CN114656625B - Antimony-catalyst-free polyester polymer easy to decompose and recover and preparation method thereof - Google Patents
Antimony-catalyst-free polyester polymer easy to decompose and recover and preparation method thereof Download PDFInfo
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- CN114656625B CN114656625B CN202210273772.7A CN202210273772A CN114656625B CN 114656625 B CN114656625 B CN 114656625B CN 202210273772 A CN202210273772 A CN 202210273772A CN 114656625 B CN114656625 B CN 114656625B
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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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- C08G63/78—Preparation processes
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- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
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- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a catalyst which is prepared by using hydrogenated pyromellitic dianhydride, ethylene glycol titanium and nano boron nitride as main raw materials, does not contain antimony element, and can achieve the catalytic effect of a conventional antimony catalyst. The catalyst is applied to the preparation of the polyester polymer by the monomer, and the prepared polyester polymer is safe to the environment and the human body, so that the application range is widened; the prepared polyester polymer is easily and thoroughly decomposed into micromolecular polyester polymer under the action of the solvent, and the recovered polyester product does not contain heavy metal antimony, so that the method is safe and environment-friendly.
Description
Technical Field
The invention relates to the field of polyester polymers, in particular to an antimony-free catalyst polyester polymer easy to decompose and recover and a preparation method thereof.
Background
The polyester is a general name of polymers obtained by polycondensing polyalcohol and polybasic acid, and is engineering plastics with excellent performance and wide application. The fiber grade polyester chip is used for manufacturing polyester staple fibers and polyester filament yarns, is a raw material for processing fibers and related products for polyester fiber enterprises, is used as a variety with the maximum yield in chemical fibers, has the applications of bottles, films and the like, is widely applied to the fields of packaging industry, electronic appliances, medical treatment and health, buildings, automobiles and the like, wherein the packaging is the non-fiber application market with the maximum polyester, and is also the field with the fastest PET growth. Polyester chip can be said to be an important intermediate product for connecting petrochemicals and various industrial products.
In the polymerization process of TA and EG, a catalyst is needed for polyester, antimony compounds are commonly used as the catalyst in the prior art to prepare polyester polymers, the polyester polymers are catalyzed into heavy metals such as antimony, and the polycondensation reaction can be greatly promoted, for example, chinese patent invention with the application number of CN200510054390.1 discloses a melt phase method for preparing polyester polymer melt phase products, wherein an antimony-containing catalyst is added into a melt phase, and the melt containing the catalyst is polycondensed in the melt phase until it.V. of the melt reaches at least 0.75dL/g. Polyester polymer melt phase pellets are obtained without solid phase polymerization. Also for example, chinese invention patent with application number CN201210087762.0 discloses an antimony/titanium composite catalyst and a method for preparing PET copolyester thereof, wherein the antimony/titanium catalyst, a first cocatalyst, a second cocatalyst and dibasic acid are mixed together and added into a reaction system, terephthalic acid or ester thereof and excessive ethylene glycol are subjected to esterification reaction at a temperature of 240 to 260 ℃,0.2 to 0.4mpa and a reaction time of 1 to 2 hours, and a comonomer is added to perform polycondensation reaction to obtain a polymer.
Among the antimony catalysts, the more commonly used antimony catalyst is antimony acetate (Sb (AC) 3 ) Antimony trioxide (Sb) 2 O 3 ) And ethylene glycol antimony (Sb) 2 (EG) 3 ) It may be added in the esterification reaction, or in the polycondensation reaction. However, antimony catalysts have severe toxicity, and exist in the fibers in a free form after polymerization, and during the fiber processing, recovery and decomposition processes, free antimony chemicals are discharged in processing liquid and solvent liquid, which cause serious harm to the environment and human bodies, easily cause chronic toxicity to human bodies, and cause cancers.
In addition, in order to reduce environmental pollution and promote sustainable development, the prior art develops chemical recovery methods such as glycolysis, alcoholysis and hydrolysis to recycle waste polyester. The chemical recovery of polyester products is carried out by decomposing into small molecules under the action of alkali and chemical compounds containing-OH group of alcohols, obtaining Terephthalic Acid (TA) and Ethylene Glycol (EG), and polymerizing into regenerated polyester. However, the polyester is ethylene terephthalate, which has high molecular chain, high polymerization degree, high crystallinity and high orientation degree, is difficult to be decomposed into small molecules under the action of alkali and chemical substances containing-OH groups of alcohols, has a lot of oligomers, and can obtain thorough low molecular products by consuming a large amount of solvent and energy, thereby finally obtaining Terephthalic Acid (TA) and Ethylene Glycol (EG). The recovery difficulty is high. Further, as described above, the polyester recovered after the decomposition contains antimony, which is a heavy metal, and is difficult to recover, causing serious environmental damage.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an antimony-free catalyst polyester polymer which is easy to decompose and recover and a preparation method thereof.
The first technical problem solved by the invention is as follows: provides a catalyst which does not contain antimony and is safe and environment-friendly. The catalyst is prepared by the following method:
(1) Adding hydrogenated pyromellitic dianhydride into an ethylene glycol solution, heating to 100-150 ℃ to fully dissolve the hydrogenated pyromellitic dianhydride, slowly adding a titanium glycol solution, heating to 110-180 ℃ until no moisture is discharged, and preserving heat for 4-12 hours to obtain a solution A;
(2) Adding ethylene glycol, a surfactant and nano boron nitride powder in sequence, stirring at a high speed, and grinding and dispersing to obtain a mixture B;
(3) Under the protection of nitrogen atmosphere, dropwise adding the mixture B into the solution A to obtain a catalyst; the mass ratio of the solution A to the mixture B is 1:0.5 to 3;
in a more preferred embodiment, in the step (1), the mass ratio of the solution a to the mixture B is 1:1-2.
Further, the ethylene glycol titanium solution in the step (1) is prepared by the following method: taking anhydrous ethylene glycol and titanium tetrachloride as raw materials, slowly adding titanium tetrachloride into excessive anhydrous ethylene glycol in a stirring state in a closed environment, keeping stirring for 5-30min, introducing ammonia gas to neutralize hydrogen chloride generated by reaction until the pH value of the solution is 7-8.5, stopping introducing ammonia gas, standing for 10-40min, and filtering to remove precipitates to obtain the titanium glycol solution.
Preferably, in the step (1), the mass ratio of the hydrogenated pyromellitic dianhydride to the ethylene glycol to the titanium glycol solution is 1:0.3-1.2:3-15;
in a more preferred embodiment, the mass ratio of the hydrogenated pyromellitic dianhydride, ethylene glycol, and titanium glycol solution is 1:1:8.
preferably, in the step (2), the surfactant is one or more of polyvinyl alcohol, alkylbenzene sulfonate and fatty alcohol-polyoxyethylene ether.
Preferably, the addition amount of the nano boron nitride powder is 2-15% of the total weight of the solution, and the addition amount of the surfactant is 3-20% of the total weight of the solution;
in a more preferred embodiment, the nano boron nitride powder is added in an amount of 5-10% by weight of the total solution, and the surfactant is added in an amount of 10-15% by weight of the total solution.
Preferably, the mass fraction of the titanium element in the catalyst is 0.5-8%;
in a more preferred embodiment, the mass fraction of titanium element in the catalyst is 2 to 5%.
The second technical problem that this application solved is: provides a preparation method of polyester polymer which is easy to decompose and recycle, and adopts the catalyst.
The preparation method comprises the following steps:
(1) Adding a first monomer and a second monomer with the molar ratio of 1.1-3.0 into a reaction kettle, and esterifying for 2-8 hours at the temperature of 220-280 ℃ and the gauge pressure of 0.08-0.6MPa to obtain an esterified substance BHET; the first monomer is purified terephthalic acid, and the second monomer is ethylene glycol;
(2) Mixing a mixture of 1:3-15 parts of a third monomer and a second monomer are added into a reaction kettle, 0.1-2% of acetate is added, the mixture is stirred and heated to 150-210 ℃, the temperature is maintained for esterification reaction, when the esterification rate reaches 50-95%, the esterification reaction is stopped to obtain esterification liquid SSIPA, and the temperature is kept for later use; the third monomer is dimethyl isophthalate-5-sodium Sulfonate (SIPM) or isophthalic acid-5-sodium Sulfonate (SIPA).
(3) Adding the esterified liquid SSIPA and the fourth monomer prepared in the step (2) into the esterified BHET prepared in the step (1), uniformly stirring, adding a catalyst, and reacting for 1-5 hours at the temperature of 260-310 ℃ and the absolute pressure of 50-200Pa to obtain the polyester polymer easy to decompose and recover; the fourth monomer is one or more of glycol, polyethylene glycol monomethyl ether, polyethylene glycol or polyether; the catalyst is as defined in any one of claims 1 to 4.
Preferably, in the step (3), the total effective component SIPA or SIPM of the esterified liquid SSIPA accounts for 1-15% of the weight of TA contained in the esterified BHET, and the weight percentage of the four monomers accounts for 2-20% of the weight percentage of PTA in the esterified BHET;
in a more preferred embodiment, the total effective component SIPA or SIPM of esterified liquid SSIPA accounts for 3-10 wt% of TA in esterified BHET, and the weight percentage of the tetra-monomer accounts for 5-15 wt% of PTA in esterified BHET.
Preferably, the amount of the catalyst used in the step (3) is 10-30pm of titanium content;
in a more preferred embodiment, the catalyst is used in an amount of 12 to 20ppm of titanium.
A third technical problem to be solved by the present application is to provide a polyester fiber, a polyester film or a polyester plastic product, which uses the polyester polymer prepared by the method for preparing the easily degradable and recyclable polyester polymer according to any one of claims 7 to 9 as a raw material.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a catalyst which is prepared by using hydrogenated pyromellitic dianhydride, ethylene glycol titanium and nano boron nitride as main raw materials, does not contain antimony element, and can achieve the catalytic effect of a conventional antimony catalyst. The catalyst is applied to the preparation of the polyester polymer by the monomer, and the prepared polyester polymer is safe to the environment and the human body, so that the application range is widened; the prepared polyester polymer is easily and thoroughly decomposed into micromolecular polyester polymer under the action of the solvent, and the recovered polyester product does not contain heavy metal antimony, so that the method is safe and environment-friendly.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: preparation of the catalyst
In a closed environment, 1 part by weight of titanium tetrachloride was slowly added to 5 parts by weight of anhydrous ethylene glycol under stirring, and the solution appeared pale yellow and white smoke was generated. Stirring was maintained for 25min while ammonia gas was introduced to neutralize the hydrogen chloride produced by the reaction. And (3) continuously generating white precipitates in the solution in the process, stopping introducing ammonia gas when the pH value of the solution is 7-8.5, standing for 35min, and filtering to remove the precipitates to obtain the titanium glycol solution, wherein the content of the titanium glycol is 16.5%.
Adding hydrogenated pyromellitic dianhydride into an ethylene glycol solution, heating to 130 ℃ to fully dissolve the hydrogenated pyromellitic dianhydride, slowly adding a titanium glycol solution, heating to 160 ℃ until no moisture is discharged, and preserving heat for 10 hours to obtain a solution A for later use. Wherein the mass ratio of the hydrogenated pyromellitic dianhydride to the ethylene glycol to the titanium glycol solution is 1:0.8:5.
sequentially adding ethylene glycol, polyvinyl alcohol and nano boron nitride powder, stirring at a high speed, grinding and dispersing to obtain a mixture B for later use; wherein, the addition amount of the nano boron nitride powder is 4 percent of the total weight of the solution, and the addition amount of the surfactant is 8 percent of the total weight of the solution.
And dropwise adding the mixture B into the solution A under the protection of nitrogen atmosphere to obtain the catalyst. The mass ratio of the solution A to the mixture B is 2:1.
by detection, in the catalyst prepared in this example, the mass fraction of the titanium element is 2.35%.
Example 2: preparation of the catalyst
In a closed environment, 2 parts by weight of titanium tetrachloride was slowly added to 5 parts by weight of anhydrous ethylene glycol under stirring, and the solution appeared pale yellow and white smoke was generated. Stirring was maintained for 25min while ammonia gas was introduced to neutralize the hydrogen chloride produced by the reaction. And (3) continuously generating white precipitates in the solution in the process, stopping introducing ammonia gas when the pH value of the solution is 7-8.5, standing for 35min, and filtering to remove the precipitates to obtain the titanium glycol solution, wherein the content of the titanium glycol is 32.1%.
Adding hydrogenated pyromellitic dianhydride into an ethylene glycol solution, heating to 130 ℃ to fully dissolve the hydrogenated pyromellitic dianhydride, slowly adding a titanium glycol solution, heating to 160 ℃ until no moisture is discharged, and preserving heat for 10 hours to obtain a solution A for later use. Wherein the mass ratio of the hydrogenated pyromellitic dianhydride to the ethylene glycol to the titanium glycol solution is 1:1:8.
sequentially adding ethylene glycol, sodium alkyl benzene sulfonate and nano boron nitride powder, stirring at a high speed, grinding and dispersing to obtain a mixture B for later use; wherein, the addition amount of the nano boron nitride powder is 8 percent of the total weight of the solution, and the addition amount of the surfactant is 13 percent of the total weight of the solution.
And dropwise adding the mixture B into the solution A under the protection of nitrogen atmosphere to obtain the catalyst. The mass ratio of the solution A to the mixture B is 1:1.
by detection, the mass fraction of the titanium element in the catalyst prepared in the example is 3.6%.
Example 3: preparation of easily decomposed and recycled polyester polymer
The preparation method comprises the following steps:
(1) Adding purified terephthalic acid and ethylene glycol into a reaction kettle according to a molar ratio of 1.
(2) Adding dimethyl isophthalate-5-sodium sulfonate and ethylene glycol into a reaction kettle according to a molar ratio of 1;
(3) Adding the esterified liquid SSIPA and polyethylene glycol (PEG) prepared in the step (2) into the esterified BHET prepared in the step (1), uniformly stirring, adding a catalyst, and reacting for 2 hours at the temperature of 270 ℃ and the absolute pressure of 140Pa to obtain the polyester polymer easy to decompose and recover.
In this embodiment, the weight percentage of the active ingredient SIPA or SIPM in the esterified liquid SSIPA in the esterified BHET is 2.8% and the weight percentage of the tetramonomer (PEG) in the esterified BHET in the PTA is 20%.
The catalyst used in this example was the catalyst prepared in example 1, and the amount of the catalyst used was 15ppm based on the weight of BHET as the titanium content.
Example 4: preparation of easily decomposed and recycled polyester polymer
The preparation method comprises the following steps:
(1) Adding purified terephthalic acid and ethylene glycol into a reaction kettle according to a molar ratio of 1.
(2) Adding dimethyl isophthalate-5-sodium sulfonate and ethylene glycol into a reaction kettle according to a molar ratio of 1;
(3) Adding the esterified liquid SSIPA and polyethylene glycol (PEG) prepared in the step (2) into the esterified BHET prepared in the step (1), uniformly stirring, adding a catalyst, and reacting for 4 hours at the temperature of 280 ℃ and the absolute pressure of 200Pa to obtain the polyester polymer easy to decompose and recover.
In this embodiment, the esterification liquid SSIPA contains SIPA or SIPM, which is 10 wt% of TA in the esterified BHET, and the tetramer, which is 8 wt% of PTA in the esterified BHET.
The catalyst used in this example was the catalyst prepared in example 1 and was used in an amount such that the titanium content was 20ppm based on the weight of BHET.
Example 5: preparation of easily decomposed and recycled polyester polymer
The preparation method comprises the following steps:
(1) Adding purified terephthalic acid and ethylene glycol into a reaction kettle according to a molar ratio of 1.
(2) Sodium 5-sulfoisophthalate and ethylene glycol were metered in a molar ratio of 1: adding 7 mol percent of the mixture into a reaction kettle, adding 0.2 percent of acetate, stirring and heating to 185 ℃, keeping the temperature for esterification reaction, calculating the esterification rate of the reaction according to the amount of the flowing methanol, stopping the esterification reaction when the esterification rate reaches 80 percent to obtain esterification liquid SSIPA, and preserving heat for later use;
(3) Adding the esterification liquid SSIPA and polyethylene glycol (PEG) prepared in the step (2) into the esterified BHET prepared in the step (1), uniformly stirring, adding a catalyst, and obtaining the easily-decomposed and recycled polyester polymer under the conditions that the temperature is 280 ℃ and the absolute pressure is 200 Pa.
In this embodiment, the esterification liquid SSIPA contains SIPA or SIPM, which is 8 wt% of TA in the esterified BHET, and the tetramer, which is 10 wt% of PTA in the esterified BHET.
The catalyst used in this example was the catalyst prepared in example 1 and was used in an amount of 12ppm based on the weight of BHET as the titanium content.
Example 6: preparation of easily decomposed and recycled polyester polymer
The preparation method comprises the following steps:
(1) Adding purified terephthalic acid and ethylene glycol into a reaction kettle according to a molar ratio of 1.
(2) Adding 5-sodium sulfoisophthalate and ethylene glycol into a reaction kettle according to a molar ratio of 1;
(3) Adding the esterified liquid SSIPA and the polyethylene glycol monomethyl ether prepared in the step (2) into the esterified BHET prepared in the step (1), uniformly stirring, adding a catalyst, and reacting for 4 hours under the conditions that the temperature is 285 ℃ and the absolute pressure is 200Pa to obtain the polyester polymer easy to decompose and recover.
In this embodiment, the total effective component SIPA or SIPM of the esterified liquid SSIPA accounts for 4.5 wt% of the TA content in the esterified BHET, and the four monomers account for 16 wt% of the PTA in the esterified BHET.
The catalyst used in this example was the catalyst prepared in example 2 and was used in an amount such that the titanium content was 25ppm based on the weight of BHET.
Comparative example: preparation of easily decomposed and recycled polyester polymer
The preparation method comprises the following steps:
(1) Adding purified terephthalic acid and ethylene glycol into a reaction kettle according to a molar ratio of 1.
(2) Adding 5-sodium sulfoisophthalate and ethylene glycol into a reaction kettle according to a molar ratio of 1;
(3) Adding the esterified liquid SSIPA and the polyethylene glycol monomethyl ether prepared in the step (2) into the esterified BHET prepared in the step (1), uniformly stirring, adding a catalyst, and reacting for 4 hours under the conditions that the temperature is 285 ℃ and the absolute pressure is 200Pa to obtain the polyester polymer easy to decompose and recover.
In this embodiment, the total effective component SIPA or SIPM of the esterified liquid SSIPA accounts for 4.5 wt% of TA contained in the esterified BHET, and the weight percentage of the four monomers accounts for 16 wt% of the esterified BHET.
The catalyst used in this example was antimony trioxide, the amount of which was 260ppm based on the weight of BHET.
Example 7: preparation of easily decomposed and recycled fibers
The easily decomposed and recycled polyester polymers prepared in examples 3-6 and comparative example were melted at 285 ℃ respectively, and the melt was sent to a spinneret assembly, and the as-spun filaments were rapidly cooled by atomizing spray after passing through the spinneret assembly. Continuously performing hot roller drafting, atomizing and spraying before winding to cool and shape the fibers, and preparing the shaped POY filaments into (DTY) filaments by conventional drafting and curling processes.
Wherein the atomized spray is gaseous water with normal temperature and relative humidity of 100%.
The filaments prepared in example 7 and the commercial filaments were tested for properties, and the fibers were tested for strength and elongation at break, as shown in table 1.
The strength test of the fiber adopts the national standard GBT 14344-2008 chemical fiber filament tensile property test method.
Specification: filaments of easily decomposed and recycled polymers: DTY,75D/36F; the method is commercially available: tung Kun polyester fiber filament, DTY 75D/36F.
TABLE 1 summary of Performance tests
| Example 3 | Example 4 | Example 5 | Example 6 | Comparative example | Commercially available "Tukunzhu" | |
| Strength, cn/dtex | 3.0 | 3.2 | 2.9 | 3.0 | 3.1 | 3.3 |
| Elongation at break,% | 27.5 | 24.3 | 26.1 | 27 | 25.2 | 27.5 |
From the performance test results, the fibers prepared by using the catalyst prepared by the method as the catalyst for monomer polymerization and using the antimony trioxide catalyst have the advantages of little difference in strength performance and slightly better elongation at break than the fibers prepared by using the antimony trioxide catalyst. Therefore, the performance requirement of the raw material for preparing the fiber can still be ensured on the premise of achieving the technical effect of environmental protection and safety by adopting the self antimony-free catalyst.
Example 8: decomposition and recovery of easily decomposed and recovered fiber
The filaments of the easily decomposable and recyclable polymer prepared in example 7, 75D/36F, and the commercially available filaments of "Tukun" polyester fiber, DTY 75D/36F, were decomposed and recycled by the respective alcoholysis and alkaline hydrolysis methods.
The specific method comprises the following steps:
firstly, respectively putting the fibers in 0.5G/L alkali liquor (NaOH), washing the fibers clean, drying the fibers and removing spinning oil; the dried fiber is respectively and sequentially fed into a reaction kettle with ethylene glycol and a catalyst according to a certain amount, before reaction, dry nitrogen is firstly used for replacing air in the reaction kettle, after reactants are fed, the reaction kettle is heated to the reaction temperature and time, and the reaction is carried out under a certain pressure. And after the reaction is finished, filtering while the mixture is hot, cooling to 200 ℃, and extracting excessive ethylene glycol in vacuum to obtain an alcoholysis product. The alcoholysis product was tested.
Wherein, the specific parameters and the comparison of the decomposition by the alcoholysis method are shown in table 2:
TABLE 2 alcoholysis parameters and comparison
| Commercially available "Tukunzhu" | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example | |
| Temperature, C | 260 | 220 | 220 | 220 | 220 | 220 |
| Reaction time, h | 4 | 2 | 2 | 2 | 2 | 2 |
| Ethylene glycol/polyester fiber mass ratio | 4:01 | 4:01 | 4:01 | 4:01 | 4:01 | 4:01 |
| Catalyst: p-toluenesulfonic acid,% | 2 | 2 | 2 | 2 | 2 | 2 |
| Pressure, MPa | 0.5 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Percentage of alcoholysis recovery% | 84.8 | 94.6 | 95.2 | 95.3 | 96.5 | 93.1 |
| Antimony content, ppm | 260 | - | - | - | - | 220 |
2. The specific parameters and comparisons for the decomposition by alkaline hydrolysis are shown in table 3:
in the solution jar, the test was carried out in two times. Adding fiber, adding NaOH solution, heating to 100 deg.C, stirring at constant speed, and holding for a certain time. After that time, the solution was filtered while hot to give a filtrate. Cooling to normal temperature and filtering to obtain filter residue A and filtrate. Adding precipitator acetic acid into the filtrate to generate white precipitate, and filtering to obtain filter residue B. And combining the filter residues A and B, and leaching with acetic acid. The washing liquid after the washing can be continuously used as a precipitator. Washing the filter residue after washing with clear water for several times, and drying to obtain the decomposed finished product. Weighing and calculating the yield.
TABLE 3 alkaline hydrolysis parameters and comparison
| Commercially available "Tung Kun" tea " | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example | |
| Temperature, C | 100 | 100 | 100 | 100 | 100 | 100 |
| Reaction time, h | 2 | 2 | 2 | 2 | 2 | 2 |
| Dodecyl trimethyl ammonium bromide% | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Pressure MPa | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| NaOH concentration (%) | 10 | 10 | 10 | 10 | 10 | 10 |
| Bath ratio | 1:08 | 1:08 | 1:08 | 1:08 | 1:08 | 1:08 |
| The decomposition yield is percent | 5% | 85% | 95% | 95% | 89% | 89% |
| Antimony content ppm | 260 | - | - | - | - | 220 |
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. A catalyst, characterized in that the catalyst is prepared by the following method:
(1) Adding hydrogenated pyromellitic dianhydride into an ethylene glycol solution, heating to 100-150 ℃ to fully dissolve the hydrogenated pyromellitic dianhydride, slowly adding a titanium glycol solution, heating to 110-180 ℃ until no moisture is discharged, and preserving heat for 4-12 hours to obtain a solution A; the mass ratio of the hydrogenated pyromellitic dianhydride to the ethylene glycol to the titanium glycol solution is 1:0.3-1.2:3-15;
the ethylene glycol titanium solution is prepared by the following method: taking anhydrous ethylene glycol and titanium tetrachloride as raw materials, slowly adding titanium tetrachloride into excessive anhydrous ethylene glycol in a stirring state in a closed environment, keeping stirring for 5-30min, introducing ammonia gas to neutralize hydrogen chloride generated by reaction until the pH value of the solution is 7-8.5, stopping introducing ammonia gas, standing for 10-40min, and filtering to remove precipitates to obtain a titanium glycol solution;
(2) Adding ethylene glycol, a surfactant and nano boron nitride powder in sequence, stirring at a high speed, and grinding and dispersing to obtain a mixture B; the adding amount of the nanometer boron nitride powder is 2-15% of the total weight of the solution, and the adding amount of the surfactant is 3-20% of the total weight of the solution;
(3) Under the protection of nitrogen atmosphere, dropwise adding the mixture B into the solution A to obtain a catalyst; the mass ratio of the solution A to the mixture B is 1:0.5 to 3;
the mass fraction of the titanium element in the catalyst is 0.5-8%.
2. A catalyst as claimed in claim 1, wherein in step (2), the surfactant is one or more of polyvinyl alcohol, alkylbenzene sulfonate, fatty alcohol-polyoxyethylene ether.
3. The preparation method of the polyester polymer easy to decompose and recycle is characterized by comprising the following steps:
(1) Adding a first monomer and a second monomer with a molar ratio of 1.1-3.0 into a reaction kettle, and esterifying for 2-8 hours at the temperature of 220-280 ℃ and the gauge pressure of 0.08-0.6MPa to obtain an esterified BHET; the first monomer is purified terephthalic acid, and the second monomer is ethylene glycol;
(2) Mixing a mixture of 1:3-15 of a third monomer and a second monomer are added into a reaction kettle, 0.1-2% of acetate is added, the mixture is stirred and heated to 150-210 ℃, the temperature is maintained for esterification reaction, when the esterification rate reaches 50-95%, the esterification reaction is stopped to obtain esterification liquid SSIPA, and the temperature is kept for standby; the third monomer is dimethyl isophthalate-5-sodium Sulfonate (SIPM) or isophthalic acid-5-sodium Sulfonate (SIPA);
(3) Adding the esterified liquid SSIPA prepared in the step (2) and a fourth monomer into the esterified BHET prepared in the step (1), uniformly stirring, adding a catalyst, and reacting for 1-5 hours under the conditions that the temperature is 260-310 ℃ and the absolute pressure is 50-200Pa to obtain a polyester polymer easy to decompose and recover; the fourth monomer is one or more of polyethylene glycol monomethyl ether and polyethylene glycol; the catalyst is the catalyst of any one of claims 1-2;
in the step (3), the total effective component SIPA or SIPM of the esterified liquid SSIPA accounts for 1-15% of the weight of terephthalic acid in the esterified BHET, and the weight percentage of the four monomers accounts for 2-20% of the weight of the refined terephthalic acid in the esterified BHET;
the dosage of the catalyst is 10-30ppm of titanium content.
4. A polyester fiber, a polyester film or a polyester plastic product, which is characterized in that the polyester polymer prepared by the preparation method of the easily decomposed and recycled polyester polymer according to claim 3 is used as a raw material.
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| JP2007056419A (en) * | 2005-08-26 | 2007-03-08 | Toray Ind Inc | Hollow polyester fiber and fabric |
| CN103509175A (en) * | 2012-06-20 | 2014-01-15 | 东丽纤维研究所（中国）有限公司 | Cationic dye dyeable polyester and preparation method thereof |
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| CN109485838A (en) * | 2018-10-14 | 2019-03-19 | 东华大学 | Copoly type high fluidity cationic polyester master batch basis material and preparation method thereof |
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| CN1583822A (en) * | 2004-06-16 | 2005-02-23 | 浙江工程学院 | Modified polyester and preparing method thereof |
| JP2007056419A (en) * | 2005-08-26 | 2007-03-08 | Toray Ind Inc | Hollow polyester fiber and fabric |
| CN103509175A (en) * | 2012-06-20 | 2014-01-15 | 东丽纤维研究所（中国）有限公司 | Cationic dye dyeable polyester and preparation method thereof |
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