Synthesis of polynorbornene grafted with poly(ε-caprolactone) by sequential controlled ring opening polymerization

(1)

Center for Education and Research on Macromolecules, University of Liège, Sart-Tilman B6, B- 4000 Liège, Belgium

http:// www.ulg.ac.be/cerm

IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099, USA

University of Mons-Hainaut,Department of Polymeric and Composite Materials,Place du Parc 20, B-7000 Mons, Belgium

**Lecomte Ph.*,**

Mecerreyes D.°, Dubois Ph. , Jérôme R.*

Synthesis of Polynorbornene Grafted with Poly- -Caprolactone

by Sequential Controlled Ring-Opening Polymerization.

e

*

°

u

Combination of ROP and ROMP

Well-defined poly(NBE-g- -CL) copolymers have been prepared using either the "grafting from" or the macromonomer technique.

e

4 5

The living Ring Opening Polymerization (ROP) of -caprolactone initiated by aluminum alkoxides is a well-known process to synthesize poly- -caprolactone (PCL).

e e 1

O

RO C

O

(CH

2

)

5

O H

ROH

1) Et

3

Al, -78°C

2) 3h, rt

toluene

ROAlEt

2

p

e

-CL

PCL

toluene, rt

“Grafting from” technique

OAc

m

OAc

n

+

[RuCl

2

(p-cymene)]

2

PCy

3

, Me

3

SiCHN

2

PhCl, 60°C

poly(NBE-OAc-co-NBE)

NBE-OAc

NBE

Synthesis of poly(NBE-OAc-co-NBE)

Synthesis of poly(NBE-g- -CL)

e

poly(NBE-OAc-co-NBE) poly(NBE-OH-co-NBE) Mn = 208,000 (SEC) ; Mw / Mn =1.2

5 mol% alcohol pendant groups 5 mol% acetate pendant groups

Mn = 190,000 (SEC) ; Mw / Mn =1.3 n-BuLi THF, 0°C O C O (CH2)5O H n m p m n OH OAcn m 1) Et3Al, toluene 2) e-CL, toluene, rt 3) H3O+ Mn = 301,000 (SEC) ; Mw / Mn =1.3 grafted PCL chains : Mn = 2,500 (1H NMR) poly(NBE-g-e-CL) References 1977 1997 1989 1998

1)Dubois, Ph.; Degée, Ph.; Ropson, N.; Jérôme, R. "Macromolecular engineering of polylactones and polylactides by Ring Opening Polymerization" Macromolecular design of Polymeric Materials, Ed. by K. Hatada, Marcel Dekker Inc. , , 247. 2)Demonceau, A.; Stumpf, A. W.; Saive, E.; Noels, A. , , 3127. 3)Grubbs, R. H. , , 907.

4)Lecomte, Ph.; Mecerreyes, D.; Dubois, Ph.; Demonceau, A.; Noels, A. F.; Jérôme, R. , , 631.

5)Mecerreyes, D.; Dahan, D.; Lecomte, Ph.; Dubois, Ph.; Demonceau, A.; Noels, A. F.; Jérôme, R. , accepted for publicatio

41 Macromolecules 30 Science 243

Polym. Bull. 40 J. Polym. Sci, Polym. Chem. n

Acknowledgment

Ph. L. is grateful the "Service des Affaires Scientifiques, Techniques et Culturelles" for financial support in the frame of the "Pôles d'Attraction Interuniversitiaires : Polymères". DM thanks IBM Belgium for financial support.

The authors are indebted to M.Lalmand for the poster design.

Ring Opening Polymerization (ROP)

[NBE] /[NBE-OAc]0 0 0/100 60/40 82/18 94/6 94/6 94 133 133 133 266 60 10 0.5 0.5 0.5 0.047 0.132 0.088 0.088 0.088 45 76 90 90 90 77,000 92,000 125,000 125,000 257,000 1.2 1.1 1.2 1.2 1.4 100 28 3 3 3 [M] /[Ru]0 0 Time (min) [M] (mol l ) 0 -1 Yield % Mn* (SEC) *Polystyrene standards M /Mw n Mol % NBE-OAc ( H NMR)1

Recently, ruthenium carbene complexes have been shown to initiate the Ring Opening Metathesis Polymerization (ROMP) of cyclic olefins such as norbornene (NBE) derivatives. For this purpose, a catalyst generated "in situ" from

Me SiCHN , [RuCl (p-cymene)] and PCy has been developed in our laboratory.

2, 3

2

3 2 2 2 3

[Ru]=CHSiMe3

[RuCl

2

(p-cymene)]

2

+ PCy

3

+

CH

Me

3

Si

N

2

TMSD

PhCl, 60°C

NBE

PNBE

m

Ring Opening Metathesis Polymerization (ROMP)

ROM -Copolymerization of PCL macromonomers

X

CH

2

O

C

O

(CH

2

)

5

O H

p

+

[RuCl

2

(p-cymene)]

2

PCy

3

, Me

3

SiCHN

2

60°C, PhCl

p

m

n

O C

O

(CH

2

)

5

O

H

X

X = H, OAc

Synthesis of macromonomers

CH

2

OH

1) Et

3

Al, toluene

2) e-CL, toluene, rt

3) H

3

O

+

CH

2

O

C

O

(CH

2

)

5

O H

p

Macromonomer technique

Code 1 2 3 4 5 13 17 13 24 16 85 95 85 95 90 2,500 3,300 5,000 5,000 10,000 2,000 3,200 4,500 ---2,100 2,900 4,500 3,600 9,600 1.10 1.15 1.10 2.05 1.20 Reaction time (h) Yield % Mn* (SEC) *PCL standards Mn (theor) Mn ( H NMR)1 M /Mw n Macromonomer Code 1 3 5 5 5 5 5 H H H H H OAc OAc 5 1 5 4 5 60 60 70 40 60 60 60 90 70 0.3 0.3 0.6 0.3 0.6 0.3 0.6 0.29 0.27 ---0.29 ---0.30 0.55 199,000 227,000 82,000 182,000 126,000 92,000 87,000 1.60 1.85 2.40 1.50 2.00 1.25 1.45 X Yield % Reaction Time (min) fCL FCL M * (SEC) n *Polystyrene standards M /Mw n

ROMP of PCL macromonomers

p

CH2O

C

O

(CH2)5

O H

PCy3, Me3SiCHN2

[RuCl2(p-cymene)]2

60°C, PhCl

O C

O

(CH2)5

O

H

n

p

Macromonomer Code 2 2 2 2 3 3 3 3 3 1.5 0.9 12 0.002 0.01 0.06 0.03 0.02 0.13 66 89 90 78 78 90 34,000 44,000 39,000 24,000 30,000 88,000 1.15 1.10 1.10 1.15 1.15 1.10 Yield % [Macro] (mol l ) 0 -1 [Macro] /[Ru]0 0 M * (SEC) n *Polystyrene standards M /Mw n