US 201502594 cu») United States BAL cz) Patent Application Publication co) Pub. No.: US 2015/0259473 Al Streng (54) METHOD AND PLANT FOR PRODUCING POLYCARBONATE (1). Applicant: EPC ENGINEERING CONSULTING GMBIH, Rodolsta (DE) (72) Inventor: Michal Streng, Maina (DE) (21) Appl.Nos — 14409,592 (2) PCT Fed: Jum, 13,2013 (86) PCT No $371 (ol), (@)Date PCTIEP2O13/062240 Dee. 19,2014 G0) Foreign Application Priori Jun. 19,2012 (DE) Publication Classification 102012 108 296.4 (1) Ime co8G 6430 BOL 198 Bois 1928 (2006.01) (2006.01) (2006.01) (43) Pub, Date Sep. 17, 2015 C086; 64/307 (2013.01); BOLT 19/248 (2013.01); BOLT 1948 (2013.01), BOL 2219724 (201301), on ABSTRACT The invention relates wo a method for producing a polycar bonate comprising at least the following steps) transesteri- fication of one oF more bisphenols with one or more diary] carbonates in atleast one transesterifcaton reactor under ccntinuons removal of the hydroxy aryl reaction product ‘leased, b) pr-polycondensation ofthe eaction product of the trnsesterification in at least one pre-polyeondensition reactor under continuous removal of the hydroxy aryl reac- ‘ion product released, e) polycondensation of the reaction pradict ofthe pre-polycondensation in at least one polyeon- ensetion reactor, wherein the aryl reaetion product is removed during the (runsesterifcation reaction and the hydroxy aryl reaction product is removed during the pre polycondensation resction through = common colvinn, ‘wherein entrained diaryl carbonate is separated from the lnydroxy aryl reaction product draw olPatent Application Publication Sep. 17, 2015 Sheet 1 of 6 US 2015/0259473 AI BPA ppc} 7 1 Frente rf 3 4 Catatyst Cat, Prep v3) pp2 FIN Filter 4 5 4 imu Granulation Fat PC Chips: Fig. 1Patent Application Publication Sep. 17, 2015 Sheet 2 of 6 US 2015/0259473 AIPatent Application Publication Sep. 17, 2015 Sheet 3 of 6 US 2015/0259473 AI aad ‘acum cy C ie ae, = "1 NK ; = }~—5- 6 14 5 {oe 12 =—O if AS B Fig. 3Patent Application Publication Sep. 17, 2015 Sheet 4 of 6 US 2015/0259473 AI Fig. 5 W If 1 3 —t Fig. 4Patent Application Publication Sep. 17, 2015 Sheet 5 of 6 US 2015/0259473 AIPatent Application Publication Sep. 17, 2015 Sheet 6 of 6 US 2015/0259473 AI 14 (Granalation | chips Fig. 6 28 Chips [GranulationUS 2015/0259473 Al METHOD AND PLANT FOR PRODUCING POLYCARBONATE, [0001] The present invention relates 10 « method and an apparatus for the prodtion of polycarbonates from bisphe- nol and diary carbonates ina mult-step reaction. 10002] Poiycarbonates are polymeric esters of earbonie cid wit diols. Because o their interesting physical proper= ties, suel as low weight, pood temperature and impact resis- tance, and excelent optical properties, in particular, polyear~ bonates ure used for many produets in the high-tech Geld. As a result, there is @ continously growing demand for high- ‘quality polyearbonate. 10003] Polycarbonate can be produced by polyeondes tion of phosgene with diols, or a process which avoids the highly toxic phosgene species —by a transesterification reac- tionofearbonie eid diestrs with bisphenol. The production ‘of polycarbonates by trunsestriication reaction of earbonic, i diesters with bisphenols is generally cari out follow Jing a melt ransesterficaton process. 10004] "The prodction of polyearhonates according to the melt transesterifcation process above is ‘known, and described by way of example in “Schnell” Chemistry and Physics of Polyearbonstes, Polymer Reviews, Vol. 9, Inter science Publishers, New York, London, Sydney 1964, in D.C. Provorsek, B. T. Debons and ¥. Kersten, Comparate Research Center, Allied Chemical Corporation, Moristown, NJ. (07960, “Synthesis of Poly(ester}carbonate Copolymers” in Journal of Polymer Science, Polymer Chemistry Edition, Vol 19, 75-00 (1980), in D. Freitag, U. Grigo, P. R. Maller, N. Nouvertne, BAYER AG, “Polyearbonates” in Encyclopedia ‘of Polymer Science and Engineering, Vol. 11, Second Edi tion, 1988, pages 648-718, and finally in Dees U. Grigo, K. icher and P.R. Miller “Polycarbonate” in BeckerBraun, Kunststoff Handbuch, Vo. 3/1, Polycarbonate, Polyacetale Polyester, Cellulosester. Carl Hanser Verlag, Munich Vienna 1992, pages 117-299. [0005] The reaction which proceeds from bisphenol and lary carbonates 1o the production of polycarbonates is rep= resented by the following equation: Sep. 17, 2015 [0006] As can be seen fom the above equation, a hhydroxyanyl reaction product—such as phenol, for example is released by the rection, In the removal thereof bby means of distillation, the phenol is obtained in the known ‘method in a highly impure form, and cannot be used further Without prior purification. As such, there i no possibility of using the phenol to produce new diary] carbonate tobe ised ‘again in the process, without intermediate putfication steps inserted. [0007] In the apparatuses described in the prorat used for the production of polycarbonates by melt transeserfeation processes, a substantial problem is that manual interventions are necessary suchas, by way of example, the cleaning of condensation units or heat exchangers, for example due 10 ‘oligomeric reaction products made of the hisphenol and cae sy carbomites. This need for manual interventions leads 10 Tengihy operation pauses with corresponding economic advantages. At the same time, dhe need for manual interven- tions also creates risk forthe operations personel in the plant As such, in eases where diphenoleasbonate (DPC) is used as the diary carbonate component, which is common, phenol is released as a reaetion product, Due to the high toxicity and aggressiveness of phenol, every manual interven- ‘ion then constitutes a potential endangerment ofthe oper tions personal [0008] An important quality feature of polycarbonates is theabsence, fo the greatest degree possible, of dseolorations ‘This s particularly important where polycarbonates are uscd or window panes, amtomobile Headlights, and’ optical devices, In the apparatuses known in the prior art for the production of polycarbonate, problems consistently arise ‘with respect to slight discolorations of the polycarbonste product, particularly in the form of yellow diseoloratons [0009] Proceeding from this point, the problem addressed by the present invention is that of providing a method and an apparatus forthe production of polycarbonates which avoid the disadvantages explained above. [0010] The problem adresse by the iavention is partic larly that of providing @ method and an apparatus fo the production of polycarbonate which enable the production of high-quality polyearbonate, wherein the mest-closed pos- sible material eyeles are used, wherein the economic et ciency is improved as a result of minimized operation pauses and wherein the need for manual interventions in the process is reduced toa miniraum, [0011] The problem acconding to the invention s addressed bya method according to claim I, Preferred embodiments are aivea in claims 2 through 9 [0012] tn the method acconting othe invention, the poly- ‘carbonate is prociced in hee reaction steps from thestarting substances bisphenol and diaryl carbonates, particulary in a {ransesterfcation reaction, « pre-polycondensstion, and a polycondensation reaction, [0013] The bisphenol are preferably diydroxy-diaryal- anes with the formula HO—Z—OH, wherein Zi divalent ‘organic moiety with 6 to 30carbon atoms, which contains one ‘ormore aromatic groups. The diary] carbonate is preferably iC, to C, gary} carbonic aed ester [0014] In one preferred embodiment, the bisphenol sedis bisphenol A, and dhe diary carbonate used is dipheny] car- ‘bonateInthiscas, the cleaved hydroxyaryl reaction product is phenolUS 2015/0259473 Al 10015] The ransesterification reaction is described forthe ‘example ofthe reaction of bisphenol A with diphenyl carbon= ate via te following formula: Sep. 17, 2015 LO-O- 10016] The tansesterfication reaction proceeds in one oF ‘more continuously stimed transesterifiation reactors, Which ae typically configured with intemal heat coils and with an ‘extemal jacket heater [0017] "The wansesterification reaction preferably procouds ‘acconting 10 the method aecorling to the invention in three sequential sransesterification reactors, [0018] The transestrification reaction i influenced by series of parameters, The most important parameters ar {0019} temperature {0020} press [0021] processing time {002] mole to of bisphenol and dary carbonate {0023} the etayst system used 10024) As can be soon fom the reaction eauation above, phenol is released during the transesterifcation reaction [Because ofthe temperature present and the vacuum condi tions, the phenol enters the vapor phase and is continuously removed from the rection mixture. 10025] -Thepolycondensation reaction which proceeds dur- fing the pre-polyeondensation and the polyeondensation method steps is represented by the following reaction dia- tgim, using the example of the reaction of bispheny] A and ‘phenyl carbonate: OO} O4fE-O10- [0026] The polycondensation reation is influenced by & series of parameters, The most important parameters ar 0027] reactive surce area [0028] temperature [029] pressure [0030] the catalyst system used 10031} In contrast to the transesterification reaction, the processing time does not play a significant roe inthe poly- ‘condensation. The most important parameter inflaneing the polycondensation reaction i the reactive surface are, 0032] "According to themethod aeconing tothe invention, the polycondensation reaction preferably proceeds ina three= sep process [sa repeonmton ep 1 rt ppb ‘condensation reactor) [0034] _pre-polycondensation step I (in & second pre- polycondensation reactor) [0035] final polycondensation step (ina polyeondensa- tion reactor (finisher) [0036] Two reactions specifically oceur during the poly- ‘sondensation reaction: [0037] The polycondensation proceeds forming polymer ‘chains, and polymer chins which have already been formed act with each other to form fonger polymer chains, Parallel to ths chain extension reaction, there are also chain breaking reactions which hat the growth of the chain lengths [0038] Using he example ofa reaction of bisphenol A with phenyl carbonate, chain breaks occur 2s per the following esction diagramUS 2015/0259473 Al O--OFO- Sep. 17, 2015 een eran ak eee 10039] Asa result ofthe chain extension reactions, further phenol is cleaved, which i removed from the reaction by the tse ofa voeutim. 10040] Inthe methods known from the prior art, the phenol reaction product is separated as cleaved phenol ina distilla- tionprocess, and isobained ata purity level of approximately 607%, One ofthe impurity fractions inthis eases the dipheny ‘carbonate, which transitions tothe gas phase in significant “amounts under the conditions at which the cleaved phenol is Femoved, The eleaved phenol with sch a high impurity n= not therefore be fiber vse without additonal purification steps [0041] Te has been surprisingly demonstrated thatthe phe nol ean be obtained a purities of 295% as a result of the use according to the ‘vention ofa column in the separation of the eleaved phenol during the transesterfieation reaction. In particular, the ‘diphenyl carbonate carried along withthe same is nearly ‘completely scparated fom the penal as result ofthe eal ‘um used, an therefore is obtained at such high purity that it ‘ean be fed back into the process 10042] A catalysts advantageously used when the method soconting to the invention scarred out. The use of eatalysts in the produetion of polycarbonates from bisphenol and dia- ry carbonates using. @ melt transesterification process is Known, It has been discovered inthe present invention that good results are surprisingly achieved by the use of a new ‘alalystin the formofa mixtire ofa leastone slkali metal salt, ‘ofan aromatic alcohol and a least one bore acid ester of an ‘aromatic alcohol. In the seope of a method according t the invention, a catalyst is particularly preferred which i in the orm ofa mixture of alkali metal phenolate and a bore acid ‘ester ofan aromatic sleahol [0043] Particularly good results are achieved when a mix- ture of 0. 102 ppm alkali metal phenolate and 0.25 to 3 ppm boric acid ester af an aromatic alcohol iad asthe catalyst. [0044] One ofthe essential parameters which characterize the properties of a polyearbonate is the OFV/aryl carbonate terminal group ratio, This rato is defined as fllows Cty boot emia gop ao = Number OH ein 10045] The detennination of the OHVaryl carbonate temni- nal group ratio ean be made, by way of example, by a separate ‘determination of the OH terminal proups by means of photo- metric determination with TIC, on the one hand, as Well as by determiation ofthe ary] carbonate terminal groups wsing HPLC with the monopheno! formed following total spor Jieaton, onthe other hand. In genera, theOHteminal groups and the aryl earbonate terial groups total 100% the polycarbonate, together. [0046] The aljustment of the desired OWVany carbonate teminal group ratio depends on many actors and is highly influenced by slight varatons i the starting stoichiometry of the bisphenols and daryl carbonates used but most ofall by the distillation loses of the diay carbonate ding the di illaion of the hydony-ary easton product 5 well {0047} Iathe methods known fromthe petra the areatest possible separation of the hydeoxyl-ary reaction product {Gleaved phenol leads (high loses ofthe diay etbonate ‘sed. This Ieads fo an enprodicable shift in the OLVaryl carbonate lerminal proup eto {0048} This problem canbe solved aeconing to the iene ‘ion by addtional diary carbonate Being add to the ite ‘mediate prodct steams betwee the lransestericution nee tion and the pr-polycondensation reaction forthe purpose oF djing the desired OlVry carbonate terminal group ratio {0049} Bocause the dar] carbonate whichis ear along Arig the Separation ofthe hydroxy-arylreation product (leased phenol) in the method according othe invention is ‘bined at hgh pry the method according tothe vention provides particular advantage. This isthe possiblity of Geely insering the dias] carbonate obtained inthis mae ner, withoutintennedatesteps, int the process by re-dosing thearyl carbonate tte intermediate produt steams follow ing the trensesterification reaction, {0080} As ares of this retwn of the diary! carbonate, Scprated frm the hydeoxyLarl reaction prac cleaved pheno} itis panicuarly posible to repreuce he orginal Suichiometry between the dary earbonstes andthe Bisphe- ‘ols in dr to achieve the dosred Ory carbonate te 2 gropo. {0081} In practice, itis not absotely necessary to perform measurement ofthe Of Vary arbonate tema group ratio Porto the addition of aryl carbonate betwoen the tans fenifition reaction and the pre-polycondensition reaction forthe purpose of adjusting the desired Oar carbonate terminal group ratio In one easboment ofthe method, the operating parameters of the method pelerably in the ‘thod sep of the tansestertication ate adjusted forthe Porposwof achiovingan average molecular weight inthe inl Polymeric polycarbonate and an asocated O1Varlcarbon- Me terminal govp ato the same dati by expeietisl “als In place of a concrete messurement of the OFay] Carbonate emia gupnit therefore possible todas a conelusion about te prevailing OVarylearbonate trialUS 2015/0259473 Al nroup ratio following the transesteriication reaction by sing suliciently precise control of the eacton conditions based ‘onexperiental values, and to accordingly contol the addition ‘of further aryl carbonate 10082] The desired average molecular weight ofthe oligo- ‘mers and polyiniers can be continuously determined by online viscometry. 10083] | However, the addition of further diaryl carbonate to the intermediate produc streams between the transesteif tion reaction andthe pre-polycondensation reaction ean also be used independently ofthe originally adjusted stichiom- ‘etry for the purpose of performing a fine adjustment of the ‘Offary carbonate terminal geoup ratio, 10054) Ic is particularly advantageous thatthe addition of| Further diagy carbonate tothe intermestate product streams, between the transesteiieation reaction and the pre-polyeon. ion product as well s oligomers carried along with the same, are condensed out of the pre-polycondensation reaction separately. 16, An apparatus aeconding to claim 10, 1, wherein the polycondensation reactor is designed as a spinaing, disk reactor 17. An apparatus acconding o lsim 10, wherein the polycondensation reaction is driven hydaically using a hydraulic Mui. 18, An apparatus according to claim 10, wherein the apparatus has means which enable the polycarbonate stream from the polycondensation reactor to the divided into two or more substreams, wherein te apparatus has two or more pelleing deviees forthe purpose of pellet- ing the to oF more sub-sireams ofthe polycarbonate reaction product. 19, An apparatus according to claim 10, wherein specially selected alkyl aromatic compound istsel asthe ‘adits heat transfer medi forthe temperature con- ditioaing of raw material melts andior hydroxyl-aryl ‘eaetion products which has good flow properties and ‘good heal transfer capacity in the temperature rng of 50-120°C. 20. 4 polycarbonate produced according to a method according to claim 1 or using.an apparatus for the production ‘fa polycarbonate having: at least one tansesterfcation reactor forthe purpose of bisphenol and atleast one diary carbonate, and forthe purpose of producing trunseserified intermediate product, ‘a least one pre-polyeondensation reactor for the pur: pose of producing a pre-condensation intermediate ‘product from the trnsesterified intermediate prot, «)at least one polycondensation reactor (finisher) forthe purpose of producing polycarbonate from the pre polycondensation intermediate produc, wherein the at least one ransesterification reactor has means orthe removal ofthe hydroxyl -arl reaction product cleaved during the ransesterfcation reaction, said meuns having at Teast one coum, 21. The use of a polycarbonate according to claim 20 for the manufacture of window panes, botles, components for automobile headlights, eyeplass lenses, lenses, disposable syringes, helmets and visors for helmes, sports goggles and sunglasses, passenger vehicle accessories, solar modules, housings for comprters and data storage devices suchas CDs and DVDs.