Controlled Coordination-Insertion Copolymerization-For the Synthesis of Functional Polyolefins -Literature Seminar 10/10/2015
Yamato Kanzaki (M1)1

1. Introduction

2

Examples of Polymers

3Characteristics of Polyethylene

Advantages

Shortages

water resistance (防水性)
electrical resistance (絶縁性)
impact resistance (衝撃耐性)
processibility (加工性)
lightweight (軽量性)
low temperature toughness (低温耐性)
low cost (安価)no dyeabillity (難染色性)no printability (難印刷性)
no compatibility (難混和性)
no adhesibility (難接着性)
gas permiability (ガス透過性)1) http://www.vec.gr.jp/lib/lib2_4.html (原典: 日本プラスチック工業連盟 )4

Examples of Functionalization

Abe, K. World Patent, 2013, 094762 A1 5

Today’s Topic

6

Introduction

7

Introduction

8

2. Copolymerization of ethylene with polar monomers
2-0. Difficulties in polar monomer incorporation
2-1. Brookhart-type catalyst (diimine ligand)2-2. Grubbs-type catalyst (imine-phenoxy ligand)2-3. Drent-type catalyst (phosphine-sulfonate ligand)a. trans influenceb. steric effectc. regio/stereo control

9Development of Polyolefin Synthesis

10Synthesis of Copolymer with Polar Monomers

Carrow, B.; Nozaki, K. Macromolecules. 2014, 47, 2541.

11

Coordination-Insertion Polymerization

12

Bottlenecks for Incorporating Polar Monomers

Nakamura, A.; Ito, S.; Nozaki, K. Chem. Rev. 2009, 109, 5215.

13

Shell Higher Olefin Process (SHOP) Catalyst

Keim, W. Angew. Chem. Int. Ed. 2013, 52, 12492.

14

3-1. Diimine Catalysts (Brookhart-Type)Brookhart, M. et al. J. Am. Chem. Soc. 1995, 117, 6414.

15

Diimine Catalysts (Brookhart-Type)16

3-2. Imine-Phenoxy Catalysts (Grubbs-Type)Grubbs, R. et al. Science. 2000, 287, 460.17

Drawbacks of Grubbs-Type Catalysts

Carrow, B. and Nozaki, K. Macromolecules. 2014, 47, 2541.

18

3-3. Phosphine-Sulfonate Catalyst (Drent-Type)1) Murray, R. US patent. 1987, 4716138 A. 2) Drent, E. et al. Chem. Comumn. 2002, 744

19

Copolymerization with Other Polar Monomers

20What is Special about Drent-Type Catalyst?

21

Trans Influence22

1. Ethylene Insertion from Trans Isomer

Morokuma, K; Nozaki, K. et al. J. Am. Chem. Soc. 2009. 131. 14088

23

2. Inhibition of β-Hydride Elimination

Morokuma, K; Nozaki, K. et al. J. Am. Chem. Soc. 2009. 131. 14088

24

P-SO3 vs N-O：What is the Critical Difference?

Nozaki, K. ; Morokuma, K. et al. J. Am. Chem. Soc. 2010. 132. 16030

25

P-SO3 vs N-O：What is the Critical Difference?

26

Short Summary for Drent-Type27

What is the Problem?

Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. and Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898

28

Exploring Steric Effect on Phosphine

Neuwald, B.; Falivene, L.; Caporaso, L.; Cavallo, L. and Mecking, S. Chem. Eur. J. 2013, 19, 17773 29

Screening of Alkyl Groups on Phosphine

Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. and Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898

30

Copolymerization with Other Polar Monomers

Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. and Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898

31

Evaluation of Steric Effect of Ligands

1) Sigman, M. S. et al. Nat Chem 2012, 4, 366. 2) Scarano, V; Cavallo, L. et al. Eur. J. Inorg. Chem. 2009, 13, 1759. 32

Evaluation of Steric Effect of Ligands

Sigman, M. S. et al. Nat Chem 2012, 4, 366

33

Polypropylene

34

Polypropylene: Regio/Stereo-Control

35

Steric Control & Rigid Backbone for Coplanarity

36

Propylene ×Polar Monomers

37Summary38

Appendix

39

1. Classification by Carothers: Reaction Mechanism402. Classification by Flory: Active Reaction Site

41

3. Key MO of Polar Monomers

42

4. Ethylene and AN Insertion43

5. Reductive Elimination

44

6. Electronic Effect45

7. Steric EffectNeuwald, B.; Falivene, L.; Caporaso, L.; Cavallo, L. and Mecking, S. Chem. Eur. J. 2013, 19, 17773 46

8. Steric EffectNeuwald, B.; Falivene, L.; Caporaso, L.; Cavallo, L. and Mecking, S. Chem. Eur. J. 2013, 19, 17773 47

9. Optically-Active Isotactic Polyketone (Stereo Control)48

10. Selected Topics Uncoverd in This Seminar

49

Classification of Copolymers

50X-ray51

DFT calculation for Catalyst A

52

DFT calculation for Catalyst A

53

Regioselectivity

54

Other Catalysts Trials

55

Other Polar Monomers

56

Bimetallic system (Grubbs-Type)

57