CN1164246A - Polymerizable composition and process for polymerizing cyclical olefins - Google Patents
Polymerizable composition and process for polymerizing cyclical olefins Download PDFInfo
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- CN1164246A CN1164246A CN 95196282 CN95196282A CN1164246A CN 1164246 A CN1164246 A CN 1164246A CN 95196282 CN95196282 CN 95196282 CN 95196282 A CN95196282 A CN 95196282A CN 1164246 A CN1164246 A CN 1164246A
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Abstract
Process for the photocatalytic polymerization of a cyclical olefin or at least two different cyclical olefins in the presence of a metal compound as the catalyst, which is characterized in that a photochemical ring-opening metathesis polymerization is carried out in the presence of a catalytic amount of at least one carbene-free, bivalent-cationic ruthenium or osmium compound which contains at least one phosphine group, at least one photolabile ligand, and optionally neutral ligands bonded to the metal atom, a total of 2 or 3 ligands being bonded, and which contains acid ions for balancing the charge. The process can also be carried out by first carrying out the irradiation and ending the polymerization by heating. The process is suitable, for example, for the preparation of thermoplastics shaping compounds and the production of coatings and images in relief.
Description
The present invention relates under a kind of ruthenium (II) or osmium (II) the catalyzer situation method of polymerized cycloolefins by photochemical open loop-transposition (Metathese)-polymerization in the applied catalysis amount, wherein catalyzer comprises an at least one phosphino-and a photo-labile part that is incorporated on the metal, and the composition that relates to this catalyzer that contains this alkene and catalytic amount.
Open loop-transposition-the polymerization of thermal initiation has been known for a long time and had repeatedly described in the literature (referring to for example Ivin under the situation of the metal catalyst of applied catalysis amount, K.J., " (the alkene transposition " (Olefin Metathesis) 1-12, Academic Press, London (1983)).Those polymkeric substance are industrial and are that commercial buying is (for example with Vestenamer
Buy).Oppose mutually that open loop transposition polymerization that photochemistry causes is rarely known by the people and use so far not occur at coml.
By US4,060,468 is known, alkene transposition polymerization is carried out with following method, make that (this metal-salt is selected from tungsten salt by metal-salt, molybdenum salt, ruthenium salt and tantalum salt) and the binary mixture formed as promotor of the phenol that replaces or benzyl alcohol be added in the reaction vessel that fills monomer alkene and then use the uviolizing complete reaction mixture.Only mention no functional group or substituent ring or non-cyclic hydrocarbon as alkene.The separate storage catalyst component and directly before reaction the method steps of mixed catalyst component make known method very expensive and loaded down with trivial details technically.
People such as Ta Nilan (Tanielan, C., Kieffer, R., Harfouch, A., " tetrahedron communication " (Tetrahedron Letters) 52:4589-4592 (1977)) have described catalyst system W (CO)
6/ CCl
4, this system can be used for the transposition polymerization of cyclopentenes and norbornylene after with the UV-optical radiation.Metallic carbonyls is an evaporable and poisonous, so it is used owing to physiological reason requires expensive sfgd.. regard the addition reaction of free radical as competing reaction under the situation of this external formation monomer 1-chloro-2-trichloromethyl-naphthenic hydrocarbon.
Known by the first-class people of holder (Ivin, K.J., Rooney, J.J., " (molecular catalyst magazine " be 15:245-270 (1982) (J.Mol.Catal.) for Thoi, H.H.), following formula-pentacarbonyl tungsten carbene complex compound,
Being a kind of open loop transposition polymeric thermocatalyst that is used for the dimethyl norbornylene, also is a kind of photocatalyst system that is used for same polymeric with the phenylacetylene as promotor.This catalyst system has important disadvantages, and it has only very low package stability as the prescription constituent that can use, and is suspicious and too low to the functional group's of cycloolefin tolerance on this carbonyl compound physiology.
Feldman and Scirocco (Feldman, J., Schrock, R.R., in:Lippard, S.J. (Hrsg.) " inorganic chemistry process " (Progress in Inorganic Chemistry), 39:1-74 (1991)) molybdenum-and tungsten-alkylidene complex described, they are separately very weak, but are to be used for the effective thermocatalyst of cyclic olefin polymerization with Lewis acid.
But this known photochemistry activatory catalyzer always needs a kind of promotor, and the polymer quality of Sheng Chaning is because reactant classification of being selected for use and the decision meeting of order institute are very unstable thus.
Can only produce polymkeric substance with high cost and unsatisfied economically mode by photochemical open loop transposition polymerization by cycloolefin with these currently known methodss.What experience as main shortcoming is to lack package stability (this package stability directly just allows the mixing of component before preparation), lacks the tolerance of functionalized cycloolefin and uses the necessity of two-pack as catalyst system.Therefore have a kind of needs, provide a kind of from technology, economical and ecological viewpoint set out improvement be used for preparing polymkeric substance by cycloolefin with method in common by photochemical open loop transposition polymerization.
In WO93/13171, described contain the molybdenum that has at least one polyenoid ligand of carbonyl-and tungsten compound and ruthenium-and the osmium compound basis on air-and water-stable single component-and two-pack-catalyzer be used for the transposition polymerization of the photoactivation of the cycloolefin, particularly norbornylene of hot replace polymerization and tensioning and norbornene derivative.Do not address other polycyclic cycloolefins, especially the polycyclic cycloolefin of non-condensed.The ruthenium compound that uses, i.e. (Ru (cumene) Cl
2)
2((C
6H
6) Ru (CH
3CN)
2Cl)
+PF
6 -Although the activation of the available ultraviolet radiation of single component-catalyzer, the package stability with composition of norbornylene is not exclusively enough.This catalyzer is not enough to replace known bicomponent catalyst.
People such as Demonceau (Demencean, A., Noels, A.F., Saive, E., Hubert, A.J., J.Mol.Catal.76:123-132 (1992)) have described ((C
6H
5)
3)
3PRuCl
2, (right-cumene) RuCl
2P (C
6H
11)
3((C
6H
5)
3)
3PRuHCl is used for norbornene open-loop transposition polymerization as thermocatalyst.Because its this catalyzer of low excessively activity is infeasible on industrial preparation.Therefore suggestion improves active by adding diazo ester.But the transposition polymerization that not mentioned radiation causes and by the radiating catalytic activation.
The osmium that has the phosphine part-and ruthenium carbene compound, for example ((H described in WO93/20111
5C
6)
3P)
2Cl
2=CH-CH=C (C
6H
5)
2, be used for the open loop transposition polymerization of tightening hoop alkene as pure thermocatalyst, wherein cyclic diolefine such as dicyclopentadiene play the catalyst-initiator effect and fail polymerization.This catalyzer is difficult to preparation and to air and moisture content instability, therefore takes special sfgd. for the storage and the manipulation require of the composition that contains this catalyzer.The transposition polymerization that wherein same not mentioned radiation causes and by the radiating catalytic activation.
Find, but the composition photochemical polymerization of forming by the cycloolefin and a single component catalyst of tensioning, if said composition contains a kind of divalent cation ruthenium that does not have a Cabbeen-or osmium compound, wherein this ruthenium-or osmium compound in have at least a phosphino-and an at least one photo-labile part that randomly replaces to be incorporated on the atoms metal.Surprising is has proved and thisly self the very stable compound of heat can be used as light-initiated open loop-transposition polymeric active catalyst, although it is photochemically reactive, by cycloolefin and ruthenium-or the mixture that osmium compound is formed under the lucifuge condition, still can keep package stability.Said composition is insensitive to air and wet steam, and this provides advantage for industrial application.Beyond expectation is that this catalyzer has just shown high reactivity under lower concentration.It can not suppressed by cycloolefin such as dicyclopentadiene when radiation.This catalyzer also is easy to preparation, and is insensitive to empty G﹠W, and even is soluble in pure hydrocarbon.Find, even cycloolefin weak tensioning and/or the most different replacements also can be aggregated in addition beyond expectationly.
A lot of this catalyzer also are general to good thermocatalyst.Find that beyond expectationly described catalyzer or just played the thermocatalyst effect or just significantly improved hot activity by of short duration radiation in the presence of cycloolefin after of short duration radiation therefore can be in conjunction with utilizing photochemistry and thermopolymerization.
A theme of the present invention is in the photochemical catalysis polymeric method of a kind of metallic compound as the cycloolefin of the cycloolefin of next tensioning of existence of catalyzer or at least two kinds of different tensionings, it is characterized in that, at at least a no Cabbeen of catalytic amount, the ruthenium of divalent cation-or the existence of osmium compound under carry out photochemistry open loop-transposition polymerization, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2-5 part altogether, and contain the acid anion that is useful on charge balance." altogether " be meant the sum of phosphino-, photo-labile part and neutral ligand within the scope of the present invention.Neutral ligand is also referred to as non-photo-labile part.
This ruthenium-preferably contain 2 or 3 parts altogether with osmium compound.
Phosphino-preferably relates to and contains 3-40, the individual also tertiary phosphine of especially preferred 3-24 C atom of preferred 3-30.
All the other valence links of ruthenium and osmium preferably use heat-staple neutral ligand saturated, and neutral ligand is known in a large number.The neutral ligand number also can surpass stoichiometrical possible numerical value (Solvate).
Can relate to member ring systems monocyclic or polycyclic condensed and/or bridge joint in the cycloolefin situation, for example have 2 to 4 rings, these rings be unsubstituted or replace and can be in one or more rings and/or for example adjacent phenylene of ring condensed aromatics or heteroaromatic, adjacent naphthylidene, adjacent pyridylidene, contain heteroatoms for example O, S, N or Si in the adjacent inferior pyrimidyl.One cyclic rings can contain 3 to 16, and preferred 3 to 12 and preferred especially 3 to 8 links.Cyclic olefin can contain two keys of other non-aromatics, according to preferred 2 to 4 the additional like this pair of keys of ring size cases.Ring substituents relates to some inert substituting groups, that is to say, they do not damage the chemical stability and the thermostability of ruthenium or osmium compound.The ring or the member ring systems that relate to tensioning in the cycloolefin situation.
Thermostability is that the ruthenium of photo catalytic activation or osmium compound can not form open loop transposition polymeric activatory compound in invention scope under heating state.This catalyzer for example can ℃ not cause open loop transposition polymerization according to appointment+40 in room temperature to high slightly temperature in several weeks under the situation of isolated light.During this period of time have only the monomer (being less than 0.2 weight %) of unimportant amount to transform.Thermostability for example can be determined like this, method is: the toluene solution with 20 weight % monomers and 0.33 weight % ruthenium or osmium catalyst 50 ℃ of amount of polymer of storing in the dark 96 hours and may generate (on the viscosity device, can recognize and in precipitation agent for example ethanol by precipitation, but filter and the drying quantitative assay) no more than 0.5 weight % and preferred no more than 0.2 weight %.
If cycloolefin contains more than 1 two key, for example 2 to 4 two keys then also can generate crosslinked polymkeric substance, depend on reaction conditions, selected monomer and catalyst amounts.
Cycloolefin is equivalent to formula I in the embodiment of a preferred the inventive method
In the formula
Q
1Be one to have the base of at least one carbon atom, it and-CH=CQ
2-Ji forms the ring of the alicyclic ring of one at least 3 joint together, and this ring contains one or more heteroatomss in case of necessity, and heteroatoms is selected from silicon, phosphorus, oxygen, nitrogen, sulphur; And it is unsubstituted or with halogen ,=O ,-CN ,-NO
2, R
1R
2R
3Si-(O)
u-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
20-alkyl, C
1-C
20-hydroxyalkyl, C
1-C
20-haloalkyl, C
1-C
6-cyano group alkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl, C
7-C
16-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
16-heteroaryl, C
4-C
16-heteroaralkyl or R
4-X-replaces; Or wherein two adjacent C atoms be with-CO-O-CO-or-CO-NR
5-CO-replaces; Or wherein condensing an alicyclic ring on the adjacent carbons of alicyclic ring in case of necessity, and ring aromatics or heteroaromatic, it is unsubstituted or with halogen ,-CN ,-NO
2, R
6R
7R
8Si-(O)
u-,-COOM ,-SO
3M ,-PO
3M ,-COOM (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
20Alkyl, C
1-C
20-haloalkyl, C
1-C
20-hydroxyalkyl, C
1-C
6-cyano group alkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl, C
7-C
16-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
16-heteroaryl, C
4-C
16-heteroaralkyl or R
13-X
1-replace;
X and X
1Respectively do for oneself-O--S-,-CO-,-SO-,-SO
2-,-O-C (O)-,-C (O)-O-,-C (O)-NR
5-,-NR
10-C (O)-,-SO
2-O-or-O-SO
2-;
R
1, R
2And R
3C respectively does for oneself
1-C
12-alkyl, C
1-C
12-perfluoroalkyl, phenyl or benzyl;
R
4And R
13C respectively does for oneself
1-C
20-alkyl, C
1-C
20-haloalkyl, C
1-C
20-hydroxyalkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl, C
7-C
16-aralkyl;
R
5And R
10The hydrogen of respectively doing for oneself, C
1-C
12-alkyl, phenyl or benzyl, wherein alkyl is unsubstituted or with C
1-C
12-alkoxyl group or C
3-C
8-cycloalkyl substituted;
R
6, R
7And R
8C respectively does for oneself
1-C
12-alkyl, C
1-C
12-perfluoroalkyl, phenyl or benzyl;
M is basic metal and M
1It is an alkaline-earth metal; With
U is 0 or 1; Wherein with Q
1The ring of the alicyclic ring that forms contains two keys of other non-aromatics in case of necessity;
Q
2Be hydrogen, C
1-C
20-alkyl, C
1-C
20-haloalkyl, C
1-C
12-alkoxyl group, halogen ,-CN, R
11-X
2-;
R
11Be C
1-C
20Alkyl, C
1-C
20-haloalkyl, C
1-C
20-hydroxyalkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl or C
7-C
16-aralkyl;
X
2Be-C (O)-O-or-C (O)-NR
12-; R
12Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; Wherein above-mentioned cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or with C
1-C
12-alkyl, C
1-C
12-alkoxyl group ,-NO
2,-CN or halogen replace, and wherein above-mentioned Heterocyclylalkyl, and the heteroatoms in heteroaryl and the heteroaralkyl is to be selected from-O-,-S-,-NR
9-and-N=; And R
9Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl.
The condensed alicyclic ring contains preferred 3 to 8, preferred especially 4 to 7 and 5 or 6 ring-C-atoms most preferably.
If there is an asymmetric center in the formula I compound, the consequence that has like this is that compound can the optical isomer form occur.Some formula I compounds can occur by tautomer (for example keto-acid-pure formula-tautomerism).If have the two keys of the C=C of an aliphatic series, geometric isomerism (E-form or Z-form) then also can occur.Outer in addition-Nei configuration also is possible.Therefore formula I comprises all possible steric isomer, and they are with enantiomorph, tautomer, and diastereomer, the form of E/Z-isomer or its mixture exists.
Alkyl in substituent definition, alkenyl and alkynyl can be straight chain or side chain.Same alkoxyl group, alkylthio, (each) moieties of alkoxy carbonyl and other the group that contains alkyl of also being applicable to.These alkyl preferably contain 1 to 12, and more preferably 1 to 8 and 1 to 4 C atom most preferably.These alkenyls and alkynyl preferably contain 2 to 12, and more preferably 2 to 8 and 2 to 4 C atoms most preferably.
Alkyl for example comprises methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, the amyl group of the tertiary butyl and different isomery, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Hydroxyalkyl for example comprises hydroxymethyl, hydroxyethyl, 1-hydroxyl sec.-propyl, 1-hydroxyl n-propyl, 2-hydroxyl-normal-butyl, 1-hydroxyl-different-butyl, 1-hydroxyl-second month in a season-butyl, the amyl group of 1-hydroxyl-tert-butyl and different isomery, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Haloalkyl for example comprises methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2, the 2-trifluoroethyl, 2-fluoro ethyl, 2-chloroethyl, 2,2,2-three chloroethyls and halogenated, particularly fluorizated or chlorating alkane, for example sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl is with the amyl group of different isomery, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Alkenyl for example comprises propenyl, pseudoallyl, and crotyl, the 3-butenyl, different-butenyl, positive penta-2,4-dialkylene, 3-methyl-but-2-ene base, positive oct-2-ene base, positive 12-2-thiazolinyl, different laurylene base, positive 18-2-thiazolinyl, positive 18-4-thiazolinyl.
Preferably relate to C in the cycloalkyl situation
5-C
8-cycloalkyl is in particular C
5Or C
6-cycloalkyl.Some examples are cyclopropyl, dimethyl cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, suberyl and ring octyl group.
The cyano group alkyl for example comprises cyano methyl (methyl nitrile), cyano ethyl (ethyl nitrile), 1-cyano group sec.-propyl, 1-cyano group-n-propyl, 2-cyano group-normal-butyl, 1-cyano group-isobutyl-, 1-cyano group-sec-butyl, the cyano group amyl group of 1-cyano group-tertiary butyl and different isomery and-hexyl.
Aralkyl preferably contains 7 to 12 C-atoms and preferred especially 7 to 10 C-atoms.For example can relate to benzyl, styroyl, 3-phenyl propyl, α-Jia Jibianji, benzene butyl or α, α-Er Jiajibianji.
Aryl preferably contains 6 to 10 C-atoms.For example can relate to phenyl, pentaline (pentalin), indenes, naphthalene, azulin or anthracene.
Heteroaryl preferably contains 4 or 5 C-atoms and one or two and is selected from O, the heteroatoms of S and N.For example can relate to the pyrroles, furans, thiophene ， oxazole, thiazole, pyridine, pyrazine, phonetic azoles, pyridazine, indoles, purine or quinoline.
Heterocyclylalkyl preferably contains 4 or 5 C-atoms and one or two and is selected from O, the heteroatoms of S and N.For example can relate to oxyethane, the azine quinoline, 1,2-Evil carries the Oran, pyrazoline, tetramethyleneimine, piperidines, piperazine, morpholine, tetrahydrofuran (THF) or tetramethylene sulfide.
Alkoxyl group for example is methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert.-butoxy.
Basic metal is interpreted as lithium in invention scope, sodium, potassium, rubidium and caesium, particularly lithium, sodium and potassium.
Alkaline-earth metal is interpreted as beryllium in invention scope, magnesium, calcium, strontium and barium, particularly magnesium and calcium.
Halogen is interpreted as fluorine in the definition in the above, chlorine, bromine and iodine, preferred fluorine, chlorine and bromine.
To the particularly suitable formula I compound of the inventive method is those Q
2Compound for hydrogen.
Preferred formula I compound is that wherein (it is by Q for the ring of alicyclic ring concerning polymerization in addition
1With-CH=CQ
2-Ji constitutes together) have 3 to 16,3 to 12 and most preferably 3 to 8 annular atomses more preferably, and wherein can relate to one monocyclic, dicyclo, trinucleated or tetracyclic member ring systems.
With the advantage of uniqueness the inventive method is implemented with these formulas I compound, in the formula
Q
1Be one to have the base of at least one carbon atom, it and-CH=CQ
2-Ji forms the ring of the alicyclic ring of one 3 to 20 joints together, and this ring contains one or more heteroatomss in case of necessity, and heteroatoms is selected from silicon, oxygen, nitrogen, sulphur; And it is unsubstituted or with halogen ,=O ,-CN ,-NO
2, R
1R
2R
3Si-(O)
u-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, C
6-C
12-aryl, C
7-C
12-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
12-heteroaryl, C
4-C
12-heteroaralkyl or R
4-X-replaces; Or wherein at this Q
1In two adjacent C-atoms be with-CO-O-CO-or-CO-NR
5-CO-replaces; Or wherein condensing an alicyclic ring on the adjacent carbons in case of necessity, and ring aromatics or heteroaromatic, it is unsubstituted or with halogen ,-CN ,-NO
2, R
6R
7R
8Si-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, C
6-C
12-aryl, C
7-C
12-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
12-heteroaryl, C
4-C
12-heteroaralkyl or R
13-X
1-replace;
X and X
1Independently be-O--S-,-CO-,-SO-,-SO separately
2-,-O-C (O)-,-C (O)-O-,-C (O)-NR
5-,-NR
10-C (O)-,-SO
2-O-or-O-SO
2-;
R
1, R
2And R
3Independently be C separately
1-C
6-alkyl, C
1-C
6-perfluoroalkyl, phenyl or benzyl;
M is basic metal and M
1It is an alkaline-earth metal;
R
4And R
13Independently be C separately
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
3-C
8-cycloalkyl, C
6-C
12-aryl, C
7-C
12-aralkyl;
R
5And R
10Be hydrogen independently of one another, C
1-C
6-alkyl, phenyl or benzyl, wherein alkyl is unsubstituted or with C
1-C
6-alkoxyl group or C
3-C
6-cycloalkyl substituted;
R
6, R
7And R
8Be C independently of one another
1-C
6-alkyl, C
1-C
6-perfluoroalkyl, phenyl or benzyl;
U is 0 or 1; Wherein with Q
1The ring of the alicyclic ring that forms contains two keys of other non-aromatics in case of necessity;
Q
2Be hydrogen, C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
6-alkoxyl group, halogen ,-CN, R
11-X
2-;
R
11Be C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
3-C
6-cycloalkyl, C
6-C
12-aryl or C
7-C
12-aralkyl;
X
2Be-C (O)-O-or-C (O)-NR
12-; And R
12Be hydrogen, C
1-C
6-alkyl, phenyl or benzyl; Cycloalkyl wherein, Heterocyclylalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or with C
1-C
6-alkyl, C
1-C
6-alkoxyl group ,-NO
2,-CN or halogen replace, and Heterocyclylalkyl wherein, and the heteroatoms in heteroaryl and the heteroaralkyl is selected from-O-,-S-,-NR
9-and-N=; And R
9Be hydrogen, C
1-C
6-alkyl, phenyl or benzyl.
It is preferred going out these formulas I compound of organizing since then, in the formula
Q
1Be one to have the base of at least one carbon atom, it and-CH=CQ
2-Ji forms the ring of the alicyclic ring of one 3 to 10-joints together, and this ring contains one in case of necessity and is selected from silicon, the heteroatoms of oxygen, nitrogen and sulphur; And it is unsubstituted or with halogen ,-CN ,-NO
2, R
1R
2R
3Si-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
6-alkyl, C
1-C
6-haloalkyl, C
1-C
6-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, phenyl, benzyl or R
4-X-replaces; Or wherein condensing an alicyclic ring on the adjacent carbon atom in case of necessity, ring aromatics or heteroaromatic, this ring are unsubstituted or with halogen ,-CN ,-NO
2, R
6R
7R
8Si-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
6-alkyl, C
1-C
6-haloalkyl, C
1-C
6-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, phenyl, benzyl or R
13-X
1-replace;
R
1, R
2And R
3Be C independently of one another
1-C
4-alkyl, C
1-C
4-perfluoroalkyl, phenyl or benzyl;
M is basic metal and M
1It is an alkaline-earth metal;
R
4And R
13Be C independently of one another
1-C
6-alkyl, C
1-C
6-haloalkyl, C
1-C
6-hydroxyalkyl or C
3-C
6-cycloalkyl;
X and X
1Be independently of one another-O-,-S-,-CO-,-SO-or-SO
2-;
R
6, R
7And R
8Be C independently of one another
1-C
4-alkyl, C
1-C
4-perfluoroalkyl, phenyl or benzyl; And Q
2Be hydrogen.
The inventive method is particularly suitable for polymerization norbornylene and norbornene derivative.These are particularly preferred in these norbornene derivatives, and they are equivalent to formula II compound
In the formula
X
3For-CHR
16-, oxygen or sulphur;
R
14And R
15Be hydrogen independently of one another ,-CN, trifluoromethyl, (CH
3)
3Si-O-, (CH
3)
3Si-or-COOR
17And
R
16And R
17Be hydrogen independently of one another, C
1-C
12-alkyl, phenyl or benzyl; Or formula III compound
In the formula
X
4For-CHR
19-, oxygen or sulphur;
R
19Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; And
R
18Be hydrogen, C
1-C
6-alkyl or halogen; Or formula IV compound
In the formula
X
5For-CHR
22-, oxygen or sulphur;
R
22Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl;
R
20And R
21Be hydrogen independently of one another, CN, trifluoromethyl, (CH
3)
3Si-O-, (CH
3)
3Si-or-COOR
23And
R
23Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; Or formula V compound
In the formula
X
6For-CHR
24-, oxygen or sulphur;
R
24Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; Y be oxygen or
And
R
25Be hydrogen, methyl, ethyl or phenyl.
Below formula I compound be particularly suitable to polymerization process of the present invention, wherein dicyclo with the polycyclic system be available by diels-Alder reaction:
In ruthenium and osmium compound that the present invention uses, single phosphine should be once, secondary or three times, preferably once be incorporated on the atoms metal, and diphosphine can once be incorporated on the atoms metal.Preferred combination 1-4 in ruthenium and osmium catalyst, more preferably 1-3 photo-labile part, a preferred especially photo-labile part.The residue valence link of ruthenium and osmium-use neutral ligand saturated if any-preferably.Preferred phosphine part is corresponding to formula VII and VIIa,
PR
26R
27R
28?????????????????????????????(VII)，
R
26R
27P-Z
1-PR
26R
27(VIIa), R wherein
26, R
27And R
28Be H independently of each other, C
1-C
20Alkyl does not replace or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6The C that alkoxyl group replaces
4-C
12Cycloalkyl; Or do not replace or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6The C that alkoxyl group replaces
6-C
16Aryl; Or it is unsubstituted or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6The C that alkoxyl group replaces
7-C
16Aralkyl; Radicals R
26And R
27Common is unsubstituted or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6Four-or the pentamethylene that alkoxyl group replaces, or unsubstituted or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6That alkoxyl group replaces and with 1 or 21,2-phenylene condensed four-or pentamethylene, and R
28Has the given implication in front; With
Z
1For straight chain or branching, do not replace or by C
1-C
4The C that alkoxyl group replaces
2-C
12Alkylidene group does not replace or by C
1-C
4Alkyl or C
1-C
4That alkoxyl group replaces, have 1 of 4-8 C atom, 2-or 1,3-cycloalkylidene, or unsubstituted or by C
1-C
4Alkyl or C
1-C
4That alkoxyl group replaces, have 5 or 6 ring elements and one and be selected from heteroatomic 1,2 or 1 of O or N, the inferior Heterocyclylalkyl of 3-.
R
26, R
27And R
28Preferably relate to identical group.
If R
26, R
27And R
28Be substituted, then preferred substituents is C
1-C
4Alkyl, C
1-C
4Haloalkyl or C
1-C
4Alkoxyl group.Halogen is preferably Cl, and more preferably F.The preferred substituted example is methyl, methoxyl group, ethyl, oxyethyl group and trifluoromethyl.R
26, R
27And R
28Preferably replaced by 1-3 substituting group.
R
26, R
27And R
28That can be straight chain or branching as alkyl and preferably contain 1-12, more preferably 1-8, especially preferred 1-6 C atom.The example of alkyl is a methyl, ethyl, just and sec.-propyl, and just, the different and tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, the isomer of octadecyl and eicosyl.Preferred examples is a methyl, ethyl, just and sec.-propyl, and just, the different and tertiary butyl, 1-, 2-or 3-amyl group and 1-, 2-, 3-or 4-hexyl.
If R
26, R
27And R
28Be cycloalkyl, then preferably relate to C
5-C
8Cycloalkyl, more preferably C
5Or C
6Cycloalkyl.Example is a cyclobutyl, suberyl, ring octyl group and especially cyclopentyl and cyclohexyl.The example of the cycloalkyl that replaces be methyl-, dimethyl-, trimethylammonium-, methoxyl group-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis trifluoromethyl and three (trifluoromethyl) cyclopentyl and cyclohexyl.
If R
26, R
27And R
28Be aryl, then it is preferably C
6-C
12Aryl, and preferred especially phenyl or naphthyl.The example of the aryl that replaces be methyl-, dimethyl-, trimethylammonium-, methoxyl group-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis trifluoromethyl and three (trifluoromethyl) phenyl.
If R
26, R
27And R
28Be aralkyl, then it is preferably C
7-C
13Aralkyl, wherein the alkylidene group in the aralkyl is preferably methylene radical.Particularly preferred aralkyl is a benzyl.The example of the aralkyl that replaces be methyl-, dimethyl-, trimethylammonium-, methoxyl group-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis trifluoromethyl and three (trifluoromethyl) benzyl.
Be incorporated on the P atom, optional replace or condensed four-or the example of pentamethylene be
Other suitable phosphine is cycloaliphatic compounds usefulness=PRa group bridgeization, that have 6-8 ring carbon atom, for example
Wherein Ra is C
1-C
6Alkyl, cyclohexyl, benzyl, unsubstituted or by 1-2 C
1-C
4The phenyl that alkyl replaces.
Work as Z
1During for straight chain or sub-branched alkyl, then it is preferably and preferably has 1 of 2-6 C atom, 2-alkylidene group or 1,3-alkylidene group, ethylidene for example, propylene or 1,2-butylidene.
Z
1Example as cycloalkylidene has 1,2-and 1,3-cyclopentylidene and 1,2-or 1,3-cyclohexylidene.Z
1Example as inferior Heterocyclylalkyl has 1,2-and 1, and the 3-pyrrolidyl, 1,2-and 1, the 3-piperidyl, and 1,2-and 1,3-tetrahydrofuran base.
In an embodiment preferred, the phosphine part is corresponding to formula VII, wherein R
26, R
27And R
28Be H independently of each other, C
1-C
6Alkyl does not replace or by C
1-C
4Cyclopentyl or cyclohexyl that alkyl replaces, or do not replace or by C
1-C
4Alkyl, C
1-C
4The phenyl that alkoxyl group or trifluoromethyl replace or unsubstituted or by C
1-C
4Alkyl, C
1-C
4Alkyl C
1-C
4The benzyl that alkoxyl group or trifluoromethyl replace.The example of especially preferred formula VII phosphine part is
(C
6H
5)
3P，(C
6H
5CH
2)
3P，(C
5H
11)
3P，(CH
3)
3P，(C
2H
5)
3P，(n-C
3H
7)
3P，(i-C
3H
7)
3P，
(n-C
4H
9)
3P，(C
6H
5)
2HP，(C
6H
5CH
2)
2HP，(C
5H
11)
2HP，(CH
3)
2HP，(C
2H
5)
2HP，
(n-C
3H
7)
2HP，(i-C
3H
7)
2HP，(n-C
4H
9)
2HP，(C
6H
5)H
2P，(i-C
3H
7)H
2P，(C
6H
5CH
2)H
2P，
(C
5H
11)H
2P，(CH
3)H
2P，(C
2H
5)H
2P，(n-C
3H
7)H
2P，(n-C
4H
9)H
2P，PH
3, (2-methyl-C6H
4)
3P，(3-CH
3-C
6H
4)
3P，(4-CH
3-C
6H
4)
3P，(2，4-Di-CH
3-C
6H
3)
3P，
(2，6-Di-CH
3-C
6H
3)
3P，(2-C
2H
5-C
6H
4)
3P，(3-C
2H
5-C
6H
4)
3P，(4-C
2H
5-C
6H
4)
3p，
(2-n-C
3H
7-C
6H
4)
3P，(3-n-C
3H
7-C
6H
4)
3P，(4-n-C
3H
7-C
6H
4)
3P，(2-i-C
3H
7-C
6H
4)
3P，
(3-i-C
3H
7-C
6H
4)
3P，(4-i-C
3H
7-C
6H
4)
3P，(2-n-C
4H
9-C
6H
4)
3P，(3-n-C
4H
9-C
6H
4)
3P，
(4-n-C
4H
9-C
6H
4)
3P，(2-i-C
4H
9-C
6H
4)
3P，(3-i-C
4H
9-C
6H
4)
3P，(4-i-C
4H
9-C
6H
4)
3P，
(2-t-C
4H
9-C
6H
4)
3P，(3-t-C
4H
9-C
6H
4)
3P，(4-t-C
4H
9-C
6H
4)
3P，(2-CH
3-6-t-C
4H
9-C
6H
3)
3P，
(3-CH
36-t-C
4H
9-C
6H
3)
3P，(3-CH
3-6-t-C
4H
9-C
6H
3)
3P，(2，6-Di-t-C
4H
9-C
6H
3)
3P，
(2，3-Di-t-C
4H
9-C
6H
3)
3P and (2,4-Di-t-C4H
9-C
6H
3)
3P.
As being used for the ruthenium used according to the invention and the part of osmium compound, can mention organic or inorganic compound, atom or ion, they are coordinated on the metal center.
Within the scope of the present invention, the photo-labile part means: when using the rayed catalyzer of visible or ultraviolet region, this part dissociates and generates from catalyzer and is used to replace the polymeric catalytic active substance.The preferred non-ionic type photo-labile of the present invention part.
The photo-labile part for example relates to nitrogen (N
2), unsubstituted or by OH, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
6-C
12The monocycle that aryl or halogen replace, encircle or condensed more, have 6-24, the aromatic hydrocarbons of preferred 6-18 and especially preferred 6-12 C atom; Or it is unsubstituted or by C
1-C
4Alkyl, C
1-C
4Alkoxy or halogen replaces, and has 3-22, preferred 4-16 and especially preferred 4-10 C atom and 1-3 be selected from O, S and N the assorted aromatic hydrocarbons of heteroatomic monocycle, condense assorted aromatic hydrocarbons or the condensed aromatics-aromatic hydrocarbons of mixing; Or it is unsubstituted or by C
1-C
4Alkyl, C
1-C
4What alkoxy or halogen replaced has 1-22, and preferred 1-18, especially preferred 1-12 and more specifically aliphatic series, cyclic aliphatic, aromatics or the araliphatic nitrile of preferred 1-7 C atom.Preferred substituted is methyl, ethyl, methoxyl group, oxyethyl group, fluorine, chlorine and bromine.Aromatic hydrocarbons and assorted aromatic hydrocarbons preferably have 1-3 substituting group.Assorted aromatic hydrocarbons is preferably the assorted aromatic hydrocarbons of electron rich.
Some examples of aromatic hydrocarbons and assorted aromatic hydrocarbons have: benzene, cumene, biphenyl, naphthalene, anthracene, acenaphthene, fluorenes, phenanthrene, pyrene, bend, fluoranthene, furans, thiophene, pyrroles, pyridine, γ-pyrans, γ-thiapyran, pyrimidine, pyrazine, indoles, cumarone, benzo-thiophene, carbazole, dibenzofuran, dibenzothiophen, pyrazoles, imidazoles, benzoglyoxaline, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline 99.9, acridine, chromene, azophenlyene, phenoxazine, thiodiphenylamine, triazine, thianthrene, purine.Preferred aromatic hydrocarbons and assorted aromatic hydrocarbons are benzene, naphthalene, thiophene and thionaphthene unsubstituted or that replace.More specifically preferred aromatic hydrocarbons is unsubstituted or by 1-3 C
1-C
4Benzene and the preferred thiophene of assorted aromatic hydrocarbons that alkyl replaces.
Nitrile for example can be replaced by methoxyl group, oxyethyl group, fluorine or chlorine; Preferred nitrile is unsubstituted.The preferred straight chain of alkyl nitrile.Some examples of nitrile have acetonitrile, propionitrile, butyronitrile, amyl group nitrile, hexyl nitrile, cyclopentyl nitrile and cyclohexyl nitrile, benzonitrile, methyl benzonitrile, benzyl nitrile and naphthyl nitrile.The preferred straight chain C of nitrile
1-C
4Alkyl nitrile or benzonitrile.The especially preferred acetonitrile of alkyl nitrile.
In one preferred time was organized, the photo-labile part related to N
2, do not replace or by 1-3 C
1-C
4Benzene, thiophene, benzonitrile or acetonitrile that alkyl replaces.
Within the scope of the present invention, non-photo-labile part (being also referred to as strong ligand) is anticipated promptly, when at visible or near ultraviolet region irradiation catalyzer, this part from catalyzer, do not dissociate or only not half dissociate.
The ligand of non-photo-labile for example can relate to and contain heteroatoms O, S or N and inorganic and organic compound solvation (they also Chang Zuowei solvent use), or unsubstituted or by C
1-C
4-alkyl, C
1-C
4-alkoxyl group, (C
1-C
4-alkyl)
3Si or (C
1-C
4-alkyl)
3Cyclopentadienyl or indenyl that SiO-replaces.The example of this compound is H
2O, H
2S, NH
3Halogenated in case of necessity, particularly fluorizated or chlorating have 1 to 18, and preferred 1 to 12 and alcohol aliphatic series or cyclic aliphatic or the mercaptan of preferred especially 1 to 6 C-atom, have 6 to 18, the aromatic alcohol or the mercaptan of preferred 6 to 12 C-atoms; Have 7 to 18, the aromatic grease group alcohol or the mercaptan of preferred 7 to 12 C atoms; Open chain or ring-type and aliphatic series, araliphatic or aromatics have 2 to 20, preferred 2 to 12 and the ether of preferred especially 2 to 6 C-atoms, thioether, sulfoxide, sulfone, ketone, aldehyde, carboxylicesters, lactone, N-C in case of necessity
1-C
4-single-or the carboxylic acid amides of dialkyl groupization and N-C in case of necessity
1-C
4-alkylating lactan; Open chain or cyclic and be aliphatic series, araliphatic or aromatics have 1 to 20, preferred 1 to 12 and preferred especially 1 to 6 C-atom the primary, the second month in a season and tertiary amine; With cyclopentadiene base class cyclopentadienyl for example, indenyl, one or cyclopentadiene base class polymethineization or trimethyl silylization or indenyl class.
The example of the ligand of this non-photo-labile is a methyl alcohol, ethanol, just and Virahol, just, different and the trimethyl carbinol, 1,1, the 1-trifluoroethanol, bis trifluoromethyl methyl alcohol, three (trifluoromethyl) methyl alcohol, amylalcohol, hexanol, methyl-or ethanethio, cyclopentanol, hexalin, cyclohexyl mercaptan, phenol, sylvan is fluoridized phenol, phenyl mercaptan, benzyl mercaptan, benzyl alcohol, diethyl ether, dme, diisopropyl ether, two-just or two-uncle-butyl ether, tetrahydrofuran (THF), tetrahydropyrans; diox, diethyl thioether, tetramethylene sulfide, methyl-sulphoxide, ethyl-sulfoxide, four-and five-methylene radical sulfoxide, dimethyl sulfone, diethyl sulfone, four-and the pentamethylene sulfone, acetone, methyl ethyl ketone, metacetone, acetophenone, methyl iso-butyl ketone (MIBK), benzyl methyl ketone, acetaldehyde, propionic aldehyde, trifluoro acetaldehyde, phenyl aldehyde, ethyl acetate, butyrolactone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyrrolidone and N-Methyl pyrrolidone, indenyl, cyclopentadienyl, methyl-or dimethyl-or pentamethyl-cyclopentadienyl and trimethyl silyl cyclopentadienyl.
Primary amine can be equivalent to formula R
29NH
2, secondary amine is equivalent to formula R
29R
30NH and tertiary amine are equivalent to formula R
29R
30R
31N, wherein R
29Be C
1-C
18Alkyl, unsubstituted or with C
1-C
4-alkyl or C
1-C
4The C that-alkoxyl group replaces
5-or C
6-cycloalkyl, or unsubstituted or with C
1-C
4-alkyl or C
1-C
4The C that-alkoxyl group replaces
6-C
18-aryl or C
7-C
12-aralkyl, R
30Has R independently
29Implication or R
29And R
30Common is tetramethylene, pentamethylene, 3-Evil-pentamethylene or-CH
2-CH
2-NH-CH
2-CH
2-or-CH
2-CH
2-N (C
1-C
4-alkyl)-CH
2-CH
2-, R
31Has R independently
29Implication.Alkyl preferably contains 1 to 12 and preferred especially 1 to 6 C-atom.Aryl preferably contains 6 to 12 C-atoms and aralkyl preferably contains 7 to 9 C-atoms.The example of amine be methyl-, dimethyl-, trimethylammonium-, ethyl-, diethyl-, triethyl-, methyl-ethyl-, dimethyl-ethyl, n-propyl-, two-n-propyl-, three-normal-butyl-, cyclohexyl-, phenyl-and benzyl amine, and tetramethyleneimine, the N-crassitude, piperidines, piperazine, morpholine and N-methylmorpholine.
The ligand of non-photo-labile relates to H in one preferred time is organized
2O, NH
3With unsubstituted or fluoric C partly or wholly
1-C
4-alkanol or cyclopentadienyl.H most preferably
2O, methyl alcohol or ethanol.
In an embodiment preferred, Ru-used in the present invention and Os-catalyzer only contain photo-labile part, phosphino-and are used for the negatively charged ion of charge balance.More specifically preferably comprise a kind of aromatic hydrocarbons as the photo-labile part, a kind of tertiary phosphine base and the monovalence or the dianion that are used for charge balance.
Suitable inorganic or organic acid negatively charged ion for example has hydrogen ion (H
Θ), halogen ion (F for example
Θ, Cl
Θ, Br
ΘAnd I
Θ), oxygen acid negatively charged ion, and BF
4 Θ, PF
6 Θ, SbF
6 ΘOr AsF
6 ΘIt should be noted that above-mentioned cyclopentadienyl is part and negatively charged ion.
Other suitable negatively charged ion is C
1-C
12-, preferred C
1-C
6Especially preferred C
1-C
4--oxyl, especially branching for example corresponding to formula RxRyRzC-O
Θ, wherein Rx is H or C
1-C
10Alkyl, Ry are C
1-C
10Alkyl and Rz are C
1-C
10Alkyl or phenyl, the C total atom number of Rx, Ry and Rz is 11.Example especially is isopropoxy and tert.-butoxy.
Other suitable negatively charged ion is C
3-C
18-, preferred C
5-C
14-and especially preferred C
5-C
12Acetylide is corresponding to formula Rw-C ≡ C
Θ, wherein Rw is C
1-C
16Alkyl, preferred alpha-branched C
3-C
12Alkyl, formula RxRyRzC-for example, or unsubstituted or by 1-3 C
1-C
4Alkyl or C
1-C
4Phenyl or benzyl that alkoxyl group replaces.Some examples be sec.-propyl-, the XOR tertiary butyl-, phenyl-, benzyl-, the 2-methyl-, 2, the 6-dimethyl-, the 2-sec.-propyl-, 2-sec.-propyl-6-methyl-, the 2-tertiary butyl-, 2,6-di-t-butyl-and 2-methyl-6-tert butyl phenylacetylene thing.
Negatively charged ion situation at oxygen acid for example can relate to sulfate radical, phosphate radical, perchlorate, hyperbromic acid root, periodate, metaantimmonic acid root, arsenate, nitrate radical, carbonate, C
1-C
8-anion of carboxylic acid is formate for example, acetate moiety, propionate, the butyric acid root, benzoate anion, phenylacetic acid root, single-, two-or trichoroacetic acid(TCA) root or single-, two-, trifluoroacetic acid root, sulfonate radical be the methylsulphonic acid root for example, the ethylsulfonic acid root, the propyl sulfonic acid root, the butyl sulfonic acid root, trifluoromethane sulfonic acid root (Triflat) is in case of necessity with C
1-C
4-alkyl, C
1-C
4Phenylbenzimidazole sulfonic acid root or benzyl sulfonate radical, for example tosylate that-alkoxy or halogen (particularly fluorine, chlorine or bromine) replaces, the methylsulfonyl root, to the bromo-benzene sulfonic acid root, right-methoxyl group-or right-ethoxyl phenenyl sulfonate radical, pentafluorophenyl group sulfonate radical or 2,4,6-triisopropyl sulfonate radical, with phosphonate radical methylphosphine acid group for example, the ethylphosphonic acid root, propyl phosphonous acid root, butyl phosphine acid group, phosphenylic acid root, p-methylphenyl phosphonate radical or benzylphosphonic acid root.
Especially preferred H
Θ, F
Θ, Cl
Θ, Br
Θ, BF
4 Θ, PF
6 Θ, SbF
6 Θ, AsF
6 Θ, CF
3SO
3 Θ, C
6H
5-SO
3 Θ, 4-methyl-C
6H
5-SO
3 Θ, 2,6-dimethyl-C
6H
5-SO
3 Θ, 2,4,6-trimethylammonium-C
6H
5-SO
3 ΘAnd 4-CF
3-C
6H
5-SO
3 ΘAnd cyclopentadienyl (Cp
Θ).
The number of non-photo-labile part depends on the quantity of phosphino-, the quantity of the size of non-photo-labile part and photo-labile part.
In preferred embodiments, ruthenium-and osmium compound especially preferably corresponding to formula VIII, VIIIa, VIIIb, VIIIc, VIIId, VIIIe or VIIIf
R
32L
1Me
2+(Z
n-)
2/n???????????????????????????????????(VIII)，
R
32L
2L
3Me
2+(Z
n-)
2/n????????????????????????????????(VIIIa)，
(R
32)
2L
2Me
2+(Z
n-)
2/n???????????????????????????????(VIIIb)，
(R
32)
3L
2Me
2+(Z
n-)
2/n???????????????????????????????(VIIIc)，
R
32L
1L
2Me
2+(Z
n-)
2/n????????????????????????????????(VIIId)，
R
32L
2L
2Me
2+(Z
n-)
2/n????????????????????????????????(VIIIe)，
R
32L
1L
3Me
2+(Z
n-)
2/n????????????????????????????????(VIIIf)，
Wherein
R
32Tertiary phosphine for formula VII or VIIa;
Me is Ru or Os;
N is several 1,2 or 3;
Z is inorganic or the organic acid negatively charged ion;
(a) L
1Be aromatic hydrocarbons or assorted aromatic hydrocarbons part;
(b) L
2For being different from L
1Monovalence photo-labile part; With
(c) L
3Be the non-photo-labile part of monovalence.
The front to each implication given preferable case be applicable to R
32, L
1, L
2And L
3
N preferably represents 1 or 2 in formula VIII-VIIIf, and more preferably 1.For the phosphine part of formula VII given preferable case be applicable to R
32, relate in particular to tertiary phosphine.
More specifically preferably use the ruthenium of formula IX, IXa, IXb, IXc, IXd, IXe or IXf-and osmium compound (R in the methods of the invention
26R
27R
28P) L
1Me
2+(Z
1-)
2(IX), (R
26R
27R
28P)
2L
2Me
2+(Z
1-)
2(IXa), (R
26R
27R
28P) L
2L
3Me
2+(Z
1-)
2(IXb), (R
26R
27R
28P)
3L
2Me
2+(Z
1-)
2(IXc), (R
26R
27R
28P) L
2L
2Me
2+(Z
1-)
2(IXd), (R
26R
27R
28P) L
1L
3Me
2+(Z
1-)
2(IXe), (R
26R
27R
28P) L
1(L
2)
mMe
2+(Z
1-)
2(IXf),
Wherein
Me represents Ru or Os;
Z represents H in formula IX-IXe
Θ, cyclopentadienyl, Cl
Θ, Br
Θ, BF
4 Θ, PF
6 Θ, SbF
6 Θ, AsF
6 Θ, CF
3SO
3 Θ, C
6H
5-SO
3 Θ, 4-methyl-C
6H
5-SO
3 Θ, 2,6-dimethyl-C
6H
5-SO
3 Θ, 2,4,6-trimethylammonium-C
6H
5-SO
3 ΘOr 4-CF
3-C
6H
5-SO
3 ΘAnd in formula IXf, represent H
Θ, cyclopentadienyl, BF
4 Θ, PF
6 Θ, SbF
6 Θ, AsF
6 Θ, CF
3SO
3 Θ, C
6H
5-SO
3 Θ, 4-methyl-C
6H
5-SO
3 Θ, 2,6-dimethyl-C
6H
5-SO
3 Θ, 2,4,6-trimethylammonium-C
6H
5-SO
3 ΘOr 4-CF
3-C
6H
5-SO
3 ΘM is 1 or 2;
R
26, R
27And R
28Be C independently of each other
1-C
6Alkyl or-alkoxyl group, unsubstituted or by 1-3 C
1-C
4Cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy that alkyl replaces, or unsubstituted or by 1-3 C
1-C
4Phenyl or benzyl or phenoxy group or benzyloxy that alkyl replaces; L
1For unsubstituted or by 1-3 C
1-C
4Alkyl, C
1-C
4Alkoxyl group ,-OH ,-C that F or Cl replace
6-C
16Aromatic hydrocarbons or C
5-C
16Assorted aromatic hydrocarbons;
L
2Be C
1-C
6Alkyl-CN, benzonitrile or benzyl nitrile; With
L
3Be H
2O or C
1-C
6Alkanol.
Preferred aromatic hydrocarbons and assorted aromatic hydrocarbons are benzene, toluene, dimethylbenzene, trimethylbenzene, naphthalene, biphenyl, anthracene, acenaphthene, fluorenes, luxuriant and rich with fragrance, pyrene, , fluoranthene, furans, thiophene, the pyrroles, pyridine, γ-pyrans, γ-thiapyran, pyrimidine, pyrazine, indoles, cumarone, benzo-thiophene, carbazole, dibenzofuran, dibenzothiophen, pyrazoles, imidazoles, benzoglyoxaline oxazole, thiazole isoxazole, isothiazole, quinoline, isoquinoline 99.9, acridine, chromene, azophenlyene phenoxazine, thiodiphenylamine, triazine, thianthrene, purine.Preferred aromatic hydrocarbons and assorted aromatic hydrocarbons are benzene, naphthalene, cumene, thiophene and thionaphthene.More specifically preferred aromatic hydrocarbons is benzene or by C
1-C
4Benzene such as toluene, dimethylbenzene, isopropyl benzene, tert.-butylbenzene or cumene and the preferred thiophene of assorted aromatic hydrocarbons that alkyl replaces.
When prepare ruthenium-or during osmium compound, can form the Ru/Os cationic complexes of solvation in as alkanol in the solvent that can be coordinated on the atoms metal, it is contained in the range of application of the present invention.
By ruthenium used in the present invention-and some enforcements of osmium compound are (Tos is a tosylate, and Cumen is a cumene): (C
6H
11)
2HPRu (p-Cumen) Cl
2, (C
6H
11)
3PRu (p-Cumen) Cl
2, (C
6H
11)
3PRu (p-Cumen) (Tos)
2, (C
6H
11)
3PRu (p-Cumen) Br
2, (C
6H
11)
3PRu (p-Cumen) ClF, (C
6H
11)
3PRu (C
6H
6) (Tos)
2, (C
6H
11)
3PRu (CH
3-C
6H
5) (Tos)
2, (C
6H
11)
3PRu (i-C
3H
7-C
6H
5) (Tos)
2, (C
6H
11)
3PRu () (Tos)
2, (C
6H
11)
3PRu (biphenyl) (Tos)
2, (C
6H
11)
3PRu (anthracene) (Tos)
2, (C
6H
11)
3PRu (C
10H
8) (Tos)
2, (i-C
3H
7)
3PRu (p-Cumen) Cl
2, (CH
3)
3PRu (p-Cumen) Cl
2, (n-C
4H
9)
3PRu (p-Cumen) Cl
2, [(C
6H
11)
3P]
2Ru (CH
3-CN) (Tos)
2, (C
6H
11)
3PRu (CH
3-CN) (C
2H
5-OH) (Tos)
2, (C
6H
11)
3PRu (p-Cumen) (CH
3-CN)
2(PF
6)
2, (C
6H
11)
3PRu (p-Cumen) (CH
3-CN)
2(Tos)
2, (n-C
4H
9)
3PRu (p-Cumen) (CH
3-CN)
2(Tos)
2, (C
6H
11)
3PRu (CH
3CN) Cl
2, (C
6H
11)
3PRu (CH
3-CN)
2Cl
2, (C
6H
11)
3PRu (p-Cumen) (C
2H
5OH) (BF
4)
2, (C
6H
11)
3PRu (p-Cumen) (C
2H
5OH)
2(BF
4)
2, (C
6H
11)
3PRu (p-Cumen) (C
2H
5OH)
2(PF
6)
2, (C
6H
11)
3PRu (C
6H
6) (C
2H
5OH)
2(Tos)
2, (C
6H
11)
3POs (p-Cumen) Cl
2, (i-C
3H
7)
3POs (p-Cumen) Cl
2, (CH
3)
3POs (p-Cumen) Cl
2, (C
6H
5)
3POs (p-Cumen) Cl
2And RuCl
2(p-Cumen) [(C
6H
11)
2PCH
2CH
2P (C
6H
11)
2]. ruthenium that the present invention uses and osmium compound be known maybe can be by known and similar method from metal halide (MeX for example
3Or (Me aromatic hydrocarbons X
2)
2And form the agent reaction with phosphine and ligand and make.
The inventive method can be carried out having in the presence of the inert solvent.One special benefits of the inventive method is can carry out without solvent in this method of liquid monomer situation.Another advantage is: polymerization even can carry out in water, polarity and protonic solvent or water/solvent mixture.
Suitable inert solvent for example is the polar of proton and non-proton solvent, and they can use separately or by at least two kinds of solvent.Example is: ether (dibutyl ether, tetrahydrofuran (THF) ， diox; glycol monomethyl methyl ether or ethylene glycol dimethyl ether, ethylene glycol monomethyl ether or ethylene glycol bisthioglycolate ethyl ether, diethylene glycol diethyl ether; the triglycol dimethyl ether), halon (methylene dichloride, chloroform; 1,2-ethylene dichloride, 1; 1,1-trichloroethane, 1; 1,2, the 2-tetrachloroethane); carboxylicesters and lactone (acetate ethyl ester, propionic acid methyl ester, phenylformic acid ethyl ester; acetate 2-methoxyl group ethyl ester, gamma-butyrolactone, δ-Wu Neizhi; the trimethylacetic acid lactone), carboxylic acid amide and lactan (N, dinethylformamide; N, N-diethylformamide, N; the N-N,N-DIMETHYLACETAMIDE, tetramethyl-urea, hexamethyl phosphoric triamide; butyrolactam, ∈-hexanolactam, N-Methyl pyrrolidone; N-acetyl-pyrrolidine ketone, the N-methyl caprolactam), sulfoxide (dimethyl sulfoxide (DMSO)); sulfone (dimethyl sulfone; the diethyl sulfone, trimethylene sulfone, tetramethylene sulfone); tertiary amine (N-methyl piperidine; N-methylmorpholine), the hydrocarbon of aliphatic and aromatics is sherwood oil for example, pentane; hexane; hexanaphthene, methylcyclohexane, the benzene (chlorobenzene of benzene or replacement; neighbour-dichlorobenzene; 1,2, the 4-trichlorobenzene; oil of mirbane; toluene, dimethylbenzene) and nitrile (acetonitrile, propionitrile; benzonitrile, benzyl cyanide).Preferred solvent is non-proton polar and nonpolar solvent.
Preferred solvent is aliphatic and the mixture of the hydrocarbon of aromatics and such solvent.
Should be ben be, the composition of being made up of an optional cycloolefin that replaces and catalyzer that uses in the methods of the invention usually be insensitive to oxygen, and this makes stock management and reaction carry out becoming possibility not protecting under the gas condition.But recommend lucifuge to store.
But formula I monomer that inventive method is used and catalyzer be separate storage but also can deposit as mixture together not only, because the catalyzer that uses has extra high stability.Mixture can be stored for the formulation that can use at the photochemical polymerization previous crops, and this is beneficial to large-scale industrial application of the present invention.Because very high sensitivity of light (especially in UV-light) is therefore stored and is answered lucifuge.
Another theme of the present invention is a photopolymerizable composition, contain the cycloolefin of the cycloolefin of a tensioning or at least two kinds of different tensionings and the ruthenium at least a no Cabbeen, divalent cation of catalytically effective amount-or osmium compound, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance.
Another theme of the present invention is a composition, contain the cycloolefin of the cycloolefin of a tensioning or at least two kinds of different tensionings and the ruthenium at least a no Cabbeen, divalent cation of catalytic amount-or osmium compound, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance, and the acid anion that is used for charge balance, P (C
6H
11)
3(right-cumene) RuCl
2With the norbornylene except combinations.
The present composition can contain additional other the comonomer of nonvolatile open chain, it and the cycloolefin formation multipolymer of tensioning.Can form crosslinked polymkeric substance when for example using diene together.The example of such comonomer is list-or two-undersaturated compound such as the alkene and the diolefine of olefinic, amylene is arranged, hexene, heptene, octene, decene, dodecylene, vinylformic acid and methacrylic acid, its ester and acid amides, vinyl ether, vinylbenzene, divinyl, isoprene and chloroprene.
In the present composition, contain other can replace polymeric alkene for example quantity until 80 weight %, preferred 0.1 to 80 weight %, more preferably 0.5 to 60 weight %, preferred especially 5 to 40 weight-%, is base with formula I compound and other polymeric alkene total amounts that can replace.
The present composition can contain the prescription auxiliary material.Known auxiliary material is a static inhibitor, antioxidant, and anti-photic aging agent, softening agent, dyestuff, pigment, filler is filled out and is increased material by force, lubricant, adhesive agent, tackifier and demoulding assistant agent.Filler can unexpected high component add, and does not pay function influence to polymerization, and for example quantity is until 70 weight-%, preferred 1 to 70 weight-%, and more preferably 5 to 60 weight-%, and preferred especially 10 to 50 weight-%, and, be base with the composition most preferably 10 to 40 weight-%.For improving optical, physics, the filler of machinery and performance electricity and toughener filler be known a large amount of numbers.Some examples are powder, the glass of ball and fibers form and quartz, metal oxide and half-metal oxide, carbonate such as MgCO
3, CaCO
3, rhombspar, metal sulfate such as gypsum and barite, natural and synthetic silicate such as talcum, zeolite, wollastonite, feldspar, clay such as Chinese clay, rock dust, single crystal fibre, charcoal fiber, regenerated fiber or artificial powder and carbon black.That tackifier especially have an olefinic unsaturated group and when polymerization, can be incorporated into transposition polymkeric substance on the polymkeric substance.These transposition polymkeric substance are known and for example by commercial name Vestenamere
Available, other tackifier are polyhutadiene, polyisoprene or sovprene, and the multipolymer of butadiene-isoprene and chlorine pentadiene and alkene.The quantity that tackifier can contain is 0.1 to 50, and is preferred 1 to 30, and preferred especially 1 to 20 weight-%, is base with the composition.It is favourable keeping the polymeric optical transparency or carry out the thin layer polymerization when using filler.
The inventive method need not keep the radiation of reaction mixture in the entire reaction phase.If photochemistry is an initiated polymerization, then the reaction process of Ji Xuing itself carries out in the dark independently.Favourable mode is, carries out optical wavelength that radiation the uses scope at 50nm to 1000nm, preferably in 200nm to 500nm scope with most preferably in the UV-scope.Radiated time depends on the light source classification.The present invention preferably uses UV-laser or UV-lamp.The radiation of catalyzer not only can be before monomer adds, in the adition process and can carry out after adding.
The applied activity of such catalysts of the present invention ground beyond expectation is high, so that just obtains required polymkeric substance after the time at short reaction.The radiated time that is fit to be from the several seconds to a few hours, especially the several seconds was until 1 hour.The addition sequence of monomer and catalyzer is not crucial.Monomer not only can be put well earlier but also can add the back at catalyzer and add.Same catalyzer can shift to an earlier date radiation and then add monomer.Also radiation-curable in addition catalyzer and the monomeric solution of containing.
The inventive method is preferably carried out in room temperature to high slightly temperature.Increase in temperature is used to improve speed of response.Mainly be that photopolymerization takes place under the temperature of selecting for accelerated reaction.But should mention, catalyzer can change into heat-activated catalysts by competent radiation.
The inventive method is especially carried out for-20 ℃ to+110 ℃ in temperature.
The complete uniqueness of the inventive method be that the ruthenium of use and osmium compound play thermocatalyst or have significantly higher activity after radiation with advantage beyond expectation.Occur this possibility thus, polymerization is continued and finish by the input heat after an of short duration radiation, this provides economical and superiority technology in the different field of preparation molding or coating.Particularly this bonded method is suitable for preparing thermoplastics.
Another theme of the present invention is the method that photochemical catalysis causes when metallic compound exists as catalyzer and follow a kind of cycloolefin of thermopolymerization or at least two kinds of different rings alkene, it is characterized in that, a) at first the ruthenium at least a no Cabbeen, divalent cation of catalytic amount-or osmium compound in the presence of the radiation cycloolefin, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance; Or the ruthenium at least a no Cabbeen, divalent cation of the catalytic amount in a kind of inert solvent-or the osmium compound randomly of irradiation earlier, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance, and mix with at least one cycloolefin then; And b) then by heating and radiationless end polymerization.
For step a), aforesaid preferable case all is suitable for.Radiated time depends primarily on desired response, when also passing through heating end polymerization by the radiation excitation polymerization, then selects for example radiation of short period of time if be.Short period of time can be radiated time less than 60 seconds, preferred 5 to 60 seconds and preferred especially 10 to 40 seconds.If polymerization mainly be under radiation, carry out and final polymerization only wish by after heat when finishing, just select for use for example than the radiated time of growing.
Heating in step b) can be from 50 to 200 ℃ of temperature of reaction, preferred 50 to 150 ℃ and preferred especially 70 to 120 ℃.
Catalytic amount is preferably consumption within the scope of the present invention 0.001 to 20mol-%, and preferred especially 0.01 to 15mol-% and especially preferred 0.01 to 10mol-%, is base with the amount of monomer.Based on highlight catalytic active, more preferred 0.001-2 weight %.
Another theme of the present invention is that a kind of preparation is used for the thermocatalyst of open loop transposition polymerized cycloolefins or improves its active method, it is characterized in that, with body form or a kind of in a solvent do not have ruthenium Cabbeen, divalent cation-or osmium compound carry out radiation, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance.
The cycloolefin of tensioning is applicable to method of the present invention, and these alkene are widely known by the people.Tetrahydrobenzene generally can not polymerization with alkene-transposition.This exception is known to the technician and for example recorded and narrated (Ivin in Ivin, K.J.in:Ivin, K.J., Saegusa, T. (Hrsg.), " ring-opening polymerization " (Ring-Opening Polymerisation) 1:139-144 Elsevier AppliedScience Publishers, London und New York (1984)).
Can prepare radiation-cured oligopolymer and polymkeric substance with the inventive method with the identical or different structural unit of formula XI
Q in the formula
1And Q
2Has the implication of having stated among the formula I.To these polymkeric substance, the suitable preferable case of stating previously.It relates to homopolymer or its polymers, graftomer or the block polymer with structural unit random distribution.They can have a molecular-weight average (Mw) for example for from 500 to 2 megadaltons, preferred 1000 to 1 megadaltons (press GPC by with the polystyrene standard comparative measurement of narrow distribution).
Can prepare with the inventive method and to be used to produce all kinds of moldings, the material of the mouldable shaping of thermoplastic of coating and embossing pattern (Reliefabbildung).
Can have very different performances according to used monomeric situation by the polymkeric substance that the present invention prepares.The characteristic of some polymkeric substance is very high oxygen permeability, low specific inductivity, good thermostability and low water-absorbent.Other then have outstanding optical property for example high-clarity and low-refraction.What should emphasize especially in addition is very low contraction.Therefore they can be used on very different technical fields.
The present composition is that very high adhesion strength is arranged as its characteristic of lip-deep coating at solid support material.Coated in addition material has the characteristic of very high surface smoothing glossiness.What should emphasize especially in good mechanical properties is the contraction of trace and high impelling strength, also has thermostability.Should mention easy release property and high solvent stability in addition.
Composition of the present invention can be processed by known shaping, for example injection molding, extruding and casting process such as molding (casting resin), die casting, mold pressing, extrudes.
These polymkeric substance are suitable for making Medical Instruments, implant or contact lens; Make the electronic structure member; As paint binder; As Modelling can photic hardened composition or have the adhesive (this type of matrix is tetrafluoroethylene for example, polyethylene, polypropylene) of the matrix of low surface energy as bonding, and as the photopolymerizable composition in the stereolithography art.Composition of the present invention also can be used for making paint by photopolymerization, wherein can use limpid (transparent) and and even painted composition on the one hand.Not only available white pigments but also available coloured pigment.Also should mention in addition by thermoplastic shaping method manufacturing molding and be used for all types of daily necessities.
Of the present inventionly photohardenable or photohardenable be particularly suitable for making protective layer and embossing pattern with heat hardenable composition.An other theme of the present invention is a scheme for preparing coated material or embossing pattern on matrix of the present invention, wherein make by cycloolefin, catalyzer and in case of necessity the composition of solvent composition be coated on the carrier as coating, for example by the dipping-, smear-, flow coat-, roller coat-, squeegee-or casting method for centrifugal, remove in case of necessity and desolvate, and radiation coating makes polymerization, or by a photomask radiation coating and then remove not radiating part with solvent.Can make the stromal surface modification in this way or be protected, or for example can make printed wiring, printing plate or printing roller.The present composition also can be used as welding termination lacquer (Lotstopplacke) when making printed wiring.Other application possibility is to make the silk screen printing mask, as offset printing, and the red ink paste used for seals of the radiation-hardenable of silk screen printing and flexographic rotary printing.
Another theme of the present invention is a kind of carrier substance, it be with low-grade polymer of the present invention or polymeric coating and contain a kind of linking agent.Another theme of the present invention is a kind of carrier substance, and it is with oligopolymer of the present invention or polymeric coating.This material is fit to by radiation (in case of necessity under a photomask situation) and then prepares protective layer or embossing pattern with solvent washing.The linking agent that is fit to, its content for example are 0.01 to 20 weight-%, and preferably organic two-fold nitride is preferred commercially available especially 2, two (4-azido-the benzylidene)-4-methyl-cyclohexyl ketone of 6-.
Theme of the present invention in addition is the carrier substance of a coating, it is characterized in that, on carrier, coat one by (a) cycloolefin or at least two kinds of different cycloolefins and (b) ruthenium at least a no Cabbeen, divalent cation of catalytic amount-or osmium compound forms layer, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance.
The carrier substance that is fit to for example is these: glass, mineral, pottery, plastics, timber, semi-metal, metal, metal oxide and metal nitride.Bed thickness depends primarily on desired purposes and for example can be 0.1 to 1000 μ m, preferred 0.5 to 500 μ m, preferred especially 1 to 100 μ m.The characteristic that is had the performance of heat that high adhesion strength becomes reconciled and machinery by the material that is coated with.
Preparing coated material of the present invention can for example smear by known method, squeegee, and cast is carried out as hanging cast or centrifugal casting.
If use such cycloolefin to be used for light transposition polymerization, this cycloolefin is additional, and to contain 1 to 3 and preferred one other two keys and it be when encircling the condensed member ring systems in invention scope more, then usually can reach good especially effect when coating.
The following examples further specify the present invention.
Abbreviation: Tos=tosylate (Tosylat), the Cumen=cumene, the RT=room temperature,
Trif=trifluoromethanesulfonic acid root
A) ruthenium-and the preparation embodiment A 1:(C of osmium phosphine
6H
11)
3PRu (C
6H
6) (Tos)
2(catalyst A)
230mgRu (C
6H
6) (H
2O)
3(Tos)
2(0.4mmol) be dissolved in the 30ml tetrahydrofuran (THF) and mix with 140mg (0.5mmol) tricyclohexyl phosphine and to be incorporated in RT and to stir 12 hours, then reflux and stirred 3 hours.Remove and desolvate, with ether debris (2 * 10ml).Productive rate: 76%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 6,16 (s, 6H); Other: 7,70 (d, J=8,0,4H), 7,14 (d, J=8.0,4H), 2,36 (s, 6H), 2,18 (m, 3H); 2,0-1,0 (m, 30H). embodiment A 2:(C
6H
11)
3PRu (right-cumene) CI
2(catalyst B)
306mg (RuCl
2(right-cumene) 2 (0.5mmol) is dissolved in the 75ml ethanol and with 280mg tricyclohexyl phosphine (1mmol) and mixes.Reflux and stirred 3 hours and then removed and desolvate.With 5ml hexane wash resistates.Productive rate: 90%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,56 (m, 4H); 2,84 (sept, J=7,0Hz, 1H); 2,09 (s, 3H); 1,29 (d, J=7,0Hz, 6H). other: 2,41 (m, 3H); 2,20-1,35 (m, 30H). embodiment A 3:(C
6H
11)
3PRu (right-cumene) (C
2H
5OH)
m(BF
4)
2(catalyzer C)
294mgRuCl
2(right-cumene) P (C
6H
11)
3(0.5mmol) be dissolved in the 20ml ethanol and with dropping mode and 253mg AgBF
4(1mmol) solution in 50ml ethanol mixes.Solution stirred 12 hours in RT, filtered and concentrated through filter plate.Productive rate: 94% ((C
6H
11)
3PRu (right-cumene) (C
2H
5OH) (BF
4)
2(C
6H
11)
3PRu (right-cumene) (C
2H
5OH)
2(BF
4)
2Mixture).
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand 5,62 (d, J=6,0Hz, 2H); 5,45 (d, J=6,0Hz, 2H); 2,76 (sept, J=7,0Hz, 1H); 2,16 (s, 3H); 1,30 (d, J=7,0Hz, 6H). other: 2,48 (m, 3H); 2,15-1,30 (m, 30H). embodiment A 4:(C
6H
11)
3PRu (right-cumene) (C
2H
5OH)
2(PF
6)
2(catalyzer D)
Be similar to routine A3, but use 195mg AgPF
6Productive rate 91%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,62 (d, J=5,5Hz, 2H); 5,45 (d, J=5,5Hz, 2H); 2,76 (sept, J=7,0Hz, 1H); 2,28 (s, 3H); 1,30 (d, J=7,0Hz, 6H).
Other: 2,50 (m, 3H); 2,15-1,30 (m, 30H). embodiment A 5:(C
6H
11)
3PRu (right-cumene) (Tos)
2(catalyzer E)
Be similar to routine A3, but use 279mg right-toluenesulphonic acids Ag.Productive rate: 90%
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,97 (d, J=5,5Hz, 2H); 5,78 (d, J=5,5Hz, 2H); 2,95 (sept, J=7,0Hz, 1H); 2,27 (s, 3H); 1,30 (d, J=7,0Hz, 6H). other: 7,53 (d, J=8,0,4H); 7,05 (d, J=8,0,4H), 2,32 (s, 6H), 2,20-1,00 (m, 33H). embodiment A 6:(C
6H
11)
3PRu (right-cumene) Br
2(catalyzer F)
0.24g (RuBr
2(right-cumene))
2(0.3mmol) be dissolved in the 75ml ethanol and and mix with 0.17g tricyclohexyl phosphine (0.6mmol).Reflux and stirred 6 hours, then remove and desolvate.(2 * 10ml) wash resistates with ether.Productive rate: 90%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,50 (m, 4H); 2,97 (sept, J=7,0Hz, 1H); 2,10 (s, 3H); 1,19 (d, J=7,0Hz, 6H). other: 2,40 (m, 3H); 2,38 (m, 6H); 1,90-1,30 (m, 24H). embodiment A 7:(is different-C
3H
7)
3PRu (right-cumene) Cl
2(catalyzer G)
306mg (RuCl
2(right-cumene)) 2 (0.5mmol) are suspended in the 40ml hexane, and mix with the 0.5ml tri isopropyl phosphine and stirred 12 hours.The precipitation that filter to generate and with hexane (2 * 30ml) wash.Productive rate: 90%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons coordination 4 bodies: 5,58 (m, 4H); 2,80 (sept, J=7,0Hz, 1H); 2,08 (s, 3H); 1,24 (d, J=7,0Hz, 6H). other: 2,72 (m, 1H); 1,35 (dd, 13,0,7,0Hz, 18H). embodiment A 8:RuCl
2(right-cumene) ((C
6H
11)
2PCH
2CH
2P (C
6H
11)
2) (catalyzer H)
500mg (RuCl
2(right-cumene)) 2 (0.915mmol) are suspended in the 50ml hexane, and with 0.93g (2.2mmol) 1,2-two (dicyclohexyl phosphino-) ethane mixes, and stirs 12 hours.The precipitation that filter to generate and with hexane (2 * 30ml) wash.Productive rate: 90%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,48 (m, 4H); 2,70 (sept, J=7,0Hz, 1H); 2,04 (s, 3H); 1,13 (d, J=7,0Hz, 6H). and other: 2,20-1,98 (m, 8H); 1,80-1,10 (m, 36H). embodiment A 9:(CH
3)
3PRu (right-cumene) Cl
2(catalyst I)
520mg (RuCl
2(right-cumene)) 2 (0.85mmol) are suspended in the 50ml hexane, and mix with the solution (3.5mmol) of 3.5ml1.0M trimethyl-phosphine in toluene and stirred 6 hours.The precipitation that filter to generate and with hexane (2 * 30ml) wash.Productive rate: 94%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,47 (m, 4H); 2,89 (sept, J=7,0Hz, 1H); 2,11 (s, 3H); 1,26 (d, J=7,0Hz, 6H). and other: 1,64 (d, J
PH=11,0Hz, 9H). embodiment A 10:(just-C
4H
9)
3PRu (right-cumene) Cl
2(catalyzer J)
380mg (RuCl
2(right-cumene))
2(0.62mmol) be dissolved in the 50ml ethanol and and mix with 480mg tributylphosphine (2.3mmol).Reflux and stirred 4 hours and then removed and desolvate.Resistates 20ml hexane wash.Productive rate: 97%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,38 (m, 4H); 2,81 (sept, J=7,0Hz, 1H); 2,10 (s, 3H); 1,22 (d, J=7,0Hz, 6H). other: 1,95 (m, 6H); 1,40 (m, 12H); 0,90 (t, 9H). embodiment A 11:(C
6H
11)
2HPRu (right-cumene) Cl
2(catalyzer K)
500mg (RuCl
2(right-cumene)) 2 (0.82mmol) are suspended in the 50ml hexane, and mix with 0.65g dicyclohexylphosphontetrafluoroborate (3.3mmol) and reflux and stirred 6 hours.The precipitation that filter to generate and with hexane (2 * 25ml) wash productive rate: 89%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,42 (m, 4H); 2,76 (sept, J=7,0Hz, 1H); 2,03 (s, 3H); 1,15 (d, J=7,0Hz, 6H). and other: 4,89,3,66 (d, J
PH=370Hz, 1H); 2,23 (m, 2H); 1,90-1,10 (m, 20H). embodiment A 12:(C
6H
11)
3POs (right-cumene) Cl
2(catalyzer L)
158mg (OsCl in the 50ml hexane
2(right-cumene))
2(0.2mmol) mix and reflux and stirred 5 hours with 168mg tricyclohexyl phosphine (0.6mmol).Be cooled to RT after-filtration precipitation and (2 * 5ml) wash with hexane.Productive rate: 96%.
1H-NMR (C
6D
6, 300MHz): coordinate aromatic hydrocarbons ligand: 5,51 (d, J=5,5Hz, 2H); 5,33 (d, J=5,5Hz, 2H); 2,79 (sept, J=7,0Hz, 1H); 1,96 (s, 3H); 1,21 (d, J=7,0Hz, 6H).
Other: 2,56 (m, 3H); 2,21 (m, 6H); 1,73-1,60 (m, 9H); 1,48-1,36 (m, 6H); 1,30-1,23 (m, 9H). embodiment A 13:(is different-C
3H
7)
3POs (right-cumene) Cl
2(catalyzer M)
158mg (OsCl in the 50ml octane
2(right-cumene))
2(0.2mmol) mix with 115 μ l tri isopropyl phosphines (0.6mmol) and reflux 5 hours.Be cooled to RT after-filtration precipitation and with hexane wash (2 * 10ml).Productive rate: 83%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,79 (d, J=5,5Hz, 2H); 5,70 (d, J=5,5Hz, 2H) 2,69 (sept, J=7,0Hz, 1H); 2,13 (s, 3H); 1,26 (d, J=7,0Hz, 6H).
Other: 2,74 (m, 3H); 1,24 (dd, J=13,0,7,0Hz, 18H). embodiment A 14:(CH
3)
3POs (right-cumene) Cl
2(catalyst n)
Be similar to routine A13, but use equivalent P (CH
3)
3Replace P (C
6H
11)
3Productive rate: 76%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,49 (d, J=5,5Hz, 2H); 5,44 (d, J=5,5Hz, 2H); 2,69 (sept, J=7,0Hz, 1H); 2,12 (s, 3H); 1,26 (d, J=7,0Hz, 6H).
Other: 1,53 (d, J
PH=10,5Hz, 9H). embodiment A 15:(C
6H
5)
3POs (right-cumene) Cl
2(catalyzer O)
158mg (OsCl in the 50ml hexane
2(right-cumene))
2(0.2mmol) mix and reflux and stirred 5 hours with 157mg triphenylphosphine (0.6mmol).Be cooled to precipitation that the RT after-filtration generates and (2 * 10ml) wash with ether.Productive rate: 92%.
1H-NMR (CDCl
3, 300MHz): coordinate aromatic hydrocarbons ligand: 5,39 (d, J=5,5Hz, 2H); 5,16 (d, J=5,5Hz, 2H); 2,75 (sept, J=7,0Hz, 1H); 1,97 (s, 3H); 1,15 (d, J=7,0Hz, 6H).
Other: 7,79-7,70 (m, 6H); 7,40-7,30 (m, 9H). embodiment A 16:(C
6H
11)
3PRu (right-cumene) (acetonitrile) (Trif)
2(catalyst P)
1g (C
6H
11)
3PRu (right-cumene) Cl
2Be dissolved in the 20ml acetonitrile.To wherein adding 920mg Ag Trif (2.1 equivalent).Stir 15 minutes final vacuums except that desolvating.Use 30mlCH
2Cl
2Extraction and evaporation subsequently obtain product.
1H-NMR (CDCl
3): δ 6.48-6.98 (dd, 4H, p-Cumen); 2.65 (s+sept, 4H, CH
3CN+ (i-C
3H
7)-H); 2.10 (s, 3HCH
3-P-Cumen); 1,29 (d, 6H, i-C
3H
7-p-Cumen) 2.25-1-10 (m, P (C
6H
11)
3) .B) the preparation Embodiment B 1-B16 of polymkeric substance:
Use as light source:
(a) 200W mercury vapour-middle pressure-UV-lamp (Osram HBO 200W/2, Spindler ﹠amp of manufacturers; Hoyer, Gottingen).
(b) self-control UV-irradiating unit has 4 * 40WR-UVA lamp TL 40W/10R and 2 * 20W TL 20W/05 (Philips), the about 25cm of distance.
500mg norbornylene and 3mg catalyzer are dissolved in 3ml CHCl
3In and the condition shown in the table 1 of press shine.
Table 1 embodiment sequence number catalyzer
*Transformation efficiency
*Time, temperature
71 2 minutes room temperatures of 100 10 minutes room temperature B2 B 60 2 minutes room temperature B4 D 34 20 minutes room temperature B6 F 100 2 minutes room temperature B8 H 80 5 minutes room temperature B10 J 67 3 minutes room temperature B12 L 100 5 minutes room temperature B14 N 15 1 hours room temperature B16 P of 100 10 minutes room temperature B15 O of 71 2 minutes room temperature B13 M of 70 3 minutes room temperature B11 K of 52 2 minutes room temperature B9 I of 50 4 minutes room temperature B7 G of 70 3 minutes room temperature B5 E of 94 30 seconds room temperature B3 C of percentage meter B1 A*The catalyzer of embodiment A 1-A16 preparation
*Transformation efficiency Embodiment B 17 from ethanol behind the redeposition:
(a) 500mg norbornylene and 5mg catalyst P unglazed stirring 3 hours in 5ml ethanol.No polymkeric substance generates.
(b) 500mg norbornylene and 5mg catalyst P are used 200W mercury vapour-middle pressure-UV-lamp (Osram HBO 200W/2, Spindler ﹠amp of manufacturers in 5ml ethanol; Hoyer, G ttingen) shone 30 minutes.Productive rate: 100% polynorbornene.Embodiment B 18:
(a) the 5mg catalyzer J in 5ml toluene mixes also unglazed stirring 3 hours with the 500mg norbornylene.Solution still is mobile.
(b) the 200W mercury vapour of the 5mg catalyzer J in 5ml toluene-middle pressure-UV-lamp (Osram HBO 200W/2, manufacturers: Spindler ﹠amp; Hoyer, G ttingen) shone 5 minutes.Then add the 500mg norbornylene.Solution gelatinization in 10 minutes.Productive rate after 3 hours: 100% polynorbornene.Embodiment B 19 to B21:
500mg monomeric compound (23) and 3mg catalyzer are dissolved in 3ml CHCl
3In and the condition shown in the table 2 of press shine.Use 200W mercury vapour-middle pressure-UV-lamp (Osram HBO 200W/2, Spindler ﹠amp of manufacturers as exposure light source; Hoyer, G ttingen).
Table 2 embodiment catalyzer
*Transformation efficiency
*Time, 85 30 minutes room temperature * of 100 30 minutes room temperature B20 of temperature B19 B J transformation efficiency behind the redeposition from ethanol is in per-cent
Claims (40)
1. the photochemical catalysis polymeric method of a kind of cycloolefin or at least two kinds of different cycloolefins when metallic compound exists as catalyzer, it is characterized in that, the ruthenium at least a no Cabbeen, divalent cation of catalytic amount-or osmium compound in the presence of carry out photochemistry open loop-transposition polymerization, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 to 5 parts altogether, and contain the acid anion that is useful on charge balance.
2. according to the method for claim 1, it is characterized in that, cycloolefin relates to monocyclic ring or polycyclic, bridging or condensed has the member ring systems of 2 to 4 rings, it is unsubstituted or replacement and contains one or more by O in case of necessity in one or more rings, S, the heteroatoms that N and Si select also contains ring condensed aromatics or heteroaromatic in case of necessity.
3. according to the method for claim 2, it is characterized in that the cyclic ring contains 3 to 16 links.
4. according to the method for claim 3, it is characterized in that the cyclic ring contains 3 to 12 links.
5. according to the method for claim 2, it is characterized in that cycloolefin contains two keys of other non-aromatics.
6. according to the method for claim 1, it is characterized in that cycloolefin is equivalent to formula I,
In the formula
Q
1Be one to have the base of at least one carbon atom, it and-CH=CQ
2-Ji forms the ring of the aliphatic series of one at least 3 joint together, and this ring contains one or more heteroatomss in case of necessity, is selected from silicon, phosphorus, oxygen, nitrogen, sulphur; And it is unsubstituted or with halogen ,=O ,-CN ,-NO
2, R
1R
2R
3Si-(O)
u-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
20-alkyl, C
1-C
20-hydroxyalkyl, C
1-C
20-haloalkyl, C
1-C
6-cyano group alkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl, C
7-C
16-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
16-heteroaryl, C
4-C
16-heteroaralkyl or R
4-X-replaces; Or wherein two adjacent C atoms be with-CO-O-CO-or-CO-NR
5-CO-replaces; Or wherein condensing an alicyclic ring on the adjacent carbons of alicyclic ring in case of necessity, and ring aromatics or heteroaromatic, it is unsubstituted or with halogen ,-CN ,-NO
2, R
6R
7R
8Si-(O)
u-,-COOM ,-SO
3M ,-PO
3M ,-COOM (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
20Alkyl, C
1-C
20-haloalkyl, C
1-C
20-hydroxyalkyl, C
1-C
6-cyano group alkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl, C
7-C
16-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
16-heteroaryl, C
4-C
16-heteroaralkyl or R
13-X
1-replace;
X and X
1Respectively do for oneself-O--S-,-CO-,-SO-,-SO
2-,-O-C (O)-,-C (O)-O-,-C (O)-NR
5-,-NR
10-C (O)-,-SO
2-O-or-O-SO
2-;
R
1, R
2And R
3C respectively does for oneself
1-C
12-alkyl, C
1-C
12-perfluoroalkyl, phenyl or benzyl;
R
4And R
13C respectively does for oneself
1-C
20-alkyl, C
1-C
20-haloalkyl, C
1-C
20-hydroxyalkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl, C
7-C
16-aralkyl;
R
5And R
10The hydrogen of respectively doing for oneself, C
1-C
12-alkyl, phenyl or benzyl, wherein alkyl is unsubstituted or with C
1-C
12-alkoxyl group or C
3-C
8-cycloalkyl substituted;
R
6, R
7And R
8C respectively does for oneself
1-C
12-alkyl, C
1-C
12-perfluoroalkyl, phenyl or benzyl;
M is basic metal and M
1It is an alkaline-earth metal; With
U is 0 or 1; Wherein with Q
1The alicyclic ring that forms contains two keys of other non-aromatics in case of necessity;
Q
2Be hydrogen, C
1-C
20-alkyl, C
1-C
20-haloalkyl, C
1-C
12-alkoxyl group, halogen ,-CN, R
11-X
2-;
R
11Be C
1-C
20Alkyl, C
1-C
20-haloalkyl, C
1-C
20-hydroxyalkyl, C
3-C
8-cycloalkyl, C
6-C
16-aryl or C
7-C
16-aralkyl;
X
2Be-C (O)-O-or-C (O)-NR
12-; R
12Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; Wherein above-mentioned cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or with C
1-C
12-alkyl, C
1-C
12-alkoxyl group ,-NO
2,-CN or halogen replace, and wherein above-mentioned Heterocyclylalkyl, and the heteroatoms in heteroaryl and the heteroaralkyl is to be selected from-O-,-S-,-NR
9-and-N=; And R
9Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl.
7. according to the method for claim 6, it is characterized in that Q
1With-CH=CQ
2The ring of-the alicyclic ring that constituted together has 3 to 16 annular atomses, and wherein relate to monocyclic, dicyclo, trinucleated or tetracyclic member ring systems.
8. according to the method for claim 6, it is characterized in that Q
2In formula I hydrogen.
9. according to the method for claim 6, it is characterized in that, in formula I compound:
Q
1Be one to have the base of at least one carbon atom, it and-CH=CQ
2-Ji forms the ring of the alicyclic ring of one 3 to 20 joints together, and this ring contains one or more heteroatomss in case of necessity, is selected from silicon, oxygen, nitrogen, sulphur; And it is unsubstituted or with halogen ,=O ,-CN ,-NO
2, R
1R
2R
3Si-(O)
u-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, C
6-C
12-aryl, C
7-C
12-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
12-heteroaryl, C
4-C
12-heteroaralkyl or R
4-X-replaces; Or wherein at this Q
1In two adjacent C-atoms be with-CO-O-CO-or-CO-NR
5-CO-replaces; Or wherein condensing an alicyclic ring on the adjacent carbons in case of necessity, and ring aromatics or heteroaromatic, it is unsubstituted or with halogen ,-CN ,-NO
2, R
6R
7R
8Si-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, C
6-C
12-aryl, C
7-C
12-aralkyl, C
3-C
6-Heterocyclylalkyl, C
3-C
12-heteroaryl, C
4-C
12-heteroaralkyl or R
13-X
1-replace;
X and X
1Independently be-O--S-,-CO-,-SO-,-SO separately
2-,-O-C (O)-,-C (O)-O-,-C (O)-NR
5-,-NR
10-C (O)-,-SO
2-O-or-O-SO
2-;
R
1, R
2And R
3Independently be C separately
1-C
6-alkyl, C
1-C
6-perfluoroalkyl, phenyl or benzyl;
M is basic metal and M
1It is an alkaline-earth metal;
R
4And R
13Independently be C separately
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
3-C
8-cycloalkyl, C
6-C
12-aryl, C
7-C
12-aralkyl;
R
5And R
10Be hydrogen independently of one another, C
1-C
6-alkyl, phenyl or benzyl, wherein alkyl is unsubstituted or with C
1-C
6-alkoxyl group or C
3-C
6-cycloalkyl substituted;
R
6, R
7And R
8Be C independently of one another
1-C
6-alkyl, C
1-C
6-perfluoroalkyl, phenyl or benzyl;
U is 0 or 1; Wherein with Q
1The ring of the alicyclic ring that forms contains two keys of other non-aromatics in case of necessity;
Q
2Be hydrogen, C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
6-alkoxyl group, halogen ,-CN, R
11-X
2-;
R
11Be C
1-C
12-alkyl, C
1-C
12-haloalkyl, C
1-C
12-hydroxyalkyl, C
3-C
6-cycloalkyl, C
6-C
12-aryl or C
7-C
12-aralkyl;
X
2Be-C (O)-O-or-C (O)-NR
12-; And R
12Be hydrogen, C
1-C
6-alkyl, phenyl or benzyl; Cycloalkyl wherein, Heterocyclylalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl are unsubstituted or with C
1-C
6-alkyl, C
1-C
6-alkoxyl group ,-NO
2,-CN or halogen replace, and Heterocyclylalkyl wherein, and the heteroatoms in heteroaryl and the heteroaralkyl is selected from-O-,-S-,-NR
9-and-N=; And R
9Be hydrogen, C
1-C
6-alkyl, phenyl or benzyl.
10. according to the method for claim 6, it is characterized in that, in formula I compound:
Q
1Be one to have the base of at least one carbon atom, it and-CH=CQ
2-Ji forms the ring of the alicyclic ring of one 3 to 10-joints together, and this ring contains one in case of necessity and is selected from silicon, the heteroatoms of oxygen, nitrogen and sulphur; And it is unsubstituted or with halogen ,-CN ,-NO
2, R
1R
2R
3Si-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
6-alkyl, C
1-C
6-haloalkyl, C
1-C
6-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, phenyl, benzyl or R
4-X-replaces; Or wherein condensing an alicyclic ring on the adjacent carbon atom in case of necessity, ring aromatics or heteroaromatic, this ring are unsubstituted or with halogen ,-CN ,-NO
2, R
6R
7R
8Si-,-COOM ,-SO
3M ,-PO
3M ,-COO (M
1)
1/2,-SO
3(M
1)
1/2,-PO
3(M
1)
1/2, C
1-C
6-alkyl, C
1-C
6-haloalkyl, C
1-C
6-hydroxyalkyl, C
1-C
4-cyano group alkyl, C
3-C
6-cycloalkyl, phenyl, benzyl or R
13-X
1-replace;
R
1, R
2And R
3Be C independently of one another
1-C
4-alkyl, C
1-C
4-perfluoroalkyl, phenyl or benzyl;
M is basic metal and M
1It is an alkaline-earth metal;
R
4And R
13Be C independently of one another
1-C
6-alkyl, C
1-C
6-haloalkyl, C
1-C
6-hydroxyalkyl or C
3-C
6-cycloalkyl;
X and X
1Be independently of one another-O-,-S-,-CO-,-SO-or-SO
2-;
R
6, R
7And R
8Be C independently of one another
1-C
4-alkyl, C
1-C
4-perfluoroalkyl, phenyl or benzyl; And Q
2Be hydrogen.
11. the method according to claim 1 is characterized in that, cycloolefin relates to norbornylene or norbornene derivative.
12. the method according to claim 11 is characterized in that, norbornene derivative relates to formula II compound
In the formula
X
3For-CHR
16-, oxygen or sulphur;
R
14And R
15Be hydrogen independently of one another ,-CN, trifluoromethyl, (CH
3)
3Si-O-, (CH
3)
3Si-or-COOR
17And
R
16And R
17Be hydrogen independently of one another, C
1-C
12-alkyl, phenyl or benzyl; Or formula III compound
In the formula
X
4For-CHR
19-, oxygen or sulphur;
R
19Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; And
R
18Be hydrogen, C
1-C
6-alkyl or halogen; Or formula IV compound
In the formula
X
5For-CHR
22-, oxygen or sulphur;
R
22Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl;
R
20And R
21Be hydrogen independently of one another, CN, trifluoromethyl, (CH
3)
3Si-O-, (CH
3)
3Si-or-COOR
23And
R
23Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; Or formula V compound
In the formula
X
6For-CHR
24-, oxygen or sulphur;
R
24Be hydrogen, C
1-C
12-alkyl, phenyl or benzyl; Y be oxygen or
And
R
25Be hydrogen, methyl, ethyl or phenyl.
13. the method according to claim 1 is characterized in that, single phosphine is incorporated into for one to three time on the atoms metal and diphosphine once is incorporated on the atoms metal.
14. the method according to claim 1 is characterized in that, the residue valence link of ruthenium and osmium is saturated with neutral ligand.
15. the method according to claim 1 is characterized in that, the phosphine part is corresponding to formula VII or VIIa.
PR
26R
27R
28????????????????????????(VII)，
R
26R
27P-Z
1-PR
26R
27(VIIa), R wherein
26, R
27And R
28Be H independently of each other, C
1-C
20Alkyl does not replace or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6The C that alkoxyl group replaces
4-C
12Cycloalkyl; Or do not replace or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6The C that alkoxyl group replaces
6-C
16Aryl; Or it is unsubstituted or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6The C that alkoxyl group replaces
7-C
16Aralkyl; Radicals R
26And R
27Common is unsubstituted or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6Four-or the pentamethylene that alkoxyl group replaces, or unsubstituted or by C
1-C
6Alkyl, C
1-C
6Haloalkyl or C
1-C
6That alkoxyl group replaces and with 1 or 21,2-phenylene condensed four-or pentamethylene, and R
28Has the given implication in front; With
Z
1For straight chain or branching, do not replace or by C
1-C
4The C that alkoxyl group replaces
2-C
12Alkylidene group does not replace or by C
1-C
4Alkyl or C
1-C
4That alkoxyl group replaces, have 1 of 4-8 C atom, 2-or 1,3-cycloalkylidene, or unsubstituted or by C
1-C
4Alkyl or C
1-C
4That alkoxyl group replaces, have 5 or 6 ring elements and one and be selected from heteroatomic 1,2 or 1 of O or N, the inferior Heterocyclylalkyl of 3-.
16. the method by claim 15 is characterized in that R
26, R
27And R
28Be identical group.
17. the method by claim 15 is characterized in that the phosphine part is corresponding to formula VII, wherein R
26, R
27And R
28Be H independently of each other, C
1-C
6Alkyl does not replace or by C
1-C
4Cyclopentyl or cyclohexyl that alkyl replaces, or do not replace or by C
1-C
4Alkyl, C
1-C
4Alkyl C
1-C
4The phenyl that alkoxyl group or trifluoromethyl replace or unsubstituted or by C
1-C
4Alkyl, C
1-C
4The benzyl that alkoxyl group or trifluoromethyl replace.
18. the method according to claim 15 is characterized in that, the phosphine part of formula VII relates to
(C
6H
5)
3P，(C
6H
5CH
2)
3P，(C
5H
11)
3P，(CH
3)
3P，(C
2H
5)
3P，
(n-C
3H
7)
3P，(i-C
3H
7)
3P，(n-C
4H
9)
3P，(C
6H
5)
2HP，(C
6H
5CH
2)
2HP，(C
6H
11)
3P，(C
5H
11)
2HP，
(C
6H
11)
2HP，(CH
3)
2HP，(C
2H
5)
2HP，(n-C
3H
7)
2HP，(i-C
3H
7)
2HP，(n-C
4H
9)
2HP，
(C
6H
5)H
2P，(C
6H
5CH
2)H
2P，(C
5H
11)H
2P，(C
6H
11)H
2P，(CH
3)H
2P，(C
2H
5)H
2P，
(n-C
3H
7)H
2P，(i-C
3H
7)H
2P，(n-C
4H
9)H
2P，PH
3, (2-methyl-C6H
4)
3P，(3-CH
3-C
6H
4)
3P，
(4-CH
3-C
6H
4)
3P，(2，4-Di-CH
3-C
6H
3)
3P，(2，6-Di-CH
3-C
6H
3)
3P，(2-C
2H
5-C
6H
4)
3P，
(3-C
2H
5-C
6H
4)
3P，(4-C
2H
5-C
6H
4)
3P，(2-n-C
3H
7-C
6H
4)
3P，(3-n-C
3H
7-C
6H
4)
3P，
(4-n-C
3H
7-C
6H
4)
3P，(2-i-C
3H
7-C
6H
4)
3P，(3-i-C
3H
7-C
6H
4)
3P，(4-i-C
3H
7-C
6H
4)
3P，
(2-n-C
4H
9-C
6H
4)
3P，(3-n-C
4H
9-C
6H
4)
3P，(4-n-C
4H
9-C
6H
4)
3P，(2-i-C
4H
9-C
6H
4)
3P，
(3-i-C
4H
9-C
6H
4)
3P，(4-i-C
4H
9-C
6H
4)
3P，(2-t-C
4H
9-C
6H
4)
3P，(3-t-C
4H
9-C
6H
4)
3P，
(4-t-C
4H
9-C
6H
4)
3P，(2-CH
3-6-t-C
4H
9-C
6H
3)
3P，(3-CH
3-6-t-C
4H
9-C
6H
3)
3P，
(3-CH
3-6-t-C
4H
9-C
6H
3)
3P，(2，6-Di-t-C
4H
9-C
6H
3)
3P，(2，3-Di-t-C
4H
9-C
6H
3)
3P or (2,4-Di-t-C4H
9-C
6H
3)
3P。
19. the method according to claim 1 is characterized in that, the photo-labile part relates to nitrogen (N
2), unsubstituted or by OH, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
6-C
12Monocycle, many rings or the condensed that aryl or halogen replace, have the aromatic hydrocarbons of 6-24 C atom, or relate to unsubstituted or by C
1-C
4Alkyl, C
1-C
4That alkoxy or halogen replaces, have the assorted aromatic hydrocarbons of heteroatomic monocycle that 3-22 C atom and 1-3 be selected from O, S and N, condense assorted aromatic hydrocarbons or the condensed aromatic hydrocarbons-aromatic hydrocarbons of mixing; Or it is unsubstituted or by C
1-C
4Alkyl, C
1-C
4The aliphatic series that has 1-22 C atom, cyclic aliphatic, aromatics or araliphatic nitrile that alkoxy or halogen replaces.
20. the method according to claim 19 is characterized in that, the photo-labile part relates to unsubstituted or by 1-3 C
1-C
4The benzene that alkyl replaces.
21. the method according to claim 19 is characterized in that, the photo-labile part relates to the nitrile that has 1-12 C atom.
22. the method according to claim 19 is characterized in that, the photo-labile part relates to unsubstituted or by 1-3 C
1-C
4The benzene that alkyl replaces, or relate to thiophene, benzonitrile or acetonitrile.
23. method according to claim 22, it is characterized in that, aromatic hydrocarbons and assorted aromatic hydrocarbons relate to benzene, right-cumene, biphenyl, naphthalene, anthracene, acenaphthene, fluorenes, phenanthrene, pyrene, bend, fluoranthene, furans, thiophene, pyrroles, pyridine, γ-pyrans, γ-thiapyran, pyrimidine, pyrazine, indoles, cumarone, benzo-thiophene, carbazole, dibenzofuran, dibenzothiophen, pyrazoles, imidazoles, benzoglyoxaline, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline 99.9, acridine, chromene, azophenlyene, phenoxazine, thiodiphenylamine, triazine, thianthrene, purine.
24. the method according to claim 1 is characterized in that neutral ligand relates to H
2O, H
2S, NH
3Choose halogenated, as to have 1-18 C atom aliphatic series or cycloaliphatic alcohol or mercaptan wantonly, have the aromatic alcohol or the mercaptan of 6-18 C atom, have the aromatic grease group alcohol or the mercaptan of 7-18 C atom; The ether, thioether, sulfoxide, sulfone, ketone, aldehyde, carboxylicesters, lactone, the optional N-C that have 2-20 C atom, open chain or cyclic and aliphatic series, araliphatic or aromatics
1-C
4-single-or bis-alkylated carboxylic acid amides and optional N-C
1-C
4Alkylating lactan; Have 1-20 C atom open chain or cyclic and aliphatic series, araliphatic or aromatics primary, the second month in a season and tertiary amine or cyclopentadienyl.
25. the method according to claim 24 is characterized in that neutral ligand relates to H
2O, NH
3Or unsubstituted or fluorizated C partially or completely
1-C
4Alkanol or relate to cyclopentadienyl.
26. the method according to claim 1 is characterized in that, inorganic or organic anion is selected from hydrogen ion, halogen ion, oxygen acid negatively charged ion, cyclopentadienyl and BF
4, PF
6, SbF
6Or AsF
6
27. the method according to claim 1 is characterized in that, the oxygen acid negatively charged ion relates to sulfate radical, phosphate radical, perchlorate, hyperbromic acid root, periodate, metaantimmonic acid root, arsenate, nitrate radical, carbonate, C
1-C
8Anion of carboxylic acid, sulfonate radical, optional by C
1-C
4Alkyl, C
1-C
4Phenylsulfonic acid root or benzene methanesulfonic acid root or phosphonate radical that alkoxy or halogen replaces.
28. the method according to claim 27 is characterized in that, acid anion is H
Θ, Cl
Θ, Br
Θ, BF
4 Θ, PF
6 Θ, SbF
6 Θ, AsF
6 Θ, CF
3SO
3 Θ, C
6H
5-SO
3 Θ, 4-methyl-C
6H
5-SO
3 Θ, 2,6-dimethyl-C
6H
5-SO
3 Θ, 2,4,6-trimethylammonium-C
6H
5-SO
3 ΘAnd 4-CF
3-C
6H
5-SO
3 ΘOr cyclopentadienyl (Cp
Θ).
29. the method according to claim 1 is characterized in that, ruthenium-and osmium compound corresponding to formula VIII, VIIIa, VIIIb, VIIIc, VIIId, VIIIe or VIIIf
R
32L
1Me
2+(Z
n-)
2/n??????????????????????(VIII)，
R
32L
2L
3Me
2+(Z
n-)
2/n???????????????????(VIIIa)，
(R
32)
2L
2Me
2+(Z
n-)
2/n??????????????????(VIIIb)，
(R
32)
3L
2Me
2+(Z
n-)
2/n??????????????????(VIIIc)，
R
32L
1L
2Me
2+(Z
n-)
2/n???????????????????(VIIId)，
R
32L
2L
2Me
2+(Z
n-)
2/n???????????????????(VIIIe)，
R
32L
1L
3Me
2+(Z
N-)
2/n(VIIIf), wherein
R
32For according to the formula VII of claim 15 or the tertiary phosphine of VIIa;
Me is Ru or Os;
N is a numeral 1,2 or 3;
Z is inorganic or organic anion;
(a) L
1Be aromatic hydrocarbons-or assorted aromatic hydrocarbons part;
(b) L
2For being different from L
1Monovalence photo-labile part; With
(c) L
3Be the non-photo-labile part of monovalence.
30. the method according to claim 1 is characterized in that, ruthenium-and osmium compound corresponding IX, IXa, IXb, IXc, IXd, IXe or IXf
(R
26R
27R
28P)L
1Me
2+(Z
1-)
2?????????(IX)，
(R
26R
27R
28P)
2L
2Me
2+(Z
1-)
2???????(IXa)，
(R
26R
27R
28P)L
2L
3Me
2+(Z
1-)
2??????(IXb)，
(R
26R
27R
28P)
3L
2Me
2+(Z
1-)
2???????(IXc)，
(R
26R
27R
28P)L
2L
2Me
2+(Z
1-)
2??????(IXd)，
(R
26R
27R
28P)L
1L
3Me
2+(Z
1-)
2??????(IXe)，
(R
26R
27R
28P)L
1(L
2)
mMe
2+(Z
1-)
2??(IXf)，
Wherein
Me represents Ru or Os;
Z represents H in formula IX-IXe
Θ, cyclopentadienyl, Cl
Θ, Br
Θ, BF
4 Θ, PF
6 Θ, SbF
6 Θ, AsF
6 Θ, 1CF
3SO
3 Θ, C
6H
5-SO
3 Θ, 4-methyl-C
6H
5-SO
3 Θ, 2,6-dimethyl-C
6H
5-SO
3 Θ, 2,4,6-trimethylammonium-C
6H
5-SO
3 ΘOr 4-CF
3-C
6H
5-SO
3 ΘAnd in formula IXf, represent H
Θ, cyclopentadienyl, BF
4 Θ, PF
6 Θ, SbF
6 Θ, AsF
6 Θ, CF
3SO
3 Θ, C
6H
5-SO
3 Θ, 4-methyl-C
6H
5-SO
3 Θ, 2,6-dimethyl-C
6H
5-SO
3 Θ, 2,4,6-trimethylammonium-C
6H
5-SO
3 ΘOr 4-CF
3-C
6H
5-SO
3 ΘM is 1 or 2;
R
26, R
27And R
28Be C independently of each other
1-C
6Alkyl or-alkoxyl group, unsubstituted or by 1-3 C
1-C
4Cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy that alkyl replaces, or unsubstituted or by 1-3 C
1-C
4Phenyl or benzyl or phenoxy group or benzyloxy that alkyl replaces;
L
1For unsubstituted or by 1-3 C
1-C
4Alkyl, C
1-C
4Alkoxyl group ,-OH ,-C that F or Cl replace
6-C
16Aromatic hydrocarbons or C
5-C
16Assorted aromatic hydrocarbons;
L
2Be C
1-C
6Alkyl-CN, benzonitrile or benzyl nitrile; With
L
3Be H
2O or C
1-C
6Alkanol.
31. the method according to claim 1 is characterized in that, ruthenium-be with osmium compound
(C
6H
11)
2HPRu(p-Cumen)Cl
2，(C
6H
11)
3PRu(p-Cumen)Cl
2，
(C
6H
11)
3PRu(p-Cumen)(Tos)
2，(C
6H
11)
3PRu(p-Cumen)Br
2，(C
6H
11)
3PRu(p-Cumen)ClF，
(C
6H
11)
3PRu(C
6H
6)(Tos)
2，(C
6H
11)
3PRu(CH
3-C
6H
5)(Tos)
2，
(C
6H
11)
3PRu(i-C
3H
7-C
6H
5)(Tos)
2，(C
6H
11)
3PRu()(Tos)
2，
(C
6H
11)
3PRu (biphenyl) (ros)
2, (C
6H
11)
3PRu (anthracene) (Tos)
2,
(C
6H
11)
3PRu(C
10H
8)(Tos)
2，(i-C
3H
7)
3PRu(p-Cumen)Cl
2，(CH
3)
3PRu(p-Cumen)Cl
2，
(n-C
4H
9)
3PRu(p-Cumen)Cl
2，[(C
6H
11)
3P]
2Ru(CH
3-CN)(Tos)
2，
(C
6H
11)
3PRu(CH
3-CN)(C
2H
5-OH)(Tos)
2，(C
6H
11)
3PRu(p-Cumen)(CH
3-CN)
2(PF
6)
2，
(C
6H
11)
3PRu(p-Cumen)(CH
3-CN)
2(ros)
2，(n-C
4H
9)
3PRu(p-Cumen)(CH
3-CN)
2(ros)
2，
(C
6H
11)
3PRu(CH
3CN)Cl
2，(C
6H
11)
3PRu(CH
3-CN)
2Cl
2，
(C
6H
11)
3PRu(p-Cumen)(C
2H
5OH)(BF
4)
2，(C
6H
11)
3PRu(p-Cumen)(C
2H
5OH)
2(BF
4)
2，
(C
6H
11)
3PRu(p-Cumen)(C
2H
5OH)
2(PF
6)
2，(C
6H
11)
3PRu(C
6H
6)(C
2H
5OH)
2(Tos)
2，
(C
6H
11)
3POs(p-Cumen)Cl
2，(i-C
3H
7)
3POs(p-Cumen)Cl
2，(CH
3)
3POs(p-Cumen)Cl
2，
(C
6H
5)
3POs (p-Cumen) Cl
2Or RuCl
2(P-Cumen) [(C
6H
11)
2PCH
2CH
2P (C
6H
11)
2]
Wherein Tos is a tosylate, and Cumen is a cumene.
32. cause and follow the method for the cycloolefin of the cycloolefin of a kind of tensioning of thermopolymerization or at least two kinds of different tensionings as photochemical catalysis in the presence of the catalyzer at metallic compound by claim 1, it is characterized in that,
A) at first the ruthenium at least a no Cabbeen, divalent cation of catalytic amount-or osmium compound in the presence of the radiation cycloolefin, this ruthenium-or osmium compound contain a phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance; Or the first radiation ruthenium at least a no Cabbeen, divalent cation of the catalytic amount in a kind of inert solvent-or osmium compound randomly, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance, and mix with the cycloolefin of at least a tensioning then; And
B) then by heating and radiationless end polymerization.
33. the method according to claim 1 and 32 is characterized in that, based on the amount of cycloolefin, uses ruthenium-and osmium compound with the amount of 0.001-20Mol%.
34. photopolymerisable compositions, contain the cycloolefin of the cycloolefin of (a) tensioning or at least two kinds of different tensionings and (b) ruthenium at least a no Cabbeen, divalent cation of catalytically effective amount-or osmium compound, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance.
35. composition, contain the cycloolefin of the cycloolefin of a tensioning or at least two kinds of different tensionings and the ruthenium at least a no Cabbeen, divalent cation of catalytically effective amount-or osmium compound, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance, P (C
6H
11)
3(right-cumene) RuCl
2With the norbornylene except combinations.
36. the carrier substance of coating, it is characterized in that, on carrier, coat one by (a) cycloolefin or at least two kinds of different cycloolefins and (b) ruthenium at least a no Cabbeen, divalent cation of catalytically effective amount-or osmium compound forms layer, this ruthenium-or osmium compound contain at least one phosphino-that is incorporated on the atoms metal, at least one photo-labile part, and optional contain neutral ligand, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance.
37. carrier substance, it contains a linking agent with one according to the oligopolymer of claim 1 preparation or polymeric coating and it.
38. the carrier substance of coating is characterized in that, is coated with the polymkeric substance of one deck according to claim 1 preparation on carrier.
39. on carrier, make the method for coated material or embossing pattern, wherein coat composition according to claim 36, optional removing desolvated, and this coating of radiation makes polymerization and heat embrittlement more in case of necessity, or by the mask radiation coating, heat embrittlement more in case of necessity, and then remove with a solvent and be not subjected to the radiating part.
40. preparation is used for the thermocatalyst of open loop transposition polymerized cycloolefins or improves its active method, it is characterized in that, to body form or a kind of in a kind of solvent do not have ruthenium Cabbeen, divalent cation-or osmium compound carry out radiation, this ruthenium-or osmium compound contain at least one photo-labile part that is incorporated on the atoms metal, and the optional neutral ligand that contains, wherein be combined with 2 or 3 parts altogether, and contain the acid anion that is useful on charge balance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95196282 CN1164246A (en) | 1994-11-17 | 1995-11-06 | Polymerizable composition and process for polymerizing cyclical olefins |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3464/94 | 1994-11-17 | ||
| CN 95196282 CN1164246A (en) | 1994-11-17 | 1995-11-06 | Polymerizable composition and process for polymerizing cyclical olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1164246A true CN1164246A (en) | 1997-11-05 |
Family
ID=5083177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95196282 Pending CN1164246A (en) | 1994-11-17 | 1995-11-06 | Polymerizable composition and process for polymerizing cyclical olefins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1164246A (en) |
-
1995
- 1995-11-06 CN CN 95196282 patent/CN1164246A/en active Pending
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