WO2004026938A1 - ポリエステルの製造方法 - Google Patents
ポリエステルの製造方法 Download PDFInfo
- Publication number
- WO2004026938A1 WO2004026938A1 PCT/JP2003/010170 JP0310170W WO2004026938A1 WO 2004026938 A1 WO2004026938 A1 WO 2004026938A1 JP 0310170 W JP0310170 W JP 0310170W WO 2004026938 A1 WO2004026938 A1 WO 2004026938A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ejector
- tank
- hot well
- butanediol
- condenser
- Prior art date
Links
Classifications
-
- 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
- C08G63/785—Preparation processes characterised by the apparatus used
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a method for producing a polyester. More specifically, the present invention relates to a method capable of realizing a stable vacuum reaction and producing a polyester of stable quality.
- Akita
- Polyester is used in various fields such as fibers, molded parts, and films because of its excellent moldability, mechanical properties, heat resistance, chemical resistance, fragrance retention, and other physical and chemical properties. Has been.
- polybutylene terephthalate which is composed of a terephthalic acid component and 1,4-butanediol component, is one of the engineering plastics that has mechanical properties and heat resistance that can replace metal materials. It is widely used in injection molded products such as precision instrument components, etc. In recent years, it has been widely used in the fields of films, sheets, monofilaments, and fibers, taking advantage of its excellent properties.
- Polyester is generally obtained by subjecting a dicarboxylic acid or an ester derivative thereof to an esterification reaction or a transesterification reaction with a diol, and then producing a low-molecular-weight substance such as water or a diol under reduced pressure of generally less than 10 kPa. Is produced by performing a polycondensation reaction while removing from the system.
- a degassing device is required to reduce the pressure in the polycondensation reaction tank.
- various types of liquid sealing pumps, oil rotary pumps, roots pumps, steam ejectors, and the like are known. Many methods have been implemented to maximize the performance by combining a plurality of these methods.
- the present invention provides a method for realizing a stable depressurized state and, therefore, a polyester of stable quality. It was made for the purpose.
- the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a hot-well tank for a condenser installed downstream of an ejector that condenses exhaust gas from an ejector driven by 1,4-butanediol vapor. It has been found that by setting the tetrahydrofuran concentration of the sealing liquid to a specific amount or less, a stable reduced pressure state can be realized, and a polyester having a stable quality can be obtained, and the present invention has been completed.
- the gist of the present invention is to provide an ejector, a condenser installed downstream of the ejector, at least one polycondensation reaction tank provided with at least one set of atmospheric legs, and a hot water connected to the condenser via the atmospheric legs.
- the ejector is driven by steam mainly containing 1,4-butanediol, and the steam mainly containing 1,4-butanediol discharged from the ejector is downstream of the ejector.
- a method for producing a polyester comprising a step of condensing with an installed capacitor and performing a polycondensation reaction in a reactor under reduced pressure, wherein the concentration of tetrahydrofuran contained in the sealing liquid of at least one hot well tank is 4% by weight or less.
- FIG. 1 is a conceptual diagram of one embodiment of a polycondensation reaction apparatus used in the production method of the present invention, and has one polycondensation reaction tank.
- FIG. 2 is a conceptual diagram of one embodiment of the polycondensation reaction apparatus used in the production method of the present invention, which was adopted in Examples 1 to 3 and Comparative Example 1.
- FIG. 3 is a conceptual diagram showing a degassing system in detail in one embodiment of the polycondensation reaction apparatus used in the production method of the present invention, which was adopted in Examples 1 and 2. .
- FIG. 4 is a conceptual diagram showing in detail a degassing system in one embodiment of the polycondensation reaction apparatus used in the production method of the present invention.
- FIG. 5 is a conceptual diagram showing a degassing system in detail in one embodiment of the polycondensation reaction apparatus used in the production method of the present invention, and a part of the sealing liquid of the hot well tank S in FIG. And 1,4-butanediol steam generation boiler Z of the ejector.
- FIG. 6 is a conceptual diagram showing a degassing system in detail in one embodiment of the polycondensation reaction apparatus used in the production method of the present invention, which is employed in Example 3 and Comparative Example 1. .
- the polyester in the present invention is a polymer having a structure in which a dicarboxylic acid unit and a diol unit are ester-bonded.
- the dicarboxylic acid include terephthalic acid. Talic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherenocarboxylic acid, 4,4, _benzophenonedicanoleponic acid, 4,4'-diphenyloxy
- Aromatic dicarboxylic acids such as ethanedicarboxylic acid, 4,4, diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicanolevonic acid, 1,3-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarbonic acid, and aliphatic dicarboxylic acids such as malonic acid, succinic acid
- dicarboxylic acid components can be provided to the reaction as a dicarboxylic acid or as an alkyl ester of a dicarboxylic acid, preferably a dialkyl ester, and may be a mixture of a dicarboxylic acid and an alkyl dicarboxylic acid ester.
- a dicarboxylic acid or as an alkyl ester of a dicarboxylic acid preferably a dialkyl ester
- There is no particular limitation on the alkyl group of the alkyl dicarboxylate but if the alkyl group is long, the boiling point of the alkyl alcohol generated during the ester exchange reaction is increased, and the alkyl alcohol is not volatilized from the reaction solution.
- an alkyl group having 4 or less carbon atoms is preferable, and a methyl group is particularly preferable.
- diol component examples include ethylene glycol, diethylene glycol, polyethylene glycolone, 1,2-propanediole, 1,3-propanediole, polypropylene glycol, 1,4-butanediol, and polytetramethylene glycol.
- diol component examples include ethylene glycol, diethylene glycol, polyethylene glycolone, 1,2-propanediole, 1,3-propanediole, polypropylene glycol, 1,4-butanediol, and polytetramethylene glycol.
- Dibutyleneglycol ⁇ / le 1,5-pentanedio ⁇ neopenti ⁇ / daricol, 1,6-hexanediol, 1,8-octanediol, etc.
- Alicyclic diols such as hexanediene, 1,4-six-hexanediole, 1,1-six-hexanedimethylone, 1,4-six-hexanedimethyronole, xylylene glycol, 4,4 'jihi Droxybiphenyl, 2,2-bis (4-hydroxydroxypheninole) propane, bis (4-hydroxydroxyphenino) ) S sulfone can be mentioned and aromatic diols such as, inter alia of the diol units, the present invention in the polyester 5 0 mol% or more is 1, 4 one-butanediol The improvement effect is remarkable.
- hydroxycarponic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-12-naphthalenecarboxylic acid, and p- ⁇ -hydroxyoxetoxybenzoic acid;
- Monofunctional components such as alkoxy carboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butyl benzoic acid, benzoyl benzoic acid, etc. , Trimethylolethane, Trimethylon Reprono ,.
- Polyfunctional components having three or more functional groups such as glycerone, glycerone and pentaerythritol can be used as the copolymer component.
- polybutylene terephthalate comprising 0,1 mol% or more, particularly preferably 95 mol% or more of 1,4-butanediol units, since the amount of THF generated during the reaction is large, the improvement effect in the present invention is large.
- the method for producing the polyester of the present invention will be described using polybutylene terephthalate as an example.
- the methods for producing polybutylene terephthalate are roughly classified into a so-called direct polymerization method using terephthalic acid as a main raw material, and a transesterification method using dialkyl terephthalate or, preferably, dimethyl terephthalate as a main raw material.
- the former has the difference that mainly water is generated during the initial esterification reaction, and the latter mainly generates alcohol during the initial transesterification reaction.
- the direct polymerization method is preferred from the viewpoint of the improvement effect of the present invention. From the viewpoint of stabilization of quality and energy efficiency, a so-called continuous method of continuously supplying raw materials and continuously obtaining polybutylene terephthalate is preferred.
- the dicarboxylic acid component mainly containing terephthalic acid and the diol component mainly containing 1,4-butanediol are mixed in a one-stage or multi-stage esterification reaction tank.
- an esterification reaction catalyst 180 to 260 ° C, preferably 200 to 245 ° C, particularly preferably 210 to 23.5 ° C, usually 10 to 133 kPa, preferably 13 to: 101 kPa, particularly preferably 60
- the reaction is carried out at a pressure of 9090 kPa for 0.5 to 5 hours, preferably for 1 to 3 hours.
- the reaction may be a batch method or a continuous method, but a continuous method is particularly preferred.
- the dicarboxylic acid ester component containing dialkyl terephthalate as a main component and the diol component containing 1,4-butanediol as a main component are transesterified in one or more stages.
- 110-260 ° C, preferably 140-245 in the reaction vessel, preferably in the presence of a transesterification catalyst.
- C particularly preferably at a temperature of 180-220 ° C., also usually 10-: 133 kPa, preferably 13-120 kPa, particularly preferably 60-! It is carried out at a pressure of OlkPa for 0.5-5 hours, preferably 1-3 hours.
- the reaction may be a batch method or a continuous method, but a continuous method is particularly preferred.
- a single-stage or multi-stage polycondensation reaction tank is used, and in the presence of a polycondensation reaction catalyst, usually at a temperature of 210 to 280 ° C, preferably 220 to 265 ° C, particularly preferably 230 to 265 ° C. 1 to 12 hours, preferably 3 to 10 hours, with stirring at a temperature of up to 245 ° C, usually 27 kPa or less, preferably 20 kPa or less, particularly preferably 13 kPa or less.
- the reaction may be a batch method or a continuous method, but a continuous method is particularly preferred.
- the ejector is driven by steam mainly containing 1,4-butanediol as a deaerator used to reduce the pressure inside the polycondensation reaction tank.
- a polycondensation reactor equipped with a device that decompresses the polycondensation reaction tank by condensing the vapors mainly containing 1,4-butanediol discharged from the reactor with a condenser installed downstream of the ejector.
- the condenser means the condenser downstream of the ejector, and the condenser installed downstream of the ejector includes all the condensers located downstream of the ejector closest to the polycondensation reaction tank.
- Examples of the capacitor used in the present invention include a surface contact type and a direct contact type such as a barometric capacitor. Among them, oligomer components and additives which are not accompanied by excessive facilities and are entrained are included. Direct contacts that are less likely to cause blockage of components are preferred.
- the main component of the sealing liquid hot c Weru tank connected via the air leg capacitor is 1, 4 one-butanediol, Other that out distillate from the steam generator and the polycondensation reaction tank THF and H 2 0 Contains alcohol, etc.
- Vapor pressure of sealing liquid in the hot well tank is, H 2 0 or alcohol, varies with the content of the other components, further conditions such as polycondensation reactions, the control is not easy for depend on production volume, etc.
- it is necessary to set the THF concentration in the sealing solution of at least one hot well tank to 4% by weight or less, preferably 3% by weight or less, especially 1.5 weight. /.
- the pressure of the condenser or the critical back pressure of the ejector is 3 kPa or less, 1 wt% or less is preferable. If the tetrahydrofuran concentration in the sealing liquid is all greater than 4% by weight, the degree of reduced pressure required for polyester production cannot be obtained stably, which is inconvenient.
- the hot-water tank sealing liquid is withdrawn so long as the THF concentration of at least one hot-well tank sealing liquid does not exceed 4% by weight.
- Part or all of the liquid can be supplied to a 1,4-butanediol vapor generation boiler used in an ejector, and it is preferable to apply a hot well tank sealing liquid having the lowest THF concentration.
- the supply amount is usually 50% by weight or less, preferably 30% by weight or less, particularly preferably 20% by weight of 1,4-butanediol used in the 1,4-butanediol steam generating poiler. % Or less.
- the hot well tank has a low THF content, usually 2% by weight or less, preferably Is supplied with 1,4-butanediol of 1% by weight or less, more preferably 0.5% by weight or less, particularly preferably 0.1% by weight or less, or by adjusting the temperature of the hot water tank, It can also be achieved by collecting and recovering the generated THF vapor with another capacitor.
- the supply of 1,4-butanediol with a low THF content to the hot well tank can be carried out directly into the hot well tank, or the 1,4-butanediol vapor condensate from the ejector can be applied to this. You can also.
- a method in which 1,4-butanediol with a low THF content is directly supplied to the hot well tank separately from the condensate of 1,4-butanediol vapor from the ejector to control it.
- a liquid having a high THF concentration corresponding to the supplied 1,4-heptanediol having a low THF content is withdrawn from the hot wool tank, and the withdrawn liquid is fed into a raw material preparation tank, an esterification reaction tank having a THF separation facility or an esterification reaction tank.
- a method of recycling a liquid having a high THF content by supplying it to an exchange reaction tank is preferable.
- 1,4-butane with low THF content in the hot well tank If the supply amount of dienediol is too large, the amount of sealing liquid to be drawn out will increase accordingly, and if the drawn sealing liquid is recycled to the raw material preparation system, it will be used as a raw material. Exceeding the amount of butanediol may impair stable operation.
- the load on the separation tower increases as the supply amount increases, or the temperature of the polycondensation reaction tank increases. Adjustment may be difficult, resulting in impaired stable operation.
- part or all of the high-THF-concentrated sealing liquid extracted from the hot well tank is sent to a THF separation treatment system to separate THF from 1,4-butanediol. It is also possible to separate components other than THF simultaneously or sequentially.
- the 1,4-butanediol from which THF has been separated can be returned to the hot well tank, condenser, condenser attached to the polycondensation reaction tank, raw material preparation system, reaction system, etc., if necessary. It is preferable to return a part or all of the separated 1,4-butanediol of THF to the hot well tank.
- distillation For the separation of THF, known methods such as distillation, stripping, adsorption separation, membrane separation, extraction and the like can be used, but distillation is preferable in terms of separation efficiency, separation accuracy, simplicity of equipment and the like.
- THF concentration sealing liquid in at least one hot well tank is 4 wt% or less, preferably H 2 0 concentration of sealing liquid in the hot well tank is under 3 wt% or less It is preferably at most 2% by weight, particularly preferably at most 1% by weight, and most preferably at most 0.5% by weight.
- a method for reducing the concentration of water in the sealing solution a method similar to the above-described method for reducing the concentration of THF to 4% by weight or less can be used.
- the polycondensation reaction apparatus used in the present invention has at least one polycondensation reaction tank including (a) an ejector, (b) a condenser installed downstream of the ejector, and (c) two or more sets of atmospheric legs. And (d) it is preferable to have two or more hot well tanks connected to the condenser via the atmosphere leg. Or (b) a polycondensation reaction tank having at least one set of an ejector, (b) a condenser installed downstream of the ejector, and (c) at least one set of atmospheric legs, and (d) a hot well tank. It is preferable to have two or more.
- the polycondensation reactor used in the present invention may have any equipment configuration as long as it satisfies the above conditions, even if the total number of each of (a), (b), (c) and (d) is different as a whole. good.
- the polycondensation reaction apparatus includes two or more polycondensation reaction tanks each including (a) an ejector, (b) a condenser installed downstream of the ejector, and (c) at least two sets of atmospheric legs.
- the overall polycondensation unit has at least four ejectors (a), at least four condensers (b), (c) at least four atmospheric legs, and (d) at least two hot tanks. Things. With such a configuration, the degree of reduced pressure appropriate for each polycondensation reaction tank in the production of polyester can be more stably controlled.
- the number of polycondensation reaction tanks may be one or more, but preferably two to five, and more preferably two to three.
- a condenser is provided between the polycondensation reaction tank and the ejector (upstream of the ejector) in order to condense or absorb the gas generated in the polycondensation reaction tank, separately from the condenser downstream of the ejector.
- a known type such as a surface type or a direct contact type.
- a direct contact type which has a high heat exchange efficiency and is less likely to be blocked by a sublimate or the like is preferable.
- a plurality of condensers upstream of the ejector attached to this polycondensation reaction tank can be provided, and by setting a plurality of condensers having different temperatures, preferably with a lower set temperature toward the downstream side, by connecting a plurality of condensers in series, the condenser to the ejector can be provided.
- the bleeding load can also be reduced.
- capacitors are provided for each ejector. If there are two ejectors, one or more capacitors should be provided for each ejector. When there are three or more ejectors, capacitors are provided for at least two ejectors.
- the condenser is provided with a hot well tank via an atmosphere leg, and the total number of the hot tanks is 1 or more, preferably 2 or more. Therefore, if there are two capacitors, there will be two hot well tanks, and the air legs of the two capacitors will be connected to separate hot well tanks. When the number of capacitors is three or more, the number of hot well tanks usually ranges from two to the number of capacitors, and when the number of hot well tanks is smaller than the number of capacitors, the number of capacitors is small. Some of the atmospheric legs are connected to the same hot well tank.
- the ejector may be arranged in series or in parallel with the polycondensation reaction tank, but is preferably arranged in series to efficiently obtain a high vacuum. It is also possible to arrange two or more sets (n sets) in parallel and two or more sets (n pieces) of n x m in series for each set. When an ejector is arranged in parallel to the polycondensation reaction tank, it is preferable that each set is provided with two or more capacitors and a hot well tank.
- Figure 1 shows one polycondensation reaction tank, three ejectors, two condensers downstream of the ejector, and two hot well tanks.
- the condenser downstream of the ejector is separated from the hot water via a large air leg.
- the conceptual diagram of the polycondensation reaction device connected to the well tank is shown.
- At least one of the polycondensation reaction tanks is the same as the apparatus described in ⁇ Embodiment when the polycondensation reaction tank is a single stage '' .
- each of the two polycondensation reaction tanks is provided with two or more ejectors and two or more condensers. Therefore, the ejector, condenser, and condenser have four or more atmospheric legs.
- the number of hot well tanks usually ranges from 2 to the number of capacitors. If the number of hot well tanks is less than the number of condensers, Are connected to the same hot well tank.
- the basic configuration of the polycondensation reaction device is the same as that described in ⁇ Embodiment in which polycondensation reaction tank has one stage '' and ⁇ Embodiment in which polycondensation reaction tank has two stages ''.
- the total number of hot well tanks is preferably 2 or more, and the configuration can be selected as appropriate.
- two or more ejectors and two or more condensers are provided in each polymerization reaction tank, and three or more hot well tanks are provided in total.
- the hot-well tanks are counted as one if they are separated by a structure in which the sealing liquid does not mix with each other, and these are usually recognized as apparently separate containers, It goes without saying that the external appearance includes the case where it looks like one but it is partitioned inside.
- the air leg of multiple condensers will be inserted into one hot well tank. It is preferable to combine the pressures near the condenser pressure or the critical back pressure of the ejector attached to the condenser, and to put the remote pressures into different hot well tanks. Specifically, when the difference between the condenser pressure and the critical back pressure of the ejector is 1 kPa or more, preferably 2 kPa or more, particularly preferably 3 kPa or more, the atmospheric pressure of the condenser It is recommended that a different hot well tank be introduced. Representative embodiments of the present invention are shown in FIGS.
- a is a first polycondensation reaction tank equipped with a stirrer
- b is a gear pump
- c is a condenser that collects gas distilled from the first polycondensation tank a.
- a wet type capacitor is shown as a typical example of a direct contact type capacitor.
- d is a tank for the liquid collected by the wet condenser c
- e is a pump
- f is a heat exchanger.
- g is a horizontal second condensation reaction tank
- h is a gear pump
- i is a wet condenser that collects gas distilled from the second double condensation reaction tank
- j is a tank for the collected liquid
- k is a pump
- m is a polymer extraction die
- n is a chip cutter
- p is a heat exchanger.
- 1 is a supply line from an esterification reaction tank or a transesterification reaction tank (not shown) to the first polycondensation reaction tank a
- 2 is a supply line from the first polycondensation reaction tank a to the second double condensation reaction tank g.
- Supply line, 3 is a vent line from the first polycondensation reaction tank a
- 4 is a drain line from the wet condenser c
- 5 is a circulation line from the tank d to the wet condenser c
- 6 is outside the condensate
- 7 is a supply line for 1,4-butanediol to tank d
- 8 is a gas extraction line to ejector A.
- 10 is a vent line from the second double condensation reactor g
- 11 is a drain line from the wet condenser i
- 12 is a tank
- 13 is a condensate
- 14 is a supply line of 1,4-butanediol to tank j
- 15 is a gas extraction line to ejector G.
- the oligomer supplied from 1 is polycondensed in the first polycondensation reaction tank a kept under reduced pressure, and sent to the second double condensation reaction tank g through 2.
- the vapor mainly composed of 1,4-heptanediol, THF and water generated in the first polycondensation reaction tank a is sent to the wet condenser c, and has a high boiling point of 1,4-butanediol and a small amount of THF and water. Is condensed here and collected in tank d. Part of this liquid is drawn out of the system through line 6 using pump e, and the remainder is circulated through 5 to wet condenser c, and used for the condensation of 1,4-butanediol. Also, from 1, supply 1,4-butanediol to tank d as needed.
- a gas mainly composed of THF and H20 having a low boiling point is sent to ejector A through 8.
- the prepolymers supplied from 2 are further polycondensed in a second double condensation reaction tank g kept under reduced pressure, and are pelletized by a chip cutter n from 9 through a die head m.
- the vapor mainly composed of 1,4-butanediol, THF, and water generated in the second double condensation reactor g is sent to the wet condenser i, and a small amount of 1,4-butanediol having a high boiling point is added.
- the THF and water are coagulated here and collected in tank j. Part of this solution is drawn out of the system through line 13 using pump k, and the rest is Circulated to the sensor i and used for the condensation of 1,4-butanediol. From 14, supply 1,4-butanediol to tank j as needed.
- a gas mainly composed of THF and H 2 O having a low boiling point is sent to the ejector G through 15.
- FIG. 3 shows the configuration of the degassing system of the first polycondensation reaction tank a and the second double condensation reaction tank g in FIG.
- A, B, G, H, J is ejector, C, D, K, L, M is barometric condenser, E, N is condenser, F, P is vacuum pump, Q, R, S is hot well tank, U Indicates a buffer tank, W indicates a separation and distillation column for THF and H20, X indicates a reboiler for the separation and distillation column w, and ⁇ , V, and ⁇ ⁇ ⁇ indicate a pump.
- distillation gas line from reactor g 16, 17, 26, 27, 28 are gas discharge lines from each barometric condenser, 18, 29 are heat exchangers E, respectively.
- Lines from N to vacuum pumps F and P, 19, 30 are discharge gas lines from vacuum pumps, 20, 20, 31, 31, 32, 33 are 1,4-butanediol supply lines
- part or all of the 1,4-butanediol is constituted by circulation from hot well tanks Q, R, and S. It is recommended that the temperature of the liquid be controlled using a heat exchanger or the like.
- Atmospheric leg, 40 is a line from hot well tanks Q, R, S, 41 is a line from pump T to buffer tank U, 42 is a line from pumper tank U, 42 is a line separated from pump V Line to distillation column W, 44 4 other than separation distillation column W, for example, feed-out line to raw material preparation system and outside, 45 5 is line for extracting 1,4-butanediol from separation distillation column W, 46 is separation Line for extracting low-boiling components mainly composed of THF and H20 from distillation column W, 47 is the discharge line of pump Y, 48 is the supply line to hot well tanks Q, R, and S, 49 is the reboiler X
- the circulation line from 50 is a hot well tank other than Q, R, S, for example, The condensation reaction vessel
- the gas mainly composed of THF and H20 distilled from the first polycondensation reaction tank a is introduced into the first-stage ejector A via the line 8.
- the 1,4-butanediol vapor discharged from the ejector A is condensed in the parometric condenser C, and the condensate is collected in the hot well tank Q through the atmospheric leg 24.
- the components not condensed by the Palometric condenser C are sent to the second stage ejector B through the line 16, and the condensate condensed by the Palometric condenser D is sent to the hot well tank R through the atmospheric leg 25. Collected.
- the components not condensed by the Palometric condenser D are sent to the condenser E through the line 17 and condensed as much as possible, and finally discharged out of the system using the vacuum pump F.
- the gas distilled from the second double condensation reaction tank g is also sent to the first-stage ejector G via the line 15 and the 1,4-butanediol vapor discharged from the ejector G is condensed by the barometric condenser K.
- the condensate is collected in the hot well tank S through the atmosphere leg 37.
- the components not condensed in the barometric condenser K are sent to the second stage ejector H through line 26, and the condensate condensed in the parometric condenser is passed to the hot well tank Q through the atmosphere leg 38. Collected.
- the components not condensed by the barometric condenser L are sent to the third-stage ejector J through the line 27, and the condensate condensed by the parometer condenser M is collected in the hot well tank R through the atmospheric leg 39.
- the components not condensed by the Palometric condenser M are sent to the condenser N through the line 28, where they are condensed as much as possible, and finally discharged out of the system using the vacuum pump P.
- the liquid mainly composed of 1,4-butanediol collected in the hot well tank (3, R, S) is sent to the buffer tank U through line 40, and a part or all of the liquid is sent to the distillation column W. It is supplied through pump V. At this time, part or all of the unpurified liquid can be used for raw materials or for discharging to the outside, etc., according to the operating conditions (line 44).
- 1,4-butanediol from which low-boiling components such as THF and H20 have been separated in the distillation separation column W, is withdrawn from the line 45, and a part or the whole thereof is passed through the line 48 to Return to double tank Q, R, S.
- Q, R, and S are divided according to the operating pressure of the parometric condenser connected through the atmospheric leg, respectively, and are arranged in the order of S, Q, and R from the low pressure side.
- Figure 3 shows a line that supplies 1,4-butanediol to all Q, R, and S hot-well tanks through 48.
- a condenser with a high operating pressure can be used for the hot well tank R with the atmospheric leg inserted.
- the supply of 1,4-butanediol which has a low THF content, is performed using the condensate of 1,4-butanediol vapor discharged from the ejectors B and J.
- reaction tank ejector
- tank ejector
- distillation column ejector
- condenser ejector
- heat exchanger ejector
- low-pressure 1,4-butanediol with a low THF concentration is supplied from outside via line 51 to the hot well tank S, into which the atmospheric leg of the condenser with low operating pressure is inserted, and operation is performed via lines 52, 53.
- the supply is sequentially performed to the hot well tanks Q and R in which the atmospheric leg of the condenser having a high pressure is introduced.
- the critical back pressure of the capacitors corresponding to S, Q, and R increases in this order, and the THF concentration of the hot water tank can be set high in this order. —It is possible to use butanediol effectively without waste.
- a part of the sealed liquid of the hot well tank S in Fig. 4 is replaced with the ejectors 1 and 2.
- the mode of supply to the boiler Z for 4-butanediol vapor generation is shown. In this way, the total amount of 1,4-butanediol used in the vacuum degassing system shown in FIG. 5 can be reduced, or the production can be changed according to various requests. Examples>
- 77 is the falling seconds of the polymer solution, ⁇ . Is the number of seconds the solvent has dropped, C is the concentration of the polymer solution (g Zd L), and K H is Huggins' constant. K H adopted 0.33.
- 43 kgZh of polybutylene terephthalate oligomer is continuously supplied to the first polycondensation reaction tank a through line 1 in the flow chart of Fig. 2, the internal temperature of the first polycondensation reaction tank is 235 ° C, and the pressure is 2.
- the polycondensation reaction was proceeded while keeping at 2 kPa and an average residence time of 1.6 hours, and the prepolymer was supplied to the second double condensation reactor g via line 2.
- the internal temperature of the second double condensation reaction tank was 240, the pressure was 0.2 kPa, the average residence time was 1.5 hours, and the polycondensation reaction was further advanced.
- each polycondensation reaction tank was controlled using the decompression system shown in Fig. 3,
- the initial pressures of the capacitors C and D were 5 kPa and 15 kPa, respectively, and the pressures of the capacitors L and M were 1.6 kPa, 5 kPa and 15 kPa, respectively.
- 1,4-butanediol containing THF condensed in the hot well tanks Q, R, and S is continuously withdrawn through 40 so that the liquid level in each hot well tank is constant.
- 1,4-butanediol having a THF concentration of 0.05% by weight or less is added to the hot well tanks S and Q at a rate of 15 kg / h, respectively, and the hot well tank R is added to the hot well tank R through line 48. 10 kgZh was supplied and excess 1,4-butanediol was withdrawn from line 50.
- the THF concentrations of the sealing liquids of the hot water tanks Q, R, and S were 1.5% by weight, 2.8% by weight, and 0.5% by weight, respectively.
- the pressures in the single condensation reaction tank a and the second double condensation reaction tank g were stable.
- the intrinsic viscosity of the polymer (polybutylene terephthalate) discharged through line 9 was 0.85.
- the THF concentration in the sealed liquid of the hot water tanks Q, R, and S and the polymer concentration The intrinsic viscosity was measured. As shown in Table 1, during the operation period, the THF concentration of the hot well tanks Q, R, and S was stable, and the intrinsic viscosity of the polymer was also stable.
- Example 1 was repeated except that the supply of purified 1,4-butanediol to the hot well tanks Q, R, and S via line 48 was stopped. At this time, the amount corresponding to the condensate from the 1,4-butanediol reaction system supplied from the ejector was withdrawn through line 40 so that the liquid level in each hot water tank was constant. Twenty-two hours after the start of oligomer supply, the THF concentrations of the hot well tanks Q, R, and S were 1.7 wt%, 5.1 wt%, and 0.6 wt%, respectively. The weight increased to 9 wt%, 5.3 wt% and 0.7 wt%, but the pressure in each polycondensation reaction tank was stable and the intrinsic viscosity of the polymer was stable.
- Example 3 The procedure was performed in the same manner as in Example 1 except that a pressure reducing system using only the hot well tank Q as shown in FIG. 6 was used. At this time, as in Example 1, 1,4-butanediol containing THF condensed in the hot water tank Q was continuously withdrawn through 40, and THF was separated in the distillation separation column S, and then through line 48. 40 kg Zh of 1,4-butanediol having a THF concentration of 0.05% or less was supplied to the hotweltan Q, and excess 1,4-butanediol was withdrawn from the line 50.
- the THF concentration of the sealed liquid in the hot well tank Q was 0.81% by weight, and the pressures in the first polycondensation reaction tank a and the second double condensation reaction tank g were stabilized. I was At this time, the intrinsic viscosity of the polymer (polybutylene terephthalate) discharged through line 9 was 0.85, and thereafter, the THF concentration in the sealing liquid of the hot water tank Q and the intrinsic viscosity of the polymer were measured four times every six hours thereafter. As shown in Table 1, during the operation period, the THF concentration of the hot well tank Q was stable, and the intrinsic viscosity of the polymer was also stable.
- Example 3 The procedure was the same as in Example 3, except that the supply of purified 1,4-heptanediol to the hot well tank Q via line 48 was stopped. At this time, the amount corresponding to the 1,4-butanediol supplied from the ejector and the condensate from the reaction system was extracted through the line 40.
- the THF concentration in the hot well tank Q became 4.9% by weight, and the ejector capacity became unstable.
- the pressure in the reactor increased, and 30 hours after the start of the oligomer, the pressure in the first polycondensation reactor a was 6.5 kPa, and the pressure in the second double condensation reactor was 3.3 kP became a.
- Hotwell tank S weight% 0.6 0.6 0.6 0.6 0.7 Intrinsic viscosity of polymer 0.85 0.85 0.85 0.85 0.85 0.85 0.85 Example 3 THF concentration Hot water tank Q weight 0 / o 0.8 0.8 0.8 0.8 Hot tank R weight% ⁇ ⁇ ⁇ ⁇ One Hotle I Tank S Weight%
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003254907A AU2003254907A1 (en) | 2002-09-20 | 2003-08-08 | Process for producing polyester |
US11/084,112 US7732556B2 (en) | 2002-09-20 | 2005-03-21 | Process of producing polyesters |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-275916 | 2002-09-20 | ||
JP2002275916 | 2002-09-20 | ||
JP2002325705 | 2002-11-08 | ||
JP2002-325705 | 2002-11-08 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/084,112 Continuation US7732556B2 (en) | 2002-09-20 | 2005-03-21 | Process of producing polyesters |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004026938A1 true WO2004026938A1 (ja) | 2004-04-01 |
Family
ID=32032891
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/010170 WO2004026938A1 (ja) | 2002-09-20 | 2003-08-08 | ポリエステルの製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US7732556B2 (ja) |
CN (1) | CN1297585C (ja) |
AU (1) | AU2003254907A1 (ja) |
MY (1) | MY143829A (ja) |
TW (1) | TWI278464B (ja) |
WO (1) | WO2004026938A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013028656A (ja) * | 2011-07-26 | 2013-02-07 | Mitsubishi Chemicals Corp | ポリエステルの製造方法 |
CN104109232A (zh) * | 2013-04-22 | 2014-10-22 | 株式会社日立制作所 | 聚酯的制造方法及制造装置 |
JP2018145220A (ja) * | 2017-03-01 | 2018-09-20 | 三菱ケミカル株式会社 | 脂肪族ポリエステルの製造方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007066393A1 (ja) * | 2005-12-07 | 2007-06-14 | Fujitsu Limited | 携帯端末装置、通信システム、電力制御方法および電力制御プログラム |
US20080183004A1 (en) * | 2007-01-30 | 2008-07-31 | Nan Ya Plastics Corporation | Method of preparing cyclohexanepolycarboxylic acid ester without phthalatic and plasticizer prepared by the same |
JP4670901B2 (ja) | 2008-05-27 | 2011-04-13 | 株式会社日立プラントテクノロジー | ポリ乳酸の製造装置およびその方法 |
JP5077170B2 (ja) * | 2008-09-22 | 2012-11-21 | 株式会社日立プラントテクノロジー | ポリヒドロキシカルボン酸の製造方法 |
DE102011007543A1 (de) | 2011-04-15 | 2012-10-18 | Aquafil Engineering Gmbh | Vorrichtung und Verfahren zur Kondensation von Dämpfen unter Vakuum |
JP2014095037A (ja) * | 2012-11-09 | 2014-05-22 | Hitachi Ltd | ポリエステルの製造装置及び製造方法 |
CN103127896B (zh) * | 2013-02-28 | 2015-06-17 | 贵州开磷(集团)有限责任公司 | 一种pvc聚合釜搅拌拖动方法 |
CN104558563B (zh) * | 2015-01-13 | 2016-07-20 | 浙江万凯新材料有限公司 | 单向拉伸膜级pet聚酯切片的合成装置及应用该装置的合成方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05214089A (ja) * | 1992-02-04 | 1993-08-24 | Kanegafuchi Chem Ind Co Ltd | 重合体の重合反応過程で副生する副生物とこれに同伴した付着性異物の分離方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57135828A (en) | 1981-02-17 | 1982-08-21 | Toray Ind Inc | Recovery of by-product tetrahydrofuran |
US4877871A (en) * | 1988-06-14 | 1989-10-31 | Nabisco Brands, Inc. | Synthesis of sucrose polyester |
CN1166503A (zh) * | 1997-01-20 | 1997-12-03 | 华东理工大学 | 由含羟基或胺基化合物合成A(B)n型共聚物的方法 |
EP1018529B1 (en) * | 1999-01-06 | 2004-03-24 | Teijin Limited | Process for producing polycarbonates |
US6703478B2 (en) * | 2000-04-27 | 2004-03-09 | Teijin Limited | Polyester continuous production process |
-
2003
- 2003-08-08 WO PCT/JP2003/010170 patent/WO2004026938A1/ja active Application Filing
- 2003-08-08 AU AU2003254907A patent/AU2003254907A1/en not_active Abandoned
- 2003-08-08 CN CNB038222981A patent/CN1297585C/zh not_active Expired - Lifetime
- 2003-09-18 MY MYPI20033562A patent/MY143829A/en unknown
- 2003-09-19 TW TW092125889A patent/TWI278464B/zh not_active IP Right Cessation
-
2005
- 2005-03-21 US US11/084,112 patent/US7732556B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05214089A (ja) * | 1992-02-04 | 1993-08-24 | Kanegafuchi Chem Ind Co Ltd | 重合体の重合反応過程で副生する副生物とこれに同伴した付着性異物の分離方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013028656A (ja) * | 2011-07-26 | 2013-02-07 | Mitsubishi Chemicals Corp | ポリエステルの製造方法 |
CN104109232A (zh) * | 2013-04-22 | 2014-10-22 | 株式会社日立制作所 | 聚酯的制造方法及制造装置 |
JP2018145220A (ja) * | 2017-03-01 | 2018-09-20 | 三菱ケミカル株式会社 | 脂肪族ポリエステルの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1681866A (zh) | 2005-10-12 |
CN1297585C (zh) | 2007-01-31 |
US7732556B2 (en) | 2010-06-08 |
US20050239999A1 (en) | 2005-10-27 |
MY143829A (en) | 2011-07-15 |
AU2003254907A1 (en) | 2004-04-08 |
TW200409788A (en) | 2004-06-16 |
TWI278464B (en) | 2007-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7732556B2 (en) | Process of producing polyesters | |
CA2396465C (en) | Continuous process for producing poly(trimethylene terephthalate) | |
US5786443A (en) | Process of making polyester prepolymer | |
CA2396469C (en) | Continuous process for producing poly(trimethylene terephthalate) | |
CA2698288C (en) | Cleaning device for separating dilactide from material mixtures, polymerisation device, method for separating dilactide from material mixtures and also use | |
KR101384445B1 (ko) | 폴리(트리메틸렌 테레프탈레이트)의 연속 제조 방법 | |
EP1412043B1 (en) | Azeotropic distillation of cyclic esters of hydroxy organic acids | |
WO1998045350A1 (en) | Late addition of supplemental ethylene glycol in the preparation of copolyesters | |
US4499261A (en) | Process for the continuous production of polybutylene terephthalate of high molecular weight | |
JP4460453B2 (ja) | トリメチレンテレフタレートオリゴマーの調製方法 | |
JP5454088B2 (ja) | ポリエステルの製造方法、並びに1,4−ブタンジオールの加熱装置及び蒸気発生装置 | |
US20150151247A1 (en) | Method for Removing an Ester From a Vapor Mixture | |
JP3812564B2 (ja) | ポリエステルの製造方法 | |
JP3812557B2 (ja) | ポリエステルの製造方法 | |
KR20140071536A (ko) | 폴리에스테르의 연속 제조방법 | |
US9527953B2 (en) | Continuous preparation for polyester | |
KR20080079688A (ko) | 폴리(트리메틸렌 테레프탈레이트) 연속 제조 방법 | |
JP2014214166A (ja) | ポリエステルの製造方法及び製造装置 | |
JP2004168978A (ja) | ポリエステルの製造方法 | |
JP4050022B2 (ja) | ポリエステルの連続製造方法 | |
Canzobre Silva | Design of a plant for polylactic acid polymer manufacture | |
MX2008007926A (es) | Proceso continuo para producir tereftalato de politrimetileno |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 20038222981 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11084112 Country of ref document: US |
|
122 | Ep: pct application non-entry in european phase |