Temperature-sensitive luminescence of tris (β-diketone) europium chelates for monitoring high-speed cationic photopolymerizations

The temperature-dependent luminescence of tris (β-diketone) chelates of europium was used for in situ temperature measurements during cationic photopolymerizations of vinyl ethers. These molecular-level luminescent probes provided a real-time, noninvasive method for monitoring temperature during these high-speed polymerizations. Two specific probes, tris (benzoyl-1, 1, 1-trifluoroacetone) europium and tris (1,1,1,5,5,5,-hexafluoroacetylacetone) europium, met several stringent spectral and performance requirements for application in our system. The luminescence from these probes exhibits a reproducible temperature dependence over a wide temperature range and is not sensitive to changes in viscosity. In situ temperature profiles obtained using this novel technique verified the importance of thermal effects during these highly exothermic photopolymerizations. These studies have demonstrated the utility of the tris(β-diketone) europium chelates for characterizing the temperature during high-speed photopolymerizations that cannot be monitored using conventional techniques. © 1995 John Wiley & Sons, Inc.     

Initiation of cationic polymerization of n-butyl vinyl ether by stable cation radicals of substituted phenothiazines

3,7-Diethyl- 10-phenylphenothiazine (DEPPT), a phenothiazine derivative whose 3,7- and 10-positions are blocked, was synthesized. Potentiostatic electrolysis of DEPPT in acetonitrile (ACN) in the presence of 0.1M of LiClO₄ at 0.7 V (vs. Ag/Ag/Cl) yielded the stable cation radical of DEPPT (DEPPT^+·) which was characterized by cyclic voltammetry, UV-visible spectroscopy, and ESR spectrometry. Stable cation radicals of 10-phenylphenothiazine and 3,7-diethyl-10-methylphenothiazine were also prepared. The cationic polymerization of n-butyl vinyl ether was initiated by these cation radicals, including DEPPT^·+. The electron transfer mechanism for the initiation step, which we proposed previously, was supported by the fact that DEPPT^·+ was capable of initiating the polymerization; dimerization of DEPPT^·+ by releasing protons is precluded because 3,7- and 10-positions are all blocked. © 1994 John Wiley & Sons, Inc.     

Photoinitiators with functional groups. V. New water‐soluble photoinitiators containing carbohydrate residues and copolymerizable derivatives thereof

The synthesis of new water‐soluble photoinitiators (PIs) based on hydroxyalkylphenones, benzophenones, and thioxanthones with carbohydrate residues such as glucose, cellobiose, and 1‐amino‐1‐deoxy‐D ‐glucitol (glucamine) is described. In addition, selected initiators were reacted with methacryloyl chloride to obtain copolymerizable initiators with improved migration stability. Results from photo differential scanning calorimetry and gel‐content measurements in commercially available water‐thinnable and emulsion‐type resins as well as 2‐hydroxyethyl acrylate are included. Glucose‐modified PIs gave the best results with respect to compatibility with the resin, reactivity, and gel content. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1504–1518, 2002     

AlCl_3／SbCl_3复合体系引发α－蒎烯／苯乙烯阳离子共聚合

比较了ＡｌＣｌ_３和ＡｌＣｌ_３／ＳｂＣｌ_３复合体系的α－蒎烯／苯乙烯阳离子共聚反应及产物的摩尔质量分布。结果表明，由于用ＡｌＣｌ_３体系两种单体活性差大而难以共聚，用ＡｌＣｌ_３／ＳｂＣｌ_３复合体系，苯乙烯聚合速率相对减小，而α－蒎烯聚合速率增大，加之苯乙烯的共催化剂作用，加速α－蒎烯聚合，可使α－蒎烯与苯乙烯进行有效共聚。考察了［Ｓｂ］／［Ａｌ］比、催化剂浓度、单体投料比等对共聚体系α－蒎烯、苯乙烯转化速率及产物Ｍ_ｎ的影响。     

阴阳离子型表面活性剂双水相萃取色氨酸衍生物和牛血清白蛋白

溴化十二烷基三乙胺（Ｃ１２ＮＥ）和十二烷基硫酸钠（ＳＤＳ）在一定条件下混合可以形成具有清晰界面的两个水相，称为阴阳离子型表面活性剂双水相。作者研究了利用该双水相萃取３种色氨酸衍生物和牛血清白蛋白的可能性．文中采用工作曲线校正扣除表面活性剂背景的影响，萃取结果准确可信。     

Cationic polymerization of diglycidyl ether of bisphenol A

The cationic nonlinear polymerization of diglycidyl ether of Bisphenol A (DGEBA) in the presence of a diluent γ-butyrolactone (BL) was initiated by the BF₃-4-methoxyaniline (MA) complex. The reaction was studied by size exclusion chromatography, DSC, and dynamic mechanical analysis. Reaction mechanism involves a fast formation of adducts of DGEBA with MA released from the initiator. Formation of spiro orthoesters (S) by reaction of BL with DGEBA and homopolymerization of DGEBA as well as copolymerization with S follow. Gelation occurs at 60°C within a few minutes at conversion of epoxy groups (ξ_E)_c = 0.20–0.45. The networks cured under optimum conditions show high glass transition temperature, T_α = 178°C. The mechanism-structure-property relations are discussed. © 1994 John Wiley & Sons, Inc.     

Regioselective hydrosilations. III. The synthesis and polymerization of ambifunctional silicon-containing epoxy monomers

Silicon-containing epoxide compounds bearing Si ? H groups can be readily prepared in high yields by the regioselective rhodium-catalyzed monohydrosilation of α,ω-dihydrogen functional siloxanes and silanes with vinyl epoxides. The remaining Si ? H groups in these compounds can be further selectively hydrosilated with unsaturated epoxides to give a series of unique ambifunctional monomers containing two different epoxide groups in the same molecule. The photopolymerization of these monomers has been studied using analytical techniques including real time infrared spectroscopy and differential scanning photocalorimetry. On photopolymerization, the new monomers yield interesting networks. © 1993 John Wiley & Sons, Inc.     

Multifunctional coupling agents for living cationic polymerization. IV. Synthesis of end-functionalized multiarmed poly(vinyl ethers) with multifunctional silyl enol ethers

Telechelic ( 8 ) and end-functionalized four-arm star polymers ( 9 ) were synthesized through the coupling reactions of end-functionalized living poly(isobutyl vinyl ether) ( 5; DP _n ～ 10) with the bi-and tetrafunctional silyl enol ethers, H_4-nC? [CH₂OC₆H₄C(OSiMe₃) = CH₂]_n ( 3: n = 2; 4: n = 4). The precursor polymers 5 were prepared by living cationic polymerization with functionalized initiators, CH₃CH(Cl)OCH₂CH₂X(6), in conjunction with zinc chloride in methylene chloride at ?15°C. The initiators 6 were obtained by the addition of hydrogen chloride gas to vinyl ethers bearing pendant functional groups X , including acetoxy [? OC(O)CH₃], styryl (? OCH₂C₆H₄-p-CH = CH₂), and methacryloyl [? OC(O)C(CH₃) = CH₂]. The coupling reactions with 3 and 4 in methylene chloride at ?15°C for 24 h afforded the end-functionalized multiarmed polymers ( 8 and 9 ) in high yield (>91%), where those with styryl or methacryloyl groups are new multifunctional macromonomers. © 1994 John Wiley & Sons, Inc.     

Removal of Endotoxin from Human Serum Albumin Solutions by Hydrophobic and Cationic Charged Membrane

Removal of end6toxin from medicine injection is very important, becauseendotoxin withpotential biological activity causes pyrogenic and shock reactions in' mammals-'on...intravenous injection even as law as "an6gram amounts. Endotoxin, a constituent ofpotential contaminant of physiological fluids and aqueous solutions 'and very stable atextreme temperature and PH values. For removing endotoxin from solutions ofbiomolecules, such as HSA, adsorption techniques are usedl.' Many methods forendot…     

Synthesis and photopolymerization of monomers bearing isopropenylphenoxy groups

The synthesis of a series of monomers containing isopropenylphenoxy groups was carried out. On irradiation with UV light in the presence of onium salt photoacid generators, these monomers undergo a chain extension reaction consisting of a dimerization followed by a Friedel-Crafts ring closure which results in the formation of polymers with indane groups in the backbone. Aryl imide-containing monomers bearing isopropenylphenoxy groups were also shown to undergo facile photoinduced cationic polymerization. The resulting polymers displayed excellent thermal stability. © 1995 John Wiley & Sons, Inc.