Novel Types of Polyesters Containing Second-Order Nonlinear Optically Active Chromophores with High Density

Nemoto, Nobukatsu; Miyata, Fusae; Yu, Na; Abe, Jiro; Hasegawa, Makoto; Shirai, Yasuo

doi:10.1021/ma951032n

Cited by 53 publications

(32 citation statements)

References 34 publications

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“…acid into dimethyl 5-hydroxyisophthalate 22 and dimethyl 5-allyloxyisophthalate. 21 The target compound was obtained by hydrolysis of methyl ester moieties in dimethyl 5-allyloxyisophthalate.…”

Section: Methodsmentioning

confidence: 99%

Photocrosslinking System Using Highly-Functionalized Epoxy Crosslinkers Having Degradable Property

Okamura

Shin

Shirai

2006

Polym J

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ABSTRACT:Multifunctional crosslinkers having two, three, four and six functionalities were synthesized using a convergent method and were applied to a photocrosslinking system having thermally degradable properties. The multifunctional crosslinkers contained epoxy units and tertiary ester linkages. When the blended films of epoxides/poly-(p-vinylphenol) with a photoacid generator were irradiated and followed by baking at relatively lower temperatures (<100 C), the films became insoluble in solvents. Heating conditions strongly affected the insoluble fraction of the blends. Insoluble fraction of the blended films increased with the number of the epoxy unit of a molecule. The crosslinked films became soluble after prolonged bake at relatively higher treatments (>120 C). The reaction pathway of the blended system was studied by in situ FT-IR measurements. [doi:10.1295/polymj.PJ2006007] KEY WORDS Photocrosslinking / Decrosslinking / Thermal Degradation / Multifunctional / Epoxide / Photoacid Generator / Reworkable resins which are easily removable after use are getting more important in terms of environmental aspects. In this point of view, some thermosets which are thermally or chemically degradable under a given condition have been extensively studied. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] We have previously reported the photocurable epoxy resins which can be re-dissolved in solvents by thermal treatments.12-18 The resins consist of epoxy moieties and tertiary ester linkages. Epoxy moieties acted as photocrosslinkable units by photo-induced acid catalyzed polymerization. Tertiary ester linkages were thermally cleavable units by heating to produce carboxylic acids and alkenes. The network was destroyed by the scission of tertiary ester linkages. In practical point of view, reactivity, sensitivity, thermal or chemical stability, and re-dissolution property of the polymers must be improved. Multifunctional epoxides are expected to show higher reactivity and sensitivity compared to mono-and difunctional epoxides. We have reported that trifunctional epoxide/poly(p-vinylphenol) (PVP) blended system works as a reworkable resin and the sensitivity of the system is higher than the difunctional epoxide/PVP blended system. 18In this paper, we report the synthesis of novel multifunctional epoxides having tertiary ester linkages. The multifunctional epoxides were synthesized by a convergent technique, where two or three molecules having both epoxy unit and tertiary ester unit in a molecule were linked together via another molecule. The multifunctional epoxides were used as crosslinkers of the system that has photocrosslinking and de-crosslinking properties. The system is a blend of PVP, the crosslinker, and a photoacid generator. The concept of the present system is shown in Figure 1. On irradiation, network formation occurs by the photoinducedacid catalyzed reaction of the epoxy moieties of the crosslinker and PVP. Thermal treatment of the crosslinked polymers induces the cleavage of the tertiary est...

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Section: Methodsmentioning

confidence: 99%

Photocrosslinking System Using Highly-Functionalized Epoxy Crosslinkers Having Degradable Property

Okamura

Shin

Shirai

2006

Polym J

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“…This shows that in all respects these PEs are suitable for NLO studies. Nemoto et al [142] prepared new types of PEs containing containing second-order NLO active chromophores with high density by the condensation polymerization between the isophthalic acid derivatives and the N-substituted diethanolamines using TPP and diethyl azodicarboxylate as the condensing agents in DMSO or NMP. The obtained amorphous PEs exhibited good solubility in common organic solvents and provided optical-quality films by spin-coating.…”

Section: Polyestersmentioning

confidence: 99%

Advances in synthetic optically active condensation polymers - A review

Mallakpour

Zadehnazari²,

Iran³

2011

Express Polym. Lett.

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Abstract. The study of optically active polymers is a very active research field, and these materials have exhibited a number of interesting properties. Much of the attention in chiral polymers results from the potential of these materials for several specialized utilizations that are chiral matrices for asymmetric synthesis, chiral stationary phases for the separation of racemic mixtures, synthetic molecular receptors and chiral liquid crystals for ferroelectric and nonlinear optical applications. Recently, highly efficient methodologies and catalysts have been developed to synthesize various kinds of optically active compounds. Some of them can be applied to chiral polymer synthesis. In a few synthetic approaches for optically active polymers, chiral monomer polymerization has essential advantages in applicability of monomer, apart from both asymmetric polymerization of achiral or prochiral monomers and enantioselective polymerization of a racemic monomer mixture. The following are the up to date successful approaches to the chiral synthetic polymers by condensation polymerization reaction of chiral monomers.

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“…In the developments of NLO polymers for electro-optic device applications, stabilization of electrically induced dipole alignment is one of important considerations; in this context, two approaches to minimize the randomization have been proposed, namely the use of cross-linked systems [5][6][7][8] and the utilization of polymers with high glass transition temperature (T g ) such as polyimides. [9][10][11][12][13][14] Various polyesters with NLO chromophores in the main chain 15,16 or side chain 17,18 have been prepared and their NLO properties studied. Polyesters with amino-sulfone azobenzene chromophores in the main chain generate strong and stable reversible birefringence.…”

Section: Introductionmentioning

confidence: 99%

“…16 Polyesters containing cyanophenylazoaniline moiety in the side chain show good temporal stability of second-order nonlinearity. 17 Main-chain NLO polymers usually have good thermal stability of dipole alignments, but they often do not dissolve in organic solvents, and their intractability make them unusable to fabricate stable films. Side-chain NLO polymers have the advantages such as good solubility, homogeneity and high loading level of NLO chromophores, but they often suffer from poor stability of dipole alignments at high temperatures.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of Novel Y-type Nonlinear Optical Polyester Containing Dioxynitroazobenzene Group with Enhanced Thermal Stability of Dipole Alignment

Kim¹,

Cho²,

Song³

et al. 2011

Bulletin of the Korean Chemical Society

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New Y-type polyester (3) containing nitrophenylazoresorcinoxy groups as NLO chromophores, which are components of the polymer backbone, was prepared and characterized. Polyester 3 is soluble in common organic solvents such as N,N-dimethylformamide and acetone. It shows a thermal stability up to 240 o C in thermogravimetric analysis with glass-transition temperature (T g ) obtained from differential scanning calorimetry near 116 o C. The second harmonic generation (SHG) coefficient (d 33 ) of poled polymer film at the 1064 nm fundamental wavelength is around 4.63 × 10 −9 esu. The dipole alignment exhibits a thermal stability even at 4 o C higher than T g , and there is no SHG decay below 120 o C due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.

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Novel Types of Polyesters Containing Second-Order Nonlinear Optically Active Chromophores with High Density

Cited by 53 publications

References 34 publications

Photocrosslinking System Using Highly-Functionalized Epoxy Crosslinkers Having Degradable Property

Photocrosslinking System Using Highly-Functionalized Epoxy Crosslinkers Having Degradable Property

Advances in synthetic optically active condensation polymers - A review

Synthesis and Properties of Novel Y-type Nonlinear Optical Polyester Containing Dioxynitroazobenzene Group with Enhanced Thermal Stability of Dipole Alignment

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