報告者：鍾承佑 報告日期 :2013/11/15 指導教授：陳文章 教授 以兩性雙結晶嵌段共聚物 PEO-b-PCL 混摻酚醛樹酯合 成中孔洞酚醛樹酯探討其微相分離及自組裝結構

Outline  Introduction  Experimantal  Results and Discussion  Conclusions  Applications

Ying, J. Y. et al. Angew. chem. Int. Ed. 1999, 38, 58. What is Mesoporous Material ？ Introduction Pore-size regimes DefinitionExamplesMacroporous >50 nm Glasses Mesoporous 2~50 nm M41S, SBA-15 Microporous <2 nm Activated carbon According to IUPAC definition, the size of porous can be divided into three types, less than 2 nm (micropore), between 2~50 nm (mesopore), and greater than 50 nm (macropore). The porous materials have some unique properties: high surface area (surface area / volume), high porosity, low density, high thermal stability and uniform pore distribution.

Self-Assembly driven by microphase separation Total degree of polymerization N=N A +N B Flory-Huggins χ ΑΒ parameter Volume fraction of blocks “f” Block Copolymer Phase diagram for conformationally symmetric diblock copolymer PEO-b-PCL

G.J.d.A. Soler-Illia et al. Current Opinion in Colloid and Interface Science 2003,8,109 Scheme of the main relationships between the solvent, the template and the inorganic center Evaporation Induced Self-assembly (EISA) in the classic sense can be defined as the spontaneous and reversible organization of molecular units into ordered structures by non-covalent interactions (e.g. Van der Waals, capillary,, hydrogen bonds) when solvent evaporates. Evaporation Induced Self-Assembly

Experimental Synthesis of PEO-b-PCL 140 ℃ Poly(ethylene glycol) methyl ether (ε-caprolactone) Poly(ethylene glycol)-block-Poly(ε-caprolactone)

Experimental Synthesis of Mesoporous Phenolic Phenolic Resin Block Copolymer Self-Assembly Hexamethylenetetramine (HMTA) Thermosetting Template removal Preparation of mesoporous phenolic resins EC1, EC2, EC3, EC4 SampleAbbreviationNMR M n PDI CL 35 EO 455 CL 35 EC EO 114 CL 84 EC EO 114 CL 130 EC EO 114 CL 168 EC

PCL-b-PEO PCL-b- PEO-b-PCL (Template) Phenolic Resin HMTA (Curing agent) Blend Blend  Curing Instrument Analysis FT-IRDSC SAXS TEMBET Experimental

Results and Discussion (a) (b) (c) SAXS patterns of mesoporous phenolic resin Profiles of Lorentz-corrected SAXS intensity of mesoporous phenolic resin from templated by (a) EC1, (b) EC2, (c) EC3, and (d) EC4 block copolymers.

TEM images of mesoporous phenolic resin Results and Discussion TEM images of mesoporous phenolic from phenolic/EC1 for (a) 30/70, (b) 40/60, (c) 50/50, and (d) 60/40, phenolic/EC2 for (e) 40/60,(f) 50/50, (g) 60/40, and (h) 70/30, phenolic/EC3 for (i) 50/50 and (j) 60/40, and phenolic/EC4 for (k) 50/50 and (l) 60/40 blends. phenolic/EC1 (a)~(d) phenolic/EC2 (e)~(h) phenolic/EC3 (i)~(j) phenolic/EC1 (k)~(l)

Results and Discussion Summary of SAXS analyses (A) and TEM images of mesoporous phenolic resin containing fixing 50 wt % phenolic resin contents withdifferent templated block copolymers for (B) EC1, (C) EC2, (D) EC3, and (E) EC4. SAXS patterns and TEM images of mesoporous phenolic resin

N2 adsorptiondesorption isotherms of mesoporous phenolicresins templated by different EC block copolymers with different phenolic weight percents (a) 50 wt %, and (b) 60 wt %. BET patterns of mesoporous phenolic resin Results and Discussion

Pore size distribution curves of mesoporous phenolic resins templated by different EC block copolymers with different phenolicweight percents: (a) 50 wt % and (b) 60 wt %. BET patterns of mesoporous phenolic resin Results and Discussion

SAXS pattern (a), TEM images (bd), N2 adsorptiondesorption isotherms (e), and pore size distribution curves (f) of mesoporous ofgyroid mesoporous carbon pyrolyzed from mesoporous phenolic resin templated by EC2 block copolymer at 50 wt % phenolic resin content at 800 C. SAXS 、 BET patterns and TEM images of mesoporous carbon Results and Discussion

(1)The self-organized mesoporous phenolic resin was observed only at wt % phenolic content by an intriguing balance of the phenolic, PEO, and PCL contents. (2) SAXS 、 TEM and BET analyses indicate that different compositions of phenolic result in different mesoporous structures through the mediation of hydrogen-bonding interactions. (3) the large and long-range order of bicontinuous gyroid type mesoporous carbon was obtained from mesoporous gyroid phenolic resin calcined at 800 C under nitrogen Conclusions

Applications Hsueh, H. Y.; Chen, H. Y.; She, M. S. 2010, 10, High surface area Special morphology Future applications Gas sensor Low n material Low k material High porosity

Types of N 2 adsorption /desorption isotherms hysteresis loop Results and Discussion

(a) DSC analysis of phenolic/EC DSC thermograms of phenolic/EC blends, having different compositions for (a) phenolic/EC1, (b) phenolic/EC2, (c) phenolic/EC3, and (d) phenolic/EC.

Results and Discussion (a) FT-IR analysis of phenolic/EC FT-IR spectra recorded at room temperature displaying the (a) hydroxyl stretching, (b) carbonyl, and (c) ether region.

Results and Discussion (a) FT-IR analysis of phenolic/EC FT-IR spectra recorded at room temperature displaying the carbonyl region of phenolic/EC blends fixing phenolic contents (50 and 60 wt %) for (a) pure EC1, (b) phenolic/EC1, (c) phenolic/EC2, (d)phenolic/EC3, and (e) phenolic/EC4.