Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 18

Special Issue: Professor Yoshio Okamoto on Retirement

15 September 2004

Volume 42, Issue 18

Pages 4479–4722

Issue edited by: Toyoji Kakuchi

  1. Foreword

    1. Top of page
    2. Foreword
    3. Highlight
    4. Articles
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      Foreword (page 4479)

      Toyoji Kakuchi and Mitsuo Sawamoto

      Article first published online: 6 AUG 2004 | DOI: 10.1002/pola.20353

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      (−)-Sparteine: The compound that most significantly influenced my research (pages 4480–4491)

      Yoshio Okamoto

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20192

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      A chiral diamine alkaloid, (−)-sparteine (Sp), has been found to be very effective as a ligand for Grignard reagents when used for the enantiomer-selective polymerization of racemic RS-1-phenylethyl methacrylate. The enantiomeric excess of the initially polymerized monomer is 93%. When triphenylmethyl methacrylate is polymerized with the Sp complex with n-butyllithium in toluene at −78 °C, an optically active, isotactic polymer [poly(triphenylmethyl methacrylate) (PTrMA)] with a one-handed helical conformation is obtained. One-handed helical PTrMA exhibits high chiral recognition to a variety of racemates as a chiral stationary phase (CSP) for high-performance liquid chromatography.

  3. Articles

    1. Top of page
    2. Foreword
    3. Highlight
    4. Articles
    1. Specific thermosensitive volume change of biopolymer gels derived from propylated poly(γ-glutamate)s (pages 4492–4501)

      Taiki Shimokuri, Tatsuo Kaneko and Mitsuru Akashi

      Article first published online: 6 AUG 2004 | DOI: 10.1002/pola.20384

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      The hydrogels of poly(γ-glutamic acid) (γ-PGA) propyl crosslinked by a chemical reaction with hexamethylene diisocyanate showed pH-responsive and thermoresponsive shrinking. However, the volume recovery was incomplete during the cooling process, presumably because of the formation of amide hydrogen bonding confirmed by a Fourier transform infrared/attenuated total reflection study. The following urea addition made it complete.

    2. Synthesis of chiral helical poly[p-(oligopinanylsiloxanyl)phenylacetylene]s and enantioselective permeability of their membranes (pages 4502–4517)

      Toshiki Aoki, Tomoyuki Fukuda, Ken-ichi Shinohara, Takashi Kaneko, Masahiro Teraguchi and Masayuki Yagi

      Article first published online: 6 AUG 2004 | DOI: 10.1002/pola.20356

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      To develop better polymeric materials for optical-resolution membranes, we synthesized nine chiral poly(phenylacetylene)s containing pinanyl groups. We used them to investigate the effects of chemical structures, including the number and position of chiral groups in the monomers, on the induction of chirality in the main chain during polymerization and on the degree of enantioselectivity in the permeation of the polymeric membranes. The membranes from polymers with a chiral helical backbone, a high content of pinanyl groups, no oligodimethylsiloxane moieties, or a combination of these showed good enantioselectivities (αR = 1.7 − 640) in permeation.

    3. Spectroscopic evidence for diastereomeric helical segments of polysilane bearing enantiopure (S)- and (R)-3,7-dimethyloctyl groups (pages 4518–4527)

      Anubhav Saxena, Roopali Rai, Akihiro Ohira and Michiya Fujiki

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20378

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      Two rodlike polysilanes, poly[(S)-3,7-dimethyloctyl-3-phenylpropylsilane] (PS1) and poly[(R)-3,7-dimethyloctyl-3-phenylpropylsilane] (PS2), underwent a thermodriven helix–helix transition at 10 °C in isooctane. Circular dichroism and UV studies demonstrated that the polysilanes adopted a preferential right-handed or left-handed screw sense at −80 °C, but above the transition temperature, both right-handed-screw-sense, tight helical segments and left-handed-screw-sense, loose helical segments coexisted in the same chains of PS1 and PS2, and this suggested the presence of diastereotopic helical segments in the silicon backbone.

    4. Asymmetric oxidative coupling polymerization affording polynaphthylene with 1,1′-bi-2-naphthol units (pages 4528–4534)

      Shigeki Habaue, Hiroharu Ajiro, Yasuhiro Yoshii and Tetsuya Hirasa

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20363

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      The asymmetric oxidative coupling polymerization of a novel monomer, 2,2′-dimethoxymethoxy-1,1′-binaphthalene-3,3′-diol, was carried out, and the obtained polymer was easily converted into a polymer with the optically pure 1,1′-bi-2-naphthol unit based on the original monomer structure, which could be used as a polymeric chiral auxiliary.

    5. Synthesis of asymmetric star-branched polymers consisting of three or four different segments in composition by means of living anionic polymerization with a new dual-functionalized 1,1-bis(3-chloromethylphenyl)ethylene (pages 4535–4547)

      Tomoya Higashihara and Akira Hirao

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20362

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      A series of A2BC, AB2C, ABC2, ABC, and ABCD asymmetric star-branched polymers with three- and four-component systems have been successfully synthesized with a methodology based on living anionic polymerization with dual-functionalized 1,1-bis(3-chloromethylphenyl)ethylene. A simple and convenient one-pot process for star-branched polymer synthesis is an advantage of this methodology. The resulting star-branched polymers have well-defined architectures and precisely controlled chain lengths, as confirmed by size exclusion chromatography, 1H and 13C NMR, vapor pressure osmometry, and static light scattering analyses. These successful results strongly demonstrate the synthetic versatility and potential of this methodology for a wide variety of well-defined asymmetric star-branched polymers.

    6. Asymmetric anionic polymerization of 2,6-dimethyl-7-phenyl-1,4-benzoquinone methide (pages 4548–4555)

      Takahiro Uno, Masaya Minari, Masataka Kubo and Takahito Itoh

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20380

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      Asymmetric anionic polymerizations of 2,6-dimethyl-7-phenyl-1,4-benzoquinone methide (1) were investigated under various conditions. Optically active polymers with configurational chirality were obtained in all cases, and a complex of fluorenyllithium (FlLi) and (−)-sparteine [(−)-Sp] afforded the polymer with the largest specific rotation. The specific rotations of the polymers were thought to be mainly governed by the aggregation state of the propagating chain end.

    7. Preparation of the enantiopure 1,2-diamine monomer and its polymerization: The efficient polymeric chiral ligand of an asymmetric hydrogenation catalyst (pages 4556–4562)

      Shinichi Itsuno, Atsushi Tsuji and Miyuki Takahashi

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20355

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      An enantiopure monomer possessing a p-vinylbenzyl group as a polymerizable group was synthesized from chiral 1,2-bis(p-hydroxyphenyl)-N,N′-bis(tert-butoxycarbonyl)-1,2-diaminoethane. The chiral monomer was copolymerized with styrene, and this was followed by deprotection, which yielded the polymer-supported chiral 1,2-diamine. The polymeric catalyst system was established with the polymeric chiral 1,2-diamine complexed with 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl/RuCl2. In the presence of potassium tert-butoxide (t-BuOK), the polymeric catalyst system worked well in the asymmetric hydrogenation of aromatic ketones. The polymeric catalyst was reused several times without a loss of catalytic activity.

    8. Enantiomer-selective radical cyclopolymerization of rac-2,4-pentanediyl dimethacrylate using a ruthenium-mediated chiral atom transfer radical polymerization initiating system (pages 4563–4569)

      Masashi Tsuji, Towako Aoki, Ryosuke Sakai, Toshifumi Satoh, Harumi Kaga and Toyoji Kakuchi

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20354

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      The enantiomer-selective radical polymerization of a racemic monomer, rac-2,4-pentanediyl dimethacrylate, was carried out with a chiral atom transfer radical polymerization initiating system consisting of methyl 2-bromoisobutyrate, dichlorotris(triphenylphosphine)ruthenium, and a chiral additive, such as (S)-1,1′-bi-2-naphthol. The polymerization enantiomer-selectively proceeded to afford an optically active polymer. According to the kinetic studies of the polymerization, the polymerization rates of each enantiomer differed appreciably on the basis of the chirality of the initiating system, and this resulted in enantiomer-selective radical polymerization.

    9. Coordinate anionic ring-opening polymerization of oxetanes with aluminum benzyl alcoholate bis(2,6-di-tert-butyl-4-methylphenolate) (pages 4570–4579)

      Shigeyoshi Kanoh, Atsushi Takemura, Koh-ichi Fukuda, Charoen Chinwanitcharoen and Masatoshi Motoi

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20359

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      Aluminum benzyl alcoholate bis(2,6-di-tert-butyl-4-methylphenolate) (BnOAD), which was prepared through the mixing of equimolar amounts of benzyl alcohol and methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate) (MAD), successfully polymerized oxetanes in a coordinate anionic ring-opening manner. The polymerization of 3-(4-bromobutoxymethyl)-3-methyloxetane (OxBr) with 5 mol % BnOAD in toluene at 25 °C produced high-molecular-weight poly(OxBr) in a moderate yield in 24 h. The polymerization was greatly accelerated by the addition of MAD and a nearly quantitative polymer yield was obtained within 24 h. In sharp contrast, the conventional cationic polymerization with boron trifluoride etherate produced low-molecular-weight poly(OxBr) along with a substantial amount of the cyclic tetramer.

    10. Helicity induction on a poly(phenylacetylene) bearing a phosphonate residue by chiral dendrons (pages 4580–4586)

      Yuko Kamikawa, Takashi Kato, Hisanari Onouchi, Daisuke Kashiwagi, Katsuhiro Maeda and Eiji Yashima

      Article first published online: 11 AUG 2004 | DOI: 10.1002/pola.20382

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      A series of optically active, first- and second-generation dendrons with a primary amino group at the terminal were prepared from L- or D-glutamic acid, and their helicity induction abilities for a poly(phenylacetylene) bearing a phosphonate pendant were investigated with ultraviolet–visible and circular dichroism spectroscopy. The magnitude of the Cotton effects of the polymer induced by the dendrons significantly increased upon complexation with a higher generation dendron. The Cotton effect signs depended on the configuration of the interior glutamate of the dendrons and were independent of the exterior glutamate configuration.

    11. Characterization of the benzene-insoluble fraction of the hydrolyzate of phenyltrimethoxysilanes in the presence of benzyltrimethylammonium hydroxide (pages 4587–4597)

      Chitsakon Pakjamsai, Noritomo Kobayashi, Mikio Koyano, Shintaro Sasaki and Yusuke Kawakami

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20381

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      The insoluble fraction obtained from the hydrolysis and condensation of [(4-dimethylamino-, 2-methyl-, and nonsubstituted)phenyl]trimethoxysilanes in the presence of benzyltrimethylammonium hydroxide in benzene was characterized. IR, 1H NMR, and 29Si NMR suggested that the insoluble fraction was composed of RSi(O[BOND])3, that is, a T3 structure. X-ray diffraction indicated the presence of a long-range ordered structure composed of a mixture of crystals. Raman spectroscopy strongly suggested a cage structure by the presence of a ring-opening vibration assignable to a cubic structure at 475–482 cm−1.

    12. Chemoenzymatic synthesis of glycoconjugate polymers starting from nonreducing disaccharides (pages 4598–4606)

      Yoshiko Miura, Natsuko Wada, Yoshihiro Nishida, Hiroshi Mori and Kazukiyo Kobayashi

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20385

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      α-D-Glucopyranosyl-(1-1)-α-D-glucopyranoside (trehalose) and α-D-galactopyranosyl-(1-1)-α-D-glucopyranoside (Gal-type trehalose) have been selectively esterified with divinyl sebacate at the respective primary Glc 6-OH and Gal 6-OH groups by lipase catalysis. The glycoconjugate polymers obtained by the radical polymerization of the resultant disaccharide vinyl esters show biological recognition activities based on the glycocluster effect. The Gal-type trehalose glycopolymer binds to Shiga toxin-1, and this suggests its stereochemical similarity to globosyl Gb2 disaccharide.

    13. Syntheses of helical polymers through the combination of axially dissymmetric segments (pages 4607–4620)

      Tomohisa Temma, Motoyasu Kobayashi, Yuya Agata, Tomoya Yamane, Jun Miura and Makoto Takeishi

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20377

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      Wholly aromatic polyamines and polyamides with helical structures were prepared through the combination of two axially dissymmetric bifunctional compounds. The palladium-catalyzed condensation of (R)-2,2-diethoxy-6,6′-dibromo-1,1′-binaphthyl [(R)-BEBN] with (R)-1,1′-binaphthyl-2,2′-diamine [(R)-BNDA] and the reaction of (S)-2,2-diethoxy-6,6′-dibromo-1,1′-binaphthyl [(S)-BEBN] with (S)-1,1′-binaphthyl-2,2′-diamine [(S)-BNDA] produced symmetric helical polyamines. The combination of (R)-BEBN with (S)-BNDA and (S)-BEBN with (R)-BNDA afforded polyamines with symmetric zigzag conformations.

    14. Synthesis and property of helical poly(phenylacetylene)s bearing chiral ruthenium complexes and real space imaging of meso- and nanoscopic structures by atomic force microscopy (pages 4621–4640)

      Shin-ichiro Sakurai, Akihiro Ohira, Yoshinori Suzuki, Riri Fujito, Tatsuya Nishimura, Masashi Kunitake and Eiji Yashima

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20357

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      Novel sets of helical poly(phenylacetylene)s bearing a chiral ruthenium complex with opposite chirality (Δ and Λ forms) as a bulky pendant were synthesized through the polymerization of the corresponding optically pure phenylacetylenes with a rhodium catalyst. The structures and morphology of the polymers in solution and on solid substrates were investigated with NMR, ultraviolet–visible, and circular dichroism spectroscopies and with atomic force microscopy (AFM), respectively. The visualization and discrimination of the right- and left-handed helical structures of the chiral polymers were achieved with high-resolution AFM imaging.

    15. Synthesis of chiral polyacetylenes carrying amino acids and azobenzenes and transformation of the higher order structure by photoirradiation (pages 4641–4647)

      Fumio Sanda, Takayuki Teraura and Toshio Masuda

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20374

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      This study examined the synthesis of copolymers of an alanine-derived chiral N-propargylamide [N-(tert-butoxycarbonyl)-L-alanine N′-propargylamide (BocA)] with an azobenzene-containing N-propargylamide [N-4-(phenylazo)benzoyl-L-alanine N′-propargylamide] and the transformation of the higher order structure of the copolymers by photoirradiation. The trans-azobenzene moiety of the copolymers isomerized into the cis one, which was accompanied by the transformation of the helical structure into a random state by UV irradiation. Visible-light irradiation induced the reisomerization of cis-azobenzene into the trans one, but it did not induce the recovery of the higher order structure.

    16. Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels (pages 4648–4655)

      Katsunari Inoue, Kazuaki Kato, Norimitsu Tohnai and Mikiji Miyata

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20376

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      We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of deoxycholic acid (DCA). The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization.

    17. Stereospecific polymerization of 9-fluorenyl methacrylate: Tacticity effects on the thermal and photophysical properties of the polymers (pages 4656–4665)

      Hideaki Ishizawa, Tamaki Nakano, Tohru Yade, Masashi Tsuji, Osamu Nakagawa and Takashi Yamaguchi

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20360

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      Poly(9-fluoreneyl methacrylate)s with different main-chain stereostructures were obtained through anionic and radical polymerization. The polymers showed different thermal and photophysical properties that depended on the tacticity.

    18. Synthesis of a polyester macromonomer via the cobalt-catalyzed alternating copolymerization of propylene oxide and carbon monoxide (pages 4666–4670)

      Koji Nakano, Kondo Fumitaka and Kyoko Nozaki

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20383

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      The alternating copolymerization of propylene oxide and carbon monoxide was investigated with cobalt complexes. The NaCo(CO)4/amine catalyst system selectively yielded oligo(3-hydroxybutyrate)s bearing a polymerizable crotonate end group, whereas the use of Co2(CO)8 as a cobalt source resulted in a smaller concentration of the crotonate end group and a high degree of polymerization. The high selectivity for the oligoesters with the crotonate end group with the NaCo(CO)4/amine system was attributed to its more basic reaction condition.

    19. Asymmetric radical cyclization of (2S,3S)-2,3-butanediyl, (2S,4S)-2,4-pentanediyl, and (2S,5S)-2,5-hexanediyl bis(4-vinylbenzoate)s as a model reaction for asymmetric cyclocopolymerization (pages 4671–4681)

      Makoto Obata, Shigenobu Yano, Kazunobu Kamino, Kazuaki Yokota and Toyoji Kakuchi

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20373

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      The asymmetric cyclization of bis(4-vinylbenzoate) of a chiral diol with styrene is a well-established method for the preparation of main-chain chiral polystyrene. The optical rotation of the resulting polymer is strongly correlated to the chiral diol used. To clarify the asymmetric induction mechanism, we conducted the asymmetric radical cyclization of bis(4-vinylbenzoate) of a chiral diol with tri-n-butyltin hydride or allyltri-n-butyltin as a model reaction. The stereochemical analysis of the asymmetric radical cyclization fairly represented the mechanism of racemo selectivity in the asymmetric cyclocopolymerization.

    20. Asymmetric anionic polymerization of optically active N-1-cyclohexylethylmaleimide (pages 4682–4692)

      Kenjiro Onimura, Yuan Zhang, Michihiro Yagyu and Tsutomu Oishi

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20358

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      The asymmetric anionic polymerizations of chiral (S)-(−)-N-1-cyclohexylethylmaleimide [(S)-CEMI] and (R)-(+)-N-1-cyclohexylethylmaleimide [(R)-CEMI] were carried out with organometal/chiral ligand complexes to obtain optically active polymers. Poly[(R)-CEMI]s obtained with anionic initiator complexes exhibited higher chiroptical properties ([α]435= −184.7 to +323.7°) than poly[(S)-CEMI]s obtained under the same polymerization conditions (+11.0 to +207.8°). The polymerization initiated by dimethylzinc/Bnbox at 0 °C for 48 h produced poly[(R)-CEMI] with the highest specific rotation (+323.7°). The chirality of the polymers was attributed not only to the chirality of optically active N-1-cyclohexylethylmaleimide units but also to stereogenic centers [(S,S) and (R,R)] in the main chain induced by the polymerization.

    21. Design and synthesis of chiral poly(binaphthyl salen zinc complex) and application of the asymmetric field based on its helical conformation to a catalytic asymmetric reaction (pages 4693–4703)

      Takeshi Maeda, Takeshi Takeuchi, Yoshio Furusho and Toshikazu Takata

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20386

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      Chiral helical poly(binaphthyl salen zinc complex)es were synthesized. In the presence of catalytic amounts of the complexes, diethylzinc reacted with benzaldehyde to enantioselectively produce 1-phenyl-1-propanol in high yields.

    22. Phenylcarbamate derivatives of cellulose and amylose immobilized onto silica gel as chiral stationary phases for high-performance liquid chromatography (pages 4704–4710)

      Takateru Kubota, Chiyo Yamamoto and Yoshio Okamoto

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20372

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      Three polysaccharide phenylcarbamate derivatives [cellulose 2,3-bis(3,5-dimethylphenylcarbamate)-6-(3,5-dimethylphenylcarbamate)/(2-methacryloyloxyethylcarbamate) (CMDMPC), cellulose 2,3-bis(3,5-dichlorophenylcarbamate)-6-(3,5-dichlorophenylcarbamate)/(2-methacryloyloxyethylcarbamate) (CMDCPC), and amylose 2,3-bis(3,5-dimethylphenylcarbamate)-6-(3,5-dimethylphenylcarbamate)/(2-methacryloyloxyethylcarbamate) (AMDMPC)] with vinyl groups were prepared and coated onto silica gel to immobilize them via radical copolymerization with 2,3-dimethylbutadiene. The copolymerization efficiently proceeded, and the coated polysaccharide derivatives were mostly immobilized on the surface of the silica gel. The immobilized polysaccharide derivatives showed high chiral recognition abilities similar to those of the corresponding coated polysaccharide derivatives. They could be used with an eluent containing chloroform, which dissolved the polysaccharide derivatives.

    23. Convenient synthesis of fully and partially deuterated stereoregular poly(phenylacetylene)s bearing a carboxy pendant and helicity induction on the polymers with chiral amines and its memory (pages 4711–4722)

      Kazuhide Morino, Takeshi Asari, Katsuhiro Maeda and Eiji Yashima

      Article first published online: 12 AUG 2004 | DOI: 10.1002/pola.20379

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      Stereoregular, cis–transoidal poly[(4-carboxyphenyl)acetylene] and its derivatives deuterated in the main chain and/or on the phenyl group (poly-1's) were conveniently synthesized by the polymerization of 4-ethynylbenzoic acid or its derivative deuterated on the phenyl group in the presence of bases with a water-soluble rhodium complex in water or deuterium oxide. Possible deuterium isotope effects of these partially and fully deuterated poly-1's during the helicity induction and its memory were investigated. The thermal cis–trans isomerization of the methyl esters of poly-1's was also studied with 1H NMR spectroscopy.

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