CA2242060A1 - Cycloolefin-based adhesive - Google Patents
Cycloolefin-based adhesive Download PDFInfo
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- CA2242060A1 CA2242060A1 CA 2242060 CA2242060A CA2242060A1 CA 2242060 A1 CA2242060 A1 CA 2242060A1 CA 2242060 CA2242060 CA 2242060 CA 2242060 A CA2242060 A CA 2242060A CA 2242060 A1 CA2242060 A1 CA 2242060A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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Abstract
The invention relates to the use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
(see fig. I) , wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
(see fig. I) , wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
Description
Cycloolefin-based adhesive The present invention relates to the use, as an adhesive, of a composition comprising a strained cycloolefin, a catalyst, a filler and a silane, and to a method of bonding substrates.
In WO 96/16100 and WO 96/20235 it is mentioned that the ROMP systems (ROMP = ring-opening metathesis polymerisation) described therein based on strained cycloolefins and specific ruthenium catalysts are suitable as adhesives for bonding Teflon, polyethylene and polypropylene. The adhesion to the substrate is inadequate for certain uses, however, owing to the low polarity of the cycloolefins.
Bonds made with reactive adhesives exhibit inner strains caused by reaction shrinkage when the relatively large intermolecular spacing between the monomers are replaced by the closer spacing of the covalent bonds between the polymer segments. The shrinkage can bereduced by the addition of suitable fillers, but the addition of fillers generally results in a breakdown of the cohesion.
Surprisingly, it has now been found that the ROMP systems described in EP-A-771 830, together with fillers, exhibit very good adhesion and can consequently be used as adhesives.
The present invention relates to the use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
OY, R--Si OY2 (I ), oy3 wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may be replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y" Y2 and Y3 are each independently of the others C,-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20alkoxyalkyl or C,-C20acyl.
When fully cured, the ROMP system exhibits an especially high degree of adhesion to metals, for example iron or aluminium. Preference is accordingly given to the use of the above-specified composition as an adhesive for metals, especially for aluminium.
Within the scope of the present invention there is to be understood by "strained cycloolefin"
any cycloolefin, with the exception of cyclohexene and derivatives thereof, which cannot be polymerised by ring-opening metathesis.
Strained cycloolefins may be monocyclic or polycyclic fused or bridged ring systems, for example having from two to four rings, that are unsubstituted or substituted and may contain hetero atoms, for example oxygen, sulfur, nitrogen or silicon, in one or more rings and/or may contain fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthyl-ene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings may contain from 3 to 16, especially from 3 to 12, and more especially from 3 to 8, ring members. The strained cyclo-olefins may contain further non-aromatic double bonds, preference being given, depending on the ring size, to from 2 to 4 such additional double bonds. The ring substituents are inert, that is to say those substituents do not impair the chemical stability and the thermostability of the ROMP catalysts.
When the strained cycloolefins contain more than one double bond, for example from 2 to 4 double bonds, it is possible also for crosslinked polymers to be formed, depending on the reaction conditions, the monomer selected and the amount of catalyst.
There is preferably used as component (a) in the composition according to the invention a compound of formula ll \ / (Il), wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2 group, forms an alicyclic ring having a minimum of three members that may contain one or more hetero atoms selected from the group silicon, phosphorus, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, =0, -CN, -NO2, R1R2R3Si-(O)u~, -COOM, -S03M, -PO3M, -COO(M,)1,2, -SO3(M,)"2, -PO3(M,)"2, C,-C20alkyl, C,-C20hydroxyalkyl, C,-C20haloalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6-aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C,6heteroaralkyl or by R4-X-; or in which two adjacent carbon atoms are bonded by -CO-O-CO- or -CO-NR5-CO-; or in which there is fused to adjacent carbon atoms of the alicyclic ring an alicyclic, aromatic or heteroaromatic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)U-, -COOM, -SO3M, -PO3M, -COO(M1)1,2, -S03(M1)"2, -PO3(M1)"2, C,-C20alkyl, C,-C20haloalkyl, C,-C20-hydroxyalkyl, C,-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6aralkyl, C3-C6heterocyclo-alkyl, C3-C,6heteroaryl, C4-C,6heteroaralkyl or by R,3-X,-; X and X1 are each independently of the other -O-, -S-, -CO-, -SO-, -SO2-, -O-CO-, -COO-, -CO-NR5-, -NR10-CO-, -SO2-O- or -O-SO2-; R1, R2 and R3 are each independently of the other C,-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl; R4 and R~3 are each independently of the other C,-C20alkyl, C,-C20-haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; R5 and R,O are each independently of the other hydrogen, C,-C,2alkyl, phenyl or benzyl, the alkyl groups in turn being unsubstituted or substituted by C,-C,2alkoxy or by C3-C8cycloalkyl; R6, R7 and R8 are each independently of the others C,-C,2alkyl, C,-C,2perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; and u is O or 1; it being possible for the alicyclic ring formed with Q, to contain further non-aromatic double bonds;
Q2 is hydrogen, C,-C20alkyl, C,-C20haloalkyl, C,-C,2alkoxy, halogen, -CN or R"-X2-; R" is C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; X2 is -COO- or -CO-NR,2-; and R,2 is hydrogen, C,-C,2alkyl, phenyl or benzyl;
wherein the above-mentioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups may be unsubstituted or substituted by C,-C,2alkyl, C,-C,2alkoxy, -NO2, -CN or by halogen, and wherein the hetero atoms of the above-mentioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -O-, -S-, -NRg- and -N=, Rg being hydrogen, C,-C,2alkyl, phenyl or benzyl.
Fused-on alicyclic rings contain preferably from 3 to 8, especially from 4 to 7, and more especially 5 or 6, ring carbon atoms.
For the purpose of crosslinking or to control the molecular weight, the composition according to the invention may contain further olefins capable of metathesis, advantageously in amounts of up to 40 mol %, especially from 0.01 to 30 mol % and more especially from 0.1 to 20 mol %, based on the total amount of the cycloolefins and olefins present.
Suitable olefins capable of metathesis are, for example, cyclooctadiene, cyclooctatriene, norbornadiene and acetylnorbornene. Also suitable are compounds such as 2-butene-1,4-diol, as described in Feast, W.J., Harrison, B., J. Mol. Catal. 65, 63 (1991), or 1-hexene (rearrangements) .
The presence of an asymmetric centre in the compounds of formula ll means that those compounds may occur in optically isomeric forms. Some compounds of formula ll may occur in the form of tautomers (e.g. keto-enol tautomerism). If an aliphatic C=C double bond is present, then also geometric isomerism may occur (E-form or Z-form). In addition, exo/endo configurations are also possible. Formula ll hence includes all possible stereoisomers, which are in the form of enantiomers, tautomers, diastereoisomers, E/Z isomers or mixtures thereof.
The alkyl, alkenyl and alkynyl groups in the definitions of the substituents may be straight-chain or branched. The same applies also to the alkyl moiety or each of the alkyl moieties of alkoxy, alkylthio, alkoxycarbonyl and other alkyl-containing groups. The alkyl groups contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 4, carbon atoms. The alkenyl and alkynyl groups contain preferably from 2 to 12, especially from 2 to 8, and more especially from 2 to 4, carbon atoms.
Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxyisobutyl, 1-hydroxy-sec-butyl, 1-hydroxy-tert-butyl and the various hydroxy-substituted isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-tri-chloroethyl and halogenated, especially fluorinated or chlorinated, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups and the various halogenated isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Cycloalkyl is preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl. Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Cyanoalkyl includes, for example, cyanomethyl (methylnitrile), cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyanoisobutyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and the various isomers of cyanopentyl and cyanohexyl.
Aralkyl contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Aryl contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Heteroaryl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, purinyl or quinolyl.
Heterocycloalkyl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, oxiranyl, azirinyl, 1,2-oxathiolanyl, pyrazolinyl, pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl or tetrahydrothiophenyl.
Alkoxy is, for example, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy or tert-butyloxy.
Within the scope of the present invention, alkali metal is to be understood as meaning lithium, sodium, potassium, rubidium or caesium, especially lithium, sodium or potassium.
Within the scope of the present invention, alkaline earth metal is to be understood as meaning beryllium, magnesium, calcium, strontium or barium, especially magnesium or calcium.
In the above definitions, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Especially well-suited compounds of formula ll in the composition according to the invention are those wherein Q2 is hydrogen.
Preference is given also to compounds of formula ll wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2- group, forms a 3- to 10-membered alicyclic ring that may contain a hetero atom selected from the group silicon, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, -CN, -NO2, R,R2R3Si-, -COOM, -SO3M, -PO3M, -COO(M,)"2, -S03(M,)"2, -PO3(M,)"2, C1-C6alkyl, C,-C6-haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R4-X-; or in which there may be fused to adjacent carbon atoms an aromatic or heteroaromatic or alicyclic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M,)1~2, -SO3(M1)1~2, -PO3(M1)1~2, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R13-X1-; R1, R2 and R3 are each independently of the others C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; R4 and R13 are each independently of the other C1-C6alkyl, C1-C6haloalkyl, C,-C6hydroxyalkyl or C3-C6cycloalkyl; X and X1 are each independently of the other-O-, -S-, -CO-, -SO- or-S02- and R6, R7 and R8 are each independently of the others C,-C4alkyl, C,-C4perfluoroalkyl, phenyl or benzyl.
Norbornene and norbornene derivatives, especially dicyclopentadiene and dicyclopentadiene derivatives, are especially preferred as component (a).
Preferred norbornene derivatives are the compounds of formulae lll, IV, V and Vl ~14 ~ (IV), R.8 ~ (V), ~ (Vl), wherein X3 is -CHR16-, oxygen or sulfur, R14 and R15 are each independently of the other hydrogen, -CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR17, and R16 and R17 are each independently of the other hydrogen, C1-C12alkyl, phenyl or benzyl;
X4 is -CHR19-, oxygen or sulfur, R19 is hydrogen, C1-C12alkyl, phenyl or benzyl and R18 is hydrogen, C1-C6alkyl or halogen;
Xs is -CHR22-, oxygen or sulfur, R22 is hydrogen, C1-C12alkyl, phenyl or benzyl, R20 and R21 are each independently of the other hydrogen, CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR23 and R23 is hydrogen, C1-C12alkyl, phenyl or benzyl;
X6 is -CHR24-, oxygen or sulfur, R24 is hydrogen, C1-C12alkyl, phenyl or benzyl, Y is oxygen or \N--R and R25 is hydrogen, methyl, ethyl or phenyl.
Examples of suitable compounds of formula ll are the following cycloolefins:
~ (2)~ ~ (3).
CA 02242060 l998-06-30 COOH ~~ COOCH3 ~\~(4), ~ (5), / (6), o O o COOCH2phenyl ~_ COOCzHs /~~ COO(CH2)~CH3 ~ (7). ~ (8), ~ (9).
COOCH2phenyl COOCzHs coo(CH2)3cH3 O O
~_ COO(CH2)sCH3 ~ COO(CH2)9CH3 ~_ COO(CH2),lCH3 ~ (10). ~ (11), ~ (12 Coo(cH2)scH3coo(cH2)9cH3 coo(cH2)1~c~l3 O O
~f(,3). ~ f~(,4) ~ f~(1s) ~ O NH
O O O
O O O
f (16), f (17)' fo (18), N ' CH3 C2H5 ~ phenyl O O O
~(19)~ 3(20), (~)(21), (22), ~ (23), [3 (24), [~ (25), b (26), b (27), ~ (28), (29), ~ ~ (30)~ b CN (31), \CH2NHCH3 1~ .
~( (32), ~V Sl(CH3)3 (33), b P(C6H5)2 (34~ b~ CH2~(CH2)5~CH3 (35 P(C6H5)2 b 3 (36), ~ ~ (37), o_ _ ~ " (38), ~3 (39)' (40~ ,3(41)~
~1 ~3 (42), ~ 3 (43) In a preferred embodiment, the strained cycloolefins contain only carbon and hydrogen atoms, and are preferably 5- or 6-membered rings, or ring systems having from one to three 5- or 6-membered rings, for example norbornenes, alkylated norbornenes and dicyclopenta-diene.
Especially preferred as component (a) is dicyclopentadiene.
A large number of compounds of the transition metals titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium are known to the person skilled in the art as catalysts for ring-opening metathesis polymerisation (ROMP catalysts). Such compounds are, for example, complex metal halides, metallo-carbenes or co-ordination catalysts of the Ziegler-Natta type. In principle, any of those known ROMP catalysts may be used as component (b) in the compositions according to the invention.
Preferably, a ruthenium(+ll) complex salt or an osmium(+ll) complex salt, especially a ruthenium(+ll) complex salt, is used as component (b).
Since the fillers according to component (c) often contain small amounts of water, it is advisable to use ROMP catalysts that are not sensitive to moisture, such as, for example, the ruthenium(+ll) and osmium(+ll) complex salts described in WO 96/16100 and WO 96/20235.
The preferred component (b) is therefore a complex salt of formula lll (R2sR3oR31p)xLyMe2+z1-z2 (111), wherein R29, R30 and R3, are each independently of the others H, C,-C20alkyl, C,-C20alkoxy, unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C4-C,2cycloalkyl or cycloalkoxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C6-C,6aryl or C6-C,6aryloxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C7-C,6aralkyl or C7-C,6aralkyloxy; the radicals R30 and R3, together are unsub-stituted or C,-C6alkyl-, C,-G6haloalkyl- or C,-C6alkoxy-substituted tetra- or penta-methylene or tetra- or penta-methylenedioxy; or are tetra- or penta-methylene or tetra- or penta-methylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy and fused with one or two 1 ,2-phenylene radicals; or are tetramethylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C1-C6haloalkyl or C,-C6alkoxy and fused in the 1,2- and 3,4-positions with 1,2-phenylene; and R3, is as defined hereinbefore;
L is a neutral ligand, Me is Ru or Os, Z,~ and Z2- are each a singly charged anion or Z,~ and Z2- together are a doubly charged anion, x is a number from 1 to 3 and y is a number from 0 to 3, such that 2 5 x+y < 4.
The ligands L in the compounds of formula lll may be identical or different.
The ruthenium and osmium compounds of formula lll are known or can be prepared according to known processes from the metal halides (for example MeX3 or [Me-areneX2]2) by reaction with phosphines of formula IV
R29R30R3, P (IV), wherein R29, R30 and R3, are as defined for formula (Ill), and ligand formers.
The radicals R29, R30 and R3, are preferably identical radicals. Also, sterically bulky radicals are preferred, for example branched, especially a-branched, alkyl or alkoxy, or cyclic radicals.
R29, R30 and R3, as alkyl may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkyl are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, CA 02242060 l998-06-30 heptadecyl, octadecyl and eicosyl. Preferred examples are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.
R29, R30 and R3, as alkoxy may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkoxy are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, and the isomers of pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy and eicosyloxy. Preferred examples are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, 1-, 2- or 3-pentyloxy and 1-, 2-, 3- or 4-hexyloxy.
Where R29, R30 and R31 are substituted, the substituents are preferably C,-C4alkyl, C1-C4--haloalkyl or C,-C4alkoxy. Halogen is preferably chlorine and especially fluorine. Examples of preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl. R29, R30 and R3, are preferably substituted by from 1 to 3 substituents.
R29, R30 and R3, as cycloalkyl are preferably C5-C8cycloalkyl and especially C5- or C6-cycloalkyl. Examples include cyclobutyl, cycloheptyl and cyclooctyl, and especially cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-cyclopentyl and -cyclohexyl.
R29, R30 and R3, as cycloalkyloxy are preferably C5-C8cycloalkyloxy and especially C5- or C6-cycloalkyloxy. Examples include cyclobutyloxy, cycloheptyloxy and cyclooctyloxy, and especially cyclopentyloxy and cyclohexyloxy. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-cyclopentyloxy and -cyclohexyloxy.
R29, R30 and R3, as aryl are preferably C6-C,2aryl and especially phenyl or naphthyl.
Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyl.
R29, R30 and R3, as aryloxy are preferably C6-C,2aryloxy and especially unsubstituted or substituted phenyloxy or naphthyloxy. Examples of substituted aryloxy are methyl-, dimethyl-, trimethyl-, methylisopropyl-, isopropyl-, diisopropyl-, triisopropyl-, tert-butyl-, methyltert-butyl-, di(tert-butyl)-, tri(tert-butyl)-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyloxy.
R29, R30 and R3, as aralkyl are preferably C7-C13aralkyl, the alkylene group in the aralkyl preferably being methylene. The aralkyl is especially benzyl. Examples of substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-benzyl.
R29, R30 and R3, as aralkyloxy are preferably unsubstituted or substituted C7-C13aralkyloxy, the alkylene group in the aralkyloxy preferably being methylene. The aralkyloxy is especially unsubstituted or substituted benzyloxy. Examples of substituted aralkyloxy are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-benzyloxy.
Special preference is given to complex salts of formula lll wherein R29, R30 and R3, are C1-C6alkyl, C,-C6alkoxy, C4-C12cycloalkyl, C4-C12cycloalkoxy, C6-C16aryl or C6-C,6aryloxy.
Especially preferred are complex salts of formula lll wherein R29, R30 and R3, are phenyl, tolyl or cyclohexyl.
Examples of suitable phosphines of formula IV are (C6Hs)3P, (C6H5CH2)3P, (C5H11)3P, (CH3)3P, (C2H5)3P, (n-C3H7)3P, (iso-C3H7)3P, (n-C4Hg)3P, (C6H5)2HP, (C6H5CH2)2HP, (C5H11)2HP, (CH3)2HP, (C2H5)2HP, (n-C3H7)2HP, (iso-C3H7)2HP, (n-C4Hg)2HP, (C6H5)H2P, (C6H5CH2)H2P, (C5H,1)H2P, (CH3)H2P, (C2H5)H2P, (n-C3H7)H2P, (iso-C3H7)H2P, (n-C4Hg)H2P, PH3, (2-CH3-C6H4)3P, (3-CH3-C6H4)3P, (4-CH3-C6H4)3P, (2,4-di-CH3-C6H3)3P, (2,6-di-CH3-C6H3)3P, (2-C2H5-C6H4)3P, (3-C2H5-C6H4)3P, (4-C2H5-C6H4)3P, (2-n-C3H7-C6H4)3P, (3-n-C3H7-C6H4)3P, (4-n-C3H7-C6H4)3P, (2-iso-C3H7-C6H4)3P, (3-iso-C3H7-C6H4)3P, (4-iso-C3H7-C6H4)3P, (2-n-C4Hg-C6H4)3P, (3-n-C4Hg-C6H4)3P, (4-n-C4Hg-C6H4)3P, (2-iso-C4Hg-C6H4)3P, (3-iso-C4Hg-C6H4)3P, (4-iso-C4Hg-C6H4)3P, (2-tert-C4Hg-C6H4)3P, (3-tert-C4Hg-C6H4)3P, (4-tert-C4Hg-C6H4)3P, (2-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (2,6-di-tert-C4Hg-C6H3)3P, (2,3-di-tert-C4Hg-C6H3)3P and (2,4-di-tert-C4Hg-C6H3)3P .
Especially preferred phosphines are triisopropylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine.
CA 02242060 l998-06-30 The ligands L bonded to the metal atom in the compounds of formula lll may be photolabile or non-photolabile ligands.
In the case of compounds of formula lll having photolabile ligands the catalytic activity is achieved by the action of light, that is to say on irradiation of the catalyst with light in the visible or ultraviolet range the photolabile ligand is removed, and a species is formed which is catalytically active for the metathesis polymerisation.
The photolabile ligands may be, for example, nitrogen (N2), unsubstituted or OH-, C,-C4alkyl-, Cj-C4alkoxy-, C6-C12aryl- or halo-substituted monocyclic, polycyclic or fused arenes having from 6 to 24, especially from 6 to 18, and more especially from 6 to 12, carbon atoms, or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted monocyclic hetero-arenes, fused heteroarenes or fused arene-heteroarenes having from 3 to 22, especially from 4 to 16, and more especially from 4 to 10, carbon atoms and from 1 to 3 hetero atoms selected from the group oxygen, sulfur and nitrogen; or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted aliphatic, cycloaliphatic, aromatic or araliphatic nitriles having from 1 to 22, especially from 1 to 18, more especially from 1 to 12, and preferably from 1 to 7, carbon atoms. The preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine. The arenes and heteroarenes are preferably substituted by from one to three radicals. The preferred heteroarenes are the electron-rich heteroarenes.
Examples of arenes and heteroarenes include benzene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoroanthrene, furan, thiophene, pyrrole, pyridine, ~-pyran, ~-thiopyran, pyrimidine, pyrazine, indole, cumarone, thionaphthene, carbazole, dibenzofuran, 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 benzthiophene. The arene is especially benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals and the heteroarene is preferably thiophene.
The nitriles may be substituted, for example, by methoxy, ethoxy, fluorine or chlorine;
preferably, the nitriles are unsubstituted. The alkylnitriles are preferably linear. Examples of CA 02242060 l998-06-30 nitriles include acetonitrile, propionitrile, butyronitrile, pentylnitrile, hexylnitrile, cyclopentyl-and cyclohexyl-nitrile, benzonitrile, methylbenzonitrile, benzylnitrile and naphthylnitrile. The nitriles are preferably linear C1-C4alkylnitriles or benzonitrile. Of the alkylnitriles, acetonitrile is especially preferred.
In a preferred sub-group, the photolabile ligands are N2, benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile or acetonitrile.
Within the scope of the present invention "non-photolabile ligand" (also called "strongly co-ordinating ligand") denotes that the ligand does not dissociate, or dissociates only to an insignificant extent, from the catalyst on irradiation of the catalyst in the visible or near ultraviolet spectral range.
The non-photolabile ligands may be, for example, solvating inorganic and organiccompounds containing the hetero atoms O, S or N, which are frequently also used as solvents. Examples of such compounds are H2O, H2S, NH3; unsubstituted or halogenated, especially fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having from 1 to 18, especially from 1 to 12, and more especially from 1 to 6, carbon atoms, aromatic alcohols or thiols having from 6 to 18, especially from 6 to 12, carbon atoms, araliphatic alcohols or thiols having from 7 to 18, especially from 7 to 12, carbon atoms;
open-chained or cyclic and aliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, carboxylic acid amides having from 2 to 20, especially from 2 to 12, and more especially from 2 to 6, carbon atoms which may be non-N-alkylated or N-C1-C4-mono- or -di-alkylated, and lactams which may be non-N-alkylated or N-C1-C4alkylated; and open-chained or cyclic and aliphatic, araliphatic or aromatic, primary, secondary and tertiary amines having from 1 to 20, especially from 1 to 12, and more especially from 1 to 6, carbon atoms.
Examples of such non-photolabile ligands are methanol, ethanol, n- and iso-propanol, n-, iso-and tert-butanol, 1,1,1-trifluoroethanol, bistrifluoromethylmethanol, tristrifluoromethyl-methanol, pentanol, hexanol, methyl- or ethyl-mercaptan, cyclopentanol, cyclohexanol, cyclohexylmercaptan, phenol, methylphenol, fluorophenol, phenylmercaptan, benzyl-mercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-tert-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydrothiophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- and penta-methylene sulfoxide, dimethylsulfone, CA 02242060 l998-06-30 diethylsulfone, tetra- and penta-methylenesulfone, acetone, methyl ethyl ketone, diethyl ketone, phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone, acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde, ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methylpyrrolidone.
The primary amines may correspond to the formula R26NH2, the secondary amines to the formula R26R27NH and the tertiary amines to the formula R26R27R28N, wherein R26 is C1-C,8alkyl, unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C5- or C6-cycloalkyl, or unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C6-C18aryl or C7-C12aralkyl, R27 independently has the meaning given for R26, or R26 and R27 together are tetramethylene, pentamethylene, 3-oxa-1,5-penty!ene or-CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C1-C4alkyl)-CH2-CH2-, and R28 independently has the meaning given for R26. The alkyl contains especially from 1 to 12, and more especially from 1 to 6, carbon atoms. The aryl contains preferably from 6 to 12 carbon atoms and the aralkyl contains preferably from 7 to 9 carbon atoms. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl-, dimethylethyl-, n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and benzyl-amine, and also pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.
Preferably, the compositions according to the invention comprise as component (b) a complex salt of formula lll wherein L is an arene, a heteroarene, a nitrile, nitrogen (N2), an alcohol, an amine, CO, H20 or NH3.
Especially preferred as component (b) is a complex salt of formula lll wherein L is benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile, acetonitrile, nitrogen (N2), an unsubstituted or partially or fully fluorinated C1-C4alcohol, CO, H20 or NH3.
In the compounds of formula lll, Z1- and Z2- may each be a singly charged anion, it being possible for Z1- and Z2- to be identical or different, or Z1- and Z2- may together be a doubly charged anion.
Suitable anions are, for example, hydride (H-), halide (for example Cl-, Br~ and 1-), BF4-, PF6-, SbF6-, AsF6-, unsubstituted or C,-C4alkyl-, C1-C4alkoxy-, (C,-C4alkyl)3Si- or (C,-C4alkyl)3SiO-substituted cyclopentadienyl~, or indenyl~, and the anions of oxyacids.
CA 02242060 l998-06-30 Further suitable anions are C,-C,2-, especially C,-C6- and more especially C1-C4-alcoholates, which are especially branched and correspond, for example, to the formula RXRyRzC~O~~
wherein Rx is H or C1-C,0alkyl, Ry is C1-C10alkyl and Rz is C1-C10alkyl or phenyl. Examples are especially isopropyloxy and tert-butyloxy.
Other suitable anions are C3-C18-, especially C5-C14- and more especially C5-C12-acetylides, which may correspond to the formula RW-C-C-~ wherein Rw is C1-C16alkyl, preferably a-branched C3-C12alkyl, for example of the formula RXRyRzC~~ or is phenyl or benzyl unsubstituted or substituted by from one to three C1-C4alkyl or C1-C4alkoxy radicals.
Examples include isopropylacetylide, iso- and tert-butylacetylide, phenylacetylide, benzylacetylide, 2-methylphenylacetylide, 2-isopropylphenylacetylide, 2-isopropyl-6-methylphenylacetylide, 2-tert-butylphenylacetylide, 2,6-di-tert-butylphenylacetylide and 2-methyl-6-tert-butylphenylacetylide.
The anions of oxyacids may be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or tri-chloro- or -fluoro-acetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate); phenylsulfonate or benzylsulfonate unsubstituted or substituted by C,-C4alkyl, C,-C4alkoxy or by halogen, especially fluorine, chlorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxy-phenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropyl-sulfonate; and phosphonates, for example methylphosphonate, ethylphosphonate, propylphoshonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate and benzylphosphonate.
Preferably, Z1- and Z2- in formula lll are H-, Cl-, Br~, BF4-, PF6-, SbF6-, AsF6-, CF3SO3-, C6H5-SO3-, p-toluenesulfonate (tosylate), 3,5-dimethylphenylsulfonate, 2,4,6-trimethylphenyl-sulfonate, 4-trifluoromethylphenylsulfonate or cyclopentadienyl.
Especially preferred ROMP catalysts of formula lll are [(cyclohexyl)3P]2RuCI2, [(C6H5)3P]3RuC12, [(C6H5)3P]3(CO)RuH2, [(C6H5)3P]3RuCl(cyclopentadienyl), CA 02242060 l998-06-30 [(cyclohexyl)3P]2(CH3OH)Ru(tosylate)2, [(o-tolyl)3P]3RuCI2, [(CH3)2CH]3P(p-cymene)RuCI2 and especially (cyclohexyl)3P(p-cymene)RuCI2.
Suitable fillers which may be used as component (c) in the compositions according to the invention are, for example, metal powders, wood dust, glass powder, glass beads, semi-metal and metal oxides, for example SiO2 (Aerosils, quartz, quartz powder, vitreous fused silica), corundum and titanium oxide, semi-metal and metal nitrides, for example silicon nitride, boron nitride and aluminium nitride, semi-metal and metal carbides (SiC), metal carbonates (dolomite, chalk, CaCO3), metal sulfates (barite, gypsum), and powdered rock and natural or synthetic minerals, mainly from the silicate series, for example talcum, mica, kaolin, wollastonite, bentonite and others.
Preferably, a metal oxide, carbonate, sulfate or silicate or SiO2 is used as component (c).
Preferred fillers are Al2O3, Al(OH)3, CaCO3, CaSiO3, SiO2, woven glass fibres, woven carbon fibres and woven aramid fibres.
Especially preferred as component (c) are Al2O3, Al(OH)3, wollastonite, quartz powder, dolomite, lime, chalk, woven glass fibres, woven carbon fibres and woven aramid fibres.
The silanes of formula I are known and can be prepared according to known methods. Some of those silanes are available commercially.
Preference is given to silanes of formula I wherein R as a monovalent organic group having from 2 to 100 carbon atoms is C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20-alkoxyalkyl, C2-C20alkenyl, C4-C25acryloxyalkyl, C4-C25methacryloxyalkyl, C2-C20aminoalkyl, C4-C25glycidyloxyalkyl, C7-C25epoxycyclohexylalkyl or the radical of a polysiloxane.
Alkyl as R, Y1, Y2 or Y3 includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Aryl as R, Y1, Y2 or Y3 contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Aralkyl as R, Y" Y2 or Y3 contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Cycloalkyl as R, Y1, Y2 or Y3iS preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl.
Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclo-pentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Examples of alkoxyalkyl as R, Y" Y2 or Y3 are 2-methoxyethyl, 2-ethoxyethyl, 2-methoxy-propyl, 3-methoxypropyl, 2-ethoxypropyl and 3-ethoxypropyl.
Alkenyl as R includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Examples of acryloxyalkyl and methacryloxyalkyl are 2-acryloxyethyl, 2-methacryloxyethyl, 3-acryloxypropyl and 3-methacryloxypropyl.
Suitable aminoalkyl groups are, for example, 2-aminoethyl, 3-aminopropyl, 3-aminobutyl and 4-aminobutyl.
Suitable glycidyloxyalkyl groups are, for example, 2-glycidyloxyethyl, 3-glycidyloxypropyl, 3-glycidyloxybutyl and 4-glycidyloxybutyl.
Epoxycyclohexylalkyl is preferably ~-(3,4-epoxycyclohexyl)ethyl.
R in formula I is preferably methyl, ethyl, n-octyl, vinyl, 3-mercaptopropyl, 3-aminopropyl, 3-glycidyloxypropyl, 3-acryloxypropyl, 3-methacryloxypropyl, ~-(3,4-epoxycyclohexyl)ethyl, N-(,B-aminoethyl)-3-aminopropyl, 3-ureidopropyl, 3-isocyanatopropyl, H2N-CH2CH2NH-CH2CH2NH-CH2CH2CH2-, (CH30)3Si-CH2CH2CH2NH-CH2CH2CH2- or a group of formula (CH30)3siCH2CH2CH2~N ~N ,cH2cH2cH2si(ocH3)3 O N ~O
Preference is given to silanes of formula I wherein R is methyl, vinyl, 3-mercaptopropyl or 3-aminopropyl.
Y" Y2 and Y3 in formula I are preferably methyl, ethyl, acetyl or 2-methoxyethyl.
Examples of suitable silanes of formula I are octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris(2-methoxyethoxy)silane, ~-methacryloxypropyltrimethoxy-silane, ~-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, y-glycidyloxypropyltrimethoxysilane, y-mercaptopropyltrimethoxysilane, ~-aminopropyltriethoxysilane, y-aminopropyltrimethoxy-silane, N-(,~-aminoethyl)-~-aminopropyltrimethoxysilane, H2NCH2CH2NHCH2CH2NHCH2CH2CH2Si(OCH3)3, bis[~-(trimethoxysilyl)propyl]amine, organically modified polydimethylsiloxane of formula (CH3)3SiO- E(CH3)2SiO~E(CH3)2 ISiO~E(CH3)2 ISi~~Si(CH3)3 wherein R and R' = alkyl or aryl, NR2 NHR'Si(OR)3 ~-ureidopropyltrimethoxysilane, ~-isocyanatopropyltriethoxysilane, 3-chloropropyltrimethoxy-silane, 3-triethoxysilylpropylsuccinic acid anhydride, 3-methacryloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane and 3-(2-aminoethylamino)propylmethyldimethoxysilane.
Vinyltrimethoxysilane is especially preferred as component (d).
It should be mentioned that when using quartz powder as filler, it is also possible to use, instead of a mixture of components (c) and (d), a quartz powder pre-treated with a silane of formula 1. Such quartz powders pre-treated with epoxysilane, alkylsilane or vinylsilane are available commercially, for example under the names Silbond~ W12 EST, Vp W12 VST and Vp W12 SST.
The amounts of components (a) to (d) in the compositions according to the invention may vary within wide limits.
Preferably, the compositions according to the invention contain from 15 to 75 % by weight of component (a), from 0.001 to 10.0 % by weight of component (b), from 20 to 80 % by weight of component (c) and from 0.01 to 20.0 % by weight of component (d), the sum of components (a), (b), (c) and (d) being 100 % by weight.
Especially preferred are compositions according to the invention containing from 25 to 65 %
by weight, especially from 30 to 50 % by weight, of component (a), from 0.01 to 2.0 % by weight, especially from 0.1 to 1.0 % by weight, of component (b), from 30 to 75 % by weight, especially from 50 to 70 % by weight, of component (c) and from 0.05 to 10.0 % by weight, especially from 0.1 to 2.0 % by weight, of component (d).
The substance mixtures according to the invention can be prepared in customary manner by mixing the components using known mixing equipment (e.g. stirrers, rollers).
In addition to components (a) to (d), the composition according to the invention may comprise further customary additives, for example anti-oxidants, light stabilisers, plasticisers, colourants, pigments, thixotropic agents, viscosity improvers, anti-foams, antistatics, lubricants and mould release agents.
The composition according to the invention may be prepared directly before polymerisation, or may be used in the form of a preformulated mixture. Before polymerisation, the mixture can be stored in the form of a ready-to-use formulation for a prolonged period, which is advantageous for use on an industrial scale. Storage with the exclusion of light is recommended, however, when the catalyst contains photolabile ligands.
The present invention relates also to a method of bonding two or more substrates, which comprises applying a curable composition comprising the above-mentioned components (a) to (d) to at least one of the substrates to be bonded, bringing the substrates to be bonded CA 02242060 l998-06-30 into contact with one another, and curing the composition by heating to a temperature , 40~C.
Advantageously, the method according to the invention is carried out at a temperature of at least 60~C. The method according to the invention is especially carried out at temperatures of from 60 to 300~C, more especially from 60 to 250~C, preferably from 60 to 200~C and especially preferably from 70 to 1 60~C. After polymerisation, it may be advantageous to temper the mixture at elevated temperatures, for example at from 80 to 200~C.
The adhesive mixture is applied to the substrate in known manner. The layer thickness of the adhesive films is generally not more than 500 ~m, and is preferably from 40 to 120,um. It is, however, possible for substantially thicker layers to be fully cured thermally.
Before being coated with the adhesive mixture, the surfaces to be bonded may, ifappropriate, be degreased and roughened.
After they have been brought together, the coated surfaces are pressed together or clamped, if appropriate.
Suitable surfaces for bonding are especially those made of metals, such as iron, steel, or especially aluminium and its alloys, for example with magnesium or silicon. The adhesive can also be used to bond two different materials, for example to bond metals to polymeric materials.
The bonds produced in accordance with the method according to the invention are distinguished especially by a high bond strength and minimal water absorption.
Example 1:
0.39 9 of Norsorex NS (thermoplastic polynorbornene, Nippon Zeon) is dissolved at 80~C in 38.91 g of dicyclopentadiene. After cooling to 60~C, 0.5 g of vinyltrimethoxysilane (Silquest~
A-171, Osi Specialties) and 0.2 g of (cyclohexyl)3P(p-cymene)RuCI2 are added, and the mixture is stirred for 20 minutes at 60~C. After the addition, in portions, of 60 g of wollastonite FW 200 (Partek Minerals), the mixture is stirred for a further 15 minutes. The mixture is then degassed for from 3 to 5 minutes in vacuo (3 mbar).
The mixture so obtained is poured into a 4 mm-thick plate mould of aluminium and then fully cured (2 h/80~C, 4 h/1 00~C, 1 h/1 50~C). It is established that the cured moulding has very good adhesion to aluminium and cannot be removed from the mould either at -180~C or at 200~C.
In WO 96/16100 and WO 96/20235 it is mentioned that the ROMP systems (ROMP = ring-opening metathesis polymerisation) described therein based on strained cycloolefins and specific ruthenium catalysts are suitable as adhesives for bonding Teflon, polyethylene and polypropylene. The adhesion to the substrate is inadequate for certain uses, however, owing to the low polarity of the cycloolefins.
Bonds made with reactive adhesives exhibit inner strains caused by reaction shrinkage when the relatively large intermolecular spacing between the monomers are replaced by the closer spacing of the covalent bonds between the polymer segments. The shrinkage can bereduced by the addition of suitable fillers, but the addition of fillers generally results in a breakdown of the cohesion.
Surprisingly, it has now been found that the ROMP systems described in EP-A-771 830, together with fillers, exhibit very good adhesion and can consequently be used as adhesives.
The present invention relates to the use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
OY, R--Si OY2 (I ), oy3 wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may be replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y" Y2 and Y3 are each independently of the others C,-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20alkoxyalkyl or C,-C20acyl.
When fully cured, the ROMP system exhibits an especially high degree of adhesion to metals, for example iron or aluminium. Preference is accordingly given to the use of the above-specified composition as an adhesive for metals, especially for aluminium.
Within the scope of the present invention there is to be understood by "strained cycloolefin"
any cycloolefin, with the exception of cyclohexene and derivatives thereof, which cannot be polymerised by ring-opening metathesis.
Strained cycloolefins may be monocyclic or polycyclic fused or bridged ring systems, for example having from two to four rings, that are unsubstituted or substituted and may contain hetero atoms, for example oxygen, sulfur, nitrogen or silicon, in one or more rings and/or may contain fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthyl-ene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings may contain from 3 to 16, especially from 3 to 12, and more especially from 3 to 8, ring members. The strained cyclo-olefins may contain further non-aromatic double bonds, preference being given, depending on the ring size, to from 2 to 4 such additional double bonds. The ring substituents are inert, that is to say those substituents do not impair the chemical stability and the thermostability of the ROMP catalysts.
When the strained cycloolefins contain more than one double bond, for example from 2 to 4 double bonds, it is possible also for crosslinked polymers to be formed, depending on the reaction conditions, the monomer selected and the amount of catalyst.
There is preferably used as component (a) in the composition according to the invention a compound of formula ll \ / (Il), wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2 group, forms an alicyclic ring having a minimum of three members that may contain one or more hetero atoms selected from the group silicon, phosphorus, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, =0, -CN, -NO2, R1R2R3Si-(O)u~, -COOM, -S03M, -PO3M, -COO(M,)1,2, -SO3(M,)"2, -PO3(M,)"2, C,-C20alkyl, C,-C20hydroxyalkyl, C,-C20haloalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6-aralkyl, C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C,6heteroaralkyl or by R4-X-; or in which two adjacent carbon atoms are bonded by -CO-O-CO- or -CO-NR5-CO-; or in which there is fused to adjacent carbon atoms of the alicyclic ring an alicyclic, aromatic or heteroaromatic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)U-, -COOM, -SO3M, -PO3M, -COO(M1)1,2, -S03(M1)"2, -PO3(M1)"2, C,-C20alkyl, C,-C20haloalkyl, C,-C20-hydroxyalkyl, C,-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, C7-C,6aralkyl, C3-C6heterocyclo-alkyl, C3-C,6heteroaryl, C4-C,6heteroaralkyl or by R,3-X,-; X and X1 are each independently of the other -O-, -S-, -CO-, -SO-, -SO2-, -O-CO-, -COO-, -CO-NR5-, -NR10-CO-, -SO2-O- or -O-SO2-; R1, R2 and R3 are each independently of the other C,-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl; R4 and R~3 are each independently of the other C,-C20alkyl, C,-C20-haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; R5 and R,O are each independently of the other hydrogen, C,-C,2alkyl, phenyl or benzyl, the alkyl groups in turn being unsubstituted or substituted by C,-C,2alkoxy or by C3-C8cycloalkyl; R6, R7 and R8 are each independently of the others C,-C,2alkyl, C,-C,2perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; and u is O or 1; it being possible for the alicyclic ring formed with Q, to contain further non-aromatic double bonds;
Q2 is hydrogen, C,-C20alkyl, C,-C20haloalkyl, C,-C,2alkoxy, halogen, -CN or R"-X2-; R" is C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or C7-C,6aralkyl; X2 is -COO- or -CO-NR,2-; and R,2 is hydrogen, C,-C,2alkyl, phenyl or benzyl;
wherein the above-mentioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups may be unsubstituted or substituted by C,-C,2alkyl, C,-C,2alkoxy, -NO2, -CN or by halogen, and wherein the hetero atoms of the above-mentioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -O-, -S-, -NRg- and -N=, Rg being hydrogen, C,-C,2alkyl, phenyl or benzyl.
Fused-on alicyclic rings contain preferably from 3 to 8, especially from 4 to 7, and more especially 5 or 6, ring carbon atoms.
For the purpose of crosslinking or to control the molecular weight, the composition according to the invention may contain further olefins capable of metathesis, advantageously in amounts of up to 40 mol %, especially from 0.01 to 30 mol % and more especially from 0.1 to 20 mol %, based on the total amount of the cycloolefins and olefins present.
Suitable olefins capable of metathesis are, for example, cyclooctadiene, cyclooctatriene, norbornadiene and acetylnorbornene. Also suitable are compounds such as 2-butene-1,4-diol, as described in Feast, W.J., Harrison, B., J. Mol. Catal. 65, 63 (1991), or 1-hexene (rearrangements) .
The presence of an asymmetric centre in the compounds of formula ll means that those compounds may occur in optically isomeric forms. Some compounds of formula ll may occur in the form of tautomers (e.g. keto-enol tautomerism). If an aliphatic C=C double bond is present, then also geometric isomerism may occur (E-form or Z-form). In addition, exo/endo configurations are also possible. Formula ll hence includes all possible stereoisomers, which are in the form of enantiomers, tautomers, diastereoisomers, E/Z isomers or mixtures thereof.
The alkyl, alkenyl and alkynyl groups in the definitions of the substituents may be straight-chain or branched. The same applies also to the alkyl moiety or each of the alkyl moieties of alkoxy, alkylthio, alkoxycarbonyl and other alkyl-containing groups. The alkyl groups contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 4, carbon atoms. The alkenyl and alkynyl groups contain preferably from 2 to 12, especially from 2 to 8, and more especially from 2 to 4, carbon atoms.
Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxyisobutyl, 1-hydroxy-sec-butyl, 1-hydroxy-tert-butyl and the various hydroxy-substituted isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-tri-chloroethyl and halogenated, especially fluorinated or chlorinated, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups and the various halogenated isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Cycloalkyl is preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl. Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Cyanoalkyl includes, for example, cyanomethyl (methylnitrile), cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyanoisobutyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and the various isomers of cyanopentyl and cyanohexyl.
Aralkyl contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Aryl contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Heteroaryl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, purinyl or quinolyl.
Heterocycloalkyl contains preferably 4 or 5 carbon atoms and one or two hetero atoms from the group oxygen, sulfur and nitrogen. It may be, for example, oxiranyl, azirinyl, 1,2-oxathiolanyl, pyrazolinyl, pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl or tetrahydrothiophenyl.
Alkoxy is, for example, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy or tert-butyloxy.
Within the scope of the present invention, alkali metal is to be understood as meaning lithium, sodium, potassium, rubidium or caesium, especially lithium, sodium or potassium.
Within the scope of the present invention, alkaline earth metal is to be understood as meaning beryllium, magnesium, calcium, strontium or barium, especially magnesium or calcium.
In the above definitions, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Especially well-suited compounds of formula ll in the composition according to the invention are those wherein Q2 is hydrogen.
Preference is given also to compounds of formula ll wherein Q, is a radical having at least one carbon atom, which radical, together with the -CH=CQ2- group, forms a 3- to 10-membered alicyclic ring that may contain a hetero atom selected from the group silicon, oxygen, nitrogen and sulfur and that is unsubstituted or substituted by halogen, -CN, -NO2, R,R2R3Si-, -COOM, -SO3M, -PO3M, -COO(M,)"2, -S03(M,)"2, -PO3(M,)"2, C1-C6alkyl, C,-C6-haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R4-X-; or in which there may be fused to adjacent carbon atoms an aromatic or heteroaromatic or alicyclic ring that is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M,)1~2, -SO3(M1)1~2, -PO3(M1)1~2, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or by R13-X1-; R1, R2 and R3 are each independently of the others C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M, is an alkaline earth metal; R4 and R13 are each independently of the other C1-C6alkyl, C1-C6haloalkyl, C,-C6hydroxyalkyl or C3-C6cycloalkyl; X and X1 are each independently of the other-O-, -S-, -CO-, -SO- or-S02- and R6, R7 and R8 are each independently of the others C,-C4alkyl, C,-C4perfluoroalkyl, phenyl or benzyl.
Norbornene and norbornene derivatives, especially dicyclopentadiene and dicyclopentadiene derivatives, are especially preferred as component (a).
Preferred norbornene derivatives are the compounds of formulae lll, IV, V and Vl ~14 ~ (IV), R.8 ~ (V), ~ (Vl), wherein X3 is -CHR16-, oxygen or sulfur, R14 and R15 are each independently of the other hydrogen, -CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR17, and R16 and R17 are each independently of the other hydrogen, C1-C12alkyl, phenyl or benzyl;
X4 is -CHR19-, oxygen or sulfur, R19 is hydrogen, C1-C12alkyl, phenyl or benzyl and R18 is hydrogen, C1-C6alkyl or halogen;
Xs is -CHR22-, oxygen or sulfur, R22 is hydrogen, C1-C12alkyl, phenyl or benzyl, R20 and R21 are each independently of the other hydrogen, CN, trifluoromethyl, (CH3)3SiO-, (CH3)3Si- or -COOR23 and R23 is hydrogen, C1-C12alkyl, phenyl or benzyl;
X6 is -CHR24-, oxygen or sulfur, R24 is hydrogen, C1-C12alkyl, phenyl or benzyl, Y is oxygen or \N--R and R25 is hydrogen, methyl, ethyl or phenyl.
Examples of suitable compounds of formula ll are the following cycloolefins:
~ (2)~ ~ (3).
CA 02242060 l998-06-30 COOH ~~ COOCH3 ~\~(4), ~ (5), / (6), o O o COOCH2phenyl ~_ COOCzHs /~~ COO(CH2)~CH3 ~ (7). ~ (8), ~ (9).
COOCH2phenyl COOCzHs coo(CH2)3cH3 O O
~_ COO(CH2)sCH3 ~ COO(CH2)9CH3 ~_ COO(CH2),lCH3 ~ (10). ~ (11), ~ (12 Coo(cH2)scH3coo(cH2)9cH3 coo(cH2)1~c~l3 O O
~f(,3). ~ f~(,4) ~ f~(1s) ~ O NH
O O O
O O O
f (16), f (17)' fo (18), N ' CH3 C2H5 ~ phenyl O O O
~(19)~ 3(20), (~)(21), (22), ~ (23), [3 (24), [~ (25), b (26), b (27), ~ (28), (29), ~ ~ (30)~ b CN (31), \CH2NHCH3 1~ .
~( (32), ~V Sl(CH3)3 (33), b P(C6H5)2 (34~ b~ CH2~(CH2)5~CH3 (35 P(C6H5)2 b 3 (36), ~ ~ (37), o_ _ ~ " (38), ~3 (39)' (40~ ,3(41)~
~1 ~3 (42), ~ 3 (43) In a preferred embodiment, the strained cycloolefins contain only carbon and hydrogen atoms, and are preferably 5- or 6-membered rings, or ring systems having from one to three 5- or 6-membered rings, for example norbornenes, alkylated norbornenes and dicyclopenta-diene.
Especially preferred as component (a) is dicyclopentadiene.
A large number of compounds of the transition metals titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium are known to the person skilled in the art as catalysts for ring-opening metathesis polymerisation (ROMP catalysts). Such compounds are, for example, complex metal halides, metallo-carbenes or co-ordination catalysts of the Ziegler-Natta type. In principle, any of those known ROMP catalysts may be used as component (b) in the compositions according to the invention.
Preferably, a ruthenium(+ll) complex salt or an osmium(+ll) complex salt, especially a ruthenium(+ll) complex salt, is used as component (b).
Since the fillers according to component (c) often contain small amounts of water, it is advisable to use ROMP catalysts that are not sensitive to moisture, such as, for example, the ruthenium(+ll) and osmium(+ll) complex salts described in WO 96/16100 and WO 96/20235.
The preferred component (b) is therefore a complex salt of formula lll (R2sR3oR31p)xLyMe2+z1-z2 (111), wherein R29, R30 and R3, are each independently of the others H, C,-C20alkyl, C,-C20alkoxy, unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C4-C,2cycloalkyl or cycloalkoxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C6-C,6aryl or C6-C,6aryloxy, or unsubstituted or C,-C6alkyl-, C,-C6haloalkyl- or C,-C6alkoxy-substituted C7-C,6aralkyl or C7-C,6aralkyloxy; the radicals R30 and R3, together are unsub-stituted or C,-C6alkyl-, C,-G6haloalkyl- or C,-C6alkoxy-substituted tetra- or penta-methylene or tetra- or penta-methylenedioxy; or are tetra- or penta-methylene or tetra- or penta-methylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy and fused with one or two 1 ,2-phenylene radicals; or are tetramethylenedioxy that is unsubstituted or substituted by C,-C6alkyl, C1-C6haloalkyl or C,-C6alkoxy and fused in the 1,2- and 3,4-positions with 1,2-phenylene; and R3, is as defined hereinbefore;
L is a neutral ligand, Me is Ru or Os, Z,~ and Z2- are each a singly charged anion or Z,~ and Z2- together are a doubly charged anion, x is a number from 1 to 3 and y is a number from 0 to 3, such that 2 5 x+y < 4.
The ligands L in the compounds of formula lll may be identical or different.
The ruthenium and osmium compounds of formula lll are known or can be prepared according to known processes from the metal halides (for example MeX3 or [Me-areneX2]2) by reaction with phosphines of formula IV
R29R30R3, P (IV), wherein R29, R30 and R3, are as defined for formula (Ill), and ligand formers.
The radicals R29, R30 and R3, are preferably identical radicals. Also, sterically bulky radicals are preferred, for example branched, especially a-branched, alkyl or alkoxy, or cyclic radicals.
R29, R30 and R3, as alkyl may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkyl are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, CA 02242060 l998-06-30 heptadecyl, octadecyl and eicosyl. Preferred examples are methyl, ethyl, n- and iso-propyl, n-, iso- and tert-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.
R29, R30 and R3, as alkoxy may be linear or branched and contain preferably from 1 to 12, especially from 1 to 8, and more especially from 1 to 6, carbon atoms. Examples of alkoxy are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, and the isomers of pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy and eicosyloxy. Preferred examples are methoxy, ethoxy, n- and iso-propyloxy, n-, iso- and tert-butyloxy, 1-, 2- or 3-pentyloxy and 1-, 2-, 3- or 4-hexyloxy.
Where R29, R30 and R31 are substituted, the substituents are preferably C,-C4alkyl, C1-C4--haloalkyl or C,-C4alkoxy. Halogen is preferably chlorine and especially fluorine. Examples of preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl. R29, R30 and R3, are preferably substituted by from 1 to 3 substituents.
R29, R30 and R3, as cycloalkyl are preferably C5-C8cycloalkyl and especially C5- or C6-cycloalkyl. Examples include cyclobutyl, cycloheptyl and cyclooctyl, and especially cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-cyclopentyl and -cyclohexyl.
R29, R30 and R3, as cycloalkyloxy are preferably C5-C8cycloalkyloxy and especially C5- or C6-cycloalkyloxy. Examples include cyclobutyloxy, cycloheptyloxy and cyclooctyloxy, and especially cyclopentyloxy and cyclohexyloxy. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-cyclopentyloxy and -cyclohexyloxy.
R29, R30 and R3, as aryl are preferably C6-C,2aryl and especially phenyl or naphthyl.
Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyl.
R29, R30 and R3, as aryloxy are preferably C6-C,2aryloxy and especially unsubstituted or substituted phenyloxy or naphthyloxy. Examples of substituted aryloxy are methyl-, dimethyl-, trimethyl-, methylisopropyl-, isopropyl-, diisopropyl-, triisopropyl-, tert-butyl-, methyltert-butyl-, di(tert-butyl)-, tri(tert-butyl)-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-phenyloxy.
R29, R30 and R3, as aralkyl are preferably C7-C13aralkyl, the alkylene group in the aralkyl preferably being methylene. The aralkyl is especially benzyl. Examples of substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)- and tris(trifluoromethyl)-benzyl.
R29, R30 and R3, as aralkyloxy are preferably unsubstituted or substituted C7-C13aralkyloxy, the alkylene group in the aralkyloxy preferably being methylene. The aralkyloxy is especially unsubstituted or substituted benzyloxy. Examples of substituted aralkyloxy are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis(trifluoromethyl)-and tris(trifluoromethyl)-benzyloxy.
Special preference is given to complex salts of formula lll wherein R29, R30 and R3, are C1-C6alkyl, C,-C6alkoxy, C4-C12cycloalkyl, C4-C12cycloalkoxy, C6-C16aryl or C6-C,6aryloxy.
Especially preferred are complex salts of formula lll wherein R29, R30 and R3, are phenyl, tolyl or cyclohexyl.
Examples of suitable phosphines of formula IV are (C6Hs)3P, (C6H5CH2)3P, (C5H11)3P, (CH3)3P, (C2H5)3P, (n-C3H7)3P, (iso-C3H7)3P, (n-C4Hg)3P, (C6H5)2HP, (C6H5CH2)2HP, (C5H11)2HP, (CH3)2HP, (C2H5)2HP, (n-C3H7)2HP, (iso-C3H7)2HP, (n-C4Hg)2HP, (C6H5)H2P, (C6H5CH2)H2P, (C5H,1)H2P, (CH3)H2P, (C2H5)H2P, (n-C3H7)H2P, (iso-C3H7)H2P, (n-C4Hg)H2P, PH3, (2-CH3-C6H4)3P, (3-CH3-C6H4)3P, (4-CH3-C6H4)3P, (2,4-di-CH3-C6H3)3P, (2,6-di-CH3-C6H3)3P, (2-C2H5-C6H4)3P, (3-C2H5-C6H4)3P, (4-C2H5-C6H4)3P, (2-n-C3H7-C6H4)3P, (3-n-C3H7-C6H4)3P, (4-n-C3H7-C6H4)3P, (2-iso-C3H7-C6H4)3P, (3-iso-C3H7-C6H4)3P, (4-iso-C3H7-C6H4)3P, (2-n-C4Hg-C6H4)3P, (3-n-C4Hg-C6H4)3P, (4-n-C4Hg-C6H4)3P, (2-iso-C4Hg-C6H4)3P, (3-iso-C4Hg-C6H4)3P, (4-iso-C4Hg-C6H4)3P, (2-tert-C4Hg-C6H4)3P, (3-tert-C4Hg-C6H4)3P, (4-tert-C4Hg-C6H4)3P, (2-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (3-CH3-6-tert-C4Hg-C6H3)3P, (2,6-di-tert-C4Hg-C6H3)3P, (2,3-di-tert-C4Hg-C6H3)3P and (2,4-di-tert-C4Hg-C6H3)3P .
Especially preferred phosphines are triisopropylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine.
CA 02242060 l998-06-30 The ligands L bonded to the metal atom in the compounds of formula lll may be photolabile or non-photolabile ligands.
In the case of compounds of formula lll having photolabile ligands the catalytic activity is achieved by the action of light, that is to say on irradiation of the catalyst with light in the visible or ultraviolet range the photolabile ligand is removed, and a species is formed which is catalytically active for the metathesis polymerisation.
The photolabile ligands may be, for example, nitrogen (N2), unsubstituted or OH-, C,-C4alkyl-, Cj-C4alkoxy-, C6-C12aryl- or halo-substituted monocyclic, polycyclic or fused arenes having from 6 to 24, especially from 6 to 18, and more especially from 6 to 12, carbon atoms, or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted monocyclic hetero-arenes, fused heteroarenes or fused arene-heteroarenes having from 3 to 22, especially from 4 to 16, and more especially from 4 to 10, carbon atoms and from 1 to 3 hetero atoms selected from the group oxygen, sulfur and nitrogen; or unsubstituted or C,-C4alkyl-, C,-C4alkoxy- or halo-substituted aliphatic, cycloaliphatic, aromatic or araliphatic nitriles having from 1 to 22, especially from 1 to 18, more especially from 1 to 12, and preferably from 1 to 7, carbon atoms. The preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine. The arenes and heteroarenes are preferably substituted by from one to three radicals. The preferred heteroarenes are the electron-rich heteroarenes.
Examples of arenes and heteroarenes include benzene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoroanthrene, furan, thiophene, pyrrole, pyridine, ~-pyran, ~-thiopyran, pyrimidine, pyrazine, indole, cumarone, thionaphthene, carbazole, dibenzofuran, 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 benzthiophene. The arene is especially benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals and the heteroarene is preferably thiophene.
The nitriles may be substituted, for example, by methoxy, ethoxy, fluorine or chlorine;
preferably, the nitriles are unsubstituted. The alkylnitriles are preferably linear. Examples of CA 02242060 l998-06-30 nitriles include acetonitrile, propionitrile, butyronitrile, pentylnitrile, hexylnitrile, cyclopentyl-and cyclohexyl-nitrile, benzonitrile, methylbenzonitrile, benzylnitrile and naphthylnitrile. The nitriles are preferably linear C1-C4alkylnitriles or benzonitrile. Of the alkylnitriles, acetonitrile is especially preferred.
In a preferred sub-group, the photolabile ligands are N2, benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile or acetonitrile.
Within the scope of the present invention "non-photolabile ligand" (also called "strongly co-ordinating ligand") denotes that the ligand does not dissociate, or dissociates only to an insignificant extent, from the catalyst on irradiation of the catalyst in the visible or near ultraviolet spectral range.
The non-photolabile ligands may be, for example, solvating inorganic and organiccompounds containing the hetero atoms O, S or N, which are frequently also used as solvents. Examples of such compounds are H2O, H2S, NH3; unsubstituted or halogenated, especially fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having from 1 to 18, especially from 1 to 12, and more especially from 1 to 6, carbon atoms, aromatic alcohols or thiols having from 6 to 18, especially from 6 to 12, carbon atoms, araliphatic alcohols or thiols having from 7 to 18, especially from 7 to 12, carbon atoms;
open-chained or cyclic and aliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, carboxylic acid amides having from 2 to 20, especially from 2 to 12, and more especially from 2 to 6, carbon atoms which may be non-N-alkylated or N-C1-C4-mono- or -di-alkylated, and lactams which may be non-N-alkylated or N-C1-C4alkylated; and open-chained or cyclic and aliphatic, araliphatic or aromatic, primary, secondary and tertiary amines having from 1 to 20, especially from 1 to 12, and more especially from 1 to 6, carbon atoms.
Examples of such non-photolabile ligands are methanol, ethanol, n- and iso-propanol, n-, iso-and tert-butanol, 1,1,1-trifluoroethanol, bistrifluoromethylmethanol, tristrifluoromethyl-methanol, pentanol, hexanol, methyl- or ethyl-mercaptan, cyclopentanol, cyclohexanol, cyclohexylmercaptan, phenol, methylphenol, fluorophenol, phenylmercaptan, benzyl-mercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-tert-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydrothiophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- and penta-methylene sulfoxide, dimethylsulfone, CA 02242060 l998-06-30 diethylsulfone, tetra- and penta-methylenesulfone, acetone, methyl ethyl ketone, diethyl ketone, phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone, acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde, ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methylpyrrolidone.
The primary amines may correspond to the formula R26NH2, the secondary amines to the formula R26R27NH and the tertiary amines to the formula R26R27R28N, wherein R26 is C1-C,8alkyl, unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C5- or C6-cycloalkyl, or unsubstituted or C1-C4alkyl- or C1-C4alkoxy-substituted C6-C18aryl or C7-C12aralkyl, R27 independently has the meaning given for R26, or R26 and R27 together are tetramethylene, pentamethylene, 3-oxa-1,5-penty!ene or-CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C1-C4alkyl)-CH2-CH2-, and R28 independently has the meaning given for R26. The alkyl contains especially from 1 to 12, and more especially from 1 to 6, carbon atoms. The aryl contains preferably from 6 to 12 carbon atoms and the aralkyl contains preferably from 7 to 9 carbon atoms. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl-, dimethylethyl-, n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and benzyl-amine, and also pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.
Preferably, the compositions according to the invention comprise as component (b) a complex salt of formula lll wherein L is an arene, a heteroarene, a nitrile, nitrogen (N2), an alcohol, an amine, CO, H20 or NH3.
Especially preferred as component (b) is a complex salt of formula lll wherein L is benzene unsubstituted or substituted by from one to three C,-C4alkyl radicals, thiophene, benzonitrile, acetonitrile, nitrogen (N2), an unsubstituted or partially or fully fluorinated C1-C4alcohol, CO, H20 or NH3.
In the compounds of formula lll, Z1- and Z2- may each be a singly charged anion, it being possible for Z1- and Z2- to be identical or different, or Z1- and Z2- may together be a doubly charged anion.
Suitable anions are, for example, hydride (H-), halide (for example Cl-, Br~ and 1-), BF4-, PF6-, SbF6-, AsF6-, unsubstituted or C,-C4alkyl-, C1-C4alkoxy-, (C,-C4alkyl)3Si- or (C,-C4alkyl)3SiO-substituted cyclopentadienyl~, or indenyl~, and the anions of oxyacids.
CA 02242060 l998-06-30 Further suitable anions are C,-C,2-, especially C,-C6- and more especially C1-C4-alcoholates, which are especially branched and correspond, for example, to the formula RXRyRzC~O~~
wherein Rx is H or C1-C,0alkyl, Ry is C1-C10alkyl and Rz is C1-C10alkyl or phenyl. Examples are especially isopropyloxy and tert-butyloxy.
Other suitable anions are C3-C18-, especially C5-C14- and more especially C5-C12-acetylides, which may correspond to the formula RW-C-C-~ wherein Rw is C1-C16alkyl, preferably a-branched C3-C12alkyl, for example of the formula RXRyRzC~~ or is phenyl or benzyl unsubstituted or substituted by from one to three C1-C4alkyl or C1-C4alkoxy radicals.
Examples include isopropylacetylide, iso- and tert-butylacetylide, phenylacetylide, benzylacetylide, 2-methylphenylacetylide, 2-isopropylphenylacetylide, 2-isopropyl-6-methylphenylacetylide, 2-tert-butylphenylacetylide, 2,6-di-tert-butylphenylacetylide and 2-methyl-6-tert-butylphenylacetylide.
The anions of oxyacids may be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or tri-chloro- or -fluoro-acetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate); phenylsulfonate or benzylsulfonate unsubstituted or substituted by C,-C4alkyl, C,-C4alkoxy or by halogen, especially fluorine, chlorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxy-phenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropyl-sulfonate; and phosphonates, for example methylphosphonate, ethylphosphonate, propylphoshonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate and benzylphosphonate.
Preferably, Z1- and Z2- in formula lll are H-, Cl-, Br~, BF4-, PF6-, SbF6-, AsF6-, CF3SO3-, C6H5-SO3-, p-toluenesulfonate (tosylate), 3,5-dimethylphenylsulfonate, 2,4,6-trimethylphenyl-sulfonate, 4-trifluoromethylphenylsulfonate or cyclopentadienyl.
Especially preferred ROMP catalysts of formula lll are [(cyclohexyl)3P]2RuCI2, [(C6H5)3P]3RuC12, [(C6H5)3P]3(CO)RuH2, [(C6H5)3P]3RuCl(cyclopentadienyl), CA 02242060 l998-06-30 [(cyclohexyl)3P]2(CH3OH)Ru(tosylate)2, [(o-tolyl)3P]3RuCI2, [(CH3)2CH]3P(p-cymene)RuCI2 and especially (cyclohexyl)3P(p-cymene)RuCI2.
Suitable fillers which may be used as component (c) in the compositions according to the invention are, for example, metal powders, wood dust, glass powder, glass beads, semi-metal and metal oxides, for example SiO2 (Aerosils, quartz, quartz powder, vitreous fused silica), corundum and titanium oxide, semi-metal and metal nitrides, for example silicon nitride, boron nitride and aluminium nitride, semi-metal and metal carbides (SiC), metal carbonates (dolomite, chalk, CaCO3), metal sulfates (barite, gypsum), and powdered rock and natural or synthetic minerals, mainly from the silicate series, for example talcum, mica, kaolin, wollastonite, bentonite and others.
Preferably, a metal oxide, carbonate, sulfate or silicate or SiO2 is used as component (c).
Preferred fillers are Al2O3, Al(OH)3, CaCO3, CaSiO3, SiO2, woven glass fibres, woven carbon fibres and woven aramid fibres.
Especially preferred as component (c) are Al2O3, Al(OH)3, wollastonite, quartz powder, dolomite, lime, chalk, woven glass fibres, woven carbon fibres and woven aramid fibres.
The silanes of formula I are known and can be prepared according to known methods. Some of those silanes are available commercially.
Preference is given to silanes of formula I wherein R as a monovalent organic group having from 2 to 100 carbon atoms is C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C,2cycloalkyl, C2-C20-alkoxyalkyl, C2-C20alkenyl, C4-C25acryloxyalkyl, C4-C25methacryloxyalkyl, C2-C20aminoalkyl, C4-C25glycidyloxyalkyl, C7-C25epoxycyclohexylalkyl or the radical of a polysiloxane.
Alkyl as R, Y1, Y2 or Y3 includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Aryl as R, Y1, Y2 or Y3 contains preferably from 6 to 10 carbon atoms. It may be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl or anthryl.
Aralkyl as R, Y" Y2 or Y3 contains especially from 7 to 12 carbon atoms and more especially from 7 to 10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, 4-phenylbutyl or a,a-dimethylbenzyl.
Cycloalkyl as R, Y1, Y2 or Y3iS preferably C5-C8cycloalkyl, especially C5- or C6-cycloalkyl.
Examples include cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclo-pentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Examples of alkoxyalkyl as R, Y" Y2 or Y3 are 2-methoxyethyl, 2-ethoxyethyl, 2-methoxy-propyl, 3-methoxypropyl, 2-ethoxypropyl and 3-ethoxypropyl.
Alkenyl as R includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
Examples of acryloxyalkyl and methacryloxyalkyl are 2-acryloxyethyl, 2-methacryloxyethyl, 3-acryloxypropyl and 3-methacryloxypropyl.
Suitable aminoalkyl groups are, for example, 2-aminoethyl, 3-aminopropyl, 3-aminobutyl and 4-aminobutyl.
Suitable glycidyloxyalkyl groups are, for example, 2-glycidyloxyethyl, 3-glycidyloxypropyl, 3-glycidyloxybutyl and 4-glycidyloxybutyl.
Epoxycyclohexylalkyl is preferably ~-(3,4-epoxycyclohexyl)ethyl.
R in formula I is preferably methyl, ethyl, n-octyl, vinyl, 3-mercaptopropyl, 3-aminopropyl, 3-glycidyloxypropyl, 3-acryloxypropyl, 3-methacryloxypropyl, ~-(3,4-epoxycyclohexyl)ethyl, N-(,B-aminoethyl)-3-aminopropyl, 3-ureidopropyl, 3-isocyanatopropyl, H2N-CH2CH2NH-CH2CH2NH-CH2CH2CH2-, (CH30)3Si-CH2CH2CH2NH-CH2CH2CH2- or a group of formula (CH30)3siCH2CH2CH2~N ~N ,cH2cH2cH2si(ocH3)3 O N ~O
Preference is given to silanes of formula I wherein R is methyl, vinyl, 3-mercaptopropyl or 3-aminopropyl.
Y" Y2 and Y3 in formula I are preferably methyl, ethyl, acetyl or 2-methoxyethyl.
Examples of suitable silanes of formula I are octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris(2-methoxyethoxy)silane, ~-methacryloxypropyltrimethoxy-silane, ~-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, y-glycidyloxypropyltrimethoxysilane, y-mercaptopropyltrimethoxysilane, ~-aminopropyltriethoxysilane, y-aminopropyltrimethoxy-silane, N-(,~-aminoethyl)-~-aminopropyltrimethoxysilane, H2NCH2CH2NHCH2CH2NHCH2CH2CH2Si(OCH3)3, bis[~-(trimethoxysilyl)propyl]amine, organically modified polydimethylsiloxane of formula (CH3)3SiO- E(CH3)2SiO~E(CH3)2 ISiO~E(CH3)2 ISi~~Si(CH3)3 wherein R and R' = alkyl or aryl, NR2 NHR'Si(OR)3 ~-ureidopropyltrimethoxysilane, ~-isocyanatopropyltriethoxysilane, 3-chloropropyltrimethoxy-silane, 3-triethoxysilylpropylsuccinic acid anhydride, 3-methacryloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane and 3-(2-aminoethylamino)propylmethyldimethoxysilane.
Vinyltrimethoxysilane is especially preferred as component (d).
It should be mentioned that when using quartz powder as filler, it is also possible to use, instead of a mixture of components (c) and (d), a quartz powder pre-treated with a silane of formula 1. Such quartz powders pre-treated with epoxysilane, alkylsilane or vinylsilane are available commercially, for example under the names Silbond~ W12 EST, Vp W12 VST and Vp W12 SST.
The amounts of components (a) to (d) in the compositions according to the invention may vary within wide limits.
Preferably, the compositions according to the invention contain from 15 to 75 % by weight of component (a), from 0.001 to 10.0 % by weight of component (b), from 20 to 80 % by weight of component (c) and from 0.01 to 20.0 % by weight of component (d), the sum of components (a), (b), (c) and (d) being 100 % by weight.
Especially preferred are compositions according to the invention containing from 25 to 65 %
by weight, especially from 30 to 50 % by weight, of component (a), from 0.01 to 2.0 % by weight, especially from 0.1 to 1.0 % by weight, of component (b), from 30 to 75 % by weight, especially from 50 to 70 % by weight, of component (c) and from 0.05 to 10.0 % by weight, especially from 0.1 to 2.0 % by weight, of component (d).
The substance mixtures according to the invention can be prepared in customary manner by mixing the components using known mixing equipment (e.g. stirrers, rollers).
In addition to components (a) to (d), the composition according to the invention may comprise further customary additives, for example anti-oxidants, light stabilisers, plasticisers, colourants, pigments, thixotropic agents, viscosity improvers, anti-foams, antistatics, lubricants and mould release agents.
The composition according to the invention may be prepared directly before polymerisation, or may be used in the form of a preformulated mixture. Before polymerisation, the mixture can be stored in the form of a ready-to-use formulation for a prolonged period, which is advantageous for use on an industrial scale. Storage with the exclusion of light is recommended, however, when the catalyst contains photolabile ligands.
The present invention relates also to a method of bonding two or more substrates, which comprises applying a curable composition comprising the above-mentioned components (a) to (d) to at least one of the substrates to be bonded, bringing the substrates to be bonded CA 02242060 l998-06-30 into contact with one another, and curing the composition by heating to a temperature , 40~C.
Advantageously, the method according to the invention is carried out at a temperature of at least 60~C. The method according to the invention is especially carried out at temperatures of from 60 to 300~C, more especially from 60 to 250~C, preferably from 60 to 200~C and especially preferably from 70 to 1 60~C. After polymerisation, it may be advantageous to temper the mixture at elevated temperatures, for example at from 80 to 200~C.
The adhesive mixture is applied to the substrate in known manner. The layer thickness of the adhesive films is generally not more than 500 ~m, and is preferably from 40 to 120,um. It is, however, possible for substantially thicker layers to be fully cured thermally.
Before being coated with the adhesive mixture, the surfaces to be bonded may, ifappropriate, be degreased and roughened.
After they have been brought together, the coated surfaces are pressed together or clamped, if appropriate.
Suitable surfaces for bonding are especially those made of metals, such as iron, steel, or especially aluminium and its alloys, for example with magnesium or silicon. The adhesive can also be used to bond two different materials, for example to bond metals to polymeric materials.
The bonds produced in accordance with the method according to the invention are distinguished especially by a high bond strength and minimal water absorption.
Example 1:
0.39 9 of Norsorex NS (thermoplastic polynorbornene, Nippon Zeon) is dissolved at 80~C in 38.91 g of dicyclopentadiene. After cooling to 60~C, 0.5 g of vinyltrimethoxysilane (Silquest~
A-171, Osi Specialties) and 0.2 g of (cyclohexyl)3P(p-cymene)RuCI2 are added, and the mixture is stirred for 20 minutes at 60~C. After the addition, in portions, of 60 g of wollastonite FW 200 (Partek Minerals), the mixture is stirred for a further 15 minutes. The mixture is then degassed for from 3 to 5 minutes in vacuo (3 mbar).
The mixture so obtained is poured into a 4 mm-thick plate mould of aluminium and then fully cured (2 h/80~C, 4 h/1 00~C, 1 h/1 50~C). It is established that the cured moulding has very good adhesion to aluminium and cannot be removed from the mould either at -180~C or at 200~C.
Claims (9)
1. Use, as an adhesive, of a composition comprising (a) at least one strained cycloolefin, (b) a catalyst for ring-opening metathesis polymerisation, (c) a filler and (d) a silane of formula I
wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
wherein R is a monovalent organic group having from 2 to 100 carbon atoms, one or more of which may have been replaced by oxygen, sulfur, nitrogen or silicon atoms, and Y1, Y2 and Y3 are each independently of the others C1-C20alkyl, C5-C20aryl, C6-C20aralkyl, C5-C12cycloalkyl, C2-C20alkoxyalkyl or C1-C20acyl.
2. The use of a composition according to claim 1 as an adhesive for metals.
3. The use of a composition according to claim 1 as an adhesive for aluminium.
4. The use of a composition according to claim 1 comprising dicyclopentadiene ascomponent (a).
5. The use of a composition according to claim 1 comprising (cyclohexyl)3P(p-cymene)RuCl2 as component (b).
6. The use of a composition according to claim 1 comprising as component (c) Al2O3, Al(OH)3, CaCO3, CaSiO3, SiO2, woven glass fibres, woven carbon fibres or woven aramid fibres.
7. The use of a composition according to claim 1 comprising as component (c) Al2O3, Al(OH)3, wollastonite, quartz powder, dolomite, lime, chalk, woven glass fibres, woven carbon fibres or woven aramid fibres.
8. The use of a composition according to claim 1 comprising vinyltrimethoxysilane as component (d).
9. A method of bonding two or more substrates, which comprises applying a curable composition comprising components (a) to (d) according to claim 1 to at least one of the substrates to be bonded, bringing the substrates to be bonded into contact with one another, and curing the composition by heating to a temperature > 40°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1619/97 | 1997-07-03 | ||
| CH161997 | 1997-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2242060A1 true CA2242060A1 (en) | 1999-01-03 |
Family
ID=4214678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2242060 Abandoned CA2242060A1 (en) | 1997-07-03 | 1998-06-30 | Cycloolefin-based adhesive |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0889107A3 (en) |
| JP (1) | JPH1180698A (en) |
| CA (1) | CA2242060A1 (en) |
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| US7160969B2 (en) | 2001-03-12 | 2007-01-09 | Ciba Specialty Chemicals Corp. | ROMP with alkoxy ether groups |
| US8597794B2 (en) | 1999-02-05 | 2013-12-03 | Materia, Inc. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| WO2015011404A1 (en) | 2013-07-23 | 2015-01-29 | Bostik Sa | Hydrocarbon polymers with two alkoxysilane end groups |
| WO2015011405A1 (en) | 2013-07-23 | 2015-01-29 | Bostik Sa | Hydrocarbon polymers having an alkoxysilane end group |
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| US9796889B2 (en) | 1999-02-05 | 2017-10-24 | Materia, Inc. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| WO2017198935A1 (en) | 2016-05-17 | 2017-11-23 | Bostik Sa | Hydrocarbon polymers with two alkoxysilane end groups and processes for preparing same |
| WO2018002473A1 (en) | 2016-06-29 | 2018-01-04 | Bostik Sa | New hydrocarbon polymers comprising two alkoxysilane end groups, and methods for preparing same |
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| US7025851B2 (en) | 1998-12-11 | 2006-04-11 | Lord Corporation | Contact metathesis polymerization |
| US6962729B2 (en) | 1998-12-11 | 2005-11-08 | Lord Corporation | Contact metathesis polymerization |
| CA2318711A1 (en) * | 2000-09-13 | 2002-03-13 | Lord Corporation | Contact metathesis polymerization |
| KR20030051686A (en) * | 2000-09-25 | 2003-06-25 | 로드코포레이션 | Contact metathesis polymerization |
| EP1241196A3 (en) * | 2001-03-12 | 2002-11-20 | Ciba SC Holding AG | ROMP with alkoxy ether groups |
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|---|---|---|---|---|
| EP0349855A3 (en) * | 1988-06-27 | 1991-01-23 | Hercules Incorporated | Molded article of metathesis polymerized polymer containing fillers and process for its preparation |
| US4910077A (en) * | 1988-08-04 | 1990-03-20 | B.F. Goodrich Company | Polynorbornene laminates and method of making the same |
| US5071701A (en) * | 1989-11-22 | 1991-12-10 | B. F. Goodrich Corporation | Copolymer for use in preparing prepregs, printed circuit wiring boards prepared from such prepregs and processes for preparing such printed circuit wiring boards |
| WO1996016100A1 (en) * | 1994-11-17 | 1996-05-30 | Ciba Specialty Chemicals Holding Inc. | Thermal metathesis polymerisation process and a polymerisable composition |
| ATE180001T1 (en) * | 1994-12-23 | 1999-05-15 | Ciba Geigy Ag | POLYMERIZABLE COMPOSITION AND POLYMERIZATION PROCESS |
| DE59610089D1 (en) * | 1995-11-02 | 2003-03-06 | Ciba Sc Holding Ag | Curable composition containing cycloolefin, silane and filler |
-
1998
- 1998-06-24 EP EP98810579A patent/EP0889107A3/en not_active Ceased
- 1998-06-30 CA CA 2242060 patent/CA2242060A1/en not_active Abandoned
- 1998-07-03 JP JP10204424A patent/JPH1180698A/en active Pending
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| EP3024856B1 (en) | 2013-07-23 | 2018-08-29 | Bostik Sa | Hydrocarbon polymers having an alkoxysilane end group |
| US20170218131A1 (en) * | 2014-08-01 | 2017-08-03 | Kolon Industries, Inc. | Curable petroleum resin and method for preparing same |
| EP3176191A4 (en) * | 2014-08-01 | 2018-02-28 | Kolon Industries, Inc. | Curable petroleum resin and method for preparing same |
| US10280266B2 (en) * | 2014-08-01 | 2019-05-07 | Kolon Industries, Inc. | Curable petroleum resin and method for preparing same |
| FR3031517A1 (en) * | 2015-01-08 | 2016-07-15 | Bostik Sa | HYDROCARBON POLYMERS WITH TWO ALCOXYSILANE TERMINAL GROUPS |
| WO2016110653A1 (en) | 2015-01-08 | 2016-07-14 | Bostik Sa | Hydrocarbon polymers with two alcoxysilane end groups |
| WO2016116680A1 (en) | 2015-01-22 | 2016-07-28 | Bostik Sa | Hydrocarbonated polymers with two alcoxysilane end groups |
| WO2017198935A1 (en) | 2016-05-17 | 2017-11-23 | Bostik Sa | Hydrocarbon polymers with two alkoxysilane end groups and processes for preparing same |
| WO2018002473A1 (en) | 2016-06-29 | 2018-01-04 | Bostik Sa | New hydrocarbon polymers comprising two alkoxysilane end groups, and methods for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0889107A2 (en) | 1999-01-07 |
| EP0889107A3 (en) | 1999-03-24 |
| JPH1180698A (en) | 1999-03-26 |
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