In order to drive in fluoro-containing aromatic polyamide 4,4'-diamino biphenyl (DABP), 2,2'-dimethyl benzidine dihydrochloride (DBHC), and 2,2'-bis( trifluoromethyl) benzidine (PFMB), respectively, were synthesized as diamine components, and 4,4'-(hexafluoroisopropylidene)bis(benzoyl chloride) (HPBC) was synthesized as diacid chloride. Aromatic polyamides having fluoro moieties in the main chain were prepared by polycondensation reaction of these monomers, and isotropic films were made from them. The structure of these monomers and polymers were determined by FT-IR, ¹H-NMR and elemental analyses. Their thermal properties were characterized by DSC and TGA. The polymers had inherent viscosities of 1.2 1.7 dL/g, and T_d was over 450℃. In order to orient molecular chain of films prepared, high temperature zone drawing method was applied at 350℃. The draw ratio up to 4.2 was achieved by drawing PFMB/HPBC film with drawing stress of 100 MPa. Birefringence of the drawn film showed the value of 0.019 ∼ 0.036. Tensile propertoes of the film increased with an increase in the draw ratio. Also, the amximum tensile strength and modulus of film up to 0.35 GPa and 8 GPa, respectively, were achieved by drawing PFMB/HPBC film. Crystal orientation index of the drawing film was below 0.9 as determined by wide angle X-ray diffraction analysis. On the other hand, maximum birefringence of over 0.035 was observed. From these facts, it was identified that the effect of amorphous orientation is more predominant than that of crystal orientation.

불소계 방향족 폴리아미드 중합체를 얻기 위하여 디아민 단량체인 4,4'-diamino biphenyl (DABP), 2,2'-dimethyl benzidine dihydrochloride (DBHC) 및 2,2'-bis(trifluoromethyl) benzidine (PFMB)을 합성하였으며 염화이산물인 4,4'-(hexafluoroisopropylidene)bis (benzoylchloride) (HPBC)를 합성하였다. 이들 단량체들의 축합중합으로 주사슬에 불소를 함유하는 방향족 폴리아미드 중합체를 합성하였으며 그들로부터 등방성 필름을 제조하였다. 합성된 단량체 및 중합체의 구조를 FT-IR, ¹H-NMR 및 원소분석으로 확인하였으며 열적성질은 DSC 및 TGA로 측정하였다. 이들 중합체들의 용액 점성도는 1.2∼1.7dL/g 였으며 분해온도는 약 450℃ 이상으로 높았다. 제조한 필름들의 분자사슬을 효과적으로 배향시키기 위해 고온 띠연신 방법으로 350℃에서 1회 띠연신하여, PFMB/HPBC 필름으로부터 연신하중 100MPa에서 최대연신비 4.2를 얻었다. 연신된 필름들의 복굴절은 0.019∼0.036의 값을 나타내었으며, 인장성질은 연신비의 증가에 따라 증가하였고 PFMB/HPBC 필름을 연신함에 의해서 최대 인장강도 0.35Gpa 및 최대 인장탄성율 8GPa인 연신필름이 얻어졌다. 광각 X-선 회절분석 결과 최대 연신된 필름의 결정배향지수는 0.9 이하였다. 반면에 최대 복굴절 값은 0.035 이상의 큰 값을 나타냄으로써 이 필름들의 배향 거동은 비결정 배향이 우세함을 확인하였다.

Keywords: fluoro-containing aromatic polyamide film; high-temperature zone drawing; amorphous orientation