Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-08-18
2001-03-20
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S171000, C526S280000, C526S283000, C526S307800, C502S155000, C502S162000
Reexamination Certificate
active
06204347
ABSTRACT:
The present invention relates to a two-component catalyst system for the ring-opening metathesis polymerization (ROMP), to a curable system comprising such a catalyst system, to a process for the preparation of moulded articles as well as to the use of the curable system as encapsulating material for electrical or electronic components.
U.S. Pat. No. 4,426,502 and EP-A-348 852 describe the ring-opening metathesis polymerization (ROMP) of strained cycloolefins by the RIM process (reaction injection moulding). In this case a two-component system consisting of a catalyst and a co-catalyst is used for the ring-opening metathesis polymerisation. According to the process described in the above publications, the polymerizable cycloolefin is divided into two portions, one half comprising the catalyst and the other half the corresponding co-catalyst. When the two portions are mixed and injected into the preheated mould, the mixture cures quickly. However, the use of organo aluminium compounds as co-catalysts requires the exclusion of moisture.
WO 96/16100 and WO 96/20235 describe ruthenium catalysts which are not susceptible to moisture but which are unsuitable for the RIM process because of their high reactivity.
It is the object of this invention to provide a two-component catalyst system for the ring-opening metathesis polymerisation which is stable against air and moisture and which is suffficiently reactive for the RIM process.
It has now been found that certain ruthenium complexes and tertiary phosphines containing secondary alkyl or cycloalkyl groups form a suitable storage-stable two-component system which affords cured products having excellent properties, in particular high heat stability, high toughness and mechanical strength.
Accordingly, this application relates to a catalyst system for the ring-opening metathesis polymerization, which consists of at least two components (a) and (b), wherein
(a) is a ruthenium compound of formula I or II
RuX
2
(L
1
)
m
(L
2
)
n
(L
3
)
o
(L
4
)
p
(I),
ARuX
2
(L
1
)
r
(L
2
)
s
(II),
wherein L
1
, L
2
, L
3
and L
4
are each independently of the other C
1
-C
18
alkylcyanide, C
6
≧C
24
-aralkylcyanide, tertiary amine, tertiary phosphine which does not contain any secondary alkyl or cycloalkyl radicals bound to the phosphorus atom, or phosphite, X is halogen, A is arene, m, n, o and p are integers from 0 to 4, where 2≦m+n+o+p≦4, r and s are integers from 0 to 2, where 1≦r+s≦2, and
(b) is a tertiary phosphine containing at least one secondary alkyl radical or cycloalkyl radical bound to the phosphorus atom.
The ruthenium compounds of formula I or II can be prepared by known processes by reacting ruthenium dihalides with the corresponding arenes, nitriles, amines, phosphines or phosphites.
C
1
-C
18
Alkylcyanides which are suitable as ligands L
1
to L
4
are, for example, acetonitrile, propionitrile, n-butyronitrile, isobutyronitrile, pivalonitrile, neo-pentylcyanide, valeronitrile, capronitrile, n-heptylcyanide, n-octylcyanide, n-nonylcyanide and n-decylcyanide. Typical examples of suitable C
6
-C
24
aralkylcyanides are phenylacetonitrile, 3-phenylpropionitrile, 4-phenylbutyronitrile and naphthylacetonitrile.
Tertiary amines suitable as ligands L
1
to L
4
are, for example, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-tert-butylamine, benzyldimethylamine, triphenylamine, tricyclohexylamine, phenyldimethylamine, phenyldiethylamine, cyclohexyldimethylamine, cyclohexyldiethylamine, urotropine, triethylenediamine, N-methylpiperidine and N-ethylpiperidine.
L
1
to L
4
defined as tertiary phosphine may be, for example, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri-n-octylphosphine, tritolylphosphine or a compound of formula III
wherein R is C
1
-C
18
alkyl, C
5
-C
14
aryl or C
6
-C
24
aralkyl.
The alkyl groups in formula III may be straight-chain or branched and preferably contain 1 to 12, particularly preferably 1 to 8 and, most preferably, 1 to 4, carbon atoms.
Alkyl encompasses, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl as well as the different isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
R defined as aryl preferably contains 6 to 10 carbon atoms and is typically phenyl, tolyl, pentalinyl, indenyl, naphtyl, azulinyl and anthryl.
R defined as aralkyl preferably contains 7 to 12 carbon atoms, particularly preferably 7 to 10 carbon atoms, and is typically benzyl, phenylethyl, 3-phenylpropyl, &agr;-methylbenzyl, 4-phenylbutyl and &agr;,&agr;-dimethylbenzyl.
Phosphites suitable as ligands L
1
to L
4
are, for example, trimethylphosphite, triethylphosphite, tri-n-propylphosphite, triisopropylphosphite, tri-n-butylphosphite, triphenylphosphite, methyldiphenylphosphite, dimethylphenylphosphite, tri-n-octylphosphite, tritolylphosphite or tris(p-nonylphenyl)phosphite, or compounds of the above formula III.
X in formula I or II is fluoro, chloro, bromo or iodo. Chloro is preferred.
The term “arene” generally stands for aromatic compounds. A in formulae II and lIl is preferably a monocyclic, polycyclic or condensed arene which is unsubstituted or substituted by OH, C
1
-C
4
alkyl, C
1
-C
4
alkoxy, C
6
-C
12
aryl or halogen and which contains 6 to 24, preferably 6 to 18, particularly preferably 6 to 12, carbon atoms.
Some examples of arenes and heteroarenes are benzene, toluene, o-xylene, p-xylene, mesitylene, ethylbenzene, cumene, 1,3,5-triisopropylbenzene, p-cymene, durene, hexamethylbenzene, naphthalene, biphenyl, diphenylmethane, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoranthrene, furan, thiophene, pyrrole, pyridine, &ggr;-pyran, &ggr;-thiopyran, pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, benzothiophene, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene and purine. Preferred arenes and heteroarenes are unsubstituted or substituted benzene, naphthalene, thiophene and benzothiophene.
Suitable components (b) of the catalyst system of this invention are, in principle, all tertiary phosphines which contain at least one secondary alkyl or cycloalkyl group bound direct to the phosphorus atom.
Examples to be mentioned of such phosphines are isopropyldimethylphosphine, diisopropylmethylphosphine, isopropyldiethylphosphine, diisopropylethylphosphine, isopropyldiphenylphosphine, diisopropylphenylphosphine, triisopropylphosphine, tri-sec-butylphosphine, tris(1-methylbutyl)phosphine, tris(1-ethylbutyl)phosphine, cyclohexyldimethylphosphine, dicyclohexylmethylphosphine and tricyclohexylphosphine.
In a preferred embodiment of this invention, component (a) is a compound of formula II, wherein A is benzene, toluene, o-xylene, p-xylene, mesitylene, ethylbenzene, cumene, 1,3,5-triisopropylbenzene, p-cymene, durene, hexamethylbenzene, naphthalene, biphenyl or diphenylmethane.
Component (a) is preferably also a compound of formula I or II, wherein one or several ligands L
1
to L
4
are acetonitrile, propionitrile, n-butyronitrile, valeronitrile or capronitrile.
Also preferred as component (a) are compounds of formula I or II, wherein one or several ligands L
1
to L
4
are triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri(n-butyl)phosphine, tri(n-octyl)phosphine, trimethylphosphite, triisopropylphosphite, triphenylphosphite, tris(p-nonylphenyl)phosphite or a compound of formula III
wherein R is C
1
-C
18
alkyl, C
5
-C
14
aryl or C
8
-C
24
aralkyl.
Component (a) is particularly preferably a compound of formula II, wherein A is p-cymene, r is 2, and L
1
is butyronitrile or capronitrile.
Component (a) is also particularly
Hafner Andreas
Muhlebach Andreas
Van Der Schaaf Paul Adriaan
Ciba Specialty Chemicals Corporation
Crichton David R.
Hall Luther A. R.
Lu Caixia
Wu David W.
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