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

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 Definition Examples

Macroporous >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=NA+NB

Flory-Huggins χΑΒ parameter Volume fraction of blocks “f”

Block CopolymerPhase 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

H3C

O

OHn

+

O

O

Sn(Oct)2

H3C

O

On

OH

O

m140 ℃

Poly(ethylene glycol) methyl ether

(ε-caprolactone) Poly(ethylene glycol)-block-Poly(ε-caprolactone)

Experimental

Synthesis of Mesoporous PhenolicPhenolic Resin

Block Copolymer

Self-Assembly

Hexamethylenetetramine (HMTA)

Thermosetting

Template removal

Preparation of mesoporous phenolic resins

EC1, EC2, EC3, EC4

Sample Abbreviation NMR Mn PDI

CL35EO455CL35 EC1 28000 1.05

EO114CL84 EC2 15000 1.31

EO114CL130 EC3 20000 1.29

EO114CL168 EC4 25000 1.31

PCL-b-PEOPCL-b- PEO-b-PCL

(Template)Phenolic Resin

HMTA(Curing agent)

Blend BlendCuring

Instrument Analysis

FT-IR DSC SAXS TEM BET

Experimental

Results and Discussion

(a) (a)

(b) (b)

(c) (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 resinResults 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

√ 𝟔

√ 𝟐𝟒√ 𝟑𝟖

√ 𝟓𝟎

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 resinResults 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 resinResults 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 40-60 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 , 4994.

http://web2.cc.nctu.edu.tw/~FMPANLAB/LowK.htm

http://web2.cc.nctu.edu.tw/~FMPANLAB/.htm

High surface area Special morphology

Future applications

Gas sensor Low n material

Low k material

High porosity

Q&A

Types of N2 adsorption /desorption isotherms hysteresis loop

Results and Discussion

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.

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.

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.