CN111286012A - Degradable bio-based 2, 5-furandicarboxylic acid-based copolyester and preparation method and application thereof - Google Patents
Degradable bio-based 2, 5-furandicarboxylic acid-based copolyester and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses degradable bio-based 2, 5-furandicarboxylic acid-based copolyester and a preparation method and application thereof, relating to the field of preparation of copolyester. The copolymerization method uniformly links PEG short chains between PEF chain segments, and the whole copolyester is endowed with certain degradability by utilizing flexible hydrophilic PEG short chains; in addition, the degradation rate of the PEF-PEG copolyester can be controlled by adjusting the content and the number average molecular weight of the PEG in the preparation process, and the bio-based copolyester with the adjustable degradation rate is prepared.
Description
Technical Field
The invention relates to the field of preparation of copolyester, in particular to degradable bio-based 2, 5-furandicarboxylic acid based copolyester and a preparation method and application thereof.
Background
In order to realize sustainable, green and environment-friendly development of high polymer materials and related fine chemical industries, bio-based raw materials capable of replacing petroleum bases are searched globally, so that the dependence on petroleum is reduced, the national energy safety is improved, and the pollution of petroleum industries to the environment is reduced. Poly (2, 5-furandicarboxylic acid) ethylene glycol ester (PEF) is a novel polyester material obtained by esterification reaction and polycondensation reaction of bio-based 2, 5-furandicarboxylic acid (FDCA) and ethylene glycol. The polyester material not only has a molecular structure similar to polyethylene terephthalate (PET), but also is prepared from bio-based materials, and is a novel polyester material which is expected to replace petroleum-based PET in the future.
At present, the PEF raw material is expensive and has a series of defects in performance, so that the polyester is not industrially produced. Firstly, in terms of raw materials, the raw materials of PEF mainly comprise bio-based 2, 5-furandicarboxylic acid and ethylene glycol, wherein the bio-based 2, 5-furandicarboxylic acid is expensive in price due to complicated preparation process, low yield and difficult product purification. In addition, 2,5-FDCA is derived from biomass raw materials, so that a trace amount of polysaccharide or other impurities exists in the 2,5-FDCA, and when the 2,5-FDCA is prepared into PEF, the problems of poor polyester color and the like are caused; in the aspect of PEF performance, although the PEF has excellent thermodynamic performance and gas barrier performance, the application field of the PEF is seriously influenced by the problems of large product brittleness, poor mechanical performance and the like caused by low molecular weight and slow crystallization rate. In addition, although the PEF raw material is derived from a biomass material, it still has a problem of being not degradable, like PET.
For example, a "method for producing 2, 5-furandicarboxylic acid based polyester" disclosed in chinese patent document, publication No. CN101899145B, discloses a method for producing 2, 5-furandicarboxylic acid based polyester, in which 2, 5-furandicarboxylic acid (FDCA) is used as a main monomer, Ethylene Glycol (EG), 1, 3-propylene glycol (PDO), 1, 4-Butanediol (BDO) or 1, 6-Hexanediol (HDO) is used as a comonomer, and 2, 5-furandicarboxylic acid based polyester is produced by two-step esterification and polycondensation. However, the method has the problems of low molecular weight, large product brittleness caused by slow crystallization rate, poor mechanical property and the like, and the adopted 2, 5-furandicarboxylic acid monomer is derived from plant straws of corns and the like, belongs to a renewable biomass raw material, but has low degradability.
Disclosure of Invention
The invention provides degradable bio-based 2, 5-furandicarboxylic acid-based copolyester and a preparation method and application thereof, aiming at solving the problems of low molecular weight, slow crystallization rate, large product brittleness, poor mechanical property, low degradability and the like of the conventional 2, 5-furandicarboxylic acid-based polyester.
In order to achieve the purpose, the invention adopts the following technical scheme:
a degradable bio-based 2, 5-furandicarboxylic acid based copolyester, the molecular chain of which is composed of bio-based polyester chain segments and functional polyether chain segments.
Preferably, the bio-based ester segment is obtained by reacting 2, 5-furandicarboxylic acid and/or an ester thereof with a diol, the bio-based dicarboxylic acid comprises 2, 5-furandicarboxylic acid, the bio-based dicarboxylic acid ester comprises dimethyl 2, 5-furandicarboxylate, the diol comprises one or more of ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol, and the functional polyether segment is polyethylene glycol.
A preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
mixing 2, 5-furandicarboxylic acid and/or ester thereof with dihydric alcohol, adding a titanium-antimony composite catalyst, a heat stabilizer and an antioxidant, uniformly stirring, and then carrying out esterification reaction at the temperature of 180-230 ℃ and under the pressure of 50-200kPa until the content of distilled micromolecules reaches more than 95 percent of a theoretical value, and terminating the reaction to obtain an esterification solution;
2) pre-polycondensation reaction:
adding polyethylene glycol into the esterification liquid, uniformly stirring, then raising the temperature to 230-245 ℃, and controlling the pressure between 100-1000Pa to perform pre-polymerization reaction to obtain a prepolymer;
3) final polycondensation reaction
And (3) performing final polycondensation reaction on the prepolymer at 230-245 ℃ and under the pressure of 1-200Pa until the current in the polymerization kettle reaches 0.140-0.160mA, and preparing the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
The invention uniformly mixes the bio-based 2, 5-furandicarboxylic acid and/or ester thereof, dihydric alcohol, titanium-antimony compound catalyst, heat stabilizer and antioxidant, carries out esterification reaction, and after the esterification reaction is finished, polyethylene glycol (PEG) short chains with different contents and different molecular weights and poly-2, 5-furandicarboxylic acid glycol ester (PEF) are added for polycondensation reaction to prepare poly-2, 5-furandicarboxylic acid glycol ester and copolyester of polyethylene glycol (PEF-PEG), namely the bio-based 2, 5-furandicarboxylic acid copolyester can be degraded.
Firstly, during the esterification reaction, the esterification temperature adopted by the method is between 180 ℃ and 230 ℃, and the 2, 5-furandicarboxylic acid and/or the ester thereof are easy to decompose at high temperature, so that if the adopted esterification temperature is too high, the raw materials are easy to degrade seriously, the product is yellow or even black, if the esterification temperature is too low, the activation energy required by the reaction can not be reached, and the esterification reaction is difficult to carry out; in the invention, a certain positive pressure is applied to the esterification reaction, and the pressure is controlled to be 50-200kPa, so that the esterification reaction can be promoted to a certain extent, but when the pressure is too high, on one hand, the requirement on a reaction device is high, and on the other hand, water molecules in a reaction system are difficult to separate from the reaction system, thereby influencing the esterification effect.
In the invention, compared with short-chain aliphatic dihydric alcohol such as ethylene glycol, 1, 3-propylene glycol and the like, the reaction activity of polyethylene glycol with certain molecular weight and 2, 5-furandicarboxylic acid and/or ester thereof is relatively low, so that if the polyethylene glycol is added in the step 1), a large amount of polyethylene glycol does not participate in esterification or ester exchange reaction, and meanwhile, part of polyethylene glycol can carry out etherification reaction to generate long-chain diethylene glycol to influence the performance of a polymer, therefore, the polyethylene glycol is added in the step 2); in the pre-polycondensation reaction, the polycondensation temperature adopted by the invention is 230-245 ℃, if the reaction temperature is too low, the pre-polycondensation reaction is difficult to carry out, if the reaction temperature is too high, the raw materials are subjected to thermal degradation, the color of the sample is poor, and meanwhile, the content of the diglycol in the sample is increased; the system pressure adopted by the invention is between 100-1000Pa, because when the pressure of the reaction system is lower, part of oligomer is extracted out of the reaction system, so that the pipeline of the reaction system is blocked, and when the pressure of the reaction system is higher, the precondensation time is longer and the efficiency is lower; the pre-polycondensation time adopted by the invention is 15-50min, if the pre-polycondensation time is longer, the pre-polycondensation product is easy to yellow under a high-temperature condition for a long time, so that the product is yellow, and if the pre-polycondensation time is shorter, part of low-viscosity esterified substance is pumped out of the reaction system in a high vacuum process, so that a pipeline is blocked.
During final polycondensation, the final polycondensation reaction temperature adopted by the invention is 230-245 ℃, the copolyester can be thermally decomposed at an excessively high reaction temperature, the hue of the copolyester is influenced, and the activation energy required by the polycondensation of the copolyester is hardly reached at an excessively low reaction temperature, so that the polymerization rate and the polymerization effect of the copolyester are influenced; the final polycondensation reaction pressure adopted by the invention is between 1 Pa and 200Pa, and in order to ensure the smooth operation of the polycondensation reaction of the copolyester, the polymerization pressure is reduced as much as possible; with the increase of the added polyethylene glycol chain segment, the polycondensation time required by the copolyester to reach the same intrinsic viscosity is relatively shortened, so that the retention time of the copolyester at high temperature is reduced, the thermal degradation caused by instability of the 2, 5-furandicarboxylic acid based copolyester at high temperature is reduced, and the yellowing of the copolyester is relieved to a certain extent.
According to the invention, flexible hydrophilic PEG short chains are uniformly linked into the PEF chain segments in a copolymerization mode, so that the polycondensation reaction time is shortened, the color of the copolyester is improved, the hydrophilicity of the copolyester is improved, the probability of water molecules attacking ester bonds is increased, the copolyester is endowed with higher degradability, and the specific degradation mechanism is shown in figure 1.
Preferably, the molar ratio of the 2, 5-furandicarboxylic acid and/or its ester to the diol in step 1) is 1: 1.4-2.0.
The molar ratio of the alcohol acid adopted by the invention is 1.4-2.0, if the molar ratio of the alcohol acid is continuously increased, the dihydric alcohol is easy to carry out self-polycondensation under the high-temperature condition, so that the content of the diglycol in the product is overhigh, and because the esterification reaction activity of the 2, 5-furandicarboxylic acid or the esterified product thereof is low, the phenomena of long esterification reaction time, serious yellowing of the product and the like are easy to cause when the molar ratio of the alcohol acid is lower.
Preferably, in the titanium-antimony composite catalyst in the step 1), the titanium catalyst and the antimony catalyst are added in a mass ratio of 0.3-1:0-0.7, and the addition amount is 0.05-0.25% of the molar content of the 2, 5-furandicarboxylic acid and/or the ester thereof; the titanium catalyst comprises one or more of tetrabutyl titanate, titanium-silicon composite catalyst, isopropanol titanate and ethylene glycol titanium, and the antimony catalyst comprises one or more of ethylene glycol antimony, antimony trioxide and antimony acetate; the antioxidant comprises one or more of antioxidant 1178, antioxidant 618, antioxidant 1010 and antioxidant 1076, and the addition amount is 0.001-0.005wt% of 2, 5-furandicarboxylic acid and/or ester thereof; the heat stabilizer comprises one or more of phosphoric acid, trimethyl phosphate, triphenyl phosphate, trimethyl phosphite and polyphosphoric acid, and the addition amount of the heat stabilizer is 0.001-0.005wt% of 2, 5-furandicarboxylic acid and/or ester thereof.
The catalyst is a titanium-antimony composite catalyst,
preferably, the number average molecular weight of the polyethylene glycol in the step 2) is 600-10000g/mol, and the adding amount is 10-60wt% of the 2, 5-furandicarboxylic acid and/or the ester thereof.
The number average molecular weight of the PEG adopted by the invention is between 600-10000g/mol, the content of the added PEG accounts for 10-60wt% of the content of 2, 5-furandicarboxylic acid and/or ester thereof, if the added PEG chain segment is too short or the content is lower, the influence on the hydrophilicity of the copolyester is smaller, and the purpose of modification cannot be achieved, and if the added PEG chain segment is too large or the content is too much, partial PEG is difficult to be copolymerized into the PEF chain segment, so that partial free PEG is blended with the copolyester.
Preferably, the prepared degradable bio-based 2, 5-furandicarboxylic acid-based copolyester contains 0.5-3wt% of nucleating agent; the nucleating agent is amino modified wood fiber aerogel particles.
The prepared degradable bio-based 2, 5-furandicarboxylic acid based copolyester is fused and compounded with the nucleating agent, the nucleating agent is amino modified wood fiber aerogel particles, when the copolyester is crystallized, the amino modified wood fiber aerogel particles can play a role in heterogeneous nucleation, the crystallization speed of the copolyester can be accelerated, the crystallization temperature is increased, and the crystallinity is increased, so that the mechanical property of the copolyester is improved, the surface roughness of the amino modified wood fiber aerogel particles is large, and in addition, the existence of terminal amino groups, the 2, 5-furandicarboxylic acid glycol ester chain segment and the polyethylene glycol chain segment in the copolyester have good adsorption capacity, and the heterogeneous nucleation effect is obvious.
Preferably, the amino-modified lignocellulosic aerogel particles comprise the following preparation steps:
a) dissolving lignin fiber in water, and uniformly stirring to prepare lignin fiber liquid;
b) adding hexamethoxy melamine formaldehyde resin into the lignin fiber liquid for mixing, then adding phosphoric acid to adjust the pH value to 3-5, then carrying out freeze drying, and carrying out heat preservation in a drying oven at the temperature of 110-140 ℃ for 8-12h to prepare the wood fiber aerogel;
c) immersing the wood fiber aerogel into ethanol, taking out, placing into an aminosilane aqueous solution, taking out after the reaction is finished, replacing and washing with water and ethanol, and freeze-drying and grinding to obtain the amino modified wood fiber aerogel particles.
According to the invention, after the lignin fiber liquid is prepared, hexamethoxy melamine formaldehyde resin is added to prepare the wood fiber aerogel, wherein hydroxyl groups rich on the surface of the lignin fiber can be crosslinked with the hexamethoxy melamine formaldehyde resin, so that the structural integrity of the wood fiber aerogel is enhanced, the mechanical property of the wood fiber aerogel is improved, and then aminosilane is grafted on the surface of the wood fiber aerogel through modification of the aminosilane, and finally amino modified wood fiber aerogel particles are prepared through drying and grinding.
Preferably, the mass ratio of the lignin fiber to the hexamethoxymelamine formaldehyde resin is 1-5: 1.
Use of the degradable bio-based copolyester of claims 1-9 in the preparation of fibers.
Therefore, the invention has the following beneficial effects:
(1) the PEG short chains are uniformly linked between the PEF chain segments by a copolymerization method, and the flexible hydrophilic PEG short chains are utilized to endow the whole copolyester with certain degradability; in addition, the degradation rate of the PEF-PEG copolyester can be controlled by adjusting the content and the number average molecular weight of the PEG in the preparation process, and the bio-based copolyester with the adjustable degradation rate is prepared;
(2) the flexible hydrophilic PEG short chains are uniformly linked to enter the PEF chain segment, so that the polycondensation reaction time can be shortened, and the color of the copolyester is improved;
(3) the dibasic acid raw material can be derived from plant straws, fructose and other biomass raw materials, so that the green and sustainable raw material source is realized;
(4) the nucleating agent developed by the invention has better adsorption capacity with the 2, 5-furandicarboxylic acid glycol ester chain segment and the polyethylene glycol chain segment in the copolyester, has obvious heterogeneous nucleation effect, can accelerate the crystallization speed of the copolyester, improve the crystallization temperature and increase the crystallinity, thereby improving the mechanical property of the copolyester;
(5) the copolyester prepared by the invention can be applied to fiber preparation, can realize the preparation of bio-based PEF polymer monofilaments, and has good mechanical properties and good application prospects.
Drawings
FIG. 1 is a schematic diagram of the degradation mechanism of the present invention.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and ethylene glycol in a molar ratio of 1:1.6, then adding tetrabutyl titanate with the content of 0.1 mol% of 2, 5-furandicarboxylic acid, 0.0015 wt% of phosphoric acid and 0.003 wt% of antioxidant 1010, and then carrying out esterification reaction at 180 ℃ and 150kPa until the content of distilled micromolecules reaches more than 95% of a theoretical value, and terminating the reaction to obtain an esterified liquid;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 2000g/mol and the content of 20 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 235 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 235 ℃ and under the pressure of 60Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 2: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and ethylene glycol in a molar ratio of 1:1.4, and then adding a titanium-antimony composite catalyst with the content of 0.15 mol% relative to the 2, 5-furandicarboxylic acid, 0.001 wt% of triphenyl phosphate and 0.005wt% of antioxidant 618, wherein the titanium-antimony composite catalyst is obtained by compounding a titanium-silicon composite catalyst and ethylene glycol antimony in a mass ratio of 0.3: 0.7; then carrying out esterification reaction at 230 ℃ and 50kPa until the content of the distilled micromolecules reaches more than 95 percent of the theoretical value, and terminating the reaction to obtain esterified liquid;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 2000g/mol and the content of 40 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 230 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) final polycondensation reaction
And (3) carrying out final polycondensation reaction on the prepolymer at 230 ℃ and under the pressure of 20Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 3: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and ethylene glycol in a molar ratio of 1:2, and then adding a titanium-antimony composite catalyst with the content of 0.25 mol% relative to the 2, 5-furandicarboxylic acid, 0.002 wt% of polyphosphoric acid and 0.005wt% of antioxidant 1010, wherein the titanium-antimony composite catalyst is obtained by compounding ethylene glycol titanium and antimony trioxide in a mass ratio of 0.6: 0.4; then carrying out esterification reaction at 190 ℃ and 200kPa until the content of the distilled micromolecules reaches more than 95% of a theoretical value, and terminating the reaction to obtain an esterification solution;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 600g/mol and the content of 40 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 240 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) final polycondensation reaction
And (3) carrying out final polycondensation reaction on the prepolymer at 240 ℃ and under the pressure of 100Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 4: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and ethylene glycol in a molar ratio of 1:1.8, and then adding a titanium-antimony composite catalyst with the content of 0.25 mol% relative to the 2, 5-furandicarboxylic acid, 0.005wt% trimethyl phosphite and 0.0025 wt% antioxidant 1178, wherein the titanium-antimony composite catalyst is obtained by compounding isopropanol titanate and antimony acetate in a mass ratio of 0.7: 0.3; then carrying out esterification reaction at 220 ℃ and 135kPa until the content of the distilled micromolecules reaches more than 95 percent of the theoretical value, and terminating the reaction to obtain esterified liquid;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 10000g/mol and the content of 40 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 240 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 240 ℃ and under the pressure of 80Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 5: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and 1, 3-propylene glycol in a molar ratio of 1:1.6, then adding tetrabutyl titanate with the content of 0.1 mol% relative to the 2, 5-furandicarboxylic acid, 0.0015 wt% of phosphoric acid and 0.003 wt% of antioxidant 1010, and then carrying out esterification reaction at 180 ℃ and 150kPa until the content of distilled micromolecules reaches more than 95% of a theoretical value, and terminating the reaction to obtain esterified liquid;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 10000g/mol and the content of 40 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 240 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 240 ℃ and under the pressure of 60Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 6: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and 1, 4-butanediol in a molar ratio of 1:1.6, then adding tetrabutyl titanate with the content of 0.1 mol% relative to the 2, 5-furandicarboxylic acid, 0.0015 wt% of phosphoric acid and 0.003 wt% of antioxidant 1010, and then carrying out esterification reaction at 180 ℃ and 150kPa until the content of distilled micromolecules reaches more than 95% of a theoretical value, and terminating the reaction to obtain esterified liquid;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 10000g/mol and the content of 40 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 240 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 240 ℃ and under the pressure of 60Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 7: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and ethylene glycol in a molar ratio of 1:1.6, and then adding a titanium-antimony composite catalyst with the content of 0.2 mol% relative to the 2, 5-furandicarboxylic acid, 0.003 wt% of trimethyl phosphite and 0.005wt% of antioxidant 1010, wherein the titanium-antimony composite catalyst is obtained by compounding tetrabutyl titanate and antimony trioxide in a mass ratio of 0.5: 0.5; then carrying out esterification reaction at 190 ℃ and 200kPa until the content of the distilled micromolecules reaches more than 95% of a theoretical value, and terminating the reaction to obtain an esterification solution;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 6000g/mol and the content of 40 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 235 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 235 ℃ and under the pressure of 70Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 8: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing dimethyl 2, 5-furandicarboxylate and ethylene glycol in a molar ratio of 1:1.6, and then adding a titanium-antimony composite catalyst with the content of 0.2 mol% relative to the dimethyl 2, 5-furandicarboxylate, 0.004 wt% of trimethyl phosphite and 0.001 wt% of antioxidant 1010, wherein the titanium-antimony composite catalyst is obtained by compounding a titanium-silicon composite catalyst and antimony trioxide in a mass ratio of 0.6: 0.4; then carrying out esterification reaction at 200 ℃ and 150kPa until the content of the distilled micromolecules reaches more than 95 percent of the theoretical value, and terminating the reaction to obtain esterified liquid;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 2000g/mol and the content of 60wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 235 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 240 ℃ and under the pressure of 50Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 9: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing dimethyl 2, 5-furandicarboxylate and ethylene glycol in a molar ratio of 1:1.6, and then adding a titanium-antimony composite catalyst with the content of 0.25 mol% relative to the dimethyl 2, 5-furandicarboxylate, 0.002 wt% of phosphoric acid and 0.005wt% of antioxidant 1010, wherein the titanium-antimony composite catalyst is obtained by compounding ethylene glycol titanium and ethylene glycol antimony in a mass ratio of 0.5: 0.5; then carrying out esterification reaction at 190 ℃ and 150kPa until the content of the distilled micromolecules reaches more than 95% of a theoretical value, and terminating the reaction to obtain an esterification solution;
2) pre-polycondensation reaction:
adding polyethylene glycol with the number average molecular weight of 2000g/mol and the content of 10 wt% relative to 2, 5-furandicarboxylic acid into the esterification solution, uniformly stirring, raising the temperature to 235 ℃, and performing pre-polycondensation reaction under the pressure of 100-1000Pa to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 235 ℃ and under the pressure of 100Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
Example 10: melting and mixing the copolyester prepared in example 1 with 0.5 wt% of amino modified wood fiber aerogel particles to prepare degradable bio-based 2, 5-furandicarboxylic acid-based copolyester containing nucleating agent amino modified wood fiber aerogel particles;
the preparation of the amino modified lignocellulosic aerogel particles comprises the following steps:
a) dissolving 10 parts of lignin fiber in water, and uniformly stirring to prepare lignin fiber liquid;
b) adding 10 parts of hexamethoxy melamine formaldehyde resin into lignin fiber liquid, mixing, then adding phosphoric acid to adjust the pH value to 3, then carrying out freeze drying, and carrying out heat preservation in a drying oven at 110 ℃ for 12 hours to prepare the wood fiber aerogel;
c) immersing the wood fiber aerogel into ethanol, taking out, placing into 5wt% of aminosilane aqueous solution, taking out after the reaction is finished, replacing and washing with water and ethanol, and freeze-drying and grinding to obtain the amino modified wood fiber aerogel particles.
Example 11: melting and mixing the copolyester prepared in example 1 with 1.5 wt% of amino modified wood fiber aerogel particles to prepare degradable bio-based 2, 5-furandicarboxylic acid-based copolyester containing nucleating agent amino modified wood fiber aerogel particles;
the preparation of the amino modified lignocellulosic aerogel particles comprises the following steps:
a) dissolving 10 parts of lignin fiber in water, and uniformly stirring to prepare lignin fiber liquid;
b) adding 2 parts of hexamethoxy melamine formaldehyde resin into lignin fiber liquid, mixing, then adding phosphoric acid to adjust the pH value to 5, then carrying out freeze drying, and carrying out heat preservation in a drying oven at 140 ℃ for 8 hours to prepare the wood fiber aerogel;
c) immersing the wood fiber aerogel into ethanol, taking out, placing into an aminosilane aqueous solution, taking out after the reaction is finished, replacing and washing with water and ethanol, and freeze-drying and grinding to obtain the amino modified wood fiber aerogel particles.
Example 12: melting and mixing the copolyester prepared in example 1 with 3wt% of amino modified wood fiber aerogel particles to prepare degradable bio-based 2, 5-furandicarboxylic acid-based copolyester containing nucleating agent amino modified wood fiber aerogel particles;
the preparation of the amino modified lignocellulosic aerogel particles comprises the following steps:
a) dissolving 10 parts of lignin fiber in water, and uniformly stirring to prepare lignin fiber liquid;
b) adding 6 parts of hexamethoxy melamine formaldehyde resin into lignin fiber liquid, mixing, then adding phosphoric acid to adjust the pH value to 4, then carrying out freeze drying, and carrying out heat preservation in a drying oven at 130 ℃ for 10 hours to prepare the wood fiber aerogel;
c) immersing the wood fiber aerogel into ethanol, taking out, placing into an aminosilane aqueous solution, taking out after the reaction is finished, replacing and washing with water and ethanol, and freeze-drying and grinding to obtain the amino modified wood fiber aerogel particles.
Comparative example 1: a preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following preparation steps:
1) esterification reaction:
uniformly mixing 2, 5-furandicarboxylic acid and ethylene glycol in a molar ratio of 1:1.6, and then adding a titanium-antimony composite catalyst with the content of 0.2 mol% relative to the 2, 5-furandicarboxylic acid, 0.002 wt% of trimethyl phosphite and 0.005wt% of antioxidant 1010, wherein the titanium-antimony composite catalyst is obtained by compounding a titanium-silicon composite catalyst and ethylene glycol in a mass ratio of 0.5: 0.5; then carrying out esterification reaction at 190 ℃ and 150kPa until the content of the distilled micromolecules reaches more than 95% of a theoretical value, and terminating the reaction to obtain an esterification solution;
2) pre-polycondensation reaction:
raising the temperature of the esterification liquid to 235 ℃, and controlling the pressure between 100 and 1000Pa to directly carry out pre-polymerization reaction to obtain a prepolymer;
3) and (3) final polycondensation reaction:
and (3) carrying out final polycondensation reaction on the prepolymer at 240 ℃ and under the pressure of 80Pa, and finishing the reaction when the current of a polymerization kettle reaches 0.140-0.160mA to prepare the poly (ethylene 2, 5-furandicarboxylate).
Comparative example 2: the difference from example 10 is that: the added nucleating agent is talcum powder.
Comparative example 3: the difference from example 10 is that: the preparation of the amino modified lignocellulosic aerogel particles comprises the following steps:
a) dissolving 10 parts of lignin fiber in water, and uniformly stirring to prepare lignin fiber liquid;
b) adding 10 parts of hexamethoxy melamine formaldehyde resin into lignin fiber liquid, mixing, then adding phosphoric acid to adjust the pH value to 3, then carrying out freeze drying, and carrying out heat preservation in a drying oven at 110 ℃ for 12 hours to prepare the wood fiber aerogel;
c) and grinding the wood fiber aerogel to prepare the wood fiber aerogel particles.
The polyesters prepared in examples 1 to 9 and comparative example 1 were characterized for melting point, thermal degradation temperature, surface water contact angle and degradability; the degradation evaluation method comprises the following steps: pressing the polyester into a film with the thickness of 0.1-0.3 mm, cutting the film into strips of 1cm multiplied by 3cm, putting the films into a vacuum oven at 50 ℃ for drying for 48h, respectively weighing the mass of a sample strip, then respectively putting the films into phosphate buffer solutions with the PH value of 7.2 and the PH value of 12, treating the films at 37 ℃ for 100 days, taking out the sample strips every 10 days, drying and then weighing the samples. The results are shown in the following table.
From the data, compared with the poly (ethylene 2, 5-furandicarboxylate) prepared by the non-blocked polyethylene glycol in the comparative example 1, the degradable bio-based 2, 5-furandicarboxylate copolyester prepared by the technical means of the invention has smaller surface water contact angle and higher hydrophilicity; and has better degradation performance in neutral and alkaline buffer solutions.
The polyesters obtained in examples 1 to 9 and comparative example 1 were characterized with respect to the final polycondensation time and color, and the results are as follows.
From the above data, it can be seen that the final polycondensation time is gradually reduced with the increase of PEG content and molecular weight, but the intrinsic viscosity of the copolyester is gradually increased, and the color is gradually changed from yellow brown to milky white, which indicates that the addition of PEG not only shortens the polycondensation time, but also improves the color of the copolyester.
The polyester prepared in the embodiments 1, 10-12 and the comparative example is subjected to crystallization property characterization, and is subjected to spinning treatment by using a single-screw extruder and a winding machine, wherein the temperature of the single screw is set to be 200-240 ℃, the winding speed of the winding machine is 10-25 m/min, a copolyester monofilament is obtained, and the strength of the monofilament is detected.
From the above data, the copolyester with the amino modified wood fiber aerogel particles added in examples 10-12 has excellent crystallization performance, higher initial crystallization temperature, larger crystallization enthalpy and shorter half crystallization time, which indicates that the amino modified wood fiber aerogel particles have good heterogeneous nucleation effect, and the crystallinity of comparative example 3 is worse than that of example 10, which indicates that the amino modified nucleating agent and the copolyester have better molecular chain combination, so the heterogeneous nucleation effect is better; and the crystallization performance of example 1 is better than that of comparative example 1, which shows that the addition of PEG can also induce crystallization and improve the crystallization rate. Meanwhile, as seen from the strength of the polyester monofilament, the better the crystallization property is, the higher the strength of the monofilament is.
Claims (10)
1. The degradable bio-based 2, 5-furandicarboxylic acid-based copolyester is characterized in that a molecular chain of the degradable bio-based 2, 5-furandicarboxylic acid-based copolyester is composed of a bio-based polyester chain segment and a functional polyether chain segment.
2. The degradable bio-based 2, 5-furandicarboxylic acid-based copolyester of claim 1, wherein the bio-based ester segment is obtained by reacting 2, 5-furandicarboxylic acid and/or its ester with a diol, the diol comprises one or more of ethylene glycol, 1, 3-propanediol, and 1, 4-butanediol, and the functional polyether segment is polyethylene glycol.
3. A preparation method of degradable bio-based 2, 5-furandicarboxylic acid-based copolyester is characterized by comprising the following preparation steps:
1) esterification reaction:
mixing 2, 5-furandicarboxylic acid and/or ester thereof with dihydric alcohol, adding a titanium-antimony composite catalyst, a heat stabilizer and an antioxidant, uniformly stirring, and then carrying out esterification reaction at the temperature of 180-230 ℃ and under the pressure of 50-200kPa until the content of distilled micromolecules reaches more than 95 percent of a theoretical value, and terminating the reaction to obtain an esterification solution;
2) pre-polycondensation reaction:
adding polyethylene glycol into the esterification liquid, uniformly stirring, then raising the temperature to 230-245 ℃, and controlling the pressure between 100-1000Pa to perform pre-polymerization reaction to obtain a prepolymer;
3) final polycondensation reaction
And (3) performing final polycondensation reaction on the prepolymer at 230-245 ℃ and under the pressure of 1-200Pa until the current in the polymerization kettle reaches 0.140-0.160mA, and preparing the degradable bio-based 2, 5-furandicarboxylic acid based copolyester.
4. The method for preparing degradable bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 3, wherein the molar ratio of 2, 5-furandicarboxylic acid and/or ester thereof to diol in step 1) is 1: 1.4-2.0.
5. The preparation method of the degradable bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 3, wherein the titanium-antimony composite catalyst in the step 1) comprises 0.3-1:0-0.7 mass ratio of titanium catalyst and antimony catalyst, and the addition amount of the titanium-antimony composite catalyst is 0.05-0.25% of the molar content of 2, 5-furandicarboxylic acid and/or ester thereof; the titanium catalyst comprises one or more of tetrabutyl titanate, titanium-silicon composite catalyst, isopropanol titanate and ethylene glycol titanium, and the antimony catalyst comprises one or more of ethylene glycol antimony, antimony trioxide and antimony acetate; the antioxidant comprises one or more of antioxidant 1178, antioxidant 618, antioxidant 1010 and antioxidant 1076, and the addition amount is 0.001-0.005wt% of 2, 5-furandicarboxylic acid and/or ester thereof; the heat stabilizer comprises one or more of phosphoric acid, trimethyl phosphate, triphenyl phosphate, trimethyl phosphite and polyphosphoric acid, and the addition amount of the heat stabilizer is 0.001-0.005wt% of 2, 5-furandicarboxylic acid and/or ester thereof.
6. The method for preparing degradable bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 3, wherein the number average molecular weight of the polyethylene glycol in step 2) is 600-10000g/mol, and the addition amount is 10-60wt% of 2, 5-furandicarboxylic acid and/or its ester.
7. The method for preparing degradable bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 3, wherein the prepared degradable bio-based 2, 5-furandicarboxylic acid-based copolyester comprises 0.5-3wt% of nucleating agent; the nucleating agent is amino modified wood fiber aerogel particles.
8. The preparation method of the degradable bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 7, wherein the amino modified wood fiber aerogel particles comprise the following preparation steps:
a) dissolving lignin fiber in water, and uniformly stirring to prepare lignin fiber liquid;
b) adding hexamethoxy melamine formaldehyde resin into the lignin fiber liquid for mixing, then adding phosphoric acid to adjust the pH value to 3-5, then carrying out freeze drying, and carrying out heat preservation in a drying oven at the temperature of 110-140 ℃ for 8-12h to prepare the wood fiber aerogel;
c) immersing the wood fiber aerogel into ethanol, taking out, placing into an aminosilane aqueous solution, taking out after the reaction is finished, replacing and washing with water and ethanol, and freeze-drying and grinding to obtain the amino modified wood fiber aerogel particles.
9. The preparation method of the degradable bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 7, wherein the mass ratio of the lignin fiber to the hexamethoxymelamine formaldehyde resin is 1-5: 1.
10. Use of the degradable biobased 2, 5-furandicarboxylic acid-based copolyester of claims 1 to 9 in the preparation of fibers.
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| CN112812645A (en) * | 2021-01-19 | 2021-05-18 | 上海贝能环保科技有限公司 | Bio-based waterproof environment-friendly coating and preparation method thereof |
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| CN115232294A (en) * | 2022-07-15 | 2022-10-25 | 华润化学材料科技股份有限公司 | Copolyester material and preparation method and application thereof |
| CN116065394A (en) * | 2023-03-30 | 2023-05-05 | 张家港市德宝化工有限公司 | Bio-based moisture-absorption sweat-release multifunctional finishing agent and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875787A (en) * | 2020-07-07 | 2020-11-03 | 浙江恒澜科技有限公司 | High-heat-resistance degradable copolyester and preparation method thereof |
| CN111875787B (en) * | 2020-07-07 | 2022-07-08 | 浙江恒逸石化研究院有限公司 | High-heat-resistance degradable copolyester and preparation method thereof |
| CN112812645A (en) * | 2021-01-19 | 2021-05-18 | 上海贝能环保科技有限公司 | Bio-based waterproof environment-friendly coating and preparation method thereof |
| CN113121804A (en) * | 2021-04-14 | 2021-07-16 | 江苏科奕莱新材料科技有限公司 | High-performance bio-polyether ester elastomer and preparation method thereof |
| CN115232294A (en) * | 2022-07-15 | 2022-10-25 | 华润化学材料科技股份有限公司 | Copolyester material and preparation method and application thereof |
| CN116065394A (en) * | 2023-03-30 | 2023-05-05 | 张家港市德宝化工有限公司 | Bio-based moisture-absorption sweat-release multifunctional finishing agent and preparation method and application thereof |
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