摘要:

AbstractDie Copolymerisation von 4‐Propenylbrenzcatechin‐Derivaten, wie Eugenol (1), Isosafrol (2), und Safrol (3), mit Vinylmonomeren, wie Acrylnitril (AN), Maleinsäureanhydrid (MA), und Methylmethacrylat (MMA), durch Tributylboran (TBB) wurde in Cyclohexanon bei 30°C unter Stickstoff untersucht. Die Propenylverbindungen copolymerisierten mit AN und MA, während MMA mit ihnen nur Homopolymeres ergab.Für die Systeme AN/Propenylbrenzcatechin‐Derivat/TBB wurden die folgenden Copolymerisationsparameter erhalten (M1= AN): AN/1/TBB‐System:r1= 2,2 undr2= 0, AN/2/TBB‐System:r1= 0,28 undr2= 0, AN/3/TBB‐System:r1= 1,8 undr2= 0. Dieses Resultat entspricht der Tatsache, daß die Propenylverbindungen1–3unter diesen Reaktionsbedingungen nicht homopolymerisierten.Das MA/2/TBB‐System ergab 1:1‐Copolymere; die Copolymerisation verlief wahrscheinlich über einen

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760201

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractCarboxyl groups can be introduced into crosslinked polystyrene by a two step process involving 2‐chlorobenzoylation and cleavage of the product using a mixture of potassiumtert‐butoxide and water. The reaction yields can be estimated easily by the change in weight of the resin and by chlorine analysis. Carboxyl groups can also be introduced via benzoylation. The previously described method of introducing carboxyl groups, in which crosslinked polystyrene is chloromethylated and the product oxidized to a formyl resin, which is then oxidized to a carboxyl resin, can be improved by using peracetic acid in methanesulphonic acid as the oxidant in the last s

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760202

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractPolymers were synthesized that contain isothiouronium, thiosulphate or dithiocarbamate residues, which occur in known radioprotectors of low molecular weight. By copolymerizing a monomer containing the radioprotective residue with 1‐vinyl‐2‐pyrrolidone or acrylic acid, polymers were formed that were soluble in water. Polymers containing isothiouronium residues were obtained directly from an ethylenic isothiouronium salt and 1‐vinyl‐2‐pyrrolidone, and by the reaction of an intermediate halogen‐containing polymer with thiourea. Polymers containing thiosulphate or dithiocarbamate residues were obtained by copolymerization of the appropriate monomer with 1‐vinyl‐2‐pyrrolidone. Molecular weights (GPC), determined for three of the copolymers, did not exceed 12000. In preliminary tests in mice, poly[S‐(2‐acryloylaminoethyl)isothiouronium chlorideco‐1‐vinyl‐2‐pyrrolidone] (4b) and poly(N,N‐diethylS‐vinyldithiocarbamate‐co‐acrylic acid) (

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760203

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractDurch Reaktion von vernetzten und unvernetzten Copolymeren ausp‐Lithiumstyrol und Styrol mit Benzonitril und nachfolgende Umsetzung mit Methanol wurden polymere (Phenyl‐4‐vinylphenyl)methanimine (5) erhalten, die auf verschiedenen Wegen am Stickstoffatom bromiert wurden.Mit den so hergestellten polymerenN‐Brom‐(phenyl‐4‐vinylphenyl)methaniminen (7) ließen sich geeignete monomere Substrate in der Seitenkette und in Allylstellung bromieren. Die auf diese Weise entbromierten makromolekularen Substanzen konnten durch erneute Bromierung am Stickstoffatom rege

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760204

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractThe polymerization ofcis‐ andtrans‐7,9‐dioxabicyclo[4.3.0]nonane (1a) and (1b) was investigated in bulk and in solution with phosphorus pentafluoride and triethyloxonium hexachloroantimonate as initiators. Thecis‐isomer1aforms in high yield the cyclic dimer2a. Thetrans‐isomer1bpolymerizes readily under similar conditions to relatively low molecular weight polymers, whereas in 1,1,2,2‐tetrachloroethane solution predominantly the cyclic dimer2bis formed. The polymerization of thetrans‐isomer1bin toluene‐d8solution is of first order with respect to monomer, and the concentration of active species appears to remain constant throughout the reaction. The polymerization of1bin toluene‐d8with PF5as initiator is completely reversible with temperature change, and the standard ceiling temperatureT c0is 118°C (cone.: 1 mol/dm3in toluene‐d8). The cyclic dimer2bpolymerizes at −25°C to the same equilibrium product composition as th

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760205

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractThe reactivity oftert‐amine groups was studied by quaternization of homopolymers and copolymers of 2‐vinyl‐, 2‐methyl‐5‐vinyl‐ and 4‐vinyl‐pyridine with butyl bromide. The reactivity of the corresponding model compounds was taken as a reference: in this case second order kinetics is obeyed until complete reaction of the pyridine derivatives. If the pyridylethylene repeating unit is included in a statistical styrene/vinylpyridine copolymer (with a low content of pyridylethylene units), the kinetics are of second order too, except for the styrene/2‐vinylpyridine copolymer. In this case the steric hindrance due to the position of the nitrogen atom is the preponderant factor. For homopolymers, in the case of the quaternization of poly(1‐pyrid‐4‐ylethylene) [poly(4‐vinylpyridine)] second order kinetics are observed, until the adjacent reactive groups are quaternized. In the case of poly[1‐(6‐methyl‐3‐pyridyl)ethylene][poly(2‐methyl‐5‐vinylpyridine)] a second order law is obeyed only until one of the ajacent groups is quaternized.For poly(1‐pyrid‐2‐ylethylene) [poly(2‐vinylpyridine)] steric hindrance effects govern strictly the behaviour of the functional group.These results were interpreted by introducing three individual vel

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760206

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractDurch Kondensation von 2,3,7,8‐Tetraoxo‐2,3,7,8‐tetrahydropyrrolo[2′,3′:1,2]naphtho[5,6‐b] pyrrol (4) mit Thiophen entsteht ein polymeres Indopheninhomologes (2).2ist ein Küpenfarbstoff und besitzt auf Grund seines koplanaren konjugierten π‐Elektronensystems ausgeprägte Eigenschaften eines polymeren organischen Halbleiters. Es ist ein p‐Leiter mit einer spezifischen elektrischen Leitfähigkeit von σ298k=1,8.10−5Ω−1cm−1bei einer thermischen Aktivierungsenergie vonE=0,34eV (≈0,54.10−19J), bei einem Druck vonp=1500kp cm−2(14700 N cm−2).2besitzt eine spezifische Spin

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760207

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractL'acétoxy‐1 butadiène (1a, b) est polymérisé par les amorceurs radicalaires aussi bien en masse, en solution benzénique ou en émulsion aqueuse. Les polyméres formés renferment 80% de motifs ‐1,4 (4) et 20% de motifs ‐3,4 (5) ainsi qu'il ressort de l'étude de modèles (2et3) de ces structures. L'importance des réactions de transfert de chaǐne au monomère a été mesurée et rend compte de la valeur faible des masses molaires moyennes (M̄n≈ 5000).La copolymérisation radicalaire a été étudiée avec des composés acryliques, vinyliques et diéniques:1a, bprésente une réactivité trés proche de celle de l'isoprène. Les copolymères ont couramment desM̄nde l'ordre de 20 000.Les polymères préparés par amorçage cationique sont instables à moins d'ětre soigneusement purifiés; enfin les amorceurs anion

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760208

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractPoly(pyromellitdiimidoarylenecarbonyliminoaryleneiminocarbonylarylene)s [poly(amide‐imide)s] (7and12) were prepared from pyromellitic dianhydride (6) and dicarbamates (5) (diurethanes) containing amide linkages. The same polymers could also be prepared directly from aromatic isocyanatocarboxylic acid chlorides (10), diamines (11) and6. In the latter method, the addition of an equimolar amount of water was required for the formation of the imide ring in the main chain of the polymer. Model reactions were carried out to determine the reaction conditions for the two methods. Reaction mechanisms are propose

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760209

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY

摘要:

AbstractOpen and closed molecule‐based associations with experimentally incompletely accessible concentration dependencies of the apparent molecular weights can be distinguished by plotting the apparent weight average molecular weight, (Mw)app, versus the inverse apparent number average molecular weight, (Mn) app−1. For closed associations, straight lines are observed for theta‐systems and concave ones for non‐theta‐systems of associating rods. Open associations in these cases give convex lines for both, theta and non‐theta‐systems. Loops can be expected for both types of associations for non‐theta‐systems at high concentrations. A similar plot can be based on apparentzand weight averag

ISSN:0025-116X    

DOI:10.1002/macp.1975.021760210

出版商:Hüthig&Wepf Verlag    

年代:1975

数据来源: WILEY