• Bulletin of the Korean Chemical Society
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• 제29권5호
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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.

• 폴리머
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• 제25권6호
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• pp.803-810
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• 2001

새로운 개념의 초분지형 비선형 광학 고분자 (PE-Azo/Hyper)를 AB$_2$형의 기능기를 가지는 단량체 4-[N,N-bis(hydroxyethyl)amino-4'-formyl]azobenzene (CHO-DOH)으로부터 Knoevenagel 축중합 반응을 통하여 합성하였다. 겔크로마토그래피상에서 폴리스티렌을 기준시료로 측정된 중합체의 무게평균분자량은 M$_{w}$ =61,800 (M$_{W}$ /M$_{n}$=1.86)이었고 중합체의 용해도를 조사한 결과 1-methyl-2-pyrrolidinone, N,N-dimethylformamide 등의 반양자성극성 유기용매에 잘 녹았으며 따라서 이들 용매를 이용하여 양질의 박막성형이 가능하였다. 또한 열시차 분석법으로 중합체 PE-Azo/Hvper의 열적 성질을 조사한 결과 녹는점이 관찰되지 않아 무정형으로 판명되었으며 유리 전이 온도는 $121^{\circ}C$로 나타났다. 폴링에 의하여 극성 배향된 중합체 박막의 2차 비선형 계수를 Nd : YAG 레이저 (1064 nm)를 이용하여 Maker fringe 방법으로 측정한 결과 $d_{33}$= 25.4 pm/V로 비교적 높은 값을 나타내어 초분지형 고분자에서도 극성배향이 이루어져 비선형성이 발현됨을 관찰할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제30권3호
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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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• 제22권7호
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• pp.753-757
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• 2001

1-(2'2'3'-Tricyano-3-carbomethoxycyclopropyl)-34-di-(2'-hydroxyethoxy)benzene, (4) was prepared by the reaction of bromomalononitrile with methyl 3,4-di-(2'-hydroxyethoxy)benzylidenecyanoacetate (3). Diol 4 was condensed with tolylene-2,4-diisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, and 1,6-hexamethylenediisocyanate to yield polyurethanes 5, 6, and 7 containing tricyanocyclopropane functionalities in the pendant group. The resulting polymers 5-7 were soluble in common organic solvents and the inherent viscosities were in the range of 0.25-0.30 dL/g. Polyurethanes 5-7 showed a thermal stability up to 300 $^{\circ}C$ in TGA thermograms. Solution-cast films showed Tg values in the range of 100-125 $^{\circ}C$ and piezoelectric coeffcients (d31) of the poled polymer films were 1.3-2.0 pC/N, which are acceptable for piezoelectric device applications.

• Bulletin of the Korean Chemical Society
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• 제20권5호
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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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• 제17권7호
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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.

• 한국광학회:학술대회논문집
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• 한국광학회 2003년도 하계학술발표회
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• pp.170-171
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• 2003

비선형 광학은 새로운 광원 개발, 광신호의 전광 고속 처리 같은 분야에 응용 가능하기 때문에 비선형 광학 특성이 좋은 물질의 개발과 정해진 특성을 극대화시킬 수 있는 여러 가지 위상정합 방법의 개발이 진행되고 있다. 우리는 특성이 클 뿐 아니라 만들기 쉽고 제조가격이 싸다는 장점을 갖는 유기 고분자에 대해 2차 비선형 광학 계수를 측정해 보았는데, 단순히 계수의 크기만을 측정하지 않고 계수의 부호도 직접 관찰하여 고분자를 이용한 준위상정합의 가능성을 확인하였다. (중략)

• Macromolecular Research
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• 제12권6호
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• pp.581-585
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• 2004

A copolymer P[OSA-MI] was synthesized by copolymerization of its corresponding monomers, N-phenyl maleimide (MI) and 2-octen-l-ylsuccinic anhydride (OSA). The polymer (poly[2-[1-(2,5-dioxo-l-phenylpyrroli­din-3-ylmethyl)heptyl]-succinic acid 4-(2-$\{$ethyl-[4-(4-nitrophen-ylazo)phenyl]amino$\}$ethyl)ester]) P[DR1MA-MI] was obtained from the reaction of P[OSA-MI] with 2-[4-(4-nitrophenylazo)-N-ethylphenylamino] ethanol (DR1). A stable monolayer of P[DRIMA-MI] was formed by spreading the solution of the polymer in chloroform. In Y-type Langmuir-Blodgett (LB) films prepared using this Langmuir-Blodgett method, the second harmonic waves generated from adjacent mono layers canceled each other out. In X-and Z-type LB films, the second harmonic intensity increased upon increasing the number of monolayers, but this increase was somewhat smaller than predicted by the square law. This phenomenon is due to defects or imperfect alignment of the dipoles in the LB film. The generation of second harmonic waves from Y-type LB films having an even number of mono layers supports this argument. The degree of imperfection seemed to increase as the number of layers increased. The second-order nonlinear optical properties of spin-cast films of these polymers were also measured. The largest second harmonic coefficient of the poled P[DRIMA-MI] film coated on a glass plate was 19 pm/V.

• 한국광학회지
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• 제13권4호
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• pp.356-362
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• 2002

비선형광학(NLO) 곁가지형 고분자계 N-(4-nitrophenul)-(L)-prolinol-poly (p-phenylene terephthalates)로 제작된 박막의 분자 배향거동을 제2 고조파발생(SHG)의 비선형광응답을 사용하여 연구하였다. 새로운 펄스 corona 배향 방법으로 NLO 발색단과 고분자 줄기를 비중심대칭 구조로 배향시켜 SHG 신호를 발생시켰다. 유리전이온도 70$^{\circ}C$를 중심으로 25$^{\circ}C$에서 80$^{\circ}C$까지 온도영역에서 반복율을 0.5 ㎑에서 10 ㎑까지 변화시키면서 인가한 펄스 고압으로 corona 배향한 결과로 곁가지 발색단과 고분자 주사슬이 스스로 재 정렬하여 형성한 구역구조를 원자간력 현미경(AFM)으로 관측하였다. 펄스 corona 전압 인가로 NLO 발색단 배향도가 증가되고, 동시에 고분자박막의 가시적손상을 획기적으로 줄이면서 SHG 신호가 증대되었으며 배향 후 이완거동도 개선되었다. 이 새로운 펄스 corona 배향 실험으로 NLO 발색단 및 고분자 주사슬이 배향과정에서 비등방으로 재배열하는 현상을 in situ로 입증할 수 있었다.

• 한국재료학회지
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• 제34권1호
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• pp.34-43
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• 2024

New piezoelectric and triboelectric materials for energy harvesting are being widely researched to reduce their processing cost and complexity and to improve their energy conversion efficiency. In this study, BaTiO₃ films of various thickness were deposited on Ni foams by R.F. magnetron sputtering to study the piezoelectric and triboelectric properties of the porous spongy structure materials. Then piezoelectric nanogenerators (PENGs) were prepared with spongy structured BaTiO₃ and PDMS composite. The output performance exhibited a positive dependence on the thickness of the BaTiO₃ film, pushing load, and poling. The PENG output voltage and current were 4.4 V and 0.453 ㎂ at an applied stress of 120 N when poled with a 300 kV/cm electric field. The electrical properties of the fabricated PENG were stable even after 5,000 cycles of durability testing. The triboelectric nanogenerators (TENGs) were fabricated using spongy structured BaTiO₃ and various polymer films as dielectrics and operated in a vertical contact separation mode. The maximum peak to peak voltage and current of the composite film-based triboelectric nanogenerator were 63.2 V and 6 ㎂, respectively. This study offers new insights into the design and fabrication of high output nanogenerators using spongy structured materials.