Highly permeable polymer materials based on silicon-substituted norbornenes

Article abstract of DOI:10.1134/S0965544110050063

An approach to the manufacture of highly permeable polymers based on the synthesis and polymerization of norbornenes, norbornadienes, and tricyclononenes with different numbers and different positions of silicon-containing substituents has been developed. It has been found that these monomers are readily involved in metathesis polymerization yielding high-molecular-mass polymers possessing good filmforming properties. The addition (vinyl) polymerization of norbornenes is a more complex process; however, the product silylated polynorbornenes exhibit a higher gas permeability than the corresponding metathesis polynorbornenes. By the level of the gas-transport parameters, the silylated addition polynorbornenes obtained in the study are grouped with the most advanced high-permeability polymers. It has been shown that the presence of Me₃Si substituent groups, their amount, and the main-chain structure are responsible for the enhancement of the gas permeability of polynorbornenes. Thus, a series of polymers with a regularly changing structure has been obtained, a result that makes it possible to reveal the polymer structure-property relations.

Full text of DOI:10.1134/S0965544110050063

ISSN 0965ꢀ5441, Petroleum Chemistry, 2010, Vol. 50, No. 5, pp. 352–361. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.L. Gringol’ts, M.V. Bermeshev, A.V. Syromolotov, L.E. Starannikova, M.F. Filatova, K.L. Makovetskii, E.Sh. Finkel’shtein, 2010, published in Neftekhimiya,
2010, Vol. 50, No. 5, pp. 363–371.
Highly Permeable Polymer Materials Based
on SiliconꢀSubstituted Norbornenes
M. L. Gringol’ts, M. V. Bermeshev, A. V. Syromolotov, L. E. Starannikova,
M. F. Filatova, K. L. Makovetskii, and E. Sh. Finkel’shtein
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991 Russia
eꢀmail: fin@ips.ac.ru
Received March 1, 2010
Abstract—An approach to the manufacture of highly permeable polymers based on the synthesis and polyꢀ
merization of norbornenes, norbornadienes, and tricyclononenes with different numbers and different posiꢀ
tions of siliconꢀcontaining substituents has been developed. It has been found that these monomers are
readily involved in metathesis polymerization yielding highꢀmolecularꢀmass polymers possessing good filmꢀ
forming properties. The addition (vinyl) polymerization of norbornenes is a more complex process; however,
the product silylated polynorbornenes exhibit a higher gas permeability than the corresponding metathesis
polynorbornenes. By the level of the gasꢀtransport parameters, the silylated addition polynorbornenes
obtained in the study are grouped with the most advanced highꢀpermeability polymers. It has been shown that
the presence of Me3Si substituent groups, their amount, and the mainꢀchain structure are responsible for the
enhancement of the gas permeability of polynorbornenes. Thus, a series of polymers with a regularly changꢀ
ing structure has been obtained, a result that makes it possible to reveal the polymer structure–property relaꢀ
tions.
DOI: 10.1134/S0965544110050063
INTRODUCTION
of the synthesis of norbornenes with different numbers
and positions of the siliconꢀcontaining substituents
and the ability of norbornenes to polymerize via metꢀ
athesis [9, 10] and addition polymerization [11, 12]
schemes yielding macromolecules with different
mainꢀchain structures. All of the above made it possiꢀ
ble to obtain series of polymers with a regularly varying
structure of the main chain and its environment and,
thus, to reveal the specific effects of the structure of
polynorbornenes on their gas separation properties.
It is noteworthy that some investigators used substiꢀ
tuted norbornenes for the synthesis of membrane
materials. The gas separation properties of halogeꢀ
nated [13, 14], dicarboxyimide [15–17], cyanoꢀsubꢀ
stituted [18], and silylated [19] derivatives of metatheꢀ
sis polynorbornenes were studied. Works concerning
the examination of the aforementioned parameters
have been recently reported for addition polynorꢀ
bornenes [20–23].
Membrane gas separation has found progressively
increasing application in various industries, including
the petrochemical industry, for the recovery and conꢀ
centration of hydrogen in hydrogenꢀrich gases, the
production of gaseous nitrogen and oxygen, the conꢀ
centration of methane, the isolation of hydrocarbon
vapors from gas streams, etc. [1–4]. In some cases, this
technique successfully competes with the convenꢀ
tional gas separation methods (absorption, cryogenic,
adsorption, etc.), since it is environmentally friendly,
less energyꢀconsuming, is safer, is run with compact
modular equipment, and has other advantages. The
efficiency of membrane gas separation is determined
to a great extent by the properties of gas separation
membranes. Industrial membranes are made largely
from glassy polymers because of their high selectivity,
high affinity, and good mechanical properties [3, 5].
Searching for new membrane materials and revealing
the factors that facilitate improvement in their gasꢀ
separation properties remain a topical issue of a wealth
of original articles and reviews [3, 6–8].
Our studies were focused on polynorbornenes
bearing the Me3Si substituent group, since it is this
substituent that occurs in wellꢀknown poly(trimethylꢀ
silylpropyne) (PTMSP), the most highly permeable
Concerning this problem, we attempted to systemꢀ glassy polymer currently available [8]. The strategy
atically study the synthesis and polymerization of norꢀ that we follow not only turned out to be effective for
bornenes bearing siliconꢀcontaining substituents, to revealing some trends in the influence of the structure
investigate their gas separation properties, and to of polynorbornenes on their gas permeability, but also
search for the system of the effective design of the most made it possible to synthesize highly permeable polyꢀ
permeable polymer membrane structures. The mers categorized with the group of largeꢀfreeꢀvolume
approach used in the study was based on the simplicity polymers, such as polyacetylenes and PTMSP [25].
352

HIGHLY PERMEABLE POLYMER MATERIALS
353
In this paper, we summarize the results obtained
earlier and report original data on the synthesis and
polymerization of new siliconꢀsubstituted norꢀ
bornenes and tricyclononenes and their gas separation
characteristics.
To examine gas permeability, films of 50ꢀ to
200ꢀ m thickness were cast from 2–5% polynorꢀ
μ
bornene solutions in toluene. After the evaporation of
the solvent, the films were evacuated to a constant
mass at room temperature in a vacuum. The gas perꢀ
meability coefficients were measured on a chromatoꢀ
graphic device at 22–24°C and a penetrant partialꢀ
pressure drop of 1 atm.
EXPERIMENTAL
Nuclear magnetic resonance spectra were recorded
on a Bruker MSLꢀ300 NMR spectrometer and a
Varian Unity Inova spectrometer operated at 300 and
125 MHz to record 1H and 13C NMR spectra, respecꢀ
tively, using CDCl3 or С6D6 as an internal standard.
Gas chromatographic–mass spectrometric (GC–
MS) analysis was carried out with a Finnigan MAT 95
XL instrument (ionization energy, 70 eV) and an HP
Synthesis of 5ꢀ(Dimethylphenysilyl)norborneneꢀ2
(NBSiPhMe2)
5ꢀ(Trichlorosilyl)norborneneꢀ2 (7.2 g, 0.031 mol)
dissolved in 10 ml of absolute diethyl ether was added
to 90 ml of a 0.5 M PhMgBr (0.045 mol) solution in
ether (prepared from 0.06 mol of Mg and 0.056 mol of
PhBr) in an inert atmosphere with stirring for 10 min.
Then, the mixture was refluxed over the course of 16 h.
After cooling, 70 ml of a 1 M MeMgI solution
(0.07 mol) in diethyl ether ((prepared from 0.09 mol
of Mg and 0.087 mol of CH3I) was gradually added to
the mixture, and the resulting mixture was refluxed
over 30 h. The diethyl ether was distilled off in a rotary
evaporator. The products were extracted from the resꢀ
6890+ chromatograph on a 30 m 0.25 mm capillary
×
column coated with the DBꢀ5 phase (polydimethylsiꢀ
loxane containing 5% phenyl groups) using helium as
the carrier gas. The molecular masses of the polymers
were determined by gelꢀpermeation chromatography
on a Waters instrument equipped with a differential
refractometric detector (Chromatopack Microgelꢀ5;
solvent, toluene; elution rate, 1 ml/min) and calcuꢀ
lated according to polystyrene standards. The glass
transition temperature in the polymers was measured
with a Mettlerꢀ4000 differential scanning calorimeter
idue with hexane (
removal of hexane, the residue was distilled in a vacꢀ
uum to have a fraction at 71–73 С/0.1 mmHg. The
3
×
50 ml of hexane). After the
at a heating rate of 20
Dicyclopentadiene, bromobenzene, isopropyl
chloride ( ꢀPrCl), and the polymer oxidation inhibitor
°C/min.
°
yield of the desired product was 4.6 g (65%). It was a
mixture of the exoꢀ and endoꢀisomers. Their NMR
signals are presented below as assigned on the basis of
APT, HSQC, and HMBC NMR experiments.
i
2,2'ꢀmethylenebis(6ꢀtertꢀbutylꢀ4ꢀmethylphenol) were
purchased from Aldrich and used as received. Trichloꢀ
rovinylsilane VinSiCl3 (Merck) was distilled in an
argon atmosphere. Tungsten hexachloride was puriꢀ
fied for the removal of oxygenꢀcontaining impurities
1H NMR (CDCl3,
, ppm): 7.55–7.52 m ((2Н,
δ
С6Н5), 7.37–7.36 (3Н, С6Н5), 6.18–6.17 m (0.34H,
C(2)Hꢀexo, C(3)Hꢀexo), 5.99–5.93 m (1.66H,
C(2)H, C(3)H), 2.96 s (0.69H, C(1)ꢀendo, C(4)Hꢀ
endo), 2.90 m (1H, C(1)H, C(4)H), 2.80 s (0.36H,
C(1)Hꢀexo, C(4)Hꢀexo), 1.94–1.90 m (0.760 H,
C(6)H2ꢀendo), 1.64–1.60 m(0.30H C(6)H2ꢀexo),
1.42–1.40 m (0.70H, C(7)H2ꢀendo), 1.37–1.34 m
(0.70H, C(5)Hꢀendo), 1.18–1.13 m (1.30H, C(7)H2ꢀ
endo, C(7)H2ꢀexo, C(6)H2ꢀexo), 1.08–1.05 m (0.70H,
C(6)H2ꢀendo), 0.97–0.96 m (0.30H, C(7)H2ꢀexo),
0.64–0.62 m (0.30H, C(5)Hꢀexo), 0.33ꢀ0.32 m (2H,
SiCH3, 0.24 s (2H, SiCH3), 0.16 s (2H, SiCH3).
(
WCl6) by their sublimation and was used as a 0.02 M
solution in toluene to catalyze the metathesis polyꢀ
merization. The cocatalyst 1,1,3,3ꢀtetramethylꢀ1,3ꢀ
disilacyclobutane (TMSB) prepared according to the
published procedure [26] was held over Na for 1.5 h,
condensed into another vessel by freezing in a vacuum,
and stored under argon. Ethylvinyl ether (Fluka)
(bp 34⎯36°C) was distilled under atmospheric presꢀ
sure. 5ꢀ(Trichlorosilyl)norbornꢀ2ꢀene (NBSiCl3) was
synthesized from cyclopentadiene and trichlorovinylꢀ
silane as described in [27].
Commercial RuCl3 H2O and the Grubbs carbene
×
13C NMR (CDCl3,
, ppm): 140.14, 139.29 (С6Н5),
δ
complex Cl2(PCy3)2Ru=CHPh (Aldrich) as metatheꢀ
sis polymerization catalysts, the addition polymerizaꢀ
tion catalyst nickel(II) naphthenate, and the cocataꢀ
lysts methyl alumoxane (1.4 M solution in toluene,
Aldrich) and B(C6F5)3 (Aldrich) were used without
additional purification. Toluene, diethyl ether, and
hexane were dried with sodium and stored over sodium
wire under argon. Ethanol was dried over magnesium,
distilled, and stored under argon. Chlorobenzene was
refluxed over 1.5 h with P2O5 and then distilled in an
argon atmosphere.
138.44 (C(3)ꢀexo), 135.61 (C(2)ꢀendo), 134.03 (C(3)ꢀ
endo), 133.84, 133.66 (C6H5), 133.44 C(2)ꢀexo),
128.76, 128.61. 127.68, (C6H5), 51.47 (C(7)ꢀendo),
46.76 (C(7)ꢀexo), 44.94, 42.45 (C(1)ꢀendo, C(4)ꢀ
endo), 43.00, 42.55 (C(1)ꢀexo, C(4)ꢀexo), 27.36
(C(6)ꢀendo), 27.35 (C(6)ꢀexo), 24.69 (C(5)ꢀendo
24.54 (C(5)ꢀexo), –2.78, –3.08, –3.38, –3.52 (CH3).
,
EI mass spectrum: 228 (2%, M+), 135 (100%,
SiMe2Ph+), 66 (30%, C6H6).
PETROLEUM CHEMISTRY Vol. 50
No. 5
2010

354
GRINGOL’TS et al.
Synthesis of 5ꢀ(Methyldiisopropylsilyl)norborneneꢀ2
transꢀdouble bonds), 2.50–1.80 m (2H), 1.75–1.00 m
(17Н, С(6)Н2, С(7)Н2, С(5)Н, iꢀC3H7), 0.19 m (3H,
(NBSiMe(iꢀPr)2)
SiСН3).
5ꢀ(Trichlorosilyl)norborneneꢀ2 (7.2 g, 0.031 mol)
dissolved in 10 ml of absolute ether was added to a
13C NMR (C6D6,
, ppm): 134.06 m, 127.97 m
δ
(C(2), C(3)), 45.41–36.71 m (C(1), C(4), C(7)),
29.66 m (C(6)), 19.04 m (C(5), CH(CH3)2), 12.79
(CH(CH3)2), –7.16 (SiСН3).
0.7ꢀM
i
ꢀPrLi solution (100 ml, 0.07 mol) in pentane
(prepared from 0.12 mol of Li and 0.11 mol of
iꢀPrCl)
in an inert atmosphere with stirring for 10 min folꢀ
lowed by refluxing over 20 h. After cooling, 45 ml of a
1 M MeMgI solution (0.045 mol) in diethyl ether
(prepared from 0.06 mol of Mg and 0.056 mol of
CH3I) was added dropwise to the mixture. The resultꢀ
ing mixture was refluxed for another 40 h. The diethyl
ether was distilled off on a rotary evaporator. The
products were extracted from the residue with anhyꢀ
Metathesis poly(3,3ꢀbis(trimethylsilyl)ꢀexoꢀtricyꢀ
clo[4.2.1.02.5]nonꢀ7ꢀene) (WCl6/TMDSCB)
1H NMR (C6D6, ppm): 5.60–5.10 m (2H, C(7)H,
C(8)H), 3.70–1.85 m (7H, C(1)H, C(6)H, C(9)H,
C(2)H, C(5)H, C(4)H2), 1.28–1.20 m (1H, C(9)H),
0.15 m (18H, Si(CH3)3).
13C NMR (C6D6, ppm): 133.19 (C(7), C(8)),
52.52, 50.65. 48.85, 45.52, 44.03 (C(1), C(6), C(9),
C(2), C(5)), 29.99, 17.36 (C(3),C(4)), 1.55, –1.36
drous hexane (
in a rotary evaporator, the residue was distilled in a
vacuum to collect the fraction at 87–89 С/2 mmHg.
The yield of the desired product was 4.1 g (63%).
1H NMR (CDCl3,
, ppm): 6.14 m (0.12H, C(2)H,
3 50 ml). After the removal of hexane
×
°
(
Si(CH3)3).
δ
C(3)H), 5.93–5.90 m (1.88H, C(2)H, C(3)H), 2.99 s,
2.90 s, 2.77 s (2H, C(1)H, C(4)H), 1.89–1.83 m (1H),
RESULTS AND DISCUSSION
1.37–1.35 m (1H), 1.21–0.79 m (18H, С(7)Н2
,
Monomer Synthesis
C(5)Hꢀendo, C(6)H2, iꢀC3H7), 0.51–0.47 m (0.11H,
C(5)Hꢀexo), –0.10 s, –0.14 s, –0.25 (–0.29) (3H,
CH3).
The nonbornene monomers were synthesized via
the diene condensation reaction of cyclopentadiene
with vinylꢀ and ethynylchlorosilane [27–34]
(Scheme 1):
13C NMR (CDCl3,
δ, ppm): 138.36, 135.44,
134.35, 132.90 (C(2), C(3)), 51.46, 47.14 (C(7)),
45.28,43.21, 42.50, 42.10 (C(1), C(4)), 27.99, 27.47
(C(6), 20.91, 20.69 (C(5)), 18.76–18.75 m, 18.35,
18.15, 12.70, 112.64 (
EI mass spectrum: 179 (15%, (M
(60%, (M
Metathesis polymerization on the WCl6/1,1,3,3
tetramethylꢀ1,3ꢀdisilacyclobutane (TMSB), RuCl3
3H2O and Grubbs carbene complex
Cl2(PCy3)2Ru=CHPh catalyst systems was conducted
according to the procedures described in [28, 29].
Addition polymerization was conducted as
described in [30].
i
ꢀC3H7), –8.62 (SiCH3)
.
R
⎯
C3H7)+), 113
R2
+ RCH=CHR1R2
⎯
C3H7–C5H6)+), 66 (100%, С5Н6).
R1
ꢀ
⋅
,
CH CSiCl3
SiCl3
70–75°С
60%
Cl3SiC
CSiCl3
SiCl3
65°С
The spectra of the polymers obtained in this manꢀ
ner are as follows:
83%
SiCl3
Scheme 1.
Metathesis
bornene) (WCl6/TMSB)
1H NMR (C6D6,
, ppm): 7.62–7.34 m (5H, С6Н5),
.45–5.32 m (2H, C(2), C(3)), 3.22 m (0.3H, C(1)H,
poly(5ꢀ(dimethylphenylsilyl)norꢀ
The electronꢀwithdrawing properties of the
trichlorosilyl groups in the dienophiles ensured that
the reaction proceeded under mild conditions (30–
δ
5
C(4)H at cisꢀdouble bonds), 2.90 m (1H), 2.51 m
(0.7H, C(1)H, C(4)H at transꢀdouble bonds), 2.30–
0.90 m (5H, С(6)Н2, С(7)Н2, C(5)H), 0.43 s (6H,
СН3).
70 С) with high yields of the corresponding norꢀ
°
bornenes (60–95%). The subsequent exchange of the
chlorine atom for the methyl, isopropyl, or phenyl
group by the Grignard reaction or the reaction with
alkyllithium was also accomplished with good yields
(60–85%). This reaction had a substantially lower rate
for geminally substituted norbornene because of the
steric hindrances due to the bulky substituents introꢀ
duced by replacing the last chlorine atom with an
alkyl. For this reason, the scheme of the synthesis of 5ꢀ
13C NMR (C6D6,
, ppm): 139.99 m, 138.80 m,
δ
(С6Н5), 134.08 m, 127.67 m (C(2), C(3), С6Н5),
45.39–38.00 m (C(1), C(4), C(7)), 36.15 m (C(6)),
32.70 m (C(5), –2.58 (СН3).
Metathesis poly(5ꢀ(methyldiisopropylsilyl)norꢀ
bornene) (WCl6/TMSB)
1H NMR (C6D6,
δ
, ppm): 5.75–5.25 m (2H, C(2), (phenyldimethylsilyl)norborneneꢀ
C(3)), 3.34 m (0.6H, C(1)H, C(4)H at cisꢀdouble and (methyldiisopropylsilyl)norborneneꢀ2
bonds), 3.03 m (1H), 2.65 m (0.4H, C(1)H, C(4)H at (NBSiMe( Pr)2)) in this study was modified to perform
2
(NBSiPhMe2)
(2
i
PETROLEUM CHEMISTRY Vol. 50
No. 5
2010

HIGHLY PERMEABLE POLYMER MATERIALS
355
the substitution of the bulky phenyl or isopropyl
group, respectively, for the chlorine atom in the first
step followed by methylation (Scheme 2):
+ RR1C=CHR2
R2
R=SiCl3; R1=R2=H
R=R1= SiCl3; R2=H
R=H; R1=R2=SiCl3
7
4
5
6
R1
3
2
1. PhMgBr/Et O
2
2. MeMgI/Et O
SiCl3
SiCl3
SiPhMe2
2
R
1
7
Scheme 3.
4
5
6
1.
iꢀPrLi/Pentane
The specific feature of this reaction is the formaꢀ
tion of tricyclononenes with the cyclobutane moiety
exceptionally in the exoꢀposition. It turned out that
the methylation of chlorosilyltricyclononenes is a
somewhat more active process than that of related
norbornenes, likely as a result of the weakening of the
steric hindrances because of a longer distance between
the substituents and the norbornene cage.
Thus, a set of monomers bearing Me3Si groups in
the exoꢀ and endoꢀpositions (in norbornenes), in
the same plane with the substituted double bond
(in norbornadienes), and different distances from
the reaction center—unsubstituted double bond—
(norbornenes, tricyclononenes) was obtained
(Schemes 2, 3).
3
2
SiiꢀPr2Me
2. MeMgI/Et O
2
1
Scheme 2.
Monosubstituted norbornenes NBSiMe(iꢀPr)2 and
NBSiPhMe2 were represented primarily by the endo
isomers (89 and 70%, respectively), since the
5ꢀtrichlorosilylnorbornene from which they were preꢀ
pared had been enriched in the endoꢀstructure. At the
same time, trimethylsilylnorborneneꢀ2, which can be
prepared in one step via the highꢀtemperature (200–
ꢀ
210 С) condensation of dicyclopentadiene with trimꢀ
°
ethylvinylsilane despite the electronꢀdonating characꢀ
ter of the Me3Si substituent, was composed of an
equimolar mixture of the endoꢀ and exoꢀisomers [31].
Metathesis Polymerization
Along with diene condensation, we employed for
monomer synthesis the novel thermal reaction of the
All of the monomers prepared in this study successꢀ
]ꢀcycloaddition of chlorovinylsilanes to fully entered into metathesis polymerization, which
[2
σ
+ 2
σ
+ 2
π
quadricyclane obtained from norbornadiene, a petroꢀ involves the opening of the bicyclic moiety and the forꢀ
chemical hydrocarbon [30, 32]:
mation of unsaturated polymers (Scheme 4) [28⎯32]:
2
6
3
7
R1
R2
1
4
cat.
cat.
cat.
6
5
R1
R1=R =SiMe3, R3=H
R1=R3=SiMe3, R2=H
R1=R2=H, R3=SiMe3
R1=R2=SiMe3, R3=H
R1=R4=SiMe3
R3
R3
R2
7
5
7
1
4
R4
R1
R1
2
3
R4
R1
8
9
1
6
2
5
R2
R3
3
4
R1
R3
R2
Scheme 4.
The catalysts used were the simple, available, clasꢀ ferent microstructures, in particular, with different
sical metathesis catalysts RuCl3/EtOH, contents of cisꢀ and transꢀdouble bonds, in their presꢀ
RuCl2(PPh3)3, and WCl6/1,1,3,3ꢀtetramethylꢀ1,3ꢀ ence. The cis trans ratio of double bonds was deterꢀ
/
disilacyclobutane (TMSB), as well as generation I and mined from NMR data according to the integrated
II Grubbs carbene complexes. The choice of the clasꢀ signals of protons at the allyl carbon atoms in the
sical catalysts is due not only to their availability but 1H NMR spectrum and the allyl carbon signals in the
also to the opportunity of obtaining polymers with difꢀ 13C NMR spectrum. The product polymers were soluꢀ
PETROLEUM CHEMISTRY Vol. 50
No. 5
2010

356
GRINGOL’TS et al.
Table 1. Metathesis polymerization of silylated norbornenes and tricyclononenes
M/Cat
molar ratio
Catalyst (Cat)
Monomer (M)
5ꢀNBSiPhMe2
Yield, %
Mw,
×
10–3
Mw/Mn
Tg
,
°
C
Z/E
500/1
500/1
500/1
100/1
180/1
180/1
180/1
50/1
96
98
98
98
79
82
85
81
98
95
98
98
617
895
1200
639
247
180
207
190
490
670
634
347
3.3
1.8
2.2
2.0
2.2
1.7
2.1
3.1
2.5
1.5
1.5
1.6
60
30/70
38/62
–
5ꢀNBSi(
i
Pr)2Me
109
98
WCl6/TMSB
25 C, 24 h
,
°
3ꢀTCNSi
3,3ꢀTCNSi2
188
61
–
5ꢀNBSiPhMe2
2/98
3/97
3/97
–
5ꢀNBSi(
i
Pr)2Me
92
RuCl3
⋅ 3H2O/EtOH,
70 C, 14 h
°
3ꢀTCNSi
104
198
57
3,3ꢀTCNSi2
5ꢀNBSiPhMe2
3000/1
46/54
40/60
10/90
28/72
5ꢀNBSi(
i
Pr)2Me 3000/1
3000/1
110
104
186
(PCy3)2Cl2Ru=CHPh,
25 C, 24 h
°
3ꢀTCNSi
3,3ꢀTCNSi2
1500/1
ble in THF, chloroform, and the aromatic solvents tolꢀ possibility for the design of macromolecules with a
uene and chlorobenzene. Their structure was proven mainꢀchain structure other than the metathesis strucꢀ
by the NMR, IR, and elemental analysis techniques. ture [11, 12]. Addition polynorbornenes are attractive
The results of the synthesis of the novel silylated norꢀ owing to their saturation: they do not contain double
bornenes bearing the ꢀSiPhMe2 and ꢀSi(iPr)2Me bonds and, as such, must be thermally and chemically
groups and polytricyclononenes bearing one or two more stable than their metathesis counterparts.
geminal Me3Si groups in the monomer units are given
in Table 1. These results are consistent with the data
obtained earlier [28–32] and show that the W catalyst
n
SiMe3
[Ni]
and the Grubbs Ru carbene complex exhibit the highꢀ
est activity. The highest selectivity was observed for the
RuCl3 catalyst, which facilitates the formation of
polynorbornenes with 93–97% of double bonds in the
transꢀconfiguration. It should be noted that owing to
the high rate of the metathesis polymerization of norꢀ
bornenes, which is thermodynamically favored
because of the opening of its strained molecular strucꢀ
ture, the series of polynorbornenes, polynorbornaꢀ
dienes, and polytricyclononenes with one or two siliꢀ
conꢀcontaining substituent groups were easy to synꢀ
thesize for the subsequent study of their gas
permeability.
SiMe3
Scheme 5.
In addition, such polymer chains exhibit a higher
rigidity because of the impeded rotation of the bulky
norbornene groups, as is indirectly indicated by a high
glass transition temperature (above 350°С) of the addiꢀ
tion polynorbornene. A high rigidity of the polymer
chain can provide for a large free volume and, hence,
a high gas permeability. Unlike metathesis polymerꢀ
ization, the addition polymerization of norbornenes
proceeds at a considerably lower rate, especially in the
case of substituted norbornenes [11]. The introduction
of the trimethylsilyl group (the volume occupied by
this group is commensurable with that of the norꢀ
bornene molecule) creates additional steric hinꢀ
Addition Polymerization
The ability of norbornenes to polymerize via both drances. Nonetheless, we have managed to find the
the metathesis and vinyl (addition) routes opened a simple catalyst system Ni(II)naphthenate/methyl aluꢀ
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HIGHLY PERMEABLE POLYMER MATERIALS
357
Table 2. Addition polymerization of 3ꢀTCNSi and 3,4ꢀTCNSi2 (M) on Ni catalystsa
M/Ni/B/MAO
molar ratio
Reaction
time, h
Catalyst
M
T
,
°
C
Yield, %
0
Mw
Mw/Mn
(Nph)2Ni
600/1/0/0
20
168
–
–
600/1/0/100b 20
600/1/0/100b 90
168
90
32
80
19
3
58700
29022
19500
26000
1.5
3.4
2.6
4.0
(Nph)2Ni/MAO
1500/1/0/500
20
700
700
3000/1/0/1000 20
Ni(OAc)2/MAO
600/1/0/100
600/1/5/100
100/1/7/0
20
20
20
20
700
72
1
8
67
44
37000
124000
58000
2.9
2.3
2.7
3,4ꢀTCNSi2
Ni(OAc)2/B(C6F5)3/MAO
Ni(COD)2/B(C6F5)3
600/1/5/100
72
240
700
240
700
67
43
28
17
8
218000
133000
119000
120000
95000
3.4
1.8
1.8
2.7
2.0
1500/1/10/500 20
1500/1/5/500
1500/1/5/500
3000/1/5/100
20
50
20
(Nph)2Ni/B(C6F5)3/ MAO
1500/1/5/500
20
168
168
168
75
66
56
241956
344135
331000
2.9
3.0
2.3
3ꢀTCNSi
3000/1/5/1000 20
4000/1/15/1200 20
a
b
[Ni] = 0.0005–0.005 mol/l. The results were obtained in [30].
moxane (MAO) to mediate the formation of poly(5ꢀ failed [30, 34, 35]. Bis(trimethylsilyl)ꢀsubstituted norꢀ
trimethylsilyl)norbornene) with Mw = (300–400)
×
bornenes were inactive in homopolymerization, but
they entered copolymerization with norbornene, 5ꢀ
103 [35, 36].
n
ꢀ
hexylnorbornene, and 5ꢀ(trimethylsilyl)norbornene
(5ꢀNBSi), although the degree of involvement and the
However, the attempt to introduce two Me3Si
groups into the monomer units of addition polynorꢀ
bornenes over conventional Pd and Ni catalysts has molecular mass were low (Scheme 6):
17
83
M
w = 17800
w = 51200
w = 172000
SiMe3
Me3Si
Me3Si
C6H13
SiMe3
[Ni, Pd]
n
[Ni]
M
SiMe3
SiMe3
Me3Si
SiMe3
C6H13
SiMe3
11
89
M
SiMe3
Me3Si
SiMe3
Scheme 6.
PETROLEUM CHEMISTRY Vol. 50
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358
GRINGOL’TS et al.
Table 3. Coefficients of gas permeability and permselectivity for some gas pairs of metathesis polynorbornenes bearing one silꢀ
iconꢀcontaining substituent group
P
,
barrer
N2
α
= /Pj
Pi
No.
1
Polymer
PNB
PNBSi [38]
PNBDSi [28]
PNBSiCSi [31]
PTCNSi
Tg, °C
H2
O2
2.8
21
20
16
28
CO2
CH4
O2/N2
H2/N2 CO2/CH4
31
21
77
81
73
119
1.5
6.2
4.9
3.7
6.8
0.45
15.4
79
64
67
112
9.1
2.5
17
8.5
8.5
14.3
0.8
1.9
4.0
4.1
4.3
4.1
4.4
14.4
12.4
16.5
19.7
17.5
36.7
6.3
4.6
7.5
7.9
7.8
2
3
4
5
6
113
108
24
98
60
PNBSiMe2Ph
16.5
2.0
11.4
SiMe3
SiMe3
SiMe3
SiMe2CH2SiMe3
n
n
n
n
n
PNB
PNBSi
PNBDSi
PNBSiCSi
PTCNSi
Silylated tricyclononenes turned out to be more
active in addition polymerization. They formed not
only copolymers with norbornenes, but also addition
homopolymers (Scheme 7) [30, 32]:
Gas Separation Properties
An important task of the synthesis of siliconꢀsubstiꢀ
tuted polynorbornenes was the examination of their
gas permeability and the selection of further routes of
the synthesis of new highly permeable polymers on the
basis of the results. For example, the study of the gas
separation properties of metathesis polynorbornenes
bearing one siliconꢀcontaining substituent has shown
that the introduction of the Me3Si substituent into
metathesis polynorbornene substantially enhances its
gas permeability (Table 3; entries 1, 2). The metathesis
polynorbornene is characterized by almost the same
permeability (Table 3, entry 3). An attempt to introꢀ
duce two methylsilyl groups at one substituent site
somewhat decreased the permeability to H2, О2, and
N2 (Table 3, entry 4), a phenomenon that can be assoꢀ
ciated with the polymer selfꢀplasticizing effect, as
indicated by a drop in the glass transition temperature
SiMe3
[Ni]
SiMe3
SiMe3
Me3Si
Scheme 7.
3,4ꢀTCNSi2
The new results of the addition polymerization of
3ꢀ(trimethylsilyl)tricyclononeneꢀ7 (3ꢀTCNSi) and
3,4ꢀbis(trimethylsilyl)tricyclononeneꢀ7 (3,4ꢀTCNSi2
)
on various Niꢀcontaining catalyst systems are preꢀ
sented in Table 2.
from 110–113 to 24 С. A somewhat higher permeabilꢀ
°
It is seen that the introduction of the Lewis acid
ity in the this series is shown by poly(3ꢀtrimethylsilylꢀ
tricyclononene) (PTCNSi). The replacement of the
methyl with the phenyl group on the silicon atom
reduces the permeability of the polymer. A similar sitꢀ
uation in the case of silylated polyacetylenes is
B(C6F5)3 as
a
third component into the
(Nph)2Ni/MAO catalytic system is the most effective.
Its presence has resulted in highꢀmolecularꢀmass
polymers with
M
w = (2–3)
105 and a yield of 67–75%
×
(Table 2). It was very important to reach the maximal explained by Savoca et al. [37] in terms of the
enhancement of the interaction between chains,
which decreases the free volume and, hence, reduces
the gas permeability of the polymers.
From the results obtained in this study, it can be
concluded that for a polymer to have better gas sepaꢀ
attainable molecular mass (MM), since the mechaniꢀ
cal properties of addition polynorbornenes are
improved with an increase in MM. The silylated addiꢀ
tion polytricyclononenes synthesized on the Ni cataꢀ
lyst are characterized by the following glass transition
temperatures, 140
°
С
for poly(3ꢀTCNSi) and 184 С for ration parameters, its monomer unit must contain
°
Me3Si groups attached directly to the cyclic moiety.
poly(3,4ꢀTCNSi2), whereas the siliconꢀsubstituted
addition polynorbornenes do not experience the glass
transition before the onset of degradation. All of the
addition polymers and copolymers synthesized in this
study are amorphous substances soluble in aromatic
and chlorinated hydrocarbons.
Table 4 presents the gas transport parameters for
disubstituted metathesis polynorbornenes. It is seen
that all of the metathesis polymers of the polynorꢀ
bornene type examined in this work are more permeꢀ
able when they contain two, rather than one, Me3Si
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HIGHLY PERMEABLE POLYMER MATERIALS
359
Table 4. Coefficients of gas permeability and permselectivity for some gas pairs of metathesis polynorbornenes bearing two
Me3Si groups
Permeability P, barrer
α
= /Pj
Pi
No.
Polymer
H2
O2
N2
CO2
CH4
O2/N2
H2/N2 CO2/CH4
1
2
3
4
5
P(5,6ꢀNBSi2) [28]
P(5,5ꢀNBSi2) [29]
P(2,3ꢀNBDSi2) [29]
P(3,4ꢀTCNSi2) [29]
P(3,3ꢀTCNSi2)
375
218
254
332
209
95
54
71
89
50
25
14
20
24
12
445
277
358
396
258
45
27
49
55
28
3.8
3.9
3.6
3.7
4.2
15.0
15.6
12.7
13.8
17.4
9.9
10.3
7.3
7.2
9.2
n
n
n
n
n
Me3Si
Me3Si
SiMe3
SiMe3
P(5,5ꢀNBSi2)
SiMe3
Me3Si
SiMe3
P(3,4ꢀTCNSi2) P(3,3ꢀTCNSi2)
SiMe3
Me3Si
Me3Si
P(5,6ꢀNBSi2)
P(2,3ꢀNBDSi2)
Table 5. Coefficients of gas permeability and permselectivity for some gas pairs of silylated addition polynorbornenes syntheꢀ
sized on Ni catalysts
P, barrer
N2 CO2
1.5 33.6
297
α
= /Pj
Pi
Run
no.
Polymer
H2
O2
6.9
CH4
C4H10 O2/N2 H2/N2 CO2/CH4 C4H10/CH4
1
2
3
4
APNB [36]
41.5
2.6
790
–
17400
–
4.6
2.6
2.9
2.0
27.6
5.7
8.1
12.9
5.5
5.9
3.7
–
22.0
–
APNBSi [36] 1700
780
450
4350
2230
APTCNSi
PMP [39]
1230
152
380
5800 2700
1330
10700
2900
11700–
23700
4.4
4.0–8.2
n
n
n
n
SiMe3
SiMe3
APNB
APNBSi
APTCNSi
PMP
groups in the repeating unit. Note that the glass tranꢀ stituents (runs 2, 5). Most likely, the different positions
of the SiMe3 groups in the monomer unit lead to a difꢀ
ference in the value and/or structure of the free volꢀ
ume. The permeability of the polytricyclononene
derivatives is close to that of the corresponding
polynorbornenes; i.e., the more distant position of the
Me3Si groups has no substantial effect of the permeꢀ
ability.
sition temperature of disubstituted polynorbornenes
168–203 ) is substantially higher than that of the
monosubstituted counterparts (24–113 ), thereby
indirectly indicating that the disubstituted polymers
have a higher chain rigidity and, consequently, a
greater free volume. From the data presented in
Table 4, it is also seen that the polymers in which
two Me3Si groups are in the transꢀvicinal position
(runs 1, 4) exhibit a higher gas permeability as comꢀ
(
°
С
°
С
The introduction of Me3Si substituent groups into
addition polynorbornene turned out to be the most
pared to the polynorbornenes with the geminal subꢀ effective from the standpoint of gas permeability. The
PETROLEUM CHEMISTRY Vol. 50
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2010

360
GRINGOL’TS et al.
study of the gas separation properties of addition
poly(5ꢀtrimethylsilylnorbornene) (APNBSi) and
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