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Cyclopolymerization XXVIII. Radical Polymerizations of N-Substituted N-Methallyl-2

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Cyclopolymerization XXVIII. Radical Polymerizations of N-Substituted N-Methallyl-2 Polymer Journal, Vol. 32, No. 2, pp 140~146 (2000) Cyclopolymerization XXVIII. Radical Polymerizations of N-Substituted N-Methallyl-2-(methoxycarbonyl)allylamines : Polymerizability ofUnconjugated Dienes with Functional Groups with Low Homopolymerization Tendency Toshiyuki KoDAIRA t, Michio URUSHISAKI, and Norio KAsAJIMA Department of Materials Science and Engineering, Faculty of Engineering, Fukui University, 3-9-1 Bunkyo, Fukui 910-8507, Japan (Received July 8, 1999) ABSTRACT : Radical cyclopolymerizations of N-substituted-N-methallyl-2-(methoxycarbonyl)allylamines (1) were studied to compare their cyclopolymerizabilities with those of N-substituted-N-allyl-2-(methoxycarbonyl)allylamines (2). Monomers 1 with a phenyl(la) and a t-butyl(lb) group as an N-substituent were employed. The phenyl group was cho­ sen, since 2 with an N-phenyl group(2a) was reported to have exceptionally low polymerization tendency among 2. Monomer lb was polymerized to see whether the bulky N-t-butyl group enhances the cyclization tendency of 1 or not, since 1 with an N-methyl group(lc) was reported to yield polymers with pendant unsaturations, though their content is low. It was found that polymerizations of la proceed very slowly like 2a, but the reason for their slow polymerizations was left unsolved. Polymers with high degree of cyclization, 96% for poly(la) and 100% for poly(lb), were obtained even in their bulk polymerizations. This could be an additional support for the proposal made previously. It states that uncon­ jugated dienes, for which monofunctional counterparts do not have homopolymerization tendency yield highly cyclized polymers. This is because both the monofunctional counterparts of 1 are considered to have essentially no homopolym­ erization tendency. The bulky t-butyl group was found to be effective to enhance cyclization tendency also in 1. Struc­ tural studies showed that poly(la) and poly(lb) contain both six- and five-membered rings as repeat cyclic units. Mecha­ nism for intramolecular cyclization was discussed. KEY WORDS Radical Cyclopolymerization I 1,6-Diene I a-Substituted Acryloyl Group / Methallyl Group I Repeat Cyclic Unit / Degree of Cyclization I Cyclopolymerizations of N-phenyl- and N-t-butyl-N­ methallyl-2-(methoxycarbonyl)allylamines (la and lb, respectively)(see Scheme 1) were undertaken to see the effect of the N-substituents on their cyclopolymerization behavior. The reasons why these groups were chosen as N-substituents are as follow. It has been proposed that the use of functional groups with a higher conjugative nature together with no homopolymerization tendency is R 2 essential for the design of 1,6-dienes with not only a high cyclization tendency but also high polymerizability. 1 N­ 1a 2a Substituted-N-allyl-2-(methoxycarbonyl)allylamines 0 1 2 · al­ (2) and N-methyl-N-methallyl-2-(methoxycarbonyl) 1b C(CH3b 2b lylamine (le) 3 are the monomers that were synthesized and polymerized to establish the validity of the proposal. 1c CH 3 2c Their a-substituted acryloyl groups were found to have a high conjugative nature, though they do not show ho­ Scheme 1. mopolymerization tendency when they exist as monoene 1 2 compounds. • However, polymerization behavior of 2 changed considerably depending on their N-substituents. Another interesting point of this study is structural in­ For examples, 2a polymerized exceptionally slowly de­ vestigations on repeat cyclic units of poly(l). The struc­ spite the fact that its a-substituted acryloyl group has a tures of the polymers derived from various diallyl com­ 7 high conjugative nature. Polymerizations of la were un­ pounds were compared in the previous paper. It showed dertaken to see how is the effect of N-phenyl group on that the substituents on their olefinic double bonds tend the polymerizations of 1, because le polymerized rapidly to favor the formation of a six-membered ring probably in accordance with the proposal.3 Bulky substituents due to the steric and radical stabilizing effect. Monomers have been known to enhance the cyclization tendency of 1 which have a structure with an additional methyl 4 6 unconjugated dienes. - This led us to the studies of cy­ group on the allyl group of 2 are supposed to yield poly­ clopolymerizations of lb to see whether the bulky N-t­ mers with a considerable amount of a six-membered ring butyl group enhances the cyclization tendency of 1 or not, as a repeat cyclic unit, different from poly(2) which con­ 1 2 since le yielded polymers with a small amount of pen­ sist exclusively of a five-membered ring. • In fact, le dant methallyl groups. yielded polymers which consist almost exclusively of a six-membered ring as a repeat cyclic unit.3 Present in­ tTo whom correspondence should be addressed. vestigation may provide us valuable information on how 140 Design of 1,6-Dienes with High Cyclization Tendency the influence of the N-substituents on the structures of placed in glass ampoules, which were then subjected to the repeat cyclic units ofpoly(l) is. several freeze-pump-thaw cycles and sealed. After poly­ merization in a constant-temperature bath, the polymer­ EXPERIMENTAL ization mixtures were poured into excess petroleum ether. Conversion of the monomer was calculated from Materials the weight of the polymer along with the residual mono­ Monomers 1 were synthesized by the equimolar reac­ mer concentration measured by gas chromatography tion between methyl a-(bromomethyl)acrylate (BMA) (GC) with tetralin as the internal standard, since some and corresponding amines based on the procedure for portion of their polymers was found to be soluble in pe­ 1 2 the preparation of 2. · Crude products obtained were troleum ether. The polymers were reprecipitated from subjected to repeated distillations to give pure liquids. benzene solution into petroleum ether to obtain pure Yields of the final stage of the synthesis of these mono­ polymers for measurements. mers were from 40 to 60% after distillations two times. Group-transfer polymerizations were carried out ac­ 8 11 The supposed structures were confirmed by NMR. The cording to the procedure reported, • using MTMP and boiling points and chemical shifts of the characteristic TBABB as initiator and catalyst, respectively. absorption peaks of 1H and 13C NMR spectra of 1 are as follow. Boiling point of la: 124°C/0.4 mmHg. 1H NMR Measurements 1 13 for la : o= 7.17 (m, m-C6H5), 6.67 (t, p-C6H5), 6.60 (d, o­ H NMR and C NMR spectra were taken on a JEOL 1 13 or a C6H5), 6.26 (s, CH2 =, acryloyl), 5.55 (s, CH2 =, acryloyl), JNM-GX-270 (270 MHz for H and 68 MHz for C) 1 125 MHz for 13C) FT 4.86 (s, CH2 =, methallyl), 4.80 (s, CH2 =, methallyl), JEOL LA-500 (500 MHz for H and 4.19 (s,>N-CHd, 3.80 (s,>N-CHd, 3.79 (s,-O-CH3), NMR spectrometer using CDC13 and tetramethylsilane 13 Size and 1.73 (s, CH2 =C (C!!a) -) ppm. C NMR for la : o = as a solvent and an internal standard, respectively. 166.9 (>C=O), 148.2 (>N-C=), 140.2 (CH2 =_Q (CH3)-), exclusion chromatography (SEC) was performed on a equipped 135.3 (CH2 =Q<, acryloyl), 129.0 (m-C6H5), 124.9 (_QH 2 Shimadzu LC-lOAD liquid chromatograph =C<, acryloyl), 116.5 (p-C6H5), 111.9 (o-C6H5), 110.6 with three polystyrene gel columns (Shodex K-804L) using (_QH 2 =C (CH3) -), 56.2 ( > N-CHd, 51.8 (-O-CH3), 51.3 and ultraviolet/refractive index dual-detectors (>N-CHd, and 20.0 (CH2 =C (CH3) -) ppm. Boiling chloroform as eluent. A molecular weight calibration point oflb: 82°C/0.l mmHg. 1H NMR for lb : o=6.16 (s, curve was obtained by using standard polystyrene. GC GC-8A gas chroma­ CH2 =, acryloyl), 5.94 (s, CH2 =, acryloyl), 4.84 (s, CH2 =, was carried out on a Shimadzu methallyl), 4.69 (s, CH2 =, methallyl), 3.73 (s,-O-CH3), tograph equipped with a silica gel column (Shimadzu 3.32 (s, > N-CHd, 3.00 (s, > N-CHd, 1.68 (s, CH2 = C DC-11). Viscosity was measured using a Ubbelohde vis­ 13 (C!:!3) -), and 1.08 (s, (C!!3)aC-) ppm. C NMR for lb : cometer at 30°C in N, N-dimethylformamide. 0=167.7 (>C=O), 145.7 (CH2 =_Q (CH3)-), 141.3 (CH2 =_Q<, acryloyl), 125.5 (_QH 2 =C<, acryloyl), 111.7 (_QH2 RESULTS =C (CH3) -), 57.3 ( > N-CHd, 55.2 ((CH3)a_Q-), 51.5 (-0 lb CH3), 50.8 (> N-CHd, 27.0 ((_QH3)aC-), and 20.7 (CH2 = Polymerizations of la and C (_QHa)-) ppm. The results of the polymerization of la and lb are Bis(2-methoxycarbonylallyl)aniline (10) was prepared summarized in Table I along with the reported results of 1 2 by the reaction of BMA with aniline based on the proce­ le and 2 · that are given for comparison. The degrees of 1 dure reported for a similar compound.8 White crystal cyclization determined based on H NMR spectra were with mp 67-68°C was obtained in 80% yield by recrys­ found to be 96% for poly(la) and 100% for poly(lb) (see tallization from methanol. 1 H NMR for 10 : o= 7 .18 (t, next section). In accordance with these structural char­ samples are sol­ m-C6H5), 6.71 (t,p-C6H5), 6.59 (d, o-C5H5), 6.28 (s, CH2 =, acteristics, both poly(la) and poly(lb) assumed acryloyl), 5.59 (s, CH2 =, acryloyl), 4.19 (s,>N-CHd, uble in common solvents. It can be reasonably 13 of 1, N-substituted and 3.80 (s,-O-CH3) ppm. C NMR for 10 : o= 166.8 ( > that both the monoene counterparts C=O), 147.6 (>N-C=), 134.9 (CH2 =_Q<), 129.2 (m-C6 N-isobutyl-2-(methoxycarbonyl)allylamines(3) (see Sch­ N-substituted N-methallyl-2-(methoxycar­ H5), 125.1 (_QH 2 =C<), 116.9 (p-C6H5), 111.8 (o-C6H5), eme 2) and 51.
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