1. Advisor : Professor Guey-Sheng Liou Reporter : Tzu-Tien Huang
103 學年度台灣大學高分子科學與工程學系
高分子合成特論
Living Anionic Polymerization of 1,4-Divinylbenzene and Its Isomers Shunsuke Tanaka, Masayoshi Matsumoto, Raita Goseki, Takashi Ishizone, and Akira Hirao, Macromolecules, 2013, 46, 146
Advisor : Professor Guey-Sheng Liou
Reporter : Tzu-Tien Huang
Date : 2014 / 12 / 26

2. Advisor : Professor Guey-Sheng Liou Reporter : Tzu-Tien Huang
103 學年度台灣大學高分子科學與工程學系
高分子合成特論
Advisor : Professor Guey-Sheng Liou
Reporter : Tzu-Tien Huang
Date : 2014 / 12 / 26

3. Polymerization of Divinylbenzene Cross-linked or Star-branched Polymer
Outline
Introduction
Motivation
Experiment
Result and Discussion
Summary
Polymerization of Divinylbenzene
Cross-linked or Star-branched Polymer
Soluble Polymer
Stable Living Polymer

4. Introduction

5. Polymerization of Divinylbenzene
Isomers
Crosslinked Polymer
Insoluble Polymer
Ion exchange resin
Column – Packing agents
Pendent vinyl group

6. Cross-linked Polymer 当溶胶相的反应程度（交联分数）P达到某一临值pc则出现凝胶化。单体平均官能度f
Flory-Huggins Theory
Gel Point 6
D. J. Worsfold, Macromolecules, 1970, 3, 514
当溶胶相的反应程度（交联分数）P达到某一临值pc则出现凝胶化。单体平均官能度f
决定了临界值pc, 且有•pc=1/(f－1

7. Star-branched Polymer
Poly(isoprenyl) – lithium + m-divinylbenzene
L. J. Fetters, Macromolecules, , 899

8. Lithium diisopropylamide (LDA)
Soluble Polymer
Lithium diisopropylamide (LDA)
Growing carbanion ↑ → life time ↓
(Chain transfer by DPA)
Reactivity
Pendent vinyl groups ＜ DVB monomer
Growing carbanion ↑ → Reactivity ↓
(Stabilized 10 π -conjugation.)
Teiji Tsuruta, J. MACROMOL. SCI.-CHEM., 1989, A26(8), 1043

9. Pendent vinyl groupContent
Charge Transfer (DPA)

10. Akira Hirao, Macromolecules, 2011, 44, 4579
Stable Living Polymer
In THF at -78 ℃ for 1 min
Initiator – Oligo ( α-methylstyryl ) lithium
( sec-BuLi / α-MeSt )
Additive - KOBut
Akira Hirao, Macromolecules, 2011, 44, 4579

11. Anionic Polymerization of 1 in THF at 78 C for 1 min
SEC profiles of polymers
DVB-1
DVB-3
DVB-4
DVB-5
Initiator
sec-BuLi
sec-BuLi/α-MeSt /KOBut
12 eq
5 eq

12. Motivation Soluble Polymer Polymerization of Divinylbenzene
Avoid Crossliked or gel
(Pendent vinyl group reation)
Soluble Polymer
High yield
High molecular weight
Small PDI
Stable Living Polymer
Expected Polymerization
Pendent vinyl group
reactivity
Time vs Temperature

13. Experiment

14. Synthesis of 1,4-Divinylbenzene
Scheme
Procedure

15. Preparation of Additives
Solution A
Solution B
Phenol or Alochol
THF at −78 ℃
Colorimetric
titration
0.5 ~ 0.8 M THF
0.3 M THF
0.05 ~ 0.1 M
Potassium Alkoxides
and Phenoxides

16. Polymerization N2 Surrounding - THF -78℃ THF -95 ℃
Initiator - Oligo ( α-methylstyryl ) lithium ( sec-BuLi / α-MeSt )
Additive - Potassium Alkoxides and Phenoxides
Monomer - 1,4 – Divinylbenzene
1,3 – Divinylbenzene
1,2 - Divinylbenzene
Terminator - Methanol N2

17. Result and Discussion

18. Akira Hirao, Macromolecules, 2011, 44, 4579
Previous - KOBut
Atom size : K+ ＞Li+
Salt effect > Solvation (Abound of K+ )
( ion-pair > ion-dissociated )
Steric bulkiness (tert-Butyl)
Main Chain ↑ → Pendant vinyl group reativity ↓
(The vinyl group of main chain is electron donating)
DVB-5
DVB-4
DVB-3
DVB-1
Akira Hirao, Macromolecules, 2011, 44, 4579

19. Effect of Metal Alkoxides - Metal
[Initiator] = 2~3 ×10-3 M ; [Monomer] = 0.2~0.9 M x
LiOBut
NaOBut
KOBut

20. Effect of Potassium Alkoxides
Reacting alcohol with potassium naphthalenide in THF at −78 ℃ (10 eq)
Acetal Oxygen Atom

21. Effect of Potassium Alkoxides
Reacting alcohol with potassium naphthalenide in THF at −78 ℃ (10 eq)
pKa small
→ The ion is stable
→ Ion-dissociated > Ion-pair
Less of steric hindrance

22. Effect of Potassium Phenoxides and Potassium Pivalate
Pivalic acid
pKa= 5 → 70%
PDI = 1.04
Phenol pKa=10 < Alcohol pKa=16~18

23. Effect of 18-Crown-6, and P4-tBu
Strongly coordinate with K+
Steric bulkiness
Soluble polymer but PDI large

24. Summary of Additive Not Absolutely Steric bulkiness
Increase the distance between chain end anion and pendent vinyl group.
Basicity
Effect the ion stability
(Compare the Interaction between Ion-dissociated and ion-pair
Soluble Polmer
Small PDI
Potassium Alkoxides
Potassium Phenoxides
Potassium Salt
(Pivalic acid)
Reacting in THF at −78 ℃
Not Absolutely

25. Effect of Temperature and Polymerization Time
In THF at −78 ℃ for 5 min
In THF at −95 ℃ for 10~30 min
Mn ↑
PDI↑
30 min
10 min
15 min

26. Anionic Polymerization of 1,2- and 1,3-Divinylbenzenes
Bulky group protect ↓

27. Anionic Polymerization of Divinylbenzenes Isomers
10 π, 5 resonace
10 π, 5 resonace
8 π, 4 resonace
1,4 and 1,2 - Divinylbenzene is more stable than 1,3 - Divinylbenzene

28. Stabilization of Chain-End Anion
tert-butyl methacrylate
-78 ℃ for 3hr (enolate anion)
-78 ℃ for 5hr (diphenyl)
1,1-diphenylethylene

29. Summary

30. Reaction Time and Temperature
Additive
Potassium Alkoxides
Potassium Phenoxides
Potassium Salt
(Pivalic acid)
Reaction Time and Temperature
In THF at −78 ℃ for 1 min
In THF at −95 ℃ for 10~30 min
Divinylbenzenes Isomers
1,4 and 1,2 - Divinylbenzene is more stable than 1,3 - Divinylbenzene
Stabilization of Chain-End Anion
tert-butyl methacrylate
1,1-diphenylethylene
Soluble Polymer
Small PDI
High Yield
Stable Living Polymer

31. Thank you for your attention !