ISSN 0012�5008, Doklady Chemistry, 2011, Vol. 437, Part 1, pp. 50–52. © Pleiades Publishing, Ltd., 2011.Original Russian Text © A.V. Syromolotov, M.V. Bermeshev, M.L. Gringolts, A.G. Kazmin, E.Sh. Finkelshtein, 2011, published in Doklady Akademii Nauk, 2011, Vol. 437, No. 1,pp. 53–55.

50

It was previously shown that norbornenes con�taining one or more Me3Si groups can undergopolymerization by metathesis mechanism irre�spective of the number of the groups [1]. Anexample of metathesis polymerization is shown inScheme 1. A more complex situation wasobserved in the case of addition polymerization of

the same monomers [2]. The presence of oneMe3Si group in the norbornene molecule mark�edly decreased its reactivity, the endo isomerbeing less reactive than the exo compound. Theintroduction of the second Me3Si group in themonomer molecule led to complete prevention ofpolymerization (Scheme 1) [2].

Scheme 1.

Me3Si SiMe3

SiMe3

SiMe3 SiMe3Me3Si

[Ru], [W]

metathesispolymerization

[Ni], [Pd]

additionpolymerization

nn

×

Recently, Japanese researchers synthesized nor�bornene with the Si(OSiMe3)3 substituent containingthree Me3Si groups and studied its polymerization.Metathesis polymerization of this monomer involvedno difficulty [3], whereas addition polymerizationproceeded in low yield to give a low�molecular�weightpolymer [4] showing poor film�forming properties.

It should be noted that works on the polymeriza�tion of silyl�substituted norbornenes have focused tothe synthesis of film�forming polymers that have highand selective gas permeability [5]. The gas�transport

Si(OSiMe3)3

n

characteristics of polynorbornenes were shown toincrease sharply with the number of Me3Si groups [1].

The task of this work is to synthesize a high�molecular�weight saturated polynorbornene con�taining three Me3Si groups in each unit. Taking intoaccount the fail of Japanese researchers [4], we sup�posed that Me3Si groups, which are likely to hinderaddition polymerization, should be moved fromthe double bond to solve this task. We accomplishedthe synthesis of 3�tris(trimethylsiloxy)silyltricy�

clo[4.2.1.02,5]nonene�7 (I) 1 by the reaction of ther�

1 1Н NMR (600 MHz, CDCl3, δ, ppm): 5.94–5.85 (m, 2H,C(7)H, C(8)H), 2.77 (s, 0.3 H, C(1)H, C(6)H), 2.56 (br s,1.7 H, C(1)H, C(6)H), 2.15–1.95 (m, 2H, C(9)H2, C(4)H2,C(2)H, C(5)H), 1.87 (m, 2.1 H, C(9)H2, C(2)H, C(5)H), 1.73(m, 0.3 H, C(3)H), 1.36 (m, 1 H, C(2)H), C(4)H2), 1.25 (m,0.7 H, C(9)H2), 1.16 (m, 0.3 H, C(9)H2), 0.77 (m, 0.7 H,C(3)H), 0.08 (m, 27H, Si(CH3)3).13C NMR (150 MHz, CDCl3, δ, ppm): 136.02, 134.77, (C(7),C(8)), 45.47, 44.56 (C(1)), 44.77, 44.15 (C(6)), 41.09, 39.83(C(9)), 38.21, 37.03, 36.71, 35.56 (C(2), C(5)), 22.04, 21.47(C(4)), 18.15, 17.75 (C(3)), 1.77, 1.75 (Si(CH3)3).

CHEMISTRY

Synthesis and Polymerizationof 3�Tris(trimethylsyloxy)silyltricyclononene�7

A. V. Syromolotova, M. V. Bermesheva, M. L. Gringoltsa, A. G. Kazminb, and E. Sh. Finkelshteina

Presented by Academician M.P. Egorov July 9, 2010

Received July 9, 2010

DOI: 10.1134/S0012500811030037

a Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991 Russia 119991

b Karpov Institute of Physical Chemistry State Research Center, ul. Obukha 10, Moscow, 103064 Russia

DOKLADY CHEMISTRY Vol. 437 Part 1 2011

SYNTHESIS AND POLYMERIZATION 51

mal condensation of quadricyclane and vinyl chlo�rides (previously found by us [6]) followed by dis�

placement of three chlorine atoms by Me3SiOgroups (Scheme 2).

Scheme 2.

SiCl3 Si(OSiMe3)3

SiCl3

t°

Me3SiONa

Et2O

I 40%

1 23

4567

8

9

The resulting monomer was successfully involvedin metathesis polymerization in the presence of theRu carbene first�generation Grubbs catalyst(PCy)3Cl2RuC(H)Ph or RuCl3/EtOH (Scheme 3).

The yield of unsaturated polymer A2 was up to 95%,

and the molecular weight was up to 8 × 105

(Scheme 3). Glass transition temperature of theobtained polymers was somewhat lower (104°C) thanthat of previously described 3,4�bis(trimethylsilyl)tri�cyclononene (130°C) and 3,3�bis(trimethylsilyl)tricy�

clononenes (200°C) [7], which could be explained bythe presence of mobile siloxane fragments causingself�plasticization.

The addition polymerization of compound Iattracts much more interest. Typical Ni�containingcatalysts of norbornene addition polymerization—Ni(Acac)2–B(C6F5)3 (Ni(Acac)2 : B(C6F5)3 : mono�

mer = 1000 : 1 : 5), Ni(COD)2–B(C6F5)3, Nf2Ni–

MAO–B(C6F5)33—proved to be inactive.

We carried out the addition polymerization ofcompound I in the presence of the Pd(Acac)2–

B(C6F5)3 and Pd(OAc)2–B(C6F5)3 catalytic systems

(Scheme 3).

Polymerization of 3�tris(trimethylsiloxy)silyltricyclononene�7

Catalyst/activator Monomer/catalyst Activator/catalyst Yield, % Mw c Mw/Mn

Metathesis polymerization

RuCl3–EtOH a 180 – 45 2.5 × 105 3.1

(PCy)3Cl2RuC(H)Ph b 3000 – 95 8.2 × 105 3.5

Addition polymerization

Pd(OAc)2 –B(C6F5)3 b 1500 75 20 7.5 × 104 1.6

Pd(Acac)2–B(C6F5)3 b 1500 5 16 5.5 × 105 2.8

1500 500 43 1.2 × 106 2.6

a 65°C, 15 h.b 25°C, 24 h. c Determined by GPC with the use of polystyrene standards.

3 COD is 1,4�cyclooctadiene, MAO is methylenealumooxane,Nf is naphthenate.

2 1H NMR (600 MHz, CDCl3, δ, ppm): 5.32–5.12 (m, 2H,C(7)H, C(8)H), 2.81 (m, 0.6 H, C(1)H, C(6)H), 2.45–1.67 (m,6.4 H, C(1)H, C(6)H, C(9)H2, C(4)H2, C(2)H, C(5)H,C(3)H), 1.23 (m, 2H), 0.06 (m, 27H, Si(CH3)3).13C NMR (150 MHz, CDCl3, δ, ppm): 132.5 (m, C(7), C(8)),52.72 m, 46.07 m, 43.76 m, 26.10 m, 23.39 m (C(6), C(1), C(9),C(2), C(5), C(4), C(3)), 1.79 (Si(CH3)3).

52

DOKLADY CHEMISTRY Vol. 437 Part 1 2011

SYROMOLOTOV et al.

Scheme 3.

Si(OSiMe3)3Si(OSiMe3)3 Si(OSiMe3)3

95%

[Ru] Pd(Acac)2

B(C6F5)3

I 43%A Б

nn

1 23

4567

8

9

We obtained for the first time norbornene�typehigh�molecular�weight addition polymer B contain�ing three Me3Si groups in monomer unit by varyingmonomer : Pd(Acac)2 and B(C6F5)3 : Pd(Acac)2

ratios. An increase in the monomer : Pd(Acac)2 ratioup to 3000 resulted in the formation of insoluble poly�mer probably on account of very high molecularweight or partial cross�linking at the siloxane frag�ments (table). Increase in B(C6F5)3 : Pd(Acac)2 ratioto 500 led to the growth of polymer yield. On the basisof these experiments, we have found the monomer :Pd(Acac)2 and B(C6F5)3 : Pd(Acac)2 ratios necessaryfor the synthesis of high�molecular�weight poly(3�

tris(trimethylsiloxy)silyltricyclononene�7) B4 in satis�factory yield. Elemental analysis data and NMR spec�tra confirm its structure.

Thus, we have found an approach to the synthe�sis of new high�molecular�weight silicon�contain�ing polymers, addition and metathesis poly(tricy�clononenes), containing three Me3Si groups inmonomer unit. The obtained polymers are promis�ing materials for studying their gas�separating prop�erties.

ACKNOWLEDGMENTS

This work was supported in part by the RussianFoundation for Basic Research (project no. 09–03–00342�a) and the Ministry of Education and Sci�ence of the Russian Federation (State contractno. 16.740.11.03.38).

REFERENCES

1. Finkelshtein, E.Sh., Gringolts, M.L., Ushakov, N.V.,et al., Polymer, 2003, vol. 44, no. 10, pp. 2843–2851.

2. Finkelshtein, E.Sh., Makovetsky, K.L., Gringolts, M.L.,et al., J. Mol. Cat. A, 2006, vol. 257, pp. 9–13.

3. Katsumata, T., Shiotsuki, M., Sanda, F., andMasuda, T., Polymer, 2009, vol. 50, pp. 1389–1394.

4. Tetsuka, H., Isobe, K., and Hagiwara, M., Polym. J.,2009, vol. 41, pp. 643–649.

5. Finkelshtein, E.Sh., Makovetsky, K.L., Gringolts, M.L.,et al., Macromolecules, 2006, vol. 39, pp. 7022–7029.

6. Gringolts, M.L., Bermeshev, M.V., Kaz’min, A.G.,and Finkelshtein, E.Sh., Dokl. Chem., 2009, vo. 424,part 2, pp. 49–51 [Dokl. Akad. Nauk, 2009, vol. 424,no. 6, pp. 774–776].

7. Gringolts, M.L., Bermeshev, M.V., Starannikova, L.E.,et al., Vysokomol. Soedin., 2009, vol. 51, no. 11,pp. 1970–1977.

4 1H NMR (600 MHz, CDCl3, δ, ppm): 2.90–0.05 (m, C(7)H,C(8)H, C(1)H, C(6)H, C(9)H2, C(4)H2, C(2)H, C(5)H, C(3)H,Si(CH3)3). For B anal. calcd. (%): C, 52.12; H, 9.23; Si, 27.08.Found (%): C, 51.95; H, 9.50; Si, 27.65.