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Modification of Polycarbonate Terminals with Benzophenone Derivative Via Transesterification

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Modification of Polycarbonate Terminals with Benzophenone Derivative Via Transesterification Polymer Journal, Vol. 29, No. 2, pp 128-133 (1997) Modification of Polycarbonate Terminals with Benzophenone Derivative via Transesterification Yoichiro MAKIMURA, Eri YOSHIDA, and Toshio KITAO Department of Polymer Science and Engineering, Faculty of Textile Science, Kyoto Institute of Technology, Matsugasaki, Sakyo, Kyoto 606, Japan (Received July 22, 1996) ABSTRACT: Reaction of PC with 2-hydroxy-4-(2-hydroxyethoxy)benzophenone (HHEBP) was carried out in the presence of FeCl 3 in a torque rheometer at 255°C. The reaction rapidly proceeded and conversion was more than 80% within 5 min. HHEBP reacted quantitatively except for the amount of HHEBP vaporized. A film of this product showed high weather-proof on weather-a-test when compared to typical PC with no benzophenone derivatives or PC containing HHEBP obtained by the control experiment. KEY WORDS Polycarbonate / Benzophenone Derivative / Torque Rheometer / Transesterification / Weatherability / Ultra-Violet Stabilizer / Among thermoplastic polymers, the aromatic poly­ as polymerization-processing of styrene20 and methyl­ carbonate, synthesized from 2,2-bis(4-hydroxyphenyl)­ methacrylate21 and functionalization ofpolymers.22 No propane and diphenylcarbonate (or phosgene) and paper describes the functionalization of polycarbonate commonly designated as Bisphenol A polycarbonate, has by reactive processing. been used in a wide range of academic studies and In the present study, transesterification between poly­ commercial applications because of its excellent optical, carbonate and 2-hydroxybenzophenone with a hydroxy­ thermal and mechanical properties1·2 The large inherent ethoxy substituent was conducted in a torque rheome­ birefrigence in connection with transparent appearance ter as a model experiment of reactive processing for the brings great advantages in studying the structure­ immobilization of UV stabilizer onto the terminal of property relationship of bulk bodies such as stress­ Bisphenol A polycarbonate in an actual twin screw ex­ induced anisotropy of polymeric materials. 3 In addition, truder. The products were characterized as functions its high glass transition temperature, 16O°C, and very of processing variables such as mixing rate, reaction time low secondary relaxation temperature around - lOO°C and temperature. make this polymer very tough at ordinary tempera­ tures. 4·5 Consequently, Bisphenol A polycarbonate is EXPERIMENTAL useful as material. 6 This high performance polycarbonate, however, is Materials known to be sensitive to UV and visible light. 7 - 14 Bisphenol A polycarbonate (PC), supplied by Idemitsu Prolonged exposure to UV and/or visible light results Petrochemical Co., Ltd., was dried at 12O°C for 12h or in the formation of yellowish coloring groups due to longer before use. 2-Hydroxy-4-(2-hydroxy-ethoxy)ben­ rearrangement of chemical structure. One of the mech­ zophenone (HHEBP) manufactured by BASF was re­ anisms may be photo-induced Fries rearrangement crystallized from methanol. Ferric chloride anhydride between an oxygen in carbonate linkage and adja­ (analytical-grade) purchased from Nacalai Tesque was cent phenyl group which subsequently forms diphenyl used as received. benzophenone sequence in the polymer. 7 Furthermore photo degradation of PC resulted from chain oxida­ Instrumentation tion.12 In commercial applications a small amount of As illustrated in Figure 1, transesterification between 2-hydroxybenzophenone or its derivative has always PC and HHEBP was conducted in the mixing chamber been dispersed in the polycarbonate to prevent the of a torque rheometer (HAAKE Rheocord 90) of 70 photo-induced degradation. 15 Unfortunately most UV cm3 • Processing variables such as temperature, mixing stabilizers, benzophenone derivatives, are immiscible time and mixing speed were accurately controlled and to polycarbonates and tend to bleed out. Immobili­ material temperature and torque were recorded as zation of benzophenone derivatives onto polycarbonate functions of mixing time. PC modified in the rheometer may thus be expected to prolong the life of this useful were subjected to the following characterizations: 1H polymer. 16 NMR spectra were recorded on JEOL JNM-EX27O. UV Reactive processing technique has begun to attract spectra were taken on Hitachi U-321O. Gel permeation notice in the field of polymer engineering, because it can chromatography (GPC) was performed at 4O°C at 1.0 simultaneously carry out both chemical reaction and ml min - 1 with SSC-7000 VHT-GPC (Senshu Scientific fabrication in a single processing instrument. 17 Various Co., Ltd.), equipped with Shodex KF8O4L x 3 col­ polymeric materials have been conveniently developed umns. The data obtained were converted to Mn and Mw using this technique. Most studies on reactive processing, being calibrated with polystyrene standards. Weather­ however, have dealt with the improvement of phase ing tests were carried out in a weather-a-meter by Dai­ stability of polymer alloys, 18·19 with few exceptions such pla Co., Ltd .. The weathering test was programed using 128 Modification of Polycarbonate via Transesterification + OHO FeCl3 1o~o-~ l o~o-~-ocH2CH20J6rc1QJ 255°C f CH3 0~ CH3 0 Scheme I. three different modes in a day: dry mode, at 30% RH Reaction Time at 63°C for 16 h under the irradiation of halogen light 100 I< >I (80.0mWcm- 2), damp mode, at 98% RH at 30°C for 6 h under irradiation, and dark mode, at 70% RH at 80 C 63°C for 2 h. Specimens were rinsed with water for 5 s before and after the damp mode. e 60 PC Cl) :, Procedure ...r:r 40 60.0g PC (approximately 70vol% of the m1xmg chamber) were loaded in two stages in every experiment: 20 At first 40 g PC loaded in the mixing chamber held at 255°C were melted completely and then the rest was 0 added. The kneading lasted for 4.5 min until the torque 0 5 IO 15 went down and leveled off. 0.6 g HHEBP and 0.6 mg Time(min) FeC1 3 (0.1 mol¾ to HHEBP) were added again and the Figure I. Torque curve of the reaction of PC (60.0 g) with HHEBP kneading was continued at a mixing speed of 30 rpm. (0.967mo1%) in the presence ofFeCl3 (0.10mol%) at 30rpm at 255°C After prescribed period of time, the operation was stopped. The products were immediately taken out from the chamber, quenched in N 2 atmosphere and cast into thin films on a thin glass plate from methylenedichloride. Control As a control, a piece of PC film containing an equivalent amount of unreacted HHEBP and FeCl3 was prepared by casting from methylene dichloride. RESULTS AND DISCUSSION b The reaction of PC with HHEBP is shown in Scheme 1. The two-stage loading of PC may be responsible for a a couple of the sharp peaks found at 1.3 and 2. 7 min in the torque-time relation shown in Figure 1. The mixing 250 300 350 400 torque decreases monotonically and then levels off Wavelength (nm) beyond 4 min, indicating the complete melting of PC loaded in the chamber. A sudden decrease at 4.5 min Figure 2. UV spectra of the control before (a) and after (b) puri­ corresponds to the stopping of the rotor. Again the fication. mixing was kept running at the same speed of 30 rpm for lOmin or longer. Figures 2 and 3 show the UV spectra of the control and product, respectively. Both specimens gave four Product characteristic absorption peaks; two sharp peaks at 264 and 272 nm, a broad one around 328 nm and a shoulder at 287 nm. The former two may be assigned to the phenyl and carbonyl groups of PC, whereas the latter two can be attributable to the phenolic hydroxy and carbonyl groups in HHEBP. After being reprecipitated from b methylenechloride, the control had only two sharp ab­ sorption at 264 and 272 nm, indicating that HHEBP in a the control was completely eliminated from the speci­ mens. The reaction product still gave similar absorp­ tion trace where peak intensities were almost unchang­ 250 300 350 400 ed. The conversion of HHEBP was estimated as 63% Wavelength (nm) from the intensity ratio of absorption at 328 nm before Figure 3. UV spectra of the product before (a) and after (b) puri­ and after the reprecipitation of the product. fication. Polym. J., Vol. 29, No. 2, 1997 129 Y. MAKIMURA, E. YOSHIDA, and T. KITAO GPC curves were determined with a 254nm UV system smaller. detector and are shown in Figure 4. The control gave a Instead of the 254nm UV detector, GPC curves were bimodal trace consisting of a larger peak from PC at recorded with a UV detector of which characteristic 1410 s and much smaller one at 1920 s of retention: The wave length was 325 nm. The results are shown in Figure former certainly comes from PC while the latter from 5. Only an absorption was recorded at 1920 s for the free HHEBP. A unimodal curve obtained for the reaction control specimen. The reaction product had a broad product suggests that the reaction in the torque rhe­ absorption over the wide range from 1250 to 1800 s in ometer resulted in a small decomposition of PC because addition to a small peak around 1920 s. This suggests the number average molecular weights estimated for that HHEBP in the product was chemically bonded with the control and the product were 29300 and 23700, PC chains, while in the control merely dispersed in the respectively. This implies that the transesterification of matrix of PC. The conversion of HHEBP in the product PC with monofunctional HHEBP in the mixing cham­ was estimated to be 64% from these UV absorption ber resulted in molecular scission of PC in random man­ intensities. ner. This is very natural because the transesterification The chemical structure of the reaction product was between PC and monofunctional HHEBP with smaller confirmed with 1 H NMR. 1 H NMR spectra of the molecular weight proceeds in accordance with the scheme control and is shown in Figure 6.
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