CN101255212A - Diene polymer and process for producing the same - Google Patents

Diene polymer and process for producing the same Download PDF

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Publication number
CN101255212A
CN101255212A CN 200810081096 CN200810081096A CN101255212A CN 101255212 A CN101255212 A CN 101255212A CN 200810081096 CN200810081096 CN 200810081096 CN 200810081096 A CN200810081096 A CN 200810081096A CN 101255212 A CN101255212 A CN 101255212A
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phenyl
polymkeric substance
dimethyl
atom
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小坂田耕太郎
竹内大介
朴世训
冈田健史
植村真
藤田正行
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene

Abstract

The invention relates to a diene polymer and a method for preparing the same.A polymer containing units represented by the defined formula (1); and a process for producing the polymer, which comprises the step of polymerizing a compound represented by the defined formula (3), the units represented by the formula (1) being polymerized units of the compound represented by the formula (3) such as 5- allyl-5-((2E)-2-butenyl)-2, 2-dimethyl-1,3-dioxane-4,6-diketone.

Description

The method of diene polymer and this diene polymer of preparation
Technical field
The method that the present invention relates to have superior stable on heating diene polymer and prepare this diene polymer.
Background technology
In the presence of addition polymerization catalyzer commonly used, by polymerization non-conjugated diene compound, the 5-allyl group-5-((2E)-crotyl)-2 that for example has two carbon-to-carbon double bonds by following formula (3) expression, 2-dimethyl-1,3-diox-4,6-diketone (5-allyl-5-((2E)-2-butenyl)-2,2-dimethyl-1,3-dioxan-4 6-dion), can not obtain having superior equilibrated diene polymer between thermotolerance and workability.What reason was that one of two carbon-to-carbon double bonds participate in is not polyaddition reaction, but for example undesirable reaction of crosslinking reaction, although another carbon-to-carbon double bond participates in polyaddition reaction, as a result of, only obtain such polymkeric substance, its (i) do not help stable on heating ring texture and (ii) not necessarily helps the thermoplastic polymer of workability in its main chain.
On the other hand, at Macromolecules, 35 volumes, the preparation method of ethene-pentamethylene alternating copolymer is disclosed in the 9640-9647 page or leaf (2002), this ethene-pentamethylene alternating copolymer has superior thermotolerance owing to contain ring texture in its main chain, described method comprises the following steps: that (a) is by coordination ring-opening polymerization copolymerization of ethylene and cyclopentenes, thereby obtain in its main chain, to have the alternating copolymer of carbon-to-carbon double bond, (b) these carbon-to-carbon double bonds of hydrogenation obtain ethene-pentamethylene alternating copolymer thus.But, described preparation method has following problem, (i) be not easy the synthetic monomer that has the substituent alternating copolymer of target that is used to prepare, even (ii) can synthesize such monomer, above-mentioned step of hydrogenation (b) is those substituting groups in the alternating copolymer that obtains in above-mentioned copolymerization step (a) of hydrogenation unfriendly also.
Summary of the invention
Consider above-mentioned situation, the purpose of this invention is to provide the method that has superior stable on heating diene polymer and this diene polymer of preparation is provided.
The present invention is a kind of unitary polymkeric substance that comprises by following formula (1) expression:
Figure A20081008109600071
X wherein 1And X 2Be the atom of 16 families in the periodic table of elements independently of one another; Y 1And Y 2Be alkoxyl group, aralkoxy or aryloxy independently of one another, and Y 1And Y 2Can be bonded to ring each other; A 1, A 2, A 3, A 4, A 5, A 6, A 7, A 8, A 9And A 10Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group (amide group), imide group (imidegroup) or sulfenyl (hydrocarbylthio group) independently of one another; And A 3And A 4, perhaps A 5And A 6Can be bonded to ring each other; With n be 1 to 20 integer.
In addition, the present invention is for being used for preparing the method that comprises by the unitary polymkeric substance of representing with following formula (1), and this method comprises the step of polymerization by the compound of following formula (3) expression:
Figure A20081008109600072
Wherein Z is-(CH 2) N-1-CHA 9A 10Group; Two wave lines that formula (3) upper right side shows are represented the variation in their configurations; And X 1, X 2, Y 1, Y 2, A 1To A 10Identical with those of definition in n and the formula (1).
Among the present invention, it is monomeric for example by the polymerized unit of the compound of formula (3) expression to be included in term " unit " expression in above-mentioned " by the unit of formula (1) expression ".
Detailed Description Of The Invention
With X in the following formula 1And X 2Example be Sauerstoffatom, sulphur atom and selenium atom.Wherein, Sauerstoffatom preferably.
With Y in the following formula 1And Y 2The example of alkoxyl group be the line style alkoxyl group, for example methoxyl group, oxyethyl group and n-butoxy; Branched alkoxy, for example isopropoxy, isobutoxy, tert.-butoxy and neopentyl oxygen; And cyclic alkoxy, for example cyclohexyloxy and ring octyloxy.Alkoxyl group can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group (sulfonategroup), silyl and cyano group.
With the Y in the following formula 1And Y 2The example of aralkoxy be benzyloxy, styroyl oxygen base, 2-methyl benzyloxy, 3-methyl benzyloxy, 4-methyl benzyloxy, 2,6-benzyloxy-dimethyl and 3,5-benzyloxy-dimethyl.Described aralkoxy can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With the Y in the following formula 1And Y 2The aryloxy example be phenoxy group, the 2-methylphenoxy, 2-ethyl phenoxy group, 2-n-propyl phenoxy group, 2-sec.-propyl phenoxy group, 2-normal-butyl phenoxy group, 2-isobutyl-phenoxy group, 2-tertiary butyl phenoxy group, the 3-methylphenoxy, 3-sec.-propyl phenoxy group, 3-normal-butyl phenoxy group, 3-tertiary butyl phenoxy group, the 4-methylphenoxy, 4-sec.-propyl phenoxy group, 4-normal-butyl phenoxy group, 4-tertiary butyl phenoxy group, 2, the 3-dimethyl phenoxy, 2, the 4-dimethyl phenoxy, 2, the 5-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 3, the 5-dimethyl phenoxy, 2,6-di-isopropyl phenoxy group, 2,6-di-t-butyl phenoxy group and naphthyloxy.Aryloxy can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
Y in following formula 1And Y 2When being bonded to ring each other, the example of ring is aliphatic series ring and aromatic ring.These rings can have one or more substituting groups.By Y 1And Y 2Between the aliphatic series ring that forms of bonding in the example of divalent group be methylene radical dioxy base, isopropylidene dioxy base, ethylidene-1,2-dioxy base, cyclohexylidene-1,2-dioxy base, cyclohexylidene-1,3-dioxy base, cyclohexylidene-1,4-dioxy base, inferior norborneol alkyl (norbornene)-1,2-dioxy base, butylidene-2,3-dioxy base, 2,3-dimethyl butylidene-2,3-dioxy base and pentylidene-2,4-dioxy base.Wherein, preferably methylene radical dioxy base, isopropylidene dioxy base, butylidene-2,3-dioxy base or 2,3-dimethyl butylidene-2,3-dioxy base.By Y 1And Y 2Between the aromatic ring that forms of bonding in the example of divalent group be phenylene-1,2-dioxy base, phenylene-1,3-dioxy base, phenylene-1,4-dioxy base, naphthylidene-1,2-dioxy base, naphthylidene-1,3-dioxy base, naphthylidene-1,4-dioxy base, naphthylidene-1,5-dioxy base, naphthylidene-1,6-dioxy base, naphthylidene-1,7-dioxy base, naphthylidene-1,8-dioxy base, naphthylidene-2,3-dioxy base, naphthylidene-2,4-dioxy base, naphthylidene-2,5-dioxy base, naphthylidene-2,6-dioxy base, naphthylidene-2,7-dioxy base, naphthylidene-2,8-dioxy base, biphenylene-2,2 '-dioxy base, dimethylene phenyl-1,2-dioxy base (dimethylenephenyl-1,2-dioxy group), dimethylene phenyl-1,3-dioxy base, dimethylene phenyl-1,4-dioxy base, diethylidene phenyl-1,2-dioxy base, diethylidene phenyl-1,3-dioxy base and diethylidene phenyl-1,4-dioxy base.
With A in the following formula 1To A 10The halogen atom example be fluorine atom, chlorine atom, bromine atoms and iodine atom.Fluorine atom preferably wherein.
With A in the following formula 1To A 10Examples of alkyl be linear alkyl, for example methyl, ethyl and normal-butyl; Branched-alkyl, for example sec.-propyl, isobutyl-, the tertiary butyl and neo-pentyl; And cyclic alkyl, for example cyclohexyl and ring octyl group.Described alkyl can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group and cyano group.
With A in the following formula 1To A 10The aralkyl example be phenmethyl, styroyl, 2-methylbenzene methyl, 3-methylbenzene methyl, 4-methylbenzene methyl, 2,6-dimethyl benzene methyl and 3,5-dimethyl benzene methyl.Aralkyl can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With A in the following formula 1To A 10The aryl example be phenyl, tolyl and mesityl.Described aryl can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With A in the following formula 1To A 10The silyl example be single silyl, for example methyl-silicane base, ethyl silicane base and phenyl silyl of replacing; Two replace silyl, for example dimetylsilyl, diethylsilane base and diphenylmethyl silylation; With three replacement silyl, for example trimethyl silyl, trimethoxysilyl, dimethylmethoxysilylgroups groups, methyl dimethoxy oxygen base silyl, triethylsilyl, triethoxysilyl, three-n-propyl silyl, triisopropyl silyl, three-normal-butyl silyl, three-sec-butyl silyl, t-butyldimethylsilyl, tri-iso-butylsilyl, t-butyldiphenylsilyl, cyclohexyl dimetylsilyl, thricyclohexyl silyl and triphenyl silyls.Described silyl can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With A in the following formula 1To A 10The siloxy-example be trimethylsiloxy, the trimethoxy siloxy-, dimethyl methoxy base siloxy-, methyl dimethoxy oxygen base siloxy-, silicoheptane alcoxyl base, triethoxy-silicane oxygen base, three-n-propyl siloxy-, the triisopropyl siloxy-, three-normal-butyl siloxy-, three-sec-butyl siloxy-, the t-butyldimethylsilyloxy base, the triisobutyl siloxy-, the tert-butyl diphenyl siloxy-, cyclohexyl dimethylsilane oxygen base, thricyclohexyl siloxy-and triphenyl siloxy-.Siloxy-can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With A in the following formula 1To A 10The alkoxyl group example be the line style alkoxyl group, for example methoxyl group, oxyethyl group and n-butoxy; Branched alkoxy, for example isopropoxy, isobutoxy, tert.-butoxy and neopentyl oxygen; And cyclic alkoxy, for example cyclohexyloxy and ring octyloxy.Alkoxyl group can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With A in the following formula 1To A 10The aralkoxy example be benzyloxy, styroyl oxygen base, 2-methyl benzyloxy, 3-methyl benzyloxy, 4-methyl benzyloxy, 2,6-benzyloxy-dimethyl and 3,5-benzyloxy-dimethyl.Described aralkoxy can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With A in the following formula 1To A 10The aryloxy example be phenoxy group, the 2-methylphenoxy, 2-ethyl phenoxy group, 2-n-propyl phenoxy group, 2-sec.-propyl phenoxy group, 2-normal-butyl phenoxy group, 2-isobutyl-phenoxy group, 2-tertiary butyl phenoxy group, the 3-methylphenoxy, 3-sec.-propyl phenoxy group, 3-normal-butyl phenoxy group, 3-tertiary butyl phenoxy group, the 4-methylphenoxy, 4-sec.-propyl phenoxy group, 4-normal-butyl phenoxy group, 4-tertiary butyl phenoxy group, 2, the 3-dimethyl phenoxy, 2, the 4-dimethyl phenoxy, 2, the 5-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 3, the 5-dimethyl phenoxy, 2,6-di-isopropyl phenoxy group, 2,6-di-t-butyl phenoxy group and naphthyloxy.Aryloxy can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group, silyl and cyano group.
With A in the following formula 1To A 10Amino example be linear alkyl amino, for example N-methylamino, N-ethylamino, N-normal-butyl amino, N, N-dimethylamino, N, N-diethylamino and N, N-di-n-butyl amino; Branched-alkyl amino, N for example, N-diisopropylaminoethyl, N, N-diisobutyl amino, N, N-two-tertiary butyl amino and N, N-di neo-pentyl amino; With cyclic alkyl amino, N for example, N-dicyclohexyl amino and N, N-two ring octyl group amino.Amino can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group and cyano group.
With A in the following formula 1To A 10The amide group example be ethanamide group, N-normal-butyl ethanamide group, N-methylacetamide group, N-ethyl acetamide group, N-normal-butyl hexanamide group, Isopropamide group, isobutyramide group, t-butyl carboxamide group, pivalyl amine groups, Cyclohexamide group (cyclohexanamide group) and cyclooctylamine group (cyclooctanamide group).
With A in the following formula 1To A 10The imide group example be succinimide group, maleimide base group and phthalimide-based group.Imide group can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group and cyano group.
With A in the following formula 1To A 10The sulfenyl example be the line style alkylthio, for example methylthio group, ethylmercapto group and positive butylthio; Branching alkylthio, for example iprotiazem base, isobutyl sulfenyl, uncle's butylthio and new penta sulfenyl; With the ring-type alkylthio, for example hexamethylene sulfenyl and cyclooctasulfur base.Sulfenyl can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group and cyano group.
Wherein, A 1To A 10Be preferably hydrogen atom, halogen atom or have the alkyl of 1 to 10 carbon atom; More preferably hydrogen atom or methyl; With further preferred hydrogen atom.
A 3And A 4, or A 5And A 6Can be bonded to ring each other.The example of ring be that aliphatic series is encircled, for example tetramethylene ring, pentamethylene ring and cyclohexane ring, and aromatic ring.Those rings can have substituting group, for example halogen atom,-oxyl, nitro, sulfonate group and cyano group.
A in the formula (1) 7And A 8Between relative configuration be not particularly limited.This configuration is preferably trans by following formula (2) expression, so that improve the thermotolerance of diene polymer of the present invention; And from the viewpoint of the excellent heat resistance of diene polymer, by the unit of formula (2) expression preferably with 50 moles of % or bigger, more preferably 95 moles of % or bigger amount are comprised in the diene polymer, and the unitary total amount of being represented by formula (1) is 100 moles of %:
Figure A20081008109600111
Those of definition are identical in all symbols that comprise in its Chinese style (2) and the formula (1).
Above-mentioned trans ratio adopts the chloroform-d that uses polymkeric substance of the present invention 1Solution obtains 13The C-NMR spectrometry. 13The peak (i) that 45 to 48ppm places present in the C-NMR spectrum belongs to the carbon atom with transconfiguration, and wherein the peak that presents, 39 to 42ppm places (ii) belongs to the carbon atom with cis-configuration, and condition is to belong to chloroform-d 1The peak present at the 77ppm place.Therefore, trans ratio (mole %) is obtained by following formula:
Trans ratio (mole %)
Area+peak area (ii) of the area at=peak (i) * 100/[peak (i)].
The taxis of polymkeric substance of the present invention determined by the absolute configuration of two unsymmetrical carbons, these two unsymmetrical carbons respectively with A 7And A 8Connect and be present in the main chain that has by the unitary polymkeric substance of formula (1) expression.In view of described taxis, there are four kinds of polymkeric substance, (a) erythro-diisotactic polymer, (b) erythro-disyndiotactic polymer, (c) threo-diisotactic polymer and (d) threo-disyndiotactic polymer are shown below:
Figure A20081008109600121
(a) erythro-diisotactic polymer
Figure A20081008109600122
(b) erythro-disyndiotactic polymer
(c) threo-diisotactic polymer
Figure A20081008109600124
(d) threo-disyndiotactic polymer
C wherein 1In the expression (1) with A 3And A 4The carbon atom of bonding; C 2The expression wherein with A 5And A 6The carbon atom of bonding; C 1And C 2Between curve be equivalent to be present in and A 3And A 4The carbon atom of bonding and and A 5And A 6Tree-like key between the carbon atom of bonding (tree bonds); Be omitted with being included in by other carbon atom in the unit of formula (1) expression and other substituting group.
Above-mentioned four kinds of polymkeric substance are defined in Encyclopedia of Polymer Science andEngineering (USA), second edition, 10 volumes, 191-203 page or leaf, John Wiley ﹠amp; Sons, 1987.
The taxis of polymkeric substance of the present invention is not particularly limited.Viewpoint from the polymkeric substance for preparing its excellent heat resistance, polymkeric substance of the present invention is that (i) is to be preferably greater than 25 moles of %, more preferably 30 moles of % or more, with further preferred 50 moles of % or more measurer the polymkeric substance of two isotactic triad of erythro or threo-diisotactic triad is arranged, unitary total amount by formula (1) expression is 100 moles of %, or (ii) to be preferably greater than 25 moles of %, more preferably 30 moles of % or more, with further preferred 50 moles of % or more measurer the polymkeric substance of two syndiotaxy triad of erythro or threo-disyndiotactic triad being arranged, is 100 moles of % by the unitary total amount of formula (1) expression.
Above-mentioned taxis is by using polymkeric substance of the present invention at chloroform-d 1In solution obtain 13The C-NMR spectrum is determined. 13The peak that 46.2 to 46.6ppm places present in the C-NMR spectrum (iii) belongs to the carbon atom derived from the threo-diisotactic triad, wherein the peak that presents, 46.9 to 47.3ppm places (iv) belongs to the carbon atom derived from the threo-disyndiotactic triad, and condition is to belong to chloroform-d 1The peak present at the 77ppm place.
Therefore, the ratio of above-mentioned threo-diisotactic triad (%) is obtained by following formula:
The ratio of threo-diisotactic triad (%)
=peak area * area+peak (iii), 100/[peak area (iv) (iii)];
With
The ratio of above-mentioned threo-disyndiotactic triad (%) is obtained by following formula:
The ratio of threo-disyndiotactic triad (%)
=peak area * area+peak (iii), 100/[peak area (iv) (iv)].
Z in the formula (3) is preferably methyl (n=1, A 9=H and A 10=H), or have alkyl (n=2 to 20, the A of 2 to 20 carbon atoms 9=H, and A 10=H).
The compound of formula (3) expression can be as known in the art.The example is the diallyl carboxylicesters.Its particularly preferred example is 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, 5-allyl group-5-((2E)-pentenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, 5-allyl group-5-((2E)-2-hexenyl)-2,2-dimethyl-1,3-diox-4,6-diketone, 5-allyl group-5-((2E)-2-heptenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, 5-allyl group-5-((2E)-2-octenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, 5-allyl group-5-((2E)-2-nonene base)-2,2-dimethyl-1,3-diox-4,6-diketone and 5-allyl group-5-((2E)-2-tridecylene base)-2,2-dimethyl-1,3-diox-4,6-diketone.
The homopolymer of the example of polymkeric substance of the present invention for obtaining by the various above-claimed cpds of homopolymerization.The representative example of described homopolymer is poly--5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, poly--5-allyl group-5-((2E)-pentenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, poly--5-allyl group-5-((2E)-2-hexenyl)-2,2-dimethyl-1,3-diox-4,6-diketone, poly--5-allyl group-5-((2E)-2-heptenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, poly--5-allyl group-5-((2E)-2-octenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, poly--5-allyl group-5-((2E)-2-nonene base)-2,2-dimethyl-1,3-diox-4,6-diketone and poly--5-allyl group-5-((2E)-2-tridecylene base)-2,2-dimethyl-1,3-diox-4,6-diketone.
Polymkeric substance of the present invention can prepare by the compound of polymerization by formula (3) expression.Described polymerization is preferably carried out in the presence of the polymerizing catalyst that contacts formation by transistion metal compound with organo-aluminium compound and/or boron compound.
Described transistion metal compound is not particularly limited,, and can be compound as known in the art as long as it has the addition polymerization activity.Wherein, the transistion metal compound that preferably has the transition metal of 4 to 10 families in the periodic table of elements or lanthanon.The example of transistion metal compound is by those of following formula (4) expression, and mu-oxo (transistion metal compound of μ-oxo), this mu-oxo transistion metal compound is by making transistion metal compound and water react the dimer that obtains:
L aM 1X 1 b (4)
M wherein 1Be 4 to 10 families of the periodic table of elements (IUPAC 1985) or the transition metal atoms of lanthanon; L contains the anionic group of cyclopentadiene or has heteroatomic group, and when having a plurality of L, and they each other can be directly or via the group bonding with carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom; X 1For halogen atom or have the alkyl of 1 to 20 carbon atom; A is for satisfying the number of 0＜a≤8; With the number of b for satisfied 0＜a≤8.
M 1Example be titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickle atom, palladium atom, samarium atom and ytterbium atom.
The above-mentioned example that contains the anionic group L of cyclopentadiene is cyclopentadienyl, has substituent cyclopentadienyl, indenyl, has substituent indenyl, fluorenyl and have substituent fluorenyl.
The particular example that contains the anionic group of cyclopentadiene is η 5-cyclopentadienyl, η 5-methyl cyclopentadienyl, η 5-tertiary butyl cyclopentadienyl, η 5-1,2-dimethyl cyclopentadienyl, η 5-1,3-dimethyl cyclopentadienyl, η 5-1-the tertiary butyl-2-methyl cyclopentadienyl, η 5-1-the tertiary butyl-3-methyl cyclopentadienyl, η 5-1-methyl-2-sec.-propyl cyclopentadienyl, η 5-1-methyl-3-sec.-propyl cyclopentadienyl, η 5-1,2,3-trimethylammonium cyclopentadienyl, η 5-1,2,4-trimethylammonium cyclopentadienyl, η 5-tetramethyl-ring pentadienyl, η 5-pentamethyl-cyclopentadienyl, η 5-indenyl, η 5-4,5,6,7-tetrahydro indenyl, η 5-2-methyl indenyl, η 5-3-methyl indenyl, η 5-4-methyl indenyl, η 5-5-methyl indenyl, η 5-6-methyl indenyl, η 5-7-methyl indenyl, η 5-2-tertiary butyl indenyl, η 5-3-tertiary butyl indenyl, η 5-4-tertiary butyl indenyl, η 5-5-tertiary butyl indenyl, η 5-6-tertiary butyl indenyl, η 5-7-tertiary butyl indenyl, η 5-2,3-dimethyl indenyl, η 5-4,7-dimethyl indenyl, η 5-2,4,7-trimethylammonium indenyl, η 5-2-methyl-4-sec.-propyl indenyl, η 5-4,5-benzo indenyl, η 5-2-methyl-4,5-benzo indenyl, η 5-4-phenyl indenyl, η 5-2-methyl-5-phenyl indenyl, η 5-2-methyl-4-phenyl indenyl, η 5-2-methyl-4-naphthyl indenyl, η 5-fluorenyl, η 5-2,7-dimethyl fluorenyl and η 5-2,7-two-tertiary butyl fluorenyl.
The above-mentioned heteroatoms example that has in the heteroatomic group L is Sauerstoffatom, sulphur atom, nitrogen-atoms and phosphorus atom.Having heteroatomic examples of groups is alkoxyl group; Aryloxy; Thio alkoxy (thioalkoxy); Thio-aryloxy (thioaryloxy); Alkylamino; Arylamino; Alkyl phosphino-(alkylphosphino); Aryl phosphino-(arylphosphino); In its ring, contain aromatic series or the aliphatic heterocyclic group that is selected from least one atom in Sauerstoffatom, sulphur atom, nitrogen-atoms and the phosphorus atom; And chelating ligand.
Having heteroatomic examples of groups is alkoxyl group, for example methoxyl group, oxyethyl group, propoxy-and butoxy; Aryloxy, for example phenoxy group, 2-methylphenoxy, 2,6-dimethyl phenoxy, 2,4,6-trimethylammonium phenoxy group, 2-ethyl phenoxy group, 4-n-propyl phenoxy group, 2-sec.-propyl phenoxy group, 2,6-di-isopropyl phenoxy group, 4-sec-butyl phenoxy group, 4-tertiary butyl phenoxy group, 2,6-two-sec-butyl phenoxy group, the 2-tertiary butyl-4-methylphenoxy and 2,6-two-tertiary butyl phenoxy group; Has substituent aryloxy, 4-methoxyl group phenoxy group, 2 for example, 6-dimethoxy phenoxy group, 3,5-dimethoxy phenoxy group, 2-chlorophenoxy, 4-nitroso-group phenoxy group, 4-nitrophenoxy, 2-amino-benzene oxygen, 3-amino-benzene oxygen, the amino sulfo-phenoxy group of 4-, 2,3,6-Trichlorophenoxy and 2,4,6-trifluoromethoxy phenoxy base; Thio alkoxy, for example sulfo-methoxyl group; Alkylamino, for example dimethylamino, diethylamino, dipropyl amino, sec.-propyl amino and tertiary butyl amino; Arylamino, for example diphenyl amino; Pyrryl; Phosphino-(phosphino), for example dimethyl phosphino-(dimethylphosphino); With aryl dioxy base group, for example 2-(2-oxygen-1-propyl group) phenoxy group group, pyrocatechol base group, Resorcinol group, 4-isopropylcatechol base group, 3-methoxyl group pyrocatechol base group, 1,8-dihydroxyl naphthyl group, 1,2-dihydroxyl naphthyl group, 2,2 '-'-biphenyl diphenol group, 1,1 '-two-beta naphthal group, 2,2 '-dihydroxyl-6,6 '-dimethyl diphenyl group, 4,4 ', 6,6 '-four-tertiary butyl-2,2 '-methylene radical two phenoxy group groups and 4,4 ', 6,6 '-tetramethyl--2,2 '-isobutylene two phenoxy group groups.
Above-mentioned chelating ligand in having heteroatomic examples of groups represents to have the part of a plurality of coordinations position.The example is methyl ethyl diketone (acetylacetonate), diimine (diimine), oxazoline (oxazoline), bisoxazoline (bisoxazoline), terpyridyl (terpyridine), acyl group hydrazone, diethylenetriamine, Triethylenetetramine (TETA), porphyrin, crown ether and kryptofix 222.
As mentioned above, when having a plurality of L, they each other Direct Bonding or via group bonding with carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom (that is, a plurality of anionic groups that contain cyclopentadiene can bonding; A plurality of have heteroatomic group can bonding; Perhaps containing the anionic group of cyclopentadiene and have heteroatomic group can bonding).Examples of groups with carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom is an alkylidene group, for example ethylidene and propylidene; Has substituent alkylidene group, for example dimethylated methylene base (isopropylidene) and phenylbenzene methylene radical; Silylene; Have substituent silylene, for example dimethylated methylene is silica-based, phenylbenzene silylene and tetramethyl-two silylenes; With heteroatoms for example nitrogen-atoms, Sauerstoffatom, sulphur atom and phosphorus atom.
X in the formula (4) 1The example of halogen atom be fluorine atom, chlorine atom, bromine atoms and iodine atom, and X wherein 1The example of alkyl with 1 to 20 carbon atom be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, phenyl and phenmethyl.
Determine the number separately of " a " and " b " in the formula (4), so that consider M 1, L and X 1Valence state separately, be neutrality by the electric charge of the transistion metal compound of formula (4) expression.
M wherein 1For other example by the transistion metal compound of formula (4) expression of titanium atom is (tertiary butyl amido) tetramethyl-ring pentadienyl-1; 2-ethane two basic titanium dichloride ((tert-butylamido) tetramethylcyclopentadienyl-1; 2-ethanediyltitaniumdichloride); (tertiary butyl amido) tetramethyl-ring pentadienyl-1; 2-ethane two basic dimethyl titaniums; (tertiary butyl amido) tetramethyl-ring pentadienyl-1; 2-ethane two basic diphenyl-methyl titaniums; (methyl amido) tetramethyl-ring pentadienyl-1; 2-ethane two basic titanium dichloride; (ethyl amido) tetramethyl-ring pentadienyl-1; 2-ethane two basic titanium dichloride; (tertiary butyl amido) tetramethyl-ring pentadienyl dimethylsilane titanium dichloride; (tertiary butyl amido) tetramethyl-ring pentadienyl dimethylsilane dimethyl titanium; (tertiary butyl amido) tetramethyl-ring pentadienyl dimethylsilane diphenyl-methyl titanium; (phenmethyl amido) tetramethyl-ring pentadienyl dimethylsilane titanium dichloride; (phenyl phosphorus base) tetramethyl-ring pentadienyl dimethylsilane diphenyl-methyl titanium; (tertiary butyl amido) indenyl-1; 2-ethane two basic titanium dichloride; (tertiary butyl amido) indenyl-1; 2-ethane two basic dimethyl titaniums; (tertiary butyl amido) tetrahydro indenyl-1; 2-ethane two basic titanium dichloride; (tertiary butyl amido) tetrahydro indenyl-1; 2-ethane two basic dimethyl titaniums; (tertiary butyl amido) fluorenyl-1; 2-ethane two basic titanium dichloride; (tertiary butyl amido) fluorenyl-1; 2-ethane two basic dimethyl titaniums; (tertiary butyl amido) indenyl dimethylsilane titanium dichloride; (tertiary butyl amido) indenyl dimethylsilane dimethyl titanium; (tertiary butyl amido) tetrahydro indenyl dimethylsilane titanium dichloride; (tertiary butyl amido) tetrahydro indenyl dimethylsilane dimethyl titanium; (tertiary butyl amido) fluorenyl dimethylsilane titanium dichloride; (tertiary butyl amido) fluorenyl dimethylsilane dimethyl titanium; (dimethylaminomethyl) tetramethyl-ring pentadienyl titanium dichloride (III); (dimethyl aminoethyl) tetramethyl-ring pentadienyl titanium dichloride (III); (dimethylaminopropyl) tetramethyl-ring pentadienyl titanium dichloride (III); (N-pyrrolidyl ethyl) tetramethyl-ring pentadienyl titanium dichloride; (B-dimethylamino boron mix benzene (borabenzene)) cyclopentadienyl zirconium dichloride; cyclopentadienyl (9-trimethylphenyl boron mix anthryl) zirconium dichloride; 2; 2 '-two (the 4-methyl-6-tert butyl phenoxy) titanium dichloride of sulphur; 2; 2 '-two [4-methyl-6-(1-methylethyl) phenoxy group] titanium dichloride of sulphur; 2; 2 '-sulphur two [4; the 6-dimethyl phenoxy] titanium dichloride; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenoxy) titanium dichloride; 2; 2 '-ethylenebis (4-methyl-6-tert butyl phenoxy) titanium dichloride; 2; 2 '-two (the 4-methyl-6-tert butyl phenoxy) titanium dichloride of sulfinyl; 2; 2 '-(4; 4 '; 6; 6 '-tetra-tert-1; 1 '-two phenoxy groups (biphenoxy)) titanium dichloride; 2; 2 '-two (4-methyl-6-tert butyl phenoxy) the diisopropoxy titaniums (2 of sulphur; 2 '-thiobis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide); 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenoxy) diisopropoxy titanium; 2; 2 '-ethylenebis (4-methyl-6-tert butyl phenoxy) diisopropoxy titanium; 2; 2 '-two (4-methyl-6-tert butyl phenoxy) the diisopropoxy titaniums of sulfinyl; (di-t-butyl-1; 3-propane diamido) titanium dichloride ((di-tert-butyl-1; 3-propanediamido) titanium dichloride); (dicyclohexyl-1; 3-propane diamido) titanium dichloride; [two (trimethyl silyl)-1; 3-propane diamido] titanium dichloride; [two (t-butyldimethylsilyl)-1; 3-propane diamido] titanium dichloride; [two (2; the 6-3,5-dimethylphenyl)-1; 3-propane diamido] titanium dichloride; [two (2; the 6-diisopropyl phenyl)-1; 3-propane diamido] titanium dichloride; [two (2; the 6-di-tert-butyl-phenyl)-1; 3-propane diamido] titanium dichloride; [two (triisopropyl silyl) naphthalene diamido] titanium dichloride; [two (trimethyl silyl) naphthalene diamido] titanium dichloride; [two (t-butyldimethylsilyl) naphthalene diamido] titanium dichloride; [two (t-butyldimethylsilyl) naphthalene diamido] dibrominated titanium; [hydrogen three (3; 5-dimethyl pyrazole base) boric acid ester] titanous chloride; [hydrogen three (3; 5-dimethyl pyrazole base) boric acid ester] titanium tribromide; [hydrogen three (3; 5-dimethyl pyrazole base) boric acid ester] titanium triiodide; [hydrogen three (3; 5-diethyl pyrazolyl) boric acid ester] titanous chloride; [hydrogen three (3; 5-diethyl pyrazolyl) boric acid ester] titanium tribromide; [hydrogen three (3; 5-diethyl pyrazolyl) boric acid ester] titanium triiodide; [hydrogen three (3; 5-di-t-butyl pyrazolyl) boric acid ester] titanous chloride; [hydrogen three (3; 5-di-t-butyl pyrazolyl) boric acid ester] titanium tribromide; [hydrogen three (3; 5-di-t-butyl pyrazolyl) boric acid ester] titanium triiodide; [three (3; 5-dimethyl pyrazole base) methyl] titanous chloride; [three (3; 5-dimethyl pyrazole base) methyl] titanium tribromide; [three (3; 5-dimethyl pyrazole base) methyl] titanium triiodide; [three (3; 5-diethyl pyrazolyl) methyl] titanous chloride; [three (3; 5-diethyl pyrazolyl) methyl] titanium tribromide; [three (3; 5-diethyl pyrazolyl) methyl] titanium triiodide; [three (3; 5-di-t-butyl pyrazolyl) methyl] titanous chloride; [three (3; 5-di-t-butyl pyrazolyl) methyl] titanium tribromide; [three (3,5-di-t-butyl pyrazolyl) methyl] titanium triiodide; mu-oxo two [isopropylidene (cyclopentadienyl) (2-phenoxy group) titanium chloride] (μ-oxobis[isopropylidene (cyclopentadienyl) is titaniumchloride (2-phenoxy)]); mu-oxo two [isopropylidene (cyclopentadienyl) (2-phenoxy group) methoxyl group titanium]; mu-oxo two [isopropylidene (cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium chloride]; mu-oxo two [isopropylidene (cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) methoxyl group titanium]; mu-oxo two [isopropylidene (methyl cyclopentadienyl) (2-phenoxy group) titanium chloride]; mu-oxo two [isopropylidene (methyl cyclopentadienyl) (2-phenoxy group) methoxyl group titanium]; mu-oxo two [isopropylidene (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium chloride]; mu-oxo two [isopropylidene (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) methoxyl group titanium]; mu-oxo two [isopropylidene (tetramethyl-ring pentadienyl) (2-phenoxy group) titanium chloride]; mu-oxo two [isopropylidene (tetramethyl-ring pentadienyl) (2-phenoxy group) methoxyl group titanium]; mu-oxo two [isopropylidene (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium chloride]; mu-oxo two [isopropylidene (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) methoxyl group titanium]; mu-oxo two [dimethylated methylene silica-based (cyclopentadienyl) (2-phenoxy group) titanium chloride]; mu-oxo two [dimethylated methylene silica-based (cyclopentadienyl) (2-phenoxy group) methoxyl group titanium]; mu-oxo two [dimethylated methylene silica-based (cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium chloride]; mu-oxo two [dimethylated methylene silica-based (cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) methoxyl group titanium]; mu-oxo two [dimethylated methylene silica-based (methyl cyclopentadienyl) (2-phenoxy group) titanium chloride]; mu-oxo two [dimethylated methylene silica-based (methyl cyclopentadienyl) (2-phenoxy group) methoxyl group titanium]; mu-oxo two [dimethylated methylene silica-based (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium chloride]; mu-oxo two [dimethylated methylene silica-based (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) methoxyl group titanium]; mu-oxo two [dimethylated methylene silica-based (tetramethyl-ring pentadienyl) (2-phenoxy group) titanium chloride]; mu-oxo two [dimethylated methylene silica-based (tetramethyl-ring pentadienyl) (2-phenoxy group) methoxyl group titanium]; mu-oxo two [dimethylated methylene silica-based (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium chloride]; mu-oxo two [dimethylated methylene silica-based (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) methoxyl group titanium]; two-mu-oxo two [isopropylidene (cyclopentadienyl) (2-phenoxy group) titanium]; two-mu-oxo two [isopropylidene (cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium]; two-mu-oxo two [isopropylidene (methyl cyclopentadienyl) (2-phenoxy group) titanium]; two-mu-oxo two [isopropylidene (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium]; two-mu-oxo two [isopropylidene (tetramethyl-ring pentadienyl) (2-phenoxy group) titanium]; two-mu-oxo two [isopropylidene (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium]; two-mu-oxo two [dimethylated methylene silica-based (cyclopentadienyl) (2-phenoxy group) titanium]; two-mu-oxo two [dimethylated methylene silica-based (cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium]; two-mu-oxo two [dimethylated methylene silica-based (methyl cyclopentadienyl) (2-phenoxy group) titanium]; two-mu-oxo two [dimethylated methylene silica-based (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium]; two-mu-oxo two [dimethylated methylene silica-based (tetramethyl-ring pentadienyl) (2-phenoxy group) titanium] and two-mu-oxo two [dimethylated methylene silica-based (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy group) titanium].
M wherein 1The compound of example for the transistion metal compound of the formula (4) of zirconium atom or hafnium atom expression for obtaining by term " titanium " with term " zirconium " or the above-mentioned titanium compound of " hafnium " replacement.
M wherein 1For the example by the transistion metal compound of formula (4) expression of vanadium atom is vanadium acetylacetonate (vanadium acetylacetonate), vanadium tetrachloride and vanadium oxytrichloride (vanadium oxytrichloride).
M wherein 1For the example by the transistion metal compound of formula (4) expression of samarium atom is two (pentamethyl-cyclopentadienyl) samariums of methyltetrahydrofuran.
M wherein 1For the example by the transistion metal compound of formula (4) expression of ytterbium atom is two (pentamethyl-cyclopentadienyl) ytterbiums of methyltetrahydrofuran.
M wherein 1The compound of example for nickle atom, cobalt atom, rhodium atom or ruthenium atom for obtaining by term " palladium " with term " nickel ", " cobalt ", the above-mentioned palladium compound of " rhodium " or " ruthenium " replacement by the transistion metal compound of formula (4) expression.
Wherein M is that the example by the transistion metal compound of formula (4) expression of iron atom is 2,6-pair-[1-(2,6-3,5-dimethylphenyl imino-) ethyl] pyridine ferrous chloride (2,6-bis-[1-(2,6-dimethylphenylimino) ethyl] pyridine iron dichloride), 2,6-pair-[1-(2,6-diisopropyl phenyl imino-) ethyl] the pyridine ferrous chloride, 2,6-pair-[1-(2,6-dichlorophenyl imino-) ethyl] the pyridine ferrous chloride, 2,6-pair-[1-(2-methyl-6-isopropyl phenyl imino-) ethyl] pyridine ferrous chloride, 2,6-pair-[1-(2-tert-butyl-phenyl imino-) ethyl] pyridine ferrous chloride, [hydrogen three (3,5-dimethyl pyrazole base) boric acid ester] iron(ic) chloride, [hydrogen three (3,5-dimethyl pyrazole base) boric acid ester] iron bromide, [hydrogen three (3,5-dimethyl pyrazole base) boric acid ester] ferric iodide, [hydrogen three (3,5-dimethyl pyrazole base) boric acid ester] methyl iron, [hydrogen three (3,5-dimethyl pyrazole base) boric acid ester] ethyl iron, [hydrogen three (3,5-dimethyl pyrazole base) boric acid ester] allyl group iron, [hydrogen three (3,5-dimethyl pyrazole base) boric acid ester] methylallyl iron, [hydrogen three (3,5-diethyl pyrazolyl) boric acid ester] iron(ic) chloride, [hydrogen three (3,5-diethyl pyrazolyl) boric acid ester] iron bromide, [hydrogen three (3,5-diethyl pyrazolyl) boric acid ester-ferric iodide, [hydrogen three (3,5-diethyl pyrazolyl) boric acid ester] methyl iron, [hydrogen three (3,5-diethyl pyrazolyl) boric acid ester] ethyl iron, [hydrogen three (3,5-diethyl pyrazolyl) boric acid ester] allyl group iron, [hydrogen three (3,5-diethyl pyrazolyl) boric acid ester] methylallyl iron, [hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester] iron(ic) chloride, [hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester] iron bromide, [hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester] ferric iodide, [hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester] methyl iron, [hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester] ethyl iron, [hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester] allyl group iron and [hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester] methylallyl iron.
M wherein 1The compound of example for cobalt atom or nickle atom for obtaining by term " iron " with term " cobalt " or the above-mentioned iron cpd of " nickel " replacement by the transistion metal compound of formula (4) expression.
Above-mentioned transistion metal compound can with its two or more be used in combination.
Described transistion metal compound is preferably the compound by following formula [I] expression:
Figure A20081008109600381
M wherein 2Transition metal atoms for the periodic table of elements 10 families; R 3And R 4Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy or aryloxy independently of one another; R 5And R 6Independently of one another for having the alkyl of 1 to 30 carbon atom; And R 7And R 8Be hydrogen atom or alkyl independently of one another with 1 to 20 carbon atom, and R 7And R 8Can be bonded to ring each other.
M 2Be preferably nickle atom or palladium atom, and palladium atom more preferably.
R 3And R 4The example of halogen atom be fluorine atom, chlorine atom, bromine atoms and iodine atom.Wherein preferably chlorine atom or bromine atoms.
R 3And R 4The example of alkyl be linear alkyl, for example methyl, ethyl and normal-butyl; Branched-alkyl, for example sec.-propyl, isobutyl-, the tertiary butyl and neo-pentyl; And cycloalkyl, for example cyclohexyl and ring octyl group.Wherein, linear alkyl preferably more preferably has the linear alkyl of 1 to 12 carbon atom and methyl further preferably.
R 3And R 4The example of aralkyl be phenmethyl and styroyl.Phenmethyl preferably wherein.
R 3And R 4The example of aryl be phenyl, naphthyl, 4-tolyl, mesityl and xenyl.Wherein preferably phenyl, 4-tolyl or mesityl.
R 3And R 4The example of silyl be mono-substituted silyl, for example methyl-silicane base, ethyl silicane base and phenyl silyl; Dibasic silyl, for example dimetylsilyl, diethylsilane base and diphenylmethyl silylation; With trisubstituted silyl, for example trimethyl silyl, trimethoxysilyl, dimethylmethoxysilylgroups groups, methyl dimethoxy oxygen base silyl, triethylsilyl, triethoxysilyl, three n-propyl silyls, triisopropyl silyl, three normal-butyl silyls, three sec-butyl silyls, t-butyldimethylsilyl, tri-iso-butylsilyl, t-butyldiphenylsilyl, cyclohexyl dimetylsilyl, thricyclohexyl silyl and triphenyl silyl.Wherein, preferably trisubstituted silyl and more preferably trimethyl silyl, triethylsilyl, triphenyl silyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, cyclohexyl dimetylsilyl or triisopropyl silyl.
R 3And R 4The example of siloxy-be trimethylsiloxy group, the trimethoxy siloxy-, dimethyl methoxy base siloxy-, methyl dimethoxy oxygen base siloxy-, silicoheptane alcoxyl base, triethoxy-silicane oxygen base, three n-propyl siloxyies, the triisopropyl siloxy-, three normal-butyl siloxyies, three sec-butyl siloxyies, the t-butyldimethylsilyloxy base, the triisobutyl siloxy-, the tert-butyl diphenyl siloxy-, cyclohexyl dimethylsilane oxygen base, thricyclohexyl siloxy-and triphenyl siloxy-.Wherein, preferably trimethylsiloxy group, silicoheptane alcoxyl base, triphenyl siloxy-, t-butyldimethylsilyloxy base, tert-butyl diphenyl siloxy-, cyclohexyl dimethylsilane oxygen base.
R 3And R 4The example of alkoxyl group be methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, neopentyl oxygen, positive hexyloxy, n-octyloxy, n-dodecane oxygen base, Pentadecane oxygen base and NSC 62789 oxygen base.Wherein, preferably have the alkoxyl group of 1 to 20 carbon atom and more preferably methoxyl group, oxyethyl group, isopropoxy or tert.-butoxy.
R 3And R 4The example of aralkoxy be benzyloxy, (2-aminomethyl phenyl) methoxyl group, (3-aminomethyl phenyl) methoxyl group, (4-aminomethyl phenyl) methoxyl group, (2, the 3-3,5-dimethylphenyl) methoxyl group, (2, the 4-3,5-dimethylphenyl) methoxyl group, (2, the 5-3,5-dimethylphenyl) methoxyl group, (2, the 6-3,5-dimethylphenyl) methoxyl group, (3, the 4-3,5-dimethylphenyl) methoxyl group, (3, the 5-3,5-dimethylphenyl) methoxyl group, (2,3, the 4-trimethylphenyl) methoxyl group, (2,3, the 5-trimethylphenyl) methoxyl group, (2,3, the 6-trimethylphenyl) methoxyl group, (2,4, the 5-trimethylphenyl) methoxyl group, (2,4, the 6-trimethylphenyl) methoxyl group, (3,4, the 5-trimethylphenyl) methoxyl group, (2,3,4, the 5-tetramethylphenyl) methoxyl group, (2,3,4, the 6-tetramethylphenyl) methoxyl group, (2,3,5, the 6-tetramethylphenyl) methoxyl group, (pentamethyl-phenyl) methoxyl group, (ethylphenyl) methoxyl group, (n-propyl phenyl) methoxyl group, (isopropyl phenyl) methoxyl group, (n-butylphenyl) methoxyl group, (secondary butyl phenenyl) methoxyl group, (tert-butyl-phenyl) methoxyl group, (n-hexyl phenyl) methoxyl group, (n-octyl phenyl) methoxyl group, (positive decyl phenyl) methoxyl group, naphthalene methoxyl group and anthracene methoxyl group.Benzyloxy preferably wherein.
R 3And R 4The example of aryloxy be phenoxy group, the 2-methylphenoxy, the 3-methylphenoxy, the 4-methylphenoxy, 2, the 3-dimethyl phenoxy, 2, the 4-dimethyl phenoxy, 2, the 5-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 3, the 4-dimethyl phenoxy, 3, the 5-dimethyl phenoxy, the 2-tertiary butyl-3-methylphenoxy, the 2-tertiary butyl-4-methylphenoxy, the 2-tertiary butyl-5-methylphenoxy, the 2-tertiary butyl-6-methylphenoxy, 2,3,4-trimethylammonium phenoxy group, 2,3,5-trimethylammonium phenoxy group, 2,3,6-trimethylammonium phenoxy group, 2,4,5-trimethylammonium phenoxy group, 2,4,6-trimethylammonium phenoxy group, the 2-tertiary butyl-3, the 4-dimethyl phenoxy, the 2-tertiary butyl-3, the 5-dimethyl phenoxy, the 2-tertiary butyl-3, the 6-dimethyl phenoxy, 2,6-di-t-butyl-3-methylphenoxy, the 2-tertiary butyl-4, the 5-dimethyl phenoxy, 2,6-di-t-butyl-4-methylphenoxy, 3,4,5-trimethylammonium phenoxy group, 2,3,4,5-tetramethyl-phenoxy group, the 2-tertiary butyl-3,4,5-trimethylammonium phenoxy group, 2,3,4,6-tetramethyl-phenoxy group, the 2-tertiary butyl-3,4,6-trimethylammonium phenoxy group, 2,6-di-t-butyl-3, the 4-dimethyl phenoxy, 2,3,5,6-tetramethyl-phenoxy group, the 2-tertiary butyl-3,5,6-trimethylammonium phenoxy group, 2,6-di-t-butyl-3,5-dimethyl phenoxy, the pentamethyl-phenoxy group, the ethyl phenoxy group, the n-propyl phenoxy group, the sec.-propyl phenoxy group, the normal-butyl phenoxy group, the sec-butyl phenoxy group, tertiary butyl phenoxy group, the n-hexyl phenoxy group, the n-octyl phenoxy group, positive decyl phenoxy group, naphthyloxy and anthracene oxygen base.The aryloxy that wherein preferably has 6 to 20 carbon atoms.
R 3And R 4Be preferably hydrogen atom, halogen atom, alkyl or aryl; More preferably hydrogen atom, halogen atom or have the unsubstituted linear alkyl of 1 to 12 carbon atom; Be preferably chlorine atom or methyl especially.
R 5And R 6The example of alkyl with 1 to 30 carbon atom be alkyl, aralkyl and aryl.Those groups can have for example substituting group of halogen atom,-oxyl, nitro, alkylsulfonyl and silyl.
R 5And R 6The example of alkyl be linear alkyl, for example methyl, ethyl and normal-butyl; Branched-alkyl, for example sec.-propyl, isobutyl-, the tertiary butyl and neo-pentyl; And cycloalkyl, for example cyclohexyl and ring octyl group.Wherein, branched-alkyl preferably more preferably has the branched-alkyl of 1 to 12 carbon atom and the further preferably sec.-propyl or the tertiary butyl.
R 5And R 6The example of aralkyl be phenmethyl and styroyl.Phenmethyl preferably wherein.
R 5And R 6The example of aryl be phenyl, the 2-aminomethyl phenyl, the 2-ethylphenyl, 2-n-propyl phenyl, the 2-isopropyl phenyl, the 2-n-butylphenyl, the 2-isobutyl phenenyl, 2-n-hexyl phenyl, the 4-aminomethyl phenyl, 2, the 6-3,5-dimethylphenyl, 2,6-diethyl phenyl, 2,6-di phenyl, 2, the 6-diisopropyl phenyl, 2,6-di-n-butyl phenyl, 2,6-diisobutyl phenyl, 2,6-di-n-hexyl phenyl, 2-methyl-6-ethylphenyl, 2-methyl-6-n-propyl phenyl, 2-methyl-6-isopropyl phenyl, 2-methyl-6-butyl phenyl, 2-ethyl-6-n-propyl phenyl, 2-ethyl-6-isopropyl phenyl, 2-ethyl-6-n-butylphenyl, 2-n-propyl-6-isopropyl phenyl, 2-n-propyl-6-n-butylphenyl, 2-sec.-propyl-6-n-butylphenyl, 2,4, the 6-trimethylphenyl, 2,4-dimethyl-6-(2-aminomethyl phenyl) phenyl, 2,4-dimethyl-6-(2-ethylphenyl) phenyl, 2,4-dimethyl-6-(2-n-propyl phenyl) phenyl, 2,4-dimethyl-6-(2-isopropyl phenyl) phenyl, 2,4-dimethyl-6-(2, the 6-3,5-dimethylphenyl) phenyl, 2,4-dimethyl-6-(2,6-diethyl phenyl) phenyl, 2,4-dimethyl-6-(2,6-di phenyl) phenyl, 2,4-dimethyl-6-(2, the 6-diisopropyl phenyl) phenyl, 2,4-dimethyl-6-(2-methyl-6-ethylphenyl) phenyl, 2,4-dimethyl-6-(2-methyl-6-n-propyl phenyl) phenyl, 2,4-dimethyl-6-(2-methyl-6-isopropyl phenyl) phenyl, 2,4-dimethyl-6-(2-ethyl-6-n-propyl phenyl) phenyl, 2,4-dimethyl-6-(2-ethyl-6-isopropyl phenyl) phenyl and 2,4-dimethyl-6-(1-naphthyl) phenyl.Wherein, preferably has the aryl of 6 to 30 carbon atoms and more preferably have the aryl of 7 to 30 carbon atoms.
R 7And R 8The example of alkyl with 1 to 20 carbon atom be alkyl and aryl.Those groups can have for example substituting group of halogen atom,-oxyl, nitro, alkylsulfonyl and silyl.
R 7And R 8The example of alkyl be linear alkyl, for example methyl, ethyl and normal-butyl; Branched-alkyl, for example sec.-propyl, isobutyl-, the tertiary butyl and neo-pentyl; And cycloalkyl, for example cyclohexyl and ring octyl group.Wherein, linear alkyl preferably more preferably has the linear alkyl of 1 to 12 carbon atom and further preferably methyl or ethyl.
R 7And R 8The example of aryl be phenyl, naphthyl, 4-tolyl and mesityl.Wherein, preferably have the aryl of 6 to 20 carbon atoms, more preferably have the aryl of 6 to 12 carbon atoms and further preferably phenyl or mesityl.
Work as R 7And R 8When being bonded to ring each other, the example of ring is aliphatic series ring and aromatic ring.Those rings can have substituting group.The example that forms the divalent group of aliphatic series ring is an ethylene, 1,2-cyclohexylidene, 1, the inferior norcamphyl (1,2-norbornene group), 2 of 2-, 3-butylidene, 2,3-dimethyl-2,3-butylidene and 2,4-pentylidene.The example that forms the divalent group of aromatic ring is 1,2-phenylene and naphthalene-1,8-two bases.Wherein, naphthalene-1 preferably, 8-two bases.Have R in a contained key and the formula [I] in each of these divalent groups 7Carbon atom bonding, and another wherein contained key with wherein have R 8Carbon atom bonding.
Contain two isotactic triad from preparation greater than 25 moles of %, and the viewpoint of the polymkeric substance of preferred threo-diisotactic triad, the transistion metal compound that uses among the present invention are preferably the compound of being contained by formula [I] by following formula [II] expression:
Figure A20081008109600421
M wherein 2, R 3, R 4, R 7And R 8With identical with those of definition in the following formula [I]; R 9And R 10Be hydrogen atom, halogen atom, alkyl, aralkyl, silyl, siloxy-, alkoxyl group, aralkoxy, amino, amide group, imide group or sulfenyl independently of one another; R 11And R 12Independently of one another for having the aryl of 7 to 20 carbon atoms; R 13And R 14Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another.
R 9And R 10Be preferably alkyl, more preferably have the alkyl of 1 to 12 carbon atom, and be preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl especially.
R 11And R 12Example be the 2-aminomethyl phenyl, the 3-aminomethyl phenyl, the 4-aminomethyl phenyl, 2, the 3-3,5-dimethylphenyl, 2, the 4-3,5-dimethylphenyl, 2, the 5-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 3, the 4-3,5-dimethylphenyl, 3, the 5-3,5-dimethylphenyl, 3, the 6-3,5-dimethylphenyl, naphthyl, 2-methyl isophthalic acid-naphthyl, 3-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 2,3-dimethyl-1-naphthyl, 2,4-dimethyl-1-naphthyl, 2,5-dimethyl-1-naphthyl, 2,6-dimethyl-1-naphthyl, 3,4-dimethyl-1-naphthyl, 3,5-dimethyl-1-naphthyl, 3,6-dimethyl-1-naphthyl, anthryl, 2-methyl isophthalic acid-anthryl, 3-methyl isophthalic acid 0-anthryl, 4-methyl isophthalic acid 0-anthryl, 2,3-dimethyl-10-anthryl, 2,4-dimethyl-10-anthryl, 2,5-dimethyl-10-anthryl, 2,6-dimethyl-10-anthryl, 3,4-dimethyl-10-anthryl, 3,5-dimethyl-10-anthryl, 3,6-dimethyl-10-anthryl and 2-methyl isophthalic acid 0-anthryl.Wherein, preferably have substituent phenyl, naphthyl or anthryl and further preferably 2-aminomethyl phenyl or naphthyl.
R 13And R 14Be preferably hydrogen atom or alkyl, more preferably hydrogen atom or have the alkyl of 1 to 12 carbon atom and more preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-.
In addition, contain two syndiotaxy triad from preparation greater than 25 moles of %, the viewpoint of the polymkeric substance of preferred threo-disyndiotactic triad, the transistion metal compound that uses among the present invention are preferably the compound of following formula [III] expression of being contained by formula [I]:
Figure A20081008109600431
M wherein 2, R 3, R 4, R 7And R 8With identical with those of definition in the following formula [I]; R 15, R 16, R 17And R 18Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another; R 19And R 20Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another.
R 15, R 16, R 17And R 18Be preferably hydrogen atom, alkyl or aryl, more preferably hydrogen atom, have the alkyl of 1 to 12 carbon atom or have the aryl of 6 to 20 carbon atoms and more preferably hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl or phenyl.
R 19And R 20Be preferably hydrogen atom, alkyl or aryl, more preferably hydrogen atom, have the alkyl of 1 to 12 carbon atom or have the aryl of 6 to 20 carbon atoms and more preferably hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl or phenyl.
Same by the compound of following formula [IV] expression preferably as the transistion metal compound that uses among the present invention:
Figure A20081008109600432
M wherein 3Transition metal atoms for the periodic table of elements 8 to 11 families; R 3And R 4With identical with those of definition in the following formula [I]; R 21To R 27Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another, and R 21To R 27Any two or morely can be bonded to ring each other.
M 3Be preferably iron atom, ruthenium atom, cobalt atom, rhodium atom, nickle atom, palladium atom or copper atom and further preferred iron atom or cobalt atom.
R 21To R 27The halogen atom example be fluorine atom, chlorine atom, bromine atoms and iodine atom.Wherein preferably chlorine atom or bromine atoms.
R 21To R 27The example of alkyl be linear alkyl, for example methyl, ethyl, n-propyl, normal-butyl and n-pentyl; Branched-alkyl, for example sec.-propyl, isobutyl-, the tertiary butyl and neo-pentyl; And cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and ring octyl group.Wherein, branched-alkyl preferably more preferably has the branched-alkyl of 1 to 12 carbon atom and the more preferably sec.-propyl or the tertiary butyl.
R 21To R 27The example of aralkyl be phenmethyl and styroyl.Phenmethyl preferably wherein.
R 21To R 27The example of aryl be phenyl, the 2-aminomethyl phenyl, the 2-ethylphenyl, 2-n-propyl phenyl, the 2-isopropyl phenyl, the 2-n-butylphenyl, the 2-isobutyl phenenyl, the 2-tert-butyl-phenyl, 2-n-hexyl phenyl, the 2-cyclohexyl phenyl, the 3-aminomethyl phenyl, the 3-ethylphenyl, 3-n-propyl phenyl, the 3-isopropyl phenyl, the 3-n-butylphenyl, the 3-isobutyl phenenyl, the 3-tert-butyl-phenyl, 3-n-hexyl phenyl, the 3-cyclohexyl phenyl, the 4-aminomethyl phenyl, the 4-ethylphenyl, 4-n-propyl phenyl, the 4-isopropyl phenyl, the 4-n-butylphenyl, the 4-isobutyl phenenyl, the 4-tert-butyl-phenyl, 4-n-hexyl phenyl, the 4-cyclohexyl phenyl, 2, the 6-3,5-dimethylphenyl, 2,6-diethyl phenyl, 2,6-di phenyl, 2, the 6-diisopropyl phenyl, 2,6-di-n-butyl phenyl, 2,6-diisobutyl phenyl, 2, the 6-di-tert-butyl-phenyl, 2,6-di-n-hexyl phenyl, 2,6-dicyclohexyl phenyl, 2-methyl-6-ethylphenyl, 2-methyl-6-n-propyl phenyl, 2-methyl-6-isopropyl phenyl, 2-methyl-6-n-butylphenyl, 2-methyl-6-isobutyl phenenyl, 2-methyl-6-tert butyl phenyl, 2-methyl-6-n-hexyl phenyl, 2-methyl-6-cyclohexyl phenyl, 2-ethyl-6-n-propyl phenyl, 2-ethyl-6-isopropyl phenyl, 2-ethyl-6-n-butylphenyl, 2-ethyl-6-isobutyl phenenyl, 2-ethyl-6-tert-butyl-phenyl, 2-ethyl-6-n-hexyl phenyl, 2-ethyl-6-cyclohexyl phenyl, 2-n-propyl-6-isopropyl phenyl, 2-n-propyl-6-n-butylphenyl, 2-n-propyl-6-isobutyl phenenyl, 2-n-propyl-6-tert-butyl-phenyl, 2-n-propyl-6-n-hexyl phenyl, 2-n-propyl-6-cyclohexyl phenyl, 2-sec.-propyl-6-n-butylphenyl, 2-sec.-propyl-6-isobutyl phenenyl, 2-sec.-propyl-6-tert-butyl-phenyl, 2-sec.-propyl-6-n-hexyl phenyl, 2-sec.-propyl-6-cyclohexyl phenyl, 2-normal-butyl-6-isobutyl phenenyl, 2-normal-butyl-6-tert-butyl-phenyl, 2-normal-butyl-6-n-hexyl phenyl, 2-normal-butyl-6-cyclohexyl phenyl, 2-isobutyl--6-tert-butyl-phenyl, 2-isobutyl--6-n-hexyl phenyl, 2-isobutyl--6-cyclohexyl phenyl, the 2-tertiary butyl-6-n-hexyl phenyl, the 2-tertiary butyl-6-cyclohexyl phenyl, 2-n-hexyl-6-cyclohexyl phenyl, 2, the 4-diisopropyl phenyl, 2,4-di-n-butyl phenyl, 2,4-diisobutyl phenyl, 2, the 4-di-tert-butyl-phenyl, 2,4-di-n-hexyl phenyl, 2,4-dicyclohexyl phenyl, 2-ethyl-4-aminomethyl phenyl, 2-n-propyl-4-aminomethyl phenyl, 2-sec.-propyl-4-aminomethyl phenyl, 2-normal-butyl-4-aminomethyl phenyl, 2-isobutyl--4-aminomethyl phenyl, the 2-tertiary butyl-4-aminomethyl phenyl, 2-n-hexyl-4-aminomethyl phenyl, 2-cyclohexyl-4-aminomethyl phenyl, 2-n-propyl-4-ethylphenyl, 2-sec.-propyl-4-ethylphenyl, 2-normal-butyl-4-ethylphenyl, 2-isobutyl--4-ethylphenyl, the 2-tertiary butyl-4-ethylphenyl, 2-n-hexyl-4-ethylphenyl, 2-cyclohexyl-4-ethylphenyl, 2-sec.-propyl-4-n-propyl phenyl, 2-normal-butyl-4-n-propyl phenyl, 2-isobutyl--4-n-propyl phenyl, the 2-tertiary butyl-4-n-propyl phenyl, 2-n-hexyl-4-n-propyl phenyl, 2-cyclohexyl-4-n-propyl phenyl, 2-normal-butyl-4-isopropyl phenyl, 2-isobutyl--4-isopropyl phenyl, the 2-tertiary butyl-4-isopropyl phenyl, 2-n-hexyl-4-isopropyl phenyl, 2-cyclohexyl-4-isopropyl phenyl, 2-isobutyl--4-n-butylphenyl, the 2-tertiary butyl-4-n-butylphenyl, 2-n-hexyl-4-n-butylphenyl, 2-cyclohexyl-4-n-butylphenyl, the 2-tertiary butyl-4-isobutyl phenenyl, 2-n-hexyl-4-isobutyl phenenyl, 2-cyclohexyl-4-isobutyl phenenyl, 2-n-hexyl-4-tert-butyl-phenyl, 2-cyclohexyl-4-tert-butyl-phenyl, 2-cyclohexyl-4-n-hexyl phenyl, 2, the 5-3,5-dimethylphenyl, 2,5-diethyl phenyl, 2,5-di phenyl, 2, the 5-diisopropyl phenyl, 2,5-di-n-butyl phenyl, 2,5-diisobutyl phenyl, 2, the 5-di-tert-butyl-phenyl, 2,5-di-n-hexyl phenyl, 2,5-dicyclohexyl phenyl, 2,4, the 6-trimethylphenyl, 2,4,6-triethyl phenyl, 2,4,6-three n-propyl phenyl, 2,4,6-triisopropyl phenyl, 2,4,6-three n-butylphenyl, 2,4,6-triisobutyl phenyl, 2,4,6-tri-tert phenyl, 2,4,6-three n-hexyl phenyl, 2,4,6-thricyclohexyl phenyl, 2,6-diethyl-4-aminomethyl phenyl, 2,6-di-4-aminomethyl phenyl, 2,6-di-isopropyl-4-aminomethyl phenyl, 2,6-di-n-butyl-4-aminomethyl phenyl, 2,6-diisobutyl-4-aminomethyl phenyl, 2,6-di-t-butyl-4-aminomethyl phenyl, 2,6-di-n-hexyl-4-aminomethyl phenyl, 2,6-dicyclohexyl-4-aminomethyl phenyl, 2,4-dimethyl-6-(2-aminomethyl phenyl) phenyl, 2,4-dimethyl-6-(2-ethylphenyl) phenyl, 2,4-dimethyl-6-(2-n-propyl phenyl) phenyl, 2,4-dimethyl-6-(2-isopropyl phenyl) phenyl, 2,4-dimethyl-6-(2, the 6-3,5-dimethylphenyl) phenyl, 2,4-dimethyl-6-(2,6 diethyl phenyl) phenyl, 2,4-dimethyl-6-(2,6-di phenyl) phenyl, 2,4-dimethyl-6-(2, the 6-diisopropyl phenyl) phenyl, 2,4-dimethyl-6-(2-methyl-6-ethylphenyl) phenyl, 2,4-dimethyl-6-(2-methyl-6-n-propyl phenyl) phenyl, 2,4-dimethyl-6-(2-methyl-6-isopropyl phenyl) phenyl, 2,4-dimethyl-6-(2-ethyl-6-n-propyl phenyl) phenyl, 2,4-dimethyl-6-(2-ethyl-6-isopropyl phenyl) phenyl and 2,4-dimethyl-6-(1-naphthyl) phenyl.
R 21To R 27The silyl example be single silyl, for example methyl-silicane base, ethyl silicane base and phenyl silyl of replacing; Two replace silyl, for example dimetylsilyl, diethylsilane base and diphenylmethyl silylation; With three replacement silyl, for example trimethyl silyl, trimethoxysilyl, dimethylmethoxysilylgroups groups, methyl dimethoxy oxygen base silyl, triethylsilyl, triethoxysilyl, three n-propyl silyls, triisopropyl silyl, three normal-butyl silyls, three sec-butyl silyls, t-butyldimethylsilyl, tri-iso-butylsilyl, t-butyldiphenylsilyl, cyclohexyl dimetylsilyl, thricyclohexyl silyl and triphenyl silyls.Wherein, preferably trisubstituted silyl and further preferably trimethyl silyl, triethylsilyl, triphenyl silyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, cyclohexyl dimetylsilyl or triisopropyl silyl.
R 21To R 27The example of siloxy-be trimethylsiloxy, the trimethoxy siloxy-, dimethyl methoxy base siloxy-, methyl dimethoxy oxygen base siloxy-, silicoheptane alcoxyl base, triethoxy-silicane oxygen base, three n-propyl siloxyies, the triisopropyl siloxy-, three normal-butyl siloxyies, three sec-butyl siloxyies, the t-butyldimethylsilyloxy base, the triisobutyl siloxy-, the tert-butyl diphenyl siloxy-, cyclohexyl dimethylsilane oxygen base, thricyclohexyl siloxy-and triphenyl siloxy-.Wherein, preferably trialkylsiloxy and further preferably trimethylsiloxy, silicoheptane alcoxyl base and triphenyl siloxy-, t-butyldimethylsilyloxy base, tert-butyl diphenyl siloxy-, cyclohexyl dimethylsilane oxygen base or triisopropyl siloxy-.
R 21To R 27The example of alkoxyl group be methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, neopentyl oxygen, positive hexyloxy, n-octyloxy, n-dodecane oxygen base, Pentadecane oxygen base and NSC 62789 oxygen base.Wherein, preferably methoxyl group, oxyethyl group, isopropoxy or tert.-butoxy.
R 21To R 27The example of aralkoxy be benzyloxy, (2-aminomethyl phenyl) methoxyl group, (3-aminomethyl phenyl) methoxyl group, (4-aminomethyl phenyl) methoxyl group, (2, the 3-3,5-dimethylphenyl) methoxyl group, (2, the 4-3,5-dimethylphenyl) methoxyl group, (2, the 5-3,5-dimethylphenyl) methoxyl group, (2, the 6-3,5-dimethylphenyl) methoxyl group, (3, the 4-3,5-dimethylphenyl) methoxyl group, (3, the 5-3,5-dimethylphenyl) methoxyl group, (2,3, the 4-trimethylphenyl) methoxyl group, (2,3, the 5-trimethylphenyl) methoxyl group, (2,3, the 6-trimethylphenyl) methoxyl group, (2,4, the 5-trimethylphenyl) methoxyl group, (2,4, the 6-trimethylphenyl) methoxyl group, (3,4, the 5-trimethylphenyl) methoxyl group, (2,3,4, the 5-tetramethylphenyl) methoxyl group, (2,3,4, the 6-tetramethylphenyl) methoxyl group, (2,3,5, the 6-tetramethylphenyl) methoxyl group, (pentamethyl-phenyl) methoxyl group, (ethylphenyl) methoxyl group, (n-propyl phenyl) methoxyl group, (isopropyl phenyl) methoxyl group, (n-butylphenyl) methoxyl group, (secondary butyl phenenyl) methoxyl group, (tert-butyl-phenyl) methoxyl group, (n-hexyl phenyl) methoxyl group, (n-octyl phenyl) methoxyl group, (positive decyl phenyl) methoxyl group, naphthyl methoxyl group and anthryl methoxyl group.Benzyloxy preferably wherein.
R 21To R 27The example of aryloxy be phenoxy group, the 2-methylphenoxy, the 3-methylphenoxy, the 4-methylphenoxy, 2, the 3-dimethyl phenoxy, 2, the 4-dimethyl phenoxy, 2, the 5-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 3, the 4-dimethyl phenoxy, 3, the 5-dimethyl phenoxy, the 2-tertiary butyl-3-methylphenoxy, 2-tertiary butyl 4-methylphenoxy, the 2-tertiary butyl-5-methylphenoxy, the 2-tertiary butyl-6-methylphenoxy, 2,3,4-trimethylammonium phenoxy group, 2,3,5-trimethylammonium phenoxy group, 2,3,6-trimethylammonium phenoxy group, 2,4,5-trimethylammonium phenoxy group, 2,4,6-trimethylammonium phenoxy group, the 2-tertiary butyl-3, the 4-dimethyl phenoxy, the 2-tertiary butyl-3, the 5-dimethyl phenoxy, the 2-tertiary butyl-3, the 6-dimethyl phenoxy, 2,6-di-t-butyl-3-methylphenoxy, the 2-tertiary butyl-4, the 5-dimethyl phenoxy, 2,6-di-t-butyl-4-methylphenoxy, 3,4,5-trimethylammonium phenoxy group, 2,3,4,5-tetramethyl-phenoxy group, the 2-tertiary butyl-3,4,5-trimethylammonium phenoxy group, 2,3,4,6-tetramethyl-phenoxy group, the 2-tertiary butyl-3,4,6-trimethylammonium phenoxy group, 2,6-di-t-butyl-3, the 4-dimethyl phenoxy, 2,3,5,6-tetramethyl-phenoxy group, the 2-tertiary butyl-3,5,6-trimethylammonium phenoxy group, 2,6-di-t-butyl-3,5-dimethyl phenoxy, the pentamethyl-phenoxy group, the ethyl phenoxy group, the n-propyl phenoxy group, the sec.-propyl phenoxy group, the normal-butyl phenoxy group, the sec-butyl phenoxy group, tertiary butyl phenoxy group, the n-hexyl phenoxy group, the n-octyl phenoxy group, positive decyl phenoxy group, naphthyloxy and anthracene oxygen base.
R 21To R 27Amino example be linear alkyl amino, for example N-methylamino, N-ethylamino, N-normal-butyl amino, N, N-dimethylamino, N, N-diethylamino and N, N-di-n-butyl amino; Branched-alkyl amino, N for example, N-diisopropylaminoethyl, N, N-diisobutyl amido, N, N-di-t-butyl amino and N, N-di neo-pentyl amino; And cycloalkyl amino, N for example, N-dicyclohexyl amino and N, N-two ring octyl group amino.
R 21To R 27The amide group example be ethanamide group, N-normal-butyl ethanamide group, N-methylacetamide group, N-ethyl acetamide group, N-normal-butyl hexanamide group, Isopropamide group, isobutyramide group, t-butyl carboxamide group, pivalyl amine groups, Cyclohexamide group and cyclooctylamine group.
R 21To R 27The example of imide group be succinimide group, maleimide base group and phthalimide-based group.
R 21To R 27The example of sulfenyl be alkylthio, for example methylthio group, ethylmercapto group, iprotiazem base and tertiary butyl sulfenyl; Arylthio, for example thiophenyl and naphthalene sulfenyl; And aromatic alkyl sulfurio, for example benzylthio and 9-fluorenyl methylthio group.
R 21To R 27Can have one or more substituting groups, for example halogen atom, alkoxyl group, aryloxy, aralkoxy, nitro, amino, amide group, imide group, silyl, siloxy-, alkylsulfonyl and sulfenyl.
Work as R 21To R 27Any two or more bondings each other when forming ring, the example of this ring be that aliphatic series is encircled and aromatic ring.Those rings can have one or more substituting groups, for example halogen atom, alkoxyl group, aryloxy, aralkoxy, nitro, amino, amide group, imide group, silyl, siloxy-, alkylsulfonyl and sulfenyl.
Work as R 21To R 27Any two each other bonding form when ring aliphatic series, the example that forms the divalent group of this aliphatic series ring is a methylene radical, ethane-1,2-two bases, propane-1,3-two bases, propane-1,2-two bases, butane-1,2-two bases, butane-1,3-two bases, butane-1,4-two bases, pentane-1,2-two bases, pentane-1,3-two bases, pentane-1,4-two bases, pentane-1,5-two bases, ethene-1,2-two bases, hexanaphthene-1,2-two bases, hexanaphthene-1,3-two bases, norbornane-1,2-two bases, norbornane-1-alkene-1,2-two bases, butane-1-alkene-1,2-two bases, butane-1-alkene-1,3-two bases, butane-1-alkene-2,3-two bases, butane-2-alkene-1,2-two bases, butane-2-alkene-1,3-two bases, butane-2-alkene-2,3-two bases, butane-1,3-diene-1,2-two bases, butane-1,3-diene-1,3-two bases, butane-1,3-diene-1,4-two bases, dimethyl-2, the 3-butene-2,3-two base and amylenes-2,4-two bases.
Work as R 21To R 27Any when two bonding forms aromatic ring each other, the example that forms the divalent group of aromatic ring is a benzene-1,2-two bases, 3-methylbenzene-1,2-two bases, 4-methylbenzene-1,2-two bases, 3-ethylbenzene-1,2-two bases, 4-ethylbenzene-1,2-two bases, 3-n-propylbenzene-1,2-two bases, 4-n-propylbenzene-1,2-two bases, 3-n-butylbenzene-1,2-two bases, 4-n-butylbenzene-1,2-two bases, 3-isopropyl benzene-1,2-two bases, 4-isopropyl benzene-1,2-two bases, 3-isobutyl-benzene-1,2-two bases, 4-isobutyl-benzene-1,2-two bases, 3-tert.-butylbenzene-1,2-two bases, 4-tert.-butylbenzene-1,2-two bases, benzene-1,3-two bases, 2-methylbenzene-1,3-two bases, 4-methylbenzene-1,3-two bases, biphenyl-2,2 '-two bases, benzene-1, the 2-dimethylene, benzene-1,3-dimethylene and naphthalene-1,8-two bases.
In each of above-mentioned divalent group a contained key with have R 21To R 27One of carbon atom bonding, and another wherein contained key with have a R 21To R 27In another carbon atom bonding.
Organo-aluminium compound among the present invention can be a compound as known in the art.The example of organo-aluminium compound is that following compound (1) arrives (3), and two or more combination:
(1) by formula E 1 dAlX 2 3-dThe organo-aluminium compound of expression;
(2) by formula { Al (E 2)-O-} eThe ring-type aikyiaiurnirsoxan beta (alumoxane) of expression; With
(3) by formula E 3{ Al (E 3)-O-} fAlE 3 2The line style aikyiaiurnirsoxan beta of expression,
E wherein 1, E 2And E 3Be alkyl independently of one another, and when there being a plurality of E 1, E 2Or E 3The time, they are same to each other or different to each other; X 2Be hydrogen atom or halogen atom, and when having a plurality of X, they are same to each other or different to each other; D is for satisfying the number of 0＜d≤3; E is 2 or bigger integer, and is preferably 2 to 40 integer; With f be 1 or bigger integer, and be preferably 1 to 40 integer.
E 1, E 2And E 3Alkyl be preferably alkyl and more preferably have the alkyl of 1 to 8 carbon atom with 1 to 8 carbon atom.E 1, E 2And E 3The example of alkyl be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl and neo-pentyl.Wherein preferably methyl or isobutyl-.
The example of above-mentioned organo-aluminium compound (1) is a trialkylaluminium, for example trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium and three hexyl aluminium; Dialkylaluminum chloride, for example dimethylaluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride and dihexylaluminum chloride; Alkyl al dichloride, for example methylaluminum dichloride, ethylaluminum dichloride, propyl group al dichloride, isobutyl-al dichloride and hexyl al dichloride; With the dialkyl group aluminum hydride, for example dimethyl hydrogenation aluminium, ADEH, dipropyl aluminum hydride, diisobutyl aluminium hydride and dihexyl aluminum hydride.Wherein preferably trialkylaluminium and more preferably triethyl aluminum or triisobutyl aluminium.
Above-mentioned ring-type aikyiaiurnirsoxan beta (2) and line style aikyiaiurnirsoxan beta (3) can be according to prepared in various methods.Those methods are not particularly limited, and can for as known in the art those.The example of described method is (i) a kind of method, comprise the step that the solution that makes the trialkylaluminium (for example trimethyl aluminium) in appropriate organic solvent (for example benzene and aliphatic hydrocrbon) contacts with water, (ii) a kind of method comprises the step that trialkylaluminium (for example trimethyl aluminium) is contacted with the metal-salt that contains crystal water (for example hydrated copper sulfate).
Boron compound among the present invention can be a compound as known in the art.The example of boron compound is that following compound (1) arrives (3), and two or more combination:
(1) by formula BQ 1Q 2Q 3The boron compound of expression;
(2) by formula G +(BQ 1Q 2Q 3Q 4) -The boron compound of expression; With
(3) by formula (J-H) +(BQ 1Q 2Q 3Q 4) -The boron compound of expression;
Wherein B is a trivalent boron atom; Q 1, Q 2, Q 3And Q 4Be halogen atom, alkyl, halo alkyl, silyl, siloxy-, alkoxyl group, amino, amido or imino-independently of one another; G +Be inorganic or organic cation; J is a neutral Lewis base; (J-H) +Be Bronsted acid.
Q in the above-mentioned formula 1, Q 2, Q 3And Q 4Be preferably halogen atom, have 1 to 20 carbon atom alkyl, have 1 to 20 carbon atom the halo alkyl, have 1 to 20 carbon atom silyl, have 1 to 20 carbon atom siloxy-, have C 2-20The amino of alkyl, have C 2-20The amido of alkyl or have C 2-20The imino-of alkyl; More preferably halogen atom, have the alkyl of 1 to 20 carbon atom or have the halo alkyl of 1 to 20 carbon atom; The C that more preferably contains one or more fluorine atoms 1-20Fluoridize alkyl; Be preferably the C that contains one or more fluorine atoms especially 6-20Fluoro aryl.
The example of above-mentioned boron compound (1) is three (pentafluorophenyl group) borine (tris (pentafluorophenyl) borane), three (2,3,5,6-tetrafluoro phenyl) borine, three (2,3,4,5-tetrafluoro phenyl) borine, three (3,4, the 5-trifluorophenyl) borine, three (2,3, the 4-trifluorophenyl) borine and two (pentafluorophenyl group) borines of phenyl.Wherein, three (pentafluorophenyl group) borine most preferably.
Inorganic cation G in the above-mentioned boron compound (2) +Example be ferrocene cation (ferrocenium cation), ferrocene cation and silver-colored positively charged ion with alkyl.Organic cation G wherein +Example be carbocation, trityl group positively charged ion for example.Wherein, G +Be preferably carbocation and be preferably the trityl group positively charged ion especially.
(BQ in above-mentioned boron compound (2) 1Q 2Q 3Q 4) -Example be four (pentafluorophenyl group) borate (tetrakis (pentafluorophenyl) borate), four (2,3,5,6-tetrafluoro phenyl) borate, four (2,3,4,5-tetrafluoro phenyl) borate, four (3,4, the 5-trifluorophenyl) borate, four (2,3,4-trifluorophenyl) borate, phenyl three (pentafluorophenyl group) borate and four (3, the 5-bis trifluoromethyl phenyl) borate.
The example of above-mentioned boron compound (2) is four (3, the 5-bis trifluoromethyl phenyl) lithium tetraborate, four (3, the 5-bis trifluoromethyl phenyl) Sodium Tetraborate, four (3, the 5-bis trifluoromethyl phenyl) potassium borate, four (pentafluorophenyl group) boric acid silver, four (pentafluorophenyl group) boric acid ferrocene, four (pentafluorophenyl group) boric acid 1,1 '-the dimethyl ferrocene, four (pentafluorophenyl group) boric acid tetrabutyl phosphorus, four (pentafluorophenyl group) boric acid tetraphenylphosphonium, four (pentafluorophenyl group) boric acid tetramethyl-ammonium, four (pentafluorophenyl group) boric acid trimethylammonium sulphur, four (pentafluorophenyl group) boric acid phenylbenzene iodine, four (pentafluorophenyl group) boric acid triphenylcarbenium and four (3, the 5-bis trifluoromethyl phenyl) boric acid triphenylcarbenium.Wherein, four (pentafluorophenyl group) boric acid triphenylcarbenium most preferably.
(J-H) in above-mentioned boron compound (3) +Example be trialkyl ammonium, N, N-dialkyl group puratized agricultural spray, dialkyl ammonium and triaryl phosphorus.(BQ wherein 1Q 2Q 3Q 4) -Example identical with above-mentioned those.
The example of above-mentioned boron compound (3) is four (pentafluorophenyl group) boric acid triethyl ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, four (3, the 5-bis trifluoromethyl phenyl) boric acid three (normal-butyl) ammonium, four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid N, N-diethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid N N-dimethyl-2,4,6-trimethylammonium puratized agricultural spray, four (3, the 5-bis trifluoromethyl phenyl) boric acid N, N-dimethyl puratized agricultural spray, four (pentafluorophenyl group) boric acid di-isopropyl ammonium, four (pentafluorophenyl group) boric acid dicyclohexyl ammonium, four (pentafluorophenyl group) boric acid triphenyl phosphorus, four (pentafluorophenyl group) boric acid, three (aminomethyl phenyl) phosphorus and four (pentafluorophenyl group) boric acid three (3,5-dimethylphenyl) phosphorus.Wherein, most preferably four (pentafluorophenyl group) boric acid, three (normal-butyl) ammoniums or four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray.
Boron compound is preferably above-mentioned boron compound (2) or (3), is preferably four (pentafluorophenyl group) boric acid triphenylcarbenium, four (pentafluorophenyl group) boric acid, three (normal-butyl) ammoniums or four (pentafluorophenyl group) boric acid N especially, N-dimethyl puratized agricultural spray.
The molecular weight of polymkeric substance of the present invention is not particularly limited.Its weight-average molecular weight (Mw) is preferably 1,000 to 10,000,000, and more preferably 2,000 to 5,000,000 and most preferably 4,000 to 3,000,000.
The molecular weight distribution of polymkeric substance of the present invention is not particularly limited.It is preferably 1.0 to 100, and more preferably 1.0 to 50 and most preferably 1.0 to 20.
The second-order transition temperature or the fusing point of polymkeric substance of the present invention is preferably-20 ℃ or higher, more preferably 20 ℃ or higher and most preferably 50 ℃ or higher.
In the present invention, make (i) above-mentioned transistion metal compound, (ii) above-mentioned organo-aluminium compound and/or boron compound (iii) are not particularly limited by the method that the compound and the (iv) above-mentioned alkene of formula (3) expression contacts with each other.
When transistion metal compound being contacted with organo-aluminium compound form polymerizing catalyst, organo-aluminium compound is preferably above-mentioned ring-type aikyiaiurnirsoxan beta, line style aikyiaiurnirsoxan beta or its combination, has highly active polymerizing catalyst so that form.When transistion metal compound, organo-aluminium compound and boron compound being contacted with each other form polymerizing catalyst, organo-aluminium compound is preferably by above-mentioned first formula E 1 dAlZ 3-dThe organo-aluminium compound of expression has highly active polymerizing catalyst so that form.
Organo-aluminium compound is with respect to each mole transistion metal compound, and usually with 0.1 to 10,000 molar part, the amount of preferred 5 to 2,000 molar part is used.Amount may cause the polymerization catalyst deficiency less than 0.1 molar part.Amount may cause generation to have low-molecular-weight polymkeric substance because for example to the chain transfer of organo-aluminium compound greater than 10,000 molar part, perhaps may produce to have SA polymerizing catalyst.Boron compound is with respect to each mole transistion metal compound, and usually with 0.01 to 100 molar part, the amount of preferred 0.5 to 10 molar part is used.Amount may cause the polymerization catalyst deficiency less than 0.01 molar part.From the economic point of view, the amount greater than 100 molar part is not preferred.
Transistion metal compound, organo-aluminium compound and boron compound all can use with the form of its solution.The example of the solvent of solution is methylene dichloride, chloroform, toluene, pentane, hexane and heptane.Wherein, preferably methylene dichloride, chloroform or toluene.
The solution of transistion metal compound has common 0.01 to 500 μ mol/L, preferred 0.05 to 100 μ mol/L and the more preferably concentration of 0.05 to 50 μ mol/L.With regard to the quantity of aluminium atom contained in the solution, the solution of organo-aluminium compound has common 0.01 to 10,000 μ mol/L, preferred 0.1 to 5,000 μ mol/L and the more preferably concentration of 0.1 to 2,000 μ mol/L.The solution of boron compound has common 0.01 to 500 μ mol/L, preferred 0.05 to 200 μ mol/L and the more preferably concentration of 0.05 to 100 μ mol/L.When the transition solution of metal compound has the concentration that is lower than 0.01 μ mol/L, when the solution of organo-aluminium compound has the concentration that is lower than 0.01 μ mol/L with regard to the quantity of aluminium atom contained in the solution, or when the solution of boron compound has the concentration that is lower than 0.01 μ mol/L, need a large amount of solvents to prepare solution, this is not preferred from the economic point of view.When the transition solution of metal compound has the concentration that is higher than 500 μ mol/L, when having, the solution of organo-aluminium compound with regard to the quantity of aluminium atom contained in the solution is higher than 10, the concentration of 000 μ mol/L, or when the solution of boron compound has the concentration that is higher than 500 μ mol/L, transistion metal compound, organo-aluminium compound or boron compound may not fully be dissolved in solvent, thereby make compound to be deposited in the solution.
Polymerizing catalyst among the present invention can with comprise inorganic or organic compound particulate carrier or support combine.The example of mineral compound is silica gel and aluminum oxide, and the example of organic compound is the polymkeric substance that contains styrene units.
In the present invention, polymerization process is not particularly limited.The example is the solution polymerization process of gaseous polymerization, mass polymerization, use suitable polymeric solvent and the suspension polymerization that uses the suitable polymeric solvent, and described method is batchwise polymerization method or continuous polymerization.Polymer solvent is not for making the solvent of polymerizing catalyst passivation.The example of solvent is a hydrocarbon solvent, for example benzene, toluene, pentane, hexane, heptane and hexanaphthene; And halogenated solvent, for example methylene dichloride and chloroform.
Polymerization temperature is not particularly limited in the present invention, and is generally-100 to 250 ℃ and preferred-50 to 200 ℃.Polymerization temperature is lower than-100 ℃ may cause the active not enough of polymerizing catalyst.Polymerization temperature is higher than 250 ℃ and may causes generation to have low-molecular-weight polymkeric substance, perhaps because the side reaction of for example isomerization reaction takes place, may cause producing the unitary polymkeric substance that contains by formula (1) expression.
Molecular weight for the polymkeric substance of regulating generation can use for example hydrogen of chain-transfer agent.
In the present invention, polymerization time is not particularly limited, and is generally 1 minute to 72 hours.Polymerization time is shorter than 1 minute polymer output deficiency that may cause producing.From the economic point of view, to be longer than 72 hours be disadvantageous to polymerization time.
Polymkeric substance of the present invention can be used in combination with various additives, and described additive for example is weather-proof stablizer, lubricant, pigment, dyestuff, static inhibitor, antioxidant, antifogging agent, rust-preventive agent, tensio-active agent and conductive agent.Polymkeric substance of the present invention also can for example new LDPE (film grade), high density polyethylene(HDPE), linear low density polyethylene, ethylene-acrylate copolymer, ethylene-methyl acrylate multipolymer, ethylene-vinyl acetate copolymer, ethene-alpha-olefin copolymer elastomerics and polypropylene be used in combination with polymkeric substance as known in the art.
Polymkeric substance of the present invention can be according to extrusion molding or injection moulding molding in addition.Those methods can be as known in the art.The example of extrusion molding is (1) blow moulding method (inflation moldingmethod), comprise that step (1-1) is via the annular die head resin melt extrusion, form thus and extrude product, (1-2) this is extruded product and be blow molded into cylindrical film or sheet material and (1-3) this film of rewinding or sheet material, (2) T pattern head moulding method, comprise that step (2-1) is via line style die head resin melt extrusion, form film or sheet material and (2-2) this film of rewinding or sheet material and (3) calendering moulding method thus.
Embodiment
Embodiment
The present invention is explained that with reference to following examples described embodiment does not limit the scope of the invention.
Reference example 1
Preparation is by the 5-allyl group-5-((2E)-crotyl)-2 of formula (3) expression, 2-dimethyl-1,3-diox-4,6-diketone
(1) preparation allyl malonic acid
In two mouthfuls of flasks of 100mL, add 9.0mL by Tokyo Chemical Industry Co., Ltd. the allyl diethyl malonate of Sheng Chaning, then to wherein adding 22.7mL ethanol and 22.7mL aqueous sodium hydroxide solution (concentration: 6M), the gained mixture was refluxed 6 hours.(concentration: 6M), the gained mixture extracts with ether to add 50mL hydrochloric acid in this reaction mixture.This extraction liquid water and sodium chloride solution successively washs.This extraction liquid through washing carries out drying by Nacalai Tesque on the anhydrous magnesium sulfate that Inc. produces.The extraction liquid of drying to remove solvent, obtains the 5.68g allyl malonic acid by distillation thus.
(2) preparation 5-allyl group-2,2-dimethyl-1,3-diox-4,6-diketone
In 100mL Schlenk pipe, place the allyl malonic acid for preparing above the 5.19g, then to wherein adding 8.64mL by Tokyo Chemical Industry Co., Ltd. the diacetyl oxide of Sheng Chaning, 0 ℃ to wherein further adding the 150 μ L vitriol oils and 5.76mLKanto Chemical Co., the dry acetone that Inc. produces.The gained mixture was stirring at room 15 hours.This reaction mixture is removed solvent by distillation, and remaining material extracts with chloroform.This extraction liquid water and sodium chloride solution successively washs.Extraction liquid through washing carries out drying by Nacalai Tesque on the anhydrous magnesium sulfate that Inc. produces.The extraction liquid of drying to remove solvent, obtains 3.91g 5-allyl group-2,2-dimethyl-1,3-diox-4,6-diketone by distillation thus.
(3) preparation 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4,6-diketone
With the 5-allyl group-2 for preparing more than the 3.5g, 2-dimethyl-1,3-diox-4,6-diketone, 130.9mg basis are at Supporting Information of The Journal of OrganicChemistry, 121 volumes, the Pd{P (OC of disclosed method preparation in 8728 pages (1999) 6H 5) 3} 4Put into 50mL Schlenk pipe with 4.34g 4A-molecular sieve.To wherein adding 9.5mL by KantoChemical Co., dry toluene that Inc. makes and 1.62mL be by Tokyo Chemical IndustryCo., the trans crotyl alcohol that Ltd. produces.The mixture of gained stirred 2 hours in argon gas atmosphere at 80 ℃.Add ether to this reaction mixture, its organic layer water washs.Organic layer through washing carries out drying by Nacalai Tesque on the anhydrous magnesium sulfate that Inc. produces.The organic layer of drying is removed solvent by distillation, and the liquid of gained distills in a vacuum then, obtains 3.26g 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4,6-diketone at 175 ℃ under the 4mmHg condition thus.
Embodiment 1
In 25mL Schlenk pipe, place the 5.7mg basis at Recueil des TravauxChimiques de Pays-Bas, 113 volumes, chlorine (the methyl) [N of disclosed method preparation in 88 pages (1994), N '-(1,2-acenaphthene-1,2-two subunits) two (2,4,6-trimethylaniline-κ N)] palladium (transistion metal compound) and 10.6mg basis is at Organometallics, 11 volumes, four (3, the 5-bis trifluoromethyl phenyl) Sodium Tetraborate (boron compound) of 3920 pages of (1992) disclosed method preparations.To wherein adding 0.5mL by Kanto Chemical Co., Inc., the dry methylene chloride of production, and the gained mixture stirred 10 minutes.To wherein add 5-allyl group-5-((2E)-crotyl)-2 that 166.7mg prepares in reference example 1,2-dimethyl-1,3-diox-4, the 6-diketone, and this mixture at room temperature is stirred 24 hours, obtains unitary 5-allyl group-5-((2E)-crotyl)-2 that 160mg has formula (1) expression thus, 2-dimethyl-1,3-diox-4, the homopolymer of 6-diketone.
This homopolymer dissolves in chloroform, methylene dichloride or tetrahydrofuran (THF), and be insoluble to hexane or methyl alcohol.This homopolymer has 7,900 number-average molecular weight (Mn), 1.68 molecular weight distribution (Mw/Mn); With regard to A 7And A 8Between the trans forms of 100 moles of % of relative configuration; No taxis; 116 ℃ second-order transition temperature in 30 ℃ and 150 ℃ of scopes.The results are shown in the table 1.
Above-mentioned number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) use the equipment by JASCO Corporation production with degasser (DG-980-50), pump (PU-980), automatic sampler (AS-950), post baking oven (CO-966), RI detector (RI-930) and UV detector (UV-975) to measure according to gel permeation chromatography (GPC) under the condition below, and typical curve uses polystyrene standard to obtain:
-two posts, SHODEX-806L is produced by Showa Denko K.K.;
-measurement temperature: 40 ℃;
-solvent: chloroform; With
-sample concentration: 1mg sample/mL solution.
The ratio basis of above-mentioned trans forms 13The C-NMR method use the equipment LA-500 that produces by JEOL LTD below condition measure; With by will by 13The C-NMR method obtains 13Signal allocation in 23 to the 50ppm scopes of C-NMR spectrum is given to be included in by the linear hydrocarbon based structures in the unit of formula (1) expression and 5 yuan of alkyl radical structure and is confirmed existence by the said units of formula (1) expression:
-measurement solvent is chloroform-d 1
-measurement temperature is a room temperature;
-sample concentration is 50mg sample/0.5mL solution;
With
-contrast material is chloroform-d 1(77ppm).
The equipment LA-500 that use is made by JEOL LTD is according to what may further comprise the steps 13The C-NMR method is measured above-mentioned taxis:
(1) at chloroform-d 1Middle preparation concentration is preferably the polymers soln of 286mg/mL;
(2) measure solution 13The C-NMR spectrum;
(3) peak area (A that exists in 46.2 to 46.6ppm in obtaining respectively composing 1) and the peak area (A that wherein in 46.9 to 47.3ppm, exists 2), condition is to belong to chloroform-d 1The peak appear at 77ppm; With
(4) calculate taxis according to following formula,
Threo-diisotactic triad (mole %)=100A 1/ (A 1+ A 2)
Threo-disyndiotactic triad (mole %)=100A 2/ (A 1+ A 2).
Above-mentioned second-order transition temperature uses SeikoInstruments ﹠amp according to dsc (DSC); The equipment SSC-5200 that Electronics Ltd. produces measures under the following conditions:
-be heated to 135 ℃ with 10 ℃/minute speed from 25 ℃, and kept 5 minutes at 135 ℃; Then,
-be cooled to-60 ℃ with 20 ℃/minute speed from 135 ℃, and kept 5 minutes at-60 ℃, then
-measure being heated under 150 ℃ of conditions from-60 ℃ with 10 ℃/minute speed.
Embodiment 2
Repeat embodiment 1, except with (i) 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone is changed into 176.6mg 5-allyl group-5-((2E)-pentenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, (ii) polymerization time is changed into 48 hours in 24 hours, obtain unitary 5-allyl group-5-((2E)-pentenyl)-2 that 150mg has formula (1) expression thus, 2-dimethyl-1,3-diox-4 is beyond the homopolymer of 6-diketone.
This homopolymer dissolves in chloroform, methylene dichloride or the tetrahydrofuran (THF), and is insoluble to hexane or methyl alcohol.This homopolymer has 16,500 number-average molecular weight (Mn); 2.0 molecular weight distribution (Mw/Mn); With regard to A 7And A 8Between relative configuration have the trans forms of 100 moles of %; No taxis; 96 ℃ second-order transition temperature in 30 ℃ and 150 ℃ of scopes.The results are shown in the table 1.
Embodiment 3
Repeat embodiment 1, except with 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone is changed into 186.4mg 5-allyl group-5-((2E)-2-hexenyl)-2,2-dimethyl-1,3-diox-4,6-diketone, obtain unitary 5-allyl group-5-((2E)-2-hexenyl)-2 that 180mg has formula (1) expression thus, 2-dimethyl-1,3-diox-4 is beyond the homopolymer of 6-diketone.
This homopolymer has 12,200 number-average molecular weight (Mn), 1.9 molecular weight distribution (Mw/Mn); With regard to A 7And A 8Between the trans forms of 100 moles of % of relative configuration; No taxis; The results are shown in the table 1.
Embodiment 4
Repeat embodiment 1, except with 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone is changed into 196.3mg 5-allyl group-5-((2E)-2-heptenyl)-2,2-dimethyl-1,3-diox-4,6-diketone, obtain unitary 5-allyl group-5-((2E)-2-heptenyl)-2 that 180mg has formula (1) expression thus, 2-dimethyl-1,3-diox-4 is beyond the homopolymer of 6-diketone.
This homopolymer dissolves in chloroform, methylene dichloride or the tetrahydrofuran (THF), and is insoluble in hexane or the methyl alcohol.This homopolymer has 10,400 number-average molecular weight (Mn), 2.0 molecular weight distribution (Mw/Mn); With regard to A 7And A 8Between the trans forms of 100 moles of % of relative configuration; With no taxis.The results are shown in the table 1.
Embodiment 5
Repeat embodiment 1, except (i) with 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone is changed into 206.1mg 5-allyl group-5-((2E)-2-octenyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone, (ii) polymerization time is changed into 48 hours in 24 hours, obtain unitary 5-allyl group-5-((2E)-2-octenyl)-2 that 41mg has formula (1) expression thus, 2-dimethyl-1,3-diox-4 is beyond the homopolymer of 6-diketone.
This homopolymer dissolves in chloroform or the methylene dichloride, and is insoluble in hexane or the methyl alcohol.This homopolymer has 10,100 number-average molecular weight (Mn), 2.3 molecular weight distribution (Mw/Mn); With regard to A 7And A 8Between the trans forms of 100 moles of % of relative configuration; With no taxis.The results are shown in the table 1.
Embodiment 6
Repeat embodiment 1, except (i) with 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone is changed into 215.1mg 5-allyl group-5-((2E)-2-nonene base)-2,2-dimethyl-1,3-diox-4, the 6-diketone, (ii) polymerization time is changed into 48 hours in 24 hours, obtain unitary 5-allyl group-5-((2E)-2-nonene base)-2 that 58mg has formula (1) expression thus, 2-dimethyl-1,3-diox-4 is beyond the homopolymer of 6-diketone.
This homopolymer dissolves in chloroform or the methylene dichloride, and is insoluble in hexane or the methyl alcohol.This homopolymer has 9,300 number-average molecular weight (Mn), 2.1 molecular weight distribution (Mw/Mn); With regard to A 7And A 8Between the trans forms of 100 moles of % of relative configuration; With no taxis.The results are shown in the table 1.
Embodiment 7
Repeat embodiment 1, except (i) with 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4, the 6-diketone is changed into 255.2mg 5-allyl group-5-((2E)-2-tridecylene base)-2,2-dimethyl-1,3-diox-4, the 6-diketone, (ii) polymerization time is changed into 48 hours in 24 hours, obtain unitary 5-allyl group-5-((2E)-2-tridecylene base)-2 that 89mg has formula (1) expression thus, 2-dimethyl-1,3-diox-4 is beyond the homopolymer of 6-diketone.
This homopolymer dissolves in chloroform or the methylene dichloride, and is insoluble in hexane or the methyl alcohol.This homopolymer has 6,900 number-average molecular weight (Mn), 1.7 molecular weight distribution (Mw/Mn); With regard to A 7And A 8Between the trans forms of 100 moles of % of relative configuration; With no taxis.The results are shown in the table 1.
Table 1
Figure A20081008109600591
Note 1:
M-1 is 5-allyl group-5-((2E)-crotyl)-2,2-dimethyl-1,3-diox-4,6-diketone.
M-2 is 5-allyl group-5-((2E)-pentenyl)-2,2-dimethyl-1,3-diox-4,6-diketone.
M-3 is 5-allyl group-5-((2E)-2-hexenyl)-2,2-dimethyl-1,3-diox-4,6-diketone.
M-4 is 5-allyl group-5-((2E)-2-heptenyl)-2,2-dimethyl-1,3-diox-4,6-diketone.
M-5 is 5-allyl group-5-((2E)-2-octenyl)-2,2-dimethyl-1,3-diox-4,6-diketone.
M-6 is 5-allyl group-5-((2E)-2-nonene base)-2,2-dimethyl-1,3-diox-4,6-diketone.
M-7 is 5-allyl group-5-((2E)-2-tridecylene base)-2,2-dimethyl-1,3-diox-4,6-diketone.

Claims (12)

1. one kind comprises the unitary polymkeric substance of being represented by following formula (1):
X wherein 1And X 2Be the atom of 16 families in the periodic table of elements independently of one another; Y 1And Y 2Be alkoxyl group, aralkoxy or aryloxy independently of one another, and Y 1And Y 2Can be bonded to ring each other; A 1, A 2, A 3, A 4, A 5, A 6, A 7, A 8, A 9And A 10Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another; And A 3And A 4, or A 5And A 6Can be bonded to ring each other; With n be 1 to 20 integer.
2. according to the polymkeric substance of claim 1, the described unit of its Chinese style (1) expression comprises the unit by following formula (2) expression, its A 7And A 8Between relative configuration be trans:
Figure A20081008109600022
Those of definition are identical in all symbols that comprise in its Chinese style (2) and the formula (1).
3. according to the polymkeric substance of claim 1, wherein said polymkeric substance is the polymkeric substance that has greater than 25 moles of % threo-diisotactic triad, and the unitary total amount of being represented by formula (1) is 100 moles of %.
4. according to the polymkeric substance of claim 1, wherein said polymkeric substance is the polymkeric substance that has greater than the two isotactic triad of 25 moles of % erythros, and the unitary total amount of being represented by formula (1) is 100 moles of %.
5. according to the polymkeric substance of claim 1, wherein said polymkeric substance is the polymkeric substance that has greater than 25 moles of % threo-disyndiotactic triad, and the unitary total amount of being represented by formula (1) is 100 moles of %.
6. according to the polymkeric substance of claim 1, wherein said polymkeric substance is the polymkeric substance that has greater than the two syndiotaxy triad of 25 moles of % erythros, and the unit total amount of being represented by formula (1) is 100 moles of %.
7. one kind prepares the method that has by the polymkeric substance of the repeating unit of following formula (1) expression, and this method comprises the step of polymerization by the compound of following formula (3) expression:
Figure A20081008109600032
X wherein 1And X 2Be the atom of 16 families in the periodic table of elements independently of one another; Y 1And Y 2Be alkoxyl group, aralkoxy or aryloxy independently of one another, and Y 1And Y 2Can be bonded to ring each other; A 1, A 2, A 3, A 4, A 5, A 6, A 7, A 8, A 9And A 10Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another; And A 3And A 4, perhaps A 5And A 6Can be bonded to ring each other; Z is-(CH 2) N-1-CHA 9A 10Group; Two wave lines that formula (3) upper right side shows are represented the variation in their configurations; With n be 1 to 20 integer.
8. according to the method for preparing polymkeric substance of claim 7, wherein, transistion metal compound carrying out polymerization by being contacted with organo-aluminium compound and/or boron compound in the presence of the polymerizing catalyst that forms.
9. the method for preparing polymkeric substance according to Claim 8, wherein said transistion metal compound are the compound by following formula [I] expression:
Figure A20081008109600041
M wherein 2Transition metal atoms for the periodic table of elements 10 families; R 3And R 4Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy or aryloxy independently of one another; R 5And R 6Independently of one another for having the alkyl of 1 to 30 carbon atom; R 7And R 8Be hydrogen atom or alkyl independently of one another with 1 to 20 carbon atom, and R 7And R 8Can be bonded to ring each other.
10. the method for preparing polymkeric substance according to Claim 8, wherein said transistion metal compound are the compound by following formula [II] expression:
Figure A20081008109600042
M wherein 2, R 3, R 4, R 7And R 8With definition in the formula [I] those are identical; R 9And R 10Be hydrogen atom, halogen atom, alkyl, aralkyl, silyl, siloxy-, alkoxyl group, aralkoxy, amino, amide group, imide group or sulfenyl independently of one another; R 11And R 12Independently of one another for having the aryl of 7 to 20 carbon atoms; R 13And R 14Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another.
11. the method for preparing polymkeric substance according to Claim 8, wherein said transistion metal compound are the compound by following formula [III] expression:
M wherein 2, R 3, R 4, R 7And R 8With definition in the formula [I] those are identical; R 15, R 16, R 17And R 18Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another with 6 carbon atoms; R 19And R 20Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another.
12. the method for preparing polymkeric substance according to Claim 8, wherein said transistion metal compound are the compound by following formula [IV] expression:
Figure A20081008109600052
M wherein 3Transition metal atoms for the periodic table of elements 8 to 11 families; R 3And R 4With definition in the formula [I] those are identical; R 21To R 27Be hydrogen atom, halogen atom, alkyl, aralkyl, aryl, silyl, siloxy-, alkoxyl group, aralkoxy, aryloxy, amino, amide group, imide group or sulfenyl independently of one another, and R 21To R 27Any two or more can be bonded to ring each other.
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