EP0000918A2 - Process for the preparation of linear, high molecular polyesters - Google Patents
Process for the preparation of linear, high molecular polyesters 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
- Authority
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 44
- 230000005494 condensation Effects 0.000 claims abstract description 39
- 150000002009 diols Chemical class 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims description 15
- 230000005484 gravity Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000007423 decrease Effects 0.000 abstract description 2
- -1 polybutylene terephthalate Polymers 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920001707 polybutylene terephthalate Polymers 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000634 wood's metal Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Images
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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Verfahren zur Herstellung von hochmolekularen linearen Polyestern, die sich von Dicarbonsäuren oder deren esterbildenden Derivaten und Diolen ableiten, durch Kondensation von Polyestervorkondensaten mit einer relativen Viskosität von mindestens 1,05 bei Temperaturen von 270 bis 340° C unter vermindertem Druck, wobei man die Kondensation bei einer Temperatur von 290 bis 340° C beginnt und mit fortschreitender Kondensation die Temperatur erniedrigt mit der Maßgabe, daß die Endtemperatur mindestens 10° C über dem Schmelzpunkt des jeweils hergestellten Polyesters liegt, sowie eine für die Durchführung des Verfahrens geeignete Vorrichtung.
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von hochmolekularen linearen Polyestern, die sich von Dicarbonsäuren oder deren esterbildenden Derivaten und Diolen ableiten durch Kondensation von Polyestervorkondensaten mit einer relativen Viskosität von mindestens 1,05 bei.Temperaturen von 270 bis 340°C unter vermindertem Druck.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.
Bei der Herstellung von hochmolekularen linearen Polyestern werden niedrig molekulare Vorkondensate mit niedriger Viskosität bei Temperaturen von 260 bis 300°C unter vermindertem Druck unter Abspaltung von Diolen in hochmolekulare Kondensate übergeführt. Bei den hohen erforderlichen Temperaturen sind Polyesterschmelzen jedoch instabil, was sich in einem erhöhten Carboxylendgruppengehalt auswirkt. Bei dem aus der DT-AS 17 45 541 bekannten Verfahren wird das Polyestervorkondensat durch eine horizontale Vorrichtung, die in Kammern unterteilt ist, geleitet, wobei in jeder Kammer die Schmelze zu einem dünnen Film geformt wird. Das Verfahren hat den Nachteil, daß es erhebliche Zeit, z.B. mehrere Stunden, in Anspruch nimmt und fortlaufend die im Film gebildete höherkondensierte Schmelze wieder in den Sumpf mit niedrigerem Molekulargewicht zurückgeführt wird. Aus der DT-OS 19 59 455 ist ferner ein Verfahren bekannt, bei dem die kondensierende Schmelze über eine Folge übereinander angeordneter Zonen geleitet wird, wobei die kondensierende Masse in jeder Zone zirkuliert und dabei abwechselnd mit der Heizwand in Berührung kommt und von Zone zu Zone unter Schwerkraft und Filmbildung fließt. Das Verfahren hat den Nachteil, daß sich innerhalb der einzelenen Zonen Toträume ausbilden, die zur Rückvermischung führen. Ferner hat das Verfahren den Nachteil, daß bei besonders empfindlichen Polyestern die Kondensationszeit immer noch zuviel Zeit in Anspruch nimmt. Das aus der FR-PS 15 45 487 bekannte Verfahren, bei dem man die kondensierende Schmelze über eine Mehrzahl von rotierenden geneigten Flächen leitet, benötigt für die Kondensation immer noch etwa 30 Minuten. Es ist bemerkenswert, daß bei sämtlichen Verfahren die Temperatur entweder auf gleichem Niveau gehalten wird oder mit zunehmender Viskosität gesteigert wird.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. 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. From DT-OS 19 59 455 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. Furthermore, 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.
Es war deshalb die technische Aufgabe gestellt, bei der Herstellung von hochmolekularen linearen Polyestern die Kondensation so durchzuführen, daß ein Minimum an Zeit beansprucht wird und auch bei empfindlichen Polyestern ein möglichst niedriger Gehalt an Carboxylendgruppen erzielt wird.It was therefore the technical task to carry out the condensation in the production of high molecular weight linear polyesters in such a way that a minimum of time is required and the lowest possible carboxyl end group content is achieved even with sensitive polyesters.
Diese technische Aufgabe wird gelöst in einem Verfahren zur Herstellung von hochmolekularen linearen Polyestern, die sich von Dicarbonsäuren oder deren esterbildenden Derivaten und Diolen ableiten, durch Kondensation von Polyestervorkondensaten mit einer relativen Viskosität von mindestens 1,05 bei Temperaturen von 270 bis 3400C unter vermindertem Druck, wobei die Kondensation bei einer Temperatur von 290 bis 340°C beginnt und mit fortschreitender Kondensation die Temperatur erniedrigt mit der Maßgabe, daß die Endtempera- ' tur mindestens 10°C über dem Schmelzpunkt des jeweils hergestellten Polyesters liegt.This technical problem is solved in 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 condensing polyester precondensates with a relative viscosity of at least 1.05 at temperatures of 270 to 340 ° C. under reduced Pressure, the condensation begins at a temperature of 290 to 340 ° C and the as the condensation progresses Temperature reduced with the proviso that the final temperature is at least 10 ° C above the melting point of the polyester produced.
Ferner ist ein Gegenstand der Erfindung eine Vorrichtung zur Herstellung von hochmolekularen linearen Polyestern, gekennzeichnet durch einen vertikalen Schacht (1), der einen gemeinsamen Brüdenraum (2) bildet mit Zuführungen für das Polyestervorkondensat (3) einer Austragsöffnung am unteren Ende (4), einem Brüdenabzug am oberen Ende (5) horizontal parallel zueinander angeordneten beheizten Rohren (6), die so untereinander angeordnet sind, daß die durch Schwerkraft herabfließende Schmelze jeweils über das darunterliegende Rohr fließt, mit der Maßgabe, daß der Durchmesser der Rohre nach unten zunimmt.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.
Das neue Verfahren hat den Vorteil, daß die Kondensation in kürzerer Zeit als bisher verläuft. Ferner hat das neue Verfahren den Vorteil, daß selbst bei empfindlichen Polyestern, wie Polybutylenterephthalat sehr niedrige Carboxylendgruppengehalte erzielt werden. Die neue Vorrichtung hat den Vorteil, daß auf jeden Fall eine Rückvermischung vermieden wird und bewegte Teile, die zu Störungen Anlaß geben, ausgeschlossen sind.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.
Das neue Verfahren ist insofern bemerkenswert als die Kondensation bei fortlaufend sinkender Temperatur durchgeführt wird. Im Hinblick auf die DT-OS 19 20 954 und die FR-PS 15 45 487 war davon auszugehen, daß man kurze Verweilzeiten nur mit ansteigender Temperatur erzielt.The new process is remarkable in that the condensation is carried out with a continuously decreasing temperature. With regard to 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.
Die hochmolekularen linearen Polyester leiten sich ebenso wie die Polyestervorkondensate ab von Dicarbonsäuren oder deren esterbildenden Derivaten, wie Alkylestern. Bevorzugt sind aliphatische und/oder aromatische Dicarbonsäuren mit einem Molekulargewicht <390. Besonders bevorzugte Dicarbonsäuren haben außer der Carboxylgruppe Kohlenwasserstoffstruktur. Besondere technische Bedeutung haben Alkandicarbonsäuren mit 5 bis 10 Kohlenstoffatomen oder Benzol-oder Naphthalindicarbonsäuren, insbesondere solche, die sich vom Benzol ableiten, erlangt. Insbesondere ist Terephthalsäure hervorzuheben. Geeignete Ausgangsstoffe sind beispielsweise Glutarsäure, Adipinsäuren, Sebacinsäure, Terephthalsäure, Isophthalsäure, Bernsteinsäure, Naphthalin-2,6-dicarbonsäure, 4,4'-Diphenyldicarbonsäure, 4,4'-Diphenoxydicarbonsäure oder deren C1- bis C4-Alkylester.Like the polyester precondensates, 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. In addition to the carboxyl group, 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.
Bevorzugte Diole sind aliphatische, cycloaliphatische oder aromatische Diole mit einem Molekulargewicht <280. Sie haben vorzugsweise, abgesehen von den Hydroxylgruppen,Koh- lenwasserstoffstruktur. Besondere technische Bedeutung haben Alkandiole, insbesondere solche mit 2 bis 6 Kohlenstoffatomen, erlangt, Geeignete Diole sind beispielsweise Äthylenglykol, Propylenglykol, Butandiol-1,4, Hexandiol-1,6, Pentandiol-1,5, Decamethylenglykol, Neopentylglykol oder 1,4-Bis-hydroxymethylcyclohexan. Besondere Bedeutung haben Äthylenglykol und Butandiol-1,4 erlangt.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.
Bevorzugte Polyester und auch deren Vorkondensate bestehen zu wenigstens 50 Mol.% aus Polyäthylenterephthalat oder Polybutylenterephthalat-Einheiten. Der Rest kann auch aus anderen kurzkettigen Polyester-Einheiten bestehen, die sich von den vorgenannten Polyester bildenden Ausgangsstoffen herleiten. Besonders bevorzugt sind Polyester, die zu 70 bis 100 Mol.% aus Polyäthylen oder Polybutylenterephthalat bestehen. Besondere Bedeutung hat das Verfahren nach der Erfindung für die Herstellung von Polybutylenterephthalat erlangt.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.
Die Polyestervorkondensate erhält man in an sich bekannter'' Weise durch Umsetzen von Dicarbonsäuren oder deren Estern mit einem Diol in Gegenwart von Katalysatoren wie Titansäureestern, Antimon-, Mangan- oder Zinkverbindungen, z.B. deren fettsaure Salze, bei Temperaturen von 150 bis 260°C. Die so erhaltenen Diglykolester von Carbonsäuren werden unter vermindertem Druck bei Temperaturen von 230 bis 270°C vorkondensiert. Solche Vorkondensate haben eine relative Viskosität von mindestens 1,05 (gemessen als 0,5 gewichtsprozentige Lösung in einem Gemisch aus Phenol und o-Dichlorbenzol im Gewichtsverhältnis 3 : 3 bei 25°Q. In der Regel geht man von Polyestervorkondensaten aus mit einer relativen Viskosität von 1,05 bis 1,2. Die Herstellung solcher Vorkondensate wird beispielsweise beschrieben in der DT-OS 25 14 116.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. The diglycol esters of carboxylic acids thus obtained are precondensed under reduced pressure at temperatures of 230 to 270 ° C. 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.
Die Kondensation der Polyestervorkondensate zu hochmolekularen Polyestern wird bei Temperaturen von 270 bis 340°C unter vermindertem Druck durchgeführt. Vorteilhaft hält man Drücke von 0,1 bis 2 Torr ein. Es versteht sich, daß die bei der Kondensation abspaltenden Diole fortlaufend aus dem Reaktionsgemisch entfernt werden.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.
Ein wesentliches Merkmal der Erfindung ist es, daß man die Kondensation zunächst bei einer Temperatur von 290 bis 340°C beginnt und mit fortschreitender Kondensation die Temperatur erniedrigt. Mit der Maßgabe, daß die Endtemperatur mindestens 10°C, vorteilhaft 30°C über dem Schmelzpunkt des jeweils hergestellten Polyesters liegt. Die Anfangstemperatur richtet sich auch nach der Art des Vorkondensats. Bei Polyäthylenterephthalat haben sich Anfangstemperaturen von 320 bis 340°C besonders bewährt, während sich bei der Herstellung von Polybutylenterephthalat Temperaturen von 290 bis 310°C besonders günstig erwiesen haben. Vorteilhaft senkt man während der Kondensation die hohe Anfangstemperatur um 30 bis 50°C. Das Absinken der Temperatur kann kontinuierlich,vorzugsweise jedoch sutfenweise,erfolgen. Die Endtemperatur richtet sich im wesentlichen nach dem Schmelzpunkt des erzeugten Polyesters und soll so hoch über dessen Schmelzpunkt liegen, damit keine Verfestigung eintritt und die weitere Verarbeitung nicht behindert wird. In der Regel haben sich Temperaturen etwa 100C über dem Schmelzpunkt als brauchbar erwiesen.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. With the proviso that 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.
Das erfindungsgemäße Verfahren läßt sich auch vorteilhaft durchführen, indem man die Temperatur durch adiabatische Arbeitsweise im Verlauf der Kondensation kontinuierlich um 30 bis 50°C senkt.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.
Diese Arbeitsweise hat den Vorteil, daß sich die optimale Reaktionstemperatur weitgehend selbständig einstellt. Ferner hat das neue Verfahren den Vorteil, daß durch den nachträglichen Einbau eines Wärmeaustauschers vor die Kondensationsstufe der Polyesterkondensation nach einem optimalen Temperaturzeitprofil in konventionellen Kondensationsreaktoren durchgeführt werden kann.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.
Zunächst wird die niedrigviskose Polyestervorkondensatschmelze vor dem Eintritt in die Polykondensationszone um 30 bis 50°C über die Temperatur erhitzt, welche der fertig kondensierte Polyester nach der Polykondensation aufweisen soll. Zweckmäßig wird die Temperatur des Polyestervorkondensats zunächst soweit erhöht, wie sie bei der nachfolgenden Polykondensation absinkt. Das Erhitzen der Polyestervorkondensatschmelze erfolgt vorteilhaft kurzzeitig in einem Wärmetauscher, z.B. Röhren- oder Plattenwärmetauscher oder in einer ähnlichen geeigneten Vorrichtung.First of all, 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.
Nach dem Eintritt der so erhitzten Polyestervorkondensatschmelze in die Kondensationszone setzt die Kondensation infolge von Umesterungsreaktionen ein. Die für die Reaktion und die Verdampfung des freigesetzten Diols und eventuellen Nebenprodukten, beispielsweise Tetrahydrofuran, bei der Kondensation von butandiol-l,4-haltigen Polyestern erforderliche Wärmeenergie wird dem Wärmeinhalt der Schmelze entnommen. Dadurch sinkt die Temperatur in dem Maße, wie die KondensationsrekatLon fortschreitet. Hierdurch stellt sich somit die optimale Reaktionstemperatur weitgehend selbständig ein. Demzufolge werden auch die Flächen in der Polykondensationszone, die mit der Schmelze in Berührung kommen, bei der Temperatur gehalten, welche der Polyester nach Polykondensation aufweisen soll, bis zu einer Temperatur, die die Endtemperatur der Polykondensation bis zu 10°C unterschreitet. Gegen Ende der Polykondensation weist dann die Schmelze eine Temperatur auf, die den mit der Schmelze in Berührung stehenden Flächen entspricht oder infolge der Aufnahme von mechanischer Energie bei der Bewegung der Schmelze die Temperatur der Berührungsflächen je nach Konstruktion der verwendeten Vorrichtung um 5 bis 100C übersteigt.After the polyester precondensate melt thus heated has entered the condensation zone, 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. As a result, the temperature drops as the condensation reaction progresses. As a result, 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. 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.
Vorzugsweise wird die Kondensation in dünner Schicht durchgeführt. Erfindungsgemäß seien als dünne Schichten solche mit bis zu 7 mm verstanden. Vorteilhaft sind die dünnen Schichten in Kontakt mit beheizten Flächen um einen raschen Wärmeübergang und eine rasche Anpassung an die fallende Kondensationstemperatur zu gewährleisten. Es hat sich deshalb bewährt, wenn man die kondensierende Schmelze als dünne Schicht unter Einfluß der Schwerkraft über eine im wesentlichen vertikale indirekt beheizte Fläche fließen läßt. Um eine von oben nach unten abgestufte Reaktionstemperatur zu erzielen, hat es sich besonders bewährt, wenn man die kondensierende Schmelze in dünner Schicht unter Einfluß der Schwerkraft nacheinander über eine Vielzahl von indi- ' rekt beheizten Flächen fließen läßt, wobei sich beim Fließen von Fläche zu Fläche jeweils Filme ausbilden. Die Zahl der erforderlichen Flächen ist apparativ bedingt. Eine geeignete Vorrichtung wird beispielsweise beschrieben in der FR-PS 15 45 487, sofern die geneigten Flächen beheizt sind. Eine andere geeignete Vorrichtung sei nachfolgend erläutert.The condensation is preferably carried out in a thin layer. According to the invention, 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. In order to achieve a reaction temperature which is graduated from top to bottom, it has proven particularly useful to influence the condensing melt in a thin layer 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.
Figur 1 zeigt einen Querschnitt durch die erfindungsgemäße Vorrichtung zur Herstellung von linearen hochmolekularen Polyestern. Die Vorrichtung besteht aus einem im wesentlichen vertikalen Schacht (1). Der Schacht kann rund oder polygon sein. Zweckmäßig läuft der Schacht am unteren Ende konisch zu,um ein Ansammeln der Schmelze zu ermöglichen. Der Schacht bildet einen gemeinsamen Brüdenraum (2). Hierdurch wird während des gesamten Kondensationsvorgangs ein gleichmäßiger Druck an jeder Stelle der Kondensation aufrechterhalten. Durch den Brüdenabzug (5) am oberen Ende des Schachtes werden die abgespaltenen Diole entfernt. Die entsprechenden Abscheider für die Brüden und die dazugehörige Vakuumvorrichtung sind nicht dargestellt. Am unteren Ende des Schachtes findet sich eine Austragsöffnung (4) für die Polyesterschmelze. Der Austrag erfolgt über Zahnradpumpen oder Extruder, die nicht gezeichnet sind. Im Schacht sind horizontal parallel zueinander beheizte Rohre (6) angeordnet. Die Rohre sind so untereinander angeordnet, daß die durch Schwerkraft herabfließende Schmelze jeweils über das darunterliegende Rohr fließt mit der Maßgabe, daß der Durchmesser der Rohre im Verlauf des Schachtes nach unten zunimmt. Das Polyestervorkondensat wird über die Zuführung (3) so zugegeben, daß die Schmelze jeweils über die gesammLänge der obersten Lage der Rohre aufgetragen wird.Figure 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). As a result, a uniform pressure is maintained at every point of the condensation throughout the entire condensation process. 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.
"Die Rohre sind über den Verlauf des Schachtes vorteilhaft in Gruppen unterteilt, wobei die oberste Gruppe aus Rohren mit dem geringsten Durchmesser besteht. Jede Gruppe kann aus mehreren Lagen Rohren bestehen. In den einzelnen Gruppen sind die Rohre zweckmäßig untereinander angeordnet. Die Zahl der Rohre und Lagen richtet sich nach den Abmessungen der jeweils verwendeten Vorrichtung. In der darauffolgenden Gruppe sind die Rohre zweckmäßig wieder in Einzellagen untereinander angeordnet. Vorteilhaft vergrößert sich der Rohrdurchmesser von Gruppe zu Gruppe um jeweils das 2,0- bis 4,0-fache. Ferner hat es sich als zweckmäßig erwiesen, wenn die Rohre einer nachfolgenden Gruppe jeweils auf Lücke zu den Rohren einer darüberliegenden Gruppe stehen. Es ergibt sich somit, daß die herabfließende Schmelze von 2 Rohren der Gruppe a auf ein Rohr der Gruppe b treffen. Die herabfließende Schmelze von 2 Rohren der Gruppe b trifft dann auf ein Rohr der Gruppe c. Durch die Vielzahl der Rohre läßt sich die abnehmende Temperatur leicht einstellen, beispielsweise von Gruppe zu Gruppe oder eine weitere Unterteilung innerhalb einer Gruppe im Verlauf des Schachtes nach unten."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. In the individual groups, 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. Advantageously, 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.
Polyester, die nach dem Verfahren der Erfindung erhältlich sind, eignen sich zur Herstellung von geformten Gebilden, wie Fäden, Folien, spritzgegossenen oder extrudierten Teilen, ferner für Überzüge.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.
Das Verfahren nach der Erfindung sei in den folgenden Beispielen veranschaulicht.The process according to the invention is illustrated in the following examples.
In einem 2-Liter-Rundkolben, ausgestattet mit Rührer, Stickstoffeinleitung und Füllkörperkolonne, wurden 1 000 g Di- ' methylterephthalat und 685 g Butandiol-1,4 auf 130°C erhitzt. Bei dieser Temperatur wurde unter Rühren 1,5 g Tetrabutylorthotitanat als Umesterungskatalysator zugegeben. Alsbald begann die Destillation von Methanol. Die Temperatur wurde innerhalb von 2 Stunden auf 220°C erhöht. Nach dieser Zeit waren 330 g Methanol abdestilliert und die Umesterungsreaktion beendet. Nun wurde die Füllkörperkolonne durch einen absteigenden Kühler ersetzt und innerhalb von 15 Minuten die Temperatur auf 250°C erhöht. Danach wurde unter schnellem Rühren der Druck stetig und linear innerhalb von 40 Minuten auf 10 Torr abgesenkt. Bei diesem Druck wurde noch 5 Minuten gerührt und dann die Vorkondensation durch Aufheben des Vakuums mit Stickstoff beendet.In a 2 liter round bottom flask equipped with a stirrer and stick Substance introduction and packed column, 1 000 g of dimethyl terephthalate and 685 g of 1,4-butanediol were heated to 130.degree. At this temperature, 1.5 g of tetrabutyl orthotitanate was added as the transesterification catalyst with stirring. The distillation of methanol soon began. The temperature was raised to 220 ° C within 2 hours. After this time, 330 g of methanol had been distilled off and the transesterification reaction had ended. The packed column was then replaced by a descending condenser and the temperature was raised to 250 ° C. in the course of 15 minutes. The pressure was then steadily and linearly reduced to 10 torr within 40 minutes with rapid stirring. At this pressure, the mixture was stirred for a further 5 minutes and then the precondensation was terminated by breaking the vacuum with nitrogen.
Das Vorkondensat wurde unter Stickstoff in eine Schale gegossen, wo es schnell erstarrte. Die relative Viskosität dieses Vorkondensats betrug 1,13.The precondensate was poured into a bowl under nitrogen, where it quickly solidified. The relative viscosity of this precondensate was 1.13.
Die Kondensation erfolgte in einem mit Rührer, Kühler, Stickstoffeinleitung ausgestatteten 250 ml großen Rundkolben, welcher durch ein Wood's-Metallbad geheizt wurde. Zur Nachkondensation wurden 50 g des Vorkondensats unter Stickstoff bei der gewählten Nachkondensationstemperatur aufgeschmolzen. Nach dem Aufschmelzen und dem Temperaturausgleich wurde der Kolben schnell auf einen Druck von ca. 0,5 Torr evakuiert. Die Rührgeschwindigkeit wurde der jeweiligen Viskosität angepaßt. Nach einer vorgegebenen Zeit wurde die Nachkondensation durch Aufheben des Vakuums mit Stickstoff unterbrochen.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. For post-condensation, 50 g of the pre-condensate were melted under nitrogen at the selected post-condensation temperature. After melting and temperature compensation, the flask was quickly evacuated to a pressure of approximately 0.5 torr. The stirring speed was adapted to the respective viscosity. After a predetermined time, the post-condensation was interrupted by removing the vacuum with nitrogen.
Die Ergebnisse sind in der folgenden Tabelle aufgeführt.
Die Vergleichsbeispiele 1 bis 4 zeigen die relative Viskosität als Funktion der Nachkondensationstemperatur nach einer Reaktionszeit von 15 Minuten. Nach dem Stand der Technik wurden die Temperaturen während der Polykondensationszeit konstant gehalten. Wenn die Temperatur von 255°C auf 280°C erhöht wird, werden auch höhere relative Viskositäten erhalten und damit ein höherer Polykondensationsgrad. Bei weiterer Erhöhung der Temperatur auf 290°C sinkt die relative Viskosität wieder ab, und es wird ein gelblich verfärbtes Produkt erhalten.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.
Die Beispiele 1 und 2 wurden dagegen nach dem erfindungsgemäßen Verfahren durchgeführt. Dazu wurde das Metallbad auf 295°C vorgeheizt und nach dem Aufschmelzen des Vorkondensats die Nachkondensationsreaktion begonnen. Im Verlauf der Nachkondensation wurde die Temperatur des Heizbades in den in der Tabelle angegebenen Schritten erniedrigt. Nach dem erfindungsgemäßen Verfahren wurde innerhalb von 12 Minuten eine relative Viskosität von 1,67 erreicht (Beispiel 2).In contrast, Examples 1 and 2 were carried out by the process according to the invention. For this purpose, the metal bath was preheated to 295 ° C. and the post-condensation reaction was started after the precondensate had melted. In the course of the post-condensation, 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).
In einem Rührkessel mit 40 1 Inhalt, ausgestattet mit Rührer, Stickstoffeinleitung und Dephlegmator wurden 20 kg Dimethylterephthalat und 13,7 kg Butandiol-1,4 auf 130°C erhitzt. Bei dieser Temperatur wurden unter Rühren 30 g Tetrabutylorthotitanat als Umesterungskatalysator zugegeben. Danach begann die Destillation von Methanol. Die Temperatur wurde innerhalb von 2 Stunden auf 220°C erhöht. Nach dieser Zeit waren 6,6 kg Methanol abdestilliert und die Umesterungsreaktion beendet. Innerhalb von 30 Minuten wurde die Temperatur auf 250°C erhöht. Danach wurde der Druck stetig und linear innerhalb von 45 Minuten auf 10 Torr abgesenkt. In diesem Stadium betrug die relative Viskosität des so erhaltenen Polybutylenterephthalat-Vorkondensats 1,12.20 kg of dimethyl terephthalate and 13.7 kg of 1,4-butanediol were heated to 130.degree. C. in a stirred tank with a capacity of 40 l, equipped with a stirrer, nitrogen inlet and dephlegmator. At this temperature, 30 g of tetrabutyl orthotitanate were added as a transesterification catalyst with stirring. Thereafter, the distillation of methanol started. The temperature was raised to 220 ° C within 2 hours. After this time, 6.6 kg of methanol had been distilled off and the transesterification reaction had ended. The temperature was raised to 250 ° C. within 30 minutes. The pressure was then steadily and linearly reduced to 10 torr within 45 minutes. At this stage, the relative viscosity of the polybutylene terephthalate precondensate thus obtained was 1.12.
Das Polybutylenterephthalat-Vorkondensat wurde durch einen Platten-Wärmeaustauscher gedrückt und dabei auf 285°C erwärmt und in einem auf 285°C mit Diphyldampf vorgeheizten Kondensationskessel von 40 1 Inhalt geleitet. Dieser Aufheizvorgang nahme 10 Minuten in Anspruch. Danach wurde der Fluß des Diphyldampfs unterbrochen und unter schnellem Rühren schlagartig ein Vakuum von 1 Torr im Kondensationskessel hergestellt.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.
Während der nun ablaufenden Polykondensation sank die Schmelztemperatur innerhalb von 33 Minuten exponentiell 2500C ab. Von diesem Zeitpunkt an wurde die Temperatur durch Diphyldampf auf 250°C gehalten. Nach weiteren 21 Minuten wurde das Vakuum aufgehoben und die Schmelze unter Stickstoffdruck ausgetragen. Die relative Viskosität des so hergestellten Polybutylenterephthalats betrug 1,72.During the polycondensation now taking place, 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.
In diesem Versuch wurde das Polybutylenterephthalat-Vorkondensat ebenfalls innerhalb von 10 Minuten durch den Platten-Wärmetauscher gedrückte die Temperatur aber auf 250°C gehalten. Der Kondensationskessel war auf 250°C vorgeheizt. Bei dieser Temperatur wurde nach dem Füllvorgang unter schnellem Rühren schlagartig ein Vakuum von 1 Torr hergestellt und unter diesen Bedingungen 54 Minuten kondensiert. Nach 54 Minuten Kondensationszeit wurde das Vakuum und die Schmelze ausgetragen. Die relative Viskosität betrug nur 1,49.In this experiment, 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.
Claims (11)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2738093 | 1977-08-24 | ||
| DE19772738093 DE2738093B1 (en) | 1977-08-24 | 1977-08-24 | Process and device for the production of linear high molecular weight polyesters |
| DE2803530 | 1978-01-27 | ||
| DE19782803530 DE2803530A1 (en) | 1978-01-27 | 1978-01-27 | Linear high mol. wt. polyester prepn. - by precondensate after-condensn. under reduced pressure while progressively decreasing process temp. opt. continuously |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0000918A2 true EP0000918A2 (en) | 1979-03-07 |
| EP0000918A3 EP0000918A3 (en) | 1979-04-04 |
| EP0000918B1 EP0000918B1 (en) | 1982-03-17 |
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ID=25772598
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100670A Expired EP0000918B1 (en) | 1977-08-24 | 1978-08-16 | Process for the preparation of linear, high molecular polyesters |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US4214072A (en) |
| EP (1) | EP0000918B1 (en) |
| JP (1) | JPS5443997A (en) |
| DE (1) | DE2861668D1 (en) |
| IT (1) | IT1097584B (en) |
Cited By (3)
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| EP0346735A3 (en) * | 1988-06-15 | 1991-01-30 | BASF Aktiengesellschaft | Process for the continuous preparation of linear thermoplastic polyesters |
| 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 |
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| DE19509551A1 (en) * | 1995-03-16 | 1996-09-19 | Basf Ag | Process for the continuous production of thermoplastic polyesters |
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| US6194609B1 (en) * | 1997-06-30 | 2001-02-27 | Bp Amoco Corporation | Crystallization in a plate heat exchanger |
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-
1978
- 1978-07-31 IT IT26342/78A patent/IT1097584B/en active
- 1978-08-10 US US05/932,632 patent/US4214072A/en not_active Expired - Lifetime
- 1978-08-16 DE DE7878100670T patent/DE2861668D1/en not_active Expired
- 1978-08-16 EP EP78100670A patent/EP0000918B1/en not_active Expired
- 1978-08-22 JP JP10151178A patent/JPS5443997A/en active Pending
-
1979
- 1979-03-27 US US06/024,298 patent/US4235844A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0346735A3 (en) * | 1988-06-15 | 1991-01-30 | BASF Aktiengesellschaft | Process for the continuous preparation of linear thermoplastic polyesters |
| 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 |
|---|---|
| US4235844A (en) | 1980-11-25 |
| IT7826342A0 (en) | 1978-07-31 |
| JPS5443997A (en) | 1979-04-06 |
| IT1097584B (en) | 1985-08-31 |
| EP0000918B1 (en) | 1982-03-17 |
| US4214072A (en) | 1980-07-22 |
| DE2861668D1 (en) | 1982-04-15 |
| EP0000918A3 (en) | 1979-04-04 |
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