방향족 디올 단량체 변화에 따른 폴리술폰계 공중합체의 합성 및 특성 연구

다국어 초록 (Multilingual Abstract)

Polysulfones are useful engineering plastics which have key properties such as thermal stability, good mechanical properties and easy processability in the melt state or in solution. The thermal and electro-optic properties are of particular interesting for the processing as well as dielectric applications. This thesis describes how to effectively control the glass transition temperature in aromatic polysulfonic copolymer system and elucidate the structure-property relationship according to their chemical structure and morphology.
At first, a series of random copolysulfones were synthesized using 6 different kinds of aromatic diol monomers such as DHDPS(dihydroxydi phenylsulfone), resorcinol, catechol, 1,7-dihydroxynaphthalene, 2,7-dihydroxy naphthalene and bisphenol-A. The composition of copolymers was easily controlled by varying the molar ratio of two different kinds of diol monomer. All the polymers were characterized through NMR, FT-IR and elemental analysis to ensure that macromolecular chain had the expected composition from stoichiometric calculation. The copolymers were also characterized through differential scanning calorimetry (DSC) to asses their glass transition temperature (Tg). To get a better understanding the relationship between Tg and composition of random copolymers, we adopted the concept of PRCL (percentage of rigid chain length), which was defined as the ratio between the rigid length (each projected length weighted by its attributed rigidity: 0% for ether and 100% for phenyl and sulfone) and the full projected length of the repeat unit. Through a slight modification that included the concept of copolymer composition, we could get a linear relationship between PRCL and Tg for copolysulfones, where the correlation coefficient(R2) is 0.984. The prediction of Tg of a series of copolymers by defining PRCL suggested the important roles of the chain mobility during glass transition. In addition, by using linear equation, we could easily choice the composition of copolymer for the appropriate application.
Secondly, the synthetic procedure for the diol monomers, 2',5'-bis(alkyloxy) -p-terphenyl-4,4"-diol, was carried out and their utility was confirmed by varying carbon numbers (n=1, 4, 8, 12, 16) of alkyloxy group. The monomeric diols were polymerized by chlorine substitution reaction with DCDPS (dichlorodiphenylsulfone) and resultants were confirmed by spectroscopic means as well as elemental analysis. The thermal behavior of the polymers was evaluated by DSC and TGA. Generally, the Tgs of polysulfones highly depended on the length of side chain length. The Tgs of given series were in the range of 32～214℃.
An attempt was made to evaluate the morphology of polymers by means of X-ray diffraction experiment in a transmission mode. It is obvious from the increase of the scattering intensity that the internal order of the polysulfone was improved with increasing side chain length. Also, the maxima in the diffractogram were shifted to a smaller 2θ, which means larger internal dimensions. In completely amorphous polysulfone having side chains, the resulting layer periods d in angstroms are plotted versus the number of carbon atoms in the alkyloxy side chain. A linear dependency was found and its slope was 0.77. The increment per methylene (CH2) unit, 0.77Å is much smaller than the theoretical value of 1.27Å calculated from the fully extended and all-trans conformation of alkyl group. From these facts, it is thought that the polysulfones prepared have loose-layered structures.
Another electronic properties such as dielectric constant and refractive index were investigated. The dielectric constant was in the range of 2.72～3.86, highly depending on the side chain length.

목차 (Table of Contents)

• 1. 서론 1
• 2. 이론적 배경 3
• 2-1. 고내열 고분자 3
• 2-2. 폴리술폰계 수지는 무엇인가 5
• 2-3. 열적 성질과 분자 구조의 관계 7
• 2-4. 엔지니어링 플라스틱의 저유전 특성 9
• 2-5. 곁가지를 이용한 엔지니어링 플라스틱 11
• 3. 실험 12
• 3-1. 시약 12
• 3-2. 폴리술폰계 수지 합성 13
• 3-2-1. 폴리술폰계 수지 합성 과정 13
• 3-2-2. 반응 용매에 따른 중합도 관찰 13
• 3-2-3. 반응 용매 DMSO 중합도 상승을 위한 실험 15
• 3-2-4. 후처리 공정 비교 실험 15
• 3-3. 폴리술폰계 공중합체 합성(diol monomer 영향) 16
• 3-4. 벌크 폴리술폰계 수지 합성 17
• 3-4-1. 폴리술폰계 수지 [PSF] 정제 17
• 3-4-2. 클로로메틸화 폴리술폰계 수지 [CMPSF] 합성 18
• 3-4-3. [PHENOL-PSF] 합성 19
• 3-4-4. [FLUOR-PSF] 합성 20
• 3-5. 유연한 곁가지를 포함한 폴리술폰계 수지 합성 21
• 3-5-1. 4-Benzyloxyphenylboronic acid 합성 22
• 3-5-2. 2,5-Bis(methoxy)-1,4-dibromobenzene 합성 24
• 3-5-3. 다양한 길이의 Alkyl (C4, C8, C12, C16) Chain 도입 반응 25
• 3-5-4. 유연한 곁가지를 가진 강직한 주사슬 terphenyl 디올 합성 26
• 3-5-5. 유연한 곁가지를 포함한 폴리술폰계 수지 합성 28
• 4. 분석 29
• 4-1. 합성 및 중합도 분석 29
• 4-2. 용해도 30
• 4-3. 열적 특성 30
• 4-4. 광학적 특성 31
• 4-5. 전기적 특성 32
• 4-6. Morphology 32
• 5. 결과 및 고찰 33
• 5-1. 방향족 디올 DHDPS를 이용한 폴리술폰계 수지 33
• 5-1-1. DHDPS를 이용한 폴리술폰계 수지 합성 33
• 5-1-2. 반응 용매 변화 따른 중합도 관찰 35
• 5-1-3. 반응 용매 DMSO에서의 중합도 상승을 위한 실험 36
• 5-1-4. 후처리 공정 비교 실험 37
• 5-2. 디올 단량체 변화에 따른 폴리술폰계 공중합체 38
• 5-2-1. 방향족 디올 단량체 7종을 이용한 폴리술폰계 공중합체 합성 38
• 5-2-2. 정적 광산란법을 이용한 폴리술폰계 공중합체 분자량 측정 41
• 5-2-3. 폴리술폰계 공중합체 필름의 광학적 특성 44
• 5-2-4. 폴리술폰계 공중합체의 유리전이온도(Tg) 45
• 5-2-5. 폴리술폰계 공중합체의 형광 특성 52
• 5-3. 벌크 폴리술폰계 수지 55
• 5-3-1. 폴리술폰계 수지 구조 분석 55
• 5-3-2. 클로로메틸화 폴리술폰계 수지 구조 분석 56
• 5-3-3. [PHENOL-PSF] 구조 분석 58
• 5-3-4. [FLOUR-PSF] 구조 분석 59
• 5-3-5. 겔 크로마토그래피를 이용한 상대 분자량 분석 60
• 5-3-6. 벌크 폴리술폰계 수지의 전기적 특성 61
• 5-4. 유연한 곁가지를 포함하는 폴리술폰계 수지 63
• 5-4-1. 4-Benzyloxybromobenzene 63
• 5-4-2. 4-Benzyloxyphenylboronic acid 63
• 5-4-3. 2,5-Bis(C1-C16)-1,4-dibromobenzene 64
• 5-4-4. 4,4''-Bis(benzyloxy)-2',5'-bis(C1-C16)-p-terphenyl 66
• 5-4-5. 2',5'-Bis(C1-C16)-p-terphenyl-4,4''-diol 68
• 5-4-6. Bis(C1-C16)-p-terphenyl 폴리술폰계 수지 합성 71
• 5-4-7. Thermo properties of [CmT-PSF] 77
• 5-4-8. Solution properties of [CmT-PSF] 79
• 5-4-9. WAXS and layer structure of [CmT-PSF] 80
• 5-4-10. Density and molar volume of [CmT-PSF] 83
• 5-4-11. Refractive index and molar refraction of [CmT-PSF] 85
• 5-4-12. Electronic properties of [CmT-PSF] 87
• 6. 결론 88
• 7. 참고문헌 89
• ABSTRACT 91