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Reactions of Bifunctional Addition-Fragmentation Chain Transfer Agents for Synthesis of Polymer Bearing Unsaturated Moieties at Both Ends

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Reactions of Bifunctional Addition-Fragmentation Chain Transfer Agents for Synthesis of Polymer Bearing Unsaturated Moieties at Both Ends Macromol. Chem. Phys. 2000, 201, 1565–1573 1565 Full Paper: Polymerizations of methyl methacrylate scopy that unsaturated and seven-membered cyclic end (MMA) and styrene (St) in the presence of bifunctional groups are formed by conventional AFCT and intramole- addition fragmentation chain transfer (AFCT) agents con- cular cyclization of the radical from the transfer agents. sisting of two a-(alkylthiomethyl)acryloyloxy groups con- However, formation of the cyclic end groups could be nected by an alkylene group are presented. The moieties suppressed by structural modification of the transfer from the transfer agent were introduced almost quantita- agent. PMMA bearing the unsaturated end group at one or tively at both ends and at the middle of PMMA under both chain ends was employed as a precursor for branched appropriate conditions. It was confirmed by NMR spectro- block copolymer preparation. Reactions of bifunctional addition-fragmentation chain transfer agents for synthesis of polymer bearing unsaturated moieties at both ends Kenta Tanaka, Bunichiro Yamada* Material Chemistry Laboratory, Faculty of Engineering, Osaka City University, Osaka 558-8585, Japan Fax: +81-6-6605-2797; E-mail: [email protected] Introduction less reactive adduct radical which would readily couple a with PSt radical leading to a star-shaped polymer consist- Some -(substituted methyl)acrylic esters have been [10] known as effective chain transfer agents through an addi- ing of two PMMA chains and up to four PSt chains. tion fragmentation chain transfer (AFCT) mechanism to yield b-carboalkoxyallyl end groups depending on the type of the substituent.[1–4] The same unsaturated end group can be obtained by catalytic chain transfer poly- merization of methyl methacrylate (MMA) using a Co(II) complex.[5] The addition of a PMMA radical to the carbo- methoxyallyl group is not a fast reaction and the adduct radical is known to readily fragment to regenerate the end group and PMMA radical. Consequently, an oligomer of MMA bearing an unsaturated end group can be utilized This paper deals with the polymerization of MMA in a as an AFCT agent and a mediator for block copolymer the presence of 2, 3, and 4 consisting of two -(alkylthio- formation through living free radical polymerization.[6, 7] methyl)acryloyl groups that are expected to function as Bi- and dual functional a-(substituted methyl)acrylate highly reactive AFCT agents similar to those in 1. The type AFCT agents have been used to synthesize branched unsaturated moieties resulting from the chain transfer MMA polymers, and MMA and styrene (St) block copo- were expected to be introduced at both ends of the poly- lymers utilizing almost quantitative bond formation mer. Quantitative introduction of the end groups and between polymer chain end and the resulting end further reaction with propagating radicals were investi- group.[8–10] When two a-(substituted methyl)acryloyl moi- gated as a novel procedure to attain branched block copo- eties are connected by an ester linkage such as 1, the lymer without gelation. bond formation as a result of AFCT could lead to PMMA bearing the unsaturated moiety at the middle and the Experimental other moieties at both ends of the polymer chain.[9] If the subsequent St polymerization was carried out in the pre- Materials sence of the PMMA, the addition of PSt radical to double MMA and St were commercially available and were purified bond of the unsaturated moiety was feasible to yield a by distillation under reduced pressure before use. Commer- Macromol. Chem. Phys. 2000, 201, No. 14 i WILEY-VCH Verlag GmbH, D-69451 Weinheim 2000 1022-1352/2000/1409–1565$17.50+.50/0 1566 K. Tanaka, B. Yamada cial 2,29-azobisisobutyronitrile (AIBN) was purified by ane or methanol was used to precipitate the resultant poly- recrystallization from methanol. MMA-d8 was obtained by mer. The polymer was dried and purified by reprecipitation. esterification of methacrylic acid-d5 prepared from acetone- [11] d6 cyanohydrin and purified by distillation. Measurements 1H and 13C NMR spectra and 2D(H-C) spectrum were taken — — Preparation of 2, 3, and 4 by a JEOR JNM a-400 spectrometer. Mn and Mw were obtained employing a Tosoh 8000 series HPLC equipped — 1,2-Ethanedithiol (3.2 g, 0.034 mol) was added dropwise to a with columns for GPC, and PSt standards (M = 5.06102 – a [12] n benzene solution of methyl -(choloromethyl)acrylate 1.096106) were used for calibration. (MCMA) (10.1 g, 0.075 mol) in the presence of triethyl- amine (7.6 g, 0.075 mol) with cooling. After stirring the mix- ture for two days at room temperature, the benzene solution Results and discussion was dried by MgSO4 after washing with water. The benzene was evaporated, and 2 was obtained as colorless crystals. Polymerizations of MMA and St Further purification of 2 was performed by recrystallization from n-hexane, and the structure of 2 was proven by 1H and The polymerizations of MMA and St in the absence and 13C NMR spectroscopies. 2: yield 6.27 g (0.022 mol, 64%), presence of 2 are compared in Tab. 1. Although 2 is a divi- mp 37–388C. nyl compound, all the polymers of St and MMA obtained 1 H NMR (CDCl3): d = 2.67 (s; SC2H4S), 3.42 (s; CH2S), were soluble in organic solvents such as benzene, chloro- 3.79 (s; OCH3), 5.68 (s; CH22), 6.23 (s; CH22). Intensity form, and acetone. Chain transfer constants (Ctr) of 2 were [13] ratio: 2:2:3:1:1. determined by Mayo plots; Ctr = 0.70 and 1.67 for 13 d 2 C NMR (CDCl3): = 31.0 (C2H4), 32.7 (CH2C ), 52.1 MMA and St polymerizations, respectively. These values 2 2 2 (OCH3), 126.2 (CH2 C), 136.6 (CH2 C), 166.4 (C O). are similar to those for the corresponding mono-functional 3 and 4 were also synthesized from the corresponding di- transfer agent, ethyl a-(tert-butylthiomethyl)acrylate, for thiols and MCMA at room temperature, and obtained as an oil the respective polymerizations.[1] A small amount of 2 and as crystals, respectively. 4 was recrystallized from n-hex- effectively reduced the molecular weight but caused only ane, and 3 was purified by a recycling preparative HPLC a slightly decrease in the polymerization rate. A plausible (Japan Analytical Industry LC-908). The structures of 3 and 4 — were confirmed by 1H and 13C NMR spectroscopies. 3: yield explanation for the decrease in Mn with increasing conver- 27%. sion is that the rate of conversion of chain transfer agent is 1 H NMR (CDCl3): d = 1.84 (q; SCH2CH2), 2.55 (t; SCH2), lower than that of MMA monomer, as indicated by the Ctr 3.38 (s; CH2C2), 3.79 (s; OCH3), 5.67 (s; CH22), 6.21 (s; value being less than unity. CH2). Intensity ratio: 1:2:2:3:1:1. 13 C NMR (CDCl3): d = 28.5 (SCH2CH2), 30.3 (SCH2CH2), 32.7 (CH2C2), 52.1 (OCH3), 126.0 (CH22C), 136.7 Structure of PMMA 2 2 8 (CH2 C), 166.6 (C O). 4: yield 46%, mp 42–43 C. According to the AFCT mechanism, addition of a poly- 1 d H NMR (CDCl3): = 1.38 (m; SCH2CH2CH2), 1.58 (m; mer radical to 2 yielding 5 followed by rapid b-fragmen- SCH2CH2), 2.45 (t; 4H, SCH2), 3.37 (s; CH2C2), 3.79 (s; OCH ), 5.65 (s; CH 2), 6.20 (s; CH ). Intensity ratio: 3 2 2 Tab. 1. Results of polymerization in the presence of 2 in ben- 2:2:2:2:3:1:1. zene at 608C.a) 13 C NMR (CDCl3): d = 28.3 (SCH2CH2CH2), 28.9 2 — –2 — — (SCH2CH2), 31.4 (SCH2CH2), 32.6 (CH2C ), 52.0 (OCH3), Monomer 2 Time Conv. Mn 610 Mw/Mn 2 2 62 125.7 (CH2 C), 136.8 (CH2 C), 166.6 (CO). M in h in wt.-% (GPC) (GPC) MMA 0 6 37.6 857 2.3 Polymerization procedure 0.0025 6 36.6 419 2.5 0.025 6 32.7 54.4 1.8 MMA and St polymerizations in the presence of the bifunc- 0.100 1 4.4 26.0 1.3 tional chain transfer agent were carried out in glass tubes 0.100 4 19.3 23.1 1.4 sealed under vacuum. After polymerization completion, the 0.100 8 34.9 20.6 1.4 contents of the tube were poured into a large excess of n-hex- 0.100 20 66.7 21.3 1.4 ane or methanol to precipitate the polymeric product, which 0.100 24 76.1 18.5 1.5 was dried and purified by reprecipitation. 0.125 6 30.5 15.6 1.5 PMMA to be used as a prepolymer for the preparation of a 0.125 15 76.8 14.7 1.5 — 0.250 6 27.9 10.6 1.3 block copolymer (PP, Mn (GPC) = 1470) was obtained by St 0 24 28.1 344 1.5 8 MMA polymerization in the presence of 2 for 15 h at 60 C: 0.0025 24 20.6 147 1.8 [MMA] = 2.0 mol/L, [2] = 0.125 mol/L, [AIBN] = 5.0 0.020 24 17.5 45.0 1.7 mmol/L. The polymerizations of MMA and St in the pre- 0.100 24 5.9 22.0 1.3 sence of PP were carried out in glass tubes sealed under vacuum. After the polymerization, a large amount of n-hex- a) [M] = 2.0 mol/L, [AIBN] = 5.0 mmol/L. Reactions of bifunctional addition-fragmentation chain transfer ..
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