Synthesis of Various Heterogeneous Poly(methyl methacrylate) Containing Systems and Their Structural Characterizations = PMMA 를 포함하는 다양한 Heterogeneous 시스템의 합성 및 그 구조 분석|RISS 상세보기

다국어 초록 (Multilingual Abstract)

This dissertation describes the synthesis of various heterogeneous poly(methyl methacrylate) (PMMA) containing systems and investigated those structural characterizations. Firstly, we reported the temperature dependence of Flory-Huggins interaction parameter χ (T) between BA and MMA components by analyzing SAXS measurements fitted to the random phase approximation (RPA) equations for molten PBA-b-PMMA diblock at various temperatures. It was found from the χ estimation (χ = 0.0103 + 14.76/T ) that the enthalpy contribution, χH, a measure for temperature susceptibility of χ, is 1.7 – 4.5 folds smaller for PBA-b-PMMA than that for the conventional styrene-dien-based block copolymers which has been widely used for thermoplastic elastomers.
And second, we investigated the segregation behavior of a molten diblock copolymer, poly(n-butyl acrylate)-b-poly(methyl methacrylate-ran-Styrene) (PBA-b-P(MMA-r-S)), wherein styrene (S) is incorporated as a comonomer in the second block to modulate the effective interaction between homopolymer and random copolymer block. The temperature dependence of the effective interaction parameter χeff between n-butyl acrylate (BA) and the average monomer of MMA-r-S random block was evaluated from small-angle X-ray scattering (SAXS) analysis using the random phase approximation (RPA) theory. The calculated χeff, as a function of the styrene fraction in the random copolymer block, shows a good agreement with the mean-field binary interaction model. This consistency indicates that the effective interaction between component BA and the average monomer of the random copolymer block is smaller than the interactions between pure components (χBA,MMA, χBA,S). The present study suggests that the introduction of random copolymer block to block copolymer can effectively reduce the degree of incompatibility of block copolymer system without altering the constituent species, which may serve as a viable methodology in designing novel thermoplastic elastomers based on triblock or multiblock copolymers.
Lastly, as one of the latest technologies using PMMA, the gloss control of super matte surface using PMMA particles was studied. For investigating the gloss control of PMMA/ABS co-extrusion sheet by cross-linked PMMA particles, six PMMA mixture samples were prepared through an extrusion process using cross-linked PMMA particles with two different sizes (13.2 μm and 17.4 μm). We investigated the effects of size and contents of cross-linked PMMA particles on the gloss and roughness of the surface of super matte PMMA/ABS co-extrusion sheet (less than 7 GU, measuring angle 60°) by using a confocal laser scanning microscope (CLSM), contact roughness tester and surface glossmeter. There was differences in the surface roughness and gloss between A-series and B-series depending on the cross-linked PMMA particle size, and the difference was also confirmed according to the sheet processing direction. We confirmed that the correlation of gloss was not only decided by the roughness effect alone but also affected by a higher presence of cross-linked particles on the surface PMMA layer with increased light scattering efficiency.

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목차 (Table of Contents)

Chapter 1. General Introduction 11
1.1 General Introduction 12
1.2 References. 15
Chapter 2. Theoretical Background 18
2.1 Technologies of Acrylic Block Copolymer 19

Chapter 1. General Introduction 11
1.1 General Introduction 12
1.2 References. 15
Chapter 2. Theoretical Background 18
2.1 Technologies of Acrylic Block Copolymer 19
2.1.1 Features of Acrylic Block Copolymer 19
2.1.2 Applications of Acrylic Block Copolymer 21
2.2 Synthesis of Block Copolymer by CRP (ATRP & NMP) 22
2.2.1 Synthesis of Acrylic Block Copolymer by ATRP 22
2.2.2 Synthesis of Acrylic Block Copolymer by NMP 24
2.3 Order-Disorder Transition(ODT) and Flory-Huggins Parameter, χ, of Block Copolymer 26
2.3.1 Order-Disorder Transition of Block Copolymer 26
2.3.2 Estimation of Flory-Huggins Parameter, χ, of Block Copolymer by SAXS Analysis 29
2.3.3 Relation between the Bridge Fraction (Φ) and the Flory-Huggins Interaction Parameter (χ) of Triblock Copolymer 32
2.4 References 34
Chapter 3. Small Angle X-Ray Scattering Analysis on the estimation of Interaction Parameter of Poly(n-butyl acrylate)-b-poly(methyl methacrylate) 37
3.1 Introduction 38
3.2 Experimental Section 39
3.2.1 Materials 39
3.2.2 Synthesis of Poly(n-butyl acrylate)(PBA) Macroinitiator 40
3.2.3 Synthesis of Poly(n- butyl acrylate)-b-poly(methyl methacrylate) (PBA-b-PMMA) Diblock Copolymer 40
3.2.4 Analytical Technique 43
3.2.5 SAXS Measurements 44
3.3 Results and Discussion 45
3.4 Conclusions 53
3.5 Appendix 54
3.6 References 56
Chapter 4. Effective Interaction between Homo- and Heteropolymer Block of Poly(n-butyl acrylate)-block-poly(methyl methacrylate-ran-styrene) Diblock Copolymers 60
4.1 Introduction 61
4.2 Experimental Section 63
4.2.1 Materials 63
4.2.2 Synthesis of Poly(n- butyl acrylate)(PBA) Macroinitiator 64
4.2.3 Synthesis of Poly(n-butyl acrylate)-b-poly(methyl methacrylate-ran-styrene)((PBA-b-P(MMA-r-S)) Diblock Copolymer 65
4.2.4 Analytical Techniques 67
4.2.5 SAXS Measurements 67
4.2.6 Characterization of Diblock Copolymer 68
4.3 Results and Discussion 74
4.4 Conclusions 90
4.5 Appendix 91
4.6 References 93
Chapter 5. Gloss Control of PMMA/ABS Co-extrusion Sheet by Cross-linked PMMA Particles 99
5.1 Introduction 100
5.2 Experimental 102
5.2.1 Materials 102
5.2.2 Characterization of Cross-linked PMMA Particles 102
5.2.3 Preparation of Super matte PMMA Mixtures (Compounding Process) 106
5.2.4 Co-extrusion Process for Super matte PMMA/ABS 108
5.3 Results and Discussion 109
5.4 Conclusions 120
5.5 References 121
Chapter 6. Summary 123

참고문헌 (Reference)

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