CN109810247B - Furyl copolyester and preparation method thereof - Google Patents
Furyl copolyester and preparation method thereof Download PDFInfo
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Abstract
The invention relates to furyl copolyester and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a first component, a second component and a third component with an esterification catalyst in a molar ratio of 1 (1.1-2.0) (0.0001-0.02) to react to obtain a first intermediate product, wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid esterified substance, the second component comprises at least one of aromatic diol and aliphatic diol, and the third component comprises anhydride with the carbonyl number more than or equal to 3; and then, carrying out prepolymerization reaction and polycondensation reaction on the first intermediate product to obtain the furyl copolyester. In the preparation method, the anhydride with the carbonyl number more than or equal to 3 is used as a chain segment connection point, so that the chain segment structure of the furyl copolyester is expanded into a network structure, and the high molecular weight furyl copolyester which is colorless or light-colored and has excellent mechanical property and gas barrier property is obtained, and further the application requirements of the furyl copolyester in the fields of packaging materials, films, fibers, engineering plastics and the like can be better met.
Description
Technical Field
The invention relates to the technical field of materials, in particular to furyl 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 furyl copolyester and a preparation method thereof; in the preparation method, the anhydride with the carbonyl number more than or equal to 3 is used as a chain segment connection point, so that the chain segment structure of the furyl copolyester is expanded from a linear structure to a network structure, and the high molecular weight furyl copolyester which is colorless or light-colored and has excellent mechanical property and gas barrier property is obtained, and further the application requirements of the furyl copolyester in the fields of packaging materials, films, fibers, engineering plastics and the like can be better met.
A preparation method of furyl copolyester comprises the following steps:
(1) providing a first component, a second component and a third component, wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid esterified substance, the second component comprises at least one of aromatic diol and aliphatic diol, and the third component comprises anhydride with the carbonyl number being more than or equal to 3;
(2) mixing the first component, the second component, the third 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 third component to the second component is 1 (1.1-2.0) to 0.0001-0.02;
(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 furyl copolyester, wherein the chain segment structure of the furyl 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 furan dicarboxylic acid ester in the step (1) comprises at least one of furan dicarboxylic acid dimethyl ester, furan dicarboxylic acid diethyl ester and furan dicarboxylic acid dibutyl ester.
In one embodiment, the aliphatic diol in step (1) comprises at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, cyclohexanedimethanol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol, 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.
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 preparation method, after the anhydride with the carbonyl number of more than or equal to 3, the furan dicarboxylic acid or the esterified product thereof and the dihydric alcohol are mixed, in the reaction process of the step (2), in addition to the esterification or ester exchange reaction of the furan dicarboxylic acid or the esterified product thereof and the dihydric alcohol, the anhydride with the carbonyl number of more than or equal to 3 is taken as a chain segment connection point, the ring opening of the anhydride with the carbonyl number of more than or equal to 3 is also taken and the esterification or ester exchange reaction of the anhydride with the dihydric alcohol or the copolyester oligomer is also taken, and under the condition of sufficient reaction conditions, the anhydride with the carbonyl number of more than or equal to 3 is fully reacted into the chain segment of the copolyester oligomer in the esterification stage, so that the molecular chain segment structure of the copolyester oligomer serving as a first intermediate product is expanded into a network structure from a linear structure, and a precondition is provided for the rapid increase of the molecular weight of the subsequent copolyester. Therefore, the preparation method can obtain the furyl copolyester with higher molecular weight by 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 furyl copolyester. Meanwhile, the short polymerization time can effectively inhibit the occurrence of high-temperature side reactions such as decarboxylation of the furandicarboxylic acid and the like, and can avoid the problem of color deepening of the furyl copolyester due to the phenomena of high-temperature degradation, oxidation, color change and the like caused by the long-time existence of the furyl copolyester in a high-temperature environment, thereby obtaining the colorless or light-colored furyl copolyester.
The furyl copolyester is obtained by the preparation method, and the chain segment structure of the furyl copolyester is a network structure.
The chain segment structure of the furyl 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 furyl copolymer ester 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 furanyl copolyester of example 1;
FIG. 2 is a schematic representation of the furyl copolyester prepared in example 11An H-NMR spectrum;
FIG. 3 is a DSC of the furyl copolyester prepared in example 1;
FIG. 4 is a TGA spectrum of the furanyl copolyester of example 1;
FIG. 5 is an FTIR spectrum of the furanyl 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-based copolyester and the preparation method thereof provided by the invention are further explained below.
The preparation method of the furyl copolyester provided by the invention comprises the following steps:
(1) providing a first component, a second component and a third component, wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid esterified substance, the second component comprises at least one of aromatic diol and aliphatic diol, and the third component comprises anhydride with the carbonyl number being more than or equal to 3;
(2) mixing the first component, the second component, the third 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 third component to the second component is 1 (1.1-2.0) to 0.0001-0.02;
(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 furyl copolyester, wherein the chain segment structure of the furyl 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.
In the step (2), if the addition amount of the third 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 can not provide enough network structures to achieve the purpose of improving the molecular weight of the polyester in a short time during subsequent polycondensation reaction; if the content of the third 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 and application of a copolyester product are not facilitated. Therefore, the molar ratio of the first component to the third component is preferably 1 (0.0003 to 0.01), and more preferably 1 (0.0005 to 0.005).
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 acid anhydride with the carbonyl number being more than or equal to 3 of the third component is taken as a chain segment connection point, the ring opening of the acid anhydride with the carbonyl number being more than or equal to 3 can also be carried out, and the esterification or ester exchange reaction of the acid anhydride with the carbonyl number being more than or equal to 3 and the dihydric alcohol or copolyester oligomer can also be carried out, under the condition that the reaction condition is enough, the acid anhydride with the carbonyl number being more than or equal to 3 can be fully reacted into the chain segment of the copolyester oligomer in the esterification stage, so that the chain segment structure of the first intermediate product is promoted to be expanded into a network structure from a linear.
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 furyl 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 network-shaped chain segment structure can be subjected to polycondensation polymerization in a shorter time to obtain the furan-based copolyester with higher molecular weight, so that the mechanical properties such as tensile modulus, tensile strength and the like of the furan-based copolyester and the gas barrier property can be improved.
Meanwhile, the short polymerization time can effectively inhibit the occurrence of high-temperature side reactions such as decarboxylation of the furandicarboxylic acid and the like, and can avoid the problem of color deepening of the furyl copolyester due to the phenomena of high-temperature degradation, oxidation, color change and the like caused by the long-time existence of the furyl copolyester in a high-temperature environment, thereby obtaining the colorless or light-colored furyl copolyester.
The invention also provides furyl copolyester, which is obtained by the preparation method and has a network structure of chain segment.
It can be understood that the proportion of the network-like structure chain segments of the furan-based copolyester in all the chain segments is related to the addition amount of the third component, and in practical cases, the structure of a small part of the chain segments in the furan-based copolyester may still be a linear structure.
Specifically, the third component is pyromellitic anhydride, and the chain segment structure of the furyl copolyester comprises:
wherein R is1、R2、R3And R4Is a structural unit of aromatic dihydric alcohol, a structural unit of aliphatic dihydric alcohol or a structure of pyromellitic dianhydrideOne of the constituent elements.
Specifically, the third component takes 1,2, 4-trimellitic anhydride as an example, and the segment structure of the furyl copolyester comprises:
wherein R is5、R6And R7Is one of a structural unit of aromatic diol, a structural unit of aliphatic diol or a structural unit of 1,2, 4-trimellitic anhydride.
Therefore, the chain segment structure of the furan-based copolyester is a network structure and has high molecular weight, so that the furan-based copolyester can be endowed with more excellent mechanical properties such as tensile modulus, tensile strength and the like and gas barrier property. Meanwhile, the furyl copolymer ester is colorless or light-colored, can better meet the application requirements in the fields of packaging materials, films, fibers, engineering plastics and the like, and is beneficial to improving the manufacturing level of high-performance engineering plastics, thereby promoting the bio-based high polymer material industry to get rid of high dependence on petroleum resources.
Hereinafter, the furyl 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 solution and 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 dianhydride and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.6:0.003:0.002, vacuumizing, filling inert gas for replacement for three times, gradually heating to 185 ℃, and reacting for 4 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-168 with the molar weight of 0.15 percent are added into a reaction kettle, the mixture is slowly vacuumized to 200Pa to 2000Pa, and prepolymerization is carried out for 1h at the temperature of 220 ℃. Then gradually raising the temperature to 250 ℃, continuously vacuumizing to below 200Pa and reacting for 2.5h to obtain the furyl copolyester.
As can be seen from FIG. 1, the furyl copolymer ester obtained in this example was very pale yellow in color.
In FIG. 2, the solvent CF is at 11.31ppm3The peak of COOD was found to be a peak (2H) for hydrogen in the furan ring at 7.17ppm and a peak (4H) for hydrogen in the ethylene glycol chain segment at 4.59 ppm. Therefore, as is clear from FIG. 2, the furyl copolymer ester obtained in this example was polyethylene furandicarboxylate.
As can be seen from FIG. 3, the glass transition temperature of the furanyl copolyester obtained in this example is 88.9 ℃.
As can be seen from FIG. 4, the thermal decomposition temperature (T) of the furyl copolyester obtained in this exampled,5％) The temperature was 365 ℃.
The furan-based copolyester obtained in the example is detected to have the intrinsic viscosity of 0.89dL/g, the tensile strength of 74.3MPa, the tensile modulus of 2.2GPa and the carbon dioxide gas barrier property of 1.0 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.0X 10-12cm3·cm/cm2·s·cmHg。
Example 2:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic dianhydride and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.6:0.0015:0.002, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 195 ℃, and reacting for 2 hours. Then antimony trioxide with the molar weight of 0.3 percent of dimethyl 2, 5-furandicarboxylate, trimethyl phosphate with the molar weight of 0.12 percent and antioxidant 1010 with the molar weight of 0.15 percent are added into a reaction kettle, the mixture is slowly vacuumized to 200Pa to 1500Pa, and prepolymerization is carried out for 0.5h at the temperature of 220 ℃. Then gradually raising the temperature to 240 ℃, and continuing to pump the vacuum degree to be less than 200Pa for reaction for 4 hours to obtain the furyl copolyester.
The furyl copolymer obtained in this example was very pale yellow and, as a result of detection, had an intrinsic viscosity of 0.97dL/g, a tensile strength of 76.5MPa, a tensile modulus of 2.4GPa, and a carbon dioxide gas barrier property of 0.8X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.0X 10-12cm3·cm/cm2·s·cmHg。
Example 3:
adding diethyl 2, 5-furandicarboxylate, ethylene glycol, 1,2, 4-trimellitic anhydride and anhydrous zinc acetate into a reaction kettle according to a molar ratio of 1:1.6:0.0005:0.001, starting stirring and gradually heating to 170 ℃ under an inert atmosphere, and reacting for 5 hours. Then antimony trioxide with the molar weight of 0.1 percent of diethyl 2, 5-furandicarboxylate, triphenyl phosphate with the molar weight of 0.1 percent and antioxidant-1076 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 225 ℃. And then gradually heating to 240 ℃, and continuously vacuumizing to below 200Pa for reaction for 4 hours to obtain the furyl copolyester.
The furyl copolyester obtained in this example is very pale yellowThe intrinsic viscosity is 0.79dL/g, the tensile strength is 70.9MPa, the tensile modulus is 2.2GPa, and the carbon dioxide gas barrier property is 1.2 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.2X 10-12cm3·cm/cm2·s·cmHg。
Example 4:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, 1,2, 4-trimellitic anhydride and anhydrous cobalt acetate into a reaction kettle according to a molar ratio of 1:1.5:0.00075:0.0005, vacuumizing, filling nitrogen for three times, starting stirring, 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-furandicarboxylic acid dimethyl ester, phosphorous acid of 0.1 percent and antioxidant-1010 of 0.05 percent into a reaction kettle, slowly vacuumizing to 200 Pa-2000 Pa, and prepolymerizing for 1.5h at the temperature of 200 ℃. And gradually heating to 235 ℃, continuously vacuumizing, controlling the vacuum degree below 200Pa, and reacting for 4 hours to obtain the furyl copolyester.
The furan-based copolyester obtained in the example is light yellow, and the intrinsic viscosity of the furan-based copolyester is detected to be 0.85dL/g, the tensile strength is 72.9MPa, the tensile modulus is 2.4GPa, and the carbon dioxide gas barrier property is 1.1 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.2X 10-12cm3·cm/cm2·s·cmHg。
Example 5:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, 1,2, 4-trimellitic anhydride and anhydrous zinc acetate into a reaction kettle according to a molar ratio of 1:1.8:0.001:0.0015, vacuumizing, introducing nitrogen for three times, gradually heating to 190 ℃, and reacting for 5 hours. Then antimony trioxide of 0.2 percent of the molar weight of 2, 5-furandicarboxylic acid dimethyl ester, triphenyl phosphate of 0.05 percent and antioxidant-1076 of 0.15 percent are added, the mixture is slowly vacuumized to 200Pa to 1000Pa, and prepolymerization is carried out for 1h at the temperature of 215 ℃. And then, raising the temperature to 260 ℃, continuously vacuumizing to below 200Pa, and reacting for 2.5 hours to obtain the furyl copolyester.
The furanyl copolyester obtained in this example was very light yellow, and was found to have an intrinsic viscosity of 0.85dL/g, in tensionThe strength is 72.5MPa, the tensile modulus is 2.3GPa, and the carbon dioxide gas barrier property is 1.0 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.2X 10-12cm3·cm/cm2·s·cmHg。
Example 6:
adding dibutyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic anhydride and anhydrous cobalt acetate into a reaction kettle according to the molar ratio of 1:1.4:0.0003:0.0025, vacuumizing, filling nitrogen for replacing three times, gradually heating to 150 ℃, and reacting for 5 hours. Then adding antimony trioxide of 0.2 percent of the molar weight of 2, 5-furandicarboxylic acid dimethyl ester, triphenyl phosphate of 0.14 percent and antioxidant-168 of 0.1 percent, slowly vacuumizing to below 200 Pa-2000 Pa, and prepolymerizing for 4 hours at the temperature of 180 ℃. And then, raising the temperature to 240 ℃, continuously vacuumizing to below 200Pa, and reacting for 1h to obtain the furyl copolyester.
The furyl copolymer obtained in this example was colorless, and was found to have an intrinsic viscosity of 0.89dL/g, a tensile strength of 73.5MPa, a tensile modulus of 2.4GPa, 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 7:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic dianhydride and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:2.0:0.002:0.002, vacuumizing, filling inert gas 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 0.15 percent and antioxidant-1010 of 0.15 percent, slowly vacuumizing to 300-1500 Pa, and pre-polymerizing for 0.5h at the temperature of 260 ℃. Then controlling the vacuum degree below 200Pa, and continuing to react for 2h at 260 ℃ to obtain the furyl copolyester.
The furyl copolymer obtained in this example was pale yellow and was found to have an intrinsic viscosity of 0.90dL/g, a tensile strength of 75.6MPa, a tensile modulus of 2.4GPa, 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。
Example 8:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and anhydrous manganese acetate into a reaction kettle according to the molar ratio of 1:1.5:0.0001:0.005, vacuumizing, filling inert gas for replacement for three times, then gradually heating to 180 ℃, and reacting for 4.5 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 300Pa to 2000Pa, and the prepolymerization is carried out for 0.5h at the temperature of 225 ℃. Then heating to 250 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 2.5h to obtain the furyl copolyester.
The furyl copolymer obtained in this example was pale yellow and was found to have an intrinsic viscosity of 0.95dL/g, a tensile strength of 77.2MPa, a tensile modulus of 2.5GPa, and a carbon dioxide gas barrier property of 0.7X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.9X 10-12cm3·cm/cm2·s·cmHg。
Example 9:
adding dimethyl 2, 5-furandicarboxylate, butanediol, pyromellitic dianhydride and dibutyltin oxide into a reaction kettle according to the molar ratio of 1:1.7:0.01:0.01, vacuumizing, filling inert gas for replacement for three times, then gradually heating to 190 ℃ and reacting for 2 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 300 Pa-1500 Pa, and pre-polymerizing for 1 hour at the temperature of 205 ℃. Then heating to 225 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 1.5h to obtain the furyl copolyester.
The furyl copolymer obtained in this example was very pale yellow and, as a result of detection, had an intrinsic viscosity of 1.02dL/g, a tensile strength of 57.7MPa, a tensile modulus of 1.3GPa, and a carbon dioxide gas barrier property of 4.3X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.1X 10-12cm3·cm/cm2·s·cmHg。
Example 10:
adding dimethyl 2, 5-furandicarboxylate, butanediol, pyromellitic dianhydride and tetrabutyl titanate into a reaction kettle according to the molar ratio of 1:1.5:0.02:0.001, vacuumizing, filling inert gas for replacement for three times, then gradually heating to 150 ℃, and reacting for 3 hours. Then tetrabutyl titanate with the molar weight of 0.05 percent of dimethyl 2, 5-furandicarboxylate, triphenyl phosphate with the molar weight of 0.5 percent and antioxidant-168 with the molar weight of 0.2 percent are added, the mixture is slowly vacuumized to 300Pa to 2000Pa, and prepolymerization is carried out for 2 hours at the temperature of 200 ℃. Then heating to 225 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 0.5h to obtain the furyl copolyester.
The furyl copolymer obtained in this example was colorless, and was found to have an intrinsic viscosity of 1.13dL/g, a tensile strength of 62.6MPa, a tensile modulus of 1.2GPa, and a carbon dioxide gas barrier property of 4.5X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.9X 10-12cm3·cm/cm2·s·cmHg。
Example 11:
adding dimethyl 2, 5-furandicarboxylate, bisphenol S, 1,2, 4-trimellitic anhydride and dibutyltin oxide into a reaction kettle according to the molar ratio of 1:1.3:0.015:0.006, vacuumizing, filling inert gas for replacing three times, and then gradually heating to 180 ℃ for reaction for 3.5 hours. Then adding dibutyl tin oxide accounting for 0.5 percent of the molar weight of the dimethyl 2, 5-furandicarboxylate and antioxidant-168 accounting for 0.5 percent, slowly vacuumizing to 200 Pa-2000 Pa, and pre-polymerizing for 1h at the temperature of 210 ℃. Then heating to 230 ℃, controlling the vacuum degree to be below 150Pa, and reacting for 1h to obtain the furyl copolyester.
The furyl copolymer obtained in this example was colorless, and was found to have an intrinsic viscosity of 1.25dL/g, a tensile strength of 67.3MPa, a tensile modulus of 1.4GPa, and a carbon dioxide gas barrier property of 3.8X 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 0.8X 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 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 1.5h 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 of 1.3X 10-12cm3·cm/cm2·s·cmHg。
Comparative example 2:
adding dimethyl 2, 5-furandicarboxylate, ethylene glycol, pyromellitic dianhydride and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.5:0.00005:0.0015, vacuumizing, filling nitrogen for replacing 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 0.2 percent and antioxidant-1010 of 0.5 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 8h to obtain the furyl copolyester.
As the addition amount of pyromellitic anhydride in the comparative example is too low, only a few part of chain segment structure can be expanded from a linear state to a network state, the polycondensation time is still longer, and the obtained furyl copolymer is dark yellow.
The detection proves that the intrinsic viscosity is 0.78dL/g, the tensile strength is 71.0MPa, the tensile modulus is 2.2GPa, and the carbon dioxide gas barrier property is 1.2 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier propertyCan be 1.3X 10-12cm3·cm/cm2·s·cmHg。
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 furyl 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.
Comparative example 4:
adding 1, 4-dimethyl terephthalate, ethylene glycol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1:1.6:0.002, vacuumizing, filling nitrogen for replacement for three times, gradually heating to 200 ℃, and reacting for 4.5 hours. Then antimony trioxide with the molar weight of 0.12 percent of 1, 4-dimethyl terephthalate, triphenyl phosphate with the molar weight of 0.1 percent and antioxidant-1010 with the molar weight of 0.1 percent are added, the mixture is slowly vacuumized to 200Pa to 1000Pa, and prepolymerization is carried out for 0.5h at the temperature of 240 ℃. Then heating to 280 ℃, controlling the vacuum degree to be below 200Pa, and reacting for 5h to obtain the polyethylene terephthalate.
The polyethylene terephthalate obtained in this comparative example was white and, as a result of detection, had an intrinsic viscosity of 0.85dL/g and a carbon dioxide gas barrier property of 1.2X 10-11cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 5.2X 10-12cm3·cm/cm2·s·cmHg。
It is thus understood that the furan dicarboxylic acid copolyester of the present invention can be used instead of polyethylene terephthalate, and therefore, the dependence on petroleum-based polymer materials can be reduced.
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 furyl copolyester is characterized by comprising the following steps:
(1) providing a first component, a second component and a third component, wherein the first component comprises at least one of furan dicarboxylic acid and furan dicarboxylic acid esterified substance, the second component comprises at least one of aromatic diol and aliphatic diol, and the third component comprises anhydride with the carbonyl number being more than or equal to 3;
(2) mixing the first component, the second component, the third 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 third component to the second component is 1 (1.1-2.0) to 0.0001-0.02;
(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 furyl copolyester, wherein the chain segment structure of the furyl copolyester is a network structure.
2. The method for preparing furyl copolyester according to claim 1, wherein the acid anhydride having a 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' - (hexafluoroisopropylidene) dititanic anhydride, and chlorinated trimellitic anhydride.
3. The method for preparing furan-based copolyester according to claim 1, wherein the furan dicarboxylic acid esterified substance in the step (1) comprises at least one of dimethyl furan dicarboxylic acid, diethyl furan dicarboxylic acid and dibutyl furan dicarboxylic acid.
4. The method for preparing furyl copolyester of claim 1, wherein the aliphatic diol in step (1) comprises at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, 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.
5. The method for preparing furyl copolyester according to claim 1, wherein the reaction temperature in step (2) is 150-220 ℃ and the reaction time is 0.5-5.0 h.
6. The process for preparing furyl copolyester of claim 1, wherein the molar amount of the esterification catalyst in step (2) is 0.05 to 1% of the molar amount of the first component.
7. The method for preparing furyl copolyester according to claim 1, wherein the reaction temperature of the prepolymerization in step (3) is 180-260 ℃ and the reaction time is 0.5-4.0 h.
8. The method for preparing furyl copolyester of claim 1, wherein 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.
9. The method for preparing furyl copolyester according to claim 1, wherein the reaction temperature of the polycondensation reaction in step (4) is 200-260 ℃ and the reaction time is 0.5-4 h.
10. The furyl copolyester is characterized by being obtained by the preparation method of any one of claims 1 to 9, and the chain segment structure of the furyl copolyester is a network structure.
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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 |