AU652418B2 - Process for producing a polyester, a polyester and its use - Google Patents
Process for producing a polyester, a polyester and its use Download PDFInfo
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- AU652418B2 AU652418B2 AU11589/92A AU1158992A AU652418B2 AU 652418 B2 AU652418 B2 AU 652418B2 AU 11589/92 A AU11589/92 A AU 11589/92A AU 1158992 A AU1158992 A AU 1158992A AU 652418 B2 AU652418 B2 AU 652418B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In a process for the production of a polyester without antimony, after transesterification with a manganese catalyst, it is blocked in the mol ratio P/Mn less than 1 by means of a phosphorus compound. 10 - 100 ppm Ge are used as a polycondensation mixed catalyst. The resulting antimony-free polyester is suitable for the production of bottles, films and filaments.
Description
OPT DATE 27/n8/92 AOJP DATE 01/10/92 APPLN. D 1589 92 1 PCT NUMBER PCT/CH92/00007 ENS (PCT)
INI
(51) Internatiovale Patentklassifikation 5 (11) Internationale Verdiffentlichungsnummer: WO 92/ 13022 C08G 63/83, 63/86 Al (43) Internationales Veroffentlichungsdatum: 6. August 1992 (06.08.92) (21) Internationales Aktenzeichen: PCT/CH92/00007 (22) Internationales Anmeldedatum: 14. Januar 1992 (14.01.92) Priorititsdaten: 107/91-0 16. Januar 1991 (16.01.91) CH (74) Anwalt: HERRMANN, Peter; Rh6ne-Poulenc Viscosuisse SA, Patentabteilung RIP, CH-6020 Emmenbrficke (C H).
(81) Bestimmungsstaaten: AT (europfiisches Patent), AU, BE (europflisches Patent), BR, CA, CH (europaisches Patent), CS, DE (europgiisches Patent), DK (europ~isches Patent), ES (europdisches Patent), FR (europ~isches Patent), GB3 (europgiisches Patent), GR (europ~iisches Patent), HU, IT (europaiisches Patent), JP, KR, LU (europ~isches Patent), MC (europgisches Patent), NL (europ~isches Patent), PL, RO, RU, SE (europaisches Patent), us.
Verdffentlicht Mil internationalem Recherchenberich.
(71) Anmielder (fir alle Bestinrnungsswaaen ausser US): RHO- NE-POULENG VISCOSUISSE SA [CH/CH]; CH- 6020 Emmenbrficke (CH).
(72) Erfinder; und Erfinder/Anmelder (nur filr US) :ENGGASSER, Josiane [FR/CH]; Benziwil 25/67, CH-6020 Emmenbrflcke STAHLIN, Roland [CH/FR]; 56, rue Maurice Flandin, F-69003 Lyon GESCHE, Paul [FR/FR]; Les Cigales, B~timent A, F-69340 Franche-Ville (FR).
6 52 41 (54) Title: PROCESS FOR PRODUCING A POLYESTER, A POLYESTER AND ITS USE (54)Bezeichnung: VERFAHREN ZUR HERSTELLUNG FINES POLYESTERS, EINEN POLYESTER SOWIE DESSEN
VERWENDUNG
(57) Abstract In a process for the production of a polyester without antimony, after trans esterification with a manganese catalyst, it is blocked in the mol ratio P/Mn less than I by means of a phosphorus compound. 10 100 ppm Ge are used as a polycondensation mixed catalyst. The resulting antimony-free polyester is suitable for the production of bottles, films and filaments.
(57) Zusammenfassung In einem Verfahren zur antimonfreien Herstellung eines Polyesters wird nach einer Umesterung mit einem Mangankatalysator dieser mittels einer Phosphorverbindung im Molverhailtnis P/Mn 1 blockiert. Als Polykondensationsmischkatalysator werden noch 10 100 ppm Ge verwendet. Der resultierende antimonfreie Polyester ist zur Herstellung von Flaschen, Folien und Filamenten geeignet. I RHONE-POULENC VISCOSUISSE SA PCT 9122 Process for the preparation of a polyester, a polyester and its use The invention relates to a process for the preparation of a polyester composed of polyethylene terephthalate units, in which process a terephthalic acid ester is transesterified with a glycol using a manganese salt as catalyst and is then subjected to a polycondensation reaction using a germanium-containing mixed catalyst, the polyester and its use.
The preparation of a polyester composed of polyethylene terephthalate units is known. To this end, customarily, an acid component, such as terephthalic acid, and a glycol component, such as ethylene glycol, are esterified directly or subjected to a transesterification reaction.
Catalysts are required in both cases, and amongst these a combination of manganese/antimony has proved to be the most suitable.
As a. consequence of the more rigorous legislation in numerous industrial countries, the disposal of antimony, which is recognised as toxic, is becoming ever more acute. Therefore, numerous solutions have been tried to prepare an antimony-free polyester.
Thus, the use of Ti glycolate, Ge glycolate or Al N t. i r,
I
U~ C l 1~ LII L~~~IVI :~~VI In this publication defined glycolates are prepared. The preparation of glycolates of constant pure quality in a separate process step is very laborious. No information is to be found in this publication with respect to the time and place at which the polycondensation catalyst is added.
DE-A-16 45 496 discloses a process for the preparation of polyesters without antimony, in which process cerium compounds which are soluble in ethylene glycol are used with simultaneous use of organic phosphorus derivatives.
The addition of a specific organic phosphorus compound together with a soluble cerium compound prior to the polycondensation reaction resulted in improved whiteness compared with that obtained by the addition of conventional phosphorus compounds.
The object of the invention is to replace antimony as polycondensation catalyst, in particular in the preparation of polyesters, by a catalyst, without the other characteristics, such as stability to heat, stability to thermal oxidation and photostability being impaired.
ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. CH 9200007 SA 55064 Thi annex lists the Patent famiv members reitine to the natent do.n tr it dpA in the shnwanntinrwA idmuinn.l nnrt- 5-R I I 3 A further object is to increase the whiteness of the polyester at the same time.
The object is achieved according to the invention in that 80-99 by weight of the active manganese salt are blocked by means of phosphorus compounds and the manganese remaining free is used after the addition of 10-100 ppm of Ge at the end of the glycol stage as co-catalyst for the catalysis of the polycondensation reaction, the P/Mn molar ratio being 1.
In a specific embodiment, the invention provides a process for the preparation of a polyester composed of polyethylene terephthalate units, in which process a terephthalic acid ester is transesterified with a glycol using a manganese salt as catalyst and is then subjected to a polycondensation reaction using a germanium-containing mixed catalyst, characterised in that 80-99 by weight of the active manganese salt are blocked by means of phosphorus compounds and the manganese remaining free is used after the addition of 10-100 ppm of Ge at the end of the glycol stage as co-catalyst for the catalysis of the polycondensation reaction under progressive vacuum, the P/Mn molar ratio being 1.
An essential advantage of an antimony-free catalyst is to be seen in the fact that no heavy metals are present in the polymer itself, but also in the fact that no leachable toxic antimony compounds are able to pass into the effluent system and into the environment. A further advantage is the use of a inorganic phosphorus compounds, which, in contrast to the organic phosphorus compounds, are not toxic.
A further advantage is that only extremely small amounts of phosphorus are required to block the manganese.
The P/Mn molar ration of 1 is far below known molar ratios.
Since some of the Mn still remains free, a small amount of polycatalyst is required. This has the advantage that fewer foreign substances are present in the polymer, which substances in most cases interfere 4C 4 during further processing.
The addition of a germanium complex immediately prior to the vacuum stage has the advantage of lowering the diethylene glycol content, because it is fed into a mixture depleted in glycol.
The germanium catalyst which has proved most suitable is a germanium salt consisting of an alkali metal cation, in particular sodium or potassium.
Preferably, 10-100 ppm of Mn and 10-100 ppm of Ge are present in the polycondensation stage.
The resulting polyester granules have a reflectance of more than 52 measured at a wavelength of 426 nm. Such a high reflectance gives a surprisingly good whiteness.
The polyester is suitable for use in bottles, sheets and filaments.
The invention will be illustrated in more detail with the aid of examples.
The following batch and processes steps 1-4 apply to all i examples.
!I
The autoclave is charged with: Dimethyl terephthalate 51.5 mol Ethylene glycol 98.2 mol Manganese acetate 2-hydrate: 90 ppm of Mn (with respect to the dimethyl terephthalate) 1. Transesterification The transesterification reaction is carried out in a stirred autoclave (40 rev/min) in the temperature range from 160 to 230°C over a period of 120 min. During this operation the methanol is distilled off quantitatively via a separating column.
2. Additives The additives are added to the reaction mass in the temperature range between 230°C and 235 0 C. The additives added are 0.4 of TiOz, as matting agent, and 0.075 of antioxidant (Irganox 1010 R (trade name of CIBA-GEIGY, Basle, Switzerland)), both suspended in ethylene glycol.
3. Ethylene qlycol stage The ethylene glycol stage is carried out in the temperature range from 230 to 245°C over a period of about 30 min.
6 4. Polycondensation The polycondensation reaction is carried out in the temperature range from 245 to 285 0 C over a period of 200 min, by, in a first step, establishing a progressive vacuum (1000 50 mbar) over a period of 40 min and, in a second step, initiating a high vacuum stage p 1 mbar.
Example 1 (Comparison Example) In Example 1 the addition is made in the customary concentration of 334 ppm of antimony (in the form of antimony trioxide) after blocking the transesterification catalyst by means of phosphorous acid in a P/Mn molar ratio of 1.2.
Example 2 (Comparison Example) In Example 2 no blocking of the transesterification catalyst whatsoever is carried out.
Examples 3 and 4 In Examples 3 and 4, after the methanol stage, the manganese transesterification catalyst is blocked at a V temperature of the reaction mass of 230°C using a P 20 compound (HPO 3 in a P/Mn molar ratio of 0.66 and 0.89 respectively. The manganese which has remained free acts 1
D
7 as polycondensation catalyst.
Examples 5 to 7 In Examples 5 to 7, the transesterification catalyst is blocked using a compound (H 3
PO
3 in a P/Mn molar ratio of 0.89 and 0.83 respectively.
At the end of the glycol stage, that is to say immediately prior to the vacuum stage, the polycondensation catalyst sodium germanate 1-hydrate, dissolved in ethylene glycol, is added. The manganese which has remained free and the germanium act as mixed catalyst.
A summary representation of the illustrative embodiments can be seen in Table 1.
!j Table 1: Illustrative embodiments Ex- Manganese P/Mn molar Antimony Germanium Inganox i0 2 amples (ppm) ratio (ppm) (ppm) 1010 1 90 1.2 334 0.4 2 90 0.075 0.4 3 90 0.66 0.075 0.4 4 90 0.89 0.075 0.4 90 0.89 75 0.075 0.4 6 90 0.89 60 0.075 0.4 7 90 0.83 75 0.075 0.4 The properties of the polymer are shown in Table 2.
9 Table 2: Properties obtained Ex- VI CEG DEG REF Tox Polycondensation amples (mol/t) at 426 nm stage time (min) 1 74.0 22 0.7 52.0 258 200 2 76.5 23 0.65 41.0 265 135 3 75.0 20 0.50 48.0 268 175 4 80.0 19 0.50 52.0 268 265 80.0 20 1.1 58.5 265 240 6 75.0 20 1.0 58.5 268 250 7 74.0 22 1.0 59.5 268 200 It can be seen from these experiments that the best polymer properties and a polycondensation time similar to that for Comparison Example 1 are obtained with Example 7.
I
IIU
Comparison of the whiteness, measured on dtex 76f30 filaments, for Examples 1 and 7.
The abbreviations have the following meanings: VI viscosity index (measured in phenol/ dichlorobenzene 1:1) CEG carboxyl end groups REF reflectance at 426 nm Tox temperature at which the oxidative decomposition starts DEG diethylene glycol L
Claims (2)
1. Process for the preparation of a polyester composed of polyethylene terephthalate units, in which process a terephthalic acid ester is transesterified with a glycol using a manganese salt as catalyst and is then subjected to a polycondensation reaction using a germanium-containing mixed catalyst, characterised in that
80-99 by weight of the active manganese salt are blocked by means of phosphorus compounds and the manganese remaining free is used after the addition of 10-100 ppm of Ge at the end of the glycol stage as co-catalyst for the catalysis of the polycondensation reaction under progressive vacuum, the P/Mn molar ratio being 1. 2. Process according to claim 1, characterised in that the Ge catalyst is added immediately prior to the vacuum stage. 3. Process according to claim 1, characterised in that the Ge salt is an alkali metal salt and is dissolved as such in glycol. 4. Process according to claim 1, characterised in that 10-100 ppm of Mn and 10-100 ppm of Ge are used as polycondensation catalyst. 5. Polyester produced according to any one of claims 1-4, characterised by a reflectance, determined on polyester granules, of 52 measured at a wavelength of 426 nm. if iij V-ss li i Use of the polyester according to claim 5 for bottles, sheets and filaments. DATED this 2nd day of June, 1994. RHONE-POULENC VISCOSUISSE S.A WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA ~11"1 (f.3 I RHONE-POULENC VISCOSUISSE SA PCT 9122 Abstract In a process for antimony-free preparation of a polyester, after transesterification using a manganese catalyst, said catalyst is blocked by means of a phosphorus compound in a P/Mn molar ratio of 1. 100 ppm of Ge are additionally used as polycondensation mixed catalyst. The resulting antimony-free polyester is suitable for the production of bottles, sheets and filaments. INTERNATIONAL SEARCH REPORT International Application No PCT/CH 92/00007 1. CLASSIFICATION OF SUBJECT MATTER (If several classification symbols apply, Indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC Int. Cl.5 C08G63/83; C08G63/86 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System I Classification Symbols 5 Int. Cl. C08G Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched a IIl. DOCUMENTS CONSIDERED TO BE RELEVANT' Category I Citation of Document, "t with Indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 X Chemical Abstracts, volume 78, No. 6, 1-2 12 February 1973, (Columbus, Ohio, see page 20, column 2, abstract 30502t, JP, A, 72 19, 178 (ASAHI CHEMICAL INDUSTRY CO., LTD) 1 June 1972 Y 1,3 Y Chemical Abstracts, volume 81, No.20, 1,3 18 November 1974, (Columbus, Ohio, see page 114, column 2, abstract 122582j, JP, A, 73 43, 190 (ASAHI CHEMICAL INDUSTRY CO.) December 1973 Y FR, A, 2 570 077 (RHONE-POULENC FILMS.) 1-4,6 14 March 1986 see claims 1,8 see page 4, line 10 line 17 see page 6, line 33 page 7, line 13 see page 2, line 26 line 31 Special categories of cited documents: 1t later document published after the International filing date document defining the general state of the art which is not or priority date and not in conflict with the application but considered to be of particular relevance ncited to understand the principle or theory underlying the earlier document but published on or after the international document of particular relevance: the claimed invention III ng 1 date"X" document of particular relevance; the claimed invention cannot be considered novel or cannot be considered to document which may throw doubts o" priority claim(s) or Involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed Invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Re.ort February 1992 (25.02.92) 5 March 1992 (05.03.92) International Searching Authority Signature of Authorized Officer European Patent Office Form PCT/ISA/210 (second sheet) (January 1985) I I -2- Intamational ApplIcation No. PCT/CH 92/00007 Ill, DOCUMENTS CONSIDERED TO ME RELEVANT (CONTINUED FROM THE SIECO1D SHEET) Category I Citation of Document, with indiction. Wer aPProplflt. of the reievant passages 1 Raeeant to Claim No Chemical Abstracts, volume 78, No. 6, 12 February 1973, (Columbus, Ohio, U.S.A), see page 23, column 2, abstract 30540d, JP, A, 72 19, 179 (ASAHI CHEMICAL INDUSTRY CO., LTD.) 1 June 1972 FR, A, 2 024 495 (GEVAERT-AGFA N.V.) 28 Auaust 1970 see claims 1-12 see page 3, line 7 line 16; example 4 see page 4, line 11 line 1-4,6 1,3-4,6 foprm PCT ISA 210 textra sneet) IWafuarY 19851 I 4 ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. CH SA 9200007 55064 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members we as contained in the European Patent Office EDP file on The European Patent Office is in no way liable for these particulars which ame merey given for the purpose of information. 25/02/92 INTERN4ATIONALER RECI-ERCHENBERICHT Interntionales Aktaenzechmn PCT/CH 92/00007 1. KLASSIFIKATIaN DES ANMEID)UNGSGEGENSTANDS (bel nulirerenasifikatnnssymbolmn sind all* anxugaban)6 Nach der Internationalen pateatkiassifikation odor nad der nationalon Alassiflation und der iPC Int.Kl. 5 C08G63/83; C08G63/86 H. RECiEXC1IERTE SACiGEBEETE Redeardcilere Mindostprilfstoff 7 Rechelrcbe nidut zum Mlfndestprilfsoff gohilren'Ie Verwifntlichungas, soweit diese unter die reduorduierton Sac~gebiete fallen' inl. MISOILAGIGE: VEROFFENThICHUNGIEN 9 A 0 1IL Kennzaclung dir Vertlffentllchung 1 soweit erforderilch unter Angabe der mallgeblichen Tle 12 Betr. Ansvuruch Nr.13 X Chemical Abstracts, Band 78, Nr. 6, 12 Februar 1-2 1973, (Columbus, Ohio, siehe Seite 20, Spalte 2, Zusammenfassung 30502t, jP,A,72 19,178 (ASAHI CHEMICAL INDUSTRY CO., LTD.) 01 Juni 1972 Y 1,3 Y Chemical Abstracts, Band 81, Nr. 20, 1,3 18 November 1974, (Columbus, Ohio, U.S.A), siehe Seite 114, Spalte 2, Zusanimenfassung 122582j, JP,A,73 43N,190 (ASAHi CHEMICAL INDUSTRY CO.) Dezember 1973 Bflsondere Kategorien von angegohonon Verdfentlichun 1n 0 W' Verfiffntlikbung, die den allgoracinon Stand dir Tedunik -r Spitero V rntlichungd.nc anitralnme n doftiit, aber nichi ais besondoss bodmnisum nijisebon i1st oeddw oo c i lttltaum Veotffentldit warden 'r I= Dkua=t,,dasJedoh at amode a& demlat=- st und unit der Anmoldungl nidut knilidlert, sondu nr ==i Ilton Dkment m dis jodo cht waroderned do. Verstlndnls des dir Erfindung zugmndeleganden Pfrn7Jp V etinn ln g dn~ id dst vort ient PricO!, 1snpr odor der ibi zagrundellegendaa Thoorso ingegoben It L Vaiflhf aunbdgeine n o i oelm dutchiehtads X' Vortiffontlichung van bosonderer B.dwungr die boanspruch. fentlichungsdstuu einor inderan ii Redherchanbericht W oEfaugkano.tasM drafaideice ii nmnten Vustiffontlichung beiogt warden soil odor die ins einoi kei botuhend betradta warden aderon besanderon Gruntd angegeben 1st (wto mnsgofnhrt) 'Y Vorilifntfichung von besondorar Bedoutung die banspruch. V- lffitichung, die sich auf i mi ullicho e t Esinun in ititml i rfnousco Ttgkelt be- nahond bermchtot worden, wan die Vestiffentlidnng asit ein. Doenaung, ciao Ausstellung odor andoro Mallnarnn Cla Odor me.m, andiren Va*Ifetlichunten dioso Kate- bedebtd Spin Vertiloung gebnacht wird nd diest Vealndung far 1w Vartffentlichung, die vor do. Internadml *en Anmddoda- anon Fachiann niheieoad 1st turn, abor ash do. bamnspruchten PrioritLtadatum vaetifet- W~ Veotffentlidrnng. die ?Mtgled derselbon Patendiutrle ift lidsi Warden 1st IV. BESCIEINIGUNG Datum des Absoblusso gor intuonalon Rechorcho Absondodatwn dos Intrndonalon Rodacdoalbalchts FEBRUAR 1992 0 5. 03a 92 lintanatiousle Rocborchonbebide Utiterscirift des bvlmlatigtes Bedionstatim EUROPAISCHES PATENTAIT. MIAO K.Y.P. P 1-- 1ei~dt ?Cr/1SAI~IO t~litt 21 (Jinx 1905 PCT/CH 92100007 Internudonnies Aktenzeichcn M. EINSCHLAGIGE VEROFFENTUCHUNGEN (Fortsgttung vona Blatt 2) Art 0 Kenzelcirnung der Vetffentlichung, soweit effordedilch tinter Anpgbe der malobllchui Telle B fev. Anspruch Nr. 1 FR,A,2 570 077 (RHONE-POULENC FILMS.) 14. Mdrz 1986 siehe AnsprUche 1,8 siehe Seite 4, Zeile 10 Zeile 17 siehe Seite 6, Zeile 33 Seite 7, Zeile 13 siehe Seite 2, Zeile 26 Zeile 31 Chemical Abstracts, Band 78, Nr. 6, 12 Februar 1973, (Columbus, Ohio, U.S.A), siehe Seite 23, Spalte 2, Zusammenfassung 30540d, JP,A,72 19,179 (ASAHI CHEMICAL INDUSTRY CO., LTD.) 01 Juni 1972 FR,A,2 024 495 (GEVAERT-AGFA 28. August 1970 siehe Anspr~che 1-12 siehe Seite 3, Zeile 7 Zeile 16; Beispiel 4 siehe Seite 4, Zeile 11 Zeile 1-4,6 1-4,6 1,3-4,6 pewag, pCTjtw2iozftb J ~S ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT C CBER DIE INTERNATIONALE PATENTANMELDUNG NR. SA 9200007 55064 In diesein Anbang sind die Mtglicder der Paentamiien der im obengematc internadonaiea Redcerdaeaabericht angciluhten Psteutdokaameie angcba. Die A89SaBCD tib die Famiicnmitgieder estqwccbaa dami Stand der Datei des iscp~ben Pstecitts am 5/29 Diese Anga dienen nur Wzit Unteiridatg und erfolgen obe Gewihr. 2/29 Im Rccberchenberirist Datum der Mitlied(er) der Datum der 1 angftdartes Pateutdvkument Veraffjndcing IPatenfamiae Verfiffugdichn FR-A-2570077 FR-A-2024495 14-03-86 28-08-70 Keine AT-A- BE-A- CH-A- OE-A- GB-A- N L-A- US-A- 294425 741156 522693 1948236 1274858 6916767 3654234 15-10-71 04-05-70 15-05-72 18-06-70 17-05-72 25-05-70 04-04-72 Ffit nibw Einzelbden zu diesem nn amng chee AcutsMatt des Europ I Wcben PatentmW Nr.12/S2
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH10791 | 1991-01-16 | ||
CH107/91 | 1991-01-16 | ||
PCT/CH1992/000007 WO1992013022A1 (en) | 1991-01-16 | 1992-01-14 | Process for producing a polyester, a polyester and its use |
Publications (2)
Publication Number | Publication Date |
---|---|
AU1158992A AU1158992A (en) | 1992-08-27 |
AU652418B2 true AU652418B2 (en) | 1994-08-25 |
Family
ID=4179434
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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AU11589/92A Ceased AU652418B2 (en) | 1991-01-16 | 1992-01-14 | Process for producing a polyester, a polyester and its use |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP0520051B1 (en) |
JP (1) | JP2693038B2 (en) |
KR (1) | KR100210220B1 (en) |
AT (1) | ATE145656T1 (en) |
AU (1) | AU652418B2 (en) |
BR (1) | BR9204103A (en) |
CA (1) | CA2077997A1 (en) |
CS (1) | CS282792A3 (en) |
DE (1) | DE59207572D1 (en) |
HU (1) | HU212900B (en) |
PL (1) | PL168199B1 (en) |
RU (1) | RU2086573C1 (en) |
SK (1) | SK279697B6 (en) |
TR (1) | TR27025A (en) |
WO (1) | WO1992013022A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP3248348B2 (en) * | 1994-03-15 | 2002-01-21 | 松下電器産業株式会社 | Communication method and communication device |
EP0745629A3 (en) * | 1995-06-01 | 1997-05-07 | Enichem Spa | Polyesters with a low crystallization rate and catalytic system for their preparation |
US6953768B2 (en) * | 2002-11-26 | 2005-10-11 | Teck Cominco Metals Ltd. | Multi-component catalyst system for the polycondensation manufacture of polyesters |
CZ201247A3 (en) * | 2012-01-23 | 2013-05-29 | Technická univerzita v Liberci | Method of polyethyleneterephthalate (PET) chemical recycling and process for preparing nanofibers from aromatic-aliphatic co-polyesters obtained in such a manner |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2570077A1 (en) * | 1984-09-11 | 1986-03-14 | Rhone Poulenc Films | Process for the preparation of polyester |
AU3886593A (en) * | 1992-04-27 | 1993-11-29 | Rhone-Poulenc Viscosuisse Sa | Method of producing a polyester, and use of the polyester thus produced |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1274858A (en) * | 1968-11-29 | 1972-05-17 | Agfa Gevaert | Improvements in the manufacture of polyesters |
JPS4843669A (en) * | 1971-10-04 | 1973-06-23 | ||
DE2811982A1 (en) * | 1978-03-18 | 1979-09-27 | Huels Chemische Werke Ag | METHOD FOR PRODUCING HIGH MOLECULAR POLY (ETHYLENE TEREPHTHALATE) |
-
1992
- 1992-01-14 AU AU11589/92A patent/AU652418B2/en not_active Ceased
- 1992-01-14 DE DE59207572T patent/DE59207572D1/en not_active Expired - Fee Related
- 1992-01-14 WO PCT/CH1992/000007 patent/WO1992013022A1/en not_active Application Discontinuation
- 1992-01-14 JP JP4502036A patent/JP2693038B2/en not_active Expired - Lifetime
- 1992-01-14 HU HU9202940A patent/HU212900B/en not_active IP Right Cessation
- 1992-01-14 CA CA002077997A patent/CA2077997A1/en not_active Abandoned
- 1992-01-14 AT AT92901742T patent/ATE145656T1/en not_active IP Right Cessation
- 1992-01-14 EP EP92901742A patent/EP0520051B1/en not_active Expired - Lifetime
- 1992-01-14 BR BR929204103A patent/BR9204103A/en not_active IP Right Cessation
- 1992-01-14 RU SU925053138A patent/RU2086573C1/en active
- 1992-01-14 KR KR1019920702223A patent/KR100210220B1/en not_active IP Right Cessation
- 1992-01-14 PL PL92296093A patent/PL168199B1/en unknown
- 1992-01-14 SK SK2827-92A patent/SK279697B6/en unknown
- 1992-04-17 TR TR00381/92A patent/TR27025A/en unknown
- 1992-09-14 CS CS922827A patent/CS282792A3/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2570077A1 (en) * | 1984-09-11 | 1986-03-14 | Rhone Poulenc Films | Process for the preparation of polyester |
AU3886593A (en) * | 1992-04-27 | 1993-11-29 | Rhone-Poulenc Viscosuisse Sa | Method of producing a polyester, and use of the polyester thus produced |
Also Published As
Publication number | Publication date |
---|---|
DE59207572D1 (en) | 1997-01-09 |
RU2086573C1 (en) | 1997-08-10 |
JP2693038B2 (en) | 1997-12-17 |
ATE145656T1 (en) | 1996-12-15 |
CA2077997A1 (en) | 1992-07-17 |
KR937000574A (en) | 1993-03-15 |
EP0520051B1 (en) | 1996-11-27 |
EP0520051A1 (en) | 1992-12-30 |
HU9202940D0 (en) | 1992-11-30 |
CS282792A3 (en) | 1992-12-16 |
HU212900B (en) | 1996-12-30 |
SK279697B6 (en) | 1999-02-11 |
PL296093A1 (en) | 1993-11-15 |
KR100210220B1 (en) | 1999-07-15 |
WO1992013022A1 (en) | 1992-08-06 |
JPH05505418A (en) | 1993-08-12 |
PL168199B1 (en) | 1996-01-31 |
BR9204103A (en) | 1993-06-08 |
TR27025A (en) | 1994-10-10 |
AU1158992A (en) | 1992-08-27 |
HUT62620A (en) | 1993-05-28 |
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