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(12) United States Patent (10) Patent No.: US 7,687,595 B2 Brunelle Et Al

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(12) United States Patent (10) Patent No.: US 7,687,595 B2 Brunelle Et Al USOO7687595 B2 (12) United States Patent (10) Patent No.: US 7,687,595 B2 Brunelle et al. (45) Date of Patent: Mar. 30, 2010 (54) SULFONATED TELECHELIC (58) Field of Classification Search ................... 528/86, POLYCARBONATES 528/171, 196, 198, 199, 373 See application file for complete search history. (75) Inventors: Daniel J. Brunelle, Burnt Hills, NY (US); Martino Colonna,s Bolognas (IT): (56)56 Refeeees Citede Maurizio Fiorini, Anzola Emilia (IT): U.S. PATENT DOCUMENTS Corrado Berti, Lugo (IT). Enrico 5,162.405 A 1 1/1992 Macleay et al. Binassi, Bologna (IT) 5,412,061 A 5/1995 King, Jr. et al. 5,644,017 A 7/1997 Drumright et al. (73) Assignee: SABIC Innovative Plastics IP B.V., 5,650,470 A 7/1997 McCloskey et al. Bergen op Zoom (NL) 5,807,962 A 9/1998 Drumright et al. 6,303,737 B1 10/2001 Lemmon et al. (*) Notice: Subject to any disclaimer, the term of this 6,323,304 B1 1 1/2001 Lemmon et al. patent is extended or adjusted under 35 6,376,640 B1 4/2002 Lemmon et al. U.S.C. 154(b) by 197 days. 6,930,164 B1 8, 2005 Brunelle et al. 2003, OOSO427 A1 3/2003 Brunelle et al. (21) Appl. No.: 11/834,417 Primary Examiner Terressa M Boykin (22) Filed: Aug. 6, 2007 (57) ABSTRACT (65) Prior Publication Data A sulfonated telechelic polycarbonate is described which is US 2009/OO43071 A1 Feb. 12, 2009 produced by melt synthesis. A dihydroxy compound is reacted with a sulfobenzoic acid salt, then with an activated (51) Int. Cl. carbonate. The method results in a sulfonated telechelic poly C08G 64/00 (2006.01) carbonate which has a high percentage of Sulfonated end COSG 63/02 (2006.01) groups, is soluble, and is transparent. (52) U.S. Cl. ......................... 528/196; 528/86; 528/171; 528/198: 528/199528/373 22 Claims, 4 Drawing Sheets U.S. Patent Mar. 30, 2010 Sheet 1 of 4 US 7,687,595 B2 FIG. 1 SO. Na' BPA 3-SBENa TMAH/NaOH O -- O ls O O OCH HCO O BMSC SONatO-O-O- Telechelic Sulfonated Polycarbonate U.S. Patent US 7.687,595 B2 uudd pe?oeeuun ENEOES U.S. Patent Mar. 30, 2010 Sheet 3 of 4 US 7.687,595 B2 sésiss- rsssss ^ -- - - - -----.S.--- as Sdnouô-puaOSWE U.S. Patent Mar. 30, 2010 Sheet 4 of 4 US 7.687,595 B2 ---------- - - - - - oswauol } } } ? ---------|------|)| -------+??------------+-----------+----- -|···,og-------------------------------+---+--------------------- ---------------|------{???- (%)% few US 7,687,595 B2 1. 2 SULFONATED TELECHELC decreasing the level of crystallinity. Telechelic ionomers (i.e. POLYCARBONATES having only functionalized end groups) provide electrostatic interactions without a deleterious effect on the symmetry of CROSS-REFERENCE TO RELATED the repeating unit. Moreover, the ionic aggregation will occur APPLICATIONS only at the end of the chain, giving rise to an electrostatic chain extension while random ionomers give rise to a gel-like The present disclosure is related to the patent application or cross linked aggregation. For this reason, lower melt vis entitled “POLYCARBONATENANOCOMPOSITES. con cosities and higher molecular weights should be more easily currently filed as U.S. Ser. No. 1 1/834,458. The present dis obtained for telechelic ionomers compared to random iono closure is also related to the patent application entitled 10 CS. ACTIVATED ESTERS FOR SYNTHESIS OF SUL U.S. Pat. No. 5,644,017 reported the preparation of telech FONATED POLYCARBONATE, concurrently filed as U.S. elic polycarbonates by melt and interfacial methods. It Ser. No. 1 1/834,437. These disclosures are hereby fully incor claimed that polycarbonate ionomers presented a strong non porated herein by reference. Newtonian melt rheology behavior along with increased sol 15 vent and flame resistance. BACKGROUND The 017 patent reported a melt method for the synthesis of telechelic Sulfonated polycarbonates by a one-pot reaction of The present disclosure relates to sulfonated telechelic the phenyl ester of sulfobenzoic acid sodium salt (SBENa), polycarbonates and to methods of producing the same. For bisphenol-A (BPA), and diphenyl carbonate (DPC). How example, the disclosure relates, in certain embodiments, to ever, this method gave rise to a consistently high amount of the melt synthesis of sulfonated telechelic polycarbonates degradation products. Furthermore, the material obtained and to the compositions produced by Such a process. was completely insoluble in dichloromethane. The dark yel Polycarbonates are synthetic thermoplastic resins derived low product was not soluble in any common organic Solvents, from bisphenols and phosgene, or their derivatives. They are nor in strong solvents such as hexafluoroisopropanol or trif linear polyesters of carbonic acid and can be formed from 25 luoroacetic acid, and therefore could not be characterized by dihydroxy compounds and carbonate diesters, or by ester GPC or NMR. This insolubility has been ascribed to interchange. Their desired properties include clarity or trans crosslinking due to the formation of Fries rearrangement parency (i.e. 90% light transmission or more), high impact by-products. It may be due to the high catalyst content (25 strength, heat resistance, weather and oZone resistance, good ppm of lithium hydroxide) and/or the temperature program ductility, being combustible but self-extinguishing, good 30 used during polymerization. The 017 patent also claimed electrical resistance, noncorrosive, nontoxic, etc. two glass transition temperatures (at 148°C. and at 217°C.). Polycarbonates can be manufactured by processes such as This fact suggests the presence of two separable components: melt polymerization, i.e. melt synthesis. Generally, in the one with Sulfonated end groups, and one without. melt polymerization process, polycarbonates may be pre The 017 patent also reported solution methods for the pared by co-reacting, in a molten state, dihydroxy 35 preparation of telechelic Sulfonated polycarbonates, via 3- or compound(s) and a diaryl carbonate ester in the presence of a 4-chlorosulfonyl benzoic acid. Example 2 reported a Tg of transesterification catalyst in a Banbury(R) mixer, twin screw 165° C. for the 4-isomer, but no Tg was reported in Example extruder, or other batch stirred reactor designed to handle 3 for the 3-isomer. Both polymers had very low molecular highly viscous materials, to form a uniform dispersion. Vola weights; the 4-isomer had a M. of 21,210 or a degree of tile monohydric phenol is removed from the molten reactants 40 polymerization (DP) of 44, while the 3-isomer had a much by distillation and the polycarbonate polymer is isolated as a lower M. (since 20% of the sulfonated end groups were molten residue. Melt processes are generally carried out in a incorporated) and a theoretical DP of only 8. Polycarbonates series of stirred tank reactors. The reaction can be carried out having a Mofless than 30,000 are usually not useful because by either a batch mode or a continuous mode. The apparatus they lack the required mechanical properties. The polycar in which the reaction is carried out can be any Suitable tank, 45 bonate of Example 3 also contained Sulfonated groups as tube, or column. Continuous processes usually involve the integral parts of the polymer backbone (i.e. not pendant from use of one or more continuous-stirred tank reactors (CSTRs) the chain). However, this type of mixed carbonic-sulfonic and one or more finishing reactors. anhydride linkage is very thermally unstable and would ulti The presence of low concentrations of covalently bonded mately cause the polycarbonate to fragment into several ionic Substituents in organic polymers is well known to pro 50 chains of lower molecular weight wherever Such an anhy duce a consistent effect on their physical and rheological dride linkage occurred, especially during thermal processing. properties. Indeed, ionomers (polymers containing less than As such, any polycarbonate with anhydride functionality 10 mole percent of ionic groups) have been shown to exhibit would not be very useful. considerably higher moduli and higher glass transition tem It would be desirable to provide telechelic sulfonated poly peratures compared to those of their non-ionic analogues. 55 Improvements in mechanical and thermal performance are carbonates having low crosslinking and high transparency. generally attributed to the formation of ionic aggregates, which act as thermo-reversible cross-links and effectively BRIEF DESCRIPTION retard the translational mobility of polymeric chains. The thermo-reversible nature of ionic aggregation may address 60 Disclosed, in various embodiments, are telechelic sul many other disadvantages associated with covalently bonded fonated polycarbonates and methods for producing Such high molecular weight polymers, such as poor melt process polycarbonates. ability, high melt viscosity, and low thermal stability at typi In embodiments, a method for the melt synthesis of a cal processing conditions such as high shear rate and tem telechelic Sulfonated polycarbonate comprises: perature. 65 reacting a mixture comprising a dihydroxy compound and It is also reported in the literature that ionic interactions a Sulfobenzoic acid salt to obtain an intermediate product; alter the crystallization kinetics and resulting morphology, adding an activated carbonate to the mixture; and US 7,687,595 B2 3 4 reacting the intermediate product with the activated car millibar to about 2 millibar while the intermediate product bonate to obtain the telechelic sulfonated polycarbonate; and the activated carbonate are reacted. The intermediate wherein the dihydroxy compound has the structure of For product and the activated carbonate may be reacted for a mula (I): period of from about 30 minutes to about 120 minutes. The mixture may further comprise a catalyst. The catalyst may be a system of tetramethyl ammonium hydroxide Formula (I) (TMAH) and sodium hydroxide (NaOH). R1, R2, R3, R4 The telechelic sulfonated polycarbonate may have a weight average molecular weight of greater than 30,000. 10 The dihydroxy compound may be 2.2-bis(4-hydroxyphe nyl)propane (bisphenol-A).
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