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(a) (b) Figure 1-2: Schematic diagram of the technique of the surface modification by means of either (a) grafting-to (b) grafting-from 14
1.5. Components of ATRP. There are five important variable components of Atom Transfer Radical Polymerizations. They are the monomer, initiator, catalyst, solvent and temperature. The following section breaks down the contributions of each component to the overall polymerization. 1.6. Monomer. Monomers that are typically used in ATRP are molecules with substituents that can stabilize the propagating radicals; for example, styrenes, (meth)acrylates, (meth)acrylamides, and acrylonitrile. [18] ATRP are successful at leading to polymers of high number average molecular weight and a narrow polydispersity index when the concentration of the propagating radical balances the rate of radical termination. Yet, the propagating rate is unique to each individual monomer. Therefore, it is important that the other components of the polymerization (initiator, catalysts, ligands and solvents) are optimized in order for the concentration of the dormant species to be greater than the concentration of the propagating radical and yet not too great to slow down or halt the reaction. 1.7. Initiator. The number of growing polymer chains is determined by the initiator. The faster the initiation, the fewer terminations and transfers, the more consistent the number of propagating chains leading to narrow molecular weight distributions. [19] Organic halides that are similar in the organic framework as the propagating radical are often chosen as initiators. Most initators for ATRP are alkyl halides. Alkyl halides such as alkyl bromides are more reactive than alkyl chlorides and both have good molecular weight control. [19] The shape or structure of your initiator can determine the architecture of your polymer. For example, initiators with multiple alkyl halide groups on a single core can lead to a star-like polymer shape. 15
Page 1 and 2: Facile Approach to Synthesize Stimu
Page 3 and 4: Acknowlwdgement This dissertation w
Page 5 and 6: Chapter 1. Table of Contents 1-1. I
Page 7 and 8: 4.2.2.4.General Procedure for Synth
Page 9 and 10: Chapter 1 General Introduction 9
Page 11 and 12: The growth in industrial applicatio
Page 13: 1.3. Grafting methods. Most of thes
Page 17 and 18: Figure 1-4:Mechanism of the Atomic
Page 19 and 20: near that of the human body, PNIPAm
Page 21 and 22: References and notes. 1. Plastiquar
Page 23 and 24: Chapter 2 Characteristics of High-D
Page 25 and 26: 2.1. INTRODUCTION. Atom transfer ra
Page 27 and 28: . Cl Si H + OH 9 + 10-undecen-1-ol
Page 29 and 30: Figure 2-3 (b): NMR spectrum of Pro
Page 31 and 32: Figure 2-4: Schematic procedure for
Page 33 and 34: 3000 2000 Wavenumber/cm -1 1000 Fig
Page 35 and 36: Figure 2-7: (a) First order kinetic
Page 37 and 38: free polymers. We performed polymer
Page 39 and 40: Figure 2-9: Contact angles of air b
Page 41 and 42: 2.4. CONCLUSION. A detailed explana
Page 43 and 44: Chapter 3 Dominant influence of the
Page 45 and 46: 3.1. Introduction. Temperature resp
Page 47 and 48: and FT-IR analyses, were used as re
Page 49 and 50: azide Figure 3-2: FT-IR spectra of
Page 51 and 52: Figure 3-3: 1 H NMR spectrum of aci
Page 53 and 54: 3.3. Results and discussion. ATRP t
Page 55 and 56: temperature. 28 Electro-negativity
Page 57 and 58: Contact Angle (degree) 141 138 135
Page 59 and 60: Figure 3-7 shows equilibrium contac
Page 61 and 62: References and Notes. (1) S.A. Prok
Page 63 and 64: Chapter 4 Precise Synthesis and Phy
Page 65 and 66:
4.1. Introduction. Stimuli-sensitiv
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4.2. Experimental Section. 4.2.1. M
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hr and at room temperature for 12 h
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chromatography with hexane/ethyl ac
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4.2.2.4.General Procedure for Synth
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Figure 4-4. Schematic illustration
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Figure 4-5. FT-IR spectra of dried
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are necessary to achieve maximum bo
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Figure 4-1-1: XPS data of (a) C 1S
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The successful deposition of CPU-dM
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where f i is the area fraction of c
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The ATRP in this condition provides
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Figure 4-1-5: AFM image of densely
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Figure 4-1-8. Graft density of PNIP
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Figure 4-1-7. Plots of Ld/Lc,w vers
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Figure 4-1-9. Thickness of high den
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Figure 4-7. a) FT-IR spectra and b)
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Figure 4-1-10 (c): Area ratio for t
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Area ratio 0.4 0.35 0.3 0.25 0.2 0.
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(a) Figure 4-1-11 . Contact angle o
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(c) Figure 4-1-11. Contact angle of
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The temperature dependence for the
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4.4 Conclusions. High-density therm
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(16) Osada, Y.; Gong, J. P. Prog. P
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2006, 22 (9), 4259-4266. L Macromol
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(76) The Young equation, cos θ = (
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Abstract. High-density polymer brus
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previously grafted chain prevents l
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5.3.1. Synthesis procedure of the A
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5.4.1. Fourier Transform Infrared S
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5.5. Result and discussion. Scheme
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graft density (chain/nm 2 ) 0.8 0.6
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Thickness (nm) 50 40 30 20 10 0 0 1
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a nm 1μm b nm 1μm Figure 5-5. The
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5.6. Conclusion. ATRP of PNIPA in D
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(17) Huang, E.; Rockford, L.; Russe
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Publications. 1. Suzuki H., Huda M.
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