摘要:

AbstractN‐acryloyl pyrrolidone (NAP) was synthesized by reaction of pyrrolidone with acryloyl chloride. First, the polymerization of NAP and copolymerization of NAP with styrene (St) were carried out at 60°C, using 2,2′‐azobisisobutyronitrile (AIBN) as an initiator. Kinetic studies showed that the rate of polymerization (Rp) could be expressed byRp=K[AIBN]0.5[NAP]1.0. The reactivity of NAP was found to be larger than that ofN‐methacryloyl pyrrolidone. The overall activation energy was calculated to be 24.3 kcal mole−1. The following monomer reactivity ratio andQandevalues were obtained. NAP(M1)—St(M2):r1= 1.50,r2= 0.35,Q1= 0.42, ande1= 1.60. Second, graft copolymers were synthesized by reacting pyrrolidone, in the presence of a catalytic amount of its potassium salt, with pol

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190201

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractThe radical cation nature of poly(p‐phenylene) (PPP) was examined by electron spin resonance (ESR) and chemical means. ESR studies revealed a radical concentration of 1.0 × 1021spins/g for the crude polymer. Workup with aqueous acid decreased the value to 1.5 × 1018spins/g. Reactions of the polymer with certain nucleophiles followed the half‐regeneration mechanism, whereas with others, electron transfer mainly occurred. The origin of halogen in the polymer was found to arise from reaction of the radical cation with the oxidant, and not with halide during workup. Oxidation of PPP with various species increased the concentration of radical ca

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190202

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractRadical copolymerizations of methyl allyl maleate (MAM) and methyl allyl fumarate (MAF) with styrene (St) are carried out in bulk using AIBN as an initiator at 60°C, and their copolymerization behaviors are compared in detail. The different rate features are observed with each other; thus in the MAF‐St copolymerization the rate was quite enhanced and, also, the maximum rate was found at the molar ratio of 1:1 in the monomer feed, whereas no maximum phenomenon of the rate was apparent for the MAM—St copolymerization. The copolymerizability of MAF with St was quite high, whereas that of MAM was very poor. The cyclization of MAM or MAF was hindered by the highly reactive St monomer. These results are discussed in terms of the formation of the charge—transfer complex between MAF and St and, furthermore, the cyclocopolymerization kinetics involving the 17 elementary reactions as the propagation rea

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190203

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractThe mechanism of two‐dimensional polymerization of octadecyl acrylate in lamellar crystal was investigated in two‐step postpolymerizations by temperature increase and stepwiseγ‐ray irradiation in lieu of the usual one‐step reaction. Two‐step postpolymerizations by these procedures are interpreted satisfactorily by the cone model, which assumes that the polymerization probability of the monomer molecules in a single layer is distributed conically around the initiation point. It was found that the propagating radicals were living, even in the saturated stage, and the effect of the polymer chains already formed on the propagating and terminating reactions was evident. Furthermore, molecular weight distributions of the resultant poly(octadecyl acrylate) measured by gel permeation chromatography (GPC) were broad. The values ofMw/Mnfor the two‐step post polymerizations were 4.71–7.03, whereas those for one‐step reaction

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190204

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractHigh‐molecular‐weight polysulfones that contained 1,3‐enyne linkages in the polymer backbone were prepared by the reaction of potassium salts of (E)‐1,3‐bis(3‐hydroxyphenyl)‐1‐buten‐3‐yne and 4,4′‐dihydroxybiphenyl with 4,4′‐dihalodiphenylsulfones in DMSO‐sulfolane solvent mixtures. The polymers were soluble in methylene chloride and exhibited intrinsic viscosities as high as 0.74 (in DMAC at 30°C) with glass transition temperatures ranging from 179 to 214°C. It was postulated that on heating the polymers would cure via a intramolecular cycloaddition reaction to from a 2‐phenylnaphthalene fused ring system along the polymer backbone. Thermal analytical data studies on cured polymer films and investigations of the products obtained from the thermal reactions of model compounds indicated that the primary curing reaction wasintermolecular rather thanintramolecular in nature. Additional data from testing fabricated composites indicated that the enyne polysulfones have suitable properties for use as high‐temperatur

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190205

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractThe oxidation of sodium bisulfite in the presence of cationic polyelectrolytes or micelles has been studied. The formation of cationic‐bisulfite complexes is indicated, and a kinetic analysis suggests the validity of the enzyme kinetics applied to determine the kinetic parameters. Distinct differences in the activity of cationics depend on the configuration of the cationics in solution; micelle‐forming cationics are more effective than nonmicellar polycationics, except in the case of poly(diallyldimethylammonium chloride), (PDADM). The oxidation rate is strongly affected by the presence of monomer in the system, especially where nonmicellar polycationics are invol

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190206

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractThe chlorination of poly(vinyl chloride) (PVC) was investigated by using deuterated polymeric models of PVC, viz., α‐deuterated PVC (α‐d‐PVC) and β,β‐dideuterated PVC (β,β‐d2‐PVC). The chlorinated samples of PVC, α‐d‐PVC, and β,β‐d2‐PVC were examined by combining infrared (IR),1H‐NMR,13C‐NMR, and mass spectroscopy. The results obtained were used in a study of the reaction mechanism of PVC chlorination. The selectivity of chlorination and the extent of the substitution and elimination‐addition mechanism of chlorination are discussed with respect to the degree of chlori

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190207

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractThe synthesis ofN‐vinyl carbazole (VCbz) copolymers, some of which contain electron‐accepting groups, is described. The new copolymers are: copoly[N‐vinyl carbazole‐di(2‐N‐carbazylethyl)‐fumarate](II); copoly(N‐vinyl carbazole‐vinyl‐2,4‐dinitrobenzene‐sulfonate)(IV); copoly(N‐vinyl carbazole‐vinyl‐2,4‐dinitrobenzene‐sulfenate)(V); copoly(n‐butyl acrylate‐t‐butyl peracrylate)(VII); copoly(n‐butyl acrylate‐t‐

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190208

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

Abstract(+) (S)‐ and (−) (R)‐trans‐1,2‐cyclopropanedicarboxylic acids (C3A), (+) (S)‐ and (−) (R)‐trans‐1,2‐diaminocyclopropanes (C3B), (+) (S)‐ and (−) (R)‐trans‐2‐phenylcyclopropylamines (øC3B), (+) (S)‐ and (−) (R)‐trans‐1,2‐bis(methylamino)‐cyclopropanes (C3MB), and (+) (S)‐ and (−) (R)‐trans‐(2‐p

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190209

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY

摘要:

AbstractThe polyamides were prepared from the dicarbonyl chloride of (+) (S)‐ or (−)(R)‐trans‐1,2‐cyclopropanedicarboxylic acid (C3A) with either the dihydrochloride salt of (+)(S)‐ or (−)(R)‐trans‐1,2‐diaminocyclopropane (C3B) or the dihydrobromide salt of (+)(S)‐ or (−)(R)‐trans‐1,2‐bis(methylamino)cyclopropane (C3MB) by interfacial polycondensation. Several diamide model compounds composed of these monomers were also synthesized. The polyamides [poly(C3A‐C3B)] derived from C3A and C3B have the capability of hydrogen bonding, while the polyamides [poly‐(C3A‐C3MB)]derived from C3A and C3MB do not. Poly(C3A‐C3B) were insoluble in common organic solvents except strong acids. Poly(C3A‐C3MB) were soluble in common organic solvents. Poly(C3A‐C3B) had melting points higher than 300°C. Poly(C3A‐C3MB) melted at 180–235°C. The ORD and CD study has shown that poly(+)C3A(+)C3B in methane sulfonic acid (MSA), 2,2,2‐trifluoroethanol (TFE) (5 v % MSA), and tetramethylenesulfone (TMS) (5 v % MSA) exhibits a very strong Cotton effect or CD peak at 212–218 mμ, attributable to a component of the split π–π*transition of the amide chromophores. Poly(+)C3A(+)C3MB in MSA and TFE (5 v % MSA) shows a strong Cotton effect or CD peak at 217–223 mμ and an intermediate Cotton effect or CD trough at 202–204 mμ as well as an intermediate Cotton effect or CD trough at 220–222 mμ and an intermediate Cotton effect or CD peak at 202–204 mμ in TFE and TMS. These peaks and troughs may be assigned to splitting of the π–π*transition. The CD spectra of poly(+)C3A(+)C3MB in nonacidic media are quite different from those in acidic media: they are almost mirror images. The CD spectra in this transition induced by MSA suggests that a transition from a compact helix to another more extended helix with opposite handedness occurs similar to poly‐L‐proline I ⇄ II. This transition may be explained by electrostatic repulsion between protonated amide groups. Viscosity data have shown that the conformation is changed to a highly extended from in acidic media. The polyamides and diamides derived from enantiomers exhibit mirror image spectra. Poly(+)C3A(+)C3B and poly(+)C3A(+)C3MB in every solvent studied exhibit a marked enhancement of the ro

ISSN:0360-6376    

DOI:10.1002/pol.1981.170190210

出版商:John Wiley&Sons, Inc.    

年代:1981

数据来源: WILEY