CN114195991A - Method for preparing polyethylene terephthalate by directly polymerizing coal-based ethylene glycol and terephthalic acid - Google Patents
Method for preparing polyethylene terephthalate by directly polymerizing coal-based ethylene glycol and terephthalic acid Download PDFInfo
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- CN114195991A CN114195991A CN202111412339.9A CN202111412339A CN114195991A CN 114195991 A CN114195991 A CN 114195991A CN 202111412339 A CN202111412339 A CN 202111412339A CN 114195991 A CN114195991 A CN 114195991A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for preparing polyethylene terephthalate by directly polymerizing coal-based ethylene glycol and terephthalic acid. The invention further provides polyethylene terephthalate. The invention also provides a spinning method of the polyethylene terephthalate. The invention further provides a polyethylene terephthalate fiber and application thereof. The method for preparing the polyethylene terephthalate by directly polymerizing the coal-based ethylene glycol and the terephthalic acid breaks through the defects that the prior coal-based ethylene glycol cannot be directly polymerized to prepare the polyethylene terephthalate and melt-spun to prepare the fiber, and the fiber meeting the requirements of the clothing industry is prepared.
Description
Technical Field
The invention belongs to the technical field of polymerization preparation of polyethylene terephthalate (PET), and relates to a method for preparing polyethylene terephthalate (PET) by directly polymerizing coal-based ethylene glycol and terephthalic acid (PTA), in particular to a method for preparing polyethylene terephthalate (PET) by directly polymerizing coal-based ethylene glycol and purified terephthalic acid and spinnability research thereof.
Background
Commercial polyester chips and fibers (terlon, Terylene) were successfully prepared in 1941 by the british engineers wheatfield and german engineers Dikson. Subsequently, DuPont in the United states further advanced the polyester synthesis and spinning technology based on Terlon and achieved industrial production in 1951 (output 16000 t/y). The polyester fiber is produced in large scale from the 70 th of the 20 th century in China, and is widely applied to the fields of clothing home textile, energy environment, transportation and the like because of the advantages of high mechanical property, strong wear resistance, good stability and the like. By 2018, the yield of the polyester fiber in China exceeds 4000 million tons (accounting for about 80 percent of the total amount of the chemical fiber), and the polyester fiber becomes a fiber material with the largest yield and the widest application.
The ethylene glycol is mainly used for producing polyester fibers, antifreeze, unsaturated polyester resin, nonionic surfactant and the like. The conventional raw materials of the existing polyester, namely ethylene glycol and terephthalic acid, are all derived from petroleum resources, and can be used as ethylene glycol and polyethylene glycol to derive various types of surfactants for producing plasticizers, dyeing and finishing auxiliaries, drying agents and softening agents, wherein a dinitro compound is an explosive, and methyl, ethyl and butyl ethers thereof are used as solvents, and the dinitro compound is also widely applied to the manufacture of synthetic fibers, rubber, polyester paint, adhesives, synthetic resins, cosmetics, lubricants, gas chromatography fixing solutions and the like.
At present, ethylene glycol products in China are mainly used for producing polyester, antifreeze, adhesives, paint solvents, cold-resistant lubricating oil, surfactants, polyester polyol and the like. The polyester is the main consumption field of ethylene glycol in China, the consumption amount of the polyester accounts for 91.5 percent of the total consumption amount in China, and the polyester is used for antifreeze, adhesive, paint solvent, cold-resistant lubricating oil, surfactant, polyester polyol and other products in about 8.5 percent. Therefore, the development of the spinning-grade PET synthesis process is of great significance for the downstream application of the ethylene glycol.
China is the first major consumer country of world ethylene glycol, the ethylene glycol demand in Asia-Pacific region accounts for more than 60% of the total demand of world, the ethylene glycol demand in China accounts for more than 1/3 of the total demand of world ethylene glycol, and polyester is the main consumer field of ethylene glycol in China. The dependence degree of the imported ethylene glycol is high, the influence of the price change of the upstream raw material ethylene on the ethylene glycol market is not obvious due to the particularity of the ethylene glycol production process, the ethylene glycol market is limited by various factors, and the production regions and manufacturers of the ethylene glycol are relatively centralized, so that the ethylene glycol market still depends on the change of supply and demand aspects under the condition that the raw material market is not strongly instructive. The coal resources in China are rich, the coal-based ethylene glycol synthesis process and the polyester process research are vigorously developed, and the method has the following remarkable benefits:
(1) economic benefits
The petroleum-based ethylene glycol process has the defects of dependence on petroleum resources, large water consumption and large energy consumption in the process, and the cost of the process fluctuates along with the international crude oil price. The supply capacity of ethane in the middle east has also been slowing down in recent years, mainly because the natural gas field in the middle east, which has been rich in ethane and propane as "wet gas", has gradually moved to "dry gas", and the ethane in natural gas is no longer abundant. The mid east region has limited growth in ethylene glycol production and supply for the next decade.
The coal-based glycol has the advantages of wide range of production raw materials, low requirement on production conditions, easy development to localization, good economic benefit in the aspect of utilization of synthesis gas, high added value and the like, and the coal resources in China are rich while the petroleum resources are relatively few.
(2) Social benefits
The coal-based ethylene glycol synthesis technology is vigorously developed, on one hand, the coal-based ethylene glycol synthesis technology can be used as a strategic storage technology of the nation and the company, and is used when the situation changes in the world and the country, the price of crude oil rises, and the price fluctuation of the international ethylene glycol market is frequent; on the other hand, the innovation capability of the ethylene glycol production process in China can be developed, at present, the ethylene glycol device in China basically adopts a foreign ethylene introduction route, the coal-based ethylene glycol polymerization process is vigorously developed, and the device is beneficial to breaking through the original technology early and forming an autonomous original technology; finally, other high-value byproducts are generated in the coal-based ethylene glycol synthesis process, and the byproducts can also be used for polymerization.
(3) Application prospect
The development of the coal-based ethylene glycol technology widens the raw material sources of ethylene glycol production, and is particularly suitable for the countries with rich coal resources in China. For a long time, the self-sufficiency of the ethylene glycol in China is maintained at a low level, the ethylene glycol still has a large gap in a certain time, and the coal-based ethylene glycol technology has a large market space. After the demonstration project of the coal-based ethylene glycol is perfect and mature, if the demonstration project can be reasonably constructed in China, the self-supply capability of the domestic ethylene glycol market can be effectively improved, and the method has important strategic and practical significance.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a method for preparing polyethylene terephthalate by directly polymerizing coal-based ethylene glycol and terephthalic acid, which can shorten the polymerization time, discharge trace impurities in coal-based ethylene glycol, and prepare fiber for the clothing industry.
In order to achieve the above and other related objects, the present invention provides in a first aspect a process for preparing polyethylene terephthalate directly using coal-based ethylene glycol polymerized with terephthalic acid, comprising: premixing terephthalic acid and coal-based ethylene glycol, esterifying, adding a catalyst, performing pre-polycondensation, and performing polycondensation to provide polyethylene terephthalate.
Preferably, the terephthalic acid is purified terephthalic acid.
Preferably, the mass ratio of the added terephthalic acid to the added coal-based ethylene glycol is 100-130: 45-55.
Preferably, the premixing is to mix terephthalic acid and coal-based ethylene glycol, stir, recharge nitrogen and then release pressure.
More preferably, the time for stirring after mixing is 10 to 20 minutes.
More preferably, the rotation speed of the stirring is 30-50 rpm.
More preferably, the reaction pressure after the nitrogen gas is filled is 100 to 200 KPa.
More preferably, the pressure is relieved to 0 KPa.
Preferably, the reaction temperature of the premixing is 50-80 ℃.
Preferably, the reaction temperature of the esterification is 220-250 ℃.
Preferably, the reaction pressure of the esterification is 200-300 KPa.
Preferably, the reaction time of the esterification is 120-130 min.
Preferably, the adding mass of the catalyst is 0.03-0.05% of the adding mass of the terephthalic acid and the coal-based ethylene glycol.
Preferably, the catalyst is selected from one or more of titanium dioxide, ethylene glycol titanium, antimony trioxide, ethylene glycol antimony, manganese acetate or zinc acetate.
More preferably, the catalyst is selected from one or more of titanium dioxide, ethylene glycol titanium, antimony trioxide, ethylene glycol antimony and manganese acetate.
Further preferably, the catalyst comprises the following components in parts by mass: 0-1 part of titanium dioxide; 0-2 parts of ethylene glycol titanium; 0-3 parts of antimony trioxide; 1-3 parts of ethylene glycol antimony; 0-1 part of manganese acetate.
Preferably, the reaction temperature of the pre-polycondensation is 275-285 ℃.
Preferably, the pressure reduction time of the pre-polycondensation is 30-50 min.
Preferably, the pre-polycondensation is depressurized to 500-1000 Pa.
Preferably, the reaction temperature of the polycondensation is 280-285 ℃.
Preferably, the polycondensation is depressurized to 10-50 Pa.
Preferably, the reaction time after the polycondensation is depressurized is 110-130 min.
Preferably, the process is carried out in a polymerization kettle.
The second aspect of the invention provides polyethylene terephthalate (PET) prepared by the above method.
Preferably, the polyethylene terephthalate (PET) has a number average molecular weight of 16000-23000, a weight average molecular weight of 20000-40000 and a melting point of 240-260 ℃.
The third aspect of the present invention provides a method for spinning polyethylene terephthalate, comprising: the polyethylene terephthalate is dried and then melt-spun in a spinning machine and then drawn to provide a polyethylene terephthalate fiber.
Preferably, the drying conditions are: the drying device is a vacuum oven; the drying temperature is 90-110 ℃; the drying pressure is 10-50 Pa; the drying time is 10-15 h.
Preferably, the process conditions of melt spinning in the spinning machine are as follows: the temperature of the screw is 260-300 ℃; the rotating speed of the screw is 40-90 r/min; the temperature of the assembly is 280-290 ℃; the rotating speed of the metering pump is 10-20 r/min; the spinning pressure is 3-5 MPa; the winding speed is 500 to 3000 m/min.
Preferably, the process conditions of the drawing are as follows: the drafting multiple is 3-8 times; the drafting temperature is 60-90 ℃; the setting temperature is 100-160 ℃.
The fourth aspect of the invention provides a polyethylene terephthalate fiber spun by the method.
Preferably, the polyethylene terephthalate fiber has a single filament fineness of 1 to 3dtex, an elongation at break of 10 to 40%, and a strength of 2.5 to 3.5 CN/dtex.
Preferably, the average value of the thermal shrinkage rate of the polyethylene terephthalate fiber is 0.1-0.9%, and the static friction coefficient is 50-100 x 10-3CN。
The fifth aspect of the invention provides a use of polyethylene terephthalate fiber in weaving clothing fabric.
As described above, the method for preparing polyethylene terephthalate by directly using coal-based ethylene glycol and terephthalic acid polymerization provided by the invention has the following beneficial effects compared with the PET polyester prepared by petroleum-based ethylene glycol and terephthalic acid (PTA) polymerization which is commonly used in the market at present:
(1) compared with the prior art that the coal-based glycol is mainly used in the fields of plasticizers, dyeing and finishing auxiliaries and drying agents and in the fields of fibers and textiles, the coal-based glycol can only be doped with petroleum-based glycol in a small amount for use.
(2) The method of the invention adopts the compound catalyst, thus shortening the polymerization time required by the polymerization of the coal-based ethylene glycol and the refined PTA; and the temperature of the polyethylene glycol terephthalate polymerization process is adjusted, so that trace impurities in the coal-based ethylene glycol can be discharged.
(3) The polyethylene glycol terephthalate prepared by the method of the invention meets the performance requirement of melt spinning, and the fiber meeting the requirement of clothing industry is prepared, and the prepared fiber can be used for clothing fiber.
(4) The method comprehensively analyzes the rule of the influence of the material forming process parameters on the structural performance of the polyester chip and the fiber material. The polymerization process is optimized by the compound catalyst, so that the properties of the polyethylene glycol terephthalate slice such as intrinsic viscosity, molecular weight, distribution and melting point of the polyethylene glycol terephthalate slice are effectively regulated and controlled, and the comprehensive properties of the polyethylene glycol terephthalate slice and the fiber are remarkably improved.
Detailed Description
The invention provides a preparation method of polyethylene terephthalate, which is directly prepared by polymerization of coal-based ethylene glycol and terephthalic acid, and comprises the following steps: premixing terephthalic acid and coal-based ethylene glycol, esterifying, adding a catalyst, performing pre-polycondensation, and performing polycondensation to provide polyethylene terephthalate.
In the above process, the terephthalic acid (PTA, CAS number 100-21-0) is purified terephthalic acid.
The purified terephthalic acid is a product obtained by using terephthalic acid as a raw material, oxidizing the liquid phase to generate crude terephthalic acid, and then performing hydrofining, crystallization, separation and drying.
The purity of the crude terephthalic acid is 82-85%, and the purity of the refined terephthalic acid is more than or equal to 98%.
The coal-based ethylene glycol, also called coal-made ethylene glycol, is ethylene glycol produced by replacing petroleum ethylene with coal.
In particular, the currently used route for the preparation of petroleum based glycols is the preparation of ethylene oxide from ethylene, followed by rehydration to obtain ethylene glycol. Petroleum-based ethylene glycol is the most main raw material for producing polyethylene terephthalate at present, and has the widest industrial application. The preparation route of the coal-based ethylene glycol is that coal is gasified, transformed and separated to prepare carbon monoxide and hydrogen, the carbon monoxide and pure oxygen are prepared to dimethyl oxalate, and the dimethyl oxalate is reacted with the hydrogen to prepare the ethylene glycol. Therefore, the preparation routes of petroleum-based ethylene glycol and coal-based ethylene glycol are completely different, and trace impurities in the two prepared ethylene glycols are different, so that the performance of a product obtained by adopting ethylene glycol to carry out polymerization reaction can be influenced. In the practice of preparing polyethylene terephthalate, the process of using petroleum-based glycol as a raw material is generally adopted, coal-based glycol can only be doped into petroleum-based glycol in a small amount for use, and the coal-based glycol cannot be directly used for preparing the polyethylene terephthalate by polymerization.
In the method, the mass ratio of the added terephthalic acid to the added coal-based ethylene glycol is 100-130: 45-55, specifically 100-110: 45-55, 110-120: 45-55, 120-130: 45-55.
In the method, the premixing is to mix the terephthalic acid and the coal-based ethylene glycol, stir the mixture, recharge nitrogen and release pressure.
In a preferred embodiment, the time for stirring after mixing is 10 to 20 minutes, specifically 10 to 15 minutes, 15 to 20 minutes.
In a preferred embodiment, the rotation speed of the stirring is 30-50 rpm. The stirring is low-speed stirring.
In a preferred embodiment, the reaction pressure after the nitrogen gas is filled is 100 to 200KPa, specifically 100 to 150KPa, 150 to 200 KPa.
In a preferred embodiment, the pressure is relieved to 0 KPa.
In the method, the reaction temperature of the premixing is 50-80 ℃, specifically 50-60 ℃, 60-70 ℃ and 70-80 ℃.
In the method, the esterification reaction temperature is 220-250 ℃, specifically 220-230 ℃, 230-240 ℃ and 240-250 ℃.
In the method, the esterification reaction pressure is 200 to 300KPa, specifically 200 to 250KPa, 250 to 300 KPa.
In the method, the esterification reaction time is 120-130 min, specifically 120-125 min and 125-130 min.
In the method, the adding mass of the catalyst is 0.03-0.05% of the adding mass of the terephthalic acid and the coal-based ethylene glycol, specifically 0.03-0.04% and 0.04-0.05%.
The esterification is a conventional esterification reaction between alcohol and carboxylic acid, and specifically refers to a reaction for generating ester and water from terephthalic acid and coal-based ethylene glycol.
In the method, the catalyst is one or more of titanium dioxide, ethylene glycol titanium, antimony trioxide, ethylene glycol antimony, manganese acetate or zinc acetate.
In a preferred embodiment, the catalyst is selected from one or more of titanium dioxide, ethylene glycol titanium, antimony trioxide, ethylene glycol antimony, manganese acetate.
In a further preferred embodiment, the catalyst comprises the following components in parts by mass: 0-1 part of titanium dioxide; 0-2 parts of ethylene glycol titanium; 0-3 parts of antimony trioxide; 1-3 parts of ethylene glycol antimony; 0-1 part of manganese acetate.
In the method, the reaction temperature of the pre-polycondensation is 275-285 ℃, specifically 275-280 ℃ and 280-285 ℃.
In the method, the pressure reduction time of the pre-polycondensation is 30-50 min, specifically 30-40 min and 40-50 min.
In the method, the pre-polycondensation is depressurized to 500-1000 Pa, specifically 500-750 Pa and 750-1000 Pa.
The pre-polycondensation is to reduce the pressure in a certain time by vacuumizing at high temperature, thereby obtaining a pre-polycondensation product.
In the method, the polycondensation reaction temperature is 280-285 ℃, specifically 280-283 ℃ and 283-285 ℃.
In the method, the polycondensation is depressurized to 10-50 Pa, specifically 10-20 Pa, 20-30 Pa, 30-40 Pa, and 40-50 Pa.
In the method, the reaction time after the polycondensation is depressurized is 110-130 min, specifically 110-120 min and 120-130 min.
The polycondensation is to obtain a polycondensation product by carrying out reaction for a period of time after vacuumizing and depressurizing again on the basis of pre-polycondensation.
In the above process, the process is carried out in a polymerization reactor.
In a second aspect, the present invention provides a polyethylene terephthalate (PET, CAS No. 25038-59-9) prepared by the above process.
In the PET, the number average molecular weight of the polyethylene terephthalate (PET) is 16000-23000, specifically 16000-23000, 16000-19000, 19000-23000; the weight average molecular weight is 20000-40000, specifically 20000-30000 and 30000-40000; the melting point is 240-260 deg.C, such as 240-250 deg.C and 250-260 deg.C.
The third aspect of the present invention provides a method for spinning polyethylene terephthalate, comprising: the polyethylene terephthalate is dried, melt-spun in a spinning machine, and then drawn to provide a polyethylene terephthalate fiber.
In the above spinning method, the drying conditions are: the drying device is a vacuum oven; the drying temperature is 90-110 ℃, specifically 90-100 ℃ and 100-110 ℃; the drying pressure is 10-50 Pa, such as 10-30 Pa and 30-50 Pa; the drying time is 10-15 h, such as 10-13 h and 13-15 h.
The above-mentioned spinning machine is a general-purpose melt spinning machine which is conventionally used and is commercially available. And putting the polyethylene glycol terephthalate into a feed inlet of a spinning machine for spinning.
In the spinning method, the process conditions of melt spinning in the spinning machine are as follows: the temperature of the screw is 260-300 ℃, specifically 260-280 ℃ and 280-300 ℃; the rotating speed of the screw is 40-90 r/min, specifically 40-65 r/min and 65-90 r/min; the temperature of the component is 280-290 ℃, specifically 280-285 ℃ and 285-290 ℃; the rotating speed of the metering pump is 10-20 r/min, specifically 10-15 r/min and 15-20 r/min; the spinning pressure is 3-5 MPa, such as 3-4 MPa and 4-5 MPa; the winding speed is 500-3000 m/min, such as 500-1500 m/min, 1500-2000 m/min, 2000-3000 m/min.
In the spinning method, the process conditions of the drawing are as follows: the draft multiple is 3-8 times, specifically 3-5 times, 5-7 times and 7-8 times; the drafting temperature is 60-90 ℃, specifically 60-70 ℃, 70-80 ℃ and 80-90 ℃; the setting temperature is 100-160 ℃, specifically 100-120 ℃, 120-140 ℃ and 140-160 ℃.
The drawing is carried out in a drawing machine. The draw frame is a general-purpose parallel draw frame which is conventionally used and is commercially available.
The fourth aspect of the invention provides a polyethylene terephthalate fiber spun by the method.
In the polyethylene terephthalate fiber, the filament number of the polyethylene terephthalate fiber is 1 to 3dtex, such as 1 to 2dtex and 2 to 3 dtex; the elongation at break is 10-40%, specifically 10-20%, 20-30%, 30-40%; the strength is 2.5 to 3.5CN/dtex, such as 2.5 to 3.0CN/dtex and 3.0 to 3.5 CN/dtex.
In the above polyethylene terephthalate fiber, the thermal shrinkage of the polyethylene terephthalate fiber is flatThe average value is 0.1-0.9%, specifically 0.1-0.5%, 0.5-0.9%; the static friction coefficient is 50-100 multiplied by 10-3CN, specifically 50 to 75X 10-3CN、75～100×10-3CN。
The polyethylene glycol terephthalate fiber reaches the standard of the clothing industry.
The fifth aspect of the invention provides a use of polyethylene terephthalate fiber in weaving clothing fabric.
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
Weighing 100 parts of purified terephthalic acid and 50 parts of coal-based ethylene glycol according to parts by weight, mixing the weighed materials, placing the mixture in a polymerization reaction kettle, stirring at a low speed, setting the temperature in the polymerization reaction kettle at 80 ℃, charging 100KPa nitrogen after 10 minutes, and releasing the pressure to 0 KPa. And setting the temperature in the polymerization reaction kettle to be 220 ℃, and carrying out esterification reaction in the polymerization reaction kettle, wherein the esterification pressure is 200KPa, and the esterification time is 130 min.
And weighing the refined terephthalic acid and the coal-based ethylene glycol according to the parts by weight, adding 0.03% of catalyst by weight into the polymerization kettle, and carrying out pre-polycondensation reaction. Wherein the catalyst is a mixture consisting of titanium dioxide, ethylene glycol titanium, antimony trioxide and ethylene glycol antimony, and the mass ratio of the titanium dioxide to the ethylene glycol titanium to the antimony trioxide to the ethylene glycol antimony is 1: 1: 3: 3. the temperature in the polymerization reactor was set at 275 ℃ and the pressure was reduced to 500Pa by evacuation within 50 min.
And finally, setting the temperature in the polymerization reaction kettle to 280 ℃ for polycondensation reaction, vacuumizing, reducing the pressure to 10Pa, and reacting for 120min to obtain the polyethylene terephthalate product 1 #.
The polyethylene terephthalate product 1# was subjected to molecular weight and melting point measurements to obtain polyethylene terephthalate product 1# having a number average molecular weight of 17232, a weight average molecular weight of 24856, and a melting point of 251 ℃.
Example 2
Weighing 110 parts of purified terephthalic acid and 55 parts of coal-based ethylene glycol, mixing the weighed materials, placing the mixture in a polymerization reaction kettle, stirring at a low speed, setting the temperature in the polymerization reaction kettle at 50 ℃, charging 200KPa nitrogen after 20 minutes, and releasing the pressure to 0 KPa. And setting the temperature in the polymerization reaction kettle to 240 ℃, and carrying out esterification reaction in the polymerization reaction kettle, wherein the esterification pressure is 300KPa, and the esterification time is 120 min.
And weighing the refined terephthalic acid and the coal-based ethylene glycol according to the parts by weight, adding 0.05% of catalyst by weight into the polymerization kettle, and carrying out pre-polycondensation reaction. Wherein the catalyst is a mixture consisting of titanium dioxide, ethylene glycol titanium, antimony trioxide and ethylene glycol antimony, and the mass ratio of the titanium dioxide to the ethylene glycol titanium to the antimony trioxide to the ethylene glycol antimony is 1: 1: 2: 2. the temperature in the polymerization reactor was set to 285 ℃ and the pressure was reduced to 1000Pa within 30min by evacuation.
And finally, setting the temperature in the polymerization reaction kettle to 285 ℃ for polycondensation reaction, and reducing the pressure to 50Pa by vacuumizing for 110min to obtain a polyethylene terephthalate product No. 2.
The polyethylene terephthalate product 2# was subjected to molecular weight and melting point measurements to obtain polyethylene terephthalate product 2# having a number average molecular weight of 17156, a weight average molecular weight of 27897, and a melting point of 251 ℃.
Example 3
Weighing 105 parts of purified terephthalic acid and 53 parts of coal-based ethylene glycol according to parts by weight, mixing the weighed materials, placing the mixture in a polymerization reaction kettle, stirring at a low speed, setting the temperature in the polymerization reaction kettle to 65 ℃, charging 150KPa nitrogen after 15 minutes, and releasing the pressure to 0 KPa. And setting the temperature in the polymerization reaction kettle to 230 ℃, and carrying out esterification reaction in the polymerization reaction kettle, wherein the esterification pressure is 250KPa, and the esterification time is 125 min.
And weighing the refined terephthalic acid and the coal-based ethylene glycol according to the parts by weight, adding a catalyst with the mass of 0.04% into the polymerization reaction kettle, and carrying out pre-polycondensation reaction. Wherein the catalyst is a mixture consisting of titanium dioxide, ethylene glycol titanium, antimony trioxide and ethylene glycol antimony, and the mass ratio of the titanium dioxide to the ethylene glycol titanium to the antimony trioxide to the ethylene glycol antimony is 1: 1: 3: 2. the temperature in the polymerization reactor was set at 280 ℃ and the pressure was reduced to 750Pa within 40min by evacuation.
And finally, setting the temperature in the polymerization reaction kettle to 283 ℃ for polycondensation reaction, vacuumizing, reducing the pressure to 30Pa, and reacting for 115min to obtain the polyethylene terephthalate product No. 3.
The polyethylene terephthalate product No. 3 was subjected to molecular weight and melting point measurements to obtain a polyethylene terephthalate product No. 3 having a number average molecular weight of 17326, a weight average molecular weight of 28976, and a melting point of 253 ℃.
Example 4
The polyethylene terephthalate products 1#, 2#, and 3# obtained in examples 1 to 3 were dried in vacuum ovens, respectively, the oven temperature was set at 90 ℃, the oven pressure was controlled to 10Pa by evacuation, and the drying time was 15 hours.
And then putting the dried polyethylene terephthalate products 1#, 2#, and 3# into a feed inlet of a spinning machine respectively for melt spinning. Wherein the screw temperature is 260 ℃, the screw rotating speed is 90r/min, the assembly temperature is 280 ℃, the metering pump rotating speed is 10r/min, the spinning pressure is 3MPa, and the winding speed is 500 m/min.
After melt spinning, drawing is carried out, wherein the drawing multiple is 3 times, the drawing temperature is 60 ℃, and the setting temperature is 100 ℃. Polyethylene terephthalate fibers 1, 2 and 3 were obtained, respectively.
The polyethylene terephthalate fibers 1, 2 and 3 are subjected to performance tests to obtain polyethylene terephthalate fibers 1, 2 and 3 with single-filament titer of 2.3, 2.4 and 2.4dtex, elongation at break of 36%, 32 and 28%, strength of 2.6CN/dtex, 2.7CN/dtex and 3.0CN/dtex, average values of heat shrinkage of 0.9, 0.7 and 0.5%, and static friction coefficient of 52 multiplied by 10-3CN、64×10-3CN、66×10-3CN。
Example 5
The performance test data of the polyethylene terephthalate fibers 1, 2 and 3 prepared in the example 4 reach the performance parameters of the common polyethylene terephthalate fibers, the fiber strength is higher than 2.5CN/dtex, and the polyethylene terephthalate fibers can be used for clothing fabric fibers. Therefore, the polyethylene glycol terephthalate can be directly prepared from the coal-made ethylene glycol and the terephthalic acid, and the performance of the prepared polyethylene glycol terephthalate can meet the requirement of clothing fibers after the polyethylene glycol terephthalate is melt-spun into fibers.
In conclusion, the method for preparing the polyethylene terephthalate by directly polymerizing the coal-based ethylene glycol and the terephthalic acid provided by the invention breaks through the defects that the coal-based ethylene glycol cannot be directly polymerized to prepare the polyethylene terephthalate and is melt-spun to prepare the fiber, and the fiber meeting the requirements of the clothing industry is prepared. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of polyethylene terephthalate, which is directly prepared by polymerization of coal-based ethylene glycol and terephthalic acid, comprises the following steps: premixing terephthalic acid and coal-based ethylene glycol, esterifying, adding a catalyst, performing pre-polycondensation, and performing polycondensation to provide polyethylene terephthalate.
2. The method for preparing polyethylene terephthalate according to claim 1, wherein the terephthalic acid is purified terephthalic acid, and the purity of the purified terephthalic acid is not less than 98%.
3. The method for preparing the polyethylene terephthalate according to claim 1, wherein the catalyst is one or more selected from titanium dioxide, ethylene glycol titanium, antimony trioxide, ethylene glycol antimony, manganese acetate and zinc acetate; the adding mass of the catalyst is 0.03-0.05% of that of the terephthalic acid and the coal-based ethylene glycol.
4. The method of claim 1, comprising any one or more of the following conditions:
1) the mass ratio of the terephthalic acid to the coal-based ethylene glycol is 100-130: 45-55;
2) the premixing is to mix terephthalic acid and coal-based ethylene glycol, stir, recharge nitrogen and release pressure;
3) the reaction temperature of the premixing is 50-80 ℃;
4) the reaction temperature of the esterification is 220-250 ℃;
5) the esterification reaction pressure is 200-300 KPa;
6) the reaction temperature of the pre-polycondensation is 275-285 ℃;
7) carrying out pre-polycondensation and reducing pressure to 500-1000 Pa;
8) the reaction temperature of the polycondensation is 280-285 ℃;
9) and reducing the pressure to 10-50 Pa in the polycondensation.
5. Polyethylene terephthalate, obtainable by the process according to any one of claims 1 to 4.
6. A method of spinning polyethylene terephthalate, comprising: the polyethylene terephthalate according to claim 5 is dried and then melt-spun in a spinning machine and then drawn to provide a polyethylene terephthalate fiber.
7. The spinning process of polyethylene terephthalate according to claim 6, characterized in that it comprises any one or more of the following conditions:
A) the drying conditions are as follows: the drying device is a vacuum oven; the drying temperature is 90-110 ℃; the drying pressure is 10-50 Pa; the drying time is 10-15 h;
B) the process conditions of melt spinning in the spinning machine are as follows: the temperature of the screw is 260-300 ℃; the rotating speed of the screw is 40-90 r/min; the temperature of the assembly is 280-290 ℃; the rotating speed of the metering pump is 10-20 r/min; the spinning pressure is 3-5 MPa; the winding speed is 500-3000 m/min;
C) the process conditions of the drafting are as follows: the drafting multiple is 3-8 times; the drafting temperature is 60-90 ℃; the setting temperature is 100-160 ℃.
8. A polyethylene terephthalate fiber spun by the process of any of claims 6-7.
9. The polyethylene terephthalate fiber according to claim 8, comprising any one or more of the following conditions:
a) the polyethylene terephthalate fiber has a filament number of 1-3 dtex, an elongation at break of 10-40% and a strength of 2.5-3.5 CN/dtex;
b) the average value of the thermal shrinkage rate of the polyethylene terephthalate fiber is 0.1-0.9%, and the static friction coefficient is 50-100 x 10-3CN。
10. Use of a polyethylene terephthalate fiber according to any of claims 8-9 in the weaving of clothing fabrics.
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