Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 9

1 May 2004

Volume 42, Issue 9

Pages 2051–2301

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Articles
    1. Solid polymer electrolytes I, preparation, characterization, and ionic conductivity of gelled polymer electrolytes based on novel crosslinked siloxane/poly(ethylene glycol) polymers (pages 2051–2059)

      Ping-Lin Kuo, Sheng-Shu Hou, Chung-Yie Lin, Chi-Chang Chen and Ten-Chin Wen

      Version of Record online: 17 MAR 2004 | DOI: 10.1002/pola.20056

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      Crosslinked siloxane/poly(ethylene glycol) (PEG) polymers were synthesized through the self-condensation reaction and the alkoxy-exchange reaction during an in situ curing stage. The crosslinked polymers were used as gel-like solid polymer electrolytes after absorbing propylene carbonate (LiClO4/PC) solution. Their conductivities were affected by the content of LiClO4/PC, the molecular weights of PEGs, and the weight fraction of siloxane.

    2. Polymerization of methyl acrylate with triphenylbismuthonium 1,2,3,4-tetraphenylcyclopentadienylide as a new radical initiator (pages 2060–2065)

      Seema Tripathi and A. K. Srivastava

      Version of Record online: 17 MAR 2004 | DOI: 10.1002/pola.10994

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      Triphenylbismuthonium 1,2,3,4-tetraphenylcyclopentadienylide in 1,4-dioxan initiated radical polymerization of methyl acrylate to ∼30% conversion without gelation because of autoacceleration. The polymer had a viscosity-average molecular weight of 200,000. The kinetic expression was Rpα[I]0.3M]1.16, that is, the system followed nonideal kinetics because of primary radical termination and degradative chain-transfer reactions. The values of kmath imagekt and the energy of activation were computed as 3.12 × 10−5 Lmol−1s−1 and 28 kJ/mol, respectively. The ylide dissociated to form a phenyl radical, which brought about polymerization of methyl acrylate.

    3. UV-ignited frontal polymerization of an epoxy resin (pages 2066–2072)

      Alberto Mariani, Simone Bidali, Stefano Fiori, Marco Sangermano, Giulio Malucelli, Roberta Bongiovanni and Aldo Priola

      Version of Record online: 26 MAR 2004 | DOI: 10.1002/pola.20051

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      UV-ignited frontal polymerization can be used to obtain UV curing of thick epoxy materials, by combining the frontal polymerization technique with the UV process. A proper cationic photoinitiator–radical thermal-initiator ratio was discovered to obtain a self-sustaining front and to make the curing of thick layers possible.

    4. Synthesis of a soluble pyrrole copolymer with phenetidine (pages 2073–2092)

      Xin-Gui Li, Run-Feng Chen, Mei-Rong Huang, Mei-Fang Zhu and Qun Chen

      Version of Record online: 17 MAR 2004 | DOI: 10.1002/pola.20053

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      A new series of soluble copolymers was synthesized through the oxidative polymerization of pyrrole and o-phenetidine with inorganic oxidants in acidic aqueous media. The influence of key polymerization parameters on the polymerization yield, intrinsic viscosity, and solubility of the copolymers was studied in detail, and the parameters were further optimized for the synthesis of copolymers with high yields and intrinsic viscosities. A structural study suggested that the observed content of pyrrole units in the copolymers was much higher than the feed pyrrole content and that the pyrrole/o-phenetidine polymer formed thus was a real random copolymer rather than a mixture of two homopolymers.

    5. Copolymerization of the macromonomer poly(ethylene oxide) with styryl end group and styrene in the presence of poly(ε-caprolactone) with 2,2,6,6-tetramethylpiperidinyl-1-oxy end group by controlled radical mechanism (pages 2093–2099)

      Yun Wang, Guangqiang Lu and Junlian Huang

      Version of Record online: 17 MAR 2004 | DOI: 10.1002/pola.20046

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      A new graft copolymer [poly(ε-caprolactone)-polystyrene-graft-poly(ethylene oxide)] was prepared by copolymerization between macromonomer poly(ethylene oxide) (PEO) with a styryl end group and styrene with poly(ε-caprolactone) (PCL) with 2,2,6,6-tetramethylpiperidinyl-1-oxy end group as a macroinitiator. The resulting copolymer showed a narrow molecular weight distribution and controlled molecular weight. The molecular weight of PCL and PEO as well as the concentration of PCL significantly affected the copolymerization.

    6. Polymerization of substituted phenylacetylenes with a novel, water-soluble Rh–vinyl complex in water (pages 2100–2105)

      Keiji Kanki, Atsushi Nakazato, Ryoji Nomura, Fumio Sanda and Toshio Masuda

      Version of Record online: 17 MAR 2004 | DOI: 10.1002/pola.11035

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      A novel, water-soluble Rh complex (nbd)Rh[PPh2(m-NaOSO2C6H4)] [C(Ph)[DOUBLE BOND]CPh2] (1) was synthesized, whose structure was determined by NMR and IR spectroscopies. The Rh catalyst 1 induced the polymerization of phenylacetylene (PA) in water to give two kinds of polymers; one was soluble in common organic solvents. The polymerizations of water-soluble substituted acteylenes, p-NaOCO-PA and p-CH3(OCH2CH2)2-OCO-PA were also investigated.

    7. Efficient and rapid synthesis of polyureas and polythioureas from the reaction of urea and thiourea with diamines under microwave irradiation (pages 2106–2111)

      Ahmad Banihashemi, Hassan Hazarkhani and Amir Abdolmaleki

      Version of Record online: 17 MAR 2004 | DOI: 10.1002/pola.20060

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      Polyureas and polythioureas were readily synthesized by the reaction of aromatic and aliphatic amines with urea and thioureas, respectively, in good to excellent yields under microwave irradiation. The effects of the microwave irradiation time and power, the nature of the solvent, and the solid content of the monomers on the inherent viscosity of the polymers were investigated.

    8. New poly(p-phenylene vinylene) derivatives with two oxadiazole rings per repeat unit: Synthesis, photophysical properties, electroluminescence, and metal ion recognition (pages 2112–2123)

      John A. Mikroyannidis, Ioakim K. Spiliopoulos, Theodoros S. Kasimis, Abhishek P. Kulkarni and Samson A. Jenekhe

      Version of Record online: 17 MAR 2004 | DOI: 10.1002/pola.20049

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      Two soluble, poly(p-phenylene vinylene) (PPV) based polymers with 1,3,4-oxadiazole rings along the main chain were synthesized. They behaved as strongly luminescent materials with photoluminescence maxima at 379–492 nm in solution and 533–555 nm in thin film. Electroluminescence (EL) was observed from light-emitting diodes of polymer OX2-PPV with an EL maximum at 555 nm and a maximum brightness of 70 cd/m2. This polymer was used as a fluorescence-mode chemosensor for recognition of various metal ions.

    9. Crosslinkable poly(p-phenylenevinylene) derivative (pages 2124–2129)

      Honghao Sun, Ze Liu, Yufeng Hu, Lixiang Wang, Dongge Ma, Xiabing Jing and Fosong Wang

      Version of Record online: 19 MAR 2004 | DOI: 10.1002/pola.20068

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      A crosslinkable poly(p-phenylenevinylene) derivative (PPVD) with styrene terminals was synthesized through the copolymerization of 2-methoxy-5-(2-ethylhexyloxy)benzene-1,4-dialdehyde, 3-vinylbenzaldehyde, and 1,4-xylylenebis (tributyl phosphonium chloride) through a Wittig-type coupling reaction. A crosslinked polymer was prepared through the curing of crosslinkable PPVD at 175 °C for 1 h. A double-layer electroluminescent device using crosslinked PPVD as an emitting layer and PBD in poly(methyl methacrylate) as an electron-transport layer was prepared by spin coating. A maximum brightness of 740 cd/m2 at 16 V and a maximum luminance efficiency of 0.70 cd/A (a 12-fold improvement with respect to that of a single-layer device) were demonstrated.

    10. Synthesis and properties of novel polyimides derived from 2,2′,3,3′-benzophenonetetracarboxylic dianhydride (pages 2130–2144)

      Xing-Zhong Fang, Qing-Xuan Li, Zhen Wang, Zheng-Hua Yang, Lian-Xun Gao and Meng-Xian Ding

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20069

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      A new synthetic route to 2,2′,3,3′-BTDA (where BTDA is benzophenonetetracarboxylic dianhydride) is described. Single-crystal X-ray diffraction analysis has shown that this dianhydride has a bent and noncoplanar structure. A trend of cyclic oligomers forming in the reaction of 2,2′,3,3′-BTDA and 4,4′-oxydianiline has been found and characterized with IR, NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and elemental analyses. The polyimides (PIs) from 2,2′,3,3′-BTDA have lower inherent viscosities and worse thermal and mechanical properties than the corresponding 2,3,3′,4′-BTDA- and 3,3′,4,4′-BTDA-based PIs. Furthermore, the PIs from 2,2′,3,3′-BTDA have better solubility, higher glass-transition temperatures, and higher melt viscosity than those from 2,3,3′,4′-BTDA and 3,3′,4,4′-BTDA.

    11. Nanoencapsulation of a hydrophobic compound by a miniemulsion polymerization process (pages 2145–2154)

      Yingwu Luo and Xiangdong Zhou

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20065

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      The nanoencapsulation of hydrophobic compounds by miniemulsion polymerization, a convenient one-step encapsulation technique for nanocapsules, was investigated in terms of the thermodynamics and kinetics.

    12. Diels–Alder reaction with anthracene and quinone derivatives on the dendritic periphery (pages 2155–2161)

      Chungkyun Kim, Hyojeong Kim and Kyungrae Park

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20080

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      Diels–Alder adducts including 24, 48, and 96 bicyclo end groups on the dendritic periphery were prepared by the reaction of anthracene on the dendrimers (first to fourth generation) and 1,4-benzoquinone as well as 1,4-naphtoquinone in boiled toluene.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Articles
    1. Polymerization of an epoxide by Woodsward's reagents as thermally latent initiators (pages 2162–2165)

      Tetsuo Hino and Takeshi Endo

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20076

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      Polymerizations with Woodsward's reagent L (2a) and Woodsward's reagent K (2b) as novel thermally latent initiators were investigated. The activities for the latent initiators were examined with glycidyl phenyl ether (GPE or 1). These reagents were found to act efficiently as thermally latent initiators, and the activity order was estimated to be 2a > 2b. In addition, reagent 2b unexpectedly acted as a crosslinking agent as well under certain polymerization conditions.

    2. Cationic ring-opening polymerization of an epoxide by tropylium salts as thermal- and photolatent initiators (pages 2166–2170)

      Tetsuo Hino and Takeshi Endo

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20077

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      Novel, cationic thermal and photopolymerizations of glycidyl phenyl ether (GPE) were attempted under various reaction conditions by tropylium salts (1ab). These polymerizations with tropylium salts served as new thermal- and photolatent initiators in the polymerization of GPE. On the basis of the relationship between conversion and irradiation time or temperature, the activity order for a thermal- and photolatent initiator should be estimated as 1a > 1b.

  3. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Articles
    1. 13C NMR determination of the microstructure of polypropylene obtained with the DADNi(NCS)2/methylaluminoxane catalyst system (pages 2171–2178)

      Griselda Barrera Galland, Luciana P. Da Silva, Marcos L. Dias, Geraldo L. Crossetti, Cláudio M. Ziglio and Carlos A. L. Filgueiras

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20047

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      A complete 13C NMR characterization of a polymer synthesized with a new Ni-diimine complex [DADNi(NCS)2, where DAD = 2,6-iPr[BOND]C6H3[BOND]N[DOUBLE BOND]C(Me)[BOND]C(Me)[DOUBLE BOND]N[BOND]2,6-iPr[BOND]C6H3] activated by methylaluminoxane by homopolymerization of propylene is presented. The amorphous material was made up mainly of blocks of syndiotactic polypropylene and ethylene–propylene copolymer. Some degree of propylene inversion (<1.2 mol %) and of long isobutyl and 2-methyl hexyl branching (<1 mol %) were assigned and quantified.

    2. Synthesis of a water-soluble diblock copolymer of polysulfonic diphenyl aniline and poly(ethylene oxide) (pages 2179–2191)

      Fengjun Hua and Eli Ruckenstein

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20042

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      The synthesis of a water-soluble diblock copolymer composed of polysulfonic diphenyl aniline (PSDA) and poly(ethylene oxide) (PEO), which was prepared by reacting an amine-terminated PSDA and tosylate PEO (PEO-Tos), is reported. The self-doping of the diblock copolymer induced aggregation in water among the PSDA backbones, which was also stimulated by the presence of the hydrophilic PEO blocks, as sketched in the scheme.

    3. Novel amphiphilic network polymers consisting of nonpolar, short primary polymer chains and polar, long crosslink units: Influence of characteristic dangling chains on swelling behavior of resulting amphiphilic gels (pages 2192–2201)

      Masato Doura, Hiroyuki Aota and Akira Matsumoto

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20054

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      Benzyl methacrylate (BzMA) was copolymerized with tricosaethylene glycol dimethacrylate (PEGDMA-23) in the presence of lauryl mercaptan as a chain-transfer agent because BzMA forms nonpolar, short primary polymer chains and PEGDMA-23 contains a polar, long poly(oxyethylene) unit. The enhanced incorporation of dangling chains into the network polymer was brought both by shortening the primary polymer chain length and by the copolymerization with methoxytricosaethylene glycol methacrylate as a mono-ene counterpart of PEGDMA-23. The profiles of the solvent-component dependencies of the swelling ratios were characteristic of amphiphilic gels. The introduction of the dangling poly(oxyethylene) chains led not only to an increased swelling ratio but also to sharpened swelling behavior of amphiphilic gels.

    4. Microencapsulation of cholesteryl alkanoate by polymerization-induced phase separation and its association with drugs (pages 2202–2213)

      Jin-Woong Kim, Kwang-Sup Lee, Hee-Kyung Ju, Jee-Hyun Ryu, Sang-Hoon Han, Ih-Seop Chang, Hak-Hee Kang, Seong-Geun Oh and Kyung-Do Suh

      Version of Record online: 22 MAR 2004 | DOI: 10.1002/pola.20082

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      A new microencapsulation technique is presented in which cholesteryl nonanoate (CN)/poly(methyl methacrylate) (PMMA) microcapsules are produced by the induction of phase separation between CN and PMMA within the droplets during the polymerization. To evaluate the effectiveness of the technique for stabilizing an unstable drug, we selected retinol (vitamin A) as a model drug and loaded it into the CN/PMMA microcapsules. We used a process called solute codiffusion. In the thermal stability test of retinol, we found that an effective association with the CN phase was the most important factor determining the limit of its molecular stability.

    5. Luminescent poly(phenylene vinylene) derivatives with m-terphenyl or 2,6-diphenylpyridine kinked segments along the main chain: Synthesis, characterization, and stimulated emission (pages 2214–2224)

      Panayiotis Karastatiris, John A. Mikroyannidis, Ioakim K. Spiliopoulos, Mihalis Fakis and Peter Persephonis

      Version of Record online: 23 MAR 2004 | DOI: 10.1002/pola.20050

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      The synthesized poly(phenylene vinylene) derivatives exhibited emission at shorter wavelengths relative to poly(p-phenylene vinylene). They formed aggregates in concentrated solutions and in thin films. The protonation of polymer with a pyridine ring in the main chain, caused a blue- or redshift of the photoluminescence maximum in solution or in film, respectively. Amplified spontaneous emission and tunable laser action were obtained from both polymers.

    6. Preparation of cationic latices comprising hollow thermostable particles (pages 2225–2234)

      V. N. Pavlyuchenko, O. V. Sorochinskaya, O. N. Primachenko, N. A. Byrdina, S. S. Ivanchev and M. Skrifvars

      Version of Record online: 24 MAR 2004 | DOI: 10.1002/pola.20048

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      Sub-micro-meter-sized, cationic hollow particles were much more thermostable as compared with initial anionic ones free of a malamine shell. The cationic hollow particles were incorporated into a thermosetting binder cured at 170 °C to obtain opaque white coating.

    7. Three-component, negative-type, alkaline-developable, thermally stable, and photosensitive polymer based on poly(2,6-dihydroxy-1,5-naphthalene), a crosslinker, and a photoacid generator (pages 2235–2240)

      Kousuke Tsuchiya, Yuji Shibasaki, Masato Suzuki and Mitsuru Ueda

      Version of Record online: 24 MAR 2004 | DOI: 10.1002/pola.20122

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      A negative working and chemically amplified photosensitive polymer based on poly(2,6-dihydroxy-1,5-naphthalene) (number-average molecular weight = 25,000), in conjunction with a crosslinker and a photoacid generator, has been developed. The polymeric system showed a photosensitivity of 8.3 mJ cm−2 and a contrast of 11 when it was exposed to 436-nm light, followed by postexposure baking at 100 °C for 5 min and development with a 2.38 wt % aqueous tetramethylammonium hydroxide solution at 25 °C. A fine negative image featuring 10-μm line-and-space patterns was obtained on a film 3 μm thick exposed to 10 mJ cm−2 of ultraviolet light at 436 nm in the contact-printed mode, which showed high thermal stability and a low dielectric constant.

    8. Hydrogels based on physiologically clotted fibrin–gelatin composites (pages 2241–2252)

      S. E. Noorjahan and T. P. Sastry

      Version of Record online: 24 MAR 2004 | DOI: 10.1002/pola.20055

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      Fibrin–gelatin composite (PFG) films were crosslinked and graft-copolymerized with poly(2-hydroxyethyl methacrylate (PHEMA) and poly(2-hydroxypropyl methacrylate) (PHPMA) with a potassium persulfate and sodium metabisulfite redox initiation system. The graft copolymers (PFG-HEMA and PFG-HPMA) were characterized for their percentage of grafting, percentage of equilibrium water content, and percentages of free water and bound water. The chemical composition and thermal, mechanical, morphological, and surface characteristics were also evaluated. PFG and its graft copolymers exhibited higher equilibrium water contents ranging from 60 to 77% when compared with those of HEMA and HPMA homopolymers. DSC studies revealed increased freezing water contents and decreased bound-water contents for the graft copolymers when compared with those of PFG alone. These properties improved the efficacy of hydrogels. IR and scanning electron microscopic studies confirmed the grafting of PHEMA and PHPMA onto PFG. Contact-angle studies demonstrated increased polarity for graft copolymers, which is a symbol for increased hydrophilicity.

    9. Preparation of epoxy-functionalized polystyrene/silica core–shell composite nanoparticles (pages 2253–2262)

      Zhong Zeng, Jian Yu and Zhao-Xia Guo

      Version of Record online: 25 MAR 2004 | DOI: 10.1002/pola.20059

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      Epoxy-functionalized polystyrene/silica (PS/SiO2) core–shell composite nanoparticles with an average size of 60–70 nm were prepared by the postaddition of glycidyl methacrylate via emulsion polymerization. The outermost shell of the obtained multilayered core–shell particles was made up of poly(glycidyl methacrylate) (PGMA). The amount of grafted PGMA was quantified by Fourier transform infrared spectroscopy and was altered in a wide range (1–50 wt % to styrene).

    10. Preparation of poly(ethylene oxide) star polymers and poly(ethylene oxide)–polystyrene heteroarm star polymers by atom transfer radical polymerization (pages 2263–2271)

      Jianzhong Du and Yongming Chen

      Version of Record online: 25 MAR 2004 | DOI: 10.1002/pola.20061

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      Poly(ethylene oxide) (PEO) star polymer with a microgel core was prepared by atom transfer radical polymerization (ATRP) of divinyl benzene (DVB) with mono-2-bromoisobutyryl PEO ester as a macroinitiator. Because of the presence of initiating groups in the core of PEO star, PEO–polystyrene heteroarm star polymer was synthesized by second ATRP of styrene with PEO star as a macroinitiator. In addition, the crosslinked DVB core of the star was obtained by hydrolysis of PEO star to remove PEO arms.

    11. Synthesis and properties of fluorinated polyimides based on 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di-tert-butylbenzene and various aromatic dianhydrides (pages 2272–2284)

      Chin-Ping Yang and Feng-Zhi Hsiao

      Version of Record online: 25 MAR 2004 | DOI: 10.1002/pola.20073

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      A novel fluorinated diamine monomer, 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di-tert-butylbenzene (2), was synthesized from 2-chloro-5-nitrobenzotrifluoride and 2,5-di-tert-butylhydroquinone. Polyimides (5a5f) were synthesized from diamine 2 and various aromatic dianhydrides via thermal or chemical imidization. The 5 series polyimides were soluble in N-methyl-2-pyrrolidone, dimethylacetamide, and N,N-dimethylformamide and even in dioxane, tetrahydrofuran, and CH2Cl2. The 5 series showed good solubility, excellent thermal stability and mechanical properties, and low color intensity and dielectric constants.

    12. Photoinitiators with functional groups. VI. Chemically bound sensitizers (pages 2285–2301)

      Robert Liska

      Version of Record online: 25 MAR 2004 | DOI: 10.1002/pola.20064

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      Several benzophenone- and thioxanthone-based photosensitizers (PSs) were covalently bonded to hydroxyalkylphenone- and aminoalkylphenone-based photoinitiators (PIs) to enhance the rate of the excitation-transfer effect due to the close vicinity of the PS to the PI. The properties of these new systems were investigated with UV spectroscopy and photo-differential scanning calorimetry. Selective excitation of the PS chromophore revealed that the energy transfer was significantly increased in covalently bonded initiators in comparison with the physical mixtures of proper PIs and PSs. This effect was most pronounced for hydroxyalkylphenones that were sensitized by suitable benzophenone derivatives, especially at low PI concentrations.

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