초록 ▼

IV. 연구개발결과
1. 민수부분
불순물 제어와 부반응 제어 그리고 재현성을 확보하기 위해 각각 개발된 장치들을 이용 하여 분자량 분포도 1.1 이하를 가지는 폴리 스타이렌 호모폴리머, 폴리 메틸메타아크릴레이트 호모 폴리머 그리고 폴리 2-비닐 피리딘 호모폴리머 등, 총 3종의 단일중합체를 생산 하였다. 또한 분자량 분포도 1.1 이하를 가지는 폴리 스타이벤 블록 폴리 메틸메타아크릴 레이트, 폴리 스타이렌 블록 폴리 2-비닐 피리딘 블록 코 폴리머 등, 총 2종의 디블록 공중합체를 생산하였고 생산 규모는 20L 상압 중합

IV. 연구개발결과
1. 민수부분
불순물 제어와 부반응 제어 그리고 재현성을 확보하기 위해 각각 개발된 장치들을 이용 하여 분자량 분포도 1.1 이하를 가지는 폴리 스타이렌 호모폴리머, 폴리 메틸메타아크릴레이트 호모 폴리머 그리고 폴리 2-비닐 피리딘 호모폴리머 등, 총 3종의 단일중합체를 생산 하였다. 또한 분자량 분포도 1.1 이하를 가지는 폴리 스타이벤 블록 폴리 메틸메타아크릴 레이트, 폴리 스타이렌 블록 폴리 2-비닐 피리딘 블록 코 폴리머 등, 총 2종의 디블록 공중합체를 생산하였고 생산 규모는 20L 상압 중합 반응기를 이용 할 경우 1회당 1Kg 이상이 며 반연속식 반응기를 이용할 경우 1회당 600g이상이다.

2. 군수부분
고에너지화 아크릴레이트 단량체인 2, 2-dinitropropyl acrylate(DNPA)와 3-azidopropyl acrylate(AzPA)를 설계합성하고, RAFT 리빙 라디칼 중합법을 이용하여 polyacrylate-b-PEO 블록공중합체형 고분자량 고에너지 결합제와 polyacrylate계 고에너지화 polyol 합성 한 후 우레탄 반응에 의하여 맞춤형 고에너지화 폴리우레탄 결합제 제조 방법 확립하였다.

(출처 : 요약문 5p)

Abstract ▼

Poly(styrene-b-methyl methacrylate) block copolymer and poly(styrene-b-2-vinyl pyridine) block copolymer has been widely researched due to their rheological behavior. Especially nanopattering technique is big issue in electric device application field by using these block copolymer which has very na

Poly(styrene-b-methyl methacrylate) block copolymer and poly(styrene-b-2-vinyl pyridine) block copolymer has been widely researched due to their rheological behavior. Especially nanopattering technique is big issue in electric device application field by using these block copolymer which has very narrow molecular weight distribution. To synthesize these well defined amphiphilic polymers, anionic polymerization(AP) method is the best way. However many complicate problem is often occurred in anionic polymerization. The living anionic polymerization technique does not only requires the reaction to proceed under the condition in which no side reaction of propagating polymeric anions is present, but also need to control the purity of the system. It is important for reproducibility. Industrial anionic polymerization process use nonpolar solvents such as toluene, hexane or cyclohexane. In toluene solution, anionic polystyrene reaction carried out at 40℃ to 80℃. But, nonpolar solvent is not suitable to synthesize these amphiphilic block copolymers due to low solubility of hydrophilic polymer block such as PMMA or P2VP. Tetrahydrofuran is one of the most commonly used solvents for well defined amphiphilic polymers in laboratory scale. And it also features good solubility properties for most anionic polymers. But there are some disadvantages with reacting anionic polymerization in THF. THF reacts readily with organic lithium compounds, such as n-butyl lithium and sec-butyl lithium. Therefore, for using n-butyl lithium as initiator, reaction temperature should be below -35℃. Due to the reason, most anionic polymerization in THF is occurred at -78℃. Such a low temperature is not easy for reactor cooling at the pilot scale. So well defined amphiphilic polymers has been synthesized in laboratory scale and even if the supplier is exist, the product is costly. In spite of the large number of laboratory anionic polymerization precesses described in the literature, there is no engineering study published so far, to the best of our knowledge, on the anionic polymerization of amphiphilic block copolymers.

In this project, we designed and developed reactors for anionic block copolymrization including for purification systems of solvent, monomers and polymers in pilot scale. At first IL, 3L and 5L AP reactors was developed as prototype. And we synthesized block copolymers with these reactor. Polystyrene block was performed using diphenyl hexyl lithium at variable temperatures (-78, -45, -25, -15℃) in tetrahydrofuran(THF). Block copolymerization of methyl methacrylate was carried out using 1,1-diphenyl ethylene anion terminated polystyrene at -78℃. And block copolymerization of 2-vinyl pyridine was carried out using polystyrene anion as initiator at -78℃ in THF. PS-PMMA and PS-P2VP block copolymers were synthesized in the presence of lithium chloride as a ligand. Both second block monomers were cooled down to -30℃ before adding them into the reactor to control their exothermic reaction of polymerization, Torque and exothermic temp were collected during the polymerization, the objective of these polymerization was to engineer a scaleable process in THF that could be used for developing 20L reactor and economical and safe piloting of well-defined block copolymers. And also the purification systems was studied for economical process. After the process optimization was complete, we scaled up the anionic polymerization system. 20L batch type reactor, semi continuous plug flow reactor(PFR) and pilot scale monomer and solvent purification equipments were developed based on the archived data from the prototype AP reactors and lab scale purification equipments. With the scaled up AP reactors, we synthesised well defined reproducible PS-PMMA, PS-P2VP that had narrow molecular weight distribution (<1.1). An amount of polymers that were polymerized by once were up to 2kg in 20L batch reactor and 600g in semi continuous PFR. And also we confirmed that these block copolymer had self assembly behavior that would be used for nanopatterning technique,

Recently developed energetic polyether-based polyurethane binders containing nitro- and azido- groups, which are used in energetic insensitive polymer bonded explosives(PBX), have the disadvantages of several vulnerable properties involving curing difficulty, processing problem and poor mechanical properties. Therefore, increasing research efforts have been focused on developing new kinds of molecular explosive-embedding energetic binders.

In this study, novel synthetic methodology for novel polyacrylate-based energetic binders, which have the high energy performance and improved oxygen balance has been provided. The acrylate monomers containing dinitro- or azido group polymerized by using radical living polymerization technique followed by the functional group interconversion via click reaction with PEO-diacetylene to give the well-defined polyacrylate-based energetic binder material.

Two kinds of polyacrylate-based polymers involving low molecular weight energetic polyol prepolymer and high molecular weight polyacrylate-b-PEO block copolymer have been prepared as the promising binder material for energetic insensitive PBXs.
- Dinitro-polyacrylate polyols and their corresponding polyurethanes
- High molecular weight dinitro-polyacrylate-b-polyethylene oxide) block copolymers

The synthetic methodology for polyacrylate-b-PEO block copolymers as the new wide spectrum of high-energetic insensitive binder materials, were provided by the click reaction of azido-energetic polyacrylate, poly(DNPA-co-AzPA(M_n= 1,000~20,000g/mol, F_n of N₃<3) and PEG-diacetylenes (M_n=300~5,000g/mol). The well-defined poly(DNPA-co-AzPA) could be obtained by the copolymerization of DNPA ans AzPA via unique low-temp. RAFT living radical polymerization method.

The typical properties of these dinitro polyacrylate-b-PEO were as followed,
- Total number average molecular weight = 5.0~10.3 x 10⁴g/mol
- Block size and content of polyacrylate block and PEO block(10~50wt%)
- Superior compatibility with high-energetic plasticizer, such as BDNPF/A
- Thermal decomposition stability above 200℃

The synthetic methodology for the synthesis of novel low-molecular weight poly(DNPA-co-HEA) polyols were developed by using the copolymerization of DNPA monomer and 2-hydroxyethyl acrylate containing hydroxy group by low-temperature RAFT living radical polymerization. The mixed polyol involving this energetic polyacrylate polyol and PEG(70/30~50/50) were cured with diisocyanates to give the corresponding high-energetic polyurethane binder with improved mechanical properties.

The typical properties of the new polyacrylate polyol and its corresponding polyurethane were as followed,
- Number average molecular weight = 2.0~3.0x10³g/mol
- OH functionality = 2~3
- Polyurethane comprising of mixed polyols involving poly(DNPA-co-HEA)
polyols and PEG had the improved controlled mechanical properties.
- Compatible with DOA plasticizer and high-energetic plasticizers
- Thermal decomposition stability up to 170℃

(출처 : SUMMARY 6p)

목차 Contents

• 표지 ... 1
• 제출문 ... 2
• 요약문 ... 3
• SUMMARY ... 6
• Contents ... 9
• 목차 ... 10
• 제1장 서론 ... 11
• 1. 연구개발의 목적 및 필요성 ... 11
• 2. 연구개발의 내용 및 범위 ... 11
• 가. 군수용 : 분자화약 맞춤형 고에너지 결합제 2종의 설계 및 합성 ... 11
• 나. 민수용 : 나노패턴용 디블록공중합체 4종의 설계 및 합성 ... 11
• 다. -90~100℃ 온도 범위 및 상압조건에서 운용할 수 있는 pilot(20L)규모 리빙 음이온 중합 장치(Batch 혹은 Semi-Continuous 공정) 개발 ... 12
• 라. 주요확보 목표기술 ... 12
• 제2장 국내외 기술개발 현황 ... 13
• 1절 국내 기술 개발 현황 ... 13
• 1. 지금까지의 연구개발 실적 ... 13
• 2. 현 기술상태의 취약성(문제점) ... 13
• 3. 앞으로의 전망 ... 14
• 2절 국외 기술 현황 ... 14
• 1. 지금까지의 연구개발 실적 ... 14
• 2. 연구개발 또는 사업화 단계 ... 15
• 제3장 연구개발수행 내용 및 결과 ... 16
• 1절 군수 부분 ... 16
• 1. 고에너지 (Meth)Acrylate 단량체 설계 및 합성 ... 17
• 2. 고분자량 Polyacrylate-PEO Block 공중합체형 고에너지 결합체 합성 ... 23
• 3. Polyacrylate polyol계 고에너지 prepolymer 합성 및 우레탄 반응 적용평가 ... 58
• 4. 화약적용 예비시험 평가 및 상용성 평가 ... 65
• 2절 민수 부분 ... 68
• 1. 반응물의 고도 정제 공정 시스템 기술 개발 ... 68
• 2. Lab 규모 상압 중합장치 개발 ... 87
• 3. 중합체의 회수 및 탈용매화 기술 개발 ... 96
• 4. 중합체의 고도 정제 기술 및 장치 개발 ... 97
• 5. 반응물의 계량, 자동이송공정 및 장치 개발 ... 100
• 6. Lab. 규모 homopolymer 중합체의 합성 기술 개발 ... 106
• 7. Lab. 규모 블록 공중합체 합성 기술 개발 ... 122
• 8. Pilot 규모 상압중합장치 개발 최적화 및 중합체 합성 ... 135
• 제4장 연구개발목표 달성도 및 대외기여도 ... 164
• 1. 연구개발 목표 및 달성도 ... 164
• 2. 대외기여도 ... 166
• 제5장 연구개발결과의 활용계획 ... 168
• 1. 군수분야 ... 168
• 2. 민수분야 ... 168
• 제6장 참고문헌 ... 169
• 끝페이지 ... 169