Polymere mit dem Zentralatom eines Makrocyclus in der Hauptkette, 1. Polykondensationsreaktionen mit Phthalocyaninsilicium- und Hemiporphyrazingermanium-Verbindungen

Dihydroxy(phthalocyanino)silicon ( 1b ) and dihydroxy(hemiporphyrazino)germanium ( 2b ) react with different monovalent alcohols to afford low-molecular bisalkoxy derivatives ( 4 and 5 ), and with thiophenol the phenylthio derivatives 11a and 11b , resp. With bivalent alcohols and phenols polymers of the structure 6 and 7 or 8a, b, 9a, b , and 10a, b , resp. are obtained. Dichloro(phthalocyanino)silicon ( 1a ) and dichloro(hemiporphyrazino)germanium ( 2a ) react also with phenol, resp. hydroquinone, to give low-molecular and polymeric phenoxy derivatives. The reaction of 1b and 2b with mono- and dibasic carboxylic acids leads to the corresponding esters. The IR-spectra of the prepared compounds are discussed. Thermogravimetric and semiconductive measurements (σ_298K ≈ 10^?7 to 10^?16Ω^?1cm^?1) are described.     

Polymere mit dem zentralatom eines makrocyclus in der hauptkette, 3.Polykondensationsreaktionen mit zinnkomplexen des meso-tetraphenylporphins,phthalocyanins und hemiporphyrazins

Dihydroxy(meso-tetraphenylporphino)tin ( 1b ), dihydroxy(phthalocyanino)tin ( 1d ), and dihydroxy(hemiporphyrazino)tin ( 1f ) react with bivalent phenols to afford polymers of type B . With 1,2-ethanediol and 1b low molecular compound 3 is obtained, which eliminates 1,2-ethanediol to give poly[oxyethyleneoxy(meso-tetraphenylporphin)stannandiyl] ( 4 ). Dehydration of the dihydroxy compounds 1b, 1d, 1f leads to polymers of type C . The IR-spectra of the prepared compounds are discussed; thermogravimetric and semiconductive measurements (σ_298K≈10^?6?10^?16Ω^?1cm^?1) are described and compared with the analogous complexes of germanium.     

Synthese und halbleitereigenschaften von phthalocyaninartigen polymeren mit Tetrathiafulvalen-Einheiten

4,5,4′,5′-Tetracyano-2,2′-bi-1,3-dithiolylidene (tetracyanotetrathiafulvalene) ( 1 ) was found to react with metal acetylacetonates ( 2a – m ) to give dark, insoluble, and infusible polymers 3a – m with phthalocyaninelike structure. The electrical conductivity of the polymers was investigated (σ_298K < 6·10^?5 Ω^?1 cm^?1), and a linear relationship between the logarithm of the electrical conductivity and the activation energy of the different polymers was found (compensation effect). Measurements of the thermoelectric power proved p-conduction.     

Synthese und halbleitereigenschaften von hemiporphyrazinartigen polymeren mit tetrathiafulvalen-einheiten

Hemiporphyrazine type macroheterocycles with 2,2′-bi-1,3-dithiolylidene (tetrathiafulvalene) units in the polymeric chains ( 3a–e ) were obtained by reaction of 2,2′-bi-1,3-dithiolylidenetetracarbonitrile (tetracyanotetrathiafulvalene) ( 1 ) with several diamines ( 2a–e ). The black polymers were characterized by elemental analyses and IR spectra. Thermoanalytic measurements showed that decomposition starts without melting at temperatures > 300°C. The polymers were found to be polymeric organic semiconductors with activation energies of 0,6–1,4eV and electrical conductivities in the range from 10^?14 to 10^?10Ω^?1.cm^?1. In the case of the polymers 3a and 3b it was possible to obtain metal complexes ( 4a–b ) by substituting the two hydrogen atoms inside the macroheterocyclic rings. Depending on the metal atoms the electrical conductivities were enhanced up to two orders of magnitude.     

Synthesen und charakterisierung polymerer cyaninfarbstoffe

From 2,3,5,6-tetramethylthiazolo[4,5-f]benzothiazoldiium diperchlorate ( 9 ) and the ortho esters 2a – d or 1,1,3,3-tetramethoxypropane ( 4 ) polymeric cyanines with trimethine ( 10a ), substituted trimethine ( 10b – d ), respectively pentamethine units ( 11 ) were synthesized. Model compounds ( 3a – e , 5 , 7a – d , 8 ) were prepared from 1a , 1b and 6 , analogously. The structures were confirmed by elemental analyses, IR, and electronic spectra. In addition, the model compounds were characterized by their ¹H NMR and mass spectra.     

Polymere schiff-basen-chelate und ihre vorstufen, 3. Synthese polymer gebundener N3O2-chelate durch N-alkylierung niedermolekularer schiff-basen

N-Alkylation of low molcular N₃O₂-ligands ( 2a , b ) with several chloromethylated polystyrenes ( 1a – e ) leads to covalently polymer bound Schiff's base ligands ( 3a – f ), which react with Co²⁺ to polymer bound N₃O₂ chelates ( 10a – f ). A second route to 3c starts from 1b and the N₃-ligand 5 over the polymer diamine 7 . The corresponding low molecular compounds were also prepared.     

Polymers and oligomers with substituted 2,5-thienylene units. Preparation and electrical conductivity properties

Ni-catalyzed dehalogenation polycondensation of 3-formyl-, 3-hydroxyiminomethyl- and 3-cyano-2,5-dibromothiophene with zinc affords oligo(3-formyl-2,5-thienylene) ( 2a ), oligo-(3-hydroxyiminomethyl-2,5-thienylene) ( 2b ), and oligo(3-cyano-2,5-thienylene) ( 2c ). Electrochemical polymerization of 3-methoxythiophene and 3,4-dimethoxythiophene give blueblack films of oligo(3-methoxy-2,5-thienylene) ( 2d ) and poly(3,4-dimethoxy-2,5-thienylene) ( 2e ). Iodine adducts of 2a – 2c show electrical conductivity values between 1,8 · 10^?11 and 8,8 · 10^?8 S · cm^?1. Doped 2d shows electrical conductivity of 2 · 10^?1 S · cm^?1, whereas doped 2e exhibits an electrical conductivity between 1,5 and 30 S · cm^?1. Doping of undoped 2d and 2e causes profound changes in their IR and NMR spectra, colour, and electrical conductivity properties.     

Polymerization of Styrene Sulfonate Ethyl Ester by ATRP: Synthesis and Characterization of Macromonomers for Suzuki Polycondensation

Summary: Macromonomers from SSE were synthesized via ATRP with initiators carrying functional groups that are polymerizable by Suzuki polycondensation. The material obtained had a monomodal molar mass distribution with a polydispersity of 1.3–1.6. The reaction kinetics in bulk and in solution were monitored by in situ ¹H NMR spectroscopy. Rate constants and the activation energy for SSE polymerization were determined to be k = 5.5 · 10^?5 s^?1 (DMF, 60 °C), 6.6 · 10^?4 s^?1/1.4 · 10^?3 s^?1/4.8 · 10^?3 s^?1 (bulk, 45/60/75 °C), E_a = 60.1 kJ · mol^?1 (bulk). Hydrolysis yielded the corresponding macromonomers of poly(styrene sulfonic acid).

Monomer conversion for different reaction temperatures and exponential fit to the data for the SSE polymerization in bulk.     

Functional metal-porphyrazine derivatives and their polymers, 12. Synthesis and properties of polyimides containing a metalphthalocyanine ring and a pyridyl group

A novel class of polyimides ( 6a – c ) containing Mt(II)-phthalocyanine rings was synthesized by solution condensation in N-methyl-2-pyrrolidone of Mt(II)-[2,9, or 10(or 2,16, or 17)bis(3,4-dicarboxybenzoyl)]phthalocyanine dianhydride [Mt(II)-dahPc: Mt(II) = Co(II), Ni(II), and Cu(II)] with 2,6-diaminopyridine, followed by thermal imidation. The polyimides showed room temperature dc-conductivities in the range of 10^?12 ? 10^?9 Ω^?1 · cm^?1, and, after quaternization of the pyridine group, the conductivities increased by 1 to 3 orders of magnitude.     

Proton‐Conducting Properties of Acid‐Doped Poly(glycidyl methacrylate)‐1,2,4‐Triazole Systems

1,2,4‐triazole‐functional PGMA polymers have been synthesized and their anhydrous proton‐conducting properties were investigated after doping with phosphoric acid and triflic acid. PGMA was prepared by solution polymerization and then modified with 1H‐1,2,4‐triazole (Tri) and 3‐amino‐1,2,4‐triazole (ATri). FT‐IR, ¹³C NMR and elemental analysis verify the high immobilization of the triazoles in the polymer chain. Phosphoric‐acid‐doped polymers showed lower T_g and higher proton conductivities. PGMA‐Tri 4 H₃PO₄ showed a maximum water‐free proton conductivity of approximately 10^?2 S · cm^?1 while that of PGMA‐ATri 2 H₃PO₄ was 10^?3 S · cm^?1. The structure and dynamics of the polymers were explored by ¹H MAS and ¹³C CP‐MAS solid‐state NMR.

     

Poly(germanium thiolate): a new class of organometallic polymers having a germanium-sulfur bond in the main chain

A novel germanium-containing copolymer 3 a having a germanium(IV) unit and a trimethylene sulfide unit alternatingly in the main chain was prepared by the combined use of a germylene, 1,3-bis(trimethylsilyl)-1,3-diaza-2-germa(II)-indan ( 1 a ) and thietane ( 2 ). The resulting copolymer has a very high molecular weight (M?_w > 10⁶). The usage of a germylene, bis[bis(trimethylsilyl)aminato]germanium(II) ( 1 b ), as a comonomer also gave an alternating copolymer 3 b with high molecular weight in good yields. On the other hand, the reaction of a germylene, bis(N-trimethylsilyl-tert-butylaminato)germanium(II) ( c ), with thietane afforded a 1 : 1 adduct 4c having a 1-thia-2-germacyclopentane structure without producing an alternating copolymer.     

Synthesis and properties of aromatic polypyrazoles from bis(β-substituted vinyl ketones) and aromatic dihydrazines

Polycyclocondensations of aromatic dihydrazines 2a and 2b with 1,6-diethoxy-1,5-hexadiene-3,4-dione ( 1a ) in m-cresol and those with bis(3-chloroacryloyl)benzenes 1b and 1c in 1-methyl-2-pyrrolidone (NMP) lead to aromatic polypyrazoles 3a – f having inherent viscosities up to 0,35 dl.g^?1. The polymers are soluble in polar aprotic solvents like NMP and some acidic media including m-cresol. Thermogravimetry shows a loss of 10 wt.-% at ≈ 500°C both in air and nitrogen.     

Capacity flow method for determination of propagation and termination rate constants in radical polymerization

The possibility of determination of the propagation and termination rate constants k_p and k_t, resp., as well as their ratios k_p/k_t and k_p/k in homogeneous radical polymerization is shown using the capacity flow method. A theoretical analysis is carried out and relatively simple equations are introduced. The essential point is that the life time of the growing polymer chain is obtained graphically from the residence time of the reactants in the reactor vessel, which is a given quantity. As an experimental example the polymerization of methyl methacrylate initiated by benzoyl peroxide in benzene is investigated in a flow reactor with perfect mixing at 80°C. It is characteristic that the process can be followed by means usually applied for studying slow reactions. The degree of conversion is measured turbidimetrically and gravimetrically, whereas the initiation rate is analysed iodometrically. Thus, through a numerical linear approximation by the method of least squares k_p/k_t = (2,28±0,45)·10^?5, k_p/k = (1,50±0,22). 10^?1 are found from the experimental data, and hence k^p = (9,95±0,83)·10² l mol^?1 s^?1 and k_t = (4,36±0,49)·10⁷ l mol^?1 s^?1 are obtained.     

Synthesis of Novel Polycations Using the Chemistry of Ionic Liquids

Summary: In this work, we report the synthesis of a great variety of polycations with varying counter‐anions. These new polymers were obtained by a simple anion exchange reaction facilitated by the phase separation of the resulting products. This strategy has been successfully applied to three different polycations, poly(1‐vinyl‐3‐ethylimidazolium bromide) poly(ViEtIm⁺Br^?), poly(1‐ethyl‐4‐vinylpyridinium bromide) poly(ViEtPy⁺Br^?), and poly(methacryloyloxyethyltrimethylammonium chloride) poly(EMTMA⁺Cl^?), with seven counter‐anions such as PF, CF₃SO, (CF₃SO₂)₂N^?, (CF₃CF₂SO₂)₂N^?, dodecylbenzenesulfonate, toluene‐4‐sulfonate, and bis(2‐ethylhexyl) hydrogen phosphate. The solubility range of the new polymeric ionic liquids becomes very broad, including apolar organic solvents and ionic liquids, depending on the nature of the counter‐anion. Thermogravimmetric experiments showed that the thermal stability of the PILs also depends on the nature of the counter‐anion improving in the order CF₃SO > (CF₃CF₂SO₂)₂N^? > C₁₂H₂₅C₆H₄SO > PF > Br^? > C₁₆H₃₄PO.

A simple anion exchange procedure similar to the reaction used in ionic liquids chemistry is used to the synthesis of new polymeric ionic liquids (PILs).     

Polymerisationsauslösung mit substituierten Ethanen, 1. Polymerisation von Methylmethacrylat mit 1,1,2,2-Tetraphenyl-1,2-diphenoxyethan

1,1,2,2-Tetraphenyl-1,2-diphenoxyethane (TPPA) initiates at 70°C the polymerization of methyl methacrylate. In the first period oligomers of the type 1 with two phenoxydiphenylmethyl end groups (P_n ≈ 1 – 20) are formed by primary radical termination. These telechelics are effective initiators of the further free radical polymerization of vinyl monomers.     

The adiabatic compressibility of polyelectrolytes: Binding of Na+ ions on the multivalent site of polymer chains

The adiabatic compressibility of a 1:0,35 acrylic acid/maleic acid copolymer (AA/MA) and of its three “sodium salts” obtained by neutralizing (25%, 50% and 100%) with sodium hydroxide was studied. In 100% neutralized AA/MA copolymer, the dissociation of the counter ions was complete so that the limiting values of the apparent molal compressibility δK and apparent molal volume δV were found to be lowest with values of ?83,0·10^?4 cm³ bar^?1 mol^?1 and 52,9 cm³/mol respectively. This showed a decrease of 89,0·10^?4 cm³ bar^?1 mol^?1 and 20,9 cm³ mol^?1 from that of the unneutralized acid copolymer. The δK and δV values were resolved into the ionic components, δK and δV. The electrostriction caused in the copolymer by an increase of the negative charge from 0 to ?0,425, from ?0,425 to ?0,85 and from ?0,85 to ?1,7 produced a decrease of 3,9.10^?4, 6,9.10^?4, and 5,7.10^?4 cm³ bar^?1 mol^?1 in δK and 3,7,4,5 and 10,2 cm³ mol^?1 in δV. Contrary to the volume change, the compressibility data showed a disproportionate decrease for the neutralized products. The reduced viscosity for the sodium salts was also found to have reduced values. A notable point emerging from this study is that the apparent ion binding on the multivalent site of the polymer chain, as obtained by the two methods—the adiabatic compressibility and density determinations—shows an appreciable variation.     

Electrochemical polymerization of some dihydrobenzodipyrroles

Anodic coupling of the dihydrobenzodipyrrole isomers 1H,8H-pyrrolo[3,2-g]indole ( 1 ), 1H,7H-pyrrolo[3,2-f]indole ( 2 ), and 1H,5H-pyrrolo[2,3-f]indole ( 3 ) in 0,1 M tetraethylammonium perchlorate in acetonitrile produces polymeric films which are reversibly oxidized around 0,3 V vs. Ag/Ag⁺ with 0,5 electrons per monomeric unit. IR reflectance, UV-vis and cyclic voltammetry show that the oxidized polymers undergo easy overoxidation at the benzene ring without affecting the charge storage ability. Conductivities (0,2–5 Ω^?1 · cm^?1) are higher than those presented by chemically prepared samples (10^?4 – 10^?1 Ω^?1 · cm^?1) and are attributed to more ordered structures of the polymers.     

Hochmolekulare produkte der kondensationspolymerisation von 4,4′-methylendibenzaldehyd mit aliphatischen diaminen und polyfunktionellen isocyanaten

Polymeric Schiff-bases ( 3a – g and 5a – c ) were synthesized by condensation polymerization of 4,4′-methylenedibenzaldehyde ( 1 ) with diamines 2a – g or diisocyanates 4a – c . In addition, a polymeric hydrazone was synthesized by reaction of the dioxime of 1 with the isocyanate 4a and a crosslinked product was prepared from a trifunctional isocyanate and 1 . The products were characterized by elemental analysis and IR spectroscopy. Their physico-chemical properties were determined and discussed as function of the number of CH₂-groups in the repeating units.     

On the photoinitiation of free radical polymerization-laser flash photolysis investigations on thioxanthone derivatives

Laser flash photolysis studies and stationary polymerizations were carried out with the aim to elucidate kinetics and mechanisms of photoinitiation processes based on thioxanthone (TX)/amine interactions. During these studies prominence was given to reactions which significantly influence the initiator efficiencies. Thus, rate constants of the reactions ³TX^* + monomer (k_q), ³TX^* + amine (k_XH), and ketyl radical + monomer (k) were determined; k_q decreases according to the series: styrene (St) > N-vinyl-2-pyrrolidone (VP) > methyl methacrylate (MMA) > acrylonitrile (AN) > butyl vinyl ether (BVE) > vinyl acetate (VA) from 6 ·10⁹ l·mol^?1·s^?;1 to 2·10⁴ l·mol^?1·s^?1. Substitution in the 2-position of TX by methyl (MTX), isopropyl (ITX) and Cl (CTX) generally causes a decrease of k_q, except for the systems CTX/VP and CTX/BVE. The k_XH values range from 6 to 8·10⁹ l·mol^?1·s^?1 for typical amines, e.g. ethyl 4-((dimethylamino)benzoate). Ketyl radicals react rather slowly with monomers; for CTX k in l·mol^?1·s^?1: 7·10³ (St), 4·10² (VP), 4·10¹ (MMA), ? 10 (BVE). O₂ reacts rapidly with ketyl radicals: k = 2·10⁹ l·mol^?1·s^?1 (TX). Rates of polymerization ν (monomer consumption) determined at [M] = 5 mol/l and [amine] = 10^?1 mol/l are equal for TX, ITX, MTX, and CTX, but increase according to the series AN < MMA < VP; ν depends on the thioxanthone and the monomer concentration according to ν ∝ [TX]^1/2[M].     

Photostability of some carbenium salts

The photolysis of triphenylmethyl salts with anions such as SbCl, FeCl and AsF was investigated in inert and oxygen atmosphere. On irradiation by visible light the characteristic bands of the cation disappeared in 20 min and in 15 h at concentrations of 10^?4 M and 10^?3 M , respectively. The main photolytes identified were triphenylmethane, triphenylchloromethane, triphenylcarbinol, benzophenone, fluorenone, fluorene, 9-hydroxy-9-phenylfluorene, 9-phenylfluorene besides 2–3% nonidentified products. The results showed that the product composition of the photolyzed mixture depended only slightly on the atmosphere used, the differences in the amounts of the products being more significant.