Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 21

1 November 2011

Volume 49, Issue 21

Pages i–iv, 4515–4720

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. You have free access to this content
      Cover Image, Volume 49, Issue 21 (pages i–ii)

      Version of Record online: 24 SEP 2011 | DOI: 10.1002/pola.25018

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      Three different cyclodextrins promote the emulsion copolymerization of a highly waterinsoluble monomer, heptadecafluorodecyl methacrylate, through reversible formation of inclusion complexes. Depending on the solubility of the inclusion complex, heterocoagulation of the fluorinated copolymer with pre-formed latex particles leads to the formation of distinctive core-shell “patchy” nanostructures, which self-assemble into highly hydrophobic latex films. More information can be found in the article On page 4518 by Chengcheng Yang, Valter Castelvetro, Dominique Scalarone, Sabrina Bianchi, and Yongming Zhang.

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      Inside Cover, Volume 49, Issue 21 (pages iii–iv)

      Version of Record online: 24 SEP 2011 | DOI: 10.1002/pola.25023

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      Polymer chains with well-defined functional end-groups can be coupled to form macrocyclic structures. Further chemical coupling of such cyclic structures to other polymer chains allows the formation of AB, AB2, and A2B miktoarm star copolymers, as presented by Daria E. Lonsdale and Michael J. Monteiro on page 4603. Block A consists of linear poly(tert-butyl acrylate) (PtBA) and block B consists of cyclic polystyrene (c-PSTY). Deprotection of PtBA to poly(acrylic acid) (PAA) affords amphiphilic miktoarm structures that when micellized in water give vesicle morphologies when the block length of PAA is 21 units and spherical core-shell micelles when the block length of PAA is 46 units.

  2. Rapid Communication

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. Tandem phenol-keto tautomerism and nucleophilic substitution reactions for the synthesis of novel soluble and crosslinkable poly(arylene ether ketone) (pages 4515–4517)

      Fangfang Dong, Binyuan Liu, Baoxing Liu and Li Zhang

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24912

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      Tandem phenol-keto and nucleophilic substitution reaction were successfully employed in preparing soluble poly(arylene ether ketone)s that can be cross-linked into high-performance networks at elevated temperature tentatively via retro-Diels-Alder reaction.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. Three different β-cyclodextrins direct the emulsion copolymerization of a highly fluorinated methacrylate toward distinctive nanostructured particle morphologies (pages 4518–4530)

      Chengcheng Yang, Valter Castelvetro, Dominique Scalarone, Sabrina Bianchi and Yongming Zhang

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24921

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      Three different β-cyclodextrins were shown to promote the emulsion copolymerization of the highly water-insoluble heptadecafluorodecyl methacrylate through reversible formation of inclusion complexes (ICs). Depending on the solubility of their respective IC, they direct the incorporation of the fluorinated copolymer in the shell of preformed latex particles with formation of distinctive nanostructures. The final shell copolymer composition and “patchy” core-shell morphology influence the thermal and surface properties of the resulting lightly fluorinated, highly hydrophobic latex film.

    2. Synthesis of polymeric ionic liquid microsphere/Pt nanoparticle hybrids for electrocatalytic oxidation of methanol and catalytic oxidation of benzyl alcohol (pages 4531–4538)

      Jianhu Yang, Lihua Qiu, Baoqiang Liu, Yingjing Peng, Feng Yan and Songmin Shang

      Version of Record online: 9 AUG 2011 | DOI: 10.1002/pola.24895

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      Crosslinked poly(ionic liquid) (PIL) microspheres (∼200 nm) were prepared via miniemulsion polymerization and used as the scaffold for immobilizing of Pt nanoparticles for electrocatalysis and heterogeneous catalysis. The resultant PIL/Pt hybrids show good electrocatalytic activity toward the electrooxidation of methanol and catalytic oxidation of benzyl alcohol.

    3. Modulating catalytic activity of polymer-based cuAAC “click” reactions (pages 4539–4548)

      Craig A. Bell, Zhongfan Jia, Sébastien Perrier and Michael J. Monteiro

      Version of Record online: 9 AUG 2011 | DOI: 10.1002/pola.24896

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      The copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction is used to synthesize complex polymer architectures. In this work, we demonstrate the control of this reaction at 25 °C between polystyrene chains through modulating the catalytic activity by varying the combinations of copper source (i.e., Cu(I)Br or copper wire), ligand (PMDETA and/or triazole ligand), and solvent (toluene or DMF). The data show that rapid rates can be obtained using copper wire and will have direct applications to the synthesis of compound where air, removal of copper, and reuse of the copper catalyst are required.

    4. Functionality of peripheral side chain for enhanced performance of conjugated polymer—F8BT as an example (pages 4549–4555)

      Wenyue Dong, Shanfeng Xue, Ping Lu, Jian Deng, Donglin Zhao, Cheng Gu and Yuguang Ma

      Version of Record online: 12 AUG 2011 | DOI: 10.1002/pola.24898

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      Modification of F8BT with peripheral carbazole groups on side chain was realized. The incorporation of carbazole units significantly increases the HOMO energy levels and hole injection ability for the polymers. The radios of fluorene and BTz unit in polymers could be adjusted to balance the electron and hole transport, and the polymer PCFBT0.2 (BTz:fluorene = 2:8) exhibits 13 times higher maximum luminous efficiency (10.8 cd/A) than F8BT (0.8 cd/A) in a double-layered device.

    5. Effects of thiols, lithium chloride, and ethoxylated monomers on the frontal polymerization of a triacrylate (pages 4556–4561)

      Veronika Viner and John A. Pojman

      Version of Record online: 12 AUG 2011 | DOI: 10.1002/pola.24914

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      Copolymerization of an acrylate and thiol results in lower front temperatures and velocities than thermal frontal polymerization of an acrylate. The functionality of the thiol, molecular weight per thiol, and molecular weight per double bond affect front velocity and temperature.

    6. Homogeneous radical polymerization of 2-hydroxyethyl methacrylate mediated by cyclometalated cationic Ruthenium(II) complexes with PF6 and Cl in protic media (pages 4562–4577)

      Maria Ortencia Gonzalez Diaz, Salvador Lopez Morales, Ronan Le Lagadec and Larissa Alexandrova

      Version of Record online: 9 AUG 2011 | DOI: 10.1002/pola.24899

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      Cationic coordinatively saturated complexes of ruthenium(II), [Ru(o-C6H4-2-py)(phen)(MeCN)2]+, bearing different counterions, PF6 and Cl, have been used in the radical polymerization of 2-hydroxyethyl methacrylate in protic media and acetone under homogeneous conditions. Both complexes led to the fast polymerization with controlled molecular weights and molecular weight distribution and proceeded in a “living” manner in methanol. The nature of the counteranion and the solubility in water of the complexes can modulate the polymerization characteristics and may serve as fine way of tuning the catalytic properties.

    7. Monitoring photopolymerization of trimethylolpropane triacrylate using a quartz crystal resonator (pages 4578–4585)

      Byoung Chul Kim and Young Han Kim

      Version of Record online: 11 AUG 2011 | DOI: 10.1002/pola.24901

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      The UV photopolymerization of trimethylolpropane triacrylate with a photoinitiator of 2-ethylanthraquinone is monitored using the variation of resonant resistance of a quartz crystal resonator to investigate the polymerization kinetics. The roles of initiator concentration and irradiation time are experimentally examined, and it is found that two different kinetics are involved in the photopolymerization. The initiator radicals produced by the UV light proceed the polymerization as long as the monomer remains even after the UV illumination has stopped. The experimental results indicate that the photopolymerization has the first-order kinetics at the first and the zero-th- order kinetics followed. With the high concentration of initiator the polymerization occurs in the first-order kinetics only, and so does with long irradiation time. The polymerization constants of the first- and zero-th- order kinetics are estimated from monitoring monomer amounts at different polymerization conditions. The photopolymerization is characterized with the FT-IR spectroscopy.

    8. Photo-induced association behavior of poly(sodium acrylate) bearing a small amount of malachite green (pages 4586–4593)

      Shouta Kousaka, Masanori Ito and Shin-Ichi Yusa

      Version of Record online: 11 AUG 2011 | DOI: 10.1002/pola.24902

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      The random copolymer of acrylic acid with 0.05 mol % of photoresponsive MG monomer [P(A/MG0.05)] was soluble in water as a unimer due to electrostatic repulsion between carboxylate pendent groups when the MG moieties were in the neutral form. On the other hand, these MG groups were converted to the cationic form upon UV irradiation, leading to polymer aggregation driven by electrostatic interactions between the cationic MG and anionic carboxylate pendent groups.

    9. In situ-generated Ru(III)-mediated ATRP from the polymeric Ru(III) complex in the absence of activator generation agents (pages 4594–4602)

      Dan He, Seok Kyun Noh and Won Seok Lyoo

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24903

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      Atom transfer radical polymerization (ATRP) of MMA with in situ-generated Ru(III) complexes with various phosphorus-containing ligands in the absence of any activator generation agents is herein reported for the first time. The polymers formed in this system have better controlled molecular weights and narrower polydispersities than Ru(II) mediated ATRP under same conditions. The use of oxidatively stable catalysts can avoid the air-sensitive properties of lower-oxidation-state metals, in addition, the application of ppm amount of Ru(III) catalyst makes much industrial attractive points for practical production of both homopolymers and copolymers.

    10. Synthesis and self-assembly of amphiphilic macrocyclic block copolymer topologies (pages 4603–4612)

      Daria E. Lonsdale and Michael J. Monteiro

      Version of Record online: 7 SEP 2011 | DOI: 10.1002/pola.24935

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      AB, AB2, and A2B miktoarm star copolymers were synthesized in which block A consisted of linear poly(tert-butyl acrylate) (PtBA) and block B consisted of cyclic polystyrene were produced using the atom transfer radical polymerization to make telechelic polymers. After modification, they were further coupled together by copper-catalyzed “click” reactions with high coupling efficiency. Deprotection of PtBA to poly(acrylic acid) afforded amphiphilic miktoarm structures that when micellized in water gave vesicle morphologies when the block length of PAA was 21 units and spherical core-shell micelles when the block length of PAA was 46 units.

    11. Selective synthesis of poly(p-oxybenzoyl) by fractional polycondensation: Enhancement of selectivity by shearing (pages 4613–4617)

      Toshimitsu Ichimori, Shinichi Yamazaki and Kunio Kimura

      Version of Record online: 11 AUG 2011 | DOI: 10.1002/pola.24904

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      Application of Shearing enhanced selectivity for preparation of poly(p-oxybensoyl) (Pp-OB) by using hydrodynamically induced phase separation during polymerization of 4-(4-acetoxybenzoyloxy)benzoic acid (p-ABAD) and m-acetoxybenzoic acid (m-ABA). The timing of the application of the shearing influenced the slectivity significatly, and the shearing just after the precipitation of the oligomers started was quite efficient to enhance the slecttivity more. The content of m-oxybenzoyl moiety of the precipitates (χp) prepared with shearing just after the precipitation was only 3.9 mol % even when the content of m-oxybenzoyl moiety in feed (χf) was 60 mol %

    12. Structure modification and annealing effect of polymer bulk heterojunction solar cells based on polyfluorene derivatives (pages 4618–4625)

      Jung-Feng Lee, Steve Lien-Chung Hsu, Po-I Lee, Hung-Yi Chuang, Jen-Sue Chen and Wei-Yang Chou

      Version of Record online: 11 AUG 2011 | DOI: 10.1002/pola.24905

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      We found that the annealing temperature had a profound effect on the power conversion efficiency (PCE) of the devices with a blend of PF12-TBT and PCBM. The PCE of the solar cell based on PF12-TBT/PCBM (1:4) annealing at 70 °C for 20 min was 4.13% with an open-circuit voltage (Voc) of 1.02 V, fill factor of 55.9%, and a short-circuit current (Jsc) of 7.24 mA/cm2.

    13. Living regioselective copolymerization of ethylene with nonconjugated bicyclic dienes using (salicylaldiminato)(β-enaminoketonato) titanium catalysts (pages 4626–4638)

      Ying-Yun Long, Yong-Xia Wang, Jing-Yu Liu, Xiao-Fang Li and Yue-Sheng Li

      Version of Record online: 11 AUG 2011 | DOI: 10.1002/pola.24906

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      A series of novel heteroligated (salicylaldiminato)(β-enaminoketonato)titanium catalysts were investigated as the catalysts for ethylene/VNB or ENB copolymerization in the presence of modified methylaluminoxane. The titanium complexes with electron-donating groups in the β-enaminoketonato ligands are able to initiate room-temperature living ethylene/VNB (or ENB) copolymerization.

    14. Synthesis of a new multiarm star polymer based on hyperbranched poly(styrene) core and poly(ε-caprolactone) arms and its use as reactive modifier of epoxy thermosets (pages 4639–4649)

      Mireia Morell, David Foix, Albena Lederer, Xavier Ramis, Brigitte Voit and Àngels Serra

      Version of Record online: 20 AUG 2011 | DOI: 10.1002/pola.24908

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      A well-defined multiarm star poly(styrene)-b-poly(ε-caprolactone) (PSOH-b-PCL) with an average number of PCL arms per molecule of 60 has been prepared. 4-Chloromethyl styrene (4-CMS) was polymerized by means of atom transfer radical polymerization (ATRP) to obtain a hyperbranched poly(styrene) with chlorines as terminal groups, which were substituted by reaction with diisopropanolamine (DIPA) to give the hydroxyl-ended derivative. The hydroxyl ended hyperbranched poly(styrene) has been used as a macroinitiator to polymerize ε-caprolactone by cationic ring-opening polymerization to obtain the star copolymer. PSOH-b-PCL was used as reactive modifier of DGEBA formulations cured by 1-methyl imidazole (1-MI) obtaining nanostructured thermosets. The curing was studied by DSC, rheology and FTIR. The thermomechanical characteristics of the modified materials were determined.

    15. Effect of water addition on the cure kinetics of an epoxy-amine thermoset (pages 4650–4659)

      Sungwon Choi, Andrew P. Janisse, Changhua Liu and Elliot P. Douglas

      Version of Record online: 12 AUG 2011 | DOI: 10.1002/pola.24909

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      Near FT-IR spectra demonstrated that a small amount of water addition significantly accelerated the cure reaction in terms of epoxide conversion, with water acting as a catalyst for the reaction. Use of a modified mechanistic model allowed direct comparison of the effect of hydroxyl groups generated from water addition to those generated from the polymer chain. The comparison of those kinetic parameters shows that the two effects are very close, in which difference in the logarithmic value of the reaction constant is less than one order of magnitude over all the reaction conditions.

    16. Photoinitiated precipitation polymerization in liquid CO2: Fast formation of crosslinked poly(acrylic acid-co-methoxy polyethylene glycol acrylate) microspheres (pages 4660–4667)

      Bo Wu, Jianbo Tan, Jianwen Yang and Zhaohua Zeng

      Version of Record online: 12 AUG 2011 | DOI: 10.1002/pola.24910

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      Photoinitiated precipitation polymerization was carried out in liquid CO2 by which monodisperse crosslinked poly(AA-co-MPEGA) microspheres have been successfully synthesized. It is found that most of microspheres were produced in the first 5 min of irradiation, showing that the reaction was very quick. The particle number increased incessantly till very late stage, which could be attributed to the direct generation of nuclei from the fast crosslinking polymerization. Ethanol as cosolvent played an important role on forming microspheres. The feeding ratio of monomers could be tuned in a wide range in the presence of ethanol without disturbing the formation of microspheres.

    17. Random and block styrenic copolymers bearing both ammonium and fluorinated side-groups (pages 4668–4679)

      David Valade, Frédéric Boschet and Bruno Ameduri

      Version of Record online: 22 AUG 2011 | DOI: 10.1002/pola.24913

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      1H,1H,2H,2H-Perfluorooctyloxymethylstyrene was prepared and copolymerized with chloromethylstyrene (CMS) by conventional or controlled (iodine transfer polymerization) radical copolymerization, leading respectively to random and diblock copolymers. The resulting copolymers were modified via a cationization step, aiming at replacing the chlorine atom in CMS units by a trimethylammonium group.

    18. Synthesis and self-assembly of diblock copolymers composed of poly(3-hexylthiophene) and poly(fluorooctyl methacrylate) segments (pages 4680–4686)

      MD. Harun-Or Rashid, Myungeun Seo, Sang Youl Kim, Yeong-Soon Gal, Jong Myung Park, Eun Young Kim, Won-Ki Lee and Kwon Taek Lim

      Version of Record online: 12 AUG 2011 | DOI: 10.1002/pola.24915

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      A new type of diblock copolymer composed of π-conjugated P3HT and semifluorinated poly(fluorooctyl methacrylate), P3HT-b-PFOMA was synthesized by atom transfer radical polymerization and the morphological property of the copolymer was investigated. The block copolymers formed micelles where PFOMA is the core and P3HT is the shell in P3HT selective chloroform solvent and produced well-defined, organized nanofibrillar-like film morphology upon drop-casting of the micellar solution. The ordering is improved by the fluorinated solvent, supercritical CO2, or thermal annealing. The nanofibrils of the copolymers possessed long-range order, leading to densely packed wires after the annealing, as investigated by TEM analysis.

    19. Preparation of novel photoreactive polycarbazole-based microparticles: Reactivity features (pages 4687–4693)

      Maria Naddaka, Ejabul Mondal and Jean-Paul Lellouche

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24916

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      Four types of innovative benzophenone- or aryl azide-containing photoreactive polycarbazole (polyCbz)-based microparticles (MPs) were prepared using an oxidative liquid phase polymerization system. Their photochemical reactivity was evaluated by their reaction with highly inert poly(2-chloro-paraxylelene) (Parylene C) films. Possible mechanisms for the photochemical reaction of those MPs with Parylene C were discussed.

    20. In situ Cu(0) catalyzed SET-LRP: The first attempt (pages 4694–4700)

      Qin Zhang, Zhengbiao Zhang, Wenxiang Wang, Zhenping Cheng, Jian Zhu, Nianchen Zhou, Wei Zhang, Zhaoqiang Wu and Xiulin Zhu

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24917

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      In this work, single electron transfer-living radical polymerization (SET-LRP) was catalyzed by in-situ Cu(0) generated from copper sulphate pentahydrate (CuSO4·5H2O) and hydrazine hydrate (N2H4·H2O) at 25 °C. The polymerization smoothly occurred with moderate control over molecular weights due to some side reactions related to N2H4·H2O. This polymerization can be conducted in unfavorable solvents for SET-LRP, such as toluene and tetrahydrofuran, owing to H2O contained in CuSO4·5H2O and N2H4·H2O. Importantly, on account of the utilization of CuSO4·5H2O, this work confirmed from experimental level that it was Cu(0) or “nascent” Cu(0) which initiated and catalyzed SET-LRP. This work provided a first example of in-situ Cu(0) catalyzing SET-LRP. Optimization work is ongoing in our lab by utilization of mild reducing agents balacencing between adequate reduction ability and minimimal side reactions.

    21. Living cationic polymerization of a coumarin-substituted vinyl ether and reversible photoinduced crosslinking of the resulting homopolymers and amphiphilic block copolymers (pages 4701–4707)

      Jin Motoyanagi, Izumi Nishimura and Masahiko Minoda

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24918

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      We have designed a novel coumarin-substituted vinyl ether (4-methyl-7-(2-vinyloxyethoxy)coumarin; CMVE) and achieved the living cationic polymerization of CMVE using CH3CH(OiBu)-Cl and SnCl4 in the presence of nBu4NBr as an added salt at 0 °C. The number-average molecular weight of the resulting polymers increased in direct proportion to the monomer conversion while retaining relatively low polydispersity. These coumarinyl moieties were cross-linked by irradiation with UV light at λmax = 366 nm, and the resulting cross-linked sites were then cleaved by irradiation with UV light at λmax = 254 nm. We have also synthesized well-defined amphiphilic block polymers bearing coumarinyl moieties by living cationic block copolymerization.

  4. Notes

    1. Top of page
    2. Cover Image
    3. Rapid Communication
    4. Articles
    5. Notes
    1. Pd(II)-pyridine macrocomplexes based on poly(lactide) (pages 4708–4713)

      Guido Giachi, Marco Frediani, Werner Oberhauser and Elisa Passaglia

      Version of Record online: 20 AUG 2011 | DOI: 10.1002/pola.24907

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      Homo- and heteroleptic Pd(II)-macrocomplexes of different geometries and bearing 4-pyridinemethylene-end-capped polymers of l and rac-lactide were successfully obtained for the first time. The reversible macroligand coordination to Pd(II) was proved to occur in solution.

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      Synthesis of photo-scissible poly(p-hydroxystyrene) derivatives by radical copolymerization of p-hydroxystyrene derivatives and methyl vinyl ketone (pages 4714–4720)

      Takeshi Ishikawa, Kazuhide Morino, Atsushi Sudo and Takeshi Endo

      Version of Record online: 11 AUG 2011 | DOI: 10.1002/pola.24894

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      A synthesis of a copolymer composed of p-hydroxystyrene (HSt) and methyl vinyl ketone (MVK) units was performed by radical copolymerization of O-protected HSt (protective group=tert-butyl, ethoxyethyl, and acetyl) with MVK followed by removal of the protective groups and photodegradable behavior of obtained copolymers. The molecular weights of these copolymers decreased under photoirradiation due to the Norrish-type II reaction of the ketone groups of MVK units. These results demonstrate that a copolymer composed of HSt and MVK units possesses good photo-scissibility.

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