AbstractThe radical copolymerizations of commercially available cationic monomers (M1) with acrylamide (M2) have been investigated at pH 6.1 in aqueous solutions. The cationic groups in copolymers were analyzed by a colloid titration method and the reactivity ratios were determined by the Fineman–Ross method. The values of r1 and r2 were 1.71 and 0.25 for methacryloyloxyethyltrimethylammonium chlorideM2, 1.68 and 1.26 for N,N‐dimethylaminoethylmethacrylateM2, 1.13 and 0.57 for methacrylamidopropyltrimethylammonium chlorideM2, 1.10 and 0.47 for N,N‐dimethylaminopropylmethacrylateM2, 0.47 and 0.95 for N,N‐dimethylaminopropylacrylamideM2, 0.48 and 0.64 for acryloyloxyethyltrimethylammonium chloride‐M2, and 0.58 and 6.7 for dimethyldiallylammonium chloride‐M2 systems. The Alfrey‐Price Q and e values were calculated and the linear relationship between log Q and ultraviolet absorption maxima of cationic monomers was found.
AbstractMolecular weight distribution of Nylon 12 was determined with hexafluoroisopropanol/toluene mixture as eluent by gel permeation chromatography. Calibration curve for Nylon 12 was easily obtained from that of polystyrene because the method of universal calibration was applicable among these polymers. The molecular weight distributions of Nylon 12 were always broader than expected by the theory of polymerization, i.e., most probable distribution. This result was not caused by broadening effect in gel permeation chromatography, but by polymerization itself.
AbstractA polymethacrylate derivative containing 6‐cyanouracil was prepared, and its photochemical reaction was studied. The 6‐cyanouracil derivative was found to show high reactivity for the photochemiccal reaction. The photochemical‐reaction product was identified as a cyclobutanetype photodimer, and the photodimer was formed in high yield even from the monomeric compound of 6‐cyanouracil under UV irradiation in low concentration. The quantum yield of the photodimerization of the 6‐cyanouracil derivative was greater than that of the thymine derivative. The photodimerization of the 6‐cyanouracil derivative could not be quenched by usual triplet quenchers, but was found to be quenched by the polymeric derivative of adenine, suggesting a specific interaction.
AbstractThe cationic polymerization of p‐methylstyrene initiated by acetyl perchlorate at −78°C led to long‐lived (living‐like) polymers with a narrow molecular weight distribution (M̄w/M̄n = 1.1–1.4) in methylene chloride containing a common ion salt (n‐Bu4NClO4) or in a less polar solvent (CH2Cl2/toluene, 1/4v/v). Under these conditions, the number‐average molecular weight (M̄n) of the polymers increased in proportion to monomer conversion and was regulated by the monomer‐to‐initiator ratio. When fresh feeds of the monomer were repeatedly added to a completely polymerized solution, the polymerization ensued at the same rate as before and the linear increase in M̄n with monomer conversion continued. The effects of solvent polarity and the common ion salt on the polymerization showed the suppression of the ionic dissociation of the propagating species, resulting in a “nondissociated species,” to be the key factor for the formation of the long‐lived polymers.
AbstractThe initiating ability of the graphite intercalation compounds (GICs) of SbCl5, FeCl3, and AlBr3 was investigated. It was found that GICs were able to initiate the polymerization of monomers of different types–cyclosiloxanes, 1,2‐epoxides, vinyl ethers, lactones, and vinyl monomers. GICs of SbCl5 initiated also the polymerization of tetrahydrofuran. The interaction of the monomers (with the exception of the lactones) caused a size increase of the GICs and deformations in their lamellar structure. Relatively high‐molecular poly(vinyl ethers) and polydimethylcyclosiloxanes were obtained. The mechanism of action of GICs was discussed.
AbstractPyrolyses of B‐triamino‐N‐triphenyl‐, B‐triamino‐N‐trimethyl‐, and B‐trianilino‐borazines were performed between 150 and 300°C. Initial stages of degradation were accompanied by liberation of ammonia in addition to the expected aniline or methylamine; this was most pronounced for the methyl borazine. Aniline elimination proceeded more readily with the B‐anilino than the B‐amino isomer. Data obtained support a ring opening mechanism resulting in telomerizaton accompanied by aniline liberation and formation first of singly then doubly bridged dimers and finally doubly bridged tetramers. Thermal exposure up to 1000°C failed to give pure boron nitride; carbon was invariably retained.
AbstractPermeations of water‐soluble, ionic fluorescent probes from a large, ultrathin nylon‐2,12 capsule membrane were largely affected by the ambient pH of the outer medium; permeations of cationic and anionic probes were accelerated by a factor of 50–100 in the basic and acidic medium, respectively, relative to that in the neutral‐pH region. The permeation of NaCl and nonionic fluorescent probes was hardly affected by the ambient pH. The nylon capsule membrane was elucidated to have an asymmetrical structure: the dense‐thin inner layer and the porous‐thick outer part. The pH‐sensitive permeation could be explained due to the ionization of a small amount of residual end‐groups (COOH and NH2) existing in the dense‐thin inner layer of the nylon capsule membrane.
AbstractThe synthesis of carbazola substituted N‐acylated polyethylenimines, namely, poly[N‐(9‐carbazolyl)acetylethylenimine] 20 and poly[N‐(2‐(9‐carbazolyl))propanoylethylenimine] 21 by a grafting reaction onto PEI and isomerization polymerization of the carbazole substituted 2‐oxazolines is reported. A complete acylation of amino groups in PEI by the 9‐carbazolylacetyl groups was achieved by the p‐nitrophenyl active ester method but PEI was only partially N‐acylated by the 2‐(9‐carbazolyl)propanoyl groups under similar reaction conditions. The carbazole substituted 2‐oxazolines, namely, 2‐(9‐carbazolyl)methyl‐2‐oxazoline 18 and (R,S)‐2‐[1‐(9‐carbazolyl)]ethyl‐2‐oxazoline 19, were prepared by a base induced cyclization of ß‐chloroamides. The ring‐opening isomerization polymerization of 18 and 19 in the molten state with a cationic initiator (dimethyl sulfate, methyl triflate, or ethylene glycol ditosylate) gave 20 and 21. Gel permeation chromatography of 20 and 21 obtained with different monomerto‐initiator ratios gave evidence of a chain transfer reaction with the monomer. The polymers were characterized by elemental analyses, IR, and 1H‐NMR spectroscopy.
AbstractNovel silicon‐containing poly‐1,2,4‐triazoles have been synthesized by the reaction of polyhydrazide precursors and aniline in polyphosphoric acid (PPA) at 260°C. The polyhydrazide intermediates were prepared from aromatic dihydrazides and silicon‐containing acid dichlorides via interfacial polycondensation. These polymers and their intermediates were characterized by infrared spectroscopy (IR), solubility, and by solution viscosity. The thermal behavior of these polytriazoles has been studied by dynamic thermogravimetry.
Journal of Polymer Science Part A: Polymer ChemistryVolume 24, Issue 1 p. 167-171 Article Novel optical resolution of an unprotected adenine derivative followed by grafting the pendant onto polyethylenimine C. G. Overberger, C. G. Overberger Department of Chemistry and the Macromolecular Research Center, The University of Michigan, Ann Arbor, MI 48109Search for more papers by this authorC. C. Chen, C. C. Chen Department of Chemistry and the Macromolecular Research Center, The University of Michigan, Ann Arbor, MI 48109Search for more papers by this author C. G. Overberger, C. G. Overberger Department of Chemistry and the Macromolecular Research Center, The University of Michigan, Ann Arbor, MI 48109Search for more papers by this authorC. C. Chen, C. C. Chen Department of Chemistry and the Macromolecular Research Center, The University of Michigan, Ann Arbor, MI 48109Search for more papers by this author First published: January 1986 https://doi.org/10.1002/pola.1986.080240115Citations: 1AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume24, Issue1January 1986Pages 167-171 RelatedInformation
AbstractMechanistic features of the reaction with thionyl chloride in pyridine were studied in a model reaction of benzoic acid with p‐chlorophenol or aniline. The yields were significantly affected by the amounts of pyridine, favorably by four equivalents, and the nature of pyridine, suggesting that pyridines are not only HCl scavengers, but are also involved in the reaction itself. The reaction was assumed to proceed via a carboxylic sulfinic‐anhydride intermediate different from acyl chloride, and the intermediate was found to be not so reactive that it was completely alcoholyzed by the phenol at high temperatures of more than 60°C. The reaction was successfully applied to the preparation of aromatic polyesters of high molecular weights by the direct polycondensation of aromatic dicarboxylic acids and bisphenols in pyridine at 80°C.
AbstractA new route to prepare optically active polyamides was established, based on the polycondensation of two new active diesters: the active diesters of 4‐chloro‐1 hydroxybenzotriazole, such as 1,1'‐(terephthaloyldioxy)bis(4‐chloro‐benzotriazole), and 1,1'‐(isophthaloyldioxy)bis(4‐chlorobenzotriazole), with optically active isomers of 2,4‐diaminopentane. Dipolar aprotic solvents such as N,N‐dimethylformamide and dimethyl sulfoxide were used as reaction solvents. The solution polycondensation carried out in solution at room temperature afforded optically active polyamides. The aminolysis of the two active diesters was carried out as a model reaction study.
Journal of Polymer Science Part A: Polymer ChemistryVolume 24, Issue 1 p. 187-189 Note Preparation of polyamides and polyesteramides by the direct polycondensation with tosyl chloride and N-methylimidazole Fukuji Higashi, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this authorToshiharu Nishi, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this authorWen-Hsin Chen, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this authorTeh-Chou Chang, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this author Fukuji Higashi, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this authorToshiharu Nishi, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this authorWen-Hsin Chen, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this authorTeh-Chou Chang, Department of Polymer Engineering, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184, JapanSearch for more papers by this author First published: January 1986 https://doi.org/10.1002/pola.1986.080240117Citations: 2AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat Citing Literature Volume24, Issue1January 1986Pages 187-189 RelatedInformation
AbstractOrtho‐vinylbenzaldehyde has been prepared in a three‐step synthesis. Vacuum‐degassed monomer was polymerized with azodiisobutyronitrile initiator in bulk and in solution in 2‐butanone. The kp/kt1/2 value at 60°C is 4.7 × 10−2 L1/2 mol−1/2s−1/2. This is about twice the ratio for styrene. Chain transfer to monomer appears to be significant. Insoluble, crosslinked products were produced at high conversions, because of chain transfer to polymer. Tg of poly(ortho‐vinylbenzaldehyde) was found to be 142°C.Polymers made under N2 atmosphere often contained acetal groups. These can be produced by acid catalysis in the presence of small concentrations of ortho‐vinylbenzyl alcohol. A laddertype structure is produced.The monomer is capable of photoinitiation. Insoluble gels were produced in bulk monomer at all conversions. The initiation rate was very high and crosslinking resulted from combination of radicals produced from photolysis of the pendant 0‐benzaldehyde groups in the macromolecules.
Journal of Polymer Science Part A: Polymer ChemistryVolume 24, Issue 1 p. 191-194 Note Radical grafting from carbon black by carbon black having hydroxy methyl group/ceric ion redox system Norio Tsubokawa, Norio Tsubokawa Faculty of Engineering, Niigata University, Ikarashi 2-nocho, Niigata 950-21, JapanSearch for more papers by this authorKazuhiro Fujiki, Kazuhiro Fujiki Faculty of Engineering, Niigata University, Ikarashi 2-nocho, Niigata 950-21, JapanSearch for more papers by this authorYasuo Sone, Yasuo Sone Faculty of Engineering, Niigata University, Ikarashi 2-nocho, Niigata 950-21, JapanSearch for more papers by this author Norio Tsubokawa, Norio Tsubokawa Faculty of Engineering, Niigata University, Ikarashi 2-nocho, Niigata 950-21, JapanSearch for more papers by this authorKazuhiro Fujiki, Kazuhiro Fujiki Faculty of Engineering, Niigata University, Ikarashi 2-nocho, Niigata 950-21, JapanSearch for more papers by this authorYasuo Sone, Yasuo Sone Faculty of Engineering, Niigata University, Ikarashi 2-nocho, Niigata 950-21, JapanSearch for more papers by this author First published: January 1986 https://doi.org/10.1002/pola.1986.080240118Citations: 8AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume24, Issue1January 1986Pages 191-194 RelatedInformation
AbstractPiperidinium dithiobenzoate and piperidinium tetrathioterephthalate react with α‐halo carbonyl compounds to give small molecules and polymers which, upon dehydrative cyclization with H2SO4, yield materials containing the 1,3‐dithiolium ring. Maximum yields are obtained by use of phase‐transfer techniques and the solvent system H2O/CH2Cl2. The cyclized polymers are soluble in sulfuric acid, and films can be made from (CF3)2 CHOH solutions.
AbstractThe reaction of polymercaptans and 2‐alkenyl azlactones has been further investigated, and several new multiazlactones which are liquids at room temperature have been prepared and characterized. Michael addition yielding the multiazlactones was found to take place slowly in the absence of and rapidly in the presence of acid catalysts. If basic impurities capable of forming mercaptide ion were present, however, the reaction underwent a substantially different course producing primarily ring‐opened products. A source of these basic impurities was determined to be the method of preparation of the alkenyl azlactone itself. When the azlactone was prepared from its acyclic N‐substituted aminoacid precursor by cyclodehydration by use of ethyl chloroformate and triethylamine, a small amount of triethylamine remained that dramatically altered the course of reaction. Nonbasic cyclodehydration agents such as dicyclohexylcarbodiimide were effective at eliminating this side reaction, as well as was the practice of adding excess acid to the reaction system to neutralize the basic impurities.
AbstractRandom and alternating thermotropic liquid‐crystalline copolyethers have been synthesized from 4,4′‐dihydroxybiphenyl and a 1/1 mol ratio of 1,5‐dibromopentane and α,ω‐dibromoalkanes by a two‐phase (organic solvent‐aqueous NaOH) phase‐transfer‐catalyzed polyetherification. Random copolyethers were prepared from α,ω‐dibromoalkanes having six to twelve methylene units. Their phase behavior was compared with those of the perfectly alternating copolyethers containing five methylene units in one spacer and eight, nine, or eleven methylene units in the other, respectively. An odd‐even dependence in thermal transitions has been observed in both oligomeric systems. In all cases, alternating copolyethers, even though comparatively lower in molecular weight, have given rise to higher melting and isotropization temperatures. Since the increase in the melting temperature is larger than the increase in the isotropization temperature, the thermal stability range of the mesophase has narrowed for alternating copolyethers with respect to their random copolyether counterparts.
AbstractGraft copolymerization of acrylonitrile (AN) onto isotactic polypropylene (PP) fiber has been studied by using gamma rays from a 2100 Ci 60Co source as initiator by preirradiation technique. The preirradiated PP was treated with AN and the mixture was graft copolymerized by heating to 100°C for different time periods. The percentage of grafting is determined as a function of total dose, reaction time, and monomer concentration. The effect of different solvents such as H2O, CH3OH, and dioxane upon percentage of grafting has been studied. The maximum effect was observed in water and the minimum in CH3OH. PP—g—PAN was characterized by IR spectroscopic and thermogravimetric methods. A plausible mechanism of gamma radiation induced grafting of AN onto PP in the absence and in the presence of solvents has been proposed. An attempt has been made to compare the relative abilities of different solvents to influence grafting.
