나일론은 내마모성, 전기절연성, 흡습성이 우수한 고분자로 엔지니어링 플라스틱 또는 섬유로써 사용되고 있다. 다양한 나일론 소재 중에서도 대표적인 소재는 나일론 6과 나일론 66이며, 우수한 물성으로 인해 수요가 많지만 석유 기반의 합성 나일론으로 여러 가지 문제점을 가지고 있다. 인구의 증가와 산업의 발전은 석유자원에 의존도가 높을뿐더러 석유자원의 한정량으로 인한 자원고갈의 문제 그리고 사용상 발생되는 환경적인 문제에 직면해있다. 석유 기반 나일론 66을 대체하고자 나일론 66과 유사한 물성을 가지고 있는 식물 자원 기반 바이오매스 소재로 나일론 56을 제조하고자 한다. 바이오매스는 환경 친화적이며 옥수수, 사탕수수, 목질계 식물자원, 팜, 해조류 등과 같이 재생 가능한 자원으로 석유자원을 대체 할 수 있는 바이오기반 첨단 신소재이며, 중요한 미래 자원으로 부각되고 있다. 나일론의 중합 방법에는 Condensation polymerization, hydrolysis polymerization, addition polymerization, interfacial polymerization 등이 있으며 나일론 66은 Diamine과 Diacid의 축합중합을 이용하여 얻을 수 있다. 본 연구에서는 바이오매스 기반 1,5-diaminopentane (Cadaverine)과 Adipic acid를 2 단계 고상중합(Solid-state polymerization)을 사용하여 바이오매스 기반 나일론 56을 제조 하였다. 중합공정 조건을 최적화하여 제조된 나일론 56은 기존 나일론 66의 대체품인 시제품 Cathay Biotech의Terryl™ PA 56과 비교실험을 진행하였다. 바이오매스 기반 나일론의 바이오 함량은 ASTM D6866-21 Method B(AMS)로 측정하였으며, 화학구조 분석을 하기 위해 Fourier Transform Infrared Spectroscopy를 측정하였다. 나일론의 결정구조와 결정화도 확인을 위하여 X-ray Diffraction과 Polarized Light Microscope를 사용하였다. 가공 및 흐름성을 연구하기 위해 Melt Indexer를 사용하여 용융지수를 측정 및 비교하였다. 중합물은 Gel Permeation Chromatography를 통해 분자량을 확인하였다. 물성 측정을 위해 Hot-press를 사용하여 필름을 제작하였고, Dynamic Mechanical Analyzer를 사용하여 나일론의 점탄성 거동을 분석하였다. Differential Scanning Calorimetry을 사용하여 나일론 56의 열적 특성을 확인하였으며, Thermogravimetric Analysis로 열안정성을 확인하였다. 인장강도는 Universal Testing Machine을 사용하여 ASTM D882 규격으로 측정하였으며, 물성을 비교하였다. 나일론 56의 유변특성을 확인하기 위해서 Rheometer를 사용하여 주파수에 따른 복소점도를 측정하였으며 바이오매스로 부터 중합 된 나일론 56이 가지는 특성과 대체 가능성을 확인하고자 하였다.
Nylon is polymer that is used to make technical plastics or fibers and has good abrasion resistance, electrical insulation, and hydroscopic properties. Representative nylon compounds include nylon 6 and nylon 66, which are popular due to their good physical qualities but have a number of drawbacks because they are petroleum-based synthetic nylon. In addition to being heavily dependent on petroleum resources, population expansion and industrial development both face the issue of resource depletion since there are only so many of these resources available and because using them causes environmental issues. Nylon 56 is designed to be produced as a biomass material based on plant resources that has qualities similar to nylon 66 in order to replace the petroleum-based nylon 66. Biomass is a resource that is environmentally beneficial and sustainable, including corn, sugar cane, woody plant materials, palm, and seaweed. It is a bio-based, high-tech substance that can replace petroleum resources and is gaining importance as a resource for the future.Condensation polymerization of diamine and diacid produces nylon 66, while other techniques of polymerizing nylon include hydrolysis polymerization, addition polymerization, and interfacial polymerization. In this study, 1,5-diaminopentane (Cadaverine) and adipic acid were used to create nylon 56 prepared from biomass by a two-step solid-state polymerization process. The polymerization method was optimized to create nylon 56, which was compared to Terryl™ PA 56, a substitute for nylon 66 produced by Cathay Biotech.By using ASTM D6866-21 Method B (AMS), the bio content of biomass-based nylon was evaluated, and the chemical structure was examined using Fourier Transform Infrared Spectroscopy. To evaluate processability and flowability, the melt flow index was calculated and compared using Melt Indexer. Gel Permeation Chromatography was used to establish the polymer''s molecular weight. A film was made using a hot press to assess the physical parameters, and nylon''s viscoelastic behavior was examined using a dynamic mechanical analyzer. Differential scanning calorimetry was used to establish nylon 56''s thermal characteristics, and thermogravimetric analysis was used to confirm nylon 56''s thermal stability. The crystal structure and crystallinity of nylon were confirmed using X-ray diffraction and a Polarized Light Microscope. Physical parameters were compared after tensile strength was assessed using a universal testing equipment in accordance with the ASTM D882 standard. A rheometer was used to evaluate the complex viscosity in accordance with frequency, and the features and replacement potential of biomass-based nylon 56 were examined in order to confirm the rheological properties of nylon 56.
차 례그림 차례 ······························ ⅲ표 차폐 ······························· ⅳ국문 요약 ······························ ⅴ제 1장 서론 ····························· 1제 2장 이론적 배경 ·························· 32.1 나일론 특징과 종류 ······················· 32.2 바이오매스 카다베린 연구 동향 ·················· 72.3 바이오플라스틱 산업 동향 ···················· 8제 3장 실험 방법 ··························· 103.1 실험재료 ···························· 103.2 나일론 56 제조 실험 ······················· 133.2.1 나일론 56 salt 제조······················ 133.2.2 고상중합을 이용한 나일론 중합················· 143.3 나일론 56 물성평가 방법 ····················· 16제 4장 실험 결과 및 고찰 ······················· 174.1 나일론 salt 제조 최적화 ····················· 174.2 가압 및 감압을 이용한 2단계 고상중합 ·············· 194.2.1 고상중합 조건 최적화 ····················· 194.3 바이오매스 기반 나일론 56 ···················· 224.3.1 고상중합을 사용한 바이오매스 기반 나일론 56·········· 224.3.2 바이오매스 함량 평가 ····················· 234.4 Hot-press를 사용한 필름 제조 ·················· 264.5 구조 분석 평가·························· 284.5.1 FT-IR을 통한 분광 분석 ···················· 284.5.2 XRD를 이용한 구조 분석 ···················· 314.5.3 POM을 이용한 표면의 결정영역 분석··············· 344.6 물성 평가 ···························· 364.6.1 용융지수(Melt Index) 측정 ·················· 364.6.2 분자량(GPC) 측정 ······················· 384.6.3 압력과 분자량의 관계 ····················· 394.7 유변특성 분석 ·························· 424.7.1 고유점도 측정························· 424.7.2 복소점도 측정························· 444.8 항산화제 첨가효과 ························ 464.9 열분석 및 평가·························· 484.9.1 유리전이온도 측정······················· 484.9.2 열적특성 및 결정화도 측정··················· 514.9.3 열안정성 평가························· 544.10 기계적 물성 분석 ························ 564.10.1 인장강도 측정 ························ 564.11 적용분야 ···························· 584.11.1 전도성 필라멘트 제조와 응용 ················· 58제 5장 결론 ····························· 61참고문헌 ······························· 62영문요약 ······························· 66