[논문]사슬연장제로서 3관능성 공단량체가 도입된 폴리(파라-페닐렌 벤조비스옥사졸) 섬유의 제조와 특성분석

정영규; 이장혁; 민병길; 윤관한

doi:10.12772/tse.2013.50.193

사슬연장제로서 3관능성 공단량체가 도입된 폴리(파라-페닐렌 벤조비스옥사졸) 섬유의 제조와 특성분석
Preparation and Characterization of Fibers Based on Poly(p-Phenylene Benzobisoxazole)s Containing Trifunctional Moiety as Chain Extender

한국섬유공학회지 = Textile science and engineering, v.50 no.3, 2013년, pp.193 - 199

정영규 (충남대학교 유기소재섬유시스템공학과) , 이장혁 (금오공과대학교 소재디자인공학과) , 민병길 (금오공과대학교 소재디자인공학과) , 윤관한 (금오공과대학교 고분자공학과)

Abstract ▼ AI-Helper

A series of poly(p-phenylene benzobisoxazole) (PBO)-based copolymers containing a trifunctional moiety in their backbones were prepared via polymerization of 4,6-diaminoresorcinol dihydrochloride (DAR) with terephthaloyl chloride (TPC) and 1,3,5-benzenetricarbonyl trichloride (BTC) in poly(phosphoric acid) (PPA). The concentration of trifunctional BTC comonomer was controlled during polymerization to be 0.0-2.0 mol% of difunctional TPC concentration. The inherent viscosity and associated average molecular weight of PBO copolymers with different BTC contents were evaluated by using solution viscometry and the Mark-Houwink equation, respectively. In addition, single fibers based on neat PBO and its copolymers were prepared by in situ dry-jet wet spinning of anisotropic liquid crystalline polymerization products in PPA dopes. The molecular structure and morphology of the as-spun fibers were determined. The effects of BTC content on the thermal stability and tensile mechanical properties of the as-spun fibers were also investigated.

주제어

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제안 방법

The average molecular weight of the neat PBO and its copolymers with different BTC contents was evaluated by measuring their solution viscosities at 30 ^oC using Ubbelohde viscometer. It has been reported that the solution properties of PBO in MSA at 30 ^oC can be expressed as the following Mark-Houwink equation [1,3,5,24]:

성능/효과

2 fiber, T_5% and T_max values were 647 and 668 ^oC, which are 20 and 5 ^oC higher than those of neat PBO fiber, respectively. For the PBO-BTC0.5 fiber, more highly improved thermal degradation performances of T_5%~651 ^oC and T_max~673 ^oC, which are 24 and 10 ^oC higher than those of neat PBO fiber, respective, were attained. Accordingly, it is envisaged that the noticeably improved thermal stability of the as-spun fibers under nitrogen gas condition originates from the increased molecular weight of PBO copolymers by incorporating the trifunctional BTC comonomer as a chain extender.
0, the initial modulus was higher than that of the neat PBO fiber. From these results, it is valid to claim that the as-spun fibers of PBO copolymers with 0.2~0.7 mol% BTC have enhanced tensile mechanical performance, compared with the neat PBO fiber, which is expected to be caused by the increased molecular weight of PBO copolymers owing to the introduction of the aromatic trifunctional BTC comonomer as chain extender. On the other hand, it should be mentioned that commercially available PBO fibers have high tenacity above 5 GPa, which is far higher than those of the as-spun fibers prepared in this study.
The resulting inherent viscosity and associated average molecular weight of neat PBO and its copolymers were summarized in Table 2. It was found that the average molecular weight of PBO copolymers was somewhat higher than that of neat PBO, which indicates that trifunctional BTC comomomer contribute efficiently to extend the chain length of PBO during the polymerization.
In addition, a broad band at 3300~3700 cm^-1, which is associated with the stretching vibration of hydroxyl and amine groups, was detected for all PBO copolymers, excepted for neat PBO. These results indicate that carbonyl groups of trifunctional BTC in PHA backbones were only partially participated in the cyclization to form the oxazole groups of PBO backbones. Therefore, PBO copolymers including trifunctional BTC comonomer synthesized in this study are expected to have a molecular structure as shown in Figure 4(B).

후속연구

On the other hand, it should be mentioned that commercially available PBO fibers have high tenacity above 5 GPa, which is far higher than those of the as-spun fibers prepared in this study. The large difference in tensile mechanical properties between commercial PBO fibers (Zylon^TM) and as-spun fibers in this study is expected to stem from the fact that commercial PBO fibers are usually manufactured through hot drawing and/or heat treatment process in order to enhance the tensile mechanical performance. Accordingly, the effects of post-drawing and/or heat treatment on structures (crystallinity and chain orientation) and mechanical properties of PBO copolymer fibers containing trifunctional BTC units are being investigated and the results will be reported.

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