CN108727575B - Preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester - Google Patents
Preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
The invention relates to a preparation method of bio-based 2, 5-furandicarboxylic acid based copolyester, which comprises the steps of uniformly mixing dibasic acid, aliphatic diol I, a guide and a titanium-silicon-cobalt composite catalyst, and then sequentially carrying out esterification reaction, pre-polycondensation reaction and final polycondensation reaction to obtain the bio-based 2, 5-furandicarboxylic acid based copolyester; the guide is an esterified substance generated by the reaction of bio-based 2, 5-furandicarboxylic acid and aliphatic diol II, the molar ratio of the diacid to the aliphatic diol I is 1: 1.05-1.10, the titanium-silicon-cobalt composite catalyst is formed by compounding a titanium-silicon composite catalyst and a cobalt catalyst, the titanium-silicon composite catalyst is obtained by loading a titanium catalyst on a silicon catalyst, and the aliphatic diol I and the aliphatic diol II are the same or different. The preparation method of the invention has the advantages of less side reaction, high reaction rate, concentrated molecular weight distribution of the prepared product, high viscosity and good quality, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of polyester preparation, relates to a preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester, and particularly relates to a preparation method of bio-based 2, 5-furandicarboxylic acid-based polyacid-aliphatic diol copolyester.
Background
Polyester is a generic term for polymers obtained by polycondensation of polyhydric alcohols and polybasic acids. Mainly polyethylene terephthalate (PET), and conventionally includes linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate. Is a polymer with excellent performance and wide application. The method is widely applied to the fields of fibers, plastics, films and the like. Compared to petroleum-based PET, monomer 2,5-FDCA of PEF is derived from bio-based resources, and can reduce the use of non-renewable resources (NREU) and the emission of greenhouse gases (GHG). With the rapid consumption of petroleum resources, polymers formed by utilizing renewable bio-based monomers in nature are a great direction for future development.
The structure of bio-based 2, 5-furandicarboxylic acid (2,5-FDCA) and terephthalic acid (TPA) is schematically shown as follows:
the molecular structure of the bio-based 2, 5-furandicarboxylic acid contains aromatic rings, and the bio-based 2, 5-furandicarboxylic acid is used for synthesizing bio-based high polymer materials and can replace terephthalic acid, isophthalic acid, adipic acid, succinic acid, bisphenol A and the like to be applied to the synthesis of bio-based polymers such as polyester, polyamide, epoxy resin and the like. It has therefore been scored by the U.S. department of energy as one of the 12 most potent bio-based platform compounds, considered by dupont and DSM as a "sleeping giant". 2, 5-furandicarboxylic acid as a bio-based polymer aromatic ring monomer with a 'rigid' planar structure can be polymerized with monomers such as diol, diamine and the like to prepare a novel bio-based polymer synthetic material with excellent performance. The biological 2, 5-furandicarboxylic acid is used for replacing or partially replacing petroleum-based terephthalic acid, and has important significance for relieving petroleum resources.
In the synthesis of bio-based 2, 5-furandicarboxylic acid based polyesters, many researchers and research institutes have conducted intensive studies. Patent CN 201610608996.3 discloses a preparation method of poly-2, 5-furandicarboxylic acid diol ester, which is subjected to esterification and polycondensation in sequence under the action of a catalyst to obtain poly-2, 5-furandicarboxylic acid diol ester. Wherein the molar ratio of the 2, 5-furandicarboxylic acid to the aliphatic diol is up to 1: 2; patent CN 201110246585.1 discloses 2, 5-furandicarboxylic acid-terephthalic acid-aliphatic diol copolyester and a preparation method thereof, under the action of a catalyst, 2, 5-furandicarboxylic acid, terephthalic acid and aliphatic diol are subjected to esterification reaction to obtain a first intermediate product, and then the first intermediate product is subjected to polycondensation reaction to obtain the 2, 5-furandicarboxylic acid-terephthalic acid-aliphatic diol copolyester, wherein the molar ratio of the sum of the 2, 5-furandicarboxylic acid and the terephthalic acid to the aliphatic diol is up to 1:3.
The prior preparation of the bio-based 2, 5-furandicarboxylic acid-based polyester has the following problems: 1) in the prior art system, the molar ratio of bio-based 2, 5-furandicarboxylic acid to diol alcohol acid is far higher than 1:1, the diol is subjected to self-polycondensation at a high alcohol acid molar ratio to generate a byproduct, which has a great influence on the fiber forming property of polyester, and meanwhile, the high molar ratio needs to consume more diol raw materials, so that the cost is increased; 2) for polyester, the esterification stage directly concerns the quality of the final polycondensation product, and the bio-based 2, 5-furandicarboxylic acid has a structure very similar to that of terephthalic acid, but the thermal stability is reduced, while the prior art needs to perform full esterification reaction under the esterification time of more than 3 hours under the high molar ratio of alcohol and acid, which easily causes side reaction in the esterification process; 3) after the esterification is finished, the polyester can be prepared only through the pre-polycondensation and final polycondensation, and the intrinsic viscosity of the pre-polycondensation product is generally above 0.25dL/g, so that the finally prepared product has the disadvantages of wider molecular weight distribution, poor processability, high possibility of generating phenomena such as broken filaments, broken ends, waste filaments and the like in the processing process.
Therefore, the development of the preparation method of the bio-based 2, 5-furandicarboxylic acid based copolyester with less side reaction, concentrated molecular weight distribution, high viscosity and good quality has practical significance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of bio-based 2, 5-furandicarboxylic acid based copolyester with less side reaction, concentrated molecular weight distribution, high viscosity and good quality.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of bio-based 2, 5-furandicarboxylic acid based copolyester comprises the steps of uniformly mixing dibasic acid, aliphatic diol I, a guide and a titanium-silicon-cobalt composite catalyst, and then sequentially carrying out esterification reaction, pre-polycondensation reaction and final polycondensation reaction to obtain the bio-based 2, 5-furandicarboxylic acid based copolyester;
the guiding substance is an esterified substance generated by the reaction of bio-based 2, 5-furandicarboxylic acid and aliphatic diol II, the molar ratio of the dibasic acid to the aliphatic diol I is 1: 1.05-1.10, the titanium-silicon-cobalt composite catalyst is formed by compounding a titanium-silicon composite catalyst and a cobalt catalyst, the titanium-silicon composite catalyst is obtained by loading a titanium catalyst on a silicon catalyst, and the aliphatic diol I and the aliphatic diol II are the same or different.
As a preferred technical scheme:
according to the preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester, the content of side reaction products in the bio-based 2, 5-furandicarboxylic acid-based copolyester is less than or equal to 1.0 wt%.
The preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing and pulping dibasic acid and aliphatic diol I according to the molar ratio of 1: 1.05-1.10, adding a titanium-silicon-cobalt composite catalyst and a guide substance, and carrying out an esterification reaction at 180-240 ℃ and 50-200 KPa until the water yield reaches 95% of the theoretical water yield; the guide is an esterified substance generated by the reaction of bio-based 2, 5-furandicarboxylic acid and aliphatic diol II; the esterification reaction time is 1.5-3.5 h, and if no guide is added, the esterification reaction is carried out according to the molar ratio of the alcohol acid, and the esterification reaction time is 3.5-5.0 h. The molar ratio of the dibasic acid to the aliphatic diol I in the esterification reaction is 1: 1.05-1.10, the existing alcohol acid has a high molar ratio, which easily causes the diol to generate self-polycondensation at high temperature to increase the proportion of side reaction products, but the low alcohol acid molar ratio can cause the esterification reaction rate to be obviously reduced, so that the reaction time is greatly prolonged; the esterification temperature is controlled to be 180-240 ℃, because the esterification process is an endothermic reaction, the esterification reaction rate can be further accelerated by overhigh temperature, but the side reaction rate can also be accelerated, and the heat requirement of the esterification reaction and the dissolving process can not be met by overlow temperature; the esterification reaction is slightly positive in pressure, and the pressure is controlled to be 50-200 KPa, because small molecular moisture is generated in the esterification process, the esterification reaction rate can be promoted under certain positive pressure. The higher pressure can put forward higher requirements to the esterification reaction device, and the esterification reaction of the invention is carried out on the prior device without further modification, thereby reducing the cost. Other catalysts except the titanium-silicon-cobalt composite catalyst can also be selected, but the side reaction is increased and the color of the product is poor.
(2) Pre-polycondensation reaction;
adding an anti-thermal oxidant and/or an antioxidant into the product obtained in the step (1), and performing pre-polycondensation reaction at 200-260 ℃ and 100-1000 Pa for 15-45 min to obtain a pre-polycondensation product with the intrinsic viscosity of less than or equal to 0.15 dL/g; the stirring speed of the pre-polycondensation reaction is 5-20 rpm;
although it is possible to obtain low-viscosity precondensate without adding anti-thermal-oxidation agents and/or antioxidants, the low-viscosity precondensate is susceptible to degradation by thermal oxidation during the polycondensation.
The pre-polycondensation reaction temperature is controlled to be 200-260 ℃, because the pre-polycondensation reaction cannot be carried out due to too low reaction temperature, the thermal degradation side reaction is enhanced in the pre-polycondensation reaction process due to too high reaction temperature, and the color of the formed product is poor.
The pre-polycondensation reaction pressure is controlled to be 100-1000 Pa, and compared with the condition that the final polycondensation vacuum degree is lower, the low-viscosity prepolymer in the pre-polycondensation reaction can be extracted due to too low pressure (namely higher vacuum effect), so that a pipeline is blocked, and a polycondensation accident is caused; too high a pressure (i.e., worse vacuum effect) may result in failure to remove small molecules in the polycondensation reaction, and failure of the pre-polycondensation reaction to proceed normally.
The pre-polycondensation reaction time is controlled to be 15-45 min, which is obviously shorter than the reaction time in the prior art, if the pre-polycondensation reaction time is too short, the viscosity of the formed prepolymer is too low (lower than 0.10-0.15 dL/g), and the prepolymer is easy to be drawn out together with small molecules of dihydric alcohol in the subsequent final polycondensation reaction under the condition of high vacuum to block a pipeline; if the pre-polycondensation reaction time is too long, the molecular weight of the formed prepolymer is gradually increased, the weight average molecular weight distribution coefficient of the product is widened, and the final polycondensation reaction is further widened, so that the aim of concentrating the weight average molecular weight distribution coefficient provided by the invention cannot be fulfilled.
The stirring speed of the pre-polycondensation reaction is 5-20 rpm, the viscosity of the material in the pre-polycondensation reaction process is higher than that of an esterification reaction product and lower than that of a final polycondensation reaction product, and the excessively high stirring speed can lead to the fact that the pre-polycondensation product with lower viscosity is brought out together with dihydric alcohol in a vacuum environment, so that the reaction is not favorable. The effect of uniformly stirring the materials cannot be achieved at an excessively low stirring speed.
(3) Final polycondensation reaction;
performing final polycondensation reaction on the pre-polycondensation product prepared in the step (2) for 1.5-3.5 hours at 220-280 ℃ under the condition of 10-100 Pa to prepare bio-based 2, 5-furandicarboxylic acid copolyester; the stirring speed of the final polycondensation reaction is 5-10 rpm.
The final polycondensation reaction temperature is controlled to be 220-280 ℃, and the final polycondensation reaction cannot be carried out due to the excessively low reaction temperature; too high a reaction temperature leads to increased thermal degradation side reactions during the final polycondensation reaction and to a deterioration in the color of the product formed.
The final polycondensation reaction pressure is controlled to be 10-100 Pa, and the requirement of excessively low pressure (namely higher vacuum effect) on equipment is higher; too high a pressure (i.e., worse vacuum effect) may result in failure to achieve removal of small molecules in the polycondensation reaction and failure of the final polycondensation reaction to proceed normally.
The final polycondensation reaction time is controlled to be 1.5-3.5 h, and if the final polycondensation reaction time is too short, the formed product cannot reach the spinning grade; if the precondensation reaction time is too long, the thermal degradation of the polymer under high temperature conditions is significantly increased, and the product rapidly decreases due to thermal degradation after reaching the maximum weight average molecular weight.
The stirring speed of the final polycondensation reaction is 5-10 rpm, the viscosity of materials in the final polycondensation reaction process is higher than that of a pre-polycondensation reaction product, the higher the viscosity of the product is, the harder the stirring is, the too high stirring speed can not realize the stirring effect on a high-viscosity polymer system, and the motor is damaged due to too large current; the effect of uniformly stirring the materials cannot be achieved at an excessively low stirring speed.
According to the preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester, the addition amount of the guide is 0.5-5.0 wt% of the addition amount of the dibasic acid in the step (1); the addition amount of the titanium-silicon-cobalt composite catalyst is 100-200 ppm of the addition amount of the dibasic acid in the step (1); the titanium-silicon-cobalt composite catalyst is prepared by compounding a titanium catalyst, a silicon catalyst and a cobalt catalyst according to a molar ratio of 1: 0.1-10.
The purpose of introducing the guide in the invention is to reduce the proportion of dihydric alcohol in the raw materials and accelerate the esterification reaction rate. The addition amount of the guide is too low, so that the effective dissolution of the dibasic acid in the raw materials cannot be realized, the esterification reaction rate is not obviously accelerated, and the esterification reaction time can be prolonged; if the amount of the guide is too high, the guide can dissolve the dibasic acid quickly, but the cost increases and the economy is poor.
The addition amount of the titanium-silicon-cobalt composite catalyst is 100-200 ppm of the mass of the dibasic acid, and the composite catalyst is selected in the invention in consideration of ensuring the catalytic effect and improving the final product. The catalyst effect is reduced due to the excessively low catalyst addition amount, the reaction time is prolonged, and the efficiency is reduced; too high a catalyst dosage can result in too rapid a reaction, potentially presenting a "popping" hazard, and also increasing costs.
According to the preparation method of the bio-based 2, 5-furandicarboxylic acid copolyester, the titanium catalyst is tetrabutyl titanate or metatitanic acid; the silicon catalyst is silicon dioxide; the cobalt catalyst is cobalt acetate. The titanium catalyst is loaded on silicon dioxide to form TiO2-SiO2Compounding the composite catalyst with a cobalt catalyst to obtain the titanium-silicon-cobalt composite catalyst.
The specific preparation method of the titanium-silicon-cobalt composite catalyst comprises the following steps:
the titanium-silicon-cobalt composite catalyst is prepared from TiO2-SiO2The composite catalyst and the cobalt catalyst are mixed and added into a polymerization system according to a certain proportion. Wherein, TiO is obtained by adopting a sol-gel method2-SiO2The composite catalyst method comprises the following steps: proper amount of ethyl orthosilicate, ethanol, distilled water and nitric acid are added into a three-neck flask in sequence and mixed evenly. The three-neck flask is placed on a magnetic stirrer to be heated and refluxed, the heating temperature is set to be 65 ℃, the stirring speed is 820r/min, and the reflux is carried out for 2 hours. After the ethyl orthosilicate is completely hydrolyzed, 40.0g of tetrabutyl titanate is added into a three-neck flask and stirredMixing with reactant for 20 min. And slowly dripping a proper amount of steam house water by using a constant-pressure burette at a certain speed. After the addition was complete, the mixture was refluxed at 65 ℃ for 2 hours. After the gel was formed, it was aged at room temperature for 12 h. Drying at 110 deg.C for 12h in a forced air drying oven, removing water and ethanol solvent in the reaction system, and grinding the dried solid in a mortar. Putting the ground powder into a muffle furnace, setting the baking temperature to be 500 ℃, starting timing when the temperature reaches the set temperature, and baking for 3 hours. After the roasting is finished, taking out the roasted material, naturally cooling the roasted material, and finally obtaining the TiO2-SiO2And (3) compounding a catalyst.
According to the preparation method of the bio-based 2, 5-furandicarboxylic acid based copolyester, the esterification rate of the bio-based 2, 5-furandicarboxylic acid and the aliphatic diol II which react to generate a guide is 90-98%; the dibasic acid is more than one of 2, 5-furandicarboxylic acid, terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; the aliphatic diol I and the aliphatic diol II are respectively one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and decanediol.
According to the preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester, the addition amount of the anti-thermoxidant is 0.005-0.05 wt% of the addition amount of the dibasic acid in the step (1); the addition amount of the antioxidant is 0.001-0.01 wt% of the addition amount of the dibasic acid in the step (1).
The preparation method of the bio-based 2, 5-furandicarboxylic acid copolyester is characterized in that the anti-thermoxidant is more than one of phosphoric acid, phosphorous acid, trimethyl phosphate, trimethyl phosphite and triphenyl phosphate; the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616.
According to the preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester, the weight average molecular weight distribution coefficient of the bio-based 2, 5-furandicarboxylic acid-based copolyester is 1.2-1.6, the intrinsic viscosity is 0.60-1.20 dL/g, and the color degree is less than or equal to 10.
According to the preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester, the bio-based 2, 5-furandicarboxylic acid-based copolyester is prepared into POY, FDY or DTY filaments, the processing waste filament rate is less than or equal to 10kg/t, and the yarn evenness rate of fibers is less than or equal to 1.0%. The bio-based 2, 5-furandicarboxylic acid based copolyester can be prepared into fibers and can also be used as a raw material of products such as films, plastics and the like. Compared with the existing petroleum-based terephthalic acid-based polyacid-aliphatic diol copolyester fiber, the polyester fiber has higher glass transition temperature (the glass transition temperature is more than or equal to 70 ℃), higher strength (the mechanical strength of the fiber is more than or equal to 4.0cN/dtex), higher modulus (the fiber modulus is more than or equal to 120cN/dtex) and good gas barrier property (under the same condition, the CO content is higher than or equal to 120cN/dtex)2Barrier property is improved by more than 1 time, O2The barrier performance is improved by more than 4 times).
The invention mechanism is as follows:
at present, the preparation process of the bio-based 2, 5-furandicarboxylic acid based copolyester is generally to perform esterification reaction under the condition of high alcohol-acid molar ratio, after the esterification reaction product is pre-condensed to prepare a pre-condensed product with high intrinsic viscosity, the final condensation reaction is performed to finally generate the bio-based 2, 5-furandicarboxylic acid based copolyester. There are the following problems: the esterification reaction time is long, the side reactions are more, the cost is high, and the intrinsic viscosity of the pre-polycondensation product is too high, so that the finally prepared bio-based 2, 5-furan diformyl copolyester product has wider molecular weight distribution and poor polyester processability.
Aiming at the problems, the esterification reaction is carried out by adopting a lower molar ratio (1: 1.05-1.10) of the alcohol acid, so that the problem of the self-polycondensation side reaction of the raw material aliphatic diol is obviously improved. Because the molar ratio of the alcohol acid is lower, the dissolving amount of the dibasic acid of the raw material is reduced, the esterification reaction rate is reduced, in order to overcome the problem, the invention adds the ester generated by the reaction of the bio-based 2, 5-furandicarboxylic acid and the aliphatic diol as a guide, the solubility of the dibasic acid of the raw material in the ester generated by the reaction of the bio-based 2, 5-furandicarboxylic acid and the aliphatic diol is high, the guide is added at the initial stage of the esterification reaction to dissolve the dibasic acid of the raw material in the ester, the dibasic acid of the raw material dissolved in the guide can rapidly carry out the esterification reaction with the aliphatic diol of the raw material to further generate the ester, and then the rest dibasic acid of the raw material is dissolved, so that the esterification reaction is. The invention realizes the dynamic strengthening in the esterification process by adding the guide at the initial stage of esterification, so that the esterification reaction enters a homogeneous reaction system in advance, the whole esterification reaction rate is obviously improved compared with the prior art, and the esterification reaction time is greatly shortened.
The intrinsic viscosity of the pre-polycondensation product is controlled within 0.15dL/g by controlling the pre-polycondensation reaction time (15-45 min) (the pre-polycondensation reaction time in the prior art is 1.0-2.0 h, and the intrinsic viscosity is above 0.25 dL/g), and finally the final polycondensation reaction is carried out, so that the molecular weight distribution of the bio-based 2, 5-furandicarboxylic acid based copolyester formed after the final polycondensation reaction is concentrated, and the spinning processing process and the quality are remarkably improved.
Has the advantages that:
(1) according to the preparation method of the bio-based 2, 5-furandicarboxylic acid based copolyester, the molar ratio of low alcohol acid is adopted, the molar ratio of the dibasic acid to the aliphatic diol is controlled to be 1: 1.05-1.10, so that the aliphatic diol is reduced to generate a self-polycondensation side reaction, the content of by-products in the finally formed bio-based 2, 5-furandicarboxylic acid based copolyester is low, the color and luster degree of the product is good, the consumption of alcohol is reduced, and the cost is reduced;
(2) according to the preparation method of the bio-based 2, 5-furandicarboxylic acid based copolyester, under the condition of low alcohol acid molar ratio, the bio-based 2, 5-furandicarboxylic acid and aliphatic diol are added at the initial stage of esterification to form an esterified substance as a guide, so that the dynamic reinforcement in the esterification process is realized, the esterification reaction enters a homogeneous reaction system in advance, compared with the prior art, the whole esterification reaction rate is remarkably improved, the esterification reaction time is greatly shortened, and the side reaction is further reduced;
(3) according to the preparation method of the bio-based 2, 5-furandicarboxylic acid-based copolyester, after the esterification reaction is finished, the intrinsic viscosity of the pre-polycondensation product is controlled within 0.15dL/g, so that the molecular weight distribution of the bio-based 2, 5-furandicarboxylic acid-based copolyester formed after the final polycondensation reaction is concentrated, and the spinning quality of the bio-based 2, 5-furandicarboxylic acid-based copolyester is remarkably improved;
(4) the prepared bio-based 2, 5-furandicarboxylic acid-based copolyester is used for POY, FDY and DTY spinning, the processing waste silk rate is less than or equal to 10kg/t, the yarn evenness of fibers is less than or equal to 1.0 percent, and the bio-based 2, 5-furandicarboxylic acid-based copolyester can be used in the field of fiber forming processing and can be applied to the fields of high-grade home textile, clothes and the like.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.05, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction under the conditions of 180 ℃ and 100KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 90% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and propylene glycol, the addition amount of the leading object is 5.0 wt% of the terephthalic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 110ppm of the mass of the terephthalic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate according to the molar ratio of 1:0.8: 0.1;
(2) pre-polycondensation reaction;
adding phosphoric acid into the product in the step (1) to perform pre-polycondensation reaction for 20min at the temperature of 200 ℃ and the pressure of 1000Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.10dL/g, wherein the pre-polycondensation reaction is performed under the stirring of the stirring speed of 10rpm, and the adding amount of the phosphoric acid is 0.03 wt% of that of the terephthalic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 2.0h at 220 ℃ under the condition of 100Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 6 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.2, the intrinsic viscosity of 1.1dL/g, the color degree of 10 and the content of side reaction products of 0.9 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 9.2kg/t, and the yarn evenness rate of the fiber is 0.99%.
Example 2
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing and pulping bio-based 2, 5-furandicarboxylic acid and propylene glycol in a molar ratio of 1:1.06, adding a titanium-silicon-cobalt composite catalyst and a guide substance under the conditions of 220 ℃ and 150KPa until the water yield reaches 95% of the theoretical water yield, wherein the guide substance is an esterified substance with an esterification rate of 95% generated by the reaction of the bio-based 2, 5-furandicarboxylic acid and the propylene glycol, the addition amount of the guide substance is 4.5 wt% of the bio-based 2, 5-furandicarboxylic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 100ppm of the mass of the bio-based 2, 5-furandicarboxylic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding metatitanic acid, silicon dioxide and cobalt acetate in a molar ratio of 1:2.5: 0.5;
(2) pre-polycondensation reaction;
adding phosphorous acid into the product obtained in the step (1), and carrying out pre-polycondensation reaction for 40min at 235 ℃ and 200Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.11dL/g, wherein the pre-polycondensation reaction is carried out under the stirring of the stirring speed of 16rpm, and the adding amount of the phosphorous acid is 0.01 wt% of that of the bio-based 2, 5-furandicarboxylic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 2.5 hours at the temperature of 250 ℃ and under the condition of 20Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 6 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.6, the intrinsic viscosity of 1.10dL/g, the color degree of 9 and the content of side reaction products of 0.8 wt%. The yarn is made into bio-based 2, 5-furandicarboxylic acid copolyester FDY yarn, the processing waste yarn rate is 8.9kg/t, and the yarn evenness rate of the fiber is 0.89%.
Example 3
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing suberic acid and butanediol according to a molar ratio of 1:1.07, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction under the conditions of 230 ℃ and 50KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 98% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and pentanediol, the addition amount of the leading object is 4.0 wt% of the suberic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 130ppm of the mass of the suberic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate according to a molar ratio of 1:5.0: 4.0;
(2) pre-polycondensation reaction;
adding trimethyl phosphate into the product in the step (1), and carrying out pre-polycondensation reaction for 25min at 240 ℃ and 100Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.12dL/g, wherein the pre-polycondensation reaction is carried out under the stirring of 8rpm, and the addition amount of the trimethyl phosphate is 0.006 wt% of that of the suberic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 1.5h at 260 ℃ under the condition of 10Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 8 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.5, the intrinsic viscosity of 0.85dL/g, the color degree of 8 and the content of side reaction products of 0.85 wt%. The obtained product is prepared into bio-based 2, 5-furandicarboxylic acid based copolyester POY, the processing waste silk rate is 9.5kg/t, and the yarn evenness rate of fibers is 0.85%.
Example 4
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing terephthalic acid and propylene glycol according to a molar ratio of 1:1.08, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction under the conditions of 235 ℃ and 80KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 92% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and pentanediol, the addition amount of the leading object is 3.5 wt% of the terephthalic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 180ppm of the mass of the terephthalic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding metatitanic acid, silicon dioxide and cobalt acetate according to the molar ratio of 1:0.1: 5.7;
(2) pre-polycondensation reaction;
adding trimethyl phosphite into the product in the step (1), and carrying out pre-polycondensation reaction for 35min at the temperature of 245 ℃ and under the condition of 100Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.13dL/g, wherein the pre-polycondensation reaction is carried out under the stirring of the stirring speed of 17rpm, and the addition amount of the trimethyl phosphite is 0.015 wt% of that of the terephthalic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 1.5h at the temperature of 240 ℃ and under the pressure of 30Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 5 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.2, the intrinsic viscosity of 0.90dL/g, the color degree of 8 and the content of side reaction products of 0.9 wt%. The obtained product is prepared into bio-based 2, 5-furandicarboxylic acid based copolyester DTY, the processing waste silk rate is 9.5kg/t, and the yarn evenness rate of the fiber is 0.88%.
Example 5
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing sebacic acid and butanediol according to a molar ratio of 1:1.09, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction at 240 ℃ and 150KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 92% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and hexanediol, the addition amount of the leading object is 3.0 wt% of the sebacic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 150ppm of the sebacic acid by mass, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate according to a molar ratio of 1:0.9: 3.6;
(2) pre-polycondensation reaction;
adding triphenyl phosphate into the product of the step (1), and carrying out pre-polycondensation reaction for 15min at 250 ℃ and 700Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.13dL/g, wherein the pre-polycondensation reaction is carried out under the stirring of the stirring speed of 20rpm, and the addition amount of the triphenyl phosphate is 0.035 wt% of that of the sebacic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 2.5 hours at 220 ℃ under 70Pa to prepare the bio-based 2, 5-furandicarboxylic acid copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 9 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.15, the intrinsic viscosity of 0.72dL/g, the color degree of 8 and the content of side reaction products of 1 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 9kg/t, and the yarn evenness of the fiber is 0.93 percent.
Example 6
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing azelaic acid and butanediol according to a molar ratio of 1:1.10, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction under the conditions of 220 ℃ and 120KPa until the water yield reaches 95% of theoretical water yield and the reaction is terminated, wherein the leading object is an esterified object with an esterification rate of 90% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and heptanediol, the addition amount of the leading object is 2.0 wt% of the azelaic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 100ppm of the mass of the azelaic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate according to the molar ratio of 1:3.8: 0.1;
(2) pre-polycondensation reaction;
adding a mixture of phosphoric acid and phosphorous acid (the mass ratio is 2:1) and an antioxidant 1010 into the product obtained in the step (1), and carrying out pre-polycondensation for 15min at the conditions of 240 ℃ and 500Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.14dL/g, wherein the pre-polycondensation reaction is carried out under stirring at the stirring speed of 11rpm, the adding amount of the mixture of phosphoric acid and phosphorous acid is 0.005 wt% of the added azelaic acid in the step (1), and the adding amount of the antioxidant 1010 is 0.001 wt% of the added azelaic acid in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 1.5 hours at 230 ℃ under the condition of 50Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 9 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.55, the intrinsic viscosity of 1.10dL/g, the color degree of 9 and the content of side reaction products of 0.8 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 9.5kg/t, and the yarn evenness rate of the fiber is 0.95%.
Example 7
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing isophthalic acid and hexanediol according to a molar ratio of 1:1.07, pulping, adding a titanium-silicon-cobalt composite catalyst and a guide, reacting at 228 ℃ and 150KPa until the water yield reaches 95% of the theoretical water yield, and terminating the reaction, wherein the guide is an esterified product with an esterification rate of 96% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and octanediol, the addition amount of the guide is 0.5 wt% of the isophthalic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 160ppm of the mass of the isophthalic acid, and the titanium-silicon-cobalt composite catalyst is compounded by metatitanic acid, silicon dioxide and cobalt acetate according to the molar ratio of 1:8.2: 0.8;
(2) pre-polycondensation reaction;
adding a mixture of trimethyl phosphate and trimethyl phosphite and an antioxidant 168 into the product obtained in the step (1), and carrying out pre-polycondensation for 25min at 230 ℃ and 300Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.15dL/g, wherein the pre-polycondensation reaction is carried out under stirring at a stirring speed of 10rpm, the adding amount of the mixture of trimethyl phosphate and trimethyl phosphite is 0.04 wt% of the adding amount of the isophthalic acid in the step (1), and the adding amount of the antioxidant 168 is 0.005 wt% of the adding amount of the isophthalic acid in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 3.5 hours at 270 ℃ under the condition of 30Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 7 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.31, the intrinsic viscosity of 0.68dL/g, the color degree of 7 and the content of side reaction products of 0.95 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 10kg/t, and the yarn evenness rate of the fiber is 0.86%.
Example 8
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing terephthalic acid/azelaic acid (the mass ratio is 2:1) and pentanediol according to the molar ratio of 1:1.06, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to carry out reaction under the conditions of 234 ℃ and 180KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with the esterification rate of 98% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and nonanediol, the addition amount of the leading object is 0.5 wt% of the terephthalic acid/azelaic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 200ppm of the mass of the terephthalic acid/azelaic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate according to the molar ratio of 1:5.0: 5.5;
(2) pre-polycondensation reaction;
adding a mixture of trimethyl phosphite and triphenyl phosphate (the mass ratio is 1:1) and an antioxidant 616 into the product obtained in the step (1), and carrying out pre-polycondensation reaction for 20min at 230 ℃ and 600Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.10dL/g, wherein the pre-polycondensation reaction is carried out under stirring at the stirring speed of 5rpm, the adding amount of the mixture of trimethyl phosphite and triphenyl phosphate is 0.05 wt% of that of the terephthalic acid/azelaic acid added in the step (1), and the adding amount of the antioxidant 616 is 0.01 wt% of that of the terephthalic acid/azelaic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 2.5 hours at the temperature of 250 ℃ and under the condition of 40Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 8 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.2, the intrinsic viscosity of 0.85dL/g, the color degree of 8 and the content of side reaction products of 0.8 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 8.1kg/t, and the yarn evenness rate of the fiber is 0.80 percent.
Example 9
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing sebacic acid and nonanediol in a molar ratio of 1:1.10, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction at 220 ℃ and 70KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 91% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and octanediol, the addition amount of the leading object is 1.5 wt% of sebacic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 200ppm of the mass of sebacic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate in a molar ratio of 1:7.5: 6.0;
(2) pre-polycondensation reaction;
adding an antioxidant 1010 into the product obtained in the step (1), and carrying out pre-polycondensation reaction for 35min at 250 ℃ and 400Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.10dL/g, wherein the pre-polycondensation reaction is carried out under stirring at a stirring speed of 15rpm, and the adding amount of the antioxidant 1010 is 0.002 wt% of that of the sebacic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 1.5 hours at 280 ℃ under 70Pa to prepare the bio-based 2, 5-furandicarboxylic acid copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 8 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.46, the intrinsic viscosity of 0.65dL/g, the color degree of 8 and the content of side reaction products of 0.85 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 9kg/t, and the yarn evenness of the fiber is 0.88%.
Example 10
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing azelaic acid and suberic alcohol according to a molar ratio of 1:1.05, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction under the conditions of 235 ℃ and 200KPa until the water yield reaches 95% of theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 98% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and nonanediol, the addition amount of the leading object is 2.0 wt% of azelaic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 180ppm of the mass of azelaic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding metatitanic acid, silicon dioxide and cobalt acetate according to the molar ratio of 1:0.3: 0.1;
(2) pre-polycondensation reaction;
adding an antioxidant 168 into the product in the step (1), and carrying out pre-polycondensation reaction for 35min at 245 ℃ and 100Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.12dL/g, wherein the pre-polycondensation reaction is carried out under the stirring of the stirring speed of 20rpm, and the adding amount of the antioxidant 168 is 0.006 wt% of that of the azelaic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 2.0h at 270 ℃ under the condition of 50Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 10 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.56, the intrinsic viscosity of 1.10dL/g, the color degree of 9.5 and the content of side reaction products of 0.9 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 9.7kg/t, and the yarn evenness rate of the fiber is 0.98%.
Example 11
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing suberic acid and nonanediol in a molar ratio of 1:1.08, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction at 231 ℃ and 100KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 94% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and heptanediol, the addition amount of the leading object is 4.0 wt% of the suberic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 150ppm of the mass of the suberic acid, and the titanium-silicon-cobalt composite catalyst is compounded by metatitanic acid, silicon dioxide and cobalt acetate in a molar ratio of 1:0.5: 10;
(2) pre-polycondensation reaction;
adding an antioxidant 616 into the product obtained in the step (1), and carrying out pre-polycondensation reaction for 40min at 250 ℃ and 800Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.10dL/g, wherein the pre-polycondensation reaction is carried out under stirring at a stirring speed of 13rpm, and the adding amount of the antioxidant 616 is 0.01 wt% of that of the suberic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 3.5 hours at the temperature of 250 ℃ and under the pressure of 50Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 5 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.5, the intrinsic viscosity of 0.63dL/g, the color degree of 7 and the content of side reaction products of 0.78 wt%. The obtained product is prepared into bio-based 2, 5-furandicarboxylic acid based copolyester POY, the processing waste silk rate is 8.5kg/t, and the yarn evenness rate of fibers is 0.75%.
Example 12
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing and pulping pimelic acid and heptanediol according to a molar ratio of 1:1.08, adding a titanium-silicon-cobalt composite catalyst, and adding a guide substance to carry out reaction under the conditions of 223 ℃ and 80KPa until the water yield reaches 95% of the theoretical water yield, wherein the guide substance is an esterified substance with an esterification rate of 96% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and pentanediol, the addition amount of the guide substance is 0.5 wt% of the pimelic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 130ppm of the mass of the pimelic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate according to a molar ratio of 1:6.0: 0.7;
(2) pre-polycondensation reaction;
adding phosphoric acid and an antioxidant 1010 into the product obtained in the step (1), and carrying out pre-polycondensation reaction for 45min at 235 ℃ and 900Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.15dL/g, wherein the pre-polycondensation reaction is carried out under stirring at a stirring speed of 7rpm, the adding amount of the phosphoric acid is 0.008 wt% of that of the terephthalic acid added in the step (1), and the adding amount of the antioxidant 1010 is 0.009 wt% of that of the pimelic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 3.0h at 260 ℃ under the condition of 100Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 10 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.5, the intrinsic viscosity of 1.12dL/g, the color degree of 9 and the content of side reaction products of 0.8 wt%. The obtained product is prepared into bio-based 2, 5-furandicarboxylic acid based copolyester DTY, the processing waste silk rate is 9.5kg/t, and the yarn evenness rate of the fiber is 0.98%.
Example 13
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing adipic acid and decanediol in a molar ratio of 1:1.05, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction at 226 ℃ and 140KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 90% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and ethylene glycol, the addition amount of the leading object is 3.0 wt% of the adipic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 180ppm of the mass of the adipic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate in a molar ratio of 1:9.2: 7.1;
(2) pre-polycondensation reaction;
adding a mixture (mass ratio is 1:1) of an antioxidant 1010 and an antioxidant 168 into the product obtained in the step (1), and carrying out pre-polycondensation for 15min at 237 ℃ and 400Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.14dL/g, wherein the pre-polycondensation reaction is carried out under stirring at a stirring speed of 16rpm, and the addition amount of the mixture of the antioxidant 1010 and the antioxidant 168 is 0.003 wt% of that of the adipic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 3.0h at 220 ℃ under the condition of 40Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 7 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.5, the intrinsic viscosity of 1.06dL/g, the color degree of 8 and the content of side reaction products of 0.9 wt%. The obtained product is prepared into bio-based 2, 5-furandicarboxylic acid based copolyester DTY, the processing waste silk rate is 9kg/t, and the yarn evenness rate of fibers is 0.9%.
Example 14
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing glutaric acid and pentanediol according to a molar ratio of 1:1.10, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction under the conditions of 230 ℃ and 170KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 97% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and decanediol, the addition amount of the leading object is 2.5 wt% of glutaric acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 190ppm of the mass of glutaric acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding metatitanic acid, silicon dioxide and cobalt acetate according to the molar ratio of 1:7.0: 0.1;
(2) pre-polycondensation reaction;
adding a mixture (mass ratio is 1:1:1) of an antioxidant 1010, an antioxidant 168 and an antioxidant 616 into the product obtained in the step (1), and carrying out pre-polycondensation for 15min at 250 ℃ and 100Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.13dL/g, wherein the pre-polycondensation reaction is carried out under stirring at a stirring speed of 5rpm, and the adding amount of the mixture of the antioxidant 1010, the antioxidant 168 and the antioxidant 616 is 0.001 wt% of that of the glutaric acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 3.5 hours at 230 ℃ under the condition of 60Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 10 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.2, the intrinsic viscosity of 0.70dL/g, the color degree of 7 and the content of side reaction products of 0.75 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 9.4kg/t, and the yarn evenness rate of the fiber is 0.95%.
Example 15
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing succinic acid and hexanediol according to a molar ratio of 1:1.10, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction at 240 ℃ and 200KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 98% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and decanediol, the addition amount of the leading object is 5.0 wt% of the succinic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 100ppm of the mass of the succinic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding tetrabutyl titanate, silicon dioxide and cobalt acetate according to the molar ratio of 1:10: 0.4;
(2) pre-polycondensation reaction;
adding a mixture of phosphoric acid and trimethyl phosphate (mass ratio is 1:2) into the product obtained in the step (1), and performing pre-polycondensation reaction for 20min at 230 ℃ and 300Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.14dL/g, wherein the pre-polycondensation reaction is performed under stirring at the stirring speed of 18rpm, and the adding amount of the mixture of phosphoric acid and trimethyl phosphate is 0.005 wt% of the succinic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 2.0h at 230 ℃ under 70Pa to prepare the bio-based 2, 5-furandicarboxylic acid copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 9 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.59, the intrinsic viscosity of 1.18dL/g, the color degree of 9 and the content of side reaction products of 0.95 wt%. The obtained product is prepared into bio-based 2, 5-furandicarboxylic acid based copolyester POY, the processing waste silk rate is 8.5kg/t, and the yarn evenness rate of fibers is 0.85%.
Example 16
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing and pulping bio-based 2, 5-furandicarboxylic acid/isophthalic acid (the mass ratio is 1:1) and propylene glycol in a molar ratio of 1:1.07, adding a titanium-silicon-cobalt composite catalyst and a guide substance under the conditions of 233 ℃ and 60KPa until the water yield reaches 95% of the theoretical water yield, and terminating the reaction, wherein the guide substance is an esterified substance with an esterification rate of 98% generated by the reaction of the bio-based 2, 5-furandicarboxylic acid and hexanediol, the addition amount of the guide substance is 5.0 wt% of the bio-based 2, 5-furandicarboxylic acid/isophthalic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 200ppm of the mass of the bio-based 2, 5-furandicarboxylic acid/isophthalic acid, and the titanium-silicon-cobalt composite catalyst is compounded by metatitanic acid, silicon dioxide and cobalt acetate in a molar ratio of 1:8.8: 10;
(2) pre-polycondensation reaction;
adding a mixture (mass ratio is 2:1) of an antioxidant 1010 and an antioxidant 168 into the product obtained in the step (1) to perform a pre-polycondensation reaction for 30min at 250 ℃ and 200Pa with phosphoric acid, wherein the pre-polycondensation reaction is performed under stirring at a stirring speed of 6rpm, the adding amount of the phosphoric acid is 0.04 wt% of the adding amount of the bio-based 2, 5-furandicarboxylic acid/isophthalic acid in the step (1), and the adding amount of the mixture of the antioxidant 1010 and the antioxidant 168 is 0.001 wt% of the adding amount of the bio-based 2, 5-furandicarboxylic acid/isophthalic acid in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 1.5h at 260 ℃ under the condition of 10Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring condition that the stirring speed is 5 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.4, the intrinsic viscosity of 1.0dL/g, the color degree of 8 and the content of side reaction products of 0.80 wt%. The obtained product is prepared into bio-based 2, 5-furandicarboxylic acid based copolyester DTY, the processing waste silk rate is 9.0kg/t, and the yarn evenness rate of the fiber is 0.8%.
Example 17
A preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester comprises the following specific steps:
(1) performing esterification reaction;
mixing terephthalic acid and propylene glycol according to a molar ratio of 1:1.07, pulping, adding a titanium-silicon-cobalt composite catalyst, and leading an object to perform reaction under the conditions of 240 ℃ and 50KPa until the water yield reaches 95% of the theoretical water yield, wherein the leading object is an esterified object with an esterification rate of 93% generated by the reaction of bio-based 2, 5-furandicarboxylic acid and butanediol, the addition amount of the leading object is 3.5 wt% of the terephthalic acid, the addition amount of the titanium-silicon-cobalt composite catalyst is 150ppm of the mass of the terephthalic acid, and the titanium-silicon-cobalt composite catalyst is formed by compounding metatitanic acid, silicon dioxide and cobalt acetate according to the molar ratio of 1:10: 5.0;
(2) pre-polycondensation reaction;
adding a mixture of phosphoric acid and phosphorous acid (the mass ratio is 2:1) and a mixture of antioxidant 1010 and antioxidant 168 (the mass ratio is 3:2) into the product obtained in the step (1), and carrying out pre-polycondensation reaction for 45min at the conditions of 260 ℃ and 150Pa to obtain a pre-polycondensation product with the intrinsic viscosity of 0.13dL/g, wherein the pre-polycondensation reaction is carried out under stirring at the stirring speed of 19rpm, the adding amount of the mixture of phosphoric acid and phosphorous acid is 0.05 wt% of that of the terephthalic acid added in the step (1), and the adding amount of the mixture of antioxidant 1010 and antioxidant 168 is 0.01 wt% of that of the terephthalic acid added in the step (1);
(3) final polycondensation reaction;
and (3) performing final polycondensation on the pre-polycondensation product prepared in the step (2) for 1.5h at the temperature of 250 ℃ and under the pressure of 30Pa to prepare the bio-based 2, 5-furandicarboxylic acid based copolyester, wherein the final polycondensation is performed under the stirring of the stirring speed of 10 rpm.
The finally prepared bio-based 2, 5-furandicarboxylic acid based copolyester has the weight average molecular weight distribution coefficient of 1.15, the intrinsic viscosity of 0.60dL/g, the color degree of 9 and the content of side reaction products of 0.95 wt%. The fiber is prepared into bio-based 2, 5-furandicarboxylic acid copolyester FDY, the processing waste silk rate is 9.5kg/t, and the yarn evenness rate of the fiber is 0.97%.
Claims (7)
1. A preparation method of bio-based 2, 5-furandicarboxylic acid copolyester is characterized by comprising the following steps: uniformly mixing dibasic acid, aliphatic dihydric alcohol I, a guide and a titanium-silicon-cobalt composite catalyst, and then sequentially carrying out esterification reaction, pre-polycondensation reaction and final polycondensation reaction to obtain the bio-based 2, 5-furandicarboxylic acid based copolyester;
the method comprises the following specific steps:
(1) performing esterification reaction;
mixing and pulping dibasic acid and aliphatic diol I, adding a titanium-silicon-cobalt composite catalyst and a guide substance, and carrying out an esterification reaction at 180-240 ℃ and 50-200 KPa until the water yield reaches 95% of the theoretical water yield;
(2) pre-polycondensation reaction;
adding an anti-thermal oxidant and/or an antioxidant into the product obtained in the step (1), and performing pre-polycondensation reaction at 200-260 ℃ and 100-1000 Pa for 15-45 min to obtain a pre-polycondensation product with the intrinsic viscosity of less than or equal to 0.15 dL/g; the stirring speed of the pre-polycondensation reaction is 5-20 rpm;
(3) final polycondensation reaction;
performing final polycondensation reaction on the pre-polycondensation product prepared in the step (2) for 1.5-3.5 hours at 220-280 ℃ under the condition of 10-100 Pa to prepare bio-based 2, 5-furandicarboxylic acid copolyester; the stirring speed of the final polycondensation reaction is 5-10 rpm;
the guiding substance is an esterified substance generated by the reaction of bio-based 2, 5-furandicarboxylic acid and aliphatic diol II, the molar ratio of the dibasic acid to the aliphatic diol I is 1: 1.05-1.10, the titanium-silicon-cobalt composite catalyst is formed by compounding a titanium-silicon composite catalyst and a cobalt catalyst, the titanium-silicon composite catalyst is obtained by loading a titanium catalyst on a silicon catalyst, and the aliphatic diol I is different from the aliphatic diol II;
the addition amount of the guide is 0.5-5.0 wt% of the addition amount of the dibasic acid in the step (1); the addition amount of the titanium-silicon-cobalt composite catalyst is 100-200 ppm of the addition amount of the dibasic acid in the step (1); the molar ratio of the titanium catalyst, the silicon catalyst and the cobalt catalyst in the titanium-silicon-cobalt composite catalyst is 1: 0.1-10;
the content of side reaction products in the bio-based 2, 5-furandicarboxylic acid-based copolyester is less than or equal to 1.0 wt%.
2. The method for preparing bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 1, wherein the titanium-based catalyst is tetrabutyl titanate or metatitanic acid; the silicon catalyst is silicon dioxide; the cobalt catalyst is cobalt acetate.
3. The method for preparing bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 1, wherein the esterification rate of the bio-based 2, 5-furandicarboxylic acid and aliphatic diol II to generate a guide is 90-98%; the dibasic acid is more than one of 2, 5-furandicarboxylic acid, terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; the aliphatic diol I and the aliphatic diol II are respectively one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and decanediol.
4. The preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 1, wherein the addition amount of the anti-thermoxidant is 0.005-0.05 wt% of the addition amount of the dibasic acid in the step (1); the addition amount of the antioxidant is 0.001-0.01 wt% of the addition amount of the dibasic acid in the step (1).
5. The method for preparing bio-based 2, 5-furandicarboxylic acid copolyester according to claim 4, wherein the anti-thermoxidant is one or more of phosphoric acid, phosphorous acid, trimethyl phosphate, trimethyl phosphite and triphenyl phosphate; the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616.
6. The preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 1, wherein the weight average molecular weight distribution coefficient of the bio-based 2, 5-furandicarboxylic acid-based copolyester is 1.2 to 1.6, the intrinsic viscosity is 0.60 to 1.20dL/g, and the color degree is less than or equal to 10.
7. The preparation method of bio-based 2, 5-furandicarboxylic acid-based copolyester according to claim 1, wherein the bio-based 2, 5-furandicarboxylic acid-based copolyester is prepared into POY, FDY or DTY filament, the processing waste filament rate is less than or equal to 10kg/t, and the yarn evenness of the fiber is less than or equal to 1.0%.
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