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13C NMR Study of Poly(Propylene Oxide)S Prepared with Organotin-Alkyl Phosphate Condensates of Various Degrees of Condensation

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13C NMR Study of Poly(Propylene Oxide)S Prepared with Organotin-Alkyl Phosphate Condensates of Various Degrees of Condensation Polymer Journal, Vol. 25, No. 7, pp 685~696 (1993) 13C NMR Study of Poly(propylene oxide)s Prepared with Organotin-Alkyl Phosphate Condensates of Various Degrees of Condensation Katsuhito MIURA,t Tatsuki KITAYAMA, Koichi HATADA,tt and Tetsuya NAKATA* Department of Chemistry, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka 560, Japan * Research Laboratories, Daiso Co., Ltd., Amagasaki, Hyogo 660, Japan (Received November 24, 1992) ABSTRACT: Polymerizations of (S)- and (RS)-propylene oxides were carried out with various organotin-alkyl phosphate condensates derived from dibutyltin oxide (Bu2SnO) and tributyl phosphate (Bu 3PO4 ) as initiators. Regioirregularity of poly((S)-( - )-propylene oxide) was studied by 13C NMR spectroscopy based on revised peak assignments. The results suggest the presence of alternating irregular units as well as isolated ones, in contrast with poly((S)-( - )­ propylene oxide)s formed with ZnEt2-H2 O and A!Et3-H20--(acetylacetone), in which only isolated irregular units exist. The benzene-hexane insoluble fraction of poly((RS)-propylene oxide) initiated with Bu 2 Sn0--Bu 3PO4 (I : 2) condensate, which was insoluble in a variety of organic solvents, had isotactic diad of 94% and isotactic triad of 91 %. The reactivity of Bu 2 Sn0--Bu 3PO4 (I : 2) condensate was higher than that of Bu2 Sn0--Bu3PO4 (1 : 4) condensate or Bu 2 SnO-Bu3PO4 (I: I) condensate. Among the Bu 2 Sn0--Bu3 PO4 (I: 2) condensates, high molecular weight condensate showed higher reactivity than the low molecular weight one. KEY WORDS Propylene Oxide / Organotin-Alkyl Phosphate Condensate / Irregular Linkage / Tacticity / 13C NMR / Organozinc and organoaluminum com­ of the monomer) is effective for rapid po­ pounds are known as highly reactive initiators lymerization of various oxirane compounds. in ring opening polymerization of oxirane Polymerization with these initiators in aliphatic compounds. The structural analyses of the hydrocarbons proceeds in slurry. For the polymers with those initiators have been pre­ polymerization of ethylene oxide by organotin­ viously reported. 1 - 10 Recently, we reported alkyl phosphate condensates, a bimetallic that organotin-alkyl phosphate condensates mechanism shown in Scheme 1 has been also functioned as efficient initiators for the suggested by one of the present authors. 11 As polymerization of oxirane compounds, 11 • 12 one of the possible mechanisms, it seems that and these have been used for the industrial such structures would be effective for steric production of epichlorohydrin-ethylene oxide control in propagation step in the polymeriza­ rubber. 13 tion of substituted oxiranes. The organotin-alkyl phosphate condensates In this work, the stereochemical structure exhibit excellent stability and can be stored of poly((RS)-propylene oxide) and the regio­ under air for a long period. A very small irregularity of optically active poly((S)-( - )­ amount of the initiators (0.01---0.5% by weight propylene oxide)prepared with dibutyltin oxide t On leave from Daiso Co., Ltd. tt To whom correspondence should be addressed. 685 K. MIURA et al. ½)\ 0 ' Sn /; L1 \~: t O 0 \ I I \ /, \ ?i p p P ,O-t-CH-CHz-O-t-P- /~ ,-+;\ / \ / ' I \ o. r o 0 :' CH3 ~..._ I \ / Sn Sn j D 0 Sn I 0 \ 0 \ I \ 11 p o-t-CH-CHz-O-t-P- / \o\ / bn3 I Sn Scheme 1. Proposed mechanism of initiation and propagation. (Bu2 SnO)-tributyl phosphate (Bu3PO4 ) con­ Measurements densates were studied by means of 13C NMR 13C NMR spectra of the polymers were spectroscopy, Effects of Bu 2 SnO/Bu 3PO4 ratio measured in benzene-d6 at 50°C on a JEOL on the tacticity of poly((RS)-propylene oxide) JNM-GX 500 spectrometer at 125 MHz, are also discussed, Chemical shifts were referred to the central peak of benzene-d6 at 128,0 ppm, Gel permea­ EXPERIMENTAL tion chromatography (GPC) was performed using a Waters model 150-C instrument Materials equipped with a differential refractometer, Racemic propylene oxide was refluxed over Tetrahydrofuran was used as an eluent at a a mixture of potassium hydroxide and cal­ flow rate of 1 ml min - 1 , The chromatograms cium dihydride, and then fractionally distilled were calibrated against standard polystyrene under nitrogen atmosphere, (S)-( - )-Propylene samples, The weight average molecular weight oxide was obtained from Aldrich Chemical of the polymers were determined by viscom­ Company, Inc; [c,:Jf/ = - 7,2° (c= 1, CHC1 3), etry in benzene at 25°C using the following 98,8% e,e, The optical purity of (S)-( - )­ equation; [11]=0,81 x 10- 4 Mw 0 ·85 , 15 The propylene oxide was measured by complexa­ number average molecular weight of the tion gas chromatography, 14 Solvents were initiator was determined by vapor pressure purified by conventional methods and distilled osmometry (VPO) in benzene at 40°C using a just before use, Corona-114 osmometer, Optical rotation of polymers derived from (S)-propylene oxide was measured in benzene at a concentration 686 Polym. J,, VoL 25, No, 7, 1993 13C NMR Study of PPO Prepared with Bu 2 Sn0-Bu3PO4 of I g dl- 1 at 20°C on a JASCO polarimeter Bu O 0 I II II model DIP-181. Melting point of polymers +sn-O-P-O-P-O+ X=Bu I I I were measured on a Perkin-Elmer differential X OBu OBu scanning calorimeter model DSC-4 at a heat­ ing rate of l0°C min - 1 . 0 II or +O-P-O+ I Preparation of Bu2 Sn0-Bu3 P04 Condensates OBu Organotin-alkyl phosphate condensates can be prepared from various combinations of or­ branched or crosslinked structure ganotin compounds such as Bu2SnO, tributyl­ tin chloride (Bu3 SnCl), and triphenyltin chlo­ Polymerizations of Propylene Oxide ride (Ph3 SnCl), with alkyl phosphates such Polymerization of propylene oxide in ben­ as Bu 3PO4 , dibutyl phosphate (Bu2PHO4 ), zene was carried out in the following manner. 11 13 and triethyl phosphate (Et3PO4 ). • In the Insoluble Bu 2 SnO-Bu3PO 4 (1: 2) condensate present work, condensates of Bu2 SnO and was dried in a glass ampoule at l 50°C for 1 h Bu3PO4 prepared in the following manner in vacuo. After cooling, benzene and racemic were used as initiators. or optically active propylene oxide were added The mixture of Bu2 SnO and Bu3PO4 was subsequently into the ampoule under dry stirred and heated at 250°C for 20--30 min nitrogen atmosphere. Polymerizations were under dry nitrogen. In the condensation reac­ carried out at 5°C for 3 or 8 h, and then tion, butane, butene, 1-butanol, and dibutyl terminated by adding methanol. The polym­ ether were distilled out. The condensates erization mixture was diluted with benzene formed in the early stage of the reaction and the insoluble initiator residue was removed were soluble in a variety of organic solvents, by centrifugation. The polymers were re­ but they became insoluble as the degree of covered from the benzene solution by evapo­ condensation increased because of the forma­ rating the solvent. Benzene-hexane (1 : 2) in­ tion of network structure. The molecular soluble fraction of the polymer was isolated by weights and elemental analyses of various centrifugation. Benzene-hexane soluble frac­ Bu2 SnO-Bu3 PO4 condensates used in the tion of the polymer was obtained by evapo­ present work are listed in Table I. These rating the solvents. Polymerization in bulk condensates were assumed to have the follow­ was carried out in a similar manner at 30°C ing structure 11 : for 2.5 or 5 h. After the solvent was evapo­ rated, the residual polymer was dried under Table I., The molecular weights and elemental analyses of various Bu 2 SnO--Bu 3 PO4 condensates Sn p C H Bu 2 SnO-Bu3PO4 condensates % % % % Bu 2 SnO-Bu3 PO4 (I: 2)" 24.5 12.7 29.9 5.7 Bu 2 SnO-Bu3 PO4 (I: 2) 11700 24.2 12.4 30.8 6.1 Bu2 SnO-Bu3 PO4 (I: 2) 8300 24.1 12.1 32.7 6.4 Bu2 Sn0-Bu3P04 (I: 2) 3000 20.1 10.2 33.1 6.4 Bu2 SnO-Bu3PO4 (I: 4) 4500 12.9 13.9 31.5 6.3 Bu 2Sn0-Bu3PO4 (I: I) 5600 28.2 8.0 34.9 6.9 • Determined by VPO. b The condensate was insoluble in a variety of organic solvents such as benzene, chloroform, and tetrahydrofuran. Polym. J., Vol. 25, No. 7, 1993 687 K. MIURA et a/. high vacuum. lowing four types of triad are distinguishable Polymerizations with diethylzinc (ZnEt2)­ by NMR spectroscopy: H2O (1: 1) and triethylaluminium(AlEt3)­ H20-acetylacetone(AcAc) (1 : 0.5: 0.5) were AAA(BBB) carried out according to the methods of -CH2-CH-O-CH2-CH-O-CH2-CH-0- Oguni6 ·9 and Vandenberg, 1 respectively. 1 I I CH 3 CH 3 CH 3 RESULTS AND DISCUSSION AAB(BBA) -CH2-CH-O-CH2-CH-O-CH-CH2-0- Polymerization of racemic or optically active I I I propylene oxide was carried out with an CH 3 CH 3 CH 3 insoluble Bu2SnO-Bu3 PO4 (1: 2) condensate ABA(BAB) in benzene. The results are shown in Table II. -CH2-CH-O-CH-CH2-0-CH2-CH-0- The polymers obtained were fractionated into 1 I I benzene-hexane (1 : 2, v/v) soluble and in­ CH 3 CH 3 CH 3 The insoluble fractions soluble fractions. BAA(ABB) showed melting points but not the soluble ones. ·The specific optical rotation of the soluble -CH-CH 2-0-CH2-CH-O-CH2-CH-O- I I I fraction of poly((S)-( - )-propylene oxide) was CH 3 CH 3 CH 3 much lower than that of the insoluble one. It should be noted that the spectrum of the Although the M w values of the soluble frac­ optically active polymer does not involve tions are lower than the insoluble ones, the stereoisomerism and can be analyzed in terms difference is not so remarkable to explain the of the above four types of triads.
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