EP0000159B2 - Verfahren zur Behandlung von Butandiol, das als Kondensat bei der Herstellung von Polybutylenterephthalaten erhalten wurde - Google Patents

Verfahren zur Behandlung von Butandiol, das als Kondensat bei der Herstellung von Polybutylenterephthalaten erhalten wurde Download PDF

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Publication number
EP0000159B2
EP0000159B2 EP78100177A EP78100177A EP0000159B2 EP 0000159 B2 EP0000159 B2 EP 0000159B2 EP 78100177 A EP78100177 A EP 78100177A EP 78100177 A EP78100177 A EP 78100177A EP 0000159 B2 EP0000159 B2 EP 0000159B2
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EP
European Patent Office
Prior art keywords
butanediol
condensate
production
solids
polybutylene terephthalates
Prior art date
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Expired
Application number
EP78100177A
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German (de)
English (en)
French (fr)
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EP0000159A1 (de
EP0000159B1 (de
Inventor
Ludwig Dr. Beer
Heinrich Mandel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation

Definitions

  • the invention relates to a process for the treatment of butanediol, which was obtained as a condensate in the production of polybutylene terephthalates, with alkaline agents.
  • the outgoing vapors contain not only 1,4-butanediol but also small amounts of bis-hydroxybutyl terephthalate and its oligomers, as well as catalyst-containing components and products with unknown composition.
  • fine droplets of polybutylene terephthalate can also be entrained.
  • the vapors from the polycondensation are condensed, for. B. on heat exchanger surfaces or in particular by means of spray condensers which are connected upstream of the vacuum units.
  • This object is achieved in a process for the treatment of butanediol, which is obtained as a condensate in the production of polybutylene terephthalates, with alkaline agents, the condensate being treated at a temperature of 40 ° C. to 60 ° C. from 0.01 to 0.2 percent by weight, based on the condensate, alkali alcoholates or alkali hydrides.
  • the new method has the advantage that the solids contained in the butanediol condensate are brought into solution in a simple and effective manner, so that no difficulties arise in the capacitors. Furthermore, the new process has the advantage that less than the stoichiometric amount of the alkaline agents according to the invention are required.
  • alkali metal alcoholates are compounds which, in their chemical activity, often correspond to the alkali metal hydroxides.
  • the amount of alkali metal alcoholates required to completely dissolve the solids in butanediol is an order of magnitude lower than the amount of sodium hydroxide required to dissolve solids in ethylene glycol, which comes from the production of polyethylene terephthalate.
  • the 1,4-butanediol in need of treatment is obtained as a condensate in the production of polybutylene terephthalates.
  • This is based, for example, on dimethyl terephthalate, esters it with 1,4-butanediol in the presence of transesterification catalysts at temperatures of 160 to 230 ° C and condenses the bis-hydroxybutyiterephthalate thus obtained, optionally in several stages at temperatures of 230 to 270 ° C and Press up to 13.3 Pa. It is also possible to use up to 40 mol%, based on dimethyl terephthalate and / or 1,4-butanediol, of other polyester-forming starting materials.
  • dimethyl esters of alkanedicarboxylic acids with 4 to 12 carbon atoms or isophthalic acid, and also alkanediols or cycloalkanediols with up to 8 carbon atoms are suitable.
  • Suitable processes are described, for example, in DT-OS 2514116 or 2214775.
  • Condensates obtained in the production of polybutylene terephthalates contain up to about 20% by weight of solids in addition to butanediol.
  • other diols are used as ester-forming components, such as their proportion z. B. up to 40% by weight in the condensate.
  • Butanediol condensates in need of treatment essentially occur in the pre- and final condensation stages.
  • a typical condensate obtained in the manufacture of polybutylene terephthalate essentially contains 1,4-butanediol and has a solids content of 3 to 6% by weight. The solids content which is insoluble at room temperature is about 1 to 3% by weight.
  • the treatment is carried out by adding alkali alcoholates or alkali hydrides.
  • Alkali alcoholates which are derived from alkanols or cycloalkanols having up to 10 carbon atoms, in particular having up to 7 carbon atoms or alkanediols having 2 to 6 carbon atoms, are particularly preferred.
  • Sodium alcoholates, which are derived from alkanols having 1 to 4 carbon atoms, have acquired particular technical importance. Suitable compounds are, for example, sodium methylate, sodium ethylate or sodium butylate.
  • Alkaline alcoholates or alkali hydrides are added to the condensate to be treated in amounts of 0.01 to 0.2% by weight, preferably 0.01 to 0.1% by weight. If you choose the amount too low, the dissolving process takes too long, but if you choose it too high, difficulties can arise due to alkali-containing solid separations during the reprocessing of the butanediol by distillation.
  • the optimal amount of alkali alcoholate can be adjusted simply by continuously checking the pH of the condensate to be treated.
  • the pH should advantageously be above 9, preferably from 10 to 12.
  • the alkali alcoholates are generally used in a concentrated alcoholic solution.
  • a methanolic sodium methylate solution has proven particularly successful.
  • the treatment is carried out at a temperature of 40 ° C. to 60 ° C., in particular 40 to 50 ° C. This temperature allows a pressure of 66.6 to 266.6 Pa without difficulty.
  • the procedure according to the invention for the treatment of butanediol is particularly well suited for all polybutylene terephthalate processes in which the butanediol distilling off during the polycondensation is condensed in suitable injection condensers which are provided with a butanediol circuit.
  • the dissolution of the solid portions is advantageously supported by stirring or pumping.
  • the process according to the invention is illustrated by the following examples.
  • the parts specified are parts by weight. They behave like parts of the room to kilograms to liters.
  • the percentages given are percentages by weight.
  • the starting point is butanediol, which was obtained as condensate in the production of polybutylene terephthalate and has a total solids content of 5%.
  • the solids content which is insoluble at room temperature is 2%.
  • 1,000 parts of butanediol of the stated quality are mixed with stirring at 55 to 60 ° C. with 1.7 parts of a 30% methanolic sodium methylate solution (corresponding to 0.05% by weight Na methylate or butanediol) and with stirring in the temperature range indicated treated further. After a reaction time of 2 hours, the solid components have completely dissolved except for a slight opalescence.
  • the pH of the solution measured by means of a hydrogen electrode is 11. The solution thus obtained no longer shows any solids deposits after standing for one day at room temperature and is therefore stable enough for the subsequent reprocessing by distillation.
  • Example 2 The procedure is as described in Example 1, but instead of sodium methylate, 6 parts of a 10% solution of sodium ethylate in butanediol (corresponding to 0.06% by weight) are used. After stirring for 2 hours, the insoluble solids content has almost completely dissolved. The pH of the solution is 11.
  • Example 2 1,000 parts of butanediol are used as described in Example 1, and 8.6 parts of a 50% strength aqueous sodium hydroxide solution (corresponding to 0.43% by weight of NaOH) are added to this at 55 to 60 ° C. with stirring. After stirring for 2 hours in the specified temperature range, the butanediol shows an unchanged strong turbidity due to the presence of undissolved solid particles. After standing for 1 hour at room temperature, large amounts of insoluble solid deposit on the bottom of the vessel.
  • a 50% strength aqueous sodium hydroxide solution corresponding to 0.43% by weight of NaOH

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78100177A 1977-06-24 1978-06-16 Verfahren zur Behandlung von Butandiol, das als Kondensat bei der Herstellung von Polybutylenterephthalaten erhalten wurde Expired EP0000159B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772728407 DE2728407A1 (de) 1977-06-24 1977-06-24 Verfahren zur behandlung von butandiol, das als kondensat bei der herstellung von polybutylenterephthalaten erhalten wurde
DE2728407 1977-06-24

Publications (3)

Publication Number Publication Date
EP0000159A1 EP0000159A1 (de) 1979-01-10
EP0000159B1 EP0000159B1 (de) 1980-07-23
EP0000159B2 true EP0000159B2 (de) 1984-12-19

Family

ID=6012217

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100177A Expired EP0000159B2 (de) 1977-06-24 1978-06-16 Verfahren zur Behandlung von Butandiol, das als Kondensat bei der Herstellung von Polybutylenterephthalaten erhalten wurde

Country Status (5)

Country Link
US (1) US4154970A (enrdf_load_stackoverflow)
EP (1) EP0000159B2 (enrdf_load_stackoverflow)
JP (1) JPS5412305A (enrdf_load_stackoverflow)
DE (2) DE2728407A1 (enrdf_load_stackoverflow)
IT (1) IT1096585B (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5910537A (ja) * 1982-07-07 1984-01-20 Daicel Chem Ind Ltd ブタンジオ−ルの取得法
US4647705A (en) * 1985-08-15 1987-03-03 Basf Corporation Process for improving the ultraviolet light transmittance of ethylene glycol
DE19608614A1 (de) * 1996-03-06 1997-09-11 Basf Ag Verfahren zur Aufarbeitung von Dihydroxyverbindungen enthaltenden Rückständen
GB2324928B (en) 1997-05-02 2001-09-12 B & W Loudspeakers Loudspeaker systems
US6245879B1 (en) * 1999-01-29 2001-06-12 Shell Oil Company Purification of 1,3-propanediol in carbonyl-containing stream
EP1867659A4 (en) 2005-04-05 2008-12-31 Jms Co Ltd SPECIAL ANTIBODY AGAINST 3,4-DGE DERIVED AGE
ES2718679T3 (es) 2013-04-12 2019-07-03 Toray Industries Procedimiento de producción de 1,4-butanodiol
CA2927166C (en) * 2013-10-23 2021-12-28 Basf Se Method for preparing 1,4-butanediol having an apha color index of less than 30
JP6652439B2 (ja) * 2016-04-11 2020-02-26 株式会社オティックス 内燃機関の可変動弁機構

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2793235A (en) * 1954-09-27 1957-05-21 Du Pont Recovery of glycols from polyester production
BE720958A (enrdf_load_stackoverflow) * 1967-09-18 1969-03-17
NL7002510A (en) * 1970-02-11 1971-08-13 Ethylene glycol purification
US3859368A (en) * 1971-09-08 1975-01-07 Halcon International Inc Method of producing polyhydric compounds such as ethylene glycol by disproportionation of its monoacetate

Also Published As

Publication number Publication date
IT1096585B (it) 1985-08-26
IT7824767A0 (it) 1978-06-20
JPS629094B2 (enrdf_load_stackoverflow) 1987-02-26
EP0000159A1 (de) 1979-01-10
DE2728407A1 (de) 1979-01-04
US4154970A (en) 1979-05-15
EP0000159B1 (de) 1980-07-23
DE2860045D1 (en) 1980-11-13
JPS5412305A (en) 1979-01-30

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