EP0000918A2 - Procédé pour la préparation de polyesters linéaires de haut poids moléculaire - Google Patents
Procédé pour la préparation de polyesters linéaires de haut poids moléculaire Download PDFInfo
- Publication number
- EP0000918A2 EP0000918A2 EP78100670A EP78100670A EP0000918A2 EP 0000918 A2 EP0000918 A2 EP 0000918A2 EP 78100670 A EP78100670 A EP 78100670A EP 78100670 A EP78100670 A EP 78100670A EP 0000918 A2 EP0000918 A2 EP 0000918A2
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- EP
- European Patent Office
- Prior art keywords
- condensation
- temperature
- polyester
- tubes
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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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
- C08G63/785—Preparation processes characterised by the apparatus used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00081—Tubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00121—Controlling the temperature by direct heating or cooling
- B01J2219/0013—Controlling the temperature by direct heating or cooling by condensation of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00168—Controlling or regulating processes controlling the viscosity
Definitions
- the invention relates to a process for the preparation of high molecular weight linear polyesters which are derived from dicarboxylic acids or their ester-forming derivatives and diols by condensation of polyester precondensates with a relative viscosity of at least 1.05 at temperatures of 270 to 340 ° C. under reduced pressure.
- polyester precondensate In the manufacture of high molecular weight linear polyesters, low molecular precondensates with low viscosity are converted into high molecular weight condensates at temperatures of 260 to 300 ° C. under reduced pressure with elimination of diols. At the high temperatures required, however, polyester melts are unstable, which results in an increased carboxyl end group content.
- the polyester precondensate In the process known from DT-AS 17 45 541, the polyester precondensate is passed through a horizontal device which is divided into chambers, the melt being formed into a thin film in each chamber. The process has the disadvantage that it takes considerable time, for example several hours, and continuously the higher-condensed melt formed in the film ze is returned to the lower molecular weight sump.
- a method is also known in which the condensing melt is passed over a series of zones arranged one above the other, the condensing mass circulating in each zone and coming into contact with the heating wall alternately and from zone to zone flows under gravity and film formation.
- the method has the disadvantage that dead spaces form within the individual zones, which lead to backmixing.
- the method has the disadvantage that the condensation time still takes too much time for particularly sensitive polyesters.
- the process known from FR-PS 15 45 487 in which the condensing melt is passed over a plurality of rotating, inclined surfaces, still requires about 30 minutes for the condensation. It is noteworthy that in all processes the temperature is either kept at the same level or increased with increasing viscosity.
- the invention also relates to a device for producing high molecular weight linear polyesters, characterized by a vertical shaft (1) which forms a common vapor space (2) with feeds for the polyester precondensate (3), a discharge opening at the lower end (4), one Vapors at the upper end (5) horizontally parallel to each other heated tubes (6) which are arranged one below the other so that the melt flowing down by gravity flows over the tube below, with the proviso that the diameter of the tubes increases downwards.
- the new process has the advantage that the condensation takes less time than before.
- the new process also has the advantage that very low carboxyl end group contents are achieved even with sensitive polyesters, such as polybutylene terephthalate.
- the new device has the advantage that backmixing is avoided in any case and moving parts which give rise to faults are excluded.
- the new process is remarkable in that the condensation is carried out with a continuously decreasing temperature.
- DT-OS 19 20 954 and FR-PS 15 45 487 it was assumed that short dwell times could only be achieved with increasing temperature.
- the high molecular weight linear polyesters are derived from dicarboxylic acids or their ester-forming derivatives, such as alkyl esters.
- Aliphatic and / or aromatic dicarboxylic acids are preferred a molecular weight ⁇ 390.
- particularly preferred dicarboxylic acids have a hydrocarbon structure.
- Alkanedicarboxylic acids with 5 to 10 carbon atoms or benzene or naphthalenedicarboxylic acids, in particular those derived from benzene, have acquired particular industrial importance. Terephthalic acid is particularly noteworthy.
- Suitable starting materials are, for example, glutaric acid, adipic acids, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenoxydicarboxylic acid or their C 1 -C 4 -alkyl esters.
- Preferred diols are aliphatic, cycloaliphatic or aromatic diols with a molecular weight ⁇ 280. Apart from the hydroxyl groups, they preferably have a hydrocarbon structure. Alkanediols, in particular those having 2 to 6 carbon atoms, have acquired particular industrial importance. Suitable diols are, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, decamethylene glycol, neopentyl glycol or 1,4- Bis-hydroxymethylcyclohexane. Ethylene glycol and 1,4-butanediol have become particularly important.
- Preferred polyesters and also their precondensates consist of at least 50 mol% of polyethylene terephthalate or polybutylene terephthalate units.
- the rest can also consist of other short-chain polyester units derived from the above-mentioned polyester-forming starting materials. Polyesters which are composed of 70 to 100 mol.% Of polyethylene or polybutylene terephthalate are particularly preferred.
- the method according to the invention has attained particular importance for the production of polybutylene terephthalate.
- the polyester precondensates are obtained in a manner known per se by reacting dicarboxylic acids or their esters with a diol in the presence of catalysts such as titanium acid esters, antimony, manganese or zinc compounds, e.g. their fatty acid salts, at temperatures from 150 to 260 ° C.
- catalysts such as titanium acid esters, antimony, manganese or zinc compounds, e.g. their fatty acid salts
- Such pre-condensates have a relative viscosity of at least 1.05 (measured as a 0.5 percent by weight solution in a mixture of phenol and o-dichlorobenzene in a weight ratio of 3: 3 at 25 ° C.)
- Polyester precondensates with a relative viscosity are generally used from 1.05 to 1.2 The preparation of such precondensates is described, for example, in DT-OS 25 14 116.
- the condensation of the polyester precondensates to high molecular weight polyesters is carried out at temperatures of 270 to 340 ° C under reduced pressure. It is advantageous to maintain pressures of 0.1 to 2 torr. It goes without saying that the diols which split off during the condensation are continuously removed from the reaction mixture.
- An essential feature of the invention is that the condensation is first started at a temperature of 290 to 340 ° C. and the temperature is lowered as the condensation proceeds.
- the final temperature is at least 10 ° C, advantageously 30 ° C above the melting point of the polyester produced.
- the initial temperature also depends on the type of pre-condensate. In the case of polyethylene terephthalate, starting temperatures of 320 to 340 ° C. have proven particularly useful, while temperatures of 290 to 310 ° C. have proven particularly favorable in the production of polybutylene terephthalate. It is advantageous to lower during the condensate sation the high initial temperature around 30 to 50 ° C. The temperature can drop continuously, but preferably in drops.
- the final temperature depends essentially on the melting point of the polyester produced and should be so high above its melting point that no solidification occurs and further processing is not hindered. As a rule, temperatures around 10 ° C. above the melting point have proven to be useful.
- the process according to the invention can also be carried out advantageously by continuously lowering the temperature by 30 to 50 ° C. in the course of the condensation by adiabatic operation.
- This procedure has the advantage that the optimal reaction temperature is largely independent. Furthermore, the new process has the advantage that the retrofitting of a heat exchanger before the condensation stage of the polyester condensation can be carried out in conventional condensation reactors after an optimal temperature-time profile.
- the low-viscosity polyester precondensate melt is heated by 30 to 50 ° C. above the temperature which the fully condensed polyester should have after the polycondensation before entering the polycondensation zone.
- the temperature of the polyester precondensate is expediently first increased to the extent that it decreases in the subsequent polycondensation.
- the polyester precondensate melt is advantageously heated briefly in a heat exchanger, for example a tube or plate heat exchanger or in a similar suitable device.
- the condensation starts as a result of transesterification reactions.
- the heat energy required for the reaction and the evaporation of the released diol and any by-products, for example tetrahydrofuran, in the condensation of butanediol-1,4-containing polyesters is taken from the heat content of the melt.
- the temperature drops as the condensation reaction progresses.
- the optimal reaction temperature is largely independent. Accordingly, the areas in the polycondensation zone which come into contact with the melt are kept at the temperature which the polyester should have after polycondensation, up to a temperature which is below the final temperature of the polycondensation up to 10 ° C.
- the melt Towards the end of the polycondensation, the melt then has a temperature which corresponds to the surfaces in contact with the melt or, as a result of the absorption of mechanical energy during the movement of the melt, the temperature of the contact surfaces by 5 to 10 ° C., depending on the design of the device used exceeds.
- the condensation is preferably carried out in a thin layer.
- thin layers are understood to be those up to 7 mm.
- the thin layers in contact with heated surfaces are advantageous in order to ensure rapid heat transfer and rapid adaptation to the falling condensation temperature. It has therefore proven itself if the condensing melt is allowed to flow as a thin layer under the influence of gravity over an essentially vertical, indirectly heated surface.
- the force of gravity can flow successively over a large number of indirectly heated surfaces, films being formed when flowing from surface to surface. The number of areas required is dependent on the equipment.
- a suitable device is described for example in FR-PS 15 45 487, provided that the inclined surfaces are heated. Another suitable device is explained below.
- FIG. 1 shows a cross section through the device according to the invention for the production of linear high molecular weight polyesters.
- the device consists of an essentially vertical shaft (1).
- the shaft can be round or polygonal.
- the shaft expediently tapers at the lower end to allow the melt to collect.
- the shaft forms a common vapor space (2).
- the split diols are removed by the vapor outlet (5) at the top of the shaft.
- the corresponding separators for the vapors and the associated vacuum device are not shown.
- At the lower end of the shaft there is a discharge opening (4) for the polyester melt. The discharge takes place via gear pumps or extruders, which are not shown.
- Heated pipes (6) are arranged horizontally in parallel in the shaft.
- the tubes are arranged one below the other so that the melt flowing down by gravity flows over the tube underneath, with the proviso that the diameter of the tubes increases downwards in the course of the shaft.
- the polyester pre-condensate is added via the feed (3) in such a way that the melt is applied over the entire length of the uppermost layer of the tubes.
- the pipes are advantageously divided into groups over the course of the shaft, the uppermost group consisting of pipes with the smallest diameter.
- Each group can consist of several layers of pipes.
- the pipes are expediently arranged one below the other.
- the number of pipes In the following group, the pipes are expediently arranged in individual layers one below the other.
- the pipe diameter increases by 2.0 to 4.0 times from group to group it has proven to be expedient if the tubes of a subsequent group are each in a gap with the tubes of an overlying group, so that the melt flowing down from two tubes of group a meets a tube of group b of 2 pipes from group b then meets a pipe from group c. Due to the large number of pipes, d Easily adjust the decreasing temperature, for example from group to group or a further subdivision within a group down the course of the shaft.
- Polyesters obtainable by the process of the invention are suitable for the production of shaped structures, such as threads, foils, injection molded or extruded parts, and also for coatings.
- the precondensate was poured into a bowl under nitrogen, where it quickly solidified.
- the relative viscosity of this precondensate was 1.13.
- the condensation was carried out in a 250 ml round-bottom flask equipped with a stirrer, cooler and nitrogen inlet, which was heated by a Wood's metal bath.
- 50 g of the pre-condensate were melted under nitrogen at the selected post-condensation temperature.
- the flask was quickly evacuated to a pressure of approximately 0.5 torr.
- the stirring speed was adapted to the respective viscosity.
- the post-condensation was interrupted by removing the vacuum with nitrogen.
- Comparative Examples 1 to 4 show the relative viscosity as a function of the post-condensation temperature after a reaction time of 15 minutes. According to the prior art, the temperatures were kept constant during the polycondensation time. If the temperature is increased from 255 ° C to 280 ° C, higher relative viscosities are obtained and thus a higher degree of polycondensation. When the temperature is further increased to 290 ° C., the relative viscosity drops again and a yellowish product is obtained.
- Examples 1 and 2 were carried out by the process according to the invention.
- the metal bath was preheated to 295 ° C. and the post-condensation reaction was started after the precondensate had melted.
- the temperature of the heating bath was lowered in the steps given in the table. According to the process of the invention, a relative viscosity of 1.67 was achieved within 12 minutes (Example 2).
- the polybutylene terephthalate precondensate was pressed through a plate heat exchanger and heated to 285 ° C and in one to 285 ° C with diphyl vapor preheated condensation boiler of 40 1 content passed. This heating process took 10 minutes. The flow of the diphyl vapor was then interrupted and, with rapid stirring, a vacuum of 1 torr was suddenly established in the condensation vessel.
- the melting temperature dropped exponentially to 250 ° C. within 33 minutes. From this point on, the temperature was kept at 250 ° C. by diphyl vapor. After a further 21 minutes, the vacuum was released and the melt was discharged under nitrogen pressure. The relative viscosity of the polybutylene terephthalate thus produced was 1.72.
- the polybutylene terephthalate precondensate was also pressed through the plate heat exchanger within 10 minutes, but the temperature was kept at 250.degree.
- the condensation boiler was preheated to 250 ° C. At this temperature, a vacuum of 1 torr was suddenly produced with rapid stirring and condensed under these conditions for 54 minutes. After a condensation time of 54 minutes, the vacuum and the melt were discharged. The relative viscosity was only 1.49.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2738093 | 1977-08-24 | ||
DE19772738093 DE2738093B1 (de) | 1977-08-24 | 1977-08-24 | Verfahren und Vorrichtung zur Herstellung von linearen hochmolekularen Polyestern |
DE2803530 | 1978-01-27 | ||
DE19782803530 DE2803530A1 (de) | 1978-01-27 | 1978-01-27 | Verfahren zur herstellung von hochmolekularen linearen polyestern |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0000918A2 true EP0000918A2 (fr) | 1979-03-07 |
EP0000918A3 EP0000918A3 (en) | 1979-04-04 |
EP0000918B1 EP0000918B1 (fr) | 1982-03-17 |
Family
ID=25772598
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100670A Expired EP0000918B1 (fr) | 1977-08-24 | 1978-08-16 | Procédé pour la préparation de polyesters linéaires de haut poids moléculaire |
Country Status (5)
Country | Link |
---|---|
US (2) | US4214072A (fr) |
EP (1) | EP0000918B1 (fr) |
JP (1) | JPS5443997A (fr) |
DE (1) | DE2861668D1 (fr) |
IT (1) | IT1097584B (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0346735A2 (fr) * | 1988-06-15 | 1989-12-20 | BASF Aktiengesellschaft | Procédé pour la préparation continue de polyesters linéaires thermoplastiques |
US7168540B2 (en) | 2004-01-14 | 2007-01-30 | Sms Eumuco Gmbh | Coupling for a mechanical press, shear, or stamper |
US7300999B2 (en) | 2004-04-23 | 2007-11-27 | Lurgi Zimmer Gmbh | Method of making polyesters |
Families Citing this family (45)
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US5520891A (en) * | 1994-02-01 | 1996-05-28 | Lee; Jing M. | Cross-flow, fixed-bed catalytic reactor |
US5869011A (en) * | 1994-02-01 | 1999-02-09 | Lee; Jing Ming | Fixed-bed catalytic reactor |
JP3001181B2 (ja) * | 1994-07-11 | 2000-01-24 | 株式会社クボタ | エチレン製造用反応管 |
DE19509551A1 (de) * | 1995-03-16 | 1996-09-19 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von thermoplastischen Polyestern |
DE19615886C1 (de) * | 1996-04-22 | 1997-07-31 | Huels Chemische Werke Ag | Verfahren zur Herstellung von rohem Dimethylterephthalat |
US6194609B1 (en) * | 1997-06-30 | 2001-02-27 | Bp Amoco Corporation | Crystallization in a plate heat exchanger |
DE19929791A1 (de) * | 1999-06-29 | 2001-02-01 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von Polybutylenterephthalat aus Terephthalsäure und Butandiol |
FR2811789B1 (fr) * | 2000-07-13 | 2003-08-15 | France Etat Ponts Chaussees | Procede et dispositif pour classifier des vehicules en categories de silhouettes et pour determiner leur vitesse, a partir de leur signature electromagnetique |
CA2430570C (fr) | 2000-12-07 | 2011-03-22 | Eastman Chemical Company | Traitement du polyester au moyen d'un reacteur tubulaire |
US6906164B2 (en) | 2000-12-07 | 2005-06-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
US7135541B2 (en) | 2003-06-06 | 2006-11-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
US7074879B2 (en) | 2003-06-06 | 2006-07-11 | Eastman Chemical Company | Polyester process using a pipe reactor |
US7332548B2 (en) | 2004-03-04 | 2008-02-19 | Eastman Chemical Company | Process for production of a polyester product from alkylene oxide and carboxylic acid |
US20060251547A1 (en) * | 2005-05-05 | 2006-11-09 | Windes Larry C | Family of stationary film generators and film support structures for vertical staged polymerization reactors |
US7432395B2 (en) | 2005-05-19 | 2008-10-07 | Eastman Chemical Company | Enriched carboxylic acid composition |
US7557243B2 (en) * | 2005-05-19 | 2009-07-07 | Eastman Chemical Company | Enriched terephthalic acid composition |
US7884231B2 (en) * | 2005-05-19 | 2011-02-08 | Eastman Chemical Company | Process to produce an enriched composition |
US7741516B2 (en) * | 2005-05-19 | 2010-06-22 | Eastman Chemical Company | Process to enrich a carboxylic acid composition |
US20060264656A1 (en) * | 2005-05-19 | 2006-11-23 | Fujitsu Limited | Enrichment process using compounds useful in a polyester process |
US7880031B2 (en) * | 2005-05-19 | 2011-02-01 | Eastman Chemical Company | Process to produce an enrichment feed |
US20060264664A1 (en) * | 2005-05-19 | 2006-11-23 | Parker Kenny R | Esterification of an exchange solvent enriched composition |
US7834208B2 (en) | 2005-05-19 | 2010-11-16 | Eastman Chemical Company | Process to produce a post catalyst removal composition |
US20060264662A1 (en) * | 2005-05-19 | 2006-11-23 | Gibson Philip E | Esterification of an enriched composition |
US7304178B2 (en) * | 2005-05-19 | 2007-12-04 | Eastman Chemical Company | Enriched isophthalic acid composition |
US7919652B2 (en) * | 2005-05-19 | 2011-04-05 | Eastman Chemical Company | Process to produce an enriched composition through the use of a catalyst removal zone and an enrichment zone |
US7897809B2 (en) * | 2005-05-19 | 2011-03-01 | Eastman Chemical Company | Process to produce an enrichment feed |
US7888529B2 (en) * | 2006-03-01 | 2011-02-15 | Eastman Chemical Company | Process to produce a post catalyst removal composition |
US7649109B2 (en) | 2006-12-07 | 2010-01-19 | Eastman Chemical Company | Polyester production system employing recirculation of hot alcohol to esterification zone |
US7943094B2 (en) | 2006-12-07 | 2011-05-17 | Grupo Petrotemex, S.A. De C.V. | Polyester production system employing horizontally elongated esterification vessel |
US7863477B2 (en) | 2007-03-08 | 2011-01-04 | Eastman Chemical Company | Polyester production system employing hot paste to esterification zone |
US7829653B2 (en) | 2007-07-12 | 2010-11-09 | Eastman Chemical Company | Horizontal trayed reactor |
US7872090B2 (en) | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Reactor system with optimized heating and phase separation |
US7868130B2 (en) | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Multi-level tubular reactor with vertically spaced segments |
US7868129B2 (en) | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Sloped tubular reactor with spaced sequential trays |
US7858730B2 (en) | 2007-07-12 | 2010-12-28 | Eastman Chemical Company | Multi-level tubular reactor with dual headers |
US7872089B2 (en) | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Multi-level tubular reactor with internal tray |
US7847053B2 (en) | 2007-07-12 | 2010-12-07 | Eastman Chemical Company | Multi-level tubular reactor with oppositely extending segments |
US7842777B2 (en) | 2007-07-12 | 2010-11-30 | Eastman Chemical Company | Sloped tubular reactor with divided flow |
US10010812B2 (en) | 2014-05-08 | 2018-07-03 | Eastman Chemical Company | Furan-2,5-dicarboxylic acid purge process |
US9944615B2 (en) | 2014-05-08 | 2018-04-17 | Eastman Chemical Company | Purifying crude furan 2,5-dicarboxylic acid by hydrogenation and a purge zone |
US9604202B2 (en) | 2014-05-08 | 2017-03-28 | Eastman Chemical Company | Furan-2,5-dicarboxylic acid purge process |
US20190023838A1 (en) | 2017-07-20 | 2019-01-24 | Eastman Chemical Company | Production of polyethylene furanoate in a retrofitted pet plant |
US10344011B1 (en) | 2018-05-04 | 2019-07-09 | Eastman Chemical Company | Furan-2,5-dicarboxylic acid purge process |
US10526301B1 (en) | 2018-10-18 | 2020-01-07 | Eastman Chemical Company | Production of purified dialkyl-furan-2,5-dicarboxylate (DAFD) in a retrofitted DMT plant |
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GB1101348A (en) * | 1964-06-16 | 1968-01-31 | Ici Ltd | Improvements in sodium bicarbonate manufacture by the ammonia-soda process |
US3499873A (en) * | 1967-06-22 | 1970-03-10 | Vickers Zimmer Ag | Preparation of polyethylene terephthalate by means of free falling films |
NL6809754A (fr) * | 1968-04-11 | 1969-10-14 | ||
DE2557580A1 (de) * | 1975-12-20 | 1977-06-30 | Dynamit Nobel Ag | Verfahren und vorrichtung zur herstellung von polykondensaten |
-
1978
- 1978-07-31 IT IT26342/78A patent/IT1097584B/it active
- 1978-08-10 US US05/932,632 patent/US4214072A/en not_active Expired - Lifetime
- 1978-08-16 EP EP78100670A patent/EP0000918B1/fr not_active Expired
- 1978-08-16 DE DE7878100670T patent/DE2861668D1/de not_active Expired
- 1978-08-22 JP JP10151178A patent/JPS5443997A/ja active Pending
-
1979
- 1979-03-27 US US06/024,298 patent/US4235844A/en not_active Expired - Lifetime
Patent Citations (6)
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FR1545487A (fr) * | 1966-11-30 | 1968-11-08 | Bemberg Spa | Procédé continu pour la production de téréphtalate de polyméthylène à haut degré de polymérisation, produit ainsi obtenu et fibres fabriquées avec ce produit |
DE1920954A1 (de) * | 1968-04-24 | 1969-11-06 | Asahi Chemical Ind | Verfahren und Vorrichtung zur Herstellung von Polymeren |
US3640962A (en) * | 1968-05-08 | 1972-02-08 | Hoechst Ag | Polyester polycondensation process under decreasing temperatures |
DE1959455A1 (de) * | 1968-11-26 | 1970-06-11 | Rhodiaceta | Verfahren und Vorrichtung zur Herstellung von Polyestern |
DE1920945A1 (de) * | 1969-04-24 | 1970-11-12 | Polysius Ag | Vorrichtung zum Kuehlen von Gut aller Art |
DE2514116A1 (de) * | 1975-03-29 | 1976-09-30 | Basf Ag | Verfahren zur kontinuierlichen herstellung von polybutylenterephthalaten |
Non-Patent Citations (2)
Title |
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CHEMICAL ABSTRACTS, vol. 73, no. 12, 21 sept 1970, Columbus, Ohio, (USA) FISYUK, L.T. GRAIZEL, L.A.: "Intensification of the poly condensation stage during the production of poly (ethylene terephtphalate), Seite 39, 1e Spalte, Zusammenfassung 57003q, KHIM. VOLOKNA 1970, (3) 70-1 * |
Fisyuk und Grajzel, Sowjetische Beiträge zur Forschung in deutscher Übersetzung, Band 7, Heft 10, Okt. 1970, S. 505/6 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0346735A2 (fr) * | 1988-06-15 | 1989-12-20 | BASF Aktiengesellschaft | Procédé pour la préparation continue de polyesters linéaires thermoplastiques |
EP0346735A3 (fr) * | 1988-06-15 | 1991-01-30 | BASF Aktiengesellschaft | Procédé pour la préparation continue de polyesters linéaires thermoplastiques |
US7168540B2 (en) | 2004-01-14 | 2007-01-30 | Sms Eumuco Gmbh | Coupling for a mechanical press, shear, or stamper |
US7300999B2 (en) | 2004-04-23 | 2007-11-27 | Lurgi Zimmer Gmbh | Method of making polyesters |
Also Published As
Publication number | Publication date |
---|---|
IT7826342A0 (it) | 1978-07-31 |
JPS5443997A (en) | 1979-04-06 |
US4214072A (en) | 1980-07-22 |
EP0000918A3 (en) | 1979-04-04 |
US4235844A (en) | 1980-11-25 |
DE2861668D1 (en) | 1982-04-15 |
EP0000918B1 (fr) | 1982-03-17 |
IT1097584B (it) | 1985-08-31 |
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