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WO2003046035A1 - Procede de fabrication d'homopolymeres ou de copolymeres d'oxymethylene - Google Patents

Procede de fabrication d'homopolymeres ou de copolymeres d'oxymethylene Download PDF

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Publication number
WO2003046035A1
WO2003046035A1 PCT/EP2002/013451 EP0213451W WO03046035A1 WO 2003046035 A1 WO2003046035 A1 WO 2003046035A1 EP 0213451 W EP0213451 W EP 0213451W WO 03046035 A1 WO03046035 A1 WO 03046035A1
Authority
WO
WIPO (PCT)
Prior art keywords
formaldehyde
polyoxymethylene glycols
water
stage
aqueous solution
Prior art date
Application number
PCT/EP2002/013451
Other languages
German (de)
English (en)
Inventor
Eckhard Ströfer
Harald Armbruster
Gitta Egbers
Reinhard Freyhof
Thorsten Friese
Ludwig E. Heck
Peter Hildenbrand
Hartmut Zeiner
Stephan Scholl
Hans-Helmut Görtz
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2002356750A priority Critical patent/AU2002356750A1/en
Priority to DE10295499T priority patent/DE10295499B4/de
Publication of WO2003046035A1 publication Critical patent/WO2003046035A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/08—Polymerisation of formaldehyde
    • 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
    • C08G4/00—Condensation polymers of aldehydes or ketones with polyalcohols; Addition polymers of heterocyclic oxygen compounds containing in the ring at least once the grouping —O—C—O—

Definitions

  • the invention relates to a process for the production of oxymethylene homo- or copolymers from an aqueous solution containing formaldehyde and polyoxymethylene glycols.
  • Polyoxymethylene homo- or copolymers are used as engineering plastics in a variety of applications.
  • polyoxymethylene homo- or copolymers are known. They can be produced, for example, by polymerizing trioxane or formaldehyde gas. The reaction is started by initiators such as BF 3 etherate and carried out with the addition of regulators such as methylal, butylal or dimethyl formal. The polymerization can be carried out in reaction extruders, shell belts, twin-screw mixers, kneaders or in suspension in an organic suspending agent.
  • Production usually starts from methanol as the starting product, which is converted into formaldehyde in large-scale industrial processes.
  • methanol is partially oxidized and dehydrated in a silver contact process.
  • an approximately 50% aqueous formaldehyde solution is obtained.
  • the formaldehyde solution is converted to trioxane after concentration in the presence of acidic catalysts.
  • the trioxane which is only about 2% in equilibrium with formaldehyde, is driven off by distillation together with water and formaldehyde and concentrated in a downstream column.
  • a water-immiscible solvent such as methylene Chloride or benzene is enriched in trioxane.
  • the trioxane must be purified further in order to be usable for the polymerization.
  • polyacetals For a general description of the production of polyacetals, reference can be made to engineering thermoplastics: polycarbonate, polyacetals, polyester, cellulose esters, publisher Ludwig Bottenbruch, ISBN 3-446-16368-9, in particular chapter 4, pages 300 to 331.
  • the known ner processes for the production of oxymethylene homo- and copolymers have a number of disadvantages.
  • numerous and complex separation steps are necessary to obtain high-purity formaldehyde or trioxane.
  • the separation is carried out using often chlorine-containing extracting agents, which have to be worked up or disposed of separately.
  • the object of the present invention is to provide a process for the preparation of oxymethylene homo- or copolymers which avoids the disadvantages of the known ner processes and in particular can be carried out more cheaply in terms of apparatus, the number of separation steps being able to be reduced.
  • the object is achieved according to the invention by a process for the production of oxymethylene homo- or copolymers from an aqueous solution containing formaldehyde and polyoxymethylene glycols
  • step (2) the polyoxymethylene glycols obtained in stage 1 are converted into oxymethylene homo- or copolymers in the presence of polycondensation catalysts with removal of water.
  • the aqueous solution used in step (1) and containing formaldehyde and polyoxymethylene glycols is preferably prepared by customary dehydrogenation of methanol. Reference can be made to the literature cited at the beginning.
  • oxymethylene homopolymers or copolymers can be prepared from polyoxymethylene glycols in an advantageous manner.
  • Formaldehyde is not only present in aqueous solutions in monomeric form, but also in the form of oligomers, so-called polyoxymethylene glycols. There is a thermodynamic equilibrium between the monomers and oligomers of different lengths.
  • the ner driving according to the invention now makes use of the fact that the oligomers present in equilibrium are themselves polyoxymethylene precursors which, according to the invention, are linked to the oxymethylene homo- or copolymers.
  • trioxane as an intermediate or a high purification, as is required in the known method, is not necessary. It has been found according to the invention that after at least partial separation of water and formaldehyde from an aqueous solution containing formaldehyde and polyoxymethylene glycols (in thermodynamic equilibrium), the phase obtained contains polyoxymethylene glycols, in which the molar ratio of polyoxymethylene glycols to formaldehyde is greater than 1: Is 0.6, can be converted directly into a polycondensation for the preparation of oxymethylene homo- or copolymers.
  • the molar ratio of polyoxymethylene glycols to monomeric formaldehyde and methylene glycol is preferably 1: 0.4 to 1: 0.
  • Polyoxymethylene glycols can have, for example, two to nine carbon atoms. In this case, mixtures of dioxymethylene glycol, trioxymethylene glycol, tetraoxymethylene glycol, pentaoxymethylene glycol, hexaoxymethylene glycol, heptaoxymethylene glycol, octaoxymethylene glycol and ⁇ onaoxymethylene glycol are used.
  • the mixture used in step (2) which contains the higher homologues of formaldehyde, can be prepared from a conventional formaldehyde solution by known methods for shifting the equilibrium to the side of the higher homologues.
  • formaldehyde and water are preferably at least partially evaporated from an aqueous solution containing formaldehyde and polyoxymethylene glycols. fung removed, and the remaining polyoxymethylene glycols are implemented in step (2) before establishing a thermodynamic equilibrium.
  • the evaporation can be carried out, for example, in a film evaporator or a distillation device.
  • Thin-film evaporators such as falling film evaporators or rotary film evaporators or reaction columns are preferably used.
  • a formaldehyde solution can be depressurized at a temperature of 50 to 150 ° C in a reaction column by greatly reducing the pressure under which the solution is, whereby the higher homologues of formaldehyde remain in the solution and monomeric formaldehyde formed from methylene glycol evaporated. Since the equilibrium between the higher homologues of formaldehyde and the monomeric formaldehyde in the solution is restored within 0.5 to 15 minutes at usual temperatures of 30 to 70 ° C, i.e.
  • the solution with the high proportion of higher homologues of formaldehyde according to the invention is preferably used within 10 minutes after its preparation in stage (1) in the process according to the invention in stage (2).
  • the further reaction is particularly preferably carried out within 5 minutes.
  • stage (1) Suitable processes for carrying out stage (1) are described, for example, in EP-A 0 934 922 and DE-A 199 25 870.
  • the polyoxymethylene glycols are used for the production of methylendi (phenylamine).
  • DE-A 199 25 870 does not contain any instructions for use.
  • a suitable device for carrying out stage (1) is described in this application, see also FIGS. 1 to 3.
  • the polyoxymethylene glycols obtained by the evaporation in stage (1) preferably have a water content of at most 35% by weight, particularly preferably at most 30% by weight, in particular at most 25% by weight, based on the mixture.
  • the reaction in step (2) can be carried out in any suitable device in which polyoxymethylene glycols can be converted to oxymethylene homo- or copolymers in the presence of polycondensation catalysts with the removal of water.
  • the reaction is preferably carried out in a list dryer, twin-shaft kneader or twin-shaft mixer with the possibility of degassing.
  • the reaction is particularly preferably carried out in a twin-screw extruder which has several degassing devices in the course of the screw.
  • a suitable twin-screw extruder is described, for example, in EP-A 0 080 656.
  • the twin-screw extruder described there (ZSK 30 from Werner and Pfleiderer) has an L: D ratio of 20.
  • the extruder has several sectors separated by baffle elements.
  • the polymerization or polycondensation is carried out in a first sector, while degassing and assembly are carried out in a second sector.
  • degassing and assembly are carried out in a second sector.
  • At least some of the water / formaldehyde mixture separated off in stage (1) can be removed, and the remaining formaldehyde can be returned to stage (1) after the thermodynamic equilibrium has been established.
  • stage (2) the polycondensation is carried out in the presence of catalysts customary for polycondensation.
  • catalysts customary for polycondensation Reference can be made to the literature cited at the beginning.
  • Typical polycondensation catalysts which can be used according to the invention are, for example, hydrochloric acid, phosphoric acid, methanesulfonic acid and their mixtures with phosphorus pentoxide, polyphosphoric acid esters, chlorine, sulfur and phosphorus-containing acids such as phosphorous acid, hypophosphorous acid and their alkali and alkaline earth metal salts, hypochlorous acid, perchloric acid and other such acids.
  • the polycondensation is carried out under conditions under which water can be continuously discharged from the reaction mixture. Pressure and temperature are set so that water can be drawn off from the reaction mixture. For example, atmospheric pressure or negative pressure can be used. The temperature is chosen to be as low as possible, for example in the range from 50 to 100.degree. In stages (1) and / or (2), customary comonomers, regulators, other auxiliaries or mixtures thereof can also be added.
  • Possible comonomers include oxocyclic compounds of small ring size with the structural features of an ether, acetal or lactone.
  • epoxides have become important, especially ethylene oxide.
  • Propylene oxide, styrene oxide, epichlorohydrin, 3,3-bis-chloromethyloxocyclobutane in addition to substituted glycidylphenyl ether or ethyl glycidate can be mentioned as further examples of polymerizable ethers.
  • Bifunctional comonomers with two polymerizable groups can also be used, so that weakly crosslinked terpolymers are obtained. These include, for example, diepoxides, diacetals or compounds each with an epoxy and cyclic acetal group.
  • Suitable cyclic acetals are dioxolane, 1,3-dioxane, 1,3-dioxepane (butanediol formal), 1,3,5-trioxepane, 1,3,6-trioxolane and substituted trioxolanes.
  • 1,3-dioxepane is used here.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé de fabrication d'homopolymères ou de copolymères d'oxyméthylène à partir d'une solution aqueuse contenant des formaldéhydes et des polyoxyméthylène glycols. Le procédé selon l'invention consiste 1) à extraire au moins partiellement, dans une étape d'extraction, de l'eau et des formaldéhydes à partir de la solution aqueuse de manière à obtenir une phase contenant des polyoxyméthylène glycols dans laquelle le rapport molaire des polyoxyméthylène glycols sur les formaldéhydes est supérieur à 1 : 0,6 ; et, 2) à transformer, en présence de catalyseurs de polycondensation, les polyoxyméthylène glycols obtenus à l'étape 1), en homopolymères ou copolymères d'oxyméthylène par extraction d'eau.
PCT/EP2002/013451 2001-11-30 2002-11-28 Procede de fabrication d'homopolymeres ou de copolymeres d'oxymethylene WO2003046035A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002356750A AU2002356750A1 (en) 2001-11-30 2002-11-28 Method for the production of oxymethylene homo- or co-polymers
DE10295499T DE10295499B4 (de) 2001-11-30 2002-11-28 Verfahren zur Herstellung von Oxymethylenhomo- oder -copolymeren

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001158813 DE10158813A1 (de) 2001-11-30 2001-11-30 Verfahren zur Herstellung von Oxymethylenhomo- oder -copolymeren
DE10158813.5 2001-11-30

Publications (1)

Publication Number Publication Date
WO2003046035A1 true WO2003046035A1 (fr) 2003-06-05

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Country Status (3)

Country Link
AU (1) AU2002356750A1 (fr)
DE (2) DE10158813A1 (fr)
WO (1) WO2003046035A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8354495B2 (en) 2008-04-16 2013-01-15 Ticona Gmbh Process for the preparation of oxymethylene polymers and apparatus suitable for this purpose
US8993709B2 (en) 2011-07-15 2015-03-31 Ticona Gmbh Process for producing oxymethylene polymers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10309286A1 (de) 2003-03-04 2004-09-16 Basf Ag Verfahren zur thermischen Stabilisierung hochkonzentrierter Formaldehydlösungen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369504A (en) * 1942-04-24 1945-02-13 Du Pont Formaldehyde polymers
DE1112505B (de) * 1958-09-27 1961-08-10 Degussa Verfahren zur Herstellung von Paraformaldehyd mit mittlerer Reaktionsfaehigkeit und einem Wassergehalt von hoechstens 0, 2 Gewichtsprozent
GB1048191A (en) * 1963-04-10 1966-11-16 Skanska Attikfabriken Ab Process for producing formaldehyde polymers
EP0080656A1 (fr) * 1981-11-28 1983-06-08 BASF Aktiengesellschaft Procédé continu pour la fabrication de polymères d'oxyméthylène
EP1063221A1 (fr) * 1999-06-07 2000-12-27 Basf Aktiengesellschaft Procédé pour la réaction d'une solution contenant un mélange

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1045613B (it) * 1973-06-15 1980-06-10 Sir Soc Italiana Resine Spa Procedimento perfezionato per pendere stabili i polimeri acetalici
HU213653B (en) * 1991-05-15 1997-09-29 Harsanyi Process for producing stable poly(oxymethylene)glycol solutions
JP2003147161A (ja) * 2001-11-14 2003-05-21 Toray Ind Inc ポリオキシメチレン樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369504A (en) * 1942-04-24 1945-02-13 Du Pont Formaldehyde polymers
DE1112505B (de) * 1958-09-27 1961-08-10 Degussa Verfahren zur Herstellung von Paraformaldehyd mit mittlerer Reaktionsfaehigkeit und einem Wassergehalt von hoechstens 0, 2 Gewichtsprozent
GB1048191A (en) * 1963-04-10 1966-11-16 Skanska Attikfabriken Ab Process for producing formaldehyde polymers
EP0080656A1 (fr) * 1981-11-28 1983-06-08 BASF Aktiengesellschaft Procédé continu pour la fabrication de polymères d'oxyméthylène
EP1063221A1 (fr) * 1999-06-07 2000-12-27 Basf Aktiengesellschaft Procédé pour la réaction d'une solution contenant un mélange

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8354495B2 (en) 2008-04-16 2013-01-15 Ticona Gmbh Process for the preparation of oxymethylene polymers and apparatus suitable for this purpose
US8993709B2 (en) 2011-07-15 2015-03-31 Ticona Gmbh Process for producing oxymethylene polymers

Also Published As

Publication number Publication date
AU2002356750A1 (en) 2003-06-10
DE10295499B4 (de) 2007-04-19
DE10295499D2 (de) 2004-10-28
DE10158813A1 (de) 2003-06-12

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