Synthesis of Functionalized Polymers by Means of Living Anionic Polymerization, 2. Synthesis of Well-Defined Chain-End and in-Chain Functionalized Polymers with 1,3-Butadienyl Groups

Haraguchi, Naoki; Sakaguchi, Yoshihiko; Sugiyama, Kenji; Hirao, Akira

doi:10.1002/1521-3935(20010701)202:11<2221::aid-macp2221>3.0.co;2-l

Cited by 12 publications

(18 citation statements)

References 7 publications

(12 reference statements)

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“…The post-polymerization reactions of living anionic polymers with almost all electrophiles were first attempted during the 1960s to introduce useful functional groups [172]. Furthermore, the 1,3-butadienyl terminus was quantitatively transformed into anhydride and diepoxy functions by Diels-Alder and oxidation reactions [182]. Since the 1990s, however, Quirk et al have re-examined such functionalization reactions and carefully characterized the degree of functionalization of the resulting polymers by using size-exclusion chromatography (SEC), high-resolution 1 H and 13 C NMR, and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry.…”

Section: Reaction Of Living Anionic Polymers With Electrophiles: Syntmentioning

confidence: 99%

Anionic Polymerization: Recent Advances

Ishizone

Hirao

2012

Materials Science and Technology

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polymerize the monomers in classes B, C, and D, but they cannot initiate the polymerization of monomers in class A. The initiators in class c can polymerize both C and D class monomers, while they are inert for the monomers in classes A and B. The least-reactive initiators in class d, such as amines and phosphines, undergo anionic polymerization of the most-reactive D class monomers Among the monomers, α-cyanoacrylate is polymerized, even with water.The relationship between a monomer and its growing chain-end anion is also important in order to understand anionic polymerization behavior. In general, the most-reactive chain-end anions derive from the least-reactive monomers and vice-versa, because they are conjugated bases and acids with each other. For example, when considering styrene (class A) and methyl methacrylate (MMA) (class B), the latter is more reactive than the former because the electron density on the C=C bond of MMA is considerably reduced by the electron-withdrawing ester carbonyl group, whereas that on the styrene C=C bond is influenced much less by the phenyl group. On the other hand, the chain-end anion derived from MMA is also reduced in electron density by the same electron-withdrawing effect, and becomes less reactive than that derived from styrene. In practice, the chain-end anion from MMA has no ability to polymerize styrene, whilst the chain-end anion from styrene can polymerize styrene and, of course, the more-reactive MMA. Thus, the monomers in class A will always produce the most reactive growing chain-end anions that can polymerize all monomers in classes A, B, C, and D. In contrast, the least-reactive chain-end anions derived from the most-reactive monomers in class D can polymerize only the monomers in class D. These relationships are very important -even critical -for selecting the correct anionic initiator in polymerization, as well as when synthesizing block copolymers.

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Section: Reaction Of Living Anionic Polymers With Electrophiles: Syntmentioning

confidence: 99%

Anionic Polymerization: Recent Advances

Ishizone

Hirao

2012

Materials Science and Technology

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“…5 Therefore, we are interested in introducing 1,3-butadienyl groups at polymer chain-ends because the resulting polymers may function as macromonomers and chain-end-functionalized polymers. Recently, we successfully introduced 1,3-butadienyl groups at chainends or in-chains by reacting either 6-bromo-3-methylene-1-hexene (1) 6 or 1-[4-(4-methylene-5-hexenyl)phenyl]-1-phenylethylene (2) 7 with living anionic polymers of styrene and isoprene. Two 1,3-butadienyl groups could also be introduced at the chain-end by the reaction of 2 with polystyryllithium (PSLi), followed by treatment with 1 as shown in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, we were successful in preparing novel chain-endfunctionalized polymers with anhydride and epoxy functions via 1,3-butadienyl groups that were difficult to be introduced by any other methods. 7 In the course of our research works, we intended to exploit the anionic polymerizability of the chainend-functionalized polymers with 1,3-butadienyl groups for the synthesis of well-defined densely comblike polymers. Although the terminal 1,3-butadienyl group was anionically polymerized to some extent, high conversions were not realized under usual conditions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Well-Defined Star-Branched Polymers by Using Chain-End-Functionalized Polystyrenes with a Definite Number of 1,3-Butadienyl Groups and Its Derivatized Functions

Higashihara¹,

Kitamura²,

Haraguchi³

et al. 2003

Macromolecules

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A series of new chain-end-functionalized polystyrenes with two, four, and eight 1,3-butadienyl groups (PS(Bd) n , n = 2, 4, and 8) were synthesized by the reaction of chain-end-functionalized polystyrenes with the same numbers of benzyl bromide moieties with the 1,1-diphenylalkyl anion prepared from oligo(α-methylstyryl)lithium and 1-[4-(4-methylene-5-hexenyl)phenyl]-1-phenylethylene. These 1,3-butadiene-functionalized polymers reacted efficiently with polystyryllithium (PSLi) to afford well-defined 3-, 5-, and 9-arm star-branched polystyrenes. A successive synthesis from (PS(Bd)4 to 5-arm followed by 9-arm star-branched polystyrenes was demonstrated by twice repeating the reaction sequence involving the reaction of PSLi with (PS(Bd)4 and subsequent in-situ introduction of 1,3-butadienyl groups via the generated anions. The terminal 1,3-butadienyl groups were quantitatively converted into highly reactive anhydride and epoxy functions by the Diels−Alder and epoxidation reactions, respectively. The resulting anhydride- and epoxy-functionalized polymers were successfully used as new polymeric coupling agents to synthesize well-defined star-branched polystyrenes.

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“…A variety of studies on the reactivity of methacryloyl‐functionalized macromonomers have been reported 7,8,12. Since the first reported macromonomer, a variety of other macromonomers have been synthesized anionically including styrenic,13 1,3‐dienyl,14–16 epoxide,17,18 and others 11,19…”

Section: Introductionmentioning

confidence: 99%

“…7‐Bromohepta‐1,3‐diene produced quantitative yields of diene‐functionalized macromonomer when used in a large excess (1.1–5 molar excess) relative to the organolithium chain end. Hirao and coworkers16 also synthesized diene‐functionalized macromonomers via the reaction of 1‐[4‐(4‐methylene‐5‐hexenyl)phenyl]‐1‐phenylethylene with poly(styryl)lithium in tetrahydrofuran at −78 °C. The reaction produced the corresponding diene‐functionalized macromonomer in quantitative yield.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Diene‐Functionalized Macromonomers via Functionalization with Hexa‐1,3,5‐triene

Quirk

Gomochak

Bhatia

et al. 2003

Macro Chemistry & Physics

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The reaction of poly(styryl)lithium (PSLi) with hexa‐1,3,5‐triene (HXT) was studied as a route to diene‐functionalized macromonomers. When PSLi was reacted with 1.5 molar equivalents of HXT for 2.5 h at −10 °C in toluene, it was found that the diene‐functionalized macromonomer was obtained in high yield; however, oligomerization of the HXT was observed by matrix‐assisted laser absorption ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). Oligomerization was eliminated by running the reaction with only 1.2 molar equivalents of HXT to PSLi and allowing the reaction to run for 15 min at −10 °C in toluene. The resulting polymer exhibited high diene chain‐end functionality and no oligomerization was observed by MALDI‐TOF MS. 13C NMR spectroscopy and the attached‐proton test (APT), along with calculated chemical shifts, showed the presence of both the 1,2‐ and 1,4‐addition chain‐end structures. Further analysis by the reaction of the functional polymer with maleic anhydride indicated that 18 wt.‐% of the product was unreactive, either because of a 1,4‐addition chain‐end structure or a nonfunctional polymer. The structure of the maleic anhydride‐modified polymer was determined by MALDI‐TOF MS and 13C NMR spectroscopy. Preliminary work on the reactivity of the diene‐functionalized macromonomers was performed by the addition of a large excess of PSLi to a solution of macromonomer followed by characterization by size‐exclusion chromatography (SEC).The formation of hexa‐1,3,5‐triene‐functionalized polystyrenes and their reaction with maleic anhydride.magnified imageThe formation of hexa‐1,3,5‐triene‐functionalized polystyrenes and their reaction with maleic anhydride.

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Synthesis of Functionalized Polymers by Means of Living Anionic Polymerization, 2. Synthesis of Well-Defined Chain-End and in-Chain Functionalized Polymers with 1,3-Butadienyl Groups

Cited by 12 publications

References 7 publications

Anionic Polymerization: Recent Advances

Anionic Polymerization: Recent Advances

Synthesis of Well-Defined Star-Branched Polymers by Using Chain-End-Functionalized Polystyrenes with a Definite Number of 1,3-Butadienyl Groups and Its Derivatized Functions

Synthesis of Diene‐Functionalized Macromonomers via Functionalization with Hexa‐1,3,5‐triene

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