Polymerizable composition, process for producing cross...

Details Polymerizable composition, process for producing cross... Polymerizable composition, process for producing cross...

1997-07-31

2001-08-28

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...

C526S172000, C526S260000, C526S280000, C526S283000, C526S309000, C502S150000, C502S156000, C502S162000, C502S158000

Reexamination Certificate

active

06281307

ABSTRACT:

The present invention relates to a composition of unsaturated polymers, in the polymer backbone of which is bonded a strained cycloalkenylene, with a one-component catalyst for metathesis polymerization which is induced thermally or by actinic radiation; a process for the polymerization of the composition; materials coated with the composition or the polymerized composition, and shaped articles of the crosslinked polymers; and crosslinkable polymers.
Thermally induced ring-opening metathesis polymerization using catalytic amounts of metal catalysts has already been known for a relatively long time and described in many cases in the literature [see, for example, Ivin, K. J., Olefin Metathesis 1-12, Academic Press, London (1983)]. Polymers obtainable in this way are prepared industrially and are commercially obtainable, for example under the trade name Vestenamer®. The industrial preparation is carried out using highly reactive two-component catalysts, as a rule transition metal halides, for example WCl
6
and metal-alkylenes, for example zinc-, aluminium- or tin-alkylene. The polymerization or gelling starts immediately after a cycloolefin has been combined with the two catalyst components. The mixtures of cycloolefin and catalyst therefore have exceptionally short pot lives, and they are suitable in practice only in the reaction injection moulding process (RIM process). The severe heating of the reaction mixture due to the heat of reaction, which imposes very high technical requirements on a controlled reaction temperature, is also a disadvantage. It is therefore difficult to adhere to a polymer specification. WO 93/13171 describes air- and water-stable one-component and two-component catalysts based on molybdenum and tungsten compounds containing carbonyl groups and ruthenium and osmium compounds having at least one polyene ligand for thermal metathesis polymerization and a photoactivated metathesis polymerization of strained cycloolefins, in particular norbornene. No other polycyclic—above all non-fused polycyclic—cycloolefins are mentioned. The one-component catalysts of the ruthenium compounds used, that is to say [Ru(cumene)Cl
2
]
2
and [(C
6
H
6
)Ru(CH
3
CN)
2
Cl]
30
PF
6
−
, can indeed be activated by UV irradiation; however, the storage stability of the compositions with norbornene are [sic] completely unsatisfactory. These catalysts can replace the known two-component catalysts only in adequately. Demonceau et al. [Demonceau, A., Noels, A. F., Saive, E., Hubert, A. J., J. Mol. Catal. 76: 123-132 (1992)] describe (p-cumene)RuCl
2
P(C
6
H
11
)
3
, (C
6
H
5
)
3
]
3
PRuCl
2
and (C
6
H
5
)
3]
3
PRuHCl as thermal catalysts for the ring-opening metathesis polymerization of norbornene, a fused polycycloolefin. Because their activity is too low, these catalysts have not found acceptance in industrial preparation. It is therefore proposed to increase the activity by the addition of diazoesters. It is also mentioned that only (p-cumene)RuCl
2
P(C
6
H
11
)
3
is capable of polymerizing norbornene in a relatively short time at 60° C. Cyclooctene is also mentioned as a further monomer. No other cycloolefins are mentioned for the methatesis [sic] polymerization.
Petasis and Fu [Petasis, N. A., Fu, D., J. Am. Chem. Soc. 115: 7208-7214 (1993)] describe the thermal ring-opening metathesis polymerization of norbornene using bis-cyclopentadienyl-bis(trimethylsilyl)methyl-titanium(IV) as a thermally active catalyst. No other cycloolefins are mentioned for the metathesis polymerization.
No other more reactive one-component catalysts have yet been disclosed. It is furthermore also not known to use polymers with a strained cycloalkenylene in the polymer backbone for the preparation of crosslinked polymers.
It has now been found that polymers with strained cycloalkenylene radicals bonded in the polymer backbone are outstandingly suitable for the preparation of crosslinked polymers under the action particularly of one-component catalysts. The compositions are storage-stable and are even insensitive to air and oxygen, depending on the catalysts used, which allows processing without particular protective measures. Processing is easy and the processing possibilities are diverse, because no particular measures have to be taken owing to excessive reactivity. The polymers are suitable both for the production of solid shaped articles and for coatings with particularly high adhesive strength. The polymers can furthermore be used for the production of images by means of irradiation under a photomask and subsequent development of the non-exposed portions with a suitable solvent.
The invention first relates to a composition comprising (a) catalytic amounts of a one-component catalyst for metathesis polymerization and (b) at least one polymer with strained cycloalkenylene radicals bonded in the polymer backbone, alone or mixed with strained cycloolefins.
In a preferred embodiment, the polymers are those with recurring structural units of the formula (a) in the polymer backbone
in which
R
01
and R
02
independently of one another are H or C
1
-C
6
alkyl, or R
01
and R
02
together are a bond, and
A, together with the C—C group, forms an unsubstituted or substituted strained cycloolefin ring. The structural units of the formula (a) can be bonded directly or via bridge groups, preferably identical bridge groups.
Alkyl R
01
and R
02
preferably contain 1 to 4 C atoms; the alkyl is preferably methyl or ethyl. R
01
and R
02
are particularly preferably H.
The susbtituents for the cycloolefin ring can be, for example, C
1
-C
8
-, and preferably C
1
-C
4
alkyl or -alkoxy, for example methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, methoxy, ethoxy or propyloxy; C
1
-C
4
haloalkyl or -alkoxy, for example trifluoromethyl, trichloromethyl, perfluoroethyl, bis(trifluoromethyl)methyl, trifluoromethoxy or bis(trifluoromethyl)methoxy; halogen, for example F, Cl or Br; —CN; —NH
2
; secondary amino having 2 to 18 C atoms; tertiary amino having 3 to 18 C atoms; —C(O)—OR
03
or —C(O)—NR
03
R
04
, in which R
03
is H, C
1
-C
18
alkyl, phenyl or benzyl and R
04
independently has the meaning of R
03
.
The strained cycloolefin ring can be monocyclic or polycyclic fused and/or bridged ring systems, for example with 2 to 6, preferably 2 to 4, and particularly preferably 2 or 3 rings, which are unsubstituted or substituted and can contain heteroatoms, for example O, S, N or Si, in one or more rings and/or fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings can contain 3 to 16, preferably 4 to 12, particularly preferably 5 to 8 ring members. The cyclic olefins can contain further non-aromatic double bonds, preferably 2 to 4 such additional double bonds, depending on the ring size.
Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 4 to 7, and especially preferably 5 or 6 ring C atoms. Fused-on aromatics are preferably naphthylene and, in particular, phenylene.
In a preferred embodiment, in formula (a)
R
01
and R
02
together are a bond, and A is unsubstituted or substituted C
1
-C
12
alkylene, preferably C
2
-C
6
alkylene; unsubstituted or substituted C
2
-C
12
heteroalkylene, preferably C
3
-C
6
heteroalkenyklene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C
5
-C
12
cycloalkylene, preferably C
5
-C
7
cycloalkylene; unsubstituted or substituted C
4
-C
12
heterocycloalkylene, preferably C
4
-C
7
heterocycloalkylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C
2
-C
12
alkenylene, preferably C
2
-C
6
-alkenylene; unsubstituted or substituted C
3
-C
12
heteroalkenylene, preferably C
3
-C
6
heteroalkenylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C
5
-C
12
cycloalkenylene, preferably C
5
-C
7
cycloalkenylene; or unsubstituted or substituted C
4
-C
12
heterocy

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