• Bulletin of the Korean Chemical Society
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• v.18 no.2
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• pp.198-203
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• 1997

Two different carbazolylnitrostilbene chromophores with second-order nonlinear optical (NLO) activity were newly synthesized by the reaction of 9-(2-hydroxyethyl)-9H-carbazol-3-carbaldehyde with 4-nitrophenylacetonitrile or 4-nitrophenylacetic acid. The NLO monomers were obtained by reaction of these chromophores with methacryloyl chloride. The side-chain nonlinear optical polymers were synthesized by the copolymerization of NLO monomer with methylmethacrylate using a free radical initiator. The chemical structures of the polymers were identified by spectroscopic means and the polymer properties such as molecular weight, Tg, solubility, UV-visible absorption, and second-harmonic generation (SHG) coefficients were investigated.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.704-709
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• 1998

Non-linear optical polymer based on poly (${\alpha}$-methylstyrene-co-maleic anhydride) (MSMA) substrate polymer was prepared by polymer reaction method and its thermal and electro-optic properties were examined. In the polymer reaction between MSMA substrate polymer and 2-[4-(4-nitrophenylazo)-N-ethylphenylamino]ethanol (DR1) chromophore, the degree of substitution of DR1 into MSMA was higher with the 4-dimethylaminopyridine (DMAP) as catalyst and 3-dicyclohexyl carbodiimide (DCC) as dehydrating agent (sample, MSMA-DC) than the one with just 4-dimethylaminopyridine as catalyst (sample, MSMA-D). The synthesized NLO polymer (MSMA-DC) exhibited electro-optic coefficient of 18 pm/V (632.8 nm) and glass transition temperature ($T_g$) of about $175^{\circ}C$.

• Macromolecular Research
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• v.8 no.3
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• pp.137-141
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• 2000

3,4-Di-(2'-hydroxyethoxy)-4-nitrostilbene (2) was prepared by the reaction of 2-iodoethanol with 3,4-dihydroxy-4-nitrostilbene (1). Diol 2 was condensed with 2,4-toluenediisocyanate ,3,3-dimethoxy-4,4'-biphenylenediisocyanate , and 1,6-hexamethylenediisocyanate to yield polyurethanes 3, 4, and 5 containing the NLO-chromophore. Polymers 3-5 were soluble in common organic solvents such as acetone and DMSO. The glass transition temperatures(T$\sub$g/) of the resulting polymers 3-5 were obseved around 100-114$^{\circ}C$. Electrooptic coefficients (r$\sub$33/) of the poled polymer films were in the range of 18-25 pm/V at 633 nm. Polymers 3-5 began to decompose around 250$^{\circ}C$ in TGA thermograms.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1509-1514
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• 2010

Methyl 3,4-di-(2'-hydroxyethoxy)benzylidenecyanoacetate (3) was prepared and condensed with terephthaloyl chloride to yield novel Y-type polyester (4) containing 3,4-dioxybenzylidenecyanoacetate groups as NLO-chromophores, which constituted parts of the polymer main chains. The resulting polymer 4 is soluble in common organic solvents such as acetone and N,N-dimethylformamide. Polymer 4 shows thermal stability up to $280^{\circ}C$ in thermogravimetric analysis with glass-transition temperature obtained from differential scanning calorimetry near $105^{\circ}C$. The second harmonic generation (SHG) coefficient ($d_{33}$) of poled polymer films at the 1064 nm fundamental wavelength is around 2.42 pm/V. The dipole alignment exhibits high thermal stability up to near $T_g$, and there is no SHG decay below $100^{\circ}C$ due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.661-666
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• 2009

1-{2,4-Di-(2-hydroxyethoxy)phenyl}-2-(2-thienyl)ethene (5) was prepared and condensed with terephthaloyl chloride to yield polyester (6). Polymer 6 was reacted with tetracyanoethylene to give novel Y-type polyester (7) containing 1-(2,4-dioxyethoxy)phenyl-2-{5-(2,2,3-tricyanovinyl)-2-thienyl)}ethenyl groups as NLO-chromophores, which are parts the polymer backbones. Polymer 7 is soluble in common organic solvents such as acetone and N,N-dimethylformamide. It showed thermal stability up to 300 ${^{\circ}C}$ in thermogravimetric analysis with glasstransition temperature obtained from differential scanning calorimetry near 134 ${^{\circ}C}$. The second harmonic generation (SHG) coefficient ($d_33$) of poled polymer film at the 1560 nm fundamental wavelength was around 6.74 x $10^{-9}$ esu. The dipole alignment exhibited high thermal stability up to the glass-transition temperature ($Tg$), and there was no SHG decay below 135 ${^{\circ}C}$ because of the partial main-chain character of polymer structure, which is acceptable for NLO device applications.

• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.242-245
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• 2010

• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3361-3366
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• 2011

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 $240^{\circ}C$ in thermogravimetric analysis with glass-transition temperature ($T_g$) obtained from differential scanning calorimetry near $116^{\circ}C$. The second harmonic generation (SHG) coefficient ($d_{33}$) of poled polymer film at the 1064 nm fundamental wavelength is around $4.63{\times}10^{-9}$ esu. The dipole alignment exhibits a thermal stability even at $4^{\circ}C$ higher than $T_g$, and there is no SHG decay below $120^{\circ}C$ due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.933-938
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• 2008

2,4-Di-(2'-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and polymerized with terephthaloyl chloride and adipoyl chloride to yield novel Y-type polyesters 4 and 5 containing dioxybenzylidenemalononitrile groups as NLO-chromophores, which constituted parts of the polymer backbone. The resulting polymers 4 and 5 are soluble in common organic solvents such as acetone and N,N-dimethylformamide. Polymers 4 and 5 showed thermal stability up to 300 ${^{\circ}C}$ in thermogravimetric analysis with glass-transition temperatures obtained from differential scanning calorimetry in the range 83-94 ${^{\circ}C}$. The second harmonic generation (SHG) coefficients ($d_{33}$) of poled polymer films at the 1064 nm fundamental wavelength were around $6.48\;{\times}\;10^{-9}$ esu. The dipole alignment exhibited high thermal stability even at 10 ${^{\circ}C}$ higher than $T_g$ and no significant SHG decay was observed below 105 ${^{\circ}C}$ partially due to the main-chain character of polymer structure, which is acceptable for NLO device applications.

• Bulletin of the Korean Chemical Society
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• v.20 no.5
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• pp.567-572
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• 1999

5-Nitro-2-(2'-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 5-nitro-2-(2'-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3-nitro-4-(2'-vinyloxyethoxy)benzylidenemalononitrile (4a), methyl 3-nitro-4-(2'-vinyloxyethoxy)benzylidenecyanoacetate (4b), 2-nitro-5-(2'-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl 2-nitro-5-(2'-vinyloxyetboxy)benzylidenecyanoacetate (6b) were prepared by the condensation of 5-nitro-2-(2'-vinyloxyethoxy)benzaldehyde (1), 3-nitro-4-(2'-vinyloxyethoxy)benzaldehyde (3), and 2-nitro-5-(2'-vinyloxyethoxy)benzaldehyde (5) with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2a-b, 4a-b, and 6a-b were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ethers) 7-9 having oxynitrobenzylidenemalononitrile and oxynitrobenzylidenecyanoacetate, which is effective chromophore for second-order nonlinear optical applications. Polymers 7-9 were soluble in common organic solvents such as acetone and DMSO. Tg values of the resulting polymers were in the range of 67-83 ℃. Electrooptic coefficient (r33) of the poled polymer films were in the range of 15-27 pm/V at 633 nm. Polymers 7-9 showed a thermal stability up to 300 ℃ in TGA thermograms, which is acceptable for NLO device applications.

• Bulletin of the Korean Chemical Society
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• v.17 no.7
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• pp.607-612
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• 1996

A series of new NLO-active poly(4-nitrophenylallylamine) derivatives was synthesized by the nucleophilic substitution reaction of several substituted 4-nitrohalobenzenes and poly(allylamine hydrochloride). All polymers obtained were amorphous and their glass transition temperatures (Tg) were observed around 148-160 ℃. For each of these polymers, their specific Tg values were dependent on characteristic electronic structures. UV-visible absorption spectra showed maximum absorption intensity at 355-393 nm for π-π* transition of alkylaminonitrophenyl groups. The χ(2)value of poly(4-nitrophenylallylamine), as determined by the second harmonic generation at 1064 nm, for a thin polymer film poled at an elevated temperature, was 1.4x10-8esu. The third-order NLO properties of poly(4-nitrophenylallylamine) derivatives were evaluated through measurement of degenerate four-wave mixing technique and χ(3) coefficient in the range of 2.7~3.2x10-12 esu at 602 nm was found with 400 fs laser pulses.