for 0.5h at the temperature of 220 ℃. Then heating to 240 ℃, controlling the vacuum degree to be below 200Pa, and reacting for 2h to obtain the furan ring-containing copolyester.
The furan ring-containing copolyester obtained in this example was very light yellow, and was found to have an intrinsic viscosity of 0.99dL/g, a tensile strength of 74.7MPa, a tensile modulus of 2.6GPa, and carbon dioxideGas barrier property of 0.7X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.9X 10-12cm3·cm/cm2·s·cmHg。
Example 8:
adding dibutyl 2, 5-furandicarboxylate, ethylene glycol, 1,2, 4-trimellitic anhydride, pentaerythritol and anhydrous zinc acetate into a reaction kettle according to a molar ratio of 1:1.5:0.003:0.0001:0.0018, vacuumizing, filling inert gas for replacement for three times, gradually heating to 180 ℃, and reacting for 4.5 hours. Then adding antimony trioxide of 0.15 percent of the molar weight of 2, 5-dibutyl furan dicarboxylate, phosphoric acid of 0.2 percent and antioxidant-1076 of 0.5 percent, slowly vacuumizing to 500 Pa-1500 Pa, and pre-polymerizing for 0.5h at the temperature of 225 ℃. Then heating to 250 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 3h to obtain the furan ring-containing copolyester.
The copolymer containing furan rings obtained in this example was pale yellow, and it was found that it had an intrinsic viscosity of 1.09dL/g, a tensile strength of 79.0MPa, a tensile modulus of 2.7GPa, and a carbon dioxide gas barrier property of 0.7X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.7X 10-12cm3·cm/cm2·s·cmHg。
Example 9:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, 1,2, 4-trimellitic anhydride, glycerol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.7:0.002:0.002:0.0013, vacuumizing, filling inert gas for replacement for three times, gradually heating to 180 ℃, and reacting for 4.5 hours. Then adding antimony trioxide of 0.5 percent of the molar weight of dimethyl 2, 5-furandicarboxylate, trimethyl phosphate of 0.2 percent and antioxidant-1010 of 0.1 percent, slowly vacuumizing to 300-1600 Pa, and prepolymerizing for 0.5h at the temperature of 200 ℃. Then heating to 255 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 2.5h to obtain the furan ring-containing copolyester.
The copolymer containing furan rings obtained in this example was pale yellow, and it was found that it had an intrinsic viscosity of 0.95dL/g, a tensile strength of 75.9MPa, a tensile modulus of 2.6GPa, and a carbon dioxide gas barrier property of 0.9X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.8X 10-12cm3·cm/cm2·s·cmHg。
Example 10:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, 1,2, 4-trimellitic anhydride, glycerol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.5:0.02:0.01:0.0015, vacuumizing, filling inert gas for replacement for three times, gradually heating to 180 ℃, and reacting for 5 hours. Then antimony trioxide with the molar weight of 0.15 percent of the dimethyl 2, 5-furandicarboxylate is added, the vacuum pumping is slowly carried out until the pressure reaches 400Pa to 2000Pa, and the prepolymerization is carried out for 0.5h at the temperature of 260 ℃. Then controlling the vacuum degree below 150Pa, and continuing to react for 0.5h at 260 ℃ to obtain the copolyester containing furan rings.
The copolymer containing furan rings obtained in this example was pale yellow, and it was found that it had an intrinsic viscosity of 0.95dL/g, a tensile strength of 74.9MPa, a tensile modulus of 2.4GPa, and a carbon dioxide gas barrier property of 1.0X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.1X 10-12cm3·cm/cm2·s·cmHg。
Example 11:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pentaerythritol, pyromellitic dianhydride and anhydrous manganese acetate into a reaction kettle according to the molar ratio of 1:1.5:0.025:0.025:0.001, vacuumizing, filling inert gas for replacement for three times, then gradually heating to 180 ℃, and reacting for 4 hours. Then adding antimony trioxide of 0.1 percent of the molar weight of dimethyl 2, 5-furandicarboxylate, triphenyl phosphate of 0.2 percent and antioxidant-1010 of 0.2 percent, slowly vacuumizing to 200 Pa-2000 Pa, and prepolymerizing for 1h at the temperature of 210 ℃. Then heating to 240 ℃, controlling the vacuum degree below 150Pa, and reacting for 0.5h to obtain the furan ring-containing copolyester.
The copolymer containing furan rings obtained in this example was colorless, and it was found that it had an intrinsic viscosity of 1.2dL/g, a tensile strength of 80.7MPa, a tensile modulus of 2.9GPa, and a carbon dioxide gas barrier property of 0.5X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.6X 10-12cm3·cm/cm2·s·cmHg。
Example 12:
adding dimethyl 2, 5-furandicarboxylate, butanediol, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, tetrol and tetrabutyl titanate into a reaction kettle according to the molar ratio of 1:1.6:0.005:0.015:0.005, vacuumizing, filling inert gas for replacement for three times, then gradually heating to 170 ℃, and reacting for 5 hours. Then adding triphenyl phosphate accounting for 0.2 percent of the molar weight of the dimethyl 2, 5-furandicarboxylate and antioxidant-1076 accounting for 0.2 percent, slowly vacuumizing to 200 Pa-2000 Pa, and pre-polymerizing for 4 hours at the temperature of 180 ℃. Then the temperature is raised to 230 ℃, the vacuum degree is controlled to be below 150Pa, and the reaction is carried out for 1.5h, thus obtaining the copolyester containing furan rings.
The copolymer having a furan ring obtained in this example was a pale yellow copolymer, and it was found that the copolymer had an intrinsic viscosity of 1.12dL/g, a tensile strength of 79.1MPa, a tensile modulus of 2.6GPa, and a carbon dioxide gas barrier property of 0.9X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.0X 10-12cm3·cm/cm2·s·cmHg。
Example 13:
adding 2, 5-furan dicarboxylic acid diethyl ester, butanediol, 1,2, 4-trimellitic anhydride, tetrol and dibutyltin oxide into a reaction kettle according to the molar ratio of 1:1.6:0.01:0.02:0.01, vacuumizing, filling inert gas for replacement for three times, then gradually heating to 170 ℃, and reacting for 5 hours. Then adding triphenyl phosphate accounting for 0.3 percent of the molar weight of the diethyl 2, 5-furandicarboxylate and antioxidant-1076 accounting for 0.2 percent, slowly vacuumizing to 200 Pa-2000 Pa, and pre-polymerizing for 0.5h at the temperature of 200 ℃. Then the temperature is raised to 230 ℃, the vacuum degree is controlled to be below 150Pa, and the reaction is carried out for 0.5h, thus obtaining the copolyester containing furan rings.
The copolymer containing furan rings obtained in this example was colorless, and it was found that it had an intrinsic viscosity of 1.18dL/g, a tensile strength of 78.5MPa, a tensile modulus of 2.5GPa, and a carbon dioxide gas barrier property of 0.6X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.7X 10-12cm3·cm/cm2·s·cmHg。
Example 14:
adding diethyl 2, 5-furandicarboxylate, bisphenol S, pyromellitic anhydride, dipentaerythritol and dibutyltin oxide into a reaction kettle according to the molar ratio of 1:1.3:0.0002:0.0003:0.006, vacuumizing, filling inert gas for replacing three times, gradually heating to 180 ℃, and reacting for 5 hours. Then adding dibutyltin oxide accounting for 0.05 percent of the molar weight of the diethyl 2, 5-furandicarboxylate, 0.2 percent of triphenyl phosphate and 0.1 percent of antioxidant-1010, slowly vacuumizing to 200 Pa-2000 Pa, and prepolymerizing for 0.5h at the temperature of 200 ℃. Then controlling the vacuum degree below 150Pa, and continuing to react for 2.5h at 200 ℃ to obtain the copolyester containing furan rings.
The copolymer containing furan rings obtained in this example was pale yellow, and it was found that it had an intrinsic viscosity of 1.1dL/g, a tensile strength of 77.7MPa, a tensile modulus of 2.5GPa, and a carbon dioxide gas barrier property of 0.9X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.9X 10-12cm3·cm/cm2·s·cmHg。
Comparative example 1:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.6:0.001, vacuumizing, filling nitrogen for replacement for three times, gradually heating to 180 ℃, and reacting for 5 hours. Then adding antimony trioxide of 0.1 percent of the molar weight of dimethyl 2, 5-furandicarboxylate, triphenyl phosphate of 0.1 percent and antioxidant-1010 of 0.1 percent, slowly vacuumizing to 200 Pa-2000 Pa, and pre-condensing for 1.5h at the temperature of 220 ℃. Then heating to 240 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 7h to obtain the poly (ethylene 2, 5-furandicarboxylate).
Since the comparative example has a long polycondensation time and the polyethylene-2, 5-furandicarboxylate exists in a high-temperature environment for a long time, the color of the polyethylene-2, 5-furandicarboxylate obtained by the comparative example is deep yellow as shown in fig. 6.
The detection proves that the intrinsic viscosity is 0.75dL/g, the tensile strength is 70.2MPa, and the carbon dioxide gas barrier property is 1.2 multiplied by 10 when the tensile modulus is 2.2GPa-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of1.3×10-12cm3·cm/cm2·s·cmHg。
Comparative example 2:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pentaerythritol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.5:0.025:0.001, vacuumizing, filling nitrogen for three times, gradually heating to 180 ℃, and reacting for 3 hours. Then adding antimony trioxide of 0.1 percent of the molar weight of dimethyl 2, 5-furandicarboxylate, triphenyl phosphate of 0.2 percent and antioxidant-1010 of 0.2 percent, slowly vacuumizing to 200 Pa-2000 Pa, and prepolymerizing for 1h at the temperature of 220 ℃. Then heating to 240 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 0.5h to obtain the furan ring-containing copolyester.
Because the addition amount of the pentaerythritol in the comparative example is too much, after the polycondensation reaction is carried out for 0.5h, the excessive hydroxyl groups generate obvious crosslinking phenomenon, molecular chains are excessively entangled, the solubility is extremely poor, and the data such as the intrinsic viscosity cannot be represented.
Comparative example 3:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic dianhydride and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.5:0.025:0.001, vacuumizing, filling nitrogen for three times, gradually heating to 180 ℃, and reacting for 4 hours. Then adding antimony trioxide of 0.1 percent of the molar weight of 2, 5-furandicarboxylic acid dimethyl ester, triphenyl phosphate of 0.1 percent and antioxidant-1010 of 0.1 percent, slowly vacuumizing to 200 Pa-2000 Pa, and prepolymerizing for 1 hour at the temperature of 220 ℃. Then heating to 240 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 0.5h to obtain the furan ring-containing copolyester.
As the addition amount of the pyromellitic anhydride in the comparative example is too much, after 0.5 hour of polycondensation reaction, a very obvious crosslinking phenomenon can occur, molecular chains are excessively entangled, the solubility is extremely poor, and data such as intrinsic viscosity and the like can not be represented.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the furan ring-containing copolyester is characterized by comprising the following steps of:
(1) providing a first component, a second component, a third component and a fourth component, wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid ester, the second component comprises at least one of aromatic diol and aliphatic diol, the third component comprises polyhydric alcohol with the number of hydroxyl groups being more than or equal to 3, and the fourth component comprises acid anhydride with the number of carbonyl groups being more than or equal to 3;
(2) mixing the first component, the second component, the third component, the fourth component and an esterification catalyst, and reacting in an inert atmosphere or a nitrogen atmosphere to obtain a first intermediate product, wherein the molar ratio of the first component to the fourth component to the second component to the third component to the fourth component is 1 (1.1-2.0) to 0.0001-0.025;
(3) under the vacuum condition, the first intermediate product is subjected to prepolymerization reaction to obtain a second intermediate product;
(4) and carrying out polycondensation reaction on the second intermediate product under a vacuum condition to obtain the furan ring-containing copolyester, wherein the chain segment structure of the furan ring-containing copolyester is a network structure.
2. The method for preparing furan ring-containing copolyester according to claim 1, wherein the acid anhydride having carbonyl group number of 3 or more in step (1) comprises at least one of 1,2, 4-trimellitic anhydride, pyromellitic anhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 4,4 '-diphenyl ether dianhydride, 3', 4,4 '-biphenyltetracarboxylic dianhydride, 4, 4' - (hexafluoroisopropylene) dititanic anhydride, and chlorinated trimellitic anhydride.
3. The method for preparing furan ring-containing copolyester according to claim 1, wherein the polyol having hydroxyl number of 3 or more in step (1) comprises at least one of glycerol, butanetriol, 2-hydroxymethyl-2-methyl-1, 3-propanediol, butanetetraol, pentaerythritol, dipentaerythritol, pentanol, hexitol, and sugar alcohol.
4. The method for preparing furan ring-containing copolyester according to claim 1, wherein the sum of the molar amounts of the third component and the fourth component in step (2) is 0.05 to 3% of the molar amount of the first component.
5. The method for preparing furan ring-containing copolyester according to claim 1, wherein the reaction temperature in the step (2) is 150 to 220 ℃ and the reaction time is 0.5 to 5.0 hours.
6. The method for preparing furan ring-containing copolyester according to claim 1, wherein the molar amount of the esterification catalyst in the step (2) is 0.05 to 1% of the molar amount of the first component.
7. The method for preparing furan ring-containing copolyester according to claim 1, wherein the reaction temperature of the prepolymerization reaction in the step (3) is 180-260 ℃ and the reaction time is 0.5-4.0 h.
8. The method for preparing furan ring-containing copolyester according to claim 1, further comprising adding a polycondensation catalyst to the first intermediate product in a molar amount of 0.05 to 0.5% of the molar amount of the first component in step (3); and/or
Adding a stabilizer to the first intermediate product, wherein the molar weight of the stabilizer is 0.05-0.5% of that of the first component; and/or
And adding an antioxidant into the first intermediate product, wherein the molar weight of the antioxidant is 0.05-0.5% of that of the first component.
9. The method for preparing furan ring-containing copolyester according to claim 1, wherein the reaction temperature of the polycondensation reaction in the step (4) is 200 to 260 ℃ and the reaction time is 0.5 to 4 hours.
10. A furan ring-containing copolyester, characterized by being obtained by the preparation method of any one of claims 1 to 9, wherein the chain segment structure of the furan ring-containing copolyester is a network structure.
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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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