報告者： 鍾 承佑 報告日期 :2013/11/15 指導教授： 陳文章 教授

1. 以兩性雙結晶嵌段共聚物PEO-b-PCL混摻酚醛樹酯合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 From Microphase Separation to Self-Organized Mesoporous Phenolic Resin through Competitive Hydrogen Bonding with Double-Crystalline Diblock Copolymers of Poly(ethylene oxide-b-ε-caprolactone) 報告者：鍾承佑 報告日期:2013/11/15 指導教授：陳文章 教授

2. Outline • Introduction • Experimantal • Results and Discussion • Conclusions • Applications

3. Introduction What is MesoporousMaterial？ 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. Ying, J. Y. et al. Angew. chem. Int. Ed. 1999, 38, 58.

4. Block Copolymer Phase diagram for conformationally symmetric diblock copolymer Self-Assembly driven by microphase separation PEO-b-PCL Total degree of polymerization N=NA+NB Flory-Huggins χΑΒparameter Volume fraction of blocks “f”

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

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

7. Experimental Phenolic Resin Synthesis of Mesoporous Phenolic Hexamethylenetetramine (HMTA) Thermosetting Self-Assembly Template removal Block Copolymer EC1, EC2, EC3, EC4 Preparation of mesoporous phenolic resins

8. Experimental • PCL-b-PEO • PCL-b- PEO-b-PCL • (Template) • Phenolic Resin • HMTA • (Curing agent) • Blend • BlendCuring • Instrument Analysis • SAXS • FT-IR • DSC • TEM • BET

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

10. Results and Discussion TEM images of mesoporousphenolic resin phenolic/EC1 (a)~(d) phenolic/EC2 (e)~(h) phenolic/EC3 (i)~(j) phenolic/EC1 (k)~(l) 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.

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

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

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

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

15. Conclusions (1)The self-organized mesoporous phenolic resin wasobserved only at 40-60 wt % phenolic content by an intriguing balance of the phenolic, PEO, and PCL contents. (2)SAXS、TEM and BETanalyses indicate that different compositions of phenolic result in different mesoporousstructuresthrough the mediation of hydrogen-bonding interactions. (3) the large and long-range order of bicontinuousgyroid type mesoporouscarbon was obtained from mesoporousgyroidphenolic resin calcined at 800 C under nitrogen

16. Future applications Applications http://web2.cc.nctu.edu.tw/~FMPANLAB/.htm Hsueh, H. Y.; Chen, H. Y.; She, M. S.2010 , 10 , 4994. http://web2.cc.nctu.edu.tw/~FMPANLAB/LowK.htm Special morphology High surface area High porosity Gas sensor Low n material Low k material

17. Thanks for your attention Q&A

18. Results and Discussion Types of N2 adsorption /desorption isotherms hysteresis loop

19. Results and Discussion (a) (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.

20. Results and Discussion (a) (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.

21. Results and Discussion (a) (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.