EP2268683A1 - Procédé de production de polymères d'oxyméthylène et dispositif approprié - Google Patents

Procédé de production de polymères d'oxyméthylène et dispositif approprié

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Publication number
EP2268683A1
EP2268683A1 EP09732885A EP09732885A EP2268683A1 EP 2268683 A1 EP2268683 A1 EP 2268683A1 EP 09732885 A EP09732885 A EP 09732885A EP 09732885 A EP09732885 A EP 09732885A EP 2268683 A1 EP2268683 A1 EP 2268683A1
Authority
EP
European Patent Office
Prior art keywords
polymerization
reactor
phase
polymer
mixture
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.)
Withdrawn
Application number
EP09732885A
Other languages
German (de)
English (en)
Inventor
Michael Haubs
Jürgen LINGNAU
Eberhard Mann
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.)
Ticona GmbH
Original Assignee
Ticona GmbH
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 Ticona GmbH filed Critical Ticona GmbH
Publication of EP2268683A1 publication Critical patent/EP2268683A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G2/04—Polymerisation by using compounds which act upon the molecular weight, e.g. chain-transferring agents
    • 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
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/24—Copolymerisation of aldehydes or ketones with acetals

Definitions

  • the present invention relates to an improved process for the preparation of oxymethylene polymers and a device suitable therefor.
  • polyoxymethylenes The preparation of polyoxymethylenes is known per se. It can on the one hand by anionic polymerization of anhydrous formaldehyde, and on the other hand by the cationic polymerization of formaldehyde or cyclic oligomers of formaldehyde, usually trioxane, take place.
  • the polymerization can be carried out both in bulk (that is to say without solvent) and in solution as precipitation polymerization and in the melt in homogeneous phase under pressure (cf., for example, DE 31
  • a disadvantage of polymerization with cationic initiators is that they also catalyze side reactions, such as hydride shift, which lead to molecular weight degradation and formation of formate end groups (see, e.g.
  • This addition can be carried out in an aqueous phase or in an organic solvent, usually at elevated temperature, with subsequent filtration, washing and drying.
  • the deactivation can also be carried out in the melt (see, for example, DE-A-3,703,790), in which case the solid crude polymer obtained is first ground,
  • Residual monomers are withdrawn, and the crude polymer is then melted and the resulting melt with the deactivator (eg, amines or phosphines) is mixed.
  • the deactivator eg, amines or phosphines
  • EP-A-673,955 describes a process in which the crude polymer is treated with a vapor stream containing a volatile base. The deactivation with alkali or alkaline earth oxides in the melt is described (see also JP-A-05 / 059,255). In all the described methods of cationic
  • the crude polymer is initially obtained in solid form, crushed, optionally heated and then treated with a deactivator. All of these methods are thus relatively expensive.
  • EP-A-999,224 describes that a separate treatment with a
  • the generally basic stabilizers take over the role of deactivation. But here, too, a solid crude polymer is produced in a first step, which is then mixed with the above-mentioned additives, melted and pelletized. This method is limited to copolymers, especially those having a relatively high content of stabilizing comonomers.
  • the object of the present invention is to provide a simple process for the preparation of oxymethylene polymers (hereinafter also referred to as "POM”) high stability, which is carried out by simple means and energetically favorable, which also allows the synthesis of oxymethylene homo- and copolymers with low comonomer content and lower melt viscosities.
  • POM oxymethylene polymers
  • the present invention relates to a process for the preparation of oxymethylene
  • the method according to the invention comprises the measures:
  • the process takes place at least in the homogeneous reaction step in a sealed system, so the reaction takes place under the autogenous pressure of the monomers, such as trioxane or formaldehyde.
  • step i) it is the known polymerization of -CH 2 -O units forming monomers, optionally in the presence of cyclic acetals, such as 1, 3-dioxolane.
  • the polymerization is carried out as a precipitation polymerization, so that solid polymer is present in addition to not yet spent monomer.
  • a -CH 2 -O- units forming monomer or a mixture of different monomers with conventional initiators of cationic polymerization and with chain transfer agents, such as acetals of formaldehyde as a regulator in a conventional manner.
  • Typical temperatures are between 40 0 C and 150 0 C.
  • the polymerization is preferably carried out at pressures of 2 to 100 bar, preferably at pressures between 5 and 40 bar.
  • the polymerization temperature in this first phase is so low that the polymer largely precipitates in the reaction mixture, i. the reaction mixture is a heterogeneous solid / liquid mixture.
  • the solid phase is formed here by precipitated polymer, while the liquid phase consists essentially of unreacted monomer.
  • the polymerization conversion is between 10% and 70%, so that there is a suitable mixture.
  • the polymerization temperature rises in such a way that the heterogeneous solid / liquid mixture becomes substantially homogeneous.
  • the temperature rise is caused on the one hand by the polymerization / crystallization heat on the other hand caused by heat from the outside. This makes it possible to polymerize at a given
  • Temperature course to perform Through a targeted temperature profile, some properties of the polymers, such as impact resistance or modulus can be selectively adjusted within certain limits.
  • the targeted use of the polymerization / Heat of crystallization allows efficient energy use of this process step.
  • other temperature profiles can also be realized within the scope of the method by means of corresponding heating and cooling elements.
  • the temperature profile over the entire polymerization typically ranges from 80 0 C to 170 0 C, but can also run from 120 0 C to 180 0 C.
  • the temperature and residence time is kept as low as possible in the second phase in order to suppress undesirable side reactions (hydride shift).
  • Typical upper temperatures are - depending on the comonomer content - at 100 0 C to
  • step iii) the homogeneous, liquid is used to complete the polymerization
  • Reaction mixture which may optionally contain small amounts of solid components, which in addition to polymer contains unreacted monomers such as trioxane and formaldehyde, brought into contact with deactivators.
  • unreacted monomers such as trioxane and formaldehyde
  • deactivators may be mixed with the polymerization batch in bulk or diluted with an inert aprotic solvent. This will be the active ones
  • Polymerization mixture still about 5 -10 wt.% Contains solid components.
  • the optional step iv) corresponds to the prior art in melt hydrolysis with the difference that the polymer can be added directly as a melt in the subsequent aggregates.
  • the first and second phases of the process according to the invention are carried out in a reactor which allows the formation of an overpressure inside the reactor with continuous introduction of reactants into the reactor and with continuous discharge of educts from the reactor and which has a plurality of independently heatable zones ,
  • This reactor is also the subject of the present invention.
  • this reactor is an extruder with a pressure-holding valve connected to the outlet of the extruder.
  • a -CH 2 -O- units-forming monomer or a mixture of different monomers is reacted in the manner described above.
  • -CH 2 -O- units forming monomers include formaldehyde or its cyclic oligomers such as 1, 3,5-trioxane (trioxane) or 1, 3,5,7-tetroxane.
  • the oxymethylene polymers are generally unbranched linear polymers which generally contain at least 80 mol%, preferably at least 90 mol%, in particular at least 95 mol%, of oxymethylene units (-CH 2 -O-).
  • the oxy-methylene polymers contain - (CH 2 ) X -O- units, where x can assume the values from 2 to 25. If desired, low
  • branching agents for example, trihydric or higher alcohols or their derivatives, preferably trihydric to hexahydric alcohols or derivatives thereof are used.
  • Preferred derivatives are formals in which two OH groups have been reacted with formaldehyde, as well as epoxides.
  • the amount of branching is not more than 1
  • the invention also encompasses the preparation of such oxymethylene polymers which, in addition to methoxy end groups, may also contain hydroxyalkylene end groups -O- (CHk) x -OH, where x may assume the values from 2 to 25.
  • These polymers can be prepared by carrying out the polymerization in the presence of diols of the general formula HO- (CH 2 ) ⁇ -OH, where x can assume the values from 2 to 25.
  • the polymerization in the presence of the diols leads by chain transfer to polymers having hydroxyalkylene end groups.
  • the concentration of diols in the reaction mixture depends on what percentage of the end groups is to be present as -O- (CH 2 ) X -OH and is between 10 ppm by weight and 2% by weight.
  • the molecular weights of these polymers expressed by the volume melt index MVR can be adjusted within wide ranges.
  • the polymers have recurring structural units of the formula - (CH 2 -O-) n - where n is the average degree of polymerization (number average) and preferably ranges from 500 to 10,000, especially from 500 to 4,000.
  • the oxymethylene polymers prepared according to the invention are derived from formaldehyde or its cyclic oligomers, such as trioxane or tetroxane.
  • oxymethylene polymers are prepared in which at least 80%, preferably at least 90%, most preferably at least 95% of all end groups are alkyl ether groups, in particular methoxy or ethoxy. Very particularly preferably produced oxymethylene polymers are derived from
  • Particularly preferably used -CH 2 -O units forming monomers are formaldehyde or very particularly preferably trioxane.
  • the molecular weight of the resulting homo- and copolymers can be adjusted by the use of acetals of formaldehyde (chain transfer agent). These also lead to the formation of etherified end groups of the polymers, so that a separate implementation with capping is dispensable.
  • the chain transfer agents used are monomeric or oligomeric acetals of formaldehyde.
  • Preferred chain transfer agents are compounds of the formula I.
  • R 1 and R 2 are independently monovalent organic radicals, preferably alkyl radicals, such as butyl, propyl, ethyl and especially methyl, and q is an integer from 1 to 50.
  • the chain transfer agents are usually used in amounts of up to 5,000 ppm, preferably from 100 to 3,000 ppm, based on the monomer (mixture).
  • Suitable initiators are the cationic initiators customarily used in the preparation of oxymethylene homopolymers and copolymers.
  • protic acids such as fluorinated or chlorinated alkyl and arylsulfonic acids, e.g. Trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, or Lewis acids, e.g. Tin tetrachloride, arsenic pentafluoride, phosphorus pentafluoride and boron trifluoride, and their complex compounds, e.g. Boron trifluoride etherates, and carbocation sources, such as triphenyl methyl hexafluorophosphate.
  • protic acids such as fluorinated or chlorinated alkyl and arylsulfonic acids, e.g. Trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, or Lewis acids, e.g. Tin t
  • the initiators are usually used in amounts of from 0.005 to 50 ppm, preferably from 0.01 to 1 ppm, more preferably from 0.02 to 0.2 ppm, based on the
  • the homogeneous, liquid reaction mixture is mixed, which contains in addition to polymer unreacted monomers such as trioxane and formaldehyde, contacted with deactivators. These may be mixed with the polymerization batch in bulk or diluted with an inert aprotic solvent. This quickly and completely disables the active chain ends.
  • deactivators it is possible to use those compounds which react with the active chain ends in such a way that the polymerization reaction is terminated.
  • examples are the organic bases triethylamine or melamine and the inorganic bases potassium carbonate or sodium acetate.
  • very weak organic bases such as carboxylic acid amides, such as dimethylformamide can be used.
  • Particularly preferred are tertiary bases such as triethylamine and hexamethylmelamine.
  • the bases are in concentrations of 1 ppm to 1 wt .-%, based on the
  • Polymerization mass used. Preferred are concentrations of 10 ppm to 5000 ppm.
  • Typical deactivation temperatures are in the range of 125 0 C to 180 0 C, particularly preferably in the range from 135 0 C to 160 0 C and most preferably in the range from 140 0 C to 150 0 C.
  • Typical deactivation pressures range from 3 to 100 bar, preferably from 5 to 40 bar.
  • the polymerization can be carried out in the known for the production of POM homo- and copolymers reactors.
  • kneaders or extruders are used which are designed to be temperature-controlled and pressure-resistant.
  • the phases i) and ii) are particularly preferably carried out in an aggregate, wherein there is a smooth transition between the heterogeneous phase polymerization and the polymerization in a substantially homogeneous phase. Both steps can also in different units be made.
  • the deactivation of the polymerization mixture can be carried out in a kneader or extruder, but also in a tubular reactor with static mixers.
  • the polymerization time can vary widely and typically ranges from 10 seconds to 10 minutes, preferably from 15 seconds to 5 minutes, and more preferably from 20 to 100 seconds.
  • End groups are brought to elevated temperature for a certain time (thermal hydrolysis). Subsequently, the liquid polymerization mixture can be transferred to a flash zone and by applying a reduced pressure residual monomers and solvents can be removed. This removal can also be done in several stages at different pressures.
  • the relaxation zone is formed by a space which is filled by the hot polymer solution or polymer melt.
  • a negative pressure preferably a pressure of less than 500 mbar, in particular less than 200 mbar, the majority of the remaining monomer and
  • Solvent residues by utilizing the temperature of the polymer solution from this aborted.
  • This process step can be carried out in a separated part of the tubular reactor, preferably in an extruder. But it can also be used other aggregates, such as a flash chamber.
  • polymer solutions under pressure they are first reduced to ambient pressure in the expansion zone before the residual monomers are removed by suction.
  • the polymer solution is transferred to step iii) while maintaining the pressure in an extruder, in which the relaxation and the suction of the monomer and solvent residues takes place.
  • twin-screw extruder is used.
  • Stabilizers and processing aids may optionally already be incorporated into the POM polymer in the relaxation zone.
  • a mixture of additives is metered in and incorporated into the hot polyoxymethylene polymer.
  • the mixture of additives may contain processing aids, for example adhesion promoters, lubricants, nucleating agents, mold release agents, fillers, reinforcing materials or antistatic agents and additives which impart a desired property to the molding composition, such as dyes and / or pigments and / or impact modifiers and / or electrical conductivity imparting agents Additives, and mixtures of these additives, but without limiting the scope of the examples mentioned.
  • the polymer melt is solidified. This can be done within or immediately after leaving the relaxation zone. Subsequently, the solidified and optionally additized polymer is granulated in a conventional manner. In an extraction stage remaining residual monomers and / or oligomers and / or solvents and / or other impurities can be removed from the polymer.
  • Granulation and extraction can be done in known aggregates.
  • Drying is preferably followed by the extraction stage in order to remove the granules from residues of the adhering extractant.
  • the POM may optionally be remelted in a conventional manner, provided with additives and re-granulated.
  • additives can be added which would be dissolved out of the polymer in the extraction stage.
  • FIG. 1 A preferred variant of the method according to the invention is shown in FIG. 1
  • a monomer (4) is a mixture of -CH 2 -O group-forming monomer, preferably trioxane, optionally a cyclic acetal, eg dioxolane, together with an acetal of formaldehyde, preferably methylal, and via a Feed of the carrier and initiator of the cationic polymerization (5) introduced.
  • the polymerization is carried out initially in a heterogeneous phase, for example at a temperature of 100 0 C and a pressure of 5 to 25 bar. By increasing the polymerization temperature, the heterogeneous polymerization mixture gradually changes in the course of the polymerization into a substantially homogeneous phase, in which the
  • the average residence time of the reaction mixture in the first reactor is about 60 seconds. Thereafter, the polymerization is terminated by addition of deactivators. Subsequently, the reaction mixture is transported in the thermal hydrolysis vessel (2). There, the polymerization mixture is heated to 190 0 C for 20 min, with thermally unstable hemiacetal chain are removed by cleavage of formaldehyde.
  • trioxane optionally a cyclic acetal, such as dioxolane and methylal, are introduced into a first reactor, b) by addition of an initiator of the cationic polymerization,
  • Polymerization is carried out at such pressures and temperatures that the reaction mixture is first present as a heterogeneous phase by precipitating polymer, c) the temperature of the polymerization mixture is increased so that the reaction mixture is in a substantially homogeneous phase d) the homogeneous reaction mixture is to terminate the polymerization Deactivator added, e) the reaction mixture is heated in a second reactor to such temperatures and for such a period of time, so that a thermal hydrolysis takes place, for example to temperatures of 190 0 C for 20 min, and f) the reaction mixture is discharged into a vented extruder in which the deactivated and thermally hydrolyzed polymer is freed from trioxane and other volatile components.
  • Oxymethylene polymers of high molecular weight and with specifically adjusted mechanical properties can be produced by the processes according to the invention.
  • the oxymethylene polymers according to the invention preferably have melt volume indices of less than 100 ml / 10 min, more preferably from 1, 5 to 40 ml / 10 min (determined according to DIN EN ISO 1133 at 190 0 C under a weight of 2.16 kg ).
  • the oxymethylene polymers produced according to the invention can be further processed into shaped articles in a manner known per se by molding processes, for example by blow molding, injection molding or extrusion.
  • the oxymethylene polymers produced according to the invention are distinguished by a high chemical and thermal stability and moldings produced therefrom show an excellent impact strength.
  • the polymerization was carried out in a gas-tight, pressure-stable twin-screw extruder with 7 approximately equal length, separately adjustable heating stages.
  • Trifluoromethanesulfonic acid and 600 ppm Triethylammoniumtriflat were pumped into the extruder at a shaft revolution speed of 120 U / min. The pressure became constant at 18 at the end of the extruder through a pressure holding valve kept bar.
  • the temperature profiles for the individual tests are listed in Table 1.
  • the residence time in the extruder was about 1 min.
  • the molecular weight distribution of the polymers from Examples 1 to 3 is shown in FIG. 1.
  • FIG. 2 shows the GPC curves of the polymers from Examples 1 to 3.
  • the polymer of Example 1 corresponds to the curve (1); the polymer of Example 2 corresponds to curve (2); the polymer of Example 3 corresponds to the curve (3)

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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)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé et un dispositif de production de polymères d'oxyméthylène. Le procédé consiste à polymériser un monomère formant des groupes oxyméthylène, éventuellement en présence d'un acétal cyclique, avec un acétal du formaldéhyde et un amorceur de polymérisation cationique, de préférence dans un malaxeur ou une extrudeuse imperméable aux gaz. Le profil de température de la polymérisation est établi, de sorte que le mélange de la polymérisation, qui est d'abord hétérogène du fait que le polymère se décante, entre dans une phase homogène à la fin de la polymérisation. La phase homogène, dans laquelle le polymère se présente sous forme liquide, est stabilisée par l'ajout d'agents de désactivation. Après élimination de composants volatils, des polymères d'oxyméthylène présentant une haute stabilité thermique et de bonnes propriétés mécaniques sont obtenus. Les polymères d'oxyméthylène peuvent être produits par un procédé énergétiquement favorable et leurs propriétés peuvent être ajustées de manière ciblée par spécification du profil de température pendant la polymérisation.
EP09732885A 2008-04-16 2009-04-14 Procédé de production de polymères d'oxyméthylène et dispositif approprié Withdrawn EP2268683A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US4531908P 2008-04-16 2008-04-16
DE102008018966A DE102008018966A1 (de) 2008-04-16 2008-04-16 Verfahren zur Herstellung von Oxymethylen-Polymeren und dafür geeignete Vorrichtung
PCT/EP2009/002713 WO2009127386A1 (fr) 2008-04-16 2009-04-14 Procédé de production de polymères d'oxyméthylène et dispositif approprié

Publications (1)

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EP2268683A1 true EP2268683A1 (fr) 2011-01-05

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Country Status (6)

Country Link
US (1) US8354495B2 (fr)
EP (1) EP2268683A1 (fr)
JP (1) JP5594483B2 (fr)
CN (1) CN102037037B (fr)
DE (1) DE102008018966A1 (fr)
WO (1) WO2009127386A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7902324B2 (en) 2006-09-26 2011-03-08 Ticona Gmbh Initiator
EP2546272A1 (fr) * 2011-07-15 2013-01-16 Ticona GmbH Procédé de production de polymères d'oxyméthylène
US20140182484A1 (en) 2012-12-31 2014-07-03 Ticona Gmbh Process For Producing Polyoxymethylene Polymers With Long-Chain Alkyl End Groups, and Polymers Made Therefrom

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JP5594483B2 (ja) 2014-09-24
JP2011516703A (ja) 2011-05-26
US20090264615A1 (en) 2009-10-22
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