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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 47 (1993), S. 1303-1308 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(N4-1-phenylethyl-L-asparagines) (1a, 1b, and 1c) containing DL-, (R)-, and (S)- side group chirality were prepared by aminolysis of poly(β-methyl-L-aspartate) (PMLA) with DL-, (R)- (+)-, and (S)- (-)-1-phenylethylamine, respectively. The PMLA was synthesized by ring-opening polymerization of β-methyl-L-aspartate-N-carboxy anhydride (NCA) using triethylamine as initiator. The conformations of these polypeptides in the film state were investigated by IR and circular dichroic spectra. The PMLA, 1a, and 1b exist mainly in β-sheet conformation, while 1c forms α-helix that is induced by the (S)-chirality of the side groups. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 46 (1992), S. 435-443 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The influence of counterions on the properties of aqueous dispersions of polyurethane (PU) anionomer have been investigated. The PU anionomers were prepared by polyaddition reaction of 4,4′-methylenebis(phenylisocyanate) with poly(propylene glycol) (PPG), dimethylolpropionic acid (DMPA), and 1,4-butanediol, followed by neutralization of pendant COOH groups by various bases. Stable dispersions are obtained for PU anionomers containing 0.8-1.1 wt % COOH groups (17.8-24.4 mmol/100 g polymer) that have been neutralized by ammonia, trimethylamine, triethylamine, LiOH, NaOH, and KOH, respectively. It is found that average particle size is determined mainly by the zeta potential of the dispersions. The number-average diameter of the dispersions containing metal cations (Li-, Na-, and K-0.9) is between 60-73 nm (zetal potential -65 to -70 mV), while that of the dispersions containing ammonium cations (AMM-, TMA-, and TEA-0.9) is between 104-251 nm (zeta potential -47 to -64 mV). The surface tension of the dispersions decreases with concentration rapidly and levels off at concentrations higher than 20 mmol/L. The decreased decomposition temperature of the PU anionomers, compared to unionized PUs, can be attributed to the disordering of hard domains after ionization or decomposition reaction catalyzed by alkali metal carboxylates. The thermal decomposition proceeds mainly via cyclic elimination.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2705-2714 
    ISSN: 0887-624X
    Keywords: coumarin derivatives ; photodimerization ; photocleavage ; reversible ; pho-tosensitizer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four photoreactive coumarin derivatives were successfully synthesized from 7-hydroxy-coumarin and 7-hydroxy-4-methylcoumarin, i.e., 7-propionyloxy-4-methylcoumarin (M1), 7-palmitoyloxy-4-methylcoumarin (M2), 7-propionyloxycoumarin (M3), and 7-palmitoy-loxycoumarin (M4). Reversible photodimerization (350 or 300 nm) and photocleavage (254 nm) of these coumarin derivatives dispersed in poly(vinyl acetate) (PVAc) were investigated by tracing their UV absorbance variations at 310 nm. The M2 and M4 with long palmitoyl chain show much better photoreaction reversibility than M1 and M3 with short propionyl chain. Moreover, photodimerization rate (under 350 nm) of M2 is greater than 200 times of that of M1. This has been explained by the formation of suitable conformation for revers-ible photodimerization due to the hydrophobic interactions. Photodimerization of M2 is ca. 3 times quicker than that of M4, indicating 4-methyl substitution enhances pho-todimerization. The influence of photodimerization wavelength (350 and 300 nm) and photosensitizer (benzophenone) have also been investigated in detail. © 1995 John Wiley & Sons. Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2999-3008 
    ISSN: 0887-624X
    Keywords: 7,7′-coumarinyl polymethylene dicarboxylate ; photopolymerization ; fluorescence ; coumarin ; dimerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: All eight 7,7′-(4-methylcoumarinyl) polymethylene dicarboxylates (3, 4) containing terminal photoreactive coumarin chromophores show strong fluorescence intensities at room temperature in dimethyl sulfoxide (DMSO) and CH2Cl2. After irradiation with 350 nm light for 2 h, the fluorescence characteristics of the dicarboxylates reveal their photopolymerization paths. On irradiation of the unsubstituted dicarboxylates (3) in DMSO, singlet excited state excimers are formed, leading to syn head-to-head coumarin dimer configuration. However, for all dicarboxylates in CH2Cl2, the dimerization of the coumarin chromophore proceeds via a triplet excited state in the presence of benzophenone to form the anti-configuration photoproducts. Further confirmations of the reaction mechanism are made by kinetic studies. At high concentration, photopolymerization of 7,7′-(4-methylcoumarinyl) polymethylene dicarboxylate (4c) obeys zero-order and first-order kinetics for coumarin chromophore and benzophenone, respectively. This is a powerful proof of the proposed mechanism of a triplet excited state reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2999-3008, 1997
    Additional Material: 9 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 2699-2707 
    ISSN: 0887-624X
    Keywords: optically-active polyurethane ; chiral stationary phase ; racemate ; direct resolution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically-active polyurethanes (2a-2c) were prepared by polyaddition reaction of diamide (1a, 1b) and diester (1c) derivatives of chiral coumarin dimer with 4,4′-diphenylmethane diisocyanate (MDI) in chloroform and methyl ethyl ketone, respectively. The inherent viscosity of the polyurethanes are between 0.13 and 0.21 dL/g in N,N-dimethylacetamide (DMAc) at 30°C. Treated silica gels were absorbed with ca. 25 wt % of the polyurethanes, and packed as chiral stationary phases for direct optical resolution of 16 racemates with aromatic groups by high-performance liquid chromatography (HPLC). Polyurethanes 2a and 2b, obtained from diamide derivatives, show efficient resolution ability to some of the racemates (α = 1.06-1.79), especially the atropic (R5) and trans (R6-R9) isomers. The recognition ability of the polyurethanes can be attributed to the simultaneous aromatic stacking and hydrogen-bonding interactions with racemates. © 1992 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1867-1875 
    ISSN: 0887-624X
    Keywords: N-(1-phenylethyl)acrylamide ; 7-acryloyloxy-4-methyl coumarin ; copolymerization ; monomer reactivity ratio ; photocrosslinking ; photocleavage ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymers containing photoreactive 4-methyl coumarin pendant groups have been prepared by radical copolymerization of N-(1-phenylethyl)acrylamide (M1) and 7-acryloyloxy-4-methyl coumarin (M2) in DMF at 70°C. The monomer reactivity ratios (MRR) of M1 and M2 are estimated by Finenam-Ross, Kelen-Tüdos, Mayo-Lewis, and YBR methods to be about r1 = 0.12-0.16 and r2 = 1.13-1.28. Dilute dioxane solutions of the copolymers (10-4-10-5 M of 4-methyl coumarin chromophores) are first photocrosslinked intramolecularly by irradiating 350 nm light (dimerization of 4-methyl coumarin) and then photo-cleaved at 254 nm (symmetric cleavage of cyclobutane). Tracing by an UV-visible spectrophotometer, it is found that photocrosslinking and photocleavage proceed simultaneously when 254 nm is the light source and finally reaches to a dynamic equilibrium. However, only photocrosslinking can be observed under 350 nm light. Kinetic results show that both photocrosslinking and photocleavage are first-order reactions. Moreover, photocrosslinking rate constant increases with mole fraction of M2 in the copolymer (F2). On the contrary, rate constant of photocleavage decreases with increasing F2. © 1994 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1319-1327 
    ISSN: 0887-624X
    Keywords: coumarin dimer ; photocleavage ; trans-2,2′-dihydroxystilbene ; interfacial polycondensation ; photocrosslinking ; characteristic curve ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The monomer, trans-2,2′-dihydroxystilbene (DHS), has been prepared by asymmetric photocleavage (254 nm) of coumarin dimer acid derived from coumarin dimer. Four new polyesters are successfully synthesized by interfacial polycondensation of the DHS with adipoyl chloride, azelaoyl chloride, sebacoyl chloride, and dodecanedioyl dichloride, respectively. The reduced viscosities of the polyesters decrease from 0.32 to 0.11 dL/g as the number of methylene unit in diacid chlorides increases from 4 to 10. From DSC investigation, it is found that the polyesters are semi-crystalline polymers with Tm = 39-192°C. Under 350 nm light, photocrosslinking behavior in solution and film-state is investigated by UV spectral change with irradiation time (350 nm). The photoreactive stilbene chromophores in the main chain dimerize to form cyclobutane derivatives, and lead to crosslinking of the polyesters. Photosensitivity in the film state has also been evaluated by their characteristic curves. Polyester from dodecanedioyl dichloride (5d) exhibits the highest initial reaction rate and ultimate crosslinking ratio. © 1995 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 26 (1988), S. 3397-3401 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 2765-2772 
    ISSN: 0887-624X
    Keywords: dispersion polymerization ; hydroxypropyl cellulose ; steric stabilizer ; nucleation ; particle growth ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dispersion polymerization of styrene in polar solvents in the presence of hydroxypropyl cellulose (HPC) produces latex particles from ca. 1 to 26 μm depending on reaction parameters. Increasing the initiator concentration or temperature decreases the molecular weight, but increases the particle size and breadth of the size distribution. The decrease in molecular weight with increasing Ri, caused by larger initiator concentration or higher temperature, is expected based of fundamental kinetic relationships. The inverse correlation between size and rate of initiation is rationalized by polarity (stabilizing ability) of the grafted HPC-polystyrene formed in situ. High polar HPC-g-PS, which contains shorter graft polystyrene chain, stabilizes particles less effectively and this leads to larger particles. The primary influence of initial styrene concentration is a solvent effect: larger particles are obtained at high styrene concentration due to high solubility of polystyrene during the initial part of the reaction. The influence of the molecular weight of HPC is to change the polarity of the HPC-g-PS stabilizer. Comparison of particle growth of three critical polymerization systems suggests that the favorable continuous-phase solubility parameter for dispersion polymerization of styrene is around 11.6 (cal/mL)1/2. Too high or too low polarity generates particles with broad size distribution because large particles are formed during the initial stage and nucleation continues as the polymerization proceeds. © 1992 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1719-1727 
    ISSN: 0887-624X
    Keywords: (1S,2S)-(+)-2-amino-3-methoxy-1-phenyl-1-propanol ; optically-active poly(urea-urethane) ; DSC ; TGA ; circular dichroism spectra ; direct resolution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five new optically active poly(urea-urethane)s were synthesized by solution polyaddition of (1S,2S)-(+)-2-amino-3-methoxy-1-phenyl-1-propanol (4) with diisocyanates (diphenylmethane-4,4′-diisocyanate, toluene-2,4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate) at 80°C for 60 h. In some cases, the reaction mixture transformed into a gel when cooled to room temperature. The reduced viscosities are between 0.14 and 0.63 dL/g depending on the solvents and diisocyanates. Thermal behaviors of these polymers were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The Tg and crystallization temperature (Tc) were in the range of 80-200°C and 220-238°C, respectively. Thermal decomposition started at about 275°C, and the residual weights at 400°C were 15-60% depending on the polymers. The conformation of the polymers in film state was studied by circular dichroism (CD) spectra, by comparison with the corresponding model compounds which were synthesized from 4 and phenyl isocyanate or propyl isocyanate. Polymers derived from aromatic diisocyanates formed as ordered conformation in the film state, while those from aliphatic diisocyanates did not. After packing as chiral stationary phases of high-performance liquid chromatography (HPLC), the polymers showed selective resolution to trans-stilbene oxide and trans-1,2-cyclopentanedicarboxanilide. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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