US009 175136B2
(12) United States Patent (10) Patent No.: US 9,175,136 B2 Louis (45) Date of Patent: *Nov. 3, 2015
(54) METHOD FOR THE MANUFACTURE OF 4,636,557 A 1/1987 Deckers POLY(ARYL ETHER KETONE)S IN THE is's A : f E. SE tal. 3. 35 PRESENCE OF SODIUM CARBONATE 4,766,197- J. A * 8/1988 ClendinningcMaster et etal..... al...... 528/125 4,767,837 A * 8/1988 Jansons ...... 528,125 (75) Inventor: Chantal Louis, Alpharetta, GA (US) 4,774.311 A * 9/1988 Kelsey ... 528,125 4,855.388 A * 8/1989 Kelsey ...... 528,125 (73) Assignee: Solvay Advanced Polymers, L.L.C., 4,867,912 A * 9/1989 Heinz et al...... 528,125 4,868,273 A 9, 1989 Daniels Alpharetta, GA (US) 4,906.784.- WW A * 3, 1990 SkolOCT ...... 528,125 4,908.425. A * 3/1990 Robeson et al. 528,125 (*) Notice: Subject to any disclaimer, the term of this 4,952,665 A * 8/1990 Ebata et al. ... 528,219 patent is extended or adjusted under 35 4,999.414 A * 3/1991 Genz et al...... 528,125 U.S.C. 154(b) by 243 days. 5,081,214. A 1/1992 Schneller 5,116,933 A * 5/1992 Newton ...... 528,125 This patent is Subject to a terminal dis- 5,120,818. A * 6/1992 Robeson et al...... 528/125 claimer. 5, 122,587 A * 6/1992 Heinz et al...... 528,126 5,122,588 A * 6/1992 Koch et al. .. 528, 179 (21) Appl. No.: 13/125,537 9 * 238; star 528,125 5.312.278 A * 5/1993 Praendner et al. ... 528,171 (22) PCT Filed: Oct. 23, 2009 5,268.444 A * 12, 1993 Jenseneral. 528,125 5,362,836 A * 1 1/1994 Helmer (86). PCT No.: PCT/EP2009/064O11 Metzmann et al...... 528,125 5,373,081 A * 12/1994 Yang et al...... 528,125 S371 (c)(1), 5,523,384 A * 6/1996 Memeger et al...... 528/392 (2), (4) Date: Apr. 21, 2011 5,580,948 A * 12/1996 Neufeld et al. 528,125 6,593.445 B2* 7/2003 Schwab ...... 528, 175 (87) PCT Pub. No.: WO2010/046484 2002fOO 10307 A1* 1 2002 Schwab ...... 528,174 2009,024.0020 A1* 9, 2009 Gharda et al. . ... 528,126 PCT Pub. Date: Apr.p 29,9 2010 2011/0201775 A1 8, 2011 Louis et al...... 528,126 (65) Prior PublicationO O Data (Continued) US 2011/0213095 A1 Sep. 1, 2011 FOREIGN PATENT DOCUMENTS CN 101215365. A T 2008 Related U.S. Application Data DE 4121139 A1 1, 1993 EP OOO1879 A1 5.1979 (60) Provisional application No. 61/108,096, filed on Oct. 24, 2008, provisional application No. 61/108,097, (Continued) filed on Oct. 24, 2008, provisional application No. 61/140,205, filed on Dec. 23, 2008. OTHER PUBLICATIONS U.S. Appl. No. 13/125,508, filed Apr. 21, 2011, Chantal Louis et al. (51) Int. Cl. U.S. Appl. No. 13/125,523, filed Apr. 21, 2011, Chantal Louis. C08G 65/40 (2006.01) Zhuo, Ni, etal "Characterization and Spectra Studies of Peek Pre C07C35/06 (2006.01) pared by Two Salting Ways'. Polymer Materials Science and Engi C08G 8/02 (2006.01) neering, 1989, n° 3. p. 64-68; 5. pgs: Includes abstract in English. COSG 75/23 (2006.01) Nassau Kurt "Color”. Kirk-Othmer Encyclopedia of Chemical (52) U.S. Cl. Technology, 2004, vol. 7, p. 303-341, John Wiley & Sons, Inc.; 39
CPC ...... C08G 65/4093 (2013.01); C07C315/06 E.ovay PProcess, ”, Wikipedia,1Kipedia, thee Free Encyclopedia, "http://ife. 65/4oS 852.2% s wikipedia.org/wiki/Solvay process”, Nov. 21, 2008; 8 pgs. C08G 75/23 (2013.01); C08G 2261/3444 (Continued) (2013.01) (58) Field of Classification Search Primary Examiner — Liam J Heincer CPC ...... C08G 2650/40: C08G 65/4087;65/4012 C08G (74) Attorney,y Agent, or Firm — Osha Liang LLP USPC ...... 528/219, 86, 222 See application file for complete search history. (57) ABSTRACT (56) References Cited Sodium carbonate (Na2CO) having a certain particle size distribution and its use in preparing poly(aryl ether ketone)S. U.S. PATENT DOCUMENTS especially PEEK. Poly(aryl ether ketone)s made using the described sodium carbonate. A method for providing a
3,655,331 A * 4/1972 Seglin et al...... 423, 207 3,904,733. A * 9/1975 Gancy et al. . ... 423,206.2 Sodium carbonate having a certain particle size distribution, 4,113,698 A * 9/1978 Staniland ...... 528,481 which is especially well suited for the preparation of poly 4,151,261 A * 4, 1979 Poncha et al...... 423,206.2 (aryl ether ketone)s. 4,176,222 A * 1 1/1979 Cinderey et al...... 528,126 4,320,224. A 3, 1982 Rose et al. 4.331,798 A 5, 1982 Staniland 13 Claims, No Drawings US 9,175,136 B2 Page 2
(56) References Cited OTHER PUBLICATIONS International Search Report and Written Opinion issued Feb. 15. U.S. PATENT DOCUMENTS 2010 in corresponding International Application No. PCT/EP2009/ 064011 (10 pages). 2011/0213115 A1 9, 2011 Louis ...... 528,126 International Preliminary Report on Patentability issued Apr. 26. 2011/0224399 A1* 9, 2011 Louis et al...... 528,126 2011 in corresponding International Application No. PCT/EP2009/ 064011 (7 pages). FOREIGN PATENT DOCUMENTS Communication pursuant to Article 94(3) EPC issued Feb. 2, 2012 in corresponding European application No. 09 737 003.5 (5 pages). EP O194062 A2 9, 1986 Communication pursuant to Article 94(3) EPC issued Jan. 10, 2013 in EP 211693 A1 2, 1987 corresponding European application No. 09 737 003.5 (3 pages). EP O3O3389 A2 2, 1989 Sodium carbonate—a versatile material; published by the Royal EP 2292673 A1 3, 2011 Society of Chemistry; “Manufacturing sodium carbonate—an over GB 2217322. A 10, 1989 view for teachers' (2 pages). WO 95.315O2 A1 11, 1995 Sodium Carbonate; SIDS Initial Assessment Report for SIAM 15; WO WOO1666.20 A2 9, 2001 Boston, USAA, Oct. 22-25, 2002; UNEP Publications (22 pages). WO WO 2009021918 A1 2, 2009 Technical Data Sheet—Light Sodium Carbonate; NovaCarb; Jan. WO WO 2010046482 A1 4/2010 2004 (2 pages). WO WO 2010046483 A1 4/2010 WO WO 2010046487 A1 4, 2010 * cited by examiner US 9, 175,136 B2 1. 2 METHOD FOR THE MANUFACTURE OF For example, U.S. Pat. No. 4,320.224 (Rose et al.) POLY(ARYL ETHER KETONE)S IN THE describes the preparation of PEEK by reacting 4,4'-difluo PRESENCE OF SODIUM CARBONATE robenzophenone with p-hydroquinone in the presence of at least one alkali metal carbonate orbicarbonate. In particular, CROSS-REFERENCE TO RELATED Rose's Example 3 (which was submitted for comparison APPLICATIONS purposes) describes a polymerization process for making The present application is a U.S. national stage entry under PEEK using a certain anhydrous Sodium carbonate as sole 35 U.S.C. S371 of International Application No. PCT/ alkali metal carbonate or bicarbonate; the PEEK made EP2009/064011 filed Oct. 23, 2009, which claims the priority accordingly suffered from a low IV (equal to 0.48) and a benefit to U.S. provisional application No. 61/108,096 filed rather dark color (absorbance of 0.20). Precisely, Rose on Oct. 24, 2008, to U.S. provisional application No. 61/108, teaches, notably on col. 7, 1.46-50, that the formation of low 097 filed on Oct. 24, 2008, and to U.S. provisional application molecular weight, dark-colored, brittle PEEK, results from No. 61/140,205 filed on Dec. 23, 2008, the whole content of all these applications being herein incorporated by reference the use of sodium carbonate or bicarbonate alone, and pro 15 poses, as Sole remedies, to use instead a higher alkali metal for all purposes. carbonate orbicarbonate (such as KCO) either alone, or in FIELD OF THE INVENTION admixture with NaCO. Unfortunately, Rose's proposed remedies are generally not as Suitable as desired; indeed, the The present invention relates to the use of a sodium car use of KCO or another higher alkali metal has also some bonate (Na,CO) having a certain particle size distribution in negative influence on polymer properties (resulting in gels preparing poly(aryl ether ketone)s, especially PEEK. Poly and discolored polymer), as described in ICI Patent applica (aryl ether ketone)s made using said sodium carbonate also tion EP001879, and in Zhuo N., Yubin Z., Zhongwen W., make up a part of the invention, as well as compositions of Xinyi T. Polymer Materials Science and Engineering, 1989, matters and shaped articles comprising said poly(aryl ether N3, P64-68. These ones are completely overlooked by Rose. ketone)S. 25 Besides, Rose provides no information on the particle size The present invention relates also to a method for providing distribution of the sodium carbonate of Example 3, except a sodium carbonate having a certain particle size distribution, that that has been sieved through a 500 um sieve; as a matter which is especially well suited for the preparation of poly of fact, based on the low IV and dark color of the resulting (aryl ether ketone)s. PEEK, it can be concluded a posteriori, accounting for the 30 Applicant's present contribution, that the Sodium carbonate BACKGROUND OF THE INVENTION used by Rose had very likely a Doo well above 250 um. More precisely, considering that that the most broadly available Poly(aryl ether ketone)s (i.e., PAEKs) are a well known Sodium carbonates are by far dense sodium carbonates (of class of engineering polymers useful in various fields of which the Ds are typically of about 400 um), it is very likely endeavor. Poly(ether ether ketone) (PEEK) and poly(ether 35 that Rose's sodium carbonate is a dense Sodium carbonate ketone) (PEK) are the most common PAEKs. PEK and PEEK that was sieved through a 500 um sieve, and the sieving are high-strength, radiation-resistant engineering plastics operation that was operated, did obviously not eliminate the whose structures combine both ether and ketone groups. Both bigamount of particles having a diameter of 400 um up to less are thermally stable and highly resistant to chemicals. Gen than 500 um which were contained in the dense sodium erally, PAEKs are prepared by aromatic nucleophilic substi 40 carbonate. Finally, it is noted that Rose does not provide any tution. For example, p-hydroquinone can be used as a nucleo information on the possible importance that the particle size philic component which is deprotonated with a base Such as distribution of the alkali metal carbonate or bicarbonate may NaOH, NaCO, KCO, or a combination of NaCO and have on the PEEK polymerization process and polymer prop KCO. The resultant phenolate may then react with, e.g., an erties. aromatic dihalocompound, in particular a dihalobenzophe 45 U.S. Pat. No. 4,636,557 is similar, using a combination of, none such as 4,4'-difluorobenzophenone to forma PAEK, e.g. e.g., sodium carbonate and calcium carbonate in the prepara PEEK, via nucleophilic substitution, with the halogen atoms tion of a PAEK and indicating that “the particle size of the of the dihalobenzophenone acting as leaving groups. Certain carbonates used according to the invention is not in itself dinucleophiles other than p-hydroquinone commonly used as critical, but they are preferably used in a finely ground state monomers in the synthesis of PAEKs are bisphenols such as 50 and mostly have particle sizes smaller than 0.3 mm. The 4,4'-dihydroxybenzophenone, 4,4'-biphenol, 1,4-bis(p-hy particle sizes are preferably between 1 and 250 um”. droxybenzoyl)benzene, 1,3-bis(p-hydroxybenzoyl) Although it is not clear exactly what carbonate particle sizes benzene. . . . . Aromatic trinucleophiles, aromatic poly(>3)- were used in the several Examples of U.S. Pat. No. 4,636,557, nucleophiles, aromatic trihalocompounds, aromatic poly(>3) Example 1 (using potassium carbonate) indicates that the halocompounds, and mixtures thereof can also be used, gen 55 particles were “ground to a particle size of less than 0.3 mm. erally in addition to the aromatic dinucleophile and the U.S. Pat. No. 5,081,214 describes a process for the prepa aromatic dihalocompound, when a branched or cross-linked ration of an aromatic polyether employing a mixture of PAEK is to be synthesized. Sodium carbonate and sodium hydrogen carbonate. The ref Often, such PAEK reactions are carried out in a solvent; the erence states that the advantages achieved according to the Solvent may be, or may contain, diphenylsulfone. Addition 60 invention are not dependent on the particle size of the carbon ally, the reaction is often, but not always, carried out using a ate compounds used, and further indicates that using a mix cosolvent which forms an azeotrope with water, to help the ture of “coarse particle'soda having a particle size from 200 removal of water from the reaction mixture, such as p-Xylene. um to 800 um and sodium bicarbonate can help prevent To the best of the inventor's knowledge, the effect of unwanted dust formation during filling of the reaction vessel. Sodium carbonate particle size on the characteristics of a 65 The Examples of U.S. Pat. No. 5,081,214 use such “coarse PAEK produced therewith has not been thoroughly or sys particle' sodium carbonate while Comparative Examples use tematically investigated. Sodium carbonate having a particle size of 80 um. US 9, 175,136 B2 3 4 Finally, both U.S. Pat. Nos. 4,868,273 and 5,194,561 relate sation auxiliary, while the presence of a Substantial amount of to the preparation of polyethers that can or must contain Such another additional condensation auxiliary, e.g. potas —SO-linking groups in the presence of sodium carbonate. sium carbonate may be necessary to synthesize high molecu In U.S. Pat. No. 4,868.273 the sodium carbonate is desirably lar weight PAEKs when sodium carbonate not meeting the used in a finely divided form in order to avoid a product with requirements is used. As already mentioned, it is known that a lower inherent viscosity (IV). For example, using sodium the use of KCO has some negative influence on polymer carbonate particles all below 0.261 mm a polymer product properties (gels and discolored polymer). with an IV of over 0.7 was obtained, whereas with at least The inventor has also unveiled an original and particularly 50% by weight of the particles over 0.376 mm the IV of the advantageous method for providing a sodium carbonate hav product obtained was less than 0.7. 10 ing a certain particle size distribution, which is suitable for U.S. Pat. No. 5,194.561 describes a process for the prepa providing a PAEK with a good properties, including Superior ration of an aromatic polyether in which metal carbonates color and, if desired, the lack of a cosolvent forming an including sodium carbonate are used in the form of finely azeotrope with water Such as p-Xylene when synthesizing the ground salts. U.S. 561 teaches that polyether sulfone synthe polymer. This method for providing a performing Sodium sis can proceed satisfactorily using sodium carbonate having 15 carbonate represents another important aspect of the present a Doo value of about 50 um; on the other hand, according to invention. As will be seen later on, the so-provided sodium U.S. 561, polyether ketone synthesis would require a more carbonate is a light sodium carbonate. Hence, in relation finely ground material, with the preference being given to Doo herewith, the inventor has also proposed a new method for values of below 30 um, in particular below 20 um. The making the commerce of a light sodium carbonate Suitable for expressed requirements in terms of particle size would result providing a PAEK with a good properties, including Superior from differences of reactivity of the monomers involved in the color and, if desired, the lack of a cosolvent forming an polycondensation reactions. azeotrope with water Such as p-Xylene when synthesizing the PAEKs are known for their exceptional balance of techni polymer, said method emphasizing the particular particle size cal properties, namely high melting point, good thermal sta distribution of the light sodium carbonate of concern. bility, high stiffness and strength, good toughness and really 25 Additional aspects and other features of the present inven excellent chemical resistance. Therefore, PAEKs have poten tion will be set forth in part in the description that follows and tial for a wide variety of uses, and their favorable properties in part will become apparent to those having ordinary skill in class them with the best of the engineering polymers. How the art upon examination of the following or may be learned ever, PAEKs currently available to the trade suffer from cer from the practice of the present invention. The advantages of tain disadvantages. 30 the present invention may be realized and obtained as particu PAEKs currently available to the trade have an inherent larly pointed out in the appended claims. As will be realized, yellow to darkgrey color as formed, which limits their use in the present invention is capable of other and different embodi certain specific applications where lighter colors are needed. ments, and its several details are capable of modifications in PAEKs having an improved, lighter color could find wider various obvious respects, all without departing from the acceptance for many applications where color is a concern. 35 present invention. The description is to be regarded as illus Lower color PAEKs are thus clearly needed by the art and trative in nature, and not as restrictive. would represent a significant improvement over the PAEKs currently available to the trade. DETAILED DESCRIPTION OF THE PREFERRED Moreover, PAEKs are very good candidates for medical EMBODIMENTS applications. For these ones, the presence in the PAEKs of 40 residues of toxic compounds like p-Xylene, which, as above In a method according to the present invention, a poly(aryl explained, is otherwise helpful for removing the water from ether ketone) is prepared by aromatic nucleophilic Substitu the reaction mixture, should desirably be avoided or at least tion in the presence of particulate Sodium carbonate, wherein reduced to a minimum. said particulate Sodium carbonate has a particle size distribu In addition, there is also a need for PAEK featuring an 45 tion as follows: Dooe45um and Doos250 um and Doss710 improved processability. lm. These and other needs are met by certain embodiments of Nucleophilic substitution forms a well-known, fundamen the present invention. tal class of Substitution reaction in which a nucleophile (i.e. a chemical compound or group that is attracted to nuclei and SUMMARY OF THE INVENTION 50 tends to donate or share electrons) chemically reacts with an electrophile (i.e. a chemical compound or group that is The inventor has thoroughly and systematically investi attracted to electrons and tends to accept electrons), by selec gated the effect of sodium carbonate particle size on the tively bonding with the positive or partially positive charge of characteristics of a PAEK produced therewith, and have iden an atom of the electrophile (for example, a carbon atom) and tified a particle size range that provides a PAEK with good 55 displacing a group or atom attached to the atom bearing the properties, including Superior colorand, if desired, the lack of positive or partially positive charge (said displaced group or a cosolventforming an azeotrope with water Such as p-Xylene atom being commonly referred to as the leaving group). when synthesizing the polymer. The present invention thus Dinucleophiles are compounds which comprise two nucleo relates to Sodium carbonate having a certain particle size philic groups, while dielectrophiles are compounds compris range and its use in PAEKs manufacture, especially PEEK. 60 ing two electrophilic groups. PAEKS made using the sodium carbonate according to the This invented method comprises generally the condensa present invention also make up a part of the invention, as well tion reaction between an aromatic dinucleophile and an aro as compositions of matters and shaped articles comprising matic dielectrophile, or the auto-condensation reaction of an said PAEKS. Among other advantages, using sodium carbon aromatic compound comprising one electrophilic group and ate powder meeting these requirements allows one to synthe 65 one nucleophilic group; an aromatic dinucleophile, an aro size easily high molecular weight PAEKs in the presence of a matic dielectrophile and an aromatic compound comprising reduced amount, or even in the absence, of any other conden one electrophilic group and one nucleophilic group can also US 9, 175,136 B2 5 6 be reacted all together. Typically, in this invented method, an ring or to carbonatoms of different benzenic rings. In certain aromatic diol. Such as a hydroquinone and/or a bisphenol, embodiments, the halogeno groups are in para position with undergoes a condensation reaction with an aromatic dihalo respect to each other. compound, or an aromatic monohydroxy-monohalocom Certain aromatic dielectrophiles useful in the synthesis of pound undergoes an auto-condensation reaction; an aromatic PAEKs in accordance with the present invention are aromatic diol, an aromatic dihalocompound and an aromatic monohy dihalocompounds selected from the group consisting of 4,4'- droxy-monohalocompound can also be reacted all together to halobenzophenone, 1,4-bis(p-halobenzoyl)benzene, 1,3-bis form the PAEK. (p-halobenzoyl)benzene 1,4-bis(p-halobenzoyl)biphenyl, Aromatic dinucleophiles for use in the present invention and any combinations thereof. Aromatic electrophiles for use are usually chosen from aromatic diols, wherein each of the 10 in the present invention are preferably chosen from 4,4'- hydroxy groups (—OH) is directly linked to a carbonatom of difluorobenzophenone, 1,4-bis(p-fluorobenzoyl)benzene, a benzenic ring. Both hydroxy groups may be directly linked 1,3-bis(p-fluorobenzoyl)benzene 1,4-bis(p-fluorobenzoyl) to different carbon atoms of the same benzenic ring, or to biphenyl, and any combinations thereof. More preferably, the carbon atoms of different benzenic rings. In certain embodi aromatic dielectrophile is 4,4'-difluorobenzophenone. Pre ments, the hydroxy groups are in paraposition with respect to 15 cisely, the Applicant has surprisingly found that, when 4,4'- each other. difluorobenzophenone is the aromatic dielectrophile, Certain aromatic dinucleophiles useful in the synthesis of improved results are obtained when said 4,4'-difluoroben PAEKs in accordance with the present invention are aromatic Zophenone complies with certain impurity limitations. diols selected from the group consisting of: Embodiment (D) Hence, in a particular embodiment (D) of the present invention, the invented method for the preparation of a poly V-OH (aryletherketone) is a method by aromatic nucleophilic sub OH stitution in the presence of particulate Sodium carbonate hav to-( )-()—on to-( ) 25 ing the particle size distribution requirements as described in the present document, said method comprising the conden sation reaction between an aromatic dinucleophile and 4,4'- OH difluorobenzophenone, wherein the 4,4'-difluorobenzophe none meets the following impurity limitation: 2,4'- OH 30 difluorobenzophenone--4-monofluorobenzophenone CO in s1250 ppm wherein the amounts of 2,4'- difluorobenzophenone and 4-monofluorobenzophenone in 4,4'-difluorobenzophenone are determined by liquid chroma tography analysis. 35 For example, the liquid chromatography determination can be carried out with a Agilent 1100 LC High Pressure Liquid Chromatography instrument using a Supelco Discovery HS F5, 5 um, 25 cmx4.6 mm column. Suitable analysis condi s-N-1s tions include: HO-H- - HOH 40 Mobile Phase: acetonitrile? deionized water 2 2 Gradient: 60/40 acetonitrile/water for 5 minutes, increase to s- N-1s 100% acetonitrile in a further 10 minutes. HO-H- -HOH Flow rate: 1 ml/minute 21 2 Detection: UV 254 nm 45 Temperature: 50° C. s- N Injection Volume: 5ul HO-H- - HOH The sample is prepared by dissolving about 0.01 g of 4,4'-difluorobenzophenone in 100 ml of acetone. 21 1\4 The amount of 2,4'-difluorobenzophenone and 4-monof 50 luorobenzophenone in 4,4'-difluorobenzophenone is typi and any combinations thereof, wherein G is independently cally determined using a calibration with three external stan selected from a carbonyl group (C=O), an oxygen atom dards of these commercially available compounds, of (—O—) or a Sulfur atom ( S-); in particular, in the last two different concentrations, to generate a calibration curve. depicted formulae, all the G may be oxygen atoms. Under the above detailed conditions, the retention time of Preferred aromatic dinucleophiles for use in the present 55 2,4'-DFBP is typically about 7.4 minutes and 7.1 minutes for invention are chosen from p-hydroquinone, 4,4'-dihydroxy 4-monofluorobenzophenone. The retention time for 4,4'- benzophenone, 4,4'-biphenol, 1,4-bis-(p-hydroxybenzoyl) DFBP is typically about 7.7 minutes. benzene and 1,3-bis-(p-hydroxybenzoyl)benzene, and any Results are expressed as parts per million of the two impu combination thereof. More preferably, the aromatic dinucleo rities. philes are chosen from p-hydroquinone, 4,4'-dihydroxyben 60 In present embodiment (D), preferably, the 4,4'-difluo Zophenone and any combinations thereof. Still more prefer robenzophenone further meets the following impurity limita ably, the aromatic dinucleophile is p-hydroquinone. tion: Aromatic electrophiles for use in the present invention are 2,4'-difluorobenzophenones750 ppm, usually chosen from aromatic dihalocompounds, wherein and, more preferably, it further meets at least one of the each of the halogeno groups is directly linked to a carbon 65 following sets of impurity limitations: atom of a benzenic ring; both halogeno groups may be Set 1: 2,4'-difluorobenzophenones750 ppm, and 4-monof directly linked to different carbonatoms of the same benzenic luorobenzophenones500 ppm, US 9, 175,136 B2 7 8 Set 2: 2,4'-difluorobenzophenones300 ppm, and 4-monof chloride is added, followed by addition of a 5.00 ml aliquot of luorobenzophenones'950 ppm. spiking solution, which contains six drops of 37% hydrochlo Aromatic compounds comprising one electrophilic group ric acid per liter, into the same titration vessel. The vessel is and one nucleophilic group for use in the present invention are then attached to the titrator cell assembly containing the buret usually chosen from aromatic monohydroxy-monohalocom tip, pH electrode, and magnetic stirrer. The vessel is then pounds compounds, wherein the hydroxy group is directly purged with carbon dioxide free nitrogen for 5-7 minutes. linked to a carbon atom of a benzenic ring and the halogeno While continuing the nitrogen purge, the vessel contents is group is also directly linked to a carbon atom of a benzenic titrated with 0.025 N tetrabutylammonium hydroxide in 1:12 ring; both groups may be linked to different carbon atoms of methanol:toluene and the volume of titrant required to reach the same benzenic ring or to carbon atoms of different ben 10 the strong acid endpoint is measured. A blank titration is Zenic rings. In certain embodiments, the hydroxy group is in performed using the same parameters, except that the sample para position with respect to the halogeno group. was omitted. Results are calculated using the following equa Certain aromatic useful in the synthesis of PAEKs in accor tion: dance with the present invention are aromatic monohydroxy 15 monohalocompounds selected from the group consisting of Acidity=(VS1 VB1)*N*100000), Win microeduiva 4-halo-4'-hydroxybenzophenone, 4-(p-halobenzoyl)-4-hy lents per gram of sample droxybiphenyl, 4-(p-halobenzoyl)-4-hydroxydiphenyl ether, where VS1 is the amount of titrant in ml required to reach the 4-halo-4'-hydroxyterephthalophenone, 4-halo-4'-hydroxy strong acid/base equivalence points when sample solution is isophthalophenone; and any combinations thereof. Preferred titrated and VB1 is the amount of titrant in ml required to aromatic monohydroxy-monohalocompounds are preferably reach the strong acid/base equivalence point when only the selected from the group consisting of 4-fluoro-4'-hydroxy blank solution is titrated, W is the sample weight, and N is the benzophenone, 4-(p-fluorobenzoyl)-4-hydroxybiphenyl, normality of the tetrabutylammonium hydroxide titrant. If 4-(p-fluorobenzoyl)-4-hydroxydiphenyl ether, 4-fluoro-4"- acidity is negative, the sample contains basic species. hydroxyterephthalophenone, 4-halo-4'-hydroxyisophth 25 alophenone; and any combinations thereof. More preferably, The Sodium, potassium, and iron content in diphenylsul the aromatic monohydroxy-monohalocompound is 4-fluoro fone can be determined as follows. Concentrations of sodium, 4'-hydroxybenzophenone. potassium, and iron are measured in diphenylsulfone by ash In accordance with the method of the present invention, the ing of the sample followed by measurement of element con poly(aryl ether ketone) (PAEK) is generally produced in a 30 centration by inductively-coupled plasma atomic emission solvent. Such PAEK reactions by aromatic nucleophilic sub spectrometry. Approximately 3 g of diphenylsulfone sample stitution are often carried out in a solvent that often is, or that is weighed into platinum crucibles using an analytical bal often contains, diphenylsulfone. However, many other Sol ance. Two drops of concentrated, trace metals grade Sulfuric vents can be used, including benzophenone, diben acid is added to each sample and the crucibles are placed into Zothiophene dioxide, etc. When the solvent is or contains 35 a muffle furnace set to 250° C. After the diphenylsulfone has diphenylsulfone, said diphenylsulfone meets advantageously vaporized, the furnace temperature is raised to 525°C. for 1 one or more impurity limitations, as specified in embodiment hour to remove any organic residues. Metallic residues are (E) hereinafter. dissolved by adding 1 ml of concentrated hydrochloric acid to Embodiment (E) the crucible and warming at 50° C. to dissolve the ash. After In a preferred embodiment (E) of the present invention, the 40 addition of 5 ml of deionized water and additional warming, invented method for the preparation of a poly(aryletherke crucible contents are quantitatively transferred to a 25-ml tone) is a method by aromatic nucleophilic Substitution in the Volumetric flask, diluted to the mark with deionized water, presence of particulate sodium carbonate having the particle and mixed well. The diluted solutions are then analyzed by size distribution requirements as described in the present ICP-AES against standards made from certified sodium, document, in a solvent comprising a diphenylsulfone, 45 potassium, and iron Standard solutions. Emission is moni wherein said diphenylsulfone meets at least one of the fol tored at the following wavelengths for the elements of inter lowing impurity limitations: est: sodium: 589.592 nm, potassium: 766.490 nm and iron: 238.204 nm. Plasma conditions used for the analysis are: plasma input power: 1300 watts, plasma argon flow: 15 liters Monomethyldiphenylsulfone content Less than 0.2 area 96 (Sum of all isomers) 50 per minute, auxiliary argon flow: 0.5 liters per minute, nebu Monochlorodiphenylsulfone content Less than 0.08 area 96 lizer flow: 1.2 liters per minute, and sample flow rate: 1.5 (Sum of all isomers) milliliters per minute. Element concentrations in the samples Sodium content Less than 55 ppm are calculated by the ICP operating software from the element Potassium content Less than 15 ppm emission line intensities. Iron content Less than 5 ppm Residual acidity content Less than 2.0 eqfg 55 The total chlorine content in diphenylsulfone can be deter Diphenylsulfide content Less than 2.0 wt.% mined as follows. Using forceps, a clean, dry combustion boat APHA of 20 wt.% solution in acetone at 25°C. Less than 50 is placed onto a microbalance, and the balance is Zeroed. 1 mg Total chlorine content Less than 120 ppm of diphenylsulfone sample is weighed into the boat and weight is recorded to 0.001 mg. The combustion boat and where ppm and wt.% are based on the total weight of the 60 sample are placed in the introduction port of a Thermo Elec diphenylsulfone and area % represents the ratio of the GC tron Corporation ECS 1200 Halogen Analyzer, and the port is peak area of the impurity of concern over the total area of all capped. The sample weight is entered into the sample weight GC peaks of the diphenylsulfone. field on the instrument computer. The sample analysis cycle is The residual acidity content in diphenylsulfone can be then started. The sample is burned in a mixture of argon and determined as follows. Approximately 3 g of diphenylsulfone 65 oxygen and the combustion products are carried by the com sample is weighed to the nearest 0.1 mg and added to an bustion gas stream into a titration cell. Hydrogen chloride empty glass titration vessel. 55 ml of high-purity methylene produced from the combustion is absorbed into the cell solu US 9, 175,136 B2 9 10 tion from the gas stream, and is coulometrically titrated with As above said, in accordance with the method of the silver ions. Total chlorine content is displayed at the end of the present invention, the poly(aryl ether ketone) (PAEK) is gen titration. erally produced in a solvent. Additionally, such PAEK reac The diphenylsulfide content in diphenylsulfone can be tions by aromatic nucleophilic Substitution may be carried out determined by liquid chromatography, as explained herein 5 in the additional presence of a cosolvent which forms an after. HPLC analysis is carried out on a Waters Alliance 2795 azeotrope with water, to help the removal of water from the LC instrument using a Supelco Discovery HS F525 cmx4.6 reaction mixture. Such as p-Xylene, chlorobenzene or toluene. mm column. The analysis conditions are: In a particular embodiment of the present invention, the poly Mobile phase: acetonitrile/deionized water. (aryl ether ketone) is produced in a solvent and in the absence 10 of p-Xylene. In another particular embodiment of the present Gradient: 60/40 acetonitrile/water, hold for 5 minutes, invention, the poly(aryl ether ketone) is produced in a solvent increase to 100% acetonitrile in further 10 minutes, hold for 5 and in the absence of any cosolvent which forms an azeotrope minutes at 100% acetonitrile with water. Flow rate: 1 ml/minute As already mentioned, the present invention relates, in part, Injection volume: 10 ul 15 to a method for the preparation of a poly(aryl ether ketone) by Detection: UV at 254 nm aromatic nucleophilic Substitution in the presence of particu The sample is prepared by dissolving 0.2 g of diphenylsul late sodium carbonate, wherein said particulate sodium car fone (DPS) in 10g of acetonitrile. The concentration of diphe bonate has a particle size distribution as follows: Dooe45um nylsulfide is determined using a low concentration diphenyl and Doos250 um and Doss710 Lim, and to the poly(aryl ether Sulfide as an external calibration standard (commercially ketone) produced by said method. available). The retention time for DPS is typically 6.2 minutes As used herein, a sodium carbonate particle size distribu and the retention time for diphenylsulfide is typically 10.7 tion expressed as DisYum refers to the percentage (XX%) of minutes. The diphenylsulfide concentration in the DPS Sodium carbonate particles by weight in a sample that are less sample is assessed by the area of the diphenylsulfide peak/ than or equal to Yum in diameter, as measured usually by total peak area of DPS plus impurities. 25 mechanical sieving, typically as described in the examples The monochlorodiphenylsulfone and monomethyldiphe (see hereinafter: “EXAMPLEs Section "Particle size distribu nylsulfone content in diphenylsulfone can be determined by tion (PSD) of NaCO determined by mechanical sieving). gas chromatography, as explained hereinafter. GC analysis is On one hand, NaCO, that is “too fine” is to be avoided as performed on an HP5890 series 11 gas chromatograph using it can notably lead to a low bulk density product that is a Restek RTX-5MS, 15 mx0.25 mm internal diameterx0.25 30 difficult to handle and synthesis reaction kinetics that are um film thickness column. The following GC conditions are difficult to control. With this regard, the Applicant found that used: NaCO with a Docs45um was required. Helium flow rate: 1 ml/minute, On the other hand, NaCO that contains a certain amount Injector temperature: 250° C. of “big” particles, and especially of “very big particles (i.e., FID temperature: 250° C. 35 typically of about 710 um or more), is also to be avoided as it Oven Temperature Program: 100° C., hold 1 minute, 30° can notably slow down the polymerization rate, or require the C./minute to 250° C., hold 1 minute use of an undesirably high amount of KCO or other higher Total run time: 14 minutes alkali metal carbonate (at fixed NaCO amount); NaCO Injection Volume: 1 ul that contains a certain amount of “big particles, and espe Split 40:1 40 cially of “very big particles, can also result in polymeriza The sample is prepared by dissolving 0.2 g of DPS in 5 ml tions having poor kinetics consistency. With this regard, the of acetone. Typically the GC retention times for monometh Applicant found that NaCO, with a Dos250 um and with a yldiphenylsulfone isomers are 8.0 and 8.1 minutes and for Dooss710 um was also required. monochlorodiphenylsulfone 8.2 minutes. The identity of the The use of particulate Sodium carbonate meeting the inven impurities is determined by GCMS run on the sample solu 45 tion particle size specifications provides several benefits, tion. The impurity concentrations are quoted as area 96, cal including the ability to synthesize PAEKs in the absence of a culated from GCFID peak areas. When several isomers are cosolvent forming an azeotrope with water Such as p-Xylene, present, the concentration includes the Sum of these isomers. and thereby prepare PAEKs with no trace of residual cosol The color (APHA) of DPS in acetone can be determined as vent (Such cosolvents, like p-Xylene, are generally toxic). follows. 20 g of diphenylsulfone are dissolved in 80 g of 50 CoSolvents forming an azeotrope with water used in the Syn acetone at 25° C. The acetone used contains less than 0.5 thesis of PAEK resins are known to those of skill in the art, wt.% water. Color of the solution is measured as compared to and in addition to p-Xylene include chlorobenzene, toluene, Pt Co standards in the APHA scale (ASTM D1209-00), etc. using a Gretag Macbeth Color Eye Ci5 Spectrophotometer The use of particulate Sodium carbonate meeting the inven for the comparison. The blank used is distilled water. 55 tion particle size specifications makes it also possible to In the method in accordance with embodiment (E) of the manufacture lower color, whiter PAEK resins. present invention, said diphenylsulfone meets preferably the The use of particulate Sodium carbonate meeting the inven impurity limitations for monomethyldiphenylsulfone, tion particle size specifications results also beneficially in monochlorodiphenylsulfone, and residual acidity. improved kinetics consistency. Additionally or alternatively, in the method in accordance 60 The invention particle size limitation Doss710 um with embodiment (E) of the present invention, said diphenyl includes, of course, Dos values of Doss700m, Doss650 sulfone meets preferably the impurity limitations for sodium, um, Dooss600 um, Dooss550 Lum, Dooss500 Lum, Dooss450 iron, diphenylsulfide, and APHA of 20 wt.% solution in um, Dooss400 um, Doss350 Lum, Doss300 Lum, Doss250 acetone at 25°C. um, Dooss224 Lum, Dooss200 lm, Dooss 150 um, etc. In this In the method in accordance with embodiment (E) of the 65 regard, where a numerical limit is stated, all values and Sub present invention, excellent results were obtained when all ranges within the limit are specifically included as if explic the impurity limitations as above recited were met. itly written out. Preferably, the Dogs of the sodium carbonate US 9, 175,136 B2 11 12 particles according to the invention is of at most 630 um; more tal revolutions and taps per minute. Also, the sieves mounted preferably, it is of at most 500 um; still more preferably, it is on the sieve shaker are advantageously in conformity with of at most 425um; most preferably, it is of at most 355 um. standard ISO 3310-1 or ASTM E-11, preferably with wire The lower limit of the Does of the sodium carbonate par stainless steel circular sieves with square meshes, metal ticles according to the invention is not critical. Obviously, it is mounting with a diameter 200 mm. The device and its sieves of at least 45um, and may be notably of at least 63 um, at least are advantageously checked periodically using a reference 75um, at least 90 Lum, at least 100 um, at least 125 um or at powder; the control frequency should be desirably be as high least 150 um. as possible for early detection of any deviation, as possibly The invention particle size limitation Dos45um includes, resulting for damaged meshes. The sieves are Superimposed of course, Doo values of Dooe75um, Doe 100 um, Dooe125 10 um, Dooa 150 um, Doe 175 um, Dooe200 um, etc. In this and assembled from top to bottom by descending order of regard, where a numerical limit is stated, all values and Sub opening mesh. A fixed weight amount of the powder to be ranges within the limit are specifically included as if explic investigated is weighed with an analytical balance and placed itly written out. Preferably, the Do of the sodium carbonate on top of the widest sieve. By vibrating the sieving machine, particles according to the invention is of at least 63 um; more 15 the powder material is conveyed through the various sieves. preferably, it is of at least 90 um; still more preferably, it is of The sieving operation is run for a fixed amount of time. The at least 112 Lum. residues on the sieves are weighed with an analytical balance The invention particle size limitation Doos250 um and related mathematically to the initial weight of material. includes, of course, Doo values of Doos200um, Doos 150 um, Notably Dso, Doo, and Doos values can be calculated from the Dooss 100 um, etc. In this regard, where a numerical limit is residues weights. This calculation is generally made as fol stated, all values and Subranges within the limit are specifi lows: cally included as if explicitly written out. Preferably, the Do 1) Calculate the weight percentage of the test specimen of the Sodium carbonate particles is of at most 212 um; more retained on each sieve. preferably, it is of at most 180 um; still more preferably, it is 2) Express the weight percentage passing through each sieve, of at most 150 um. 25 and cumulated. In preferred embodiments of the invention the sodium car For example, with the set of sieves as described in the bonate has the following particle size distributions: “EXAMPLES’ section of the present application, the cumu Dooss630 um, Doos212 um, and Dooe45um; or lative percent retained on the 250 um sieve can determined by Dooss500 um, Doos212 um, and Dooe45um; or adding the weights of the particles on the 1000, 500 and 250 Dooss425um, Doos212 um, and Dooe45um; or 30 um, dividing the Sum by the total weight of the original Dooss630 um, Doos 180 um, and Dooe45um; or sample and multiplying by 100. The results can be displayed Dooss500 LM, Doos 180 Lim, and Doos45um; or on a graph were the Y-coordinate represents the cumulative Dooss425um, Doos 180 Lim, and Dooe45um; or weight percent particles retained on a particular sieve. The Dooss630 um, Doos212 um, and Dooe63 um; or X-coordinate corresponds to sieve size. The Y-value for a Dooss500 um, Doos212 um, and Dooe63 um; or 35 particular sieve can be determined by adding the weight of the Dooss425um, Doos212 um, and Dooe63 um; or particles retained on that sieve plus the weights of the par Dooss630 um, Doos212 um, and Dooe90 Lum; or ticles retained on all larger sieves above it and dividing the Dooss500 um, Doos212 um, and Dooe90 um; or sum by the total weight of the sample. Dooss425um, Doos212 um, and Dooe90 Lum. In more general terms, a total of n sieves (wherein n is a The particle size distribution of the sodium carbonate can 40 positive integer generally equal to at least 5, preferably of at be determined by any appropriate means. Among others, it least 8, when the whole particle size distribution is to be can be notably cited Dynamic Light Scattering (DLS) and measured) of nominal aperture size x, (wherein i=1 to n) are mechanical sieving. However, for easiness, broad availability ranked in order of increasing size, i.e. X, is larger than X,. and excellent repeatability, preference is given to mechanical The nominal aperture sizes of the sieves form advanta sieving. The analysis is typically based on the mechanical 45 geously a geometric progression (thus, X. k. X, for i=1 to separation of the various fractions on a series of Superim n-1, wherein k is a constant); as common choices for the “k” posed sieves. The analysis can be made in full accordance constant, it can be cited 2,2'' (1.4142) and 2'' (1.1892). with ASTM E359-00 (reapproved 2005), the whole content The sieves may be ISO 3310-1 or ASTM E-11 test sieves of which being herein incorporated by reference; ASTM E having a diameter of 200 mm, as notably commercialized by 359-00 (reapproved 2005) concerns various measurements 50 LAVAL LAB Inc. These ones are generally characterized by: made specifically on Sodium carbonate, notably sieve analy insofar as their full height is concerned: overall height of 65 sis. Alternatively, the analysis can include certain but not all mm, and depth to cloth of 50 mm: the requirements set forth in ASTM E 359-00 (reapproved concerning insofar has their halfheight is concerned: over 2005); for example, the analysis can include all the require all height of 40 mm, and depth to cloth of 25 mm. ments set forth in ASTM E 359-00 ASTM E 359-00, except 55 They can be constructed notably with a brass frame and a using a different set of sieves. The particle size distribution is stainless steel cloth, or with a stainless steel frame and a advantageously determined with an automatic mechanical stainless steel cloth. sieving device, such Ro-Tap RX-29 sieve shaker (as commer Certain Suitable sets of sieves are composed of eight or ten cialized by W. S. Tyler Company). Said automatic mechanical ISO 3310-1 or ASTM E-11 test sieves having a diameter of sieving device comprises means for mounting nested, screen 60 200 mm, having the following aperture size or ASTM open bottomed pans in a frame. The mounting frame is provided ing designation: with translational motion means at one end and circular 2000 um (ASTM No. 10), 1000 um (ASTM No. 18), 500 motion means at the other to provide continual movement of um (ASTM No. 35), 250 um (ASTM No. 60), 125 um particles on the sieves. The device is thus able to transmit (ASTM (No. 120), 90 um (ASTM No. 170), 63 um combined movements in the horizontal plane and shocks 65 (ASTM No. 230) and 45 um (ASTM No. 325); along the vertical axis to a pile of Superimposed sieves. The 1000 um (ASTMNo. 18),500 um (ASTMNo.35), 250 um device is advantageously set with a fixed number of horizon (ASTM No. 60), 180 um (ASTM No. 80), 125 um US 9, 175,136 B2 13 14 (ASTM (No. 120), 90 um (ASTM No. 170), 63 um using these ten other ISO 3310-1 or ASTM E-11 test sieves (ASTM No. 230) and 45 um (ASTM No. 325); having a diameter of 200 mm: 1000 um (ASTMNo. 18), 710 um (ASTMNo. 25),500 um (set II) 250 um (ASTM No. 60), 212 um (ASTM No. 70), (ASTM No. 35), 355 um (ASTM No. 45), 250 um 150 um (ASTM No. 100), 125um (ASTM No. 120), (ASTM No. 60), 180 um (ASTM No. 80), 125 um 106 um (ASTM (No. 140), 90 um (ASTM No. 170), (ASTM (No. 120), 90 um (ASTM No. 170), 63 um 75 um (ASTM No. 200), 63 um (ASTM No. 230), (ASTM No. 230) and 45 um (ASTM No. 325); and 53 um (ASTM No. 270), 45 um (ASTM No. 325). 850 um (ASTM No. 20), 600 um (ASTM No. 30), 425um The particle size distribution of the sodium carbonate used (ASTM No. 40), 300 um (ASTM No. 50), 212 um in the method for preparing PEEK in accordance with the 10 present invention is advantageously determined on a sample (ASTM No. 70), 150 um (ASTM No. 100), 106 um which is representative of the whole sodium carbonate which (ASTM (No. 140), 75 um (ASTM No. 200), 53 um is used in said method. For the purpose of the present inven (ASTM No. 270) and 38 um (ASTM No. 400). tion, a representative sample can be defined as a sample of The sieves of the last two above sets are characterized by a which at least the Do and Dos values are essentially identi k-constant equal the square root of 2. 15 cal, if not identical, to the ones of the whole sodium carbonate At the end of the sieving analysis, the weight fraction which is used in said method. To achieve appropriate sam caught on each screen is calculated. dd, the fraction on sieve pling, the skilled person will advantageously rely upon all i., of size X, is thus: those sampling recommendations which do form part of the general knowledge and are broadly described in various ency clopedias, including but not limited to "Sampling. Reg. Davies, in “Kirk-Othmer Encyclopedia of Chemical Technol ogy', online Ed. 2000, the whole content of which is herein incorporated by reference. Since Sodium carbonate can be viewed as a free-flowing powder, Sampling procedures Suit wherein w, is the weight of powder collected on sieve isample 25 able for stored free-flowing powders will be used preferably. weight For sodium carbonate stored in bags, the use of a thief sampler to sample different parts of the bag is generally preferred; the The percentage under the size X, P, is thus defined as: particle size analysis is then conducted on a composite sample. For Small containers (e.g. 500 g reagent jar), it is 30 typically preferred that the container be thoroughly shaken and several (3 or more) samples be scooped out of it; a composite sample is then used for the particle size analysis. Provided the particle size distribution of the carbonate is not affected by Subsequent packaging, transporting and/or stor To obtain the cumulative curve, P, the percentage under 35 ing operations, it may be convenient to proceed with the the size X, is plotted versus X. The curve can be built by sampling "at-line directly at the production site on flowing considering in each point the following slope: streams of the powder, by extracting from the product stream by the projection of a sample tube into the flow. In another preferred embodiment the sodium carbonate is 40 anhydrous. However, the Sodium carbonate does not need to be dry since situations occur where, e.g., at the temperature at which the intended reaction is run, any moisture would be driven off. It is typically very important to measure the mois 3) Determine D values (0
(I) ------O
(II)
-()--O-O-O-to-O- (III)
(IV)
() () ( ) - - (V) US 9, 175,136 B2 25 26 wherein: b, c, d and e are 0 or 1, Aris independently a divalent aromatic radical selected from phenylene, biphenylene or naphthylene, a is an integer9. of 1 to 4, and X is independently O, C(=O) or a direct bond, preferably, d is 0 when b is 1. n is an integer of from 0 to 3, More preferably, recurring units (R1) are chosen from:
(VI) (VII) -o-K)--()—O —()--()--()--O (VIII) (IX) O O OC -()-o-()--()-- –K)--O-o-K)-to-K) ()-co –K)--() ( )—co- (XII)
-O-O-O-O-O-O--
-( )-()--() ()-- (XIX) US 9, 175,136 B2 27 28 -continued (XXI)
(XXII)
Coolcro (XXIII) corolor(XXIV) o'color(XXV)
Still more preferably, recurring (R1) are chosen from: 30 recurring units (R1) of formula (VII). APEKhomopolymer is intended to denote any polymer of essentially all (if not, all) the recurring units are recurring units (R1) of formula (VI). (VI) The poly(aryl ether ketone) may be notably a homopoly O mer, a random, alternate or block copolymer. When the poly 35 (aryletherketone) is a copolymer, it may notably contain (i) recurring units (R1) of at least two different formulae chosen from formulae (VI) to (XXV), or (ii) recurring units (R1) of one or more formulae (VI) to (XXV) and recurring units (R1*) different from recurring units (R1). 40 Preferably more than 70 wt.%, more preferably more than 85 wt.% of the recurring units of the poly(aryletherketone) -()--()--()--- are recurring units (R1). Still more preferably, essentially all (VIII) the recurring units of the poly(aryletherketone) are recurring units (R1). Most preferably, all the recurring units of the 45 poly(aryletherketone) are recurring units (R1). As noted above, PAEKs are generally prepared by aromatic nucleophilic substitution. In a preferred embodiment, in the method according to the present invention, an aromatic diol. which can be selected from the group consisting of hydro 50 quinones, bisphenols and mixtures thereof, is deprotonated with sodium carbonate of a particle size as described herein, Most preferably, recurring units (R1) are: and the resultant phenoxide may then react with, e.g., a diha lobenzophenone via nucleophilic Substitution. Semi-crystal line PAEKs prepared by such a nucleophilic substitution (VII) 55 method, particularly in the absence of a cosolventforming an O azeotrope with water, using the invention Sodium carbonate optionally in admixture with another base such as potassium carbonate, make up a part of this invention, as does their –K)--()--K)-- method of preparation. 60 PAEKS prepared according the invention using the A PEEK polymer is intended to denote any polymer of invented Sodium carbonate have advantageously the follow which more than 50 wt.% of the recurring units are recurring ing color characteristics: units (R1) of formula (VII). A PEK polymer is intended to Powder color L*>85, preferably L*>86, more preferably denote any polymer of which more than 50 wt.% of the L*>87; recurring units are recurring units (R1) of formula (VI). 65 Powder color a* is in the range of -1 to 2, preferably A PEEK homopolymer is intended to denote any polymer -1
TABLE 2 Description of the particulate K2CO3 used in the examples Examples Description of the particulate KCO that were used 1 to 13 “Extra fine glass grade EF-90 K2CO commercially available from the Armand Products Company, having a Dogs of 75 m, a Doo of 28 m and a Dso of 14 m, as measured by dynamic light scattering using a Microtrac (R) S3500 analyzer (dry mode, 55 psi nitrogen) 14 Ground EF-80 KCO. grade available from the Armand Products Company, having a Dogs of 1941m, a Doo of 84 m and a Dso of 19m, as measured by dynamic light scattering using a Microtrac (R) S3500 analyzer (dry mode, 55 psi nitrogen) US 9, 175,136 B2 35 36 TABLE 2-continued Description of the particulate K2CO3 used in the examples Examples Description of the particulate KCO that were used 15 Aldrich KCOs, ACS reagent, having a Doss of 475 m, a Doo of 388 m and a Dso of 300 m, as measured by dynamic light scattering using a Microtrac (R) S3500 analyzer (dry mode, 55 psi nitrogen) 16 Aldrich K2CO3, reagent grade, powder-325 mesh, having a Dogs of 65 m, a Doo of 42 m and a Dso of 12 m, as measured by dynamic light scattering using a Microtrac (R) S3500 analyzer (dry mode, 55 psi nitrogen)
Table 3 Summarizes certain important technical features of 15 water, high molecular weight PEEK can be obtained but the exemplified processes, and the RV of the formed PEEK residual p-xylene is detected and the 20 powder can be pink (a-2). TABLE 3 C3 and C4 show that, with Aldrich ACS reagent, 99.95 100.05%, NaCO or with a high-size fraction thereof (not Technical features of the examplified processes and PEEK RV meeting the particle size requirements), and in the absence of Co solvent a cosolvent forming an azeotrope with water, only low forming an Na2CO3 Na2CO3, Na2CO molecular weight is obtained. azeotrope KNa D99.5 Doo Dso RV C11 and C12 show that using Aldrich ACS reagent, 99.95 Example with water (mol/mol) (Lm) (Lm) (Lm) (dg) 100.05%, or a screened fraction thereofusing a 500 um or 425 C1 p-xylene O.OS 900 700 258 O.94 25 um sieve (not meeting the particle size requirements), and in C2 p-xylene O.OS 900 700 258 O.91 the absence of a cosolvent forming an azeotrope with water, C3 O.OS 900 700 258 O48 C4 O.OS 900 82O 395 O.38 only low molecular weight is obtained. C5 O.OS <45 <45 <45 2.36 C5 shows that, with finely ground light Soda ash (not meet 6 O.OS 249 219 141 O.82 ing the particle size requirements), and in the absence of a 7 O.OS 335 135 43 1.60 30 cosolvent forming an azeotrope with water, the reaction can 8 O.OS 335 135 43 1.86 9 O.OS 18O 137 98 1.08 not be controlled and a very high molecular weight is attained 10 O.O2 335 135 43 O.99 in a very short time (about 5 minutes at 310° C.). C11 — O.OOS 579 462 298 0.37 Example 6 (using Aldrich ACS reagent NaCO screened C12 — O.OOS 498 445 239 O3S through 250 um 13 O.OOS 335 135 43 O.89 35 14 O.OOS 335 135 43 1.18 Sieve, meeting the particle size requirements) and 15 O.OOS 335 135 43 1.19 examples 7 and 8 (using a lot of a commercial unground light 16 O.OOS 335 135 43 1.23 Soda ash which meets also the particle size requirements) show that a good control of the reaction kinetics is possible and good quality (color, p-Xylene) polymer is obtained. Table 4 shows the powder color, color characteristics, 40 Examples 13 through 16 show that, using light NaCO a residual cosolvent content, and RV. lot of a commercial unground light soda ash meeting the PSD requirements, high molecular weight, low color PEEK can be TABLE 4 obtained with low levels of KCO. Different grades of Characterization of the PEEK prepared KCOs were used and shown to give similar results. according to examples 1 to 10 45 The above written description of the invention provides a manner and process of making and using it such that any p-xylene in final person skilled in this art is enabled to make and use the same, Powder powder RV this enablement being provided in particular for the subject Example color L* a: b* (ppm) (dg) matter of the appended claims, which make up a part of the 50 original description and including. C1 Off white >10 O.94 C2 Light pink 87.04 2.17 6.95 >10 O.91 As used herein, the phrases “selected from the group con C3 Off white <10 O.48 sisting of “chosen from.” and the like include mixtures of C4 Off white <10 O.38 the specified materials. Terms such as “contain(s) and the C5 Off white 88.61 O.32 4.78 <10 2.36 6 Off white <10 O.82 like as used herein are open terms meaning including at least 7 White 91.93 0.44 5.1 <10 1.60 55 unless otherwise specifically noted. Phrases such as “mention 8 Off white 89.15 0.40 S.13 <10 186 may be made etc. preface examples of materials that can be 9 Off White 85.49 0.64 7.54 <10 1.08 used and do not limit the invention to the specific materials, 10 White 90.40 0.15 4.92 <10 O.99 C11 Off white <10 0.37 etc., listed. C12 Off white <10 O.35 All references, patents, applications, tests, standards, 13 White 85.26 0.43 6.87 <10 O.89 60 documents, publications, brochures, texts, articles, etc. men 14 White 88.54 0.22 6.75 <10 1.18 tioned herein are incorporated herein by reference. Where a 15 White 88.S1 O.23 6.76 <10 1.19 numerical limit or range is stated, the endpoints are included. 16 White 89.91 0.24 S.97 <10 1.23 Also, all values and Subranges within a numerical limit or range are specifically included as if explicitly written out. Examples C1 and C2 show that, using Aldrich ACS 65 The above description is presented to enable a person reagent, 99.95-100.05%, NaCO (not meeting the particle skilled in the art to make and use the invention, and is pro size requirements) and a cosolventforming an azeotrope with vided in the context of a particular application and its require US 9, 175,136 B2 37 38 ments. Various modifications to the preferred embodiments 4. The method according to claim 1, wherein said particu will be readily apparent to those skilled in the art, and the late sodium carbonate has a particle size distribution as fol generic principles defined herein may be applied to other lows: Dooss500 um. embodiments and applications without departing from the 5. The method according to claim 1, wherein said particu spirit and scope of the invention. Thus, this invention is not 5 late sodium carbonate has a particle size distribution as fol intended to be limited to the embodiments shown, but is to be lows: Dooe45um and Doos 180 Lum and Doss425um. accorded the widest scope consistent with the principles and 6. The method according to claim 1, wherein said particu features disclosed herein. In this regard, certain embodiments late sodium carbonate has a calcium weight content, within the invention may not show every benefit of the inven expressed in CaO, of at most 75 ppm. tion, considered broadly. 10 7. The method according to claim 1, wherein the poly(ether The invention claimed is: ether ketone) produced has an L*>87. 1. A method for the preparation of a poly(ether ether 8. The method according to claim 1, wherein the poly(ether ketone) (PEEK), comprising: ether ketone) produced has an a <2. preparing the PEEK by aromatic nucleophilic substitution 9. The method according to claim 1, wherein the poly(ether in the presence of particulate Sodium carbonate, wherein 15 ether ketone) is produced in a solvent and in the absence of said particulate sodium carbonate has a particle size p-Xylene. distribution as follows : Doos45 um and Doos250 um 10. The method according to claim 9, wherein the poly and Doss710 um, wherein said particle size distribu (ether ether ketone) is produced in the absence of any cosol tion is measured by mechanical sieving in accordance vent which forms an azeotrope with water. with ASTM E 359-00 (reapproved 2005), wherein said 11. The method according to claim 1, wherein the poly measurement is based on the mechanical separation of (ether ether ketone) is prepared in the presence of the particu various fractions on a series of Superimposed sieves late Sodium carbonate and KCOs, wherein KCO is present which are Superimposed by descending order of opening in a ratio of no more than 0.01 mol K/mol Na. mesh of 1000 um, 500 um, 250 um, 180 um, 125 L, 90 12. The method according to claim 1, wherein said particu um, 63 um, and 45um. 25 late sodium carbonate has a particle size distribution as fol 2. The method according to claim 1, wherein said particu lows: Dooe75um and Doos250 Lum and Doss 710 um. late Sodium carbonate has a particle size distribution as fol 13. The method according to claim 1, wherein the poly lows: Dooe63 um and Doos250 Lum. (ether ether ketone) is prepared in the presence of the particu 3. The method according to claim 1, wherein said particu- 30 late Sodium carbonate and KCOs, wherein KCO is present late Sodium carbonate has a particle size distribution as fol in a ratio of no more than 0.05 mol K/mol Na. lows: Doos212 um and Dooe45. k k k k k UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 9,175,136 B2 Page 1 of 1 APPLICATIONNO. : 13/125537 DATED : November 3, 2015 INVENTOR(S) : Chantal Louis It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:
In the claims, Claim 1, column 37, line 24, the phrase “125u should read -- 125um --.
Signed and Sealed this Twenty-second Day of March, 2016 74-4-04- 2% 4 Michelle K. Lee Director of the United States Patent and Trademark Office