United States Patent
`Neufeld et al.
`
`[19]
`
`IIIIlllllllllllllllllllllllllllllllllllllllllilillllllllllllllilllllllllll!
`US005580948A
`[11] Patent Number:
`5,580,948
`Date of Patent:
`Dec. 3, 1996
`
`[45]
`
`5,081,215
`
`1/1992 Koch et al.
`
`.............................
`
`528/125
`
`FOREIGN PATENT DOCUMENTS
`
`314384
`
`5/1989
`
`European Pa!.
`
`OIT.
`
`Primary Examiner-James 1. Seidleck
`Assistant Examiner-Duc Truong
`Agent, or Firm-Keil & Weinkauf
`Attorney,
`
`[54]
`
`[75J
`
`[73]
`
`[21]
`
`[22]
`
`[30]
`
`Aug.
`
`[51]
`(52]
`
`[58]
`
`[56]
`
`PREPARATION OF POLYARYLENE ETHER
`KETONES
`
`Inventors: Eckhard Neufeld, Limburgerhof;
`Bärbel Arnold-Mauer, Kallstadt;
`Jürgen Hofmann, Ludwigshafen;
`Thomas Heitz,
`Dannstadt-Schauernheim; Christoph
`Sachsenweger, Obrigheim; Petra
`Wieland, Worms, all of Germany
`
`Assignee: RASF Aktiengesellschaft,
`Ludwigshafen, Germany
`
`Appl. No.: 285,120
`Filed:
`Aug. 3, 1994
`Foreign Application Priority Data
`
`Germany
`
`[DE]
`
`10, 1993
`Int. Cl.°
`U.S. Cl. ..........................
`
`..............................
`
`Field of Search .....................................
`
`...-.
`
`..................
`
`43 26 774.2
`C08G 8/02; COBG 14/00
`528/125; 528/126; 528/128;
`528/219; 526/65; $26/66
`528/125, 126.
`528/128, 219; 526/65, 66
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`[57]
`
`is
`
`ABSTRACT
`the preparation of polyarylene etherketones by Friedel-
`For
`Crafts polycondensation,
`reaction mixture consisting of
`a monomer system,
`A.
`a Lewis acid,
`B.
`if required,
`a Lewis base and
`C.
`an inert solvent
`D.
`subjected to polycondensation
`reaction zones,
`in two
`discharged from the second reaction zone with plug flow and
`compounded. The reaction mixture is subjected to polycon-
`reaction zone while stirring
`densation in the
`first
`to
`of aboul 2,000 mPa.s,
`transferred to the second
`viscosity
`is
`reaction zone and is discharged therefrom by means of an
`inerl SolYent or Of an inert gas saluraled with the solvent,
`to 65, preferably from 10 to 25, bar,
`under from about
`the
`transport pressure being reduced in at
`two stages and
`Icast
`the pressure reduction in the first stage being not more than
`60%.
`
`a
`
`6
`
`a
`
`3.791,890
`
`2/1974 Gander
`
`et
`
`al.
`
`............................
`
`260/61
`
`6 Claims, 1 Drawing Sheet
`
`3\
`
`2
`
`D
`
`6
`
`8
`
`D2
`
`D3
`
`EXHIBIT
`
`Page10f5 g
`E 3 -23
`SNF Holding Cornpany et al v BASF Corporation, IPR2015-00600
`
`-
`
`

`
`U.S. Patent
`
`nee. a, 1996
`
`5,580,948
`
`D¡
`
`6
`
`7
`
`8
`
`4
`
`8
`
`D2
`
`Page 2 of 5
`
`D3
`
`

`
`1
`PREPARATION OF POLYARYLENE ETHER
`
`5,580,948
`
`2
`the deficiencies described and in particular permits
`free of
`the reaction mixture without
`transport
`a mechanical
`of
`discharge aid.
`the generic compounds of
`the preparation of
`For
`the
`is achieved by the mea-
`this object
`the preamble of claim 1
`We have found
`that
`invention,
`from a known
`starts
`based on DE-A-38 29 520,
`in which polyarylene
`process
`sures according to the defining clause of claim 1.
`are prepared by electrophilic polycondensa-
`ether ketones
`Suitable components for
`the prepa-
`the novel process
`for
`tion by reacting
`ration of polyarylene ether ketones are those described in
`A. a monomer system comprising
`acid chloride or phosgene 10 DE-A-38 29 520. The polycondensation,
`is carried out
`(a) an aromatic dicarboxylic
`too,
`and an essentially equimolar amount of a polynuclear
`in the manner described there.
`aromatic which contains two hydrogen atoms
`replace-
`A. Preferred monomer systems A are;
`able by clectrophilic
`substitution or
`al) terephthaloyl
`chloride and 4,4'-diphenoxybenzophe-
`a polynuclear aromatic carboxylic acid chloride which
`none, which leads to a polyarylene ether ketone having the
`has one hydrogen atom replaceable by electrophilic
`structure
`substitution and is capable of autocondensation and
`
`5
`
`is
`
`(b)
`
`-
`
`0-
`
`Co
`
`o
`
`co
`
`co-
`
`(c)
`
`if required, amonofunctional reagent for blocking the
`terminal groups,
`a Lewis
`in an amount of
`one mol
`least
`acid
`per
`at
`nucleophilic group in the reaction mixture and in addition
`a small excess which is sufficient
`to catalyze the reaction,
`if required, a Lewis base in an amount of
`from 0.01 to 4
`mol per mol of acid groups and
`D. a solvent which is inert under the æaction conditions
`
`B.
`
`C.
`
`*
`
`30
`
`terephthaloyl
`a2)
`which leads to
`
`chloride
`
`and 4,4'-diphenoxybenzene,
`
`-
`
`o
`
`o -
`
`co
`
`co-
`
`chloride and 1,4-bis(phenoxybenzoyl-
`terephthaloyl
`a3)
`)benzene, which leads to
`
`o-
`
`Co-
`
`Co-
`
`o-
`
`Co-
`
`Co-.
`
`in the presence of
`catalyst The polycon-
`a Friedel-Crafts
`in two reaction zones, mixing of
`densation is carried out
`the
`liquid and solid reaction components and prepolymerization
`reaction zone in a stirred kettle.
`being effected
`in the first
`The reaction mixture is
`transported by means of gas pressure
`into and, with plug flow,
`through the second reaction zone,
`allowed to undergo complete polycondensation,
`discharged 45
`via a screw unit and compounded. The prob-
`continuously
`is ensuring uniform product discharge
`lem here, however,
`from the second reaction zone. Transport by means of gas
`in a reduction in the amount of solvent
`pressum may result
`in the polymer surface at the interface with the gas phase,
`ie.
`the polymer surface
`out. This leads
`dries
`to excessive
`layer
`adhesion of
`the wall, and the surface
`the surface
`to
`a vortex, which is very undesirable since
`it causes
`forms
`the products. Obstacles to flow in the lower
`deposits
`of
`the æaction zone and corresponding linings of
`region of
`the
`it possible to avoid this phenomenon 55
`reaction zone make
`only to a limited extent. The transport of
`the polycondensate
`the second reaction zone is also unsatisfactory. The
`out of
`screw unit provided for
`this purpose, whose product-con-
`parts must be provided with an antiadhesion coatin8
`veying
`since otherwise the reaction mixture cannot be transported, o
`has proved to be very susceptible to faults. The approach of
`the screw unit
`filled screw is particularly
`in the case of
`problematic owing to the high energy
`dissipation, which
`may lead to thermal damage to the product
`in the case of
`nondecomplexed polyarylene ether ketone.
`It is an object of
`the present invention to provide a process
`the preparation of polyarylene
`ether ketones which is
`
`acid chloride and the poly-
`The aromatic dicarboxylic
`40 OUCleaf BTOmatic are used in essentially equimolar amounts,
`deviations being possible in order
`to regulate the
`small
`molecular weight.
`b) The autopolycondensation
`ride leads to
`
`of p-phenoxybenzoyl
`
`chlo-
`
`so
`
`6s
`
`o
`
`co-
`
`c) Monofunctional reagents for chain termination are,
`for
`example, benzoyl chloride and phenoxybenzophenone.
`important
`They are particularly
`in the polycondensation
`the monomers b)
`regulation of
`the molecular weight;
`for
`of
`they are also used for stabilizing the polymers in the melt.
`in amounts of
`from 1
`They are employed in general
`to 10%,
`based on the monomers a) or b).
`B) A preferred Lewis acid is aluminum chloride, but alumi-
`num bromide, antimony pentachloride, boron trifluoride,
`titanium tetrachloride
`iron(III) chloride,
`zinc chloride,
`and tin(II) chloride are also suitable. They are used in an
`least one mol per nucleophilic
`amount of at
`group in the
`reaction mixture, it being necessary
`to use a small excess
`which is sullicient to catalyze the polycondensation reac-
`tion.
`
`Page 3 of 5
`
`a
`
`for
`
`

`
`5,580,948
`
`5
`
`10
`
`15
`
`20
`
`-30°
`
`3
`C) The reaction mixture preferably contains a Lewis base,
`for example an alkali metal halide, such as LiCl or NaCl,
`as well
`as polar organic compounds,
`such as N-meth-
`ylpyrrolidone, N,N-dimethylformamide, l-methyl-2-pyr-
`tetrameth-
`rolidone, dimethyl sulfone, diphenyl sulfone,
`sulfone (sulfolane),
`dimethyl
`imidazolc,
`ylene
`sulfide,
`benzophenone and trimethylamine. LiCl and dimethyl
`sulfone are preferred. They are used in amounts of
`from
`0.01 to 4 mol per mol of acid groups.
`D) Suitable inert solvents
`are methylene chloride, o-dichlo-
`1,2,4-trichlorobenzenc,
`1,2-dichlorcethane
`robenzene,
`and 1,1,2,2-tetrachloroethane.
`The polycondensation is usually carried out at from--70°
`to +150° C. Advantageously,
`reaction
`it is started in the first
`low temperatures,
`for example from -50°
`zone at
`to -10°
`C.,
`and the temperature is
`then allowed to increase to,
`for
`to +30° C. The total
`example,
`reaction should be
`carried out at
`least under superatmospheric pressure,
`advan-
`in particular
`from 2 to 10, bar,
`in order
`tageously abovc 1.1,
`to prevent escape
`the hydrogen chloride formed and
`of
`hence foaming. This should also be borne in mind in the
`reaction zone. To
`first
`to the second
`passage
`from the
`from the stirred preliminary reactor
`transfer the prepolymer
`it is advantageous to set
`to the subsequent reactor,
`a higher
`pressure in the preliminary reactor
`than in the subsequent
`It may be useful slightly to reduce the pressure in the
`reactor.
`subsequent reactor during introduction
`into
`of prepolymer
`the pressure should not be reduced to
`said reactor. However,
`the reaction material
`such an extent
`that
`foams.
`Mixing of
`the liquid and solid reaction components and
`prepolymerization
`are carried out
`reaction zone
`in the first
`while stirring, advantageously
`in a cooled stirred kettle
`which advantageously consists
`of a corrosion-rcsistant
`alloy,
`eg. Hastelloy. The initial value of
`the viscosity is about 0.5
`mPa.s. Polycondensation is carried out
`reaction 35
`in the first
`zone until the viscosity
`has increased to 20-2,000, prefer-
`In the case of
`the polycondensation of
`ably 50-200, mPa.s.
`chloride with diphenoxybenzophenone,
`terephthaloyl
`this
`takes from about 15 to 25 minutes from the addition of
`the
`fmal monomer.
`The prepolymer
`then introduced directly into the sec-
`is
`ond reaction zone. This is effected
`by gravitational
`force or
`pressure from an inert gas. The viscosity
`during transfer
`of
`to the subsequent reactor should be sufH-
`the prepolymer
`the aluminum chlotide from settling 45
`ciently high to prevent
`in the subsequent reactor, since otherwise a high molecu-
`out
`lar weight polyether
`ketone is not
`formed. However,
`it
`should still be sufEciently low to permit complete transfer
`of
`the prepolymer
`to the subsequent reactor.
`The second reaction zone consists
`of a tube reactor which so
`can be fed via one or more stirred kettles. A tube reactor
`the novel process
`suitable for
`is shown schematically in the
`It comprises essentially a vertical
`drawing.
`tube element (1)
`which has a cylindrical cross-section and whose inner lateral
`surface is coated or lined with an antiadhesive material
`inert
`to the reaction mixture,
`for example with polytetrafluoroet-
`hylene. The tube element has a height/diameter
`ratio of
`from
`the reaction mixture and for a
`6 to 15. Feeds (2) and (3)
`for
`inert gas or
`inert gas/solvent mixture for
`solvent
`and an
`the reaction mixture are provided at
`forcing out
`the
`the top of
`tube element. The lower end of
`the tube element
`is conically
`inclination of <45°, preferably from 5°
`tapered,
`angles of
`to
`28° C. having proven useful. The diameter D2 is dependent
`in general
`on the mass flow of
`the reaction mixture and is
`more than 50 mm. An advantageously right angled outflow 65
`pipe (4) which is likewise tapered at
`its free end and has a
`shutoff element
`(5) directly before the taper is connected to
`
`25
`
`30
`
`40
`
`55
`
`60
`
`4
`(6, 7) denote means for
`radioactive level measure-
`the cone.
`ment and (8) denotes connections for
`further
`inert
`feeding a
`gas stream which is generally saturated with an inert solvent
`The reaction mixture introduced into the tube
`reactor
`during a residence time of
`therein completely
`condenses
`6 hours. Furthermore, an inert solvent
`from about 4 to about
`or an incit gas,
`in particular nitrogen, which is saturated with
`is passed into the second reaction zone, and
`the inett solvent,
`the now gel-like polyarylene ether ketone is discharged from
`the second reaction zone with plug flow under the action of
`the solvent and/or of
`the inert gas. The solvent or
`inert gas
`from about 6 to 65, preferably from 10 to 25, bar.
`pressure is
`During the discharge of
`the polyarylene ether ketone,
`the
`reduced in at
`transport pressure is
`two stages,
`least
`the
`reduction in the first
`ie. up to the transition
`pressure
`stage,
`from the cone to the outflow pipe, being not more than 60%,
`it is sufficient
`preferably up to 20%.
`In the simplcst case,
`for
`this purpose appropriately
`to establish the
`ratio of
`the
`diameters D, and D2 and,
`the further pressure stage,
`for
`the
`In general, a ratio of diameters Di:D, of
`diameter Ds.
`from
`2:1 to 20:1 has proven particularly
`advantageous. The pol-
`yarylene ether ketone is subsequently compounded in a
`for example in a mill.
`working up unit,
`By transporting the polyarylene ether ketone with the aid
`of an inert solvent
`it
`or of a solvent-saturated inert gas,
`is
`to avoid vortex
`possible completely
`formation
`the
`and
`second reaction zone is free of product residue which would
`have to be removed by an expensive procedure or would
`lead to impuritics in subsequent product batches. The uni-
`form product quality,
`in particular with regard to the degree
`of polymerization,
`is especially noteworthy.
`advantageous embodiment of
`the novel
`In a particularly
`the inert solvent passed
`into the second reaction
`process,
`zone is metered in an amount such that
`the
`the surface
`of
`reaction mixture is completely covered with solvent, and the
`reaction mixture is discharged by means
`of an inert gas
`under a gas pressure from about 6 to 65, preferably from 10
`it possible to reduce the apparatus
`to 25, bar. This makes
`required for carrying out
`the process and for corresponding
`safety measures.
`According to a further
`an inert
`the invention,
`of
`feature
`into the reaction mixture in the
`is passed countercurrent
`gas
`reaction zone. This feed
`inert
`second
`of
`effected
`gas
`is
`immediately after
`the reaction mixture from
`the transfer of
`in an additional mixing
`reaction zone and results
`the first
`the precondensate can be transferred earlier
`effect,
`so that
`and with a substantially lower viscosity,
`for example about
`from the first
`to the second reaction zone, and a
`100 mPa.s,
`In general,
`considerable reduction in the excess catalyst.
`the
`inert
`is saturated with the inert solvent used
`in the
`gas
`reactionofthecomponentsinthefirstreactionzone.Forthis
`purpose,
`the inert gas
`is passed through a solvent bath at a
`corresponding pressure and at a temperature which is at least
`the reaction mixture in the second
`close to the temperature of
`reaction zone. The inert gas absorbs
`solvent
`in an amount
`corresponding to its saturation vapor pressure.
`The Example which follows
`illustrates the process:
`In a 20 1 pressure-resistant
`(24.62 mol) of
`vessel, 3,283 g
`aluminum chloride were suspended in 5,212 ml of methyl-
`ene chloride and cooled to below 0° C. 63537 g
`(6.75 mol)
`of dimethyl sulfone,
`(4.5 mol) of
`913.61 g
`terephthaloyl
`(0.18 mol) of benzyl chloride were
`chloride and 25.30 g
`added in succession while cooling. The mixture is cooled to
`<-10° C. after which 1,681.85 g
`(4.59 mol) of 4,4-diphe-
`noxybenzophenone were also metered in. The vessel was
`it was gas-tight, and nitrogen under about 10
`closed so that
`the pressure. With slow
`in to maintain
`bar was
`forced
`
`Page 4 of 5
`
`

`
`5,580,948
`
`(b)
`
`s
`
`B.
`
`for blocking
`
`from 0.01 to
`
`6
`5
`the reaction mixture increased to
`a polynuclear
`chloride
`carboxylic
`aromatic
`heating,
`acid
`of
`the viscosity
`which has one hydrogen atom replaceable by elec-
`about 2,000 mPa.s in the comme of about 15 to 20 minutes.
`The temperature was then about 20° C. and the volume of
`trophilic substitution and is capable of autoconden-
`the precondensate was about 9,000 ml. By means
`sation
`and
`the
`of
`a monofunctional reagent
`(c) optionally,
`applied nitrogen pressure,
`the reaction mixture could be
`the terminal groups,
`discharged in the course of 2 minutes through the bottom
`a Lewis acid in an amount of at
`least one mol per
`and transferred to a pressure-resistant
`outlet valve
`subse-
`reaction mixture and
`group in
`nucleophilic
`quent reactor coated on the inside with FI'FE.
`in
`the
`addition a small excess which is sufEcient
`to catalyze
`The diameter D, of
`the subsequent reactor was 130 mm,
`the reaction,
`the cylindrical part was 800 mm and the angle 10
`the length of
`the cone was 10°. The outflow of
`C. optionally,
`a Lewis base in an amount of
`the subsequent reactor
`of
`had a diameter D, of 50 mm. Before the mill,
`4 mol per mol of acid groups and
`the outflow
`pipe, which had a length of about 500 mm, was reduced to
`a solvent which is inert under the reaction conditions
`D.
`taper of 10°. All
`a diameter Da of 20 mm with an angle of
`is subjected to polycondensation
`reaction zone
`in a
`first
`the subsequent reactor were 15 while stirring to a viscosity of about 2,000 mPa.s,
`product-conveying
`surfaces
`of
`is trans-
`coated with PTFE-
`ported into and through a
`reaction zone,
`vertical
`second
`transfer of
`the reaction mixture to the
`60 minutes after
`allowed to undergo complete polycondensation
`and dis-
`reactor, 300 ml of methylene
`chloride were
`subsequent
`charged from said reaction zone with plug flow, wherein,
`added to the reaction mixture. The subsequent reactor was
`the reaction mixture to the second reaction
`transfer of
`after
`operated in such a way that, after aresidence time of 5 hours,
`zone, an inert solvent
`or an inert gas saturated with the inert
`reaction mixture was discharged in the course of 45
`the total
`solvent
`is passed into said reaction zone and the reaction
`minutes with the aid of an inert gas stream at 10 bar via a
`mixture is discharged by means of
`the solvent or
`inert gas
`mill. The temperature in the subsequent reactor was 25
`under from about 6 to 65 bar,
`the transport pressure being
`C-
`and the pressure after
`the first pressure stage was about9 bar-
`reduced in at
`two stages and the pressure reduction in
`least
`The discharged reaction material was worked up using a
`stage being not more than 60%.
`the first
`hammer mill, 200 l/h of water being sprayed
`in to hydrolyze
`as defined in claim 1, wherein the inert
`2. A process
`the polymer/aluminumchloride complex. At athroughput of
`solvent passed into the second reaction zone is metered in an
`about 3.0 kg of polymer per hour, the power consumption of
`amount such
`the reaction mixture is
`that
`surface
`of
`the
`the mill was 1.0 kW.
`completely covered with solvent,
`and the reaction mixture is
`The polymer was then freed
`from catalyst
`by
`residues
`discharged by means of an inert gas under a gas pressure of
`repeated extraction with water and was dried under atmo-
`from about 6 to 65 bar.
`spheric pressure at 290° C-
`as defined in claim 1, wherein the reaction
`3. A process
`The polymer obtained bad an intrinsic viscosity
`mixture is
`of 1.07
`transported through the
`reaction zone
`second
`(measured in concentrated sulfuric
`acid, 0.5/100 ml).
`Its
`under from 10 to 25 bar.
`melting point was 375° C.
`as defined in claim 1, wherein an inert gas
`4. A process
`is
`We claim:
`into the reaction mixture in the second
`passed countercurrent
`the preparation of a polyarylene ether
`for
`1. A process
`reaction zone,
`ketone by Friedel-Crafts polycondensation,
`in which a reac-
`as defmed in claim 4, wherein the inert gas
`5. A process
`tion mixture consisting of
`is saturated with the inert solvent stated in claim 1 under D.
`as defined in claim 2, wherein the reaction
`A. a monomer system comprising
`6. A process
`(a) an aromatic dicarboxylic acid chloride or phosgene
`mixture is
`transported through the second reaction zone
`an essentially equimolar amount of
`a poly-
`under from 10 to 25 bar.
`and
`nuclear aromatic which
`contains
`two hydrogen
`replaceable by electrophilic
`substitution or
`atoms
`
`20
`
`25
`
`30
`
`35
`
`*
`
`*
`
`*
`
`*
`
`*
`
`*
`
`Page 5 of 5