Reactant preordering in solid polymer matrices. 2. Effect of decoupling the reactant groups from the polymer backbone

Lin, Anshyang A.; Chu, Chi Fung; Reiser, Arnost

doi:10.1021/ma00217a012

Cited by 7 publications

(5 citation statements)

References 3 publications

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“…The [2 + 2] photocycloaddition is a powerful carbon−carbon bond forming reaction in organic chemistry and has attracted remarkable attention from both a synthetic viewpoint and its mechanism . Poly(vinyl cinnamate) readily underwent this photocyclization to form a four-membered ring to be used as a well-known negative-type photoresist. − Since 6 and poly( 3 ) included either the cinnamate moiety or conjugated carbon−carbon double bonds activated by the electron-withdrawing CN group, they are also expected to act as photo-cross-linkable polymers.…”

Section: Resultsmentioning

confidence: 99%

“…30 Poly(vinyl cinnamate) readily underwent this photocyclization to form a four-membered ring to be used as a well-known negative-type photoresist. [1][2][3][4][5][6] Since 6 and poly(3) included either the cinnamate moiety or conjugated carbon-carbon double bonds activated by the electron-withdrawing CdN group, they are also expected to act as photo-crosslinkable polymers.…”

Section: Deprotection Of Poly(3)mentioning

confidence: 99%

“…The performance of these photoreactive polymers should strongly depend not only on inherent chemical structures and physical properties but also on primary structures of polymers such as molecular weight, molecular weight distribution (MWD), and tacticity. Photoreactive polymers are usually prepared by chemical modifications using commercially available and conventional polymers. − For instance, poly(vinyl cinnamate), a well-known negative acting photoresist, has been prepared by the polymer reaction of poly(vinyl alcohol) and cinnamoyl chloride. − Obviously, its primary structure was not regulated or well-controlled, although those features should be very important factors for the intermolecular photo-cross-linking. The controlled polymerization of monomers bearing a photosensitive moiety is a suitable route to obtain directly photoreactive polymers having well-defined architectures.…”

Section: Introductionmentioning

confidence: 99%

“…Photoreactive polymers are usually prepared by chemical modifications using commercially available and conventional polymers. [2][3][4][5][6][7] For instance, poly(vinyl cinnamate), a well-known negative acting photoresist, has been prepared by the polymer reaction of poly(vinyl alcohol) and cinnamoyl chloride. [2][3][4][5][6] Obviously, its primary structure was not regulated or well-controlled, although those features should be very important factors for the intermolecular photo-cross-linking.…”

Section: Introductionmentioning

confidence: 99%

“…[2][3][4][5][6][7] For instance, poly(vinyl cinnamate), a well-known negative acting photoresist, has been prepared by the polymer reaction of poly(vinyl alcohol) and cinnamoyl chloride. [2][3][4][5][6] Obviously, its primary structure was not regulated or well-controlled, although those features should be very important factors for the intermolecular photo-cross-linking. The controlled polymerization of monomers bearing a photosensitive moiety is a suitable route to obtain directly photoreactive polymers having well-defined architectures.…”

Section: Introductionmentioning

confidence: 99%

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Protection and Polymerization of Functional Monomers. 27. Synthesis of Well-Defined Poly(4-vinyl-α-methylcinnamic Acid) by Means of Anionic Living Polymerization of 2-[1-Methyl-2-(4-ethenylphenyl)ethenyl]-4,4-dimethyl-2-oxazoline

et al. 1998

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Anionic polymerizations of 2-[2-(4-ethenylphenyl)ethenyl]-4,4-dimethyl-2-oxazoline (1), 2-[2-(4-isopropenylphenyl)ethenyl]-4,4-dimethyl-2-oxazoline (2), and 2-[1-methyl-2-(4-ethenylphenyl)ethenyl]-4,4-dimethyl-2-oxazoline (3) were carried out in tetrahydrofuran at −78 °C with (1,1,4,4-tetraphenylbutanediyl)dipotassium. Poly(1) was quantitatively obtained after 24 h but the molecular weight distribution (MWD) of the polymer was relatively broad (M w/M n = 1.3−1.4). The 1H NMR analysis of the polymer suggested that side reactions toward the conjugated CC−oxazoline linkage occurred during the polymerization. No apparent polymerization of 2 was observed under similar condition. On the other hand, the polymerization of 3 proceeded rather rapidly within 1 h and quantitatively gave poly(3) having a narrow MWD (M w/M n < 1.1) and the predicted molecular weight based on the molar ratio of monomer to initiator. The living character of the propagating carbanion of poly(3) was confirmed by the quantitative initiation efficiency in the postpolymerization. Novel tailored block copolymers, poly(3-b-isoprene-b-3), poly(3-b-styrene-b-3), and poly(tert-butyl methacrylate-b-3-b-tert-butyl methacrylate), were synthesized by sequential block copolymerizations of 3 and corresponding comonomers. It was elucidated from the results of block copolymerization that anionic polymerizability of 3 was higher than that of styrene and could be estimated to be the same level of 2-vinylpyridine. The oxazoline protecting moiety of poly(3) was completely hydrolyzed by treating with 3 N HCl in THF and subsequently with 15% NaOH (aq) in MeOH to give a well-defined poly(4-vinyl-α-methylcinnamic acid). The resulting poly(4-vinyl-α-methylcinnamic acid) could be quantitatively converted into its methyl ester by the reaction with diazomethane. The UV irradiation of poly(3) and poly(methyl 4-vinyl-α-methylcinnamate) at room temperature gave insoluble materials in moderate yields, indicating the photo-cross-linkable potential of these polymers.

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Section: Resultsmentioning

confidence: 99%

Section: Deprotection Of Poly(3)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Protection and Polymerization of Functional Monomers. 27. Synthesis of Well-Defined Poly(4-vinyl-α-methylcinnamic Acid) by Means of Anionic Living Polymerization of 2-[1-Methyl-2-(4-ethenylphenyl)ethenyl]-4,4-dimethyl-2-oxazoline

et al. 1998

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Some aspects of the reactivity of photo‐dimerizable esters grafted onto silicone main chain polymers

et al. 1991

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The reactivity under UV light and at room temperature of two series of photo-crosslinkable silicone polymers containing pendant cinnamic or a-cyano-8-styrylacrylic a) (CSA) esters was examined by means of UV spectroscopy. Two types of behaviour were evidenced on the basis of qualitative spectrum observation and quantitative measurements of reaction rates. Polymers with trans-cinnamic pendant groups were found to undergo during the first moments of 280 nm irradiation a fast photo-isomerization, preceding the dimerization process which takes place with a smaller rate. The mobility of the reactive cinnamic chromophores attached to the highly flexible silicone main chain leads to a collision-controlled process contrasting with the behaviour of the polymers containing more polar CSA esters. In this case, a clean dimerization with high reversibility suggests a matrix-controlled process. This is supported by kinetic data indicating a levelled reactivity for several polymers containing different amounts of CSA esters.

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Photophysics of a polyether containing tetramethylanthracene units

Bruss¹,

Sahyun²,

Schmidt³

et al. 1993

J. Polym. Sci. A Polym. Chem.

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PESA is a rigid rod polymer incorporating anthrylene units in its backbone. The photophysics of PESA in solution are representative of the isolated anthracene chromophore. In the solid state, strong interchain excimer emission is observed. Solid PESA undergoes efficient photocrosslinking which we assign to interchain anthracene dimer formation. Competitive quenching of photocrosslinking by diphenyliodonium hexafluorophosphate suggests that localized singlet excitation energy can migrate among chains until trapped by excimer formation. The excimer state is intermediate in photocrosslinking. © 1993 John Wiley & Sons, Inc.

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Reactant preordering in solid polymer matrices. 2. Effect of decoupling the reactant groups from the polymer backbone

Abstract: In blends of electron donor and electron acceptor substituted poly( vinyl cinnamates) a significant enhancement of photosensitivity over the mean of the sensitivities of the pure components was reported earlier.1

Cited by 7 publications

References 3 publications

Protection and Polymerization of Functional Monomers. 27. Synthesis of Well-Defined Poly(4-vinyl-α-methylcinnamic Acid) by Means of Anionic Living Polymerization of 2-[1-Methyl-2-(4-ethenylphenyl)ethenyl]-4,4-dimethyl-2-oxazoline

Protection and Polymerization of Functional Monomers. 27. Synthesis of Well-Defined Poly(4-vinyl-α-methylcinnamic Acid) by Means of Anionic Living Polymerization of 2-[1-Methyl-2-(4-ethenylphenyl)ethenyl]-4,4-dimethyl-2-oxazoline

Some aspects of the reactivity of photo‐dimerizable esters grafted onto silicone main chain polymers

Photophysics of a polyether containing tetramethylanthracene units

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