FILE HISTORY
`US 5,580,948
`
`5,580,948
`PATENT:
`1NVENTORS: Neufeld, Eckhard
`Arnold Mauer, Barbel
`Hofmann, Jurgen
`Heitz, Thomas
`Sachsenweger,
`Wieland, Petra
`
`Christoph
`
`TITLE:
`
`Preparation of polyarylene ether ketones
`
`APPLICATION US1994285120A
`NO:
`03AUG 1994
`FILED:
`1SSUED:
`03 DEC 1996
`
`COMPILED:
`
`08 DEC 2014
`
`SNF Holding Company et al v BASF Corporation,
`
`Page 1 of 145
`IPR2015-00600
`
`EXHIBIT
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`S->Ÿ -
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`IAI
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`PATENT
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`DATED
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`A E
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`1
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`5580948
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`STATE OR SHEETS
`COUNTRY
`DRWGS
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`TOTA1.
`CLAIMS
`
`INDEP.
`CLAIMS
`
`FiLING FEE
`ARCEIVED
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`ATTONNEY
`DOCKETNO
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`S
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`--
`
`U.S DEPT, of COMM.-Pat.
`
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`TM ONice-PTO-436L
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`TS OF APPLICATION
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`Assislant E×arpiner
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`xaminer
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`ClaimsCLAIMS
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`ALP
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`Total
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`Cam
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`.
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`DRAWING
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`Slieels Drwg
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`Theinformation
`the United States Code
`by
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`Patent
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`Page 2 of 145
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`
`5,580,948
`
`PREPARATION OF POLYARYLENE ETHER KETONES
`
`TransactionHistory
`
`in GAU
`
`Transaction Description
`Preliminary Amendment
`Notice Mailed--Application Incomplete--Filing Date Assigned
`Information Disclosure Statement (IDS) Filed
`Information Disclosure Statement (IDS) Filed
`Application Is Now Complete
`Application Captured on Microfilm
`Case Docketed to Examiner in GAU
`Non-Final Rejection
`Mail Non-Final Rejection
`Response after Non-Final Action
`Date Forwarded to Examiner
`Case Docketed to Examiner
`Final Rejection
`Mail Final Rejection (PTOL - 326)
`Notice of Appeal Filed
`Appeal Brief Filed
`for Extension of Time - Granted
`Request
`Date Forwarded to Examiner
`Mail Notice of Allowance
`Notice of Allowance Data Verification Completed
`Issue Fee Payment Verified
`Information Disclosure Statement (IDS) Filed
`Information Disclosure Statement (IDS) Filed
`Request for Foreign Priority (Priority Papers May Be Included)
`Mail Acknowledgement
`of Priority Papers
`Priority Paper Acknowledgement
`Mailroom Date of Drawing(s)
`Drawing(s) Received at Publications
`Drawing(s) Matched to Application
`Drawing(s) Processing Completed
`Issue Notification Mailed
`Recordation of Patent Grant Mailed
`
`Date
`08-03-1994
`09-07-1994
`10-11-1994
`10-11-1994
`12-06-1994
`01-03-1995
`01-13-1995
`01-20-1995
`01-27-1995
`04-28-1995
`05-17-1995
`05-17-1995
`07-24-1995
`08-03-1995
`11-06-1995
`03-07-1996
`03-07-1996
`03-20-1996
`05-31-1996
`05-31-1996
`06-03-1996
`06-20-1996
`06-20-1996
`07-31-1996
`08-15-1996
`08-15-1996
`09-03-1996
`09-10-1996
`09-13-1996
`09-20-1996
`10-29-1996
`12-03-1996
`
`Page 3 of 145
`
`

`
`285120
`
`.
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`Date
`Entered
`Counted
`
`PATENT APPLICATION .
`MillMllilil
`
`08285120
`
`|
`
`CONTENTS
`
`1. Ap
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`cati
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`papers.
`
`APPROVED FOR LICEÑSE
`
`INITIALS
`
`Date
`.cey.
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`UP150
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`RECEl
`JNO9
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`Y
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`Û
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`32.
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`pygg
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`03 Mb
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`DEC
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`Page 5 of 145
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`POSITION
`CLASSIFIER
`EXAMINER
`- TYPIST
`VERIFIER
`CORPS CORR.
`SPEC. HAND
`FILE MAINT.
`DRAFTING
`
`INDEXOF CLAIMS
`
`Cd
`
`Date
`
`Claim
`
`Date
`
`20
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`23
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`I
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`27
`
`4
`
`36
`
`37
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`Page 6 of 145
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`

`
`ARCHED
`
`Class
`
`Sub.
`
`Date
`
`Exmr.
`
`I
`
`SEARCH NOTES
`
`Date
`
`Exmr.
`
`INTERFERENCE SEARCHED
`Exmr.
`Sub.
`Date
`Class
`
`'
`
`(RIGHT OUTslDE)
`
`Page 7 of 145
`
`

`
`=>
`s
`thodB)
`
`L1
`(PR
`
`=>
`
`s
`
`L2
`
`or polyaryleneatherketonen) and
`
`(procementi
`
`or me
`
`(polyary1ene ether ketonen
`1259 POLYARYLENE
`1G2150 ETHER
`86480 KETONEN
`24 POLYARYLENE ETHER KETONEN
`(POLYARYLENEXW)ETHER(W)KETOHEM)
`& POLYARYLENEETHERKETONEN
`871691
`PROCESSHH
`953520 METHODM
`(90LYARYLEHE ETHER KETONEN
`30
`
`OR POLYARYLENEETHERK€TONEN)
`
`:
`
`AMD
`
`OCESSON OR METHODM)
`11 and polycondensation
`19068 POLYCOHDENSATION
`3 L1 ANÖ PDLYCONDENSATION
`
`=>
`
`d
`
`12 1-3
`1994, Po-ly(arylene other ketone),
`5,290,986, Mar.
`__Ilf.etmis_.
`1,
`EDT
`1.
`use; Shunichi Matsumura, et a.l.,
`$28/125,
`428/357,
`pÞoducing
`and its
`same
`411.1; 525/390,
`AVAILABLE3
`534; 528/126,
`220 EIMAGE
`174,
`175,
`394,
`364,
`1993, Polyary1ene others; Rudolf Pfaendner, et
`5,.212,278,
`16,
`2.
`May
`528/171; $25/390,
`334; 528/125,
`219,
`826,
`128,
`174,
`220,
`175,
`126,
`al.,
`391 CIMAGE AVAILABLE]
`5,881,215,
`Jan.
`3.
`et al.,
`Juergen Koch,
`AVAILABLE]
`
`1992., Preparation of
`golYALY.leneatherketone±
`LA,
`î28,
`66; $28/126,
`$26/66,
`328/125;
`219 CIMAGE
`
`;
`
`s 12 and chloriden
`257373 CHLORIDEN
`L2 AND CHLORIDEN
`acidh
`s 13 and lewis
`LEWIS
`19467
`ACIDA
`358272
`LEWIS ACIDH
`13606
`(L¶WIS(W)ACIDU)
`2 L3 AND LEWIS ACIDS
`14 and solventH and inert-
`275630 SQLVENTH
`INERT ,,
`177518
`2 L4 AND SOLVEHTi
`
`3
`
`>
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`L3
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`=>
`
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`'
`
`s
`
`AND
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`INERT
`
`,
`
`=>
`
`d
`
`15 1-2
`for
`1994, Poly(arylene ether ketone)9
`5,290,986, Mar.
`-2CERS.S.1-
`1.
`use; Shunichi Matsumura,
`588/125;
`producing
`et
`al.,
`and itä
`same
`411.1; 525/390,
`220 EIMAGE AVAILABLELI
`534¡ 52ß/126,
`174,
`175,
`394,
`364,
`gggyg gleneetherketones ;
`1992, Preparation of
`5,0ß1,215,
`Jan.
`14,
`2.
`$26/66,
`66; $28/186,
`219s.CIMAGE
`et
`528/125;
`128,
`Juergen Koch,
`al-,
`AVAILABLE3
`
`.1,
`
`.408/357,
`
`Page8of145
`
`

`
`United States Patent
`Neufeld et al.
`
`(19]
`
`[54] PREPARATION OF POLYARYLENE ETHER
`KETONES
`
`[75]
`
`[73]
`
`[21]
`
`(22]
`
`130]
`
`Aug.
`
`[51]
`[52]
`
`[58]
`
`[56]
`
`Inventors: Eckhard Neufeld, Limburgerhof;
`Blirbel Arnald-Mauer, Kallstadt;
`Jilrgen Bonnann, Ludwigshafen;
`Thomas Belta
`Dannstadt-Schauemheim; Christoph
`Sachsenweger, Obrigheim; Petra
`Wieland, Worms, all of Germany
`Assignee(cid:127) BASF Aktiengeseuschaft.
`Ludwigshafen, Germany
`
`Appl. No.: 285,120
`Filed
`Aug. 3, 1994
`Foreign Application Priority Data
`........................ 43 26 774.2
`Germany
`1993
`[DE)
`COSG 8/02; CO8G 14/00
`..................-..... 528/125; 528/126; 528/128;
`5281219; 526165; 526166
`528/125, 126.
`528/128, 219; 526/65, 66
`
`10,
`
`Int. CL6
`U.S. Cl.
`
`.............................
`
`Field of Search .----.................
`
`References Cited
`
`IllllHIllllllEERilllllilliMIEll!
`US005580948A
`5,580,948
`Patent Number:
`[45] Date of Patent:
`Dec. 3, 1996
`
`(11]
`
`5,081,215
`
`1/1992 Koch et al.
`
`...............
`
`........ 528/125
`FOREIGN PATENT DOCUMENTS
`314384
`5/1989
`
`.
`
`Ï57]
`
`a
`
`and
`
`Buropean Pat. Off.
`Primary Eraminer-James J. Seidleck
`Assistant Ermniner-Duc Tiuong
`Anomey, Agent, or Firm-Keil & Weinkauf
`ABSTRACT
`the preparation of polyarylene ether ketones by Friedel-
`For
`Crafts polycondensation,
`a reaction mixture consisting of
`a monomer system,
`A.
`a Lewis acid,
`B.
`lawis base
`If required,
`C.
`an incrt solvent
`D.
`is subjected to polycondensation
`in two reaction zones,
`discharged from the second reaction zone with plug flow and
`compounded. The teaction mixture is subjected to polycon-
`densation in
`reaction zonc while stirring to a
`first
`the
`viscosity of about 2,000 mPa.s, is
`transferred to the second
`reaction zone and is discharged therefrom by means of an
`inen solvent or of an inert Bas sammted with the solvent,
`under from about 6
`to 65, preferably from 10 to 25, bar,
`the
`transport pressure being reduced in at
`two stages
`least
`and
`the pressure reducdon in the first stage being not more than
`60%.
`
`DOCUMENTS
`U.S. PATEFTT
`3,791,890 2/1974 Gander et al.
`
`-.....-..............
`
`260/61
`
`6 Claims,
`
`1 Drawing Sheet
`
`D¡
`
`3
`
`6
`
`7
`
`8
`
`D2
`
`Page 9 of 145
`
`

`
`U.S. Patent
`
`Dec. 3, 1996
`
`5,580,948
`
`D¡
`
`6
`
`7
`
`8
`
`8
`
`D2
`
`Page 10 of 145
`
`

`
`5,580,948
`
`1
`PREPARATION OF POLYARYLENE ETHER
`
`2
`free of the deliciencies described and in particular permits
`transpon of
`the reaction mixture without
`a mechanical
`discharge aid,
`the preparation of
`For
`the generic compounds of
`the
`invention,
`the preamble of claim 1
`We have found that this object
`from a known
`is achieved by the mea-
`stans
`based on DE-A-38 29 520,
`in which polyarylene
`process
`according to the defming clause of claim 1.
`sures
`cther ketones are prepared by electrophilic polycondensa-
`Suitable components for the novel process
`for the prepa-
`tion by reacting
`ration of polyasylene other ketones are
`a monomer system comprising
`A.
`thosc described in
`(a) an aromatic dicarboxylic
`acid chloride or phosgene lo DE-A-38 29 520. The polycandensation,
`too, is carried out
`and an essentially equimolar amount of
`a polynuclear
`in the manner described there.
`aromatic which comains two hydrogen atoms replace
`A. Prefened monomer systems A are:
`able by electrophilic substitution or
`al) terephthaloyl chloride and 4,4'-diphenoxybenzophe-
`(b) a polynuclear aromatic carboxylic acid chloride which
`cone, which leads to a polyarylene ether ketone having the
`one hydrogen atom replaceable by electrophilic
`has
`substitution and is capable of autocondensation and
`structure
`
`s
`
`15
`
`o
`
`co
`
`0-
`
`CO
`
`Co-
`
`(c)
`
`B.
`
`C.
`
`D.
`
`if required,
`a monofunctional
`terminal groups,
`a Lewis acid
`in an ammmt of
`one mol
`least
`per
`at
`nucleophilic group in the reaction mixture and in addition
`a small excess which is sußicient
`to catalyze the reaction,
`if required, a Lewis base in an amount of from0.01 to 4
`mol per mal of acid groups and
`a solvent which is
`inert HEder
`
`reagent for blocking the
`
`the reaction conditions
`
`a2)
`
`terephthaloy! chloride and 4,4'-diphenoxybenzene,
`which leads to
`
`\
`
`/
`
`~
`
`o
`
`\
`
`/
`
`¯
`
`o
`
`/
`
`-
`
`\ œ /
`
`\
`
`¯
`
`co-
`
`a3)
`
`terephthaloyl chloride and
`)benzene, which leads to
`
`l,4-bis(phenoxybenmyl-
`
`o
`
`co
`
`co
`
`o -
`
`Co
`
`co-,
`
`in the presence of
`a Friedel-Crafts catalyst The polycon-
`in two reaction zones, mixing of the '
`densation is carried out
`liquid and solid reaction components and prepolymerization
`being effected in the first
`Icaction zone in a stirred kettle.
`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
`condnuously via a screw unit and compounded. The prob-
`lem here, however,
`is ensuring uniform product discharge
`from the second reacdon zone. Transport by means of gas
`pressure may tesult
`in a reduction in the amount of solvent
`in the polymer surface at the interface with the gas phase,
`ie.
`the polymer
`surface dries
`out. This leads
`to excessive
`adhesion of
`the surface layer
`the wall, and the surface
`to
`forms a vortex, which is very undesirable since
`it causes
`O
`
`go
`
`ze
`
`e
`
`f
`reaction zone make it possible to avoid this phenomenon 55
`only to alimited extent. The transport of the polycondensate
`out of
`the accond reacdon zone is also unsatisfactory. The
`screw unit provided for this purpose, whose product-con-
`veying parts must be provided with an antiadhesion coatin8
`ym
`i
`the screw unit
`in the case of
`filled scmw is particularly
`problematic owing to the high onergy dissipation, which
`may Icad to thermal damage to the product
`in the case of
`nondecomplexed polyarylene other kelanc.
`lt is an object of thepresent invention to provide aprocess
`the preparation of polyarylene ether ketones which is
`
`e
`
`a
`
`f
`
`as
`
`for
`
`The aromatic dicarboxylic
`acid chloride and the poly-
`nuclear aromatic alt used in essentially equimolar amounts,
`small deviations being
`possible in order
`to regulate the
`molecular weight.
`b) The autopolycondensation of p-phenoxybenzoy! chlo-
`ride leads to
`
`o
`
`co-
`
`c) Monofunctional
`(CimülatlOR Sft, f0r
`reagcEIS f0T CllaiD
`example, benzoyl chloride and phenoxybenzophenone.
`They are particularly important
`in the polycondensation
`of the monomers b)
`regulation of the molecular weight;
`for
`they are also used for stabilizing the polymers in
`the melt.
`They are employed in general in amounts of from 1
`to 10%,
`based on the monomers a) or b).
`B) A preferred Lewis acid is aluminum chloride, but alumi-
`num bromide, antanony pentachloride, boron trinuoride,
`iron(III) chloride,
`zinc chloride,
`titanium tetrachloride
`and tin(II) chloride are also suitable. They are used in an
`amount of at
`one mol per nucleophilic group in the
`Icast
`reaction mixture,
`It being necessary to use a small excess
`which is sufEcient to catalyze the polycondensation reao-
`tion.
`
`Page 11 of 145
`
`

`
`3
`It.wis base,
`C) 111e reaction mixture preferably contains a
`for example an alkali metal halide, such as LiCI or NaCl,
`as well
`as polar organic compounds,
`as N-meth-
`such
`ylpyrrolidone, N,N-dimethylformamide,
`1-methyl-2-pyr-
`rolidone, dimethyl sulfonc, diphenyl sulfone, tetrameth-
`ylene sulfone (sulfolane), dimethyl sulfide,
`imidazole,
`benzophenonc and trimethylamine.
`LiCl
`and dimethyl
`sulfone are prefened. They are used in amoums of from
`0.01 to 4 mol per mol of acid groups,
`D) Suitable incrt solvents are methylene chloride, o-dichla.
`robenzene,
`1,2,4-trichlorobenzenc,
`1,2-dichloroethanc
`and 1,l,2,2-tetrachlornethane.
`out at from-70*
`The polycondensation is usually carried
`to +150* C. Advantageously,
`it
`is started in the first scaction
`zoneatlow temperatnæs,forexamplefrom-50°to-10°C.,
`the temperature is
`then allowed to
`increase to,
`and
`for
`to +30° C. The
`example,
`total
`reaclion should be
`carried out at
`least under superatmospheric pressure, advan-
`tageously above 1.1,
`in particular from 2
`in order
`to 10, bar,
`to prevent escape of
`the hydrogen chloride formed and
`hence foaming. This should also be borne in mind in the
`from the first
`to the second reaction zone.
`passage
`To
`trEnsfer the prepolymer from the stirred preliminary reactor
`to the subsequent reactor, it
`is advantageous to set
`a higher
`pressure in the preliminary reactor than in the subsequent
`reactor.It may be useful slightly to reduce the pressure in the
`subsequent reactor during imroduction of prepolymer
`into
`said reactor. However, the pressure should not be n:duced to
`such an extent that the reaction material
`foams.
`Mixing of the liquid and solid reaction components and
`prepolymerization are carried out in the first
`reaction zone
`while stirring, advantageously in a cooled stirred
`kettic
`which advantageously consists of acorrosion-resistant alloy,
`eg. Hastelloy. The inilial value of the viscosity is about 0.5
`mPa.s. Polyccadensation is carried out
`reaction 35
`in the first
`zone until
`the viscosity has
`increased to 2O2,000, prefer-
`ably 50-200, mPa.s. In the case of the polycondensation of
`terephthaloyl chloride with diphenoxybenzophenone,
`this
`takes from about 15
`to 25 minutes from the addition of the
`final monomer.
`The prepolymer
`then introduced directly into the sec-
`ond reaction zone. This
`is effected by gmvitational
`force or
`pressure from an inert gas. The viscosity during transfer of
`the prepolymer
`to the subsequent reactor should be sufli-
`ciently high to prevent the aluminum chloride from settling
`out in the subsequent reactor, since otherwise ahigh molecu-
`Iar weight polyether ketone is
`formed. However,
`not
`it
`should still be sufliciently low to permh complete transfer of
`the prepolymer
`to the subsequent reactor.
`ne second reacdon zone consists of a tube reactor which so
`fed via one or more stirred
`kettles. A tube reactor
`can be
`suitable for the novel process
`is shown schematically in the
`drawing.
`It comprises essentially a vertical tube element (1)
`which has
`a cylindrical cross-secdon and whose inner lateral
`surfaceis coated or lined with an andadhesive material inert
`to the reaction mixtme,
`far example with polytetraffuaract-
`hylene.Re tube elemem has
`a height/diameter ratio of from
`to 15. Feeds (2) and (3)
`for the reaction mixture and for a
`solvent and an
`inert gas
`inert gas/solvent mixture for
`or
`forcing out the reaction mixture are provided at the top of the 60
`tube element The lower end of the tube element is conically
`tapered, angles of inclination of<45°, preferably from 5°
`to
`28* C. having proven usefut ne diameter D2 is dependent
`flow of the reaction mixture and is
`on the mass
`in gencral
`more than 50 mm. An advantageously right angled omflow 6s
`pipe (4) which is
`likewise tapered at
`free end and
`its
`has
`shutoffelement(5)directlybeforethetaperisconnectedto
`
`-30°
`
`is
`
`6
`
`a
`
`5,580,948
`
`5
`
`In
`
`15
`
`20
`
`25
`
`so
`
`40
`
`45
`
`55
`
`)
`
`is
`
`4
`(6, 7) denote means for radioactive level measure-
`the cone.
`further inert
`ment and (8) denotes connections for
`feeding a
`gas stream which is generally saturated with an inert solvenL
`reaction mixture introduced into the tube reactor
`The
`condenses therein completely during a
`residence time of
`from about 4
`to about 6 hours. Furthermore, an inert solvent
`or an inert gas,
`in particular nitrogen, which is saturated with
`the inert solvent.is passed imo the second reaction zone, and
`the now gel-like polyarylene ether ketone is discharged from
`the second reaction zone with plug now under the action of
`the solvent and/or of the inert gas. The solvent or
`inert gas
`from about 6 to 65, preferably finm 10 to 25, bar.
`pressure is
`During the discharge
`of
`the
`the polyarylene cther ketone,
`transport pressure
`reduced in at
`two stages,
`least
`the
`pressure reduction in the first
`ie. up to the transition
`stage,
`from the conc to the outflow pipe, being not more than 60%,
`preferably up to 20%.
`In the simplest case,
`is sufEcient for
`it
`this purpose appropriately
`to establish the ratio of
`the
`diameters D, and D2 and,
`for the further pressure stage,
`the
`diameter D,,
`a ratio of diameters D,:D2 of from
`In general,
`to 20:1 has proven particularly advantageous. The pol-
`2:1
`yarylene ether ketone is subsequendy compounded in a
`working up unit, for example in
`a mill.
`By transporting the polyarylene ether ketone with the aid
`of an inert solvent or of a solvent-saturated inert gas,
`it
`is
`possible completely to avoid vortex formation and
`the
`second mact!on zone is
`free of product residuc which would
`have to be removed by an expensive procedure or would
`lead to impurities in subsequent product batches. The uni-
`form product quality, in particular with regard to the degree
`of polymerization,
`is especially noteworthy.
`In a particularly advantageous embodiment of the novel
`the inert solvent passed into the second reaction
`process,
`zone is metered in an amount such
`that the surface of
`the
`reaction mixtureis completely coveted 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
`to 25,
`bar. This makes it possible to
`the apparatus
`reduce
`rcquired for carrying out the process and for corresponding
`safety measures.
`According to a
`further
`feature of the invemion,
`inert
`an
`is passed countercurrent
`into the reaction mixture in the
`gas
`reaction zone. This feed of
`is effected
`second
`inert
`gas
`immediately after the transfer of the reaction mixture from
`reaction zone and results
`the Brst
`in an additional mixing
`the precondensate can
`effect, so
`be transferred earlier
`that
`and with a substantially lower viscosity,
`for example about
`from the Arst
`to the second n:action zone, and a
`100 mPa,s,
`considerable reduction in the excess catalyst. In general, the
`is saturated with the inett solvent used
`inert
`gas
`in the
`reaction of the components in the first reaction zone. For
`this
`purpose, the inert gas
`is passed through a solvent bath at a
`corresponding pressum and at atemperature which is at
`least
`close to the temperature of the reaction mixture in the second
`reaction zone. He 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 vessel, 3,283 g
`(24.62 mol) of
`aluminum chloride were suspended in 5,212 ml of methyl-
`ene chloride and cooled to below 0° C. 635.37 g
`(6.75 mol)
`of dimethyl sulfone, 913.61 g
`(4.5 mol) of
`terephthaloy!
`chloride and 25.30 g
`(0.18 mol) of benzyl chloride were
`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
`closed so that it was gas-tf8ht, and nitrogen under about 10
`forced in to maintain the pressure. With slow
`bar was
`
`Page 12 of 145
`
`

`
`5,580,948
`
`5
`heating,
`the viscosity of
`the reaction mixture increased to
`about 2.000 mPa.s in the course of about 15 to 20 minutes.
`The temperature was then about 20°
`C. and the volume of
`the precondensate was about 9,000 mL By means of
`the
`applied nitrogen pressure,
`the reaction mixture could be
`discharged in the course of
`2 minutes through the bottom
`outlet valve and transferred to
`a pressure-resistant subse-
`quent reactor coated on the inside with PTFE.
`The diameter D2 of the subsequem reactor was 130 mm,
`the length of the cylindrical part was 800 mm and the angle
`of the cone was 10°. The outBow of
`the subsequent reactor
`had a diameter D2 of 50 mm. Before the mill,
`the outflow
`pipe, which had a
`len8th of about 500 mm, was reduced to
`a diameter Da of 20 mm with an angle of taper of 10°. All
`product-conveying surfaces
`the subsequent reactor were
`of
`coated with FFFIL
`60 minutes after
`the reaction mixture to the
`transfer of
`subsequent reactor, 300 ml of methylene chloride were
`added to the reaction mixture.1te subsequent reactor was
`operated in such
`a way that, after
`a residence time of 5 hours,
`the total reaction mixture was discharged in the course of 45
`minutes with the aid of an inert
`gas stream at
`10 bar via a
`mill. The tempemtute in the subsequent reactor was 25° C-
`and the pressure after the first pressure stage was about9bar.
`The discharged reaction material was worked up using
`hammer mill, 200 I/h of water being sprayed in to hydrolyze
`the polymer/aluminum chloride complex. AL a throughput of
`about 3.0 kg of polymer per hour, the power consumption of
`the mill was 1.0 kW.
`11:e polymer was
`then freed from camlyst
`residues
`by
`repeated extraction with water and was dried under atmo-
`spheric pressure at 290° C.
`The polymer obtained had an
`imrinsic viscosity of 1.07
`(measured in concentrated sulfuric acid, 0.5/100 ml).
`Its
`melting poim was 375* C.
`We claim:
`the preparation of
`a polyarylene other
`1. A process
`for
`ketane by Friedel-Crafts polycondensation,
`in which a reac-
`tion mixture consisting of
`a monomer system comprising
`A.
`(a) an aromatic dicarboxylic acid chloride or phosgene
`an essentially equimolar amount of
`a poly-
`and
`nuclear aromatic which contains two bydrogen
`atoms replaceable by electrophilic substitution or
`
`a
`
`(b)
`
`B.
`
`5
`
`10
`
`20
`
`25
`
`30
`
`35
`
`40
`
`6
`a polynuclear aromatic carboxylic
`acid chloride
`which has one hydrogen atom replaceable by elec-
`trophilic substitution and is capable of autoconden-
`ution and
`(c) optionally,
`a monofunctional
`the terminal groups,
`a Lewis acid in an amount of at
`least one mol per
`nucleophilic
`group in the
`reaction mixture and
`in
`addition a small excess which is sufEcicut
`to catalyze
`the reaction,
`lowis base
`C. optionally,
`in an amount of from 0.01 to
`4 mol per mol of acid groups and
`a solvent which is
`inert under the reaction conditions
`D.
`is subjected to polycondensation in a
`reastion zone
`first
`15 while stirring
`to a viscosity of about 2,000 mPa.s, is
`trans-
`ported into mid through a second vertical sesction zonc,
`allowed to undergo complete polycondensation and dis-
`from said reaction zone with plug
`flow, wherein,
`charged
`after transfer of the reacdon minure to the second reaction
`zone, an inert solvent or an inert gas saturated with the inett
`solvent
`is passed into said reaction zone and the reaction
`mixtme is dischar8ed by means of
`the solvent or
`inert gas
`under from about 6
`to 65 har
`the transport pressure being
`reduced in at
`two stages
`and the pressure reduction in
`least
`the fust stage being not mme tlian 60%.
`as defined in claim 1, wherein the inert
`2. A process
`solvent passed into the second reaction zone is metered in an
`amount such
`that
`the surface of
`the reaction mixture is
`completely covered with solvent, and the reaction mixture is
`discharged by means of an inest gas under a gas pressure of
`from about 6
`to 65 bar.
`as defined in claim 1, wherein the reaction
`3. A process
`mixune is
`transported through the second reaction zone
`under from 10 to 25 bar.
`as defined in claim 1, wherein an inert gas
`4. A process
`passed countercurrent into the reaction mixture in the second
`rcaction zone.
`as defined in claim 4, wherein the inert gas
`5. A process
`is samrated with the inert solvent stated in claim 1 under D.
`as defined in claim 2, wherein the reaction
`6. A process
`mixture is
`transported through the second reaction zone
`under from 10
`to 25 bar.
`
`reagent for blocking
`
`a
`
`is
`
`*
`
`*
`
`*
`
`*
`
`*
`
`Page 13 of 145
`
`

`
`BAR CODE LABEL
`
`U.S. PATENT APPLICATION
`
`SERIAL
`
`NUMBER
`
`08/285, 120
`
`FlUNG DATE
`
`CLASS
`
`ROUP ART UNIT
`
`08/03/94
`
`528
`
`-
`
`1503
`
`ECKHARD NBUPELD, LIHBURGERHOFr
`BARBEL ARNOLD-MAUER,
`REP GERMANY;
`FED
`MALLSTADT,
`LUDWIGSHAFEN,
`JURGEN HOFMANN,
`REP GERMANY;
`PED
`HEITz, DANNSTADT-SCHAU, FED
`REP GERMANY;
`FED
`THOMAS
`REP GERMANY;
`CHRISTOPH SACHSENWEGER,
`0BRIGHEIM,
`PETRA WIELAND, WORMS,
`REP GERHANY;
`FED
`REP GERMANY.
`FED
`
`**CONTINUING DATA***************...
`VERIPIED
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`**FOREIGN/PCT APPLICATIONS************
`.
`VERIFIED
`P 43 26 174.2
`REP GERMANY
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`FED
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`08/10/93
`
`STATE
`OR
`COUNTRY
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`SHE£TS
`ORAWrNG
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`~
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`OTAL
`LAIMS
`
`INOSPENDENT
`CLAIMS
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`$840.00
`
`KEIL & WEINKAUF
`1101 CONNECTICUT AVENUE
`DCe20036
`WASHINGTON
`
`NW
`
`This is
`to certifv
`that annexed hereto is
`true copy from the records of
`the United States
`Patent and Trademark Office of
`the appücation which is
`.
`identified above.
`By authorityof
`the
`COMMISSIONER OF PATENTS
`
`AND TRADEMARKS
`
`a
`
`Data
`
`Certifying
`
`Officer
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`Page 14 of 145
`
`

`
`i
`
`WW MMCEON SERIAL N
`
`/ 85120
`
`U.S. DEPARTMENT
`OF COMMERCE
`PATENT
`TRADEMARK OFFICE
`AND
`RECORD SHEET
`FEE
`
`090 BA 08/11/94 0
`
`8
`
`0
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`101
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`1
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`710.00 CK 0-Z-0050-442
`
`PTO-1556
`(5/87)
`
`'
`
`Page 15 of 145
`
`

`
`08/285120
`
`THE UNITED STATES PATENT AND
`TRADEMARK OFFICE
`ssioner of Patents
`and Trademarks
`D.C. 20231
`
`Washington,
`sir:
`AU6 -
`3 1994
`is the patent application of:
`Transmitted herewith for
`filing
`INVENTORS: Eckhard NEUFELD, Barbel Arnold-KAGER,
`Jurgen
`HOFMANN
`Thomas HEÏTE, Christoph SACHSENWEGER, Petra WIELAND
`For: PREPARATION OP POLYARYLENE ETHER KETONES
`are:
`Also enclosed
`pages of specification,
`including
`sheet(s) of
`formal/informal drawing(s)
`fee has been calculated as shown below:
`The filing
`Number
`SMALL/LARGE
`Number
`Filed
`For:
`Extra
`ENTITY
`Basic
`Fee............................................
`Total Claims:
`$11./$22.
`Indep. Claims:
`537./$74.
`x
`] Multiple Dependent claim(s) presented:S115./230
`for the filing
`fee.
`A check
`is enclosed
`the difference is
`"0".
`than zero, enter
`less
`for $710.00 for the filing
`A check
`is enclosed
`fee
`is hereby authorized to charge any other fee
`The Commissioner
`required,
`including the
`connection with the
`fee,
`issue
`in
`and prosecution of
`this application,
`and to the extent
`filing
`hereby petition for extension(s)
`necessary, applicant(s)
`of
`time
`to our Deposit
`under
`1.136,
`to be
`charged
`37
`·
`Account 11-0345.
`claimed
`is
`from Apgust
`Priority
`application Serial No.
`43 26 774.2.
`[X)
`The priority
`document(s) will
`be submitted
`The
`documents(s)
`submitted
`priority
`were
`application Serial No.
`.
`Respectfully submitted,
`REI
`& WEINKAUF
`
`12
`
`1
`
`]
`
`[
`[
`*If
`[X]
`[X]
`
`[
`
`]
`
`claim(s),
`
`5
`
`BASIC FEE
`$355./$710.
`710.00
`
`S
`
`=
`
`710.00
`
`S
`
`5
`
`1
`
`-20
`
`-3
`
`=
`
`=
`
`x
`
`CFR
`
`P
`
`10,
`
`1993
`
`, based on
`
`German
`
`at
`
`later date.
`a
`original
`with
`
`.
`
`1101 Connecticut Ave., N.W
`Washington, D.C.
`20036
`(202)659-0100
`
`Herbert B. Keil
`Reg. No. 18,967
`
`Page16of145
`
`

`
`THE.'
`
`12
`
`I
`
`]
`
`(
`[
`*If
`[X]
`
`(X)
`
`[
`
`]
`
`-
`
`3
`
`1994
`
`claim(s),
`
`5
`
`5
`
`1
`
`-20
`
`-3
`
`=
`
`=
`
`x
`
`BASIC FEE
`$355./4710.
`710.00
`
`$
`
`=
`
`710.00
`
`$
`
`NITED STATES PATENT AND TRADEMARK OFFICE
`of Patents and Trademarks
`Hon. CommÎssioner
`Washington, D.C. 20231
`sir:
`AU6
`the patent application of:
`Transmitted herewith for
`is
`filing
`INVENTORS: Eckhard NEUFELD, Barbel Arnold-MAUER,
`Jurgen
`HOFMANN
`Thomas HEITE, Christoph SACHSENWEGER,
`Petra WIELAND
`For: PREPARATION OF POLYARYLENE ETHER KETONES
`are:
`Also
`enclosed
`cages of specification,
`including
`sheet(s) of
`formallinformal drawing(s)
`fee has been calculated as
`shown below:
`The filing
`Number
`Number
`SMALL/LARGE
`Filed
`For:
`Extra
`ENTITY
`Basic
`Fee............................................
`Total.Claims:
`$11./$22.
`$37./$74.
`Indep. Claims:
`x
`] Multiple Dependent Claim(s)
`presented:S115./230 =
`for
`fee.
`is enclosed
`A check
`the filing
`the difference is less
`than zero, enter "0".
`for 8710.00
`for
`fee is enclosed
`the filing
`A check
`is hereby authorized to charge any other fee
`The Commissioner
`in connection with the
`required,
`including the
`fee,
`issue
`this application, and to the extent
`and prosecution of
`filing
`necessary, applica.nt(s) hereby petition for extension(s)
`to our Deposit
`charged
`of
`time
`under
`1.136,
`be
`t.o
`37
`Account 11-0345.
`from August
`is
`claimed
`Priority
`application Serial No.
`P 43 26 774.2.
`The' priority document(s)
`will
`(X)
`be
`The priority documents(s)
`were
`application Serial No.
`
`I
`
`CFR
`
`10,
`
`1993
`
`, based on
`
`German
`
`later date.
`at
`submitted
`submitted with original
`
`a
`
`.
`
`Respectfully submitted,
`KEI
`& WEINKAUF
`
`1101 Connecticut Ave., N.W
`Washington, D.C.
`20036
`(202)659-0100
`
`Herbert B. Keil
`Reg, No. 18,967
`
`Page 17of145
`
`

`
`08/285120
`0.2.
`0050/44228
`Preparatiqn of pelyarylene ether ketones
`the preparation of
`the generic
`For
`nds of
`invention,
`of claim 1 starts
`the
`the
`from a
`preamble
`in which poly-
`process
`based on DB-A-38 29
`known
`520,
`arylene ether
`ketones
`are
`prepared
`electrophilic
`polycondensation by
`reacting
`system comprising
`A.
`a monomer
`chloride
`dicarboxylic
`acid
`aromatic
`or
`(a)
`an
`phosgene and an essentially equimolar
`amount of
`polynuclear aromatic which
`contains
`two
`a
`replaceable by electrophilie
`hydrogen
`atoms
`substitution
`.
`
`by
`
`or
`(b)
`
`a polynuclear aromatic carboxylic acid chloride
`atom replaceable by
`which
`hydrogen
`one
`has
`electrophilic substitution and
`capable
`of
`is
`autocondensation
`
`sa
`
`reagent
`
`for
`
`from 0.01
`
`the
`
`reaction
`
`and
`(c)
`
`B.
`
`c.
`
`D.
`
`required,
`a monotunctional
`if
`blocking the terminal groups,
`least one mol per
`acid
`in an amount
`of at
`a Lewis
`nucleophilic group
`in the reaction mixture and
`in
`addition a
`to
`small
`is
`excess
`which
`sufficient
`catalyze the reaction,
`required, a.Lewie
`if
`base in an amount of
`to 4 mol per mol of acid groups
`and
`inert
`solvent which
`is
`under
`a
`conditions
`in the presence.of a Friedel-Crafts catalyst.
`The poly-
`condensation is carried out
`in two reaction zones, mixing
`liquid and solid reaction components
`and pre-
`the
`of
`polymerization being effected in the first
`reaction zone
`in a stirred kettle. The reaction mixture is transported
`flow,
`into and, with plug
`of
`pressure
`by means
`gas
`through the
`reaction zone,
`to undergo
`second
`allowed
`continuously via a
`complete polycondensation, discharged
`screw unit and compounded.
`The problem here, however,
`is
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`Page 18ofi45
`
`

`
`-
`
`-
`
`2
`
`.for
`
`.the
`
`0.2.
`0050/44228
`discharge from the
`ensuring uniform product
`second
`gas pressure may
`Transport by means of
`reaction zone.
`in the
`result
`amount of solvent
`reduction in
`in a
`the
`ie.
`the interface with the gas phase,
`polymer surface at
`to excessive
`the polymer surface dries out.. This
`leads
`the wall,
`surface layer
`the
`to
`the
`and
`of
`adhesion
`a vortex, which is very undesirable since
`surface forms
`the products. Obstacles to flow in
`causes deposits of
`it
`the reaction zone and corresponding
`lower region of
`the
`it possible to avoid
`linings of
`reaction zone make
`the
`The transport
`limited extent.
`this phenomenon only to a
`the second reaction zone
`is
`the polycondensate out of
`of
`screw unit provided for
`this
`also unsatisfactory.
`The
`be provided
`whose product-conveying parts must
`purpose,
`15 with an antiadhesion coating sinde otherwise the reaction
`be very
`transported,
`mixture cannot
`to
`proved
`has
`be
`the screw unit in
`susceptible to faults. The approach of
`is particularly problematic
`the case of
`a filled
`screw
`owing to the high energy dissipation, which may
`to
`lead
`thermal
`product
`in
`non-
`damage to
`case
`of
`the
`the
`decomplexed polyarylene ether ketone.
`invention to
`the present
`an object
`of
`is
`It
`the preparation of polyarylene
`provide a
`process
`the deficiencies described
`ether ketones which is free of
`reaction
`transport of
`permits
`in particúlar
`and
`discharge aid.
`mixture without a mechanical
`is achieved by
`this object
`We have foúnd that
`of claim 1.
`measures according to the defining clause
`for the
`for the novel process
`Suitable components
`polyarylene ether
`those
`prep